Results from the FIN-2 formal comparison

NASA Astrophysics Data System (ADS)

Connolly, Paul; Hoose, Corinna; Liu, Xiaohong; Moehler, Ottmar; Cziczo, Daniel; DeMott, Paul

2017-04-01

During the Fifth International Ice Nucleation Workshop (FIN-2) at the AIDA Ice Nucleation facility in Karlsruhe, Germany in March 2015, a formal comparison of ice nucleation measurement methods was conducted. During the experiments the samples of ice nucleating particles were not revealed to the instrument scientists, hence this was referred to as a "blind comparison". The two samples used were later revealed to be Arizona Test Dust and an Argentina soil sample. For these two samples seven mobile ice nucleating particle counters sampled directly from the AIDA chamber or from the aerosol preparation chamber at specified temperatures, whereas filter samples were taken for two offline deposition nucleation instruments. Wet suspension methods for determining IN concentrations were also used with 10 different methods employed. For the wet suspension methods experiments were conducted using INPs collected from the air inside the chambers (impinger sampling) and INPs taken from the bulk samples (vial sampling). Direct comparisons of the ice nucleating particle concentrations are reported as well as derived ice nucleation active site densities. The study highlights the difficulties in performing such analyses, but generally indicates that there is reasonable agreement between the wet suspension techniques. It is noted that ice nucleation efficiency derived from the AIDA chamber (quantified using the ice active surface site density approach) is higher than that for the cold stage techniques. This is both true for the Argentina soil sample and, to a lesser extent, for the Arizona Test Dust sample too. Other interesting effects were noted: for the ATD the impinger sampling demonstrated higher INP efficiency at higher temperatures (>255 K) than the vial sampling, but agreed at the lower temperatures (<255K), whereas the opposite was true for the Argentina soil sample. The results are analysed to better understand the performance of the various techniques and to address any size-sorting effects and / or sampling line loses.

Cirrus Parcel Model Comparison Project. Phase 1

NASA Technical Reports Server (NTRS)

Lin, Ruei-Fong; Starr, David O'C.; DeMott, Paul J.; Cotton, Richard; Jensen, Eric; Sassen, Kenneth

2000-01-01

The Cirrus Parcel Model Comparison (CPMC) is a project of the GEWEX Cloud System Study Working Group on Cirrus Cloud Systems (GCSS WG2). The primary goal of this project is to identify cirrus model sensitivities to the state of our knowledge of nucleation and microphysics. Furthermore, the common ground of the findings may provide guidelines for models with simpler cirrus microphysics modules. We focus on the nucleation regimes of the warm (parcel starting at -40 C and 340 hPa) and cold (-60 C and 170 hPa) cases studied in the GCSS WG2 Idealized Cirrus Model Comparison Project. Nucleation and ice crystal growth were forced through an externally imposed rate of lift and consequent adiabatic cooling. The background haze particles are assumed to be lognormally-distributed H2SO4 particles. Only the homogeneous nucleation mode is allowed to form ice crystals in the HN-ONLY runs; all nucleation modes are switched on in the ALL-MODE runs. Participants were asked to run the HN-lambda-fixed runs by setting lambda = 2 (lambda is further discussed in section 2) or tailoring the nucleation rate calculation in agreement with lambda = 2 (exp 1). The depth of parcel lift (800 m) was set to assure that parcels underwent complete transition through the nucleation regime to a stage of approximate equilibrium between ice mass growth and vapor supplied by the specified updrafts.

Homogeneous Freezing of Water Droplets and its Dependence on Droplet Size

NASA Astrophysics Data System (ADS)

Schmitt, Thea; Möhler, Ottmar; Höhler, Kristina; Leisner, Thomas

2014-05-01

The formulation and parameterisation of microphysical processes in tropospheric clouds, such as phase transitions, is still a challenge for weather and climate models. This includes the homogeneous freezing of supercooled water droplets, since this is an important process in deep convective systems, where almost pure water droplets may stay liquid until homogeneous freezing occurs at temperatures around 238 K. Though the homogeneous ice nucleation in supercooled water is considered to be well understood, recent laboratory experiments with typical cloud droplet sizes showed one to two orders of magnitude smaller nucleation rate coefficients than previous literature results, including earlier results from experiments with single levitated water droplets and from cloud simulation experiments at the AIDA (Aerosol Interaction and Dynamics in the Atmosphere) facility. This motivated us to re-analyse homogeneous droplet freezing experiments conducted during the previous years at the AIDA cloud chamber. This cloud chamber has a volume of 84m3 and operates under atmospherically relevant conditions within wide ranges of temperature, pressure and humidity, whereby investigations of both tropospheric mixed-phase clouds and cirrus clouds can be realised. By controlled adiabatic expansions, the ascent of an air parcel in the troposphere can be simulated. According to our new results and their comparison to the results from single levitated droplet experiments, the homogeneous freezing of water droplets seems to be a volume-dependent process, at least for droplets as small as a few micrometers in diameter. A contribution of surface induced freezing can be ruled out, in agreement to previous conclusions from the single droplet experiments. The obtained volume nucleation rate coefficients are in good agreement, within error bars, with some previous literature data, including our own results from earlier AIDA experiments, but they do not agree with recently published lower volume nucleation rate coefficients. This contribution will show the results from the re-analysis of AIDA homogeneous freezing experiments with pure water droplets and will discuss the comparison to the literature data.

Comparison of the SAWNUC model with CLOUD measurements of sulphuric acid-water nucleation.

PubMed

Ehrhart, Sebastian; Ickes, Luisa; Almeida, Joao; Amorim, Antonio; Barmet, Peter; Bianchi, Federico; Dommen, Josef; Dunne, Eimear M; Duplissy, Jonathan; Franchin, Alessandro; Kangasluoma, Juha; Kirkby, Jasper; Kürten, Andreas; Kupc, Agnieszka; Lehtipalo, Katrianne; Nieminen, Tuomo; Riccobono, Francesco; Rondo, Linda; Schobesberger, Siegfried; Steiner, Gerhard; Tomé, António; Wimmer, Daniela; Baltensperger, Urs; Wagner, Paul E; Curtius, Joachim

2016-10-27

Binary nucleation of sulphuric acid-water particles is expected to be an important process in the free troposphere at low temperatures. SAWNUC (Sulphuric Acid Water Nucleation) is a model of binary nucleation that is based on laboratory measurements of the binding energies of sulphuric acid and water in charged and neutral clusters. Predictions of SAWNUC are compared for the first time comprehensively with experimental binary nucleation data from the CLOUD chamber at European Organization for Nuclear Research. The experimental measurements span a temperature range of 208-292 K, sulphuric acid concentrations from 1·10 6 to 1·10 9  cm -3 , and distinguish between ion-induced and neutral nucleation. Good agreement, within a factor of 5, is found between the experimental and modeled formation rates for ion-induced nucleation at 278 K and below and for neutral nucleation at 208 and 223 K. Differences at warm temperatures are attributed to ammonia contamination which was indicated by the presence of ammonia-sulphuric acid clusters, detected by an Atmospheric Pressure Interface Time of Flight (APi-TOF) mass spectrometer. APi-TOF measurements of the sulphuric acid ion cluster distributions ( (H2SO4)i·HSO4- with i = 0, 1, ..., 10) show qualitative agreement with the SAWNUC ion cluster distributions. Remaining differences between the measured and modeled distributions are most likely due to fragmentation in the APi-TOF. The CLOUD results are in good agreement with previously measured cluster binding energies and show the SAWNUC model to be a good representation of ion-induced and neutral binary nucleation of sulphuric acid-water clusters in the middle and upper troposphere.

On atomic structure of Ge huts growing on the Ge/Si(001) wetting layer

NASA Astrophysics Data System (ADS)

Arapkina, Larisa V.; Yuryev, Vladimir A.

2013-09-01

Structural models of growing Ge hut clusters—pyramids and wedges—are proposed on the basis of data of recent STM investigations of nucleation and growth of Ge huts on the Si(001) surface in the process of molecular beam epitaxy. It is shown that extension of a hut base along ⟨110⟩ directions goes non-uniformly during the cluster growth regardless of its shape. Growing pyramids, starting from the second monolayer, pass through cyclic formation of slightly asymmetrical and symmetrical clusters, with symmetrical ones appearing after addition of every fourth monolayer. We suppose that pyramids of symmetrical configurations composed by 2, 6, 10, etc., monolayers over the wetting layer are more stable than asymmetrical ones. This might explain less stability of pyramids in comparison with wedges in dense arrays forming at low temperatures of Ge deposition. Possible nucleation processes of pyramids and wedges on wetting layer patches from identical embryos composed by 8 dimers through formation of 1 monolayer high 16-dimer nuclei different only in their symmetry is discussed. Schematics of these processes are presented. It is concluded from precise STM measurements that top layers of wetting layer patches are relaxed when huts nucleate on them.

On atomic structure of Ge huts growing on the Ge/Si(001) wetting layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arapkina, Larisa V.; Yuryev, Vladimir A.

Structural models of growing Ge hut clusters—pyramids and wedges—are proposed on the basis of data of recent STM investigations of nucleation and growth of Ge huts on the Si(001) surface in the process of molecular beam epitaxy. It is shown that extension of a hut base along <110> directions goes non-uniformly during the cluster growth regardless of its shape. Growing pyramids, starting from the second monolayer, pass through cyclic formation of slightly asymmetrical and symmetrical clusters, with symmetrical ones appearing after addition of every fourth monolayer. We suppose that pyramids of symmetrical configurations composed by 2, 6, 10, etc., monolayersmore » over the wetting layer are more stable than asymmetrical ones. This might explain less stability of pyramids in comparison with wedges in dense arrays forming at low temperatures of Ge deposition. Possible nucleation processes of pyramids and wedges on wetting layer patches from identical embryos composed by 8 dimers through formation of 1 monolayer high 16-dimer nuclei different only in their symmetry is discussed. Schematics of these processes are presented. It is concluded from precise STM measurements that top layers of wetting layer patches are relaxed when huts nucleate on them.« less

An aggregation-volume-bias Monte Carlo investigation on the condensation of a Lennard-Jones vapor below the triple point and crystal nucleation in cluster systems: an in-depth evaluation of the classical nucleation theory.

PubMed

Chen, Bin; Kim, Hyunmi; Keasler, Samuel J; Nellas, Ricky B

2008-04-03

The aggregation-volume-bias Monte Carlo based simulation technique, which has led to our recent success in vapor-liquid nucleation research, was extended to the study of crystal nucleation processes. In contrast to conventional bulk-phase techniques, this method deals with crystal nucleation events in cluster systems. This approach was applied to the crystal nucleation of Lennard-Jonesium under a wide range of undercooling conditions from 35% to 13% below the triple point. It was found that crystal nucleation in these model clusters proceeds initially via a vapor-liquid like aggregation followed by the formation of crystals inside the aggregates. The separation of these two stages of nucleation is distinct except at deeper undercooling conditions where the crystal nucleation barrier was found to diminish. The simulation results obtained for these two nucleation steps are separately compared to the classical nucleation theory (CNT). For the vapor-liquid nucleation step, the CNT was shown to provide a reasonable description of the critical cluster size but overestimate the barrier heights, consistent with previous simulation studies. On the contrary, for the crystal nucleation step, nearly perfect agreement with the barrier heights was found between the simulations and the CNT. For the critical cluster size, the comparison is more difficult as the simulation data were found to be sensitive to the definition of the solid cluster, but a stringent criterion and lower undercooling conditions generally lead to results closer with the CNT. Additional simulations at undercooling conditions of 40% or above indicate a nearly barrierless transition from the liquid to crystalline-like structure for sufficiently large clusters, which leads to further departure of the barrier height predicted by the CNT from the simulation data for the aggregation step. This is consistent with the latest experimental results on argon that show an unusually large underestimation of the nucleation rate by the CNT toward deep undercooling conditions.

Immersion and contact freezing experiments in the Mainz wind tunnel laboratory

NASA Astrophysics Data System (ADS)

Eppers, Oliver; Mayer, Amelie; Diehl, Karoline; Mitra, Subir; Borrmann, Stephan; Szakáll, Miklós

2016-04-01

Immersion and contact freezing are of outmost important ice nucleation processes in mixed phase clouds. Experimental studies are carried out in the Mainz vertical wind tunnel laboratory in order to characterize these nucleation processes for different ice nucleating particles (INP), such as for mineral dust or biological particles. Immersion freezing is investigated in our laboratory with two different experimental techniques, both attaining contact-free levitation of liquid droplets and cooling of the surrounding air down to about -25 °C. In an acoustic levitator placed in the cold room of our laboratory, drops with diameters of 2 mm are investigated. In the vertical air stream of the wind tunnel droplets with diameter of 700 micron are freely floated at their terminal velocities, simulating the flow conditions of the free atmosphere. Furthermore, the wind tunnel offers a unique platform for contact freezing experiments. Supercooled water droplets are floated in the vertical air stream at their terminal velocities and INP are injected into the tunnel air stream upstream of them. As soon as INP collides with the supercooled droplet the contact freezing is initiated. The first results of immersion and contact freezing experiments with cellulose particles both in the acoustic levitator and in the wind tunnel will be presented. Cellulose is considered as typical INP of biological origin and a macrotracer for plant debris. Nucleating properties of cellulose will be provided, mainly focusing on the temperature, INP concentration, and specific surface area dependences of the freezing processes. Direct comparison between the different experimental techniques (acoustic levitator and wind tunnel), as well as between nucleation modes (immersion and contact freezing) will be presented. The work is carried out within the framework of the German research unit INUIT.

The kinetics of heterogeneous nucleation and growth: an approach based on a grain explicit model

NASA Astrophysics Data System (ADS)

Rouet-Leduc, B.; Maillet, J.-B.; Denoual, C.

2014-04-01

A model for phase transitions initiated on grain boundaries is proposed and tested against numerical simulations: this approach, based on a grain explicit model, allows us to consider the granular structure, resulting in accurate predictions for a wide span of nucleation processes. Comparisons are made with classical models of homogeneous (JMAK: Johnson and Mehl 1939 Trans. Am. Inst. Min. Eng. 135 416; Avrami 1939 J. Chem. Phys. 7 1103; Kolmogorov 1937 Bull. Acad. Sci. USSR, Mat. Ser. 1 335) as well as heterogeneous (Cahn 1996 Thermodynamics and Kinetics of Phase Transformations Im et al (Pittsburgh: Materials Research Society)) nucleation. A transition scale based on material properties is proposed, allowing us to discriminate between random and site-saturated regimes. Finally, we discuss the relationship between an Avrami-type exponent and the transition regime, establishing conditions for its extraction from experiments.

The double nucleation model for sickle cell haemoglobin polymerization: full integration and comparison with experimental data.

PubMed

Medkour, Terkia; Ferrone, Frank; Galactéros, Frédéric; Hannaert, Patrick

2008-06-01

Sickle cell haemoglobin (HbS) polymerization reduces erythrocyte deformability, causing deleterous vaso-occlusions. The double-nucleation model states that polymers grow from HbS aggregates, the nuclei, (i) in solution (homogeneous nucleation), (ii) onto existing polymers (heterogeneous nucleation). When linearized at initial HbS concentration, this model predicts early polymerization and its characteristic delay-time (Ferrone et al. J Mol Biol 183(4):591-610, 611-631, 1985). Addressing its relevance for describing complete polymerization, we constructed the full, non-linearized model (Simulink), The MathWorks). Here, we compare the simulated outputs to experimental progress curves (n = 6-8 different [HbS], 3-6 mM range, from Ferrone's group). Within 10% from start, average root mean square (rms) deviation between simulated and experimental curves is 0.04 +/- 0.01 (25 degrees C, n = 8; mean +/- standard error). Conversely, for complete progress curves, averaged rms is 0.48 +/- 0.04. This figure is improved to 0.13 +/- 0.01 by adjusting heterogeneous pathway parameters (p < 0.01): the nucleus stability (sigma(2) micro( cc ): + 40%), and the fraction of polymer surface available for nucleation (phi), from 5e(-7), (3 mM) to 13 (6 mM). Similar results are obtained at 37 degrees C. We conclude that the physico-chemical description of heterogeneous nucleation warrants refinements in order to capture the whole HbS polymerization process.

Surface structure, crystallographic and ice-nucleating properties of cellulose

NASA Astrophysics Data System (ADS)

Hiranuma, Naruki; Möhler, Ottmar; Kiselev, Alexei; Saathoff, Harald; Weidler, Peter; Shutthanandan, Shuttha; Kulkarni, Gourihar; Jantsch, Evelyn; Koop, Thomas

2015-04-01

Increasing evidence of the high diversity and efficient freezing ability of biological ice-nucleating particles is driving a reevaluation of their impact upon climate. Despite their potential importance, little is known about their atmospheric abundance and ice nucleation efficiency, especially non-proteinaceous ones, in comparison to non-biological materials (e.g., mineral dust). Recently, microcrystalline cellulose (MCC; non-proteinaceous plant structural polymer) has been identified as a potential biological ice-nucleating particle. However, it is still uncertain if the ice-nucleating activity is specific to the MCC structure or generally relevant to all cellulose materials, such that the results of MCC can be representatively scaled up to the total cellulose content in the atmosphere to address its role in clouds and the climate system. Here we use the helium ion microscopy (HIM) imaging and the X-ray diffraction (XRD) technique to characterize the nanoscale surface structure and crystalline properties of the two different types of cellulose (MCC and fibrous cellulose extracted from natural wood pulp) as model proxies for atmospheric cellulose particles and to assess their potential accessibility for water molecules. To complement these structural characterizations, we also present the results of immersion freezing experiments using the cold stage-based droplet freezing BINARY (Bielefeld Ice Nucleation ARaY) technique. The HIM results suggest that both cellulose types have a complex porous morphology with capillary spaces between the nanoscale fibrils over the microfiber surface. These surface structures may make cellulose accessible to water. The XRD results suggest that the structural properties of both cellulose materials are in agreement (i.e., P21 space group; a=7.96 Å, b=8.35 Å, c=10.28 Å) and comparable to the crystallographic properties of general monoclinic cellulose (i.e., Cellulose Iβ). The results obtained from the BINARY measurements suggest that there is no significant difference of the immersion ice nucleation activity of MCC and fibrous cellulose in supercooled water. Overall, our findings support the view that MCC may be a good proxy for inferring water uptake, wettability and ice nucleating properties of various cellulose materials. In addition, we discuss the ice-nucleating efficiencies of both cellulose samples and plant debris from the AIDA (Aerosol Interaction and Dynamics in the Atmosphere) chamber experiments in comparison to the BINARY results. The influence of the acid processing of cellulose on its ice nucleation propensity may also be discussed to further demonstrate their atmospheric relevancy. Acknowledgement: We acknowledge support by German Research Society (DFG) and Ice Nuclei research UnIT (FOR 1525 INUIT).

Sensitivity of CAM5-simulated Arctic clouds and radiation to ice nucleation parameterization

DOE PAGES

Xie, Shaocheng; Liu, Xiaohong; Zhao, Chuanfeng; ...

2013-08-06

Sensitivity of Arctic clouds and radiation in the Community Atmospheric Model, version 5, to the ice nucleation process is examined by testing a new physically based ice nucleation scheme that links the variation of ice nuclei (IN) number concentration to aerosol properties. The default scheme parameterizes the IN concentration simply as a function of ice supersaturation. The new scheme leads to a significant reduction in simulated IN concentration at all latitudes while changes in cloud amounts and properties are mainly seen at high- and midlatitude storm tracks. In the Arctic, there is a considerable increase in midlevel clouds and amore » decrease in low-level clouds, which result from the complex interaction among the cloud macrophysics, microphysics, and large-scale environment. The smaller IN concentrations result in an increase in liquid water path and a decrease in ice water path caused by the slowdown of the Bergeron–Findeisen process in mixed-phase clouds. Overall, there is an increase in the optical depth of Arctic clouds, which leads to a stronger cloud radiative forcing (net cooling) at the top of the atmosphere. The comparison with satellite data shows that the new scheme slightly improves low-level cloud simulations over most of the Arctic but produces too many midlevel clouds. Considerable improvements are seen in the simulated low-level clouds and their properties when compared with Arctic ground-based measurements. As a result, issues with the observations and the model–observation comparison in the Arctic region are discussed.« less

Nucleation and crystal growth behavior of nepheline in simulated high-level waste glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fox, K.; Amoroso, J.; Mcclane, D.

The Savannah River National Laboratory (SRNL) has been tasked with supporting glass formulation development and process control strategies in key technical areas, relevant to the Department of Energy’s Office of River Protection (DOE-ORP) and related to high-level waste (HLW) vitrification at the Waste Treatment and Immobilization Plant (WTP). Of specific interest is the development of predictive models for crystallization of nepheline (NaAlSiO4) in HLW glasses formulated at high alumina concentrations. This report summarizes recent progress by researchers at SRNL towards developing a predicative tool for quantifying nepheline crystallization in HLW glass canisters using laboratory experiments. In this work, differential scanningmore » calorimetry (DSC) was used to obtain the temperature regions over which nucleation and growth of nepheline occur in three simulated HLW glasses - two glasses representative of WTP projections and one glass representative of the Defense Waste Processing Facility (DWPF) product. The DWPF glass, which has been studied previously, was chosen as a reference composition and for comparison purposes. Complementary quantitative X-ray diffraction (XRD) and optical microscopy confirmed the validity of the methodology to determine nucleation and growth behavior as a function of temperature. The nepheline crystallization growth region was determined to generally extend from ~ 500 to >850 °C, with the maximum growth rates occurring between 600 and 700 °C. For select WTP glass compositions (high Al2O3 and B2O3), the nucleation range extended from ~ 450 to 600 °C, with the maximum nucleation rates occurring at ~ 530 °C. For the DWPF glass composition, the nucleation range extended from ~ 450 to 750 °C with the maximum nucleation rate occurring at ~ 640 °C. The nepheline growth at the peak temperature, as determined by XRD, was between 35 - 75 wt.% /hour. A maximum nepheline growth rate of ~ 0.1 mm/hour at 700 °C was measured for the DWPF composition using optical microscopy. This research establishes a viable alternative to more traditional techniques for evaluating nepheline crystallization in large numbers of glasses, which are prohibitively time consuming or otherwise impractical. The ultimate objective is to combine the nucleation and growth information obtained from DSC, like that presented in this report, with computer simulations of glass cooling within the canister to accurately predict nepheline crystallization in HLW during processing through WTP.« less

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 properties, such as cloud longevity and initiation, compared to previous parameterizations.

Thermodynamics and Kinetics of Prenucleation Clusters, Classical and Non-Classical Nucleation

PubMed Central

Zahn, Dirk

2015-01-01

Recent observations of prenucleation species and multi-stage crystal nucleation processes challenge the long-established view on the thermodynamics of crystal formation. Here, we review and generalize extensions to classical nucleation theory. Going beyond the conventional implementation as has been used for more than a century now, nucleation inhibitors, precursor clusters and non-classical nucleation processes are rationalized as well by analogous concepts based on competing interface and bulk energy terms. This is illustrated by recent examples of species formed prior to/instead of crystal nucleation and multi-step nucleation processes. Much of the discussed insights were obtained from molecular simulation using advanced sampling techniques, briefly summarized herein for both nucleation-controlled and diffusion-controlled aggregate formation. PMID:25914369

Nucleation of insulin crystals in a wide continuous supersaturation gradient.

PubMed

Penkova, Anita; Dimitrov, Ivaylo; Nanev, Christo

2004-11-01

Modifying the classical double pulse technique, by using a supersaturation gradient along an insulin solution contained in a glass capillary tube, we found conditions appropriate for the direct measurement of nucleation parameters. The nucleation time lag has been measured. Data for the number of crystal nuclei versus the nucleation time were obtained for this hormone. Insulin was chosen as a model protein because of the availability of solubility data in the literature. A comparison with the results for hen-egg-white lysozyme, HEWL was performed.

Overview: Experimental studies of crystal nucleation: Metals and colloids.

PubMed

Herlach, Dieter M; Palberg, Thomas; Klassen, Ina; Klein, Stefan; Kobold, Raphael

2016-12-07

Crystallization is one of the most important phase transformations of first order. In the case of metals and alloys, the liquid phase is the parent phase of materials production. The conditions of the crystallization process control the as-solidified material in its chemical and physical properties. Nucleation initiates the crystallization of a liquid. It selects the crystallographic phase, stable or meta-stable. Its detailed knowledge is therefore mandatory for the design of materials. We present techniques of containerless processing for nucleation studies of metals and alloys. Experimental results demonstrate the power of these methods not only for crystal nucleation of stable solids but in particular also for investigations of crystal nucleation of metastable solids at extreme undercooling. This concerns the physical nature of heterogeneous versus homogeneous nucleation and nucleation of phases nucleated under non-equilibrium conditions. The results are analyzed within classical nucleation theory that defines the activation energy of homogeneous nucleation in terms of the interfacial energy and the difference of Gibbs free energies of solid and liquid. The interfacial energy acts as barrier for the nucleation process. Its experimental determination is difficult in the case of metals. In the second part of this work we therefore explore the potential of colloidal suspensions as model systems for the crystallization process. The nucleation process of colloids is observed in situ by optical observation and ultra-small angle X-ray diffraction using high intensity synchrotron radiation. It allows an unambiguous discrimination of homogeneous and heterogeneous nucleation as well as the determination of the interfacial free energy of the solid-liquid interface. Our results are used to construct Turnbull plots of colloids, which are discussed in relation to Turnbull plots of metals and support the hypothesis that colloids are useful model systems to investigate crystal nucleation.

Effects of shear flow on phase nucleation and crystallization.

PubMed

Mura, Federica; Zaccone, Alessio

2016-04-01

Classical nucleation theory offers a good framework for understanding the common features of new phase formation processes in metastable homogeneous media at rest. However, nucleation processes in liquids are ubiquitously affected by hydrodynamic flow, and there is no satisfactory understanding of whether shear promotes or slows down the nucleation process. We developed a classical nucleation theory for sheared systems starting from the molecular level of the Becker-Doering master kinetic equation and we analytically derived a closed-form expression for the nucleation rate. The theory accounts for the effect of flow-mediated transport of molecules to the nucleus of the new phase, as well as for the mechanical deformation imparted to the nucleus by the flow field. The competition between flow-induced molecular transport, which accelerates nucleation, and flow-induced nucleus straining, which lowers the nucleation rate by increasing the nucleation energy barrier, gives rise to a marked nonmonotonic dependence of the nucleation rate on the shear rate. The theory predicts an optimal shear rate at which the nucleation rate is one order of magnitude larger than in the absence of flow.

Studies of thin water films and relevance to the heterogeneous nucleation of ice

NASA Astrophysics Data System (ADS)

Ochshorn, Eli

The research that I will present in this dissertation concerns qualitative factors relevant to thin water films and ice nucleation. The immediate goal is not to develop a precise quantitative theory of ice nucleation. Instead, the focus is on characterizing some molecular properties (e.g., bond strengths, bond orientations, range of surface effects, etc.) of freezing catalysts and interfacial water over a range of temperatures relevant to the ice nucleation process (i.e., 20 to -20 °C). From this, we can evaluate the plausibility of different mechanistic freezing hypotheses through comparison with experiment. In all studies, I use Fourier transform infrared spectroscopy to study the intermolecular details of water and a surface species of interest. The dissertation is arranged with an introductory chapter, which primarily serves to place the research within the context of the field, then three chapters containing original research, each of which is a self-contained study that has either already been published or is currently under consideration for publication in a peer-reviewed journal. Finally, an appendix at the end provides some additional details that have not been included in the articles.

Spatial distribution of nuclei in progressive nucleation: Modeling and application

NASA Astrophysics Data System (ADS)

Tomellini, Massimo

2018-04-01

Phase transformations ruled by non-simultaneous nucleation and growth do not lead to random distribution of nuclei. Since nucleation is only allowed in the untransformed portion of space, positions of nuclei are correlated. In this article an analytical approach is presented for computing pair-correlation function of nuclei in progressive nucleation. This quantity is further employed for characterizing the spatial distribution of nuclei through the nearest neighbor distribution function. The modeling is developed for nucleation in 2D space with power growth law and it is applied to describe electrochemical nucleation where correlation effects are significant. Comparison with both computer simulations and experimental data lends support to the model which gives insights into the transition from Poissonian to correlated nearest neighbor probability density.

Verification of an Analytical Method for Measuring Crystal Nucleation Rates in Glasses from DTA Data

NASA Technical Reports Server (NTRS)

Ranasinghe, K. S.; Wei, P. F.; Kelton, K. F.; Ray, C. S.; Day, D. E.

2004-01-01

A recently proposed analytical (DTA) method for estimating the nucleation rates in glasses has been evaluated by comparing experimental data with numerically computed nucleation rates for a model lithium disilicate glass. The time and temperature dependent nucleation rates were predicted using the model and compared with those values from an analysis of numerically calculated DTA curves. The validity of the numerical approach was demonstrated earlier by a comparison with experimental data. The excellent agreement between the nucleation rates from the model calculations and fiom the computer generated DTA data demonstrates the validity of the proposed analytical DTA method.

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

DOE PAGES

Malila, Jussi; McGraw, Robert; Laaksonen, Ari; ...

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

Vapor nucleation paths in lyophobic nanopores.

PubMed

Tinti, Antonio; Giacomello, Alberto; Casciola, Carlo Massimo

2018-04-19

In recent years, technologies revolving around the use of lyophobic nanopores gained considerable attention in both fundamental and applied research. Owing to the enormous internal surface area, heterogeneous lyophobic systems (HLS), constituted by a nanoporous lyophobic material and a non-wetting liquid, are promising candidates for the efficient storage or dissipation of mechanical energy. These diverse applications both rely on the forced intrusion and extrusion of the non-wetting liquid inside the pores; the behavior of HLS for storage or dissipation depends on the hysteresis between these two processes, which, in turn, are determined by the microscopic details of the system. It is easy to understand that molecular simulations provide an unmatched tool for understanding phenomena at these scales. In this contribution we use advanced atomistic simulation techniques in order to study the nucleation of vapor bubbles inside lyophobic mesopores. The use of the string method in collective variables allows us to overcome the computational challenges associated with the activated nature of the phenomenon, rendering a detailed picture of nucleation in confinement. In particular, this rare event method efficiently searches for the most probable nucleation path(s) in otherwise intractable, high-dimensional free-energy landscapes. Results reveal the existence of several independent nucleation paths associated with different free-energy barriers. In particular, there is a family of asymmetric transition paths, in which a bubble forms at one of the walls; the other family involves the formation of axisymmetric bubbles with an annulus shape. The computed free-energy profiles reveal that the asymmetric path is significantly more probable than the symmetric one, while the exact position where the asymmetric bubble forms is less relevant for the free energetics of the process. A comparison of the atomistic results with continuum models is also presented, showing how, for simple liquids in mesoporous materials of characteristic size of ca. 4nm, the nanoscale effects reported for smaller pores have a minor role. The atomistic estimates for the nucleation free-energy barrier are in qualitative accord with those that can be obtained using a macroscopic, capillary-based nucleation theory.

Heterogeneity in homogeneous nucleation from billion-atom molecular dynamics simulation of solidification of pure metal.

PubMed

Shibuta, Yasushi; Sakane, Shinji; Miyoshi, Eisuke; Okita, Shin; Takaki, Tomohiro; Ohno, Munekazu

2017-04-05

Can completely homogeneous nucleation occur? Large scale molecular dynamics simulations performed on a graphics-processing-unit rich supercomputer can shed light on this long-standing issue. Here, a billion-atom molecular dynamics simulation of homogeneous nucleation from an undercooled iron melt reveals that some satellite-like small grains surrounding previously formed large grains exist in the middle of the nucleation process, which are not distributed uniformly. At the same time, grains with a twin boundary are formed by heterogeneous nucleation from the surface of the previously formed grains. The local heterogeneity in the distribution of grains is caused by the local accumulation of the icosahedral structure in the undercooled melt near the previously formed grains. This insight is mainly attributable to the multi-graphics processing unit parallel computation combined with the rapid progress in high-performance computational environments.Nucleation is a fundamental physical process, however it is a long-standing issue whether completely homogeneous nucleation can occur. Here the authors reveal, via a billion-atom molecular dynamics simulation, that local heterogeneity exists during homogeneous nucleation in an undercooled iron melt.

Structural Basis of Actin Filament Nucleation by Tandem W Domains

PubMed Central

Chen, Xiaorui; Ni, Fengyun; Tian, Xia; Kondrashkina, Elena; Wang, Qinghua; Ma, Jianpeng

2013-01-01

SUMMARY Spontaneous nucleation of actin is very inefficient in cells. To overcome this barrier, cells have evolved a set of actin filament nucleators to promote rapid nucleation and polymerization in response to specific stimuli. However, the molecular mechanism of actin nucleation remains poorly understood. This is hindered largely by the fact that actin nucleus, once formed, rapidly polymerizes into filament, thus making it impossible to capture stable multisubunit actin nucleus. Here, we report an effective double-mutant strategy to stabilize actin nucleus by preventing further polymerization. Employing this strategy, we solved the crystal structure of AMPPNP-actin in complex with the first two tandem W domains of Cordon-bleu (Cobl), a potent actin filament nucleator. Further sequence comparison and functional studies suggest that the nucleation mechanism of Cobl is probably shared by the p53 cofactor JMY, but not Spire. Moreover, the double-mutant strategy opens the way for atomic mechanistic study of actin nucleation and polymerization. PMID:23727244

Nucleation and microstructure development in Cr-Mo-V tool steel during gas atomization

NASA Astrophysics Data System (ADS)

Behúlová, M.; Grgač, P.; Čička, R.

2017-11-01

Nucleation studies of undercooled metallic melts are of essential interest for the understanding of phase selection, growth kinetics and microstructure development during their rapid non-equilibrium solidification. The paper deals with the modelling of nucleation processes and microstructure development in the hypoeutectic tool steel Ch12MF4 with the chemical composition of 2.37% C, 12.06 % Cr, 1.2% Mo, 4.0% V and balance Fe [wt. %] in the process of nitrogen gas atomization. Based on the classical theory of homogeneous nucleation, the nucleation temperature of molten rapidly cooled spherical particles from this alloy with diameter from 40 μm to 600 μm in the gas atomization process is calculated using various estimations of parameters influencing the nucleation process - the Gibbs free energy difference between solid and liquid phases and the solid/liquid interfacial energy. Results of numerical calculations are compared with experimentally measured nucleation temperatures during levitation experiments and microstructures developed in rapidly solidified powder particles from the investigated alloy.

Processing and Characterization of High Strength, High Ductility Hadfield Steel

DTIC Science & Technology

1990-04-01

precipitation in high carbon content Hadfield steel resulting in the introduction of a grain boundary void nucleation softening mechanism leading to plastic...hardening, in comparison to the thin twin spacing of Fe-Ni martensite and inferred that carbon may have an important role in contributing to Hadfield steel ...approaches to strengthening from alloying or precipitation mechanisms are introduced, the deformation mechanisms responsible for Hadfield steel

The atomic-scale nucleation mechanism of NiTi metallic glasses upon isothermal annealing studied via molecular dynamics simulations.

PubMed

Li, Yang; Li, JiaHao; Liu, BaiXin

2015-10-28

Nucleation is one of the most essential transformation paths in phase transition and exerts a significant influence on the crystallization process. Molecular dynamics simulations were performed to investigate the atomic-scale nucleation mechanisms of NiTi metallic glasses upon devitrification at various temperatures (700 K, 750 K, 800 K, and 850 K). Our simulations reveal that at 700 K and 750 K, nucleation is polynuclear with high nucleation density, while at 800 K it is mononuclear. The underlying nucleation mechanisms have been clarified, manifesting that nucleation can be induced either by the initial ordered clusters (IOCs) or by the other precursors of nuclei evolved directly from the supercooled liquid. IOCs and other precursors stem from the thermal fluctuations of bond orientational order in supercooled liquids during the quenching process and during the annealing process, respectively. The simulation results not only elucidate the underlying nucleation mechanisms varied with temperature, but also unveil the origin of nucleation. These discoveries offer new insights into the devitrification mechanism of metallic glasses.

Rate of Homogenous Nucleation of Ice in Supercooled Water.

PubMed

Atkinson, James D; Murray, Benjamin J; O'Sullivan, Daniel

2016-08-25

The homogeneous freezing of water is of fundamental importance to a number of fields, including that of cloud formation. However, there is considerable scatter in homogeneous nucleation rate coefficients reported in the literature. Using a cold stage droplet system designed to minimize uncertainties in temperature measurements, we examined the freezing of over 1500 pure water droplets with diameters between 4 and 24 μm. Under the assumption that nucleation occurs within the bulk of the droplet, nucleation rate coefficients fall within the spread of literature data and are in good agreement with a subset of more recent measurements. To quantify the relative importance of surface and volume nucleation in our experiments, where droplets are supported by a hydrophobic surface and surrounded by oil, comparison of droplets with different surface area to volume ratios was performed. From our experiments it is shown that in droplets larger than 6 μm diameter (between 234.6 and 236.5 K), nucleation in the interior is more important than nucleation at the surface. At smaller sizes we cannot rule out a significant contribution of surface nucleation, and in order to further constrain surface nucleation, experiments with smaller droplets are necessary. Nevertheless, in our experiments, it is dominantly volume nucleation controlling the observed nucleation rate.

Computational modeling of soot nucleation

NASA Astrophysics Data System (ADS)

Chung, Seung-Hyun

Recent studies indicate that soot is the second most significant driver of climate change---behind CO2, but ahead of methane---and increased levels of soot particles in the air are linked to health hazards such as heart disease and lung cancer. Within the soot formation process, soot nucleation is the least understood step, and current experimental findings are still limited. This thesis presents computational modeling studies of the major pathways of the soot nucleation process. In this study, two regimes of soot nucleation---chemical growth and physical agglomeration---were evaluated and the results demonstrated that combustion conditions determine the relative importance of these two routes. Also, the dimerization process of polycyclic aromatic hydrocarbons, which has been regarded as one of the most important physical agglomeration processes in soot formation, was carefully examined with a new method for obtaining the nucleation rate using molecular dynamics simulation. The results indicate that the role of pyrene dimerization, which is the commonly accepted model, is expected to be highly dependent on various flame temperature conditions and may not be a key step in the soot nucleation process. An additional pathway, coronene dimerization in this case, needed to be included to improve the match with experimental data. The results of this thesis provide insight on the soot nucleation process and can be utilized to improve current soot formation models.

Kinetics of spontaneous filament nucleation via oligomers: Insights from theory and simulation

NASA Astrophysics Data System (ADS)

Šarić, Andela; Michaels, Thomas C. T.; Zaccone, Alessio; Knowles, Tuomas P. J.; Frenkel, Daan

2016-12-01

Nucleation processes are at the heart of a large number of phenomena, from cloud formation to protein crystallization. A recently emerging area where nucleation is highly relevant is the initiation of filamentous protein self-assembly, a process that has broad implications in many research areas ranging from medicine to nanotechnology. As such, spontaneous nucleation of protein fibrils has received much attention in recent years with many theoretical and experimental studies focussing on the underlying physical principles. In this paper we make a step forward in this direction and explore the early time behaviour of filamentous protein growth in the context of nucleation theory. We first provide an overview of the thermodynamics and kinetics of spontaneous nucleation of protein filaments in the presence of one relevant degree of freedom, namely the cluster size. In this case, we review how key kinetic observables, such as the reaction order of spontaneous nucleation, are directly related to the physical size of the critical nucleus. We then focus on the increasingly prominent case of filament nucleation that includes a conformational conversion of the nucleating building-block as an additional slow step in the nucleation process. Using computer simulations, we study the concentration dependence of the nucleation rate. We find that, under these circumstances, the reaction order of spontaneous nucleation with respect to the free monomer does no longer relate to the overall physical size of the nucleating aggregate but rather to the portion of the aggregate that actively participates in the conformational conversion. Our results thus provide a novel interpretation of the common kinetic descriptors of protein filament formation, including the reaction order of the nucleation step or the scaling exponent of lag times, and put into perspective current theoretical descriptions of protein aggregation.

Kinetics of spontaneous filament nucleation via oligomers: Insights from theory and simulation.

PubMed

Šarić, Anđela; Michaels, Thomas C T; Zaccone, Alessio; Knowles, Tuomas P J; Frenkel, Daan

2016-12-07

Nucleation processes are at the heart of a large number of phenomena, from cloud formation to protein crystallization. A recently emerging area where nucleation is highly relevant is the initiation of filamentous protein self-assembly, a process that has broad implications in many research areas ranging from medicine to nanotechnology. As such, spontaneous nucleation of protein fibrils has received much attention in recent years with many theoretical and experimental studies focussing on the underlying physical principles. In this paper we make a step forward in this direction and explore the early time behaviour of filamentous protein growth in the context of nucleation theory. We first provide an overview of the thermodynamics and kinetics of spontaneous nucleation of protein filaments in the presence of one relevant degree of freedom, namely the cluster size. In this case, we review how key kinetic observables, such as the reaction order of spontaneous nucleation, are directly related to the physical size of the critical nucleus. We then focus on the increasingly prominent case of filament nucleation that includes a conformational conversion of the nucleating building-block as an additional slow step in the nucleation process. Using computer simulations, we study the concentration dependence of the nucleation rate. We find that, under these circumstances, the reaction order of spontaneous nucleation with respect to the free monomer does no longer relate to the overall physical size of the nucleating aggregate but rather to the portion of the aggregate that actively participates in the conformational conversion. Our results thus provide a novel interpretation of the common kinetic descriptors of protein filament formation, including the reaction order of the nucleation step or the scaling exponent of lag times, and put into perspective current theoretical descriptions of protein aggregation.

Effect of Controlled Ice Nucleation on Stability of Lactate Dehydrogenase During Freeze-Drying.

PubMed

Fang, Rui; Tanaka, Kazunari; Mudhivarthi, Vamsi; Bogner, Robin H; Pikal, Michael J

2018-03-01

Several controlled ice nucleation techniques have been developed to increase the efficiency of the freeze-drying process as well as to improve the quality of pharmaceutical products. Owing to the reduction in ice surface area, these techniques have the potential to reduce the degradation of proteins labile during freezing. The objective of this study was to evaluate the effect of ice nucleation temperature on the in-process stability of lactate dehydrogenase (LDH). LDH in potassium phosphate buffer was nucleated at -4°C, -8°C, and -12°C using ControLyo™ or allowed to nucleate spontaneously. Both the enzymatic activity and tetramer recovery after freeze-thawing linearly correlated with product ice nucleation temperature (n = 24). Controlled nucleation also significantly improved batch homogeneity as reflected by reduced inter-vial variation in activity and tetramer recovery. With the correlation established in the laboratory, the degradation of protein in manufacturing arising from ice nucleation temperature differences can be quantitatively predicted. The results show that controlled nucleation reduced the degradation of LDH during the freezing process, but this does not necessarily translate to vastly superior stability during the entire freeze-drying process. The capability of improving batch homogeneity provides potential advantages in scaling-up from lab to manufacturing scale. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Thermodynamics and Kinetics of Prenucleation Clusters, Classical and Non-Classical Nucleation.

PubMed

Zahn, Dirk

2015-07-20

Recent observations of prenucleation species and multi-stage crystal nucleation processes challenge the long-established view on the thermodynamics of crystal formation. Here, we review and generalize extensions to classical nucleation theory. Going beyond the conventional implementation as has been used for more than a century now, nucleation inhibitors, precursor clusters and non-classical nucleation processes are rationalized as well by analogous concepts based on competing interface and bulk energy terms. This is illustrated by recent examples of species formed prior to/instead of crystal nucleation and multi-step nucleation processes. Much of the discussed insights were obtained from molecular simulation using advanced sampling techniques, briefly summarized herein for both nucleation-controlled and diffusion-controlled aggregate formation. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

Observation of ice nucleation in acoustically levitated water drops

NASA Astrophysics Data System (ADS)

Lü, Y. J.; Xie, W. J.; Wei, B.

2005-10-01

The supercooling and nucleation of acoustically levitated water drops were investigated at two different sound pressure levels (SPL). These water drops were supercooled by 13to16K at the low SPL of 160.6dB, whereas their supercoolings varied from 5to11K at the high SPL of 164.4dB. The maximum supercooling obtained in the experiments is 32K. Statistical analyses based on the classical nucleation theory reveal that the occurrence of ice nucleation in water drops is mainly confined to the surface region under acoustic levitation conditions and the enlargement of drop surface area caused by the acoustic radiation pressure reduces water supercoolability remarkably. A comparison of the nucleation rates at the two SPLs indicates that the sound pressure can strengthen the surface-dominated nucleation of water drops. The acoustic stream around levitated water drops and the cavitation effect associated with ultrasonic field are the main factors that induce surface-dominated nucleation.

Improved performance of GaN based light emitting diodes with ex-situ sputtered AlN nucleation layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Shuo-Wei; Epistar Corporation, Hsinchu 300, Taiwan; Li, Heng

The crystal quality, electrical and optical properties of GaN based light emitting diodes (LEDs) with ex-situ sputtered physical vapor deposition (PVD) aluminum nitride (AlN) nucleation layers were investigated. It was found that the crystal quality in terms of defect density and x-ray diffraction linewidth was greatly improved in comparison to LEDs with in-situ low temperature GaN nucleation layer. The light output power was 3.7% increased and the reverse bias voltage of leakage current was twice on LEDs with ex-situ PVD AlN nucleation layers. However, larger compressive strain was discovered in LEDs with ex-situ PVD AlN nucleation layers. The study showsmore » the potential and constrain in applying ex-situ PVD AlN nucleation layers to fabricate high quality GaN crystals in various optoelectronics.« less

Condensation Temperature in Non-Equilibrium Condensation.

NASA Astrophysics Data System (ADS)

Tanaka, K. K.; Tanaka, H.; Nakazawa, K.

1999-09-01

In investigation of the origins of the presolar grains, it is important to clear the formation process of grains in ejecta of AGB stars or supernovae, where most presolar grains are suggested to be formed. The grain formation has been investigated based on the classical nucleation theory in many previous studies. On the other hand it has been pointed out that the classical nucleation rate is significantly different from that obtained by experiments, and should not be applied to grain formation in astrophysical environments (Donn and Nuth, 1985, ApJ 288, 187-190). Recently Dillmann and Meier (1991, J. Chem. Phys. 94, 3872-3884) proposed new semi-phenomological nucleation model, which achieved excellent agreements with experiments. In this study we applied the nucleation rate in the semi-phenomological model to the grain formation in astrophysical environment in order to make it clear how the grain formation changes due to the new nucleation rate. For various parameters determined by surface energy of grain and cooling time of vapor, we solved equations describing the grain formation. From the comparison between the results obtained by new nucleation rate and that by classical one we found that there is no significant difference in grain number density and grain size, but the condensation temperature is considerably different from the previous one. For example in carbon rich AGB star the condensation temperature of graphite is lower than that obtained by classical one by a few hundreds Kelvin: this means the condensation temperature is lower than the equilibrium condensation temperature by about 500 Kelvin. Furthermore we investigated the condensation of vapor in which grain impurities are already present. We obtained the condition for formation of core-mantle type grains. Our obtained condition would give constraint on the formation of core-mantle type presolar grains.

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 can be measured by noncontact optical pyrometry, the mass of the sample is known, and post processing analysis can be conducted on the sample. The disadvantages are that temperature measurement must have exceptionally high precision, and it is not possible to isolate specific heterogeneous sites as in droplet dispersions.

Modeling the Hydrological Cycle in the Atmosphere of Mars: Influence of a Bimodal Size Distribution of Aerosol Nucleation Particles

NASA Astrophysics Data System (ADS)

Shaposhnikov, Dmitry S.; Rodin, Alexander V.; Medvedev, Alexander S.; Fedorova, Anna A.; Kuroda, Takeshi; Hartogh, Paul

2018-02-01

We present a new implementation of the hydrological cycle scheme into a general circulation model of the Martian atmosphere. The model includes a semi-Lagrangian transport scheme for water vapor and ice and accounts for microphysics of phase transitions between them. The hydrological scheme includes processes of saturation, nucleation, particle growth, sublimation, and sedimentation under the assumption of a variable size distribution. The scheme has been implemented into the Max Planck Institute Martian general circulation model and tested assuming monomodal and bimodal lognormal distributions of ice condensation nuclei. We present a comparison of the simulated annual variations, horizontal and vertical distributions of water vapor, and ice clouds with the available observations from instruments on board Mars orbiters. The accounting for bimodality of aerosol particle distribution improves the simulations of the annual hydrological cycle, including predicted ice clouds mass, opacity, number density, and particle radii. The increased number density and lower nucleation rates bring the simulated cloud opacities closer to observations. Simulations show a weak effect of the excess of small aerosol particles on the simulated water vapor distributions.

Effect of nucleation time on bending response of ionic polymer–metal composite actuators

DOE PAGES

Kim, Suran; Hong, Seungbum; Choi, Yoon-Young; ...

2013-07-02

We attempted an autocatalytic electro-less plating of nickel in order to replace an electroless impregnation-reduction (IR) method in ionic polymer–metal composite (IPMC) actuators to reduce cost and processing time. Because nucleation time of Pd–Sn colloids is the determining factor of overall processing time, we used the nucleation time as our control parameter. In order to optimize nucleation time and investigate its effect on the performance of IPMC actuators, we analyzed the relationship between the nucleation time, interface morphology and electrical properties. The optimized nucleation time was 10 h. Furthermore, the trends of the performance and electrical properties as a functionmore » of nucleation time were attributed to the fact that the Ni penetration depth was determined by the minimum diffusion length of either Pd–Sn colloids or reducing agent ions. The Ni-IPMC actuators can be fabricated less than 14 h processing time without deteriorating performance of the actuators, which is comparable to Pt-IPMC prepared by IR method.« less

Ice nucleation in the upper troposphere: Sensitivity to aerosol number density, temperature, and cooling rate

NASA Technical Reports Server (NTRS)

Jensen, E. J.; Toon, O. B.

1994-01-01

We have investigated the processes that control ice crystal nucleation in the upper troposphere using a numerical model. Nucleation of ice resulting from cooling was simulated for a range of aerosol number densities, initial temperatures, and cooling rates. In contrast to observations of stratus clouds, we find that the number of ice crystals that nucleate in cirrus is relatively insensitive to the number of aerosols present. The ice crystal size distribution at the end of the nucleation process is unaffected by the assumed initial aerosol number density. Essentially, nucleation continues until enough ice crystals are present such that their deposition growth rapidly depletes the vapor and shuts off any further nucleation. However, the number of ice crystals nucleated increases rapidly with decreasing initial temperature and increasing cooling rate. This temperature dependence alone could explain the large ice crystal number density observed in very cold tropical cirrus.

Molecular-dynamics simulations of urea nucleation from aqueous solution

PubMed Central

Salvalaglio, Matteo; Perego, Claudio; Giberti, Federico; Mazzotti, Marco; Parrinello, Michele

2015-01-01

Despite its ubiquitous character and relevance in many branches of science and engineering, nucleation from solution remains elusive. In this framework, molecular simulations represent a powerful tool to provide insight into nucleation at the molecular scale. In this work, we combine theory and molecular simulations to describe urea nucleation from aqueous solution. Taking advantage of well-tempered metadynamics, we compute the free-energy change associated to the phase transition. We find that such a free-energy profile is characterized by significant finite-size effects that can, however, be accounted for. The description of the nucleation process emerging from our analysis differs from classical nucleation theory. Nucleation of crystal-like clusters is in fact preceded by large concentration fluctuations, indicating a predominant two-step process, whereby embryonic crystal nuclei emerge from dense, disordered urea clusters. Furthermore, in the early stages of nucleation, two different polymorphs are seen to compete. PMID:25492932

Molecular-dynamics simulations of urea nucleation from aqueous solution.

PubMed

Salvalaglio, Matteo; Perego, Claudio; Giberti, Federico; Mazzotti, Marco; Parrinello, Michele

2015-01-06

Despite its ubiquitous character and relevance in many branches of science and engineering, nucleation from solution remains elusive. In this framework, molecular simulations represent a powerful tool to provide insight into nucleation at the molecular scale. In this work, we combine theory and molecular simulations to describe urea nucleation from aqueous solution. Taking advantage of well-tempered metadynamics, we compute the free-energy change associated to the phase transition. We find that such a free-energy profile is characterized by significant finite-size effects that can, however, be accounted for. The description of the nucleation process emerging from our analysis differs from classical nucleation theory. Nucleation of crystal-like clusters is in fact preceded by large concentration fluctuations, indicating a predominant two-step process, whereby embryonic crystal nuclei emerge from dense, disordered urea clusters. Furthermore, in the early stages of nucleation, two different polymorphs are seen to compete.

Misfit paradox on nucleation potency of MgO and MgAl{sub 2}O{sub 4} for Al

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, D.; Wang, L.

MgO and MgAl{sub 2}O{sub 4} are believed to be effective heterogeneous nuclei for Al based alloys due to their small lattice misfits with Al. However, there is a strong evidence to suggest that liquid Al reacts with MgO and MgAl{sub 2}O{sub 4} phases but the heterogeneous nucleation behavior of such phases is rarely discussed. In order to identify the nucleation mechanism of Al, under the interference of the chemical reaction, the heterogeneous nucleation process is systematically investigated through thermal analysis and high resolution transmission electron microscopy (HRTEM). The observed multi-nucleation interfaces (Al/MgO, Al/MgAl{sub 2}O{sub 4} and Al/Al{sub 2}O{sub 3}) andmore » scattered experimental undercooling data indicate an independent multi-phase nucleation process in these systems. - Highlights: •Theoretical lattice misfit doesn’t always disclose nucleation potency. •The nucleation of liquid can be triggered by multi-nucleation interfaces. •An independent multi-agents nucleation was verified in the study.« less

Evaluation of nucleated red blood cell count by Sysmex XE-2100 in patients with thalassaemia or sickle cell anaemia and in neonates.

PubMed

Buoro, Sabrina; Vavassori, Mauro; Pipitone, Silvia; Benegiamo, Anna; Lochis, Eleonora; Fumagalli, Sabina; Falanga, Anna; Marchetti, Marina; Crippa, Alberto; Ottomano, Cosimo; Lippi, Giuseppe

2015-10-01

Current haematology analysers have variable sensitivity and accuracy for counting nucleated red blood cells in samples with low values and in all those conditions characterised by altered sensitivity of red blood cells to the lysing process, such as in beta-thalassaemia or sickle-cell diseases and in neonates. The aim of our study was to evaluate the performance of the automated analyser XE-2100 at counting nucleated red blood cells in the above-mentioned three categories of subjects with potentially altered red blood cell lysis sensitivity and yet a need for accurate nucleated red blood cell counts. We measured nucleated red blood cell count by XE-2100 in peripheral blood samples of 187 subjects comprising 55 patients with beta-thalassaemia (40 major and 15 traits), 26 sickle-cell patients, 56 neonates and 50 normal subject. Results were compared with those obtained by optical microscopy. Agreement between average values of the two methods was estimated by means of Pearson's correlation and bias analysis, whereas diagnostic accuracy was estimated by analysis of receiver operating characteristic curves. The comparison between the two methods showed a Pearson's correlation of 0.99 (95% CI; 0.98-0.99; p<0.001) and bias of -0.61 (95% CI, -1.5-0.3). The area under the curve of the nucleated red blood cell count in all samples was 0.98 (95% CI, 0.96-1.00; p<0.001). Sub-analysis revealed an area under curve of 0.99 (95% CI, 0.98-1.00; p<0.001) for patients with thalassaemia, 0.94 (95% CI, 0.85-1.00; p<0.001) for patients with sickle cell anaemia, and 1.00 (95% CI, 1.0-1.0) for neonates. XE-2100 has excellent performance for nucleated red blood cell counting, especially in critical populations such as patients with haemoglobinopathies and neonates.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

NASA Astrophysics Data System (ADS)

Kumar, Amit; Arruda, Thomas M.; Tselev, Alexander; Ivanov, Ilia N.; Lawton, Jamie S.; Zawodzinski, Thomas A.; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V.

2013-04-01

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes.

PubMed

Kumar, Amit; Arruda, Thomas M; Tselev, Alexander; Ivanov, Ilia N; Lawton, Jamie S; Zawodzinski, Thomas A; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V

2013-01-01

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

PubMed Central

Kumar, Amit; Arruda, Thomas M.; Tselev, Alexander; Ivanov, Ilia N.; Lawton, Jamie S.; Zawodzinski, Thomas A.; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V.

2013-01-01

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes. PMID:23563856

Insights Regarding Ice Nucleating Particle Measurement Capabilities from Laboratory and Field Measurements During the Fifth International Ice Nucleation Workshop

NASA Astrophysics Data System (ADS)

DeMott, P. J.; Mohler, O.; Cziczo, D. J.; Hiranuma, N.; Brooks, S. D.; Petters, M.

2017-12-01

Improvement in the ability to quantify the role of aerosols in primary ice formation in clouds is vital to improving prediction of natural and anthropogenic impacts on cold cloud properties and reducing uncertainties in climate predictions. A host of common and new methods for quantifying the atmospheric abundance of ice nucleating particles (INPs) have recently been developed. To realize the utility of such data for numerical model parameterization development and validation, it is important to understand similarities, differences, and biases in different methods. To achieve this goal, it is common to challenge instruments with a range of aerosol types in laboratory studies. Only a few comparisons have occurred in atmospheric situations. This presentation highlights comparisons made in laboratory and field phases of the Fifth International Ice Nucleation workshop (FIN) during 2015. The FIN-2 laboratory workshop was conducted at the AIDA facility of the Karlsruhe Institute of Technology, involving nine real-time INP instruments and several sampling methods for wet suspensions and filter collection and resuspension for INP measurements. The FIN-3 atmospheric activity was conducted at the Desert Research Institute's Storm Peak Laboratory (SPL), with a reduced set of participants. Lessons and insights were gained during analyses of data from both workshops regarding the capabilities and comparability of present ice nucleation measurement systems. The FIN-2 and FIN-3 results show typical one order of magnitude agreement within basic measurement types and overall for characterizing the concentrations (over several orders of magnitude dynamic range from -5 to -35 C) of a variety of INP types and ambient INPs active in the immersion-freezing mode. Discrepancies are least for lab sampling of natural soil particle INPs and greatest for materials with steep d[INP]/dT functions, such as K-feldspar or bacterial INPs processed warmer than -8 C. Varied reasons and implications for atmospheric measurements will be discussed. FIN-3 ambient studies also showed correspondence for the first time between online and offline assessment of the contrasting INP concentrations active in deposition and immersion freezing (much higher numbers) regimes. Major contributions from the FIN participant teams are acknowledged.

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 temperature can be measured by noncontact optical pyrometry, the mass of the sample is known, and post processing analysis can be conducted on the sample. The disadvantages are that temperature measurement must have exceptionally high precision, and it is not possible to isolate specific heterogeneous sites as in droplet dispersions.

Performance of some nucleation theories with a nonsharp droplet-vapor interface.

PubMed

Napari, Ismo; Julin, Jan; Vehkamäki, Hanna

2010-10-21

Nucleation theories involving the concept of nonsharp boundary between the droplet and vapor are compared to recent molecular dynamics (MD) simulation data of Lennard-Jones vapors at temperatures above the triple point. The theories are diffuse interface theory (DIT), extended modified liquid drop-dynamical nucleation theory (EMLD-DNT), square gradient theory (SGT), and density functional theory (DFT). Particular attention is paid to thermodynamic consistency in the comparison: the applied theories either use or, with a proper parameter adjustment, result in the same values of equilibrium vapor pressure, bulk liquid density, and surface tension as the MD simulations. Realistic pressure-density correlations are also used. The best agreement between the simulated nucleation rates and calculations is obtained from DFT, SGT, and EMLD-DNT, all of which, in the studied temperature range, show deviations of less than one order of magnitude in the nucleation rate. DIT underestimates the nucleation rate by up to two orders of magnitude. DFT and SGT give the best estimate of the molecular content of the critical nuclei. Overall, at the vapor conditions of this study, all the investigated theories perform better than classical nucleation theory in predicting nucleation rates.

Forward flux sampling calculation of homogeneous nucleation rates from aqueous NaCl solutions.

PubMed

Jiang, Hao; Haji-Akbari, Amir; Debenedetti, Pablo G; Panagiotopoulos, Athanassios Z

2018-01-28

We used molecular dynamics simulations and the path sampling technique known as forward flux sampling to study homogeneous nucleation of NaCl crystals from supersaturated aqueous solutions at 298 K and 1 bar. Nucleation rates were obtained for a range of salt concentrations for the Joung-Cheatham NaCl force field combined with the Extended Simple Point Charge (SPC/E) water model. The calculated nucleation rates are significantly lower than the available experimental measurements. The estimates for the nucleation rates in this work do not rely on classical nucleation theory, but the pathways observed in the simulations suggest that the nucleation process is better described by classical nucleation theory than an alternative interpretation based on Ostwald's step rule, in contrast to some prior simulations of related models. In addition to the size of NaCl nucleus, we find that the crystallinity of a nascent cluster plays an important role in the nucleation process. Nuclei with high crystallinity were found to have higher growth probability and longer lifetimes, possibly because they are less exposed to hydration water.

Forward flux sampling calculation of homogeneous nucleation rates from aqueous NaCl solutions

NASA Astrophysics Data System (ADS)

Jiang, Hao; Haji-Akbari, Amir; Debenedetti, Pablo G.; Panagiotopoulos, Athanassios Z.

2018-01-01

We used molecular dynamics simulations and the path sampling technique known as forward flux sampling to study homogeneous nucleation of NaCl crystals from supersaturated aqueous solutions at 298 K and 1 bar. Nucleation rates were obtained for a range of salt concentrations for the Joung-Cheatham NaCl force field combined with the Extended Simple Point Charge (SPC/E) water model. The calculated nucleation rates are significantly lower than the available experimental measurements. The estimates for the nucleation rates in this work do not rely on classical nucleation theory, but the pathways observed in the simulations suggest that the nucleation process is better described by classical nucleation theory than an alternative interpretation based on Ostwald's step rule, in contrast to some prior simulations of related models. In addition to the size of NaCl nucleus, we find that the crystallinity of a nascent cluster plays an important role in the nucleation process. Nuclei with high crystallinity were found to have higher growth probability and longer lifetimes, possibly because they are less exposed to hydration water.

Homogeneous SPC/E water nucleation in large molecular dynamics simulations.

PubMed

Angélil, Raymond; Diemand, Jürg; Tanaka, Kyoko K; Tanaka, Hidekazu

2015-08-14

We perform direct large molecular dynamics simulations of homogeneous SPC/E water nucleation, using up to ∼ 4 ⋅ 10(6) molecules. Our large system sizes allow us to measure extremely low and accurate nucleation rates, down to ∼ 10(19) cm(-3) s(-1), helping close the gap between experimentally measured rates ∼ 10(17) cm(-3) s(-1). We are also able to precisely measure size distributions, sticking efficiencies, cluster temperatures, and cluster internal densities. We introduce a new functional form to implement the Yasuoka-Matsumoto nucleation rate measurement technique (threshold method). Comparison to nucleation models shows that classical nucleation theory over-estimates nucleation rates by a few orders of magnitude. The semi-phenomenological nucleation model does better, under-predicting rates by at worst a factor of 24. Unlike what has been observed in Lennard-Jones simulations, post-critical clusters have temperatures consistent with the run average temperature. Also, we observe that post-critical clusters have densities very slightly higher, ∼ 5%, than bulk liquid. We re-calibrate a Hale-type J vs. S scaling relation using both experimental and simulation data, finding remarkable consistency in over 30 orders of magnitude in the nucleation rate range and 180 K in the temperature range.

Preface: Special Topic on Nucleation: New Concepts and Discoveries.

PubMed

Kelton, K F; Frenkel, Daan

2016-12-07

Many phenomena in the world around us depend on infrequent, yet short-lived, events that completely alter how a system subsequently develops in time. In the physical sciences, there are many examples of such crucial "rare events." Among the most important of these are nucleation processes, in which, due to a rare fluctuation, a new phase forms spontaneously within a meta-stable parent phase. Because nucleation processes are both rare and rapid and happen on a microscopic spatial scale, their experimental study is challenging. In recent years, there have been major developments both in the experimental study of nucleation phenomena and in the numerical simulation of such processes. As the articles in this special issue demonstrate, these recent advances in the ability to probe nucleation phenomena have transformed our understanding of the field.

Experiments on Nucleation in Different Flow Regimes

NASA Technical Reports Server (NTRS)

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

1998-01-01

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. 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. 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 can be measured by noncontact optical pyrometry, the mass of the sample is known, and post-processing analysis can be conducted on the sample. The disadvantages are that temperature measurement must have exceptionally high precision, and it is not possible to isolate specific heterogeneous sites as in droplet dispersions. Levitation processing of refractory materials in ultra high vacuum provides an avenue to conduct these kinetic studies on single samples. Two experimental methods have been identified where ultra high vacuum experiments are possible; electrostatic levitation in ground-based experiments and electromagnetic processing in low earth orbit on TEMPUS. Such experiments, reported here, were conducted on zirconium. Liquid zirconium is an excellent solvent and has a high solubility for contaminants contained in the bulk material as well as those contaminants found in the vacuum environment. Oxides, nitrides, and carbides do not exist in the melt, and do not form on the surface of molten zirconium, for the materials and vacuum levels used in this study. Ground-based experiments with electrostatic levitation have shown that the statistical nucleation kinetic experiments are viable and yield results which are consistent with classical nucleation theory. The advantage of low earth orbit experiments is the ability to vary the flow conditions in the liquid prior to nucleation. The put-pose of nucleation experiments in TEMPUS was to examine.

A computationally efficient description of heterogeneous freezing: A simplified version of the Soccer ball model

NASA Astrophysics Data System (ADS)

Niedermeier, Dennis; Ervens, Barbara; Clauss, Tina; Voigtländer, Jens; Wex, Heike; Hartmann, Susan; Stratmann, Frank

2014-01-01

In a recent study, the Soccer ball model (SBM) was introduced for modeling and/or parameterizing heterogeneous ice nucleation processes. The model applies classical nucleation theory. It allows for a consistent description of both apparently singular and stochastic ice nucleation behavior, by distributing contact angles over the nucleation sites of a particle population assuming a Gaussian probability density function. The original SBM utilizes the Monte Carlo technique, which hampers its usage in atmospheric models, as fairly time-consuming calculations must be performed to obtain statistically significant results. Thus, we have developed a simplified and computationally more efficient version of the SBM. We successfully used the new SBM to parameterize experimental nucleation data of, e.g., bacterial ice nucleation. Both SBMs give identical results; however, the new model is computationally less expensive as confirmed by cloud parcel simulations. Therefore, it is a suitable tool for describing heterogeneous ice nucleation processes in atmospheric models.

Controlling the crystal polymorph by exploiting the time dependence of nucleation rates.

PubMed

Little, Laurie J; King, Alice A K; Sear, Richard P; Keddie, Joseph L

2017-10-14

Most substances can crystallise into two or more different crystal lattices called polymorphs. Despite this, there are no systems in which we can quantitatively predict the probability of one competing polymorph forming instead of the other. We address this problem using large scale (hundreds of events) studies of the competing nucleation of the alpha and gamma polymorphs of glycine. In situ Raman spectroscopy is used to identify the polymorph of each crystal. We find that the nucleation kinetics of the two polymorphs is very different. Nucleation of the alpha polymorph starts off slowly but accelerates, while nucleation of the gamma polymorph starts off fast but then slows. We exploit this difference to increase the purity with which we obtain the gamma polymorph by a factor of ten. The statistics of the nucleation of crystals is analogous to that of human mortality, and using a result from medical statistics, we show that conventional nucleation data can say nothing about what, if any, are the correlations between competing nucleation processes. Thus we can show that with data of our form it is impossible to disentangle the competing nucleation processes. We also find that the growth rate and the shape of a crystal depend on it when nucleated. This is new evidence that nucleation and growth are linked.

Heterogeneous ice nucleation of α-pinene SOA particles before and after ice cloud processing

NASA Astrophysics Data System (ADS)

Wagner, Robert; Höhler, Kristina; Huang, Wei; Kiselev, Alexei; Möhler, Ottmar; Mohr, Claudia; Pajunoja, Aki; Saathoff, Harald; Schiebel, Thea; Shen, Xiaoli; Virtanen, Annele

2017-05-01

The ice nucleation ability of α-pinene secondary organic aerosol (SOA) particles was investigated at temperatures between 253 and 205 K in the Aerosol Interaction and Dynamics in the Atmosphere cloud simulation chamber. Pristine SOA particles were nucleated and grown from pure gas precursors and then subjected to repeated expansion cooling cycles to compare their intrinsic ice nucleation ability during the first nucleation event with that observed after ice cloud processing. The unprocessed α-pinene SOA particles were found to be inefficient ice-nucleating particles at cirrus temperatures, with nucleation onsets (for an activated fraction of 0.1%) as high as for the homogeneous freezing of aqueous solution droplets. Ice cloud processing at temperatures below 235 K only marginally improved the particles' ice nucleation ability and did not significantly alter their morphology. In contrast, the particles' morphology and ice nucleation ability was substantially modified upon ice cloud processing in a simulated convective cloud system, where the α-pinene SOA particles were first activated to supercooled cloud droplets and then froze homogeneously at about 235 K. As evidenced by electron microscopy, the α-pinene SOA particles adopted a highly porous morphology during such a freeze-drying cycle. When probing the freeze-dried particles in succeeding expansion cooling runs in the mixed-phase cloud regime up to 253 K, the increase in relative humidity led to a collapse of the porous structure. Heterogeneous ice formation was observed after the droplet activation of the collapsed, freeze-dried SOA particles, presumably caused by ice remnants in the highly viscous material or the larger surface area of the particles.

Analysis of the Effect of Water Activity on Ice Formation Using a New Theory of Nucleation

NASA Technical Reports Server (NTRS)

Barahona, Donifan

2013-01-01

In this work a new theory of nucleation is developed and used to investigate the effect of water activity on the formation of ice within super-cooled droplets. The new theory is based on a novel concept where the interface is assumed to be made of liquid molecules trapped by the solid matrix. Using this concept new expressions are developed for the critical ice germ size and the nucleation work, with explicit dependencies on temperature and water activity. However unlike previous approaches, the new theory does not depend on the interfacial tension between liquid and ice. Comparison against experimental results shows that the new theory is able to reproduce the observed effect of water activity on nucleation rate and freezing temperature. It allows for the first time a theoretical derivation of the constant shift in water activity between melting and nucleation. The new theory offers a consistent thermodynamic view of ice nucleation, simple enough to be applied in atmospheric models of cloud formation.

Total nucleated cell and leukocyte differential counts in canine pleural and peritoneal fluid and equine synovial fluid samples: comparison of automated and manual methods.

PubMed

Brudvig, Jean M; Swenson, Cheryl L

2015-12-01

Rapid and precise measurement of total and differential nucleated cell counts is a crucial diagnostic component of cavitary and synovial fluid analyses. The objectives of this study included (1) evaluation of reliability and precision of canine and equine fluid total nucleated cell count (TNCC) determined by the benchtop Abaxis VetScan HM5, in comparison with the automated reference instruments ADVIA 120 and the scil Vet abc, respectively, and (2) comparison of automated with manual canine differential nucleated cell counts. The TNCC and differential counts in canine pleural and peritoneal, and equine synovial fluids were determined on the Abaxis VetScan HM5 and compared with the ADVIA 120 and Vet abc analyzer, respectively. Statistical analyses included correlation, least squares fit linear regression, Passing-Bablok regression, and Bland-Altman difference plots. In addition, precision of the total cell count generated by the VetScan HM5 was determined. Agreement was excellent without significant constant or proportional bias for canine cavitary fluid TNCC. Automated and manual differential counts had R(2)  < .5 for individual cell types (least squares fit linear regression). Equine synovial fluid TNCC agreed but with some bias due to the VetScan HM5 overestimating TNCC compared to the Vet abc. Intra-assay precision of the VetScan HM5 in 3 fluid samples was 2-31%. The Abaxis VetScan HM5 provided rapid, reliable TNCC for canine and equine fluid samples. The differential nucleated cell count should be verified microscopically as counts from the VetScan HM5 and also from the ADVIA 120 were often incorrect in canine fluid samples. © 2015 American Society for Veterinary Clinical Pathology.

Two-Dimensional Nucleation on the Terrace of Colloidal Crystals with Added Polymers.

PubMed

Nozawa, Jun; Uda, Satoshi; Guo, Suxia; Hu, Sumeng; Toyotama, Akiko; Yamanaka, Junpei; Okada, Junpei; Koizumi, Haruhiko

2017-04-04

Understanding nucleation dynamics is important both fundamentally and technologically in materials science and other scientific fields. Two-dimensional (2D) nucleation is the predominant growth mechanism in colloidal crystallization, in which the particle interaction is attractive, and has recently been regarded as a promising method to fabricate varieties of complex nanostructures possessing innovative functionality. Here, polymers are added to a colloidal suspension to generate a depletion attractive force, and the detailed 2D nucleation process on the terrace of the colloidal crystals is investigated. In the system, we first measured the nucleation rate at various area fractions of particles on the terrace, ϕ area . In situ observations at single-particle resolution revealed that nucleation behavior follows the framework of classical nucleation theory (CNT), such as single-step nucleation pathway and existence of critical size. Characteristic nucleation behavior is observed in that the nucleation and growth stage are clearly differentiated. When many nuclei form in a small area of the terrace, a high density of kink sites of once formed islands makes growth more likely to occur than further nucleation because nucleation has a higher energy barrier than growth. The steady-state homogeneous 2D nucleation rate, J, and the critical size of nuclei, r*, are measured by in situ observations based on the CNT, which enable us to obtain the step free energy, γ, which is an important parameter for characterizing the nucleation process. The γ value is found to change according to the strength of attraction, which is tuned by the concentration of the polymer as a depletant.

Controlled ice nucleation in the field of freeze-drying: fundamentals and technology review.

PubMed

Geidobler, R; Winter, G

2013-10-01

In the scientific community as well as in commercial freeze-drying, controlled ice nucleation has received a lot of attention because increasing the ice nucleation temperature can significantly reduce primary drying duration. Furthermore, controlled ice nucleation enables to reduce the randomness of the ice nucleation temperature, which can be a serious scale-up issue during process development. In this review, fundamentals of ice nucleation in the field of freeze-drying are presented. Furthermore, the impact of controlled ice nucleation on product qualities is discussed, and methods to achieve controlled ice nucleation are presented. Copyright © 2013 Elsevier B.V. All rights reserved.

Effects of pre-existing ice crystals on cirrus clouds and comparison between different ice nucleation parameterizations with the Community Atmosphere Model (CAM5)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Xiangjun; Liu, Xiaohong; Zhang, Kai

In order to improve the treatment of ice nucleation in a more realistic manner in the Community Atmosphere Model version 5.3 (CAM5.3), the effects of pre-existing ice crystals on ice nucleation in cirrus clouds are considered. In addition, by considering the in-cloud variability in ice saturation ratio, homogeneous nucleation takes place spatially only in a portion of the cirrus cloud rather than in the whole area of the cirrus cloud. Compared to observations, the ice number concentrations and the probability distributions of ice number concentration are both improved with the updated treatment. The pre-existing ice crystals significantly reduce ice numbermore » concentrations in cirrus clouds, especially at mid- to high latitudes in the upper troposphere (by a factor of ~10). Furthermore, the contribution of heterogeneous ice nucleation to cirrus ice crystal number increases considerably. Besides the default ice nucleation parameterization of Liu and Penner (2005, hereafter LP) in CAM5.3, two other ice nucleation parameterizations of Barahona and Nenes (2009, hereafter BN) and Kärcher et al. (2006, hereafter KL) are implemented in CAM5.3 for the comparison. In-cloud ice crystal number concentration, percentage contribution from heterogeneous ice nucleation to total ice crystal number, and pre-existing ice effects simulated by the three ice nucleation parameterizations have similar patterns in the simulations with present-day aerosol emissions. However, the change (present-day minus pre-industrial times) in global annual mean column ice number concentration from the KL parameterization (3.24 × 10 6 m -2) is less than that from the LP (8.46 × 10 6 m -2) and BN (5.62 × 10 6 m -2) parameterizations. As a result, the experiment using the KL parameterization predicts a much smaller anthropogenic aerosol long-wave indirect forcing (0.24 W m -2) than that using the LP (0.46 W m −2) and BN (0.39 W m -2) parameterizations.« less

Effects of pre-existing ice crystals on cirrus clouds and comparison between different ice nucleation parameterizations with the Community Atmosphere Model (CAM5)

DOE PAGES

Shi, Xiangjun; Liu, Xiaohong; Zhang, Kai

2015-02-11

In order to improve the treatment of ice nucleation in a more realistic manner in the Community Atmosphere Model version 5.3 (CAM5.3), the effects of pre-existing ice crystals on ice nucleation in cirrus clouds are considered. In addition, by considering the in-cloud variability in ice saturation ratio, homogeneous nucleation takes place spatially only in a portion of the cirrus cloud rather than in the whole area of the cirrus cloud. Compared to observations, the ice number concentrations and the probability distributions of ice number concentration are both improved with the updated treatment. The pre-existing ice crystals significantly reduce ice numbermore » concentrations in cirrus clouds, especially at mid- to high latitudes in the upper troposphere (by a factor of ~10). Furthermore, the contribution of heterogeneous ice nucleation to cirrus ice crystal number increases considerably. Besides the default ice nucleation parameterization of Liu and Penner (2005, hereafter LP) in CAM5.3, two other ice nucleation parameterizations of Barahona and Nenes (2009, hereafter BN) and Kärcher et al. (2006, hereafter KL) are implemented in CAM5.3 for the comparison. In-cloud ice crystal number concentration, percentage contribution from heterogeneous ice nucleation to total ice crystal number, and pre-existing ice effects simulated by the three ice nucleation parameterizations have similar patterns in the simulations with present-day aerosol emissions. However, the change (present-day minus pre-industrial times) in global annual mean column ice number concentration from the KL parameterization (3.24 × 10 6 m -2) is less than that from the LP (8.46 × 10 6 m -2) and BN (5.62 × 10 6 m -2) parameterizations. As a result, the experiment using the KL parameterization predicts a much smaller anthropogenic aerosol long-wave indirect forcing (0.24 W m -2) than that using the LP (0.46 W m −2) and BN (0.39 W m -2) parameterizations.« less

Quantifying the Effect of Stress on Sn Whisker Nucleation Kinetics

NASA Astrophysics Data System (ADS)

Chason, Eric; Vasquez, Justin; Pei, Fei; Jain, Nupur; Hitt, Andrew

2018-01-01

Although Sn whiskers have been studied extensively, there is still a need to understand the driving forces behind whisker nucleation and growth. Many studies point to the role of stress, but confirming this requires a quantitative comparison between controlled stress and the resulting whisker evolution. Recent experimental studies applied stress to a Sn layer via thermal cycling and simultaneously monitored the evolution of the temperature, stress and number of nuclei. In this work, we analyze these nucleation kinetics in terms of classical nucleation theory to relate the observed behavior to underlying mechanisms including a stress dependent activation energy and a temperature and stress-dependent whisker growth rate. Non-linear least squares fitting of the data taken at different temperatures and strain rates to the model shows that the results can be understood in terms of stress decreasing the barrier for whisker nucleation.

Monte-Carlo simulation of defect-cluster nucleation in metals during irradiation

NASA Astrophysics Data System (ADS)

Nakasuji, Toshiki; Morishita, Kazunori; Ruan, Xiaoyong

2017-02-01

A multiscale modeling approach was applied to investigate the nucleation process of CRPs (copper rich precipitates, i.e., copper-vacancy clusters) in α-Fe containing 1 at.% Cu during irradiation. Monte-Carlo simulations were performed to investigate the nucleation process, with the rate theory equation analysis to evaluate the concentration of displacement defects, along with the molecular dynamics technique to know CRP thermal stabilities in advance. Our MC simulations showed that there is long incubation period at first, followed by a rapid growth of CRPs. The incubation period depends on irradiation conditions such as the damage rate and temperature. CRP's composition during nucleation varies with time. The copper content of CRPs shows relatively rich at first, and then becomes poorer as the precipitate size increases. A widely-accepted model of CRP nucleation process is finally proposed.

Heterogeneous Nucleation of Methane Hydrate in a Water-Decane-Methane Emulsion

NASA Astrophysics Data System (ADS)

Shestakov, V. A.; Kosyakov, V. I.; Manakov, A. Yu.; Stoporev, A. S.; Grachev, E. V.

2018-07-01

Heterogeneous nucleation in disperse systems with metastable disperse phases plays an important role in the mechanisms of environmental and technological processes. The effect the concentration and activity of particles that initiate the formation of a new phase have on nucleation processes in such systems is considered. An approach is proposed that allows construction of a spectrum of particle activity characterizing the features of nucleation in a sample, based on the fraction of crystallized droplets depending on the level of supercooling and the use of Weibull's distribution. The proposed method is used to describe experimental data on the heterogeneous nucleation of methane hydrate in an emulsion in a water-decane-methane system.

Surface nanobubble nucleation dynamics during water-ethanol exchange

NASA Astrophysics Data System (ADS)

Chan, Chon U.; Ohl, Claus-Dieter

2015-11-01

Water-ethanol exchange has been a promising nucleation method for surface attached nanobubbles since their discovery. In this process, water and ethanol displace each other sequentially on a substrate. As the gas solubility is 36 times higher in ethanol than water, it was suggested that the exchange process leads to transient supersaturation and is responsible for the nanobubble nucleation. In this work, we visualize the nucleation dynamics by controllably mixing water and ethanol. It depicts the temporal evolution of the conventional exchange in a single field of view, detailing the conditions for surface nanobubble nucleation and the flow field that influences their spatial organization. This technique can also pattern surface nanobubbles with variable size distribution.

A Monte Carlo method for the simulation of coagulation and nucleation based on weighted particles and the concepts of stochastic resolution and merging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kotalczyk, G., E-mail: Gregor.Kotalczyk@uni-due.de; Kruis, F.E.

Monte Carlo simulations based on weighted simulation particles can solve a variety of population balance problems and allow thus to formulate a solution-framework for many chemical engineering processes. This study presents a novel concept for the calculation of coagulation rates of weighted Monte Carlo particles by introducing a family of transformations to non-weighted Monte Carlo particles. The tuning of the accuracy (named ‘stochastic resolution’ in this paper) of those transformations allows the construction of a constant-number coagulation scheme. Furthermore, a parallel algorithm for the inclusion of newly formed Monte Carlo particles due to nucleation is presented in the scope ofmore » a constant-number scheme: the low-weight merging. This technique is found to create significantly less statistical simulation noise than the conventional technique (named ‘random removal’ in this paper). Both concepts are combined into a single GPU-based simulation method which is validated by comparison with the discrete-sectional simulation technique. Two test models describing a constant-rate nucleation coupled to a simultaneous coagulation in 1) the free-molecular regime or 2) the continuum regime are simulated for this purpose.« less

The Stress-Dependent Activation Parameters for Dislocation Nucleation in Molybdenum Nanoparticles.

PubMed

Chachamovitz, Doron; Mordehai, Dan

2018-03-02

Many specimens at the nanoscale are pristine of dislocations, line defects which are the main carriers of plasticity. As a result, they exhibit extremely high strengths which are dislocation-nucleation controlled. Since nucleation is a thermally activated process, it is essential to quantify the stress-dependent activation parameters for dislocation nucleation in order to study the strength of specimens at the nanoscale and its distribution. In this work, we calculate the strength of Mo nanoparticles in molecular dynamics simulations and we propose a method to extract the activation free-energy barrier for dislocation nucleation from the distribution of the results. We show that by deforming the nanoparticles at a constant strain rate, their strength distribution can be approximated by a normal distribution, from which the activation volumes at different stresses and temperatures are calculated directly. We found that the activation energy dependency on the stress near spontaneous nucleation conditions obeys a power-law with a critical exponent of approximately 3/2, which is in accordance with critical exponents found in other thermally activated processes but never for dislocation nucleation. Additionally, significant activation entropies were calculated. Finally, we generalize the approach to calculate the activation parameters for other driving-force dependent thermally activated processes.

Classical nucleation theory in the phase-field crystal model

NASA Astrophysics Data System (ADS)

Jreidini, Paul; Kocher, Gabriel; Provatas, Nikolas

2018-04-01

A full understanding of polycrystalline materials requires studying the process of nucleation, a thermally activated phase transition that typically occurs at atomistic scales. The numerical modeling of this process is problematic for traditional numerical techniques: commonly used phase-field methods' resolution does not extend to the atomic scales at which nucleation takes places, while atomistic methods such as molecular dynamics are incapable of scaling to the mesoscale regime where late-stage growth and structure formation takes place following earlier nucleation. Consequently, it is of interest to examine nucleation in the more recently proposed phase-field crystal (PFC) model, which attempts to bridge the atomic and mesoscale regimes in microstructure simulations. In this work, we numerically calculate homogeneous liquid-to-solid nucleation rates and incubation times in the simplest version of the PFC model, for various parameter choices. We show that the model naturally exhibits qualitative agreement with the predictions of classical nucleation theory (CNT) despite a lack of some explicit atomistic features presumed in CNT. We also examine the early appearance of lattice structure in nucleating grains, finding disagreement with some basic assumptions of CNT. We then argue that a quantitatively correct nucleation theory for the PFC model would require extending CNT to a multivariable theory.

Classical nucleation theory in the phase-field crystal model.

PubMed

Jreidini, Paul; Kocher, Gabriel; Provatas, Nikolas

2018-04-01

A full understanding of polycrystalline materials requires studying the process of nucleation, a thermally activated phase transition that typically occurs at atomistic scales. The numerical modeling of this process is problematic for traditional numerical techniques: commonly used phase-field methods' resolution does not extend to the atomic scales at which nucleation takes places, while atomistic methods such as molecular dynamics are incapable of scaling to the mesoscale regime where late-stage growth and structure formation takes place following earlier nucleation. Consequently, it is of interest to examine nucleation in the more recently proposed phase-field crystal (PFC) model, which attempts to bridge the atomic and mesoscale regimes in microstructure simulations. In this work, we numerically calculate homogeneous liquid-to-solid nucleation rates and incubation times in the simplest version of the PFC model, for various parameter choices. We show that the model naturally exhibits qualitative agreement with the predictions of classical nucleation theory (CNT) despite a lack of some explicit atomistic features presumed in CNT. We also examine the early appearance of lattice structure in nucleating grains, finding disagreement with some basic assumptions of CNT. We then argue that a quantitatively correct nucleation theory for the PFC model would require extending CNT to a multivariable theory.

Nanostructures nucleation in carbon-metal gaseous phase: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Galiullina, G. M.; Orekhov, N. D.; Stegailov, V. V.

2018-01-01

We perform nonequilibrium molecular dynamics simulation of carbon nanoclusters nucleation and early stages of growth from the gaseous phase. We analyze the catalytic effect of iron atoms on the nucleation kinetics and structure of the resultant nanoparticles. Reactive Force Field (ReaxFF) is used in the simulations for the description of bond formation and dissociation during the nucleation process at the nanoscale. The catalytic effect of iron reveals itself even on nanosecond simulation times: iron atoms accelerate the process of clustering but result in less graphitized carbon structures.

Heterogeneous Nucleation of Colloidal Crystals on a Glass Substrate with Depletion Attraction.

PubMed

Guo, Suxia; Nozawa, Jun; Hu, Sumeng; Koizumi, Haruhiko; Okada, Junpei; Uda, Satoshi

2017-10-10

The heterogeneous nucleation of colloidal crystals with attractive interactions has been investigated via in situ observations. We have found two types of nucleation processes: a cluster that overcomes the critical size for nucleation with a monolayer, and a method that occurs with two layers. The Gibbs free energy changes (ΔG) for these two types of nucleation processes are evaluated by taking into account the effect of various interfacial energies. In contrast to homogeneous nucleation, the change in interfacial free energy, Δσ, is generated for colloidal nucleation on a foreign substrate such as a cover glass in the present study. The Δσ and step free energy of the first layer, γ 1 , are obtained experimentally based on the equation deduced from classical nucleation theory (CNT). It is concluded that the ΔG of q-2D nuclei is smaller than of monolayer nuclei, provided that the same number of particles are used, which explains the experimental result that the critical size in q-2D nuclei is smaller than that in monolayer nuclei.

Modeling Studying the Role of Bacteria on ice Nucleation Processes

NASA Astrophysics Data System (ADS)

Sun, J.

2006-12-01

Certain air-borne bacteria have been recognized as active ice nuclei at the temperatures warm than - 10°C. Ice nucleating bacteria commonly found in plants and ocean surface. These ice nucleating bacteria are readily disseminated into the atmosphere and have been observed in clouds and hailstones, and their importance in cloud formation process and precipitation, as well as causing diseases in plants and animal kingdom, have been considered for over two decades, but their significance in atmospheric processes are yet to be understood. A 1.5-D non-hydrostatic cumulus cloud model with bin-resolved microphysics is developed and is to used to examine the relative importance of sulphate aerosol concentrations on the evolution of cumulus cloud droplet spectra and ice multiplication process, as well as ice initiation process by ice nucleating bacteria in the growing stage of cumulus clouds and the key role of this process on the ice multiplication in the subsequent dissipating stage of cumulus clouds. In this paper, we will present some sensitivity test results of the evolution of cumulus cloud spectra, ice concentrations at various concentrations of sulfate aerosols, and at different ideal sounding profiles. We will discuss the implication of our results in understanding of ice nucleation processes.

Crystal Nucleation and Growth in Undercooled Melts of Pure Zr, Binary Zr-Based and Ternary Zr-Ni-Cu Glass-Forming Alloys

NASA Astrophysics Data System (ADS)

Herlach, Dieter M.; Kobold, Raphael; Klein, Stefan

2018-03-01

Glass formation of a liquid undercooled below its melting temperature requires the complete avoidance of crystal nucleation and subsequent crystal growth. Even though they are not part of the glass formation process, a detailed knowledge of both processes involved in crystallization is mandatory to determine the glass-forming ability of metals and metallic alloys. In the present work, methods of containerless processing of drops by electrostatic and electromagnetic levitation are applied to undercool metallic melts prior to solidification. Heterogeneous nucleation on crucible walls is completely avoided giving access to large undercoolings. A freely suspended drop offers the additional benefit of showing the rapid crystallization process of an undercooled melt in situ by proper diagnostic means. As a reference, crystal nucleation and dendrite growth in the undercooled melt of pure Zr are experimentally investigated. Equivalently, binary Zr-Cu, Zr-Ni and Zr-Pd and ternary Zr-Ni-Cu alloys are studied, whose glass-forming abilities differ. The experimental results are analyzed within classical nucleation theory and models of dendrite growth. The findings give detailed knowledge about the nucleation-undercooling statistics and the growth kinetics over a large range of undercooling.

Quantification of an atmospheric nucleation and growth process as a single source of aerosol particles in a city

NASA Astrophysics Data System (ADS)

Salma, Imre; Varga, Veronika; Németh, Zoltán

2017-12-01

Effects of a new aerosol particle formation (NPF) and particle diameter growth process as a single source of atmospheric particle number concentrations were evaluated and quantified on the basis of experimental data sets obtained from particle number size distribution measurements in the city centre and near-city background of Budapest for 5 years. Nucleation strength factors for a nucleation day (NSFNUC) and for a general day (NSFGEN) were derived separately for seasons and full years. The former characteristic represents the concentration increment of ultrafine (UF) particles specifically on nucleation days with respect to accumulation-mode (regional background) concentrations (particles with equivalent diameters of 100-1000 nm; N100-1000) due solely to the nucleation process. The latter factor expresses the contribution of nucleation to particle numbers on general days; thus, it represents a longer time interval such as season or year. The nucleation source had the largest effect on the concentrations around noon and early afternoon, as expected. During this time interval, it became the major source of particles in the near-city background. Nucleation increased the daily mean concentrations on nucleation days by mean factors of 2.3 and 1.58 in the near-city background and city centre, respectively. Its effect was largest in winter, which was explained by the substantially lower N100-1000 levels on nucleation days than those on non-nucleation days. On an annual timescale, 37 % of the UF particles were generated by nucleation in the near-city background, while NPF produced 13 % of UF particles in the city centre. The differences among the annual mean values, and among the corresponding seasonal mean values, were likely caused by the variability in controlling factors from year to year. The values obtained represent the lower limits of the contributions. The shares determined imply that NPF is a non-negligible or substantial source of particles in near-city background environments and even in city centres, where the vehicular road emissions usually prevail. Atmospheric residence time of nucleation-mode particles was assessed by a decay curve analysis, and a mean of 02:30 was obtained. The present study suggests that the health-related consequences of the atmospheric NPF and growth process in cities should also be considered in addition to its urban climate implications.

Modeling of light-induced degradation due to Cu precipitation in p-type silicon. II. Comparison of simulations and experiments

NASA Astrophysics Data System (ADS)

Vahlman, H.; Haarahiltunen, A.; Kwapil, W.; Schön, J.; Inglese, A.; Savin, H.

2017-05-01

The presence of copper impurities is known to deteriorate the bulk minority carrier lifetime of silicon. In p-type silicon, the degradation occurs only under carrier injection (e.g., illumination), but the reason for this phenomenon called copper-related light-induced degradation (Cu-LID) has long remained uncertain. To clarify the physics of this problem, a mathematical model of Cu-LID was introduced in Paper I of this article. Within the model, kinetic precipitation simulations are interlinked with a Schottky junction model for electric behavior of metallic precipitates. As this approach enables simulating precipitation directly at the minority carrier lifetime level, the model is verified in this second part with a direct comparison to the corresponding degradation experiments and literature data. Convincing agreement is found with different doping and Cu concentrations as well as at increased temperature, and in the dark, both simulated degradation and measured degradation are very slow. In addition, modeled final lifetimes after illumination are very close to experimental final lifetimes, and a correlation with the final precipitate size is found. However, the model underestimates experimentally observed differences in the degradation rate at different illumination intensities. Nevertheless, the results of this work support the theory of Cu-LID as a precipitate formation process. Part of the results also imply that heterogeneous nucleation sites play a role during precipitate nucleation. The model reveals fundamental aspects of the physics of Cu-LID including how doping and heterogeneous nucleation site concentrations can considerably influence the final recombination activity.

Numerical investigation of homogeneous cavitation nucleation in a microchannel

NASA Astrophysics Data System (ADS)

Lyu, Xiuxiu; Pan, Shucheng; Hu, Xiangyu; Adams, Nikolaus A.

2018-06-01

The physics of nucleation in water is an important issue for many areas, ranging from biomedical to engineering applications. Within the present study, we investigate numerically homogeneous nucleation in a microchannel induced by shock reflection to gain a better understanding of the mechanism of homogeneous nucleation. The liquid expands due to the reflected shock and homogeneous cavitation nuclei are generated. An Eulerian-Lagrangian approach is employed for modeling this process in a microchanel. Two-dimensional axisymmetric Euler equations are solved for obtaining the time evolution of shock, gas bubble, and the ambient fluid. The dynamics of dispersed vapor bubbles is coupled with the surrounding fluid in a Lagrangian framework, describing bubble location and bubble size variation. Our results reproduce nuclei distributions at different stages of homogeneous nucleation and are in good agreement with experimental results. We obtain numerical data for the negative pressure that water can sustain under the process of homogeneous nucleation. An energy transformation description for the homogeneous nucleation inside a microchannel flow is derived and analyzed in detail.

Adherent nanoparticles-mediated micro- and nanobubble nucleation

NASA Astrophysics Data System (ADS)

Chan, Chon U.; Chen, Long Quan; Lippert, Alexander; Arora, Manish; Ohl, Claus-Dieter

2014-11-01

Surface nanobubbles are commonly nucleated through water-ethanol-water exchange. It is believed that the higher gas solubility in ethanol and exothermic mixing leads to a supersaturation of gas in water. However details of the nucleation dynamic are still unknown. Here we apply the exchange process onto a glass surface deposited with nanoparticles and monitor the dynamics optically at video frame rates. During exchange bubbles of a few micron in diameter nucleate at the sites of nanoparticles. These microbubbles eventually dissolve in ethanol but are stable in water. This agrees with the nucleation process observed for surface nanobubbles. Also we find a reduction of surface attached nanobubbles near the particles, which might be due to gas uptake from the microbubble growth. Finally, high speed recordings reveal stick-slip motion of the triple contact line during the growth process. We will discuss possibilities of utilizing the findings for contamination detection and ultrasonic cleaning.

The significance of intergranular diffusion to the mechanisms and kinetics of porphyroblast crystallization

NASA Astrophysics Data System (ADS)

Carlson, William D.

1989-09-01

The spatial disposition, compositional zoning profiles, and size distributions of garnet crystals in 11 specimens of pelitic schist from the Picuris Range of New Mexico (USA) demonstrate that the kinetics of intergranular diffusion controlled the nucleation and growth mechanisms of porphyroblasts in these rocks. An ordered disposition of garnet centers and a significant correlation between crystal radius and near-neighbor distances manifest suppressed nucleation of new crystals in diffusionally depleted zones surrounding pre-existing crystals. Compositional zoning profiles require diffusionally controlled growth, the rate of which increases exponentially as temperature increases with time; an acceleration factor for growth rate can be estimated from a comparison of compositional profiles for crystals of different sizes in each specimen. Crystal size distributions are interpreted as the result of nucleation rates that accelerate exponentially with increasing temperature early in the crystallization process, but decline in the later stages because of suppression effects in the vicinity of earlier-formed nuclei. Simulations of porphyroblast crystallization, based upon thermally accelerated diffusionally influenced nucleation kinetics and diffusionally controlled growth kinetics, quantitatively replicate textural relations in the rocks. The simulations employ only two variable parameters, which are evaluated by fitting of crystal size distributions. Both have physical significance. The first is an acceleration factor for nucleation, with a magnitude reflecting the prograde increase during the nucleation interval of the chemical affinity for the reaction in undepleted regions of the rock. The second is a measure of the relative sizes of the porphyroblast and the diffusionally depleted zone surrounding it. Crystal size distributions for the Picuris Range garnets correspond very closely to those in the literature from a variety of other localities for garnet and other minerals. The same kinetic model accounts quantitatively for crystal size distributions of porphyroblastic garnet, phlogopite, sphene, and pyroxene in rocks from both regional and contact metamorphic occurrences. These commonalities indicate that intergranular diffusion may be the dominant kinetic factor in the crystallization of porphyroblasts in a wide variety of metamorphic environments.

Leipzig Ice Nucleation chamber Comparison (LINC): intercomparison of four online ice nucleation counters

NASA Astrophysics Data System (ADS)

Burkert-Kohn, Monika; Wex, Heike; Welti, André; Hartmann, Susan; Grawe, Sarah; Hellner, Lisa; Herenz, Paul; Atkinson, James D.; Stratmann, Frank; Kanji, Zamin A.

2017-09-01

Ice crystal formation in atmospheric clouds has a strong effect on precipitation, cloud lifetime, cloud radiative properties, and thus the global energy budget. Primary ice formation above 235 K is initiated by nucleation on seed aerosol particles called ice-nucleating particles (INPs). Instruments that measure the ice-nucleating potential of aerosol particles in the atmosphere need to be able to accurately quantify ambient INP concentrations. In the last decade several instruments have been developed to investigate the ice-nucleating properties of aerosol particles and to measure ambient INP concentrations. Therefore, there is a need for intercomparisons to ensure instrument differences are not interpreted as scientific findings.In this study, we intercompare the results from parallel measurements using four online ice nucleation chambers. Seven different aerosol types are tested including untreated and acid-treated mineral dusts (microcline, which is a K-feldspar, and kaolinite), as well as birch pollen washing waters. Experiments exploring heterogeneous ice nucleation above and below water saturation are performed to cover the whole range of atmospherically relevant thermodynamic conditions that can be investigated with the intercompared chambers. The Leipzig Aerosol Cloud Interaction Simulator (LACIS) and the Portable Immersion Mode Cooling chAmber coupled to the Portable Ice Nucleation Chamber (PIMCA-PINC) performed measurements in the immersion freezing mode. Additionally, two continuous-flow diffusion chambers (CFDCs) PINC and the Spectrometer for Ice Nuclei (SPIN) are used to perform measurements below and just above water saturation, nominally presenting deposition nucleation and condensation freezing.The results of LACIS and PIMCA-PINC agree well over the whole range of measured frozen fractions (FFs) and temperature. In general PINC and SPIN compare well and the observed differences are explained by the ice crystal growth and different residence times in the chamber. To study the mechanisms responsible for the ice nucleation in the four instruments, the FF (from LACIS and PIMCA-PINC) and the activated fraction, AF (from PINC and SPIN), are compared. Measured FFs are on the order of a factor of 3 higher than AFs, but are not consistent for all aerosol types and temperatures investigated. It is shown that measurements from CFDCs cannot be assumed to produce the same results as those instruments exclusively measuring immersion freezing. Instead, the need to apply a scaling factor to CFDCs operating above water saturation has to be considered to allow comparison with immersion freezing devices. Our results provide further awareness of factors such as the importance of dispersion methods and the quality of particle size selection for intercomparing online INP counters.

Comparison of ice nuclei from fruit juices and their properties

NASA Astrophysics Data System (ADS)

Fiala, Bianca; Felgitsch, Laura; Grothe, Hinrich

2017-04-01

Heterogeneous ice nucleation is a crucial process in the atmosphere. Recent findings indicate the importance of biological ice nuclei (IN) in this process. Pratt et al. (2009) sampled ice-crystal residues at approx. 8 km high altitude over Wyoming, U.S.. They found a third of the dry residues to be biological and further that 60% of the highly abundant mineral dusts to be internally mixed with biological or humic substances. Huffman et al. (2013) showed a burst of biological IN over woodlands connected to rain events. Previous investigations in our group (Pummer et al. 2012) showed that pollen and pollen washing water from several plants native to the boreal forests trigger heterogeneous ice nucleation. Recent work from our group (Felgitsch et al. 2016) showed that several juices of berries are ice nucleation active. Based on this research we examined ice nucleation activity (INA) and general properties of five juices: sea buckthorn, black currant, chokeberry, acerola, and elder berry. We elucidated particle size dependency of the ice nucleation activity to differentiate between coarse ice nucleating particles and nanoparticles or macromolecules. Investigations with different solvents and with chaotropic agents were performed in order to further clarify properties concerning chemical polarity of the IN, and the importance of hydrogen bonds and other structure forming polar interactions. The results are compared to known plant originated IN. Our results suggest similarities in terms of nucleation temperature and structure stability between different IN of plant materials. These properties show a clear differentiation to known bacterial and fungal IN. Felgitsch , L., Bichler, M., Häusler, T., Hitzenberger, R., and Grothe, H.: Heterogeneous freezing of water triggered by berry juices from perenneal plants, submitted, 2016. Huffman, J.A., Prenni, A.J., DeMott, P.J., Pöhlker, C., Mason, R.H., Robinson, N.H., Frohlich-Nowoisky, J., Tobo, Y., Després, V.R., Garcia, E., Gochis, D.J., Harris, E., Müller-Germann, I., Ruzene, C., Schmer, B., Sinha, B., Day, D.A., Andreae, M.O., Jimenez, J.L., Gallagher, M., Kreidenweis, S.M., Bertram, A.K., and Pöschl, U.: High concentrations of biological aerosol particles and ice nuclei during and after rain, Atmos. Chem. Phys., 13, 1651-1664, 2013. Pratt, K.A., DeMott, P.J., French, J.R., Wang, Z., Westphal, D.L., Heymsfield, A.J., Twohy, C.H., Prenni, A.J., and Prather, K.A.: In situ detection of biological particles in cloud ice-crystals, Nat. Geosci., 2, 298-401, 2009. Pummer, B.G., Bauer, H., Bernardi, J., Bleicher, S., and Grothe, H.: Suspendable macromolecules are responsible for ice nucleation activity of birch and conifer pollen, Atmos. Chem. Phys., 12, 2541-2550, 2012.

How does spallation microdamage nucleate in bulk amorphous alloys under shock loading?

NASA Astrophysics Data System (ADS)

Huang, X.; Ling, Z.; Zhang, H. S.; Ma, J.; Dai, L. H.

2011-11-01

Specially designed plate-impact experiments have been conducted on a Zr-based amorphous alloy using a single-stage light gas gun. To understand the microdamage nucleation process in the material, the samples are subjected to dynamic tensile loadings of identical amplitude (˜ 3.18 GPa) but with different durations (83-201 ns). A cellular pattern with an equiaxed shape is observed on the spallation surface, which shows that spallation in the tested amorphous alloy is a typical ductile fracture and that microvoids have been nucleated during the process. Based on the observed fracture morphologies of the spallation surface and free-volume theory, we propose a microvoid nucleation model of bulk amorphous alloys. It is found that nucleation of microvoids at the early stage of spallation in amorphous alloys results from diffusion and coalescence of free volume, and that high mean tensile stress plays a dominant role in microvoid nucleation.

Mutagenic analysis of the nucleation propensity of oxidized Alzheimer's beta-amyloid peptide.

PubMed

Christopeit, Tony; Hortschansky, Peter; Schroeckh, Volker; Gührs, Karlheinz; Zandomeneghi, Giorgia; Fändrich, Marcus

2005-08-01

The formation of polypeptide aggregates represents a nucleated polymerization reaction in which an initial nucleation event (lag phase) is followed by the extension of newly formed nuclei into larger aggregates, including fibrils (growth phase). The efficiencies of these reactions relate to the lag time (lag phase) and to the rate of aggregation (growth phase), which can be determined from experimental aggregation curves. Here we present a mutagenic analysis in which we replace valine 18 of the Alzheimer's Abeta (1-40) peptide with 17 different amino acids and determine its effect on the lag time, and therefore, on the propensity of nucleation. Comparison with various physico-chemical properties shows that nucleation is affected in a predictable manner depending on the beta-sheet propensity and hydrophobicity of residue 18. In addition, we observe a direct proportionality between the lag time and the rate of aggregation. These data imply that the two reactions, nucleation and polymerization, are governed by very similar physicochemical principles and that they involve the formation of the same types of noncovalent interactions.

Advances in Understanding the Role of Aerosols on Ice Clouds from the Fifth International Ice Nucleation (FIN) Workshops

NASA Astrophysics Data System (ADS)

Cziczo, D. J.; Moehler, O.; DeMott, P. J.

2015-12-01

The relationship of ambient aerosol particles to the formation of ice-containing clouds is one of the largest uncertainties in understanding climate. This is due to several poorly understood processes including the microphysics of how particles nucleate ice, the number of effective heterogeneous ice nuclei and their atmospheric distribution, the role of anthropogenic activities in producing or changing the behavior of ice forming particles and the interplay between effective heterogeneous ice nuclei and homogeneous ice formation. Our team recently completed a three-part international workshop to improve our understanding of atmospheric ice formation. Termed the Fifth International Ice Nucleation (FIN) Workshops, our motivation was the limited number of measurements and a lack of understanding of how to compare data acquired by different groups. The first activity, termed FIN1, addressed the characterization of ice nucleating particle size, number and chemical composition. FIN2 addressed the determination of ice nucleating particle number density. Groups modeling ice nucleation joined FIN2 to provide insight on measurements critically needed to model atmospheric ice nucleation and to understand the performance of ice chambers. FIN1 and FIN2 took place at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) chamber at the Karlsruhe Institute of Technology. A particular emphasis of FIN1 and FIN2 was the use of 'blind' intercomparisons using a highly characterized, but unknown to the instrument operators, aerosol sample. The third activity, FIN3, took place at the Desert Research Institute's Storm Peak Laboratory (SPL). A high elevation site not subject to local emissions, SPL allowed for a comparison of ice chambers and subsequent analysis of the ice residuals under the challenging conditions of low particle loading, temperature and pressure found in the atmosphere. The presentation focuses on the improvement in understanding how mass spectra from different instruments can be compared from FIN1 and FIN3. The complementary nature of different ice chamber to access the diverse regimes of temperature and relative humidity space will also be discussed. As a result of the FIN Workshops we believe the performance of instruments in the field can now be quantified and compared.

Investigating the Sensitivity of Nucleation Parameterization on Ice Growth

NASA Astrophysics Data System (ADS)

Gaudet, L.; Sulia, K. J.

2017-12-01

The accurate prediction of precipitation from lake-effect snow events associated with the Great Lakes region depends on the parameterization of thermodynamic and microphysical processes, including the formation and subsequent growth of frozen hydrometeors. More specifically, the formation of ice hydrometeors has been represented through varying forms of ice nucleation parameterizations considering the different nucleation modes (e.g., deposition, condensation-freezing, homogeneous). These parameterizations have been developed from in-situ measurements and laboratory observations. A suite of nucleation parameterizations consisting of those published in Meyers et al. (1992) and DeMott et al. (2010) as well as varying ice nuclei data sources are coupled with the Adaptive Habit Model (AHM, Harrington et al. 2013), a microphysics module where ice crystal aspect ratio and density are predicted and evolve in time. Simulations are run with the AHM which is implemented in the Weather Research and Forecasting (WRF) model to investigate the effect of ice nucleation parameterization on the non-spherical growth and evolution of ice crystals and the subsequent effects on liquid-ice cloud-phase partitioning. Specific lake-effect storms that were observed during the Ontario Winter Lake-Effect Systems (OWLeS) field campaign (Kristovich et al. 2017) are examined to elucidate this potential microphysical effect. Analysis of these modeled events is aided by dual-polarization radar data from the WSR-88D in Montague, New York (KTYX). This enables a comparison of the modeled and observed polarmetric and microphysical profiles of the lake-effect clouds, which involves investigating signatures of reflectivity, specific differential phase, correlation coefficient, and differential reflectivity. Microphysical features of lake-effect bands, such as ice, snow, and liquid mixing ratios, ice crystal aspect ratio, and ice density are analyzed to understand signatures in the aforementioned modeled dual-polarization radar variables. Hence, this research helps to determine an ice nucleation scheme that will best model observations of lake-effect clouds producing snow off of Lake Ontario and Lake Erie, and analyses will highlight the sensitivity of the evolution of the cases to a given nucleation scheme.

Chemical characterization of individual particles and residuals of cloud droplets and ice crystals collected on board research aircraft in the ISDAC 2008 study

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Brooks, S. D.; Moffet, R. C.; Glen, A.; Laskin, A.; Gilles, M. K.; Liu, P.; MacDonald, A. M.; Strapp, J. W.; McFarquhar, G. M.

2013-06-01

Ambient particles and the dry residuals of mixed-phase cloud droplets and ice crystals were collected during the Indirect and Semi-Direct Aerosol Campaign (ISDAC) near Barrow, Alaska, in spring of 2008. The collected particles were analyzed using Computer Controlled Scanning Electron Microscopy with Energy Dispersive X-ray analysis and Scanning Transmission X-ray Microscopy coupled with Near Edge X-ray Absorption Fine Structure spectroscopy to identify physico-chemical properties that differentiate cloud-nucleating particles from the total aerosol population. A wide range of individually mixed components was identified in the ambient particles and residuals including organic carbon compounds, inorganics, carbonates, and black carbon. Our results show that cloud droplet residuals differ from the ambient particles in both size and composition, suggesting that both properties may impact the cloud-nucleating ability of aerosols in mixed-phase clouds. The percentage of residual particles which contained carbonates (47%) was almost four times higher than those in ambient samples. Residual populations were also enhanced in sea salt and black carbon and reduced in organic compounds relative to the ambient particles. Further, our measurements suggest that chemical processing of aerosols may improve their cloud-nucleating ability. Comparison of results for various time periods within ISDAC suggests that the number and composition of cloud-nucleating particles over Alaska can be influenced by episodic events bringing aerosols from both the local vicinity and as far away as Siberia.

Partitioning of ice nucleating particles: Which modes matter?

NASA Astrophysics Data System (ADS)

Hande, Luke; Hoose, Corinna

2017-04-01

Ice particles in clouds have a large impact on cloud lifetime, precipitation amount, and cloud radiative properties through the indirect aerosol effect. Thus, correctly modelling ice formation processes is important for simulations preformed on all spatial and temporal scales. Ice forms on aerosol particles through several different mechanisms, namely deposition nucleation, immersion freezing, and contact freezing. However there is conflicting evidence as to which mode dominates, and the relative importance of the three heterogeneous ice nucleation mechanisms, as well as homogeneous nucleation, remains an open question. The environmental conditions, and hence the cloud type, have a large impact on determining which nucleation mode dominates. In order to understand this, simulations were performed with the COSMO-LES model, utilising state of the art parameterisations to describe the different nucleation mechanisms for several semi-idealised cloud types commonly occurring over central Europe. The cloud types investigated include a semi-idealised, and an idealised convective cloud, an orographic cloud, and a stratiform cloud. Results show that immersion and contact freezing dominate at warmer temperatures, and under most conditions, deposition nucleation plays only a minor role. In clouds where sufficiently high levels of water vapour are present at colder temperatures, deposition nucleation can play a role, however in general homogeneous nucleation dominates at colder temperatures. Since contact nucleation depends on the environmental relative humidity, enhancements in this nucleation mode can be seen in areas of dry air entrainment. The results indicate that ice microphysical processes are somewhat sensitve to the environmental conditions and therefore the cloud type.

Nucleation in Polymers and Soft Matter

NASA Astrophysics Data System (ADS)

Xu, Xiaofei; Ting, Christina L.; Kusaka, Isamu; Wang, Zhen-Gang

2014-04-01

Nucleation is a ubiquitous phenomenon in many physical, chemical, and biological processes. In this review, we describe recent progress on the theoretical study of nucleation in polymeric fluids and soft matter, including binary mixtures (polymer blends, polymers in poor solvents, compressible polymer-small molecule mixtures), block copolymer melts, and lipid membranes. We discuss the methodological development for studying nucleation as well as novel insights and new physics obtained in the study of the nucleation behavior in these systems.

An integrated process analytical technology (PAT) approach to monitoring the effect of supercooling on lyophilization product and process parameters of model monoclonal antibody formulations.

PubMed

Awotwe Otoo, David; Agarabi, Cyrus; Khan, Mansoor A

2014-07-01

The aim of the present study was to apply an integrated process analytical technology (PAT) approach to control and monitor the effect of the degree of supercooling on critical process and product parameters of a lyophilization cycle. Two concentrations of a mAb formulation were used as models for lyophilization. ControLyo™ technology was applied to control the onset of ice nucleation, whereas tunable diode laser absorption spectroscopy (TDLAS) was utilized as a noninvasive tool for the inline monitoring of the water vapor concentration and vapor flow velocity in the spool during primary drying. The instantaneous measurements were then used to determine the effect of the degree of supercooling on critical process and product parameters. Controlled nucleation resulted in uniform nucleation at lower degrees of supercooling for both formulations, higher sublimation rates, lower mass transfer resistance, lower product temperatures at the sublimation interface, and shorter primary drying times compared with the conventional shelf-ramped freezing. Controlled nucleation also resulted in lyophilized cakes with more elegant and porous structure with no visible collapse or shrinkage, lower specific surface area, and shorter reconstitution times compared with the uncontrolled nucleation. Uncontrolled nucleation however resulted in lyophilized cakes with relatively lower residual moisture contents compared with controlled nucleation. TDLAS proved to be an efficient tool to determine the endpoint of primary drying. There was good agreement between data obtained from TDLAS-based measurements and SMART™ technology. ControLyo™ technology and TDLAS showed great potential as PAT tools to achieve enhanced process monitoring and control during lyophilization cycles. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Boreal pollen contain ice-nucleating as well as ice-binding ‘antifreeze’ polysaccharides

NASA Astrophysics Data System (ADS)

Dreischmeier, Katharina; Budke, Carsten; Wiehemeier, Lars; Kottke, Tilman; Koop, Thomas

2017-02-01

Ice nucleation and growth is an important and widespread environmental process. Accordingly, nature has developed means to either promote or inhibit ice crystal formation, for example ice-nucleating proteins in bacteria or ice-binding antifreeze proteins in polar fish. Recently, it was found that birch pollen release ice-nucleating macromolecules when suspended in water. Here we show that birch pollen washing water exhibits also ice-binding properties such as ice shaping and ice recrystallization inhibition, similar to antifreeze proteins. We present spectroscopic evidence that both the ice-nucleating as well as the ice-binding molecules are polysaccharides bearing carboxylate groups. The spectra suggest that both polysaccharides consist of very similar chemical moieties, but centrifugal filtration indicates differences in molecular size: ice nucleation occurs only in the supernatant of a 100 kDa filter, while ice shaping is strongly enhanced in the filtrate. This finding may suggest that the larger ice-nucleating polysaccharides consist of clusters of the smaller ice-binding polysaccharides, or that the latter are fragments of the ice-nucleating polysaccharides. Finally, similar polysaccharides released from pine and alder pollen also display both ice-nucleating as well as ice-binding ability, suggesting a common mechanism of interaction with ice among several boreal pollen with implications for atmospheric processes and antifreeze protection.

Boreal pollen contain ice-nucleating as well as ice-binding ‘antifreeze’ polysaccharides

PubMed Central

Dreischmeier, Katharina; Budke, Carsten; Wiehemeier, Lars; Kottke, Tilman; Koop, Thomas

2017-01-01

Ice nucleation and growth is an important and widespread environmental process. Accordingly, nature has developed means to either promote or inhibit ice crystal formation, for example ice-nucleating proteins in bacteria or ice-binding antifreeze proteins in polar fish. Recently, it was found that birch pollen release ice-nucleating macromolecules when suspended in water. Here we show that birch pollen washing water exhibits also ice-binding properties such as ice shaping and ice recrystallization inhibition, similar to antifreeze proteins. We present spectroscopic evidence that both the ice-nucleating as well as the ice-binding molecules are polysaccharides bearing carboxylate groups. The spectra suggest that both polysaccharides consist of very similar chemical moieties, but centrifugal filtration indicates differences in molecular size: ice nucleation occurs only in the supernatant of a 100 kDa filter, while ice shaping is strongly enhanced in the filtrate. This finding may suggest that the larger ice-nucleating polysaccharides consist of clusters of the smaller ice-binding polysaccharides, or that the latter are fragments of the ice-nucleating polysaccharides. Finally, similar polysaccharides released from pine and alder pollen also display both ice-nucleating as well as ice-binding ability, suggesting a common mechanism of interaction with ice among several boreal pollen with implications for atmospheric processes and antifreeze protection. PMID:28157236

Surface Crystallization of Cloud Droplets: Implications for Climate Change and Ozone Depletion

NASA Technical Reports Server (NTRS)

Tabazadeh, A.; Djikaev, Y. S.; Reiss, H.; Gore, Warren J. (Technical Monitor)

2002-01-01

The process of supercooled liquid water crystallization into ice is still not well understood. Current experimental data on homogeneous freezing rates of ice nucleation in supercooled water droplets show considerable scatter. For example, at -33 C, the reported freezing nucleation rates vary by as much as 5 orders of magnitude, which is well outside the range of measurement uncertainties. Until now, experimental data on the freezing of supercooled water has been analyzed under the assumption that nucleation of ice took place in the interior volume of a water droplet. Here, the same data is reanalyzed assuming that the nucleation occurred "pseudoheterogeneously" at the air (or oil)-liquid water interface of the droplet. Our analysis suggest that the scatter in the nucleation data can be explained by two main factors. First, the current assumption that nucleation occurs solely inside the volume of a water droplet is incorrect. Second, because the nucleation process most likely occurs on the surface, the rates of nuclei formation could differ vastly when oil or air interfaces are involved. Our results suggest that ice freezing in clouds may initiate on droplet surfaces and such a process can allow for low amounts of liquid water (approx. 0.002 g per cubic meters) to remain supercooled down to -40 C as observed in the atmosphere.

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

Nucleation control and separation of paracetamol polymorphs through swift cooling crystallization process

NASA Astrophysics Data System (ADS)

Sudha, C.; Srinivasan, K.

2014-09-01

Polymorphic nucleation behavior of pharmaceutical solid paracetamol has been investigated by performing swift cooling crystallization process. Saturated aqueous solution prepared at 318 K was swiftly cooled to 274 K in steps of every 1 K in the temperature range from 274 K to 313 K with uniform stirring of 100 rpm. The resultant supersaturation generated in the mother solution favours the nucleation of three different polymorphs of paracetamol. Lower supersaturation region σ=0.10-0.83 favours stable mono form I; the intermediate supersaturation region σ=0.92-1.28 favours metastable ortho form II and the higher supersaturation region σ=1.33-1.58 favours unstable form III polymorphic nucleation. Depending upon the level of supersaturation generated during swift cooling process and the corresponding solubility limit and metastable zone width (MSZW) of each polymorph, the nucleation of a particular polymorph occurs in the system. The type of polymorphs was identified by in-situ optical microscopy and the internal structure was confirmed by Powder X-ray diffraction (PXRD) study. By this novel approach, the preferred nucleation regions of all the three polymorphs of paracetamol are optimized in terms of different cooling ranges employed during the swift cooling process. Also solution mediated polymorphic transformations from unstable to mono and ortho to mono polymorphs have been studied by in-situ.

Effect of Sn Micro-alloying on Recrystallization Nucleation and Growth Processes of Ferritic Stainless Steels

NASA Astrophysics Data System (ADS)

He, Tong; Bai, Yang; Liu, Xiuting; Guo, Dan; Liu, Yandong

2018-04-01

We investigated the effect of Sn micro-alloying on recrystallization nucleation and growth processes of ferritic stainless steels. The as-received hot rolled sheets were cold rolled up to 80% reduction and then annealed at 740-880 °C for 5 min. The cold rolling and recrystallization microstructures and micro-textures of Sn-containing and Sn-free ferritic stainless steels were all determined by electron backscatter diffraction. Our Results show that Sn micro-alloying has important effects on recrystallization nucleation and growth processes of ferritic stainless steels. Sn micro-alloying conduces to grain fragmentation in the deformation band, more fragmented grains are existed in Sn-containing cold rolled sheets, which provides more sites for recrystallization nucleation. Sn micro-alloying also promotes recrystallization process and inhibits the growth of recrystallized grains. The recrystallization nucleation and growth mechanism of Sn-containing and Sn-free ferritic stainless steels are both characterized by orientation nucleation and selective growth, but Sn micro-alloying promotes the formation of γ-oriented grains. Furthermore, Sn micro-alloying contributes to the formation of Σ13b CSL boundaries and homogeneous γ-fiber texture. Combining the results of microstructure and micro-texture, the formability of Sn-containing ferritic stainless steels will be improved to some extent.

Realizing controllable graphene nucleation by regulating the competition of hydrogen and oxygen during chemical vapor deposition heating.

PubMed

Zhang, Haoran; Zhang, Yaqian; Zhang, Yanhui; Chen, Zhiying; Sui, Yanping; Ge, Xiaoming; Deng, Rongxuan; Yu, Guanghui; Jin, Zhi; Liu, Xinyu

2016-08-24

Oxygen can passivate Cu surface active sites when graphene nucleates. Thus, the nucleation density is decreased. The CuO/Cu substrate was chosen for graphene domain synthesis in our study. The results indicate that the CuO/Cu substrate is beneficial for large-scale, single-crystal graphene domain synthesis. Graphene grown on the CuO/Cu substrate exhibits fewer nucleation sites than on Cu foils, suggesting that graphene follows an oxygen-dominating growth. Hydrogen treatment via a heating process could weaken the surface oxygen's role in limiting graphene nucleation under the competition of hydrogen and oxygen and could transfer the synthesis of graphene into a hydrogen-dominating growth. However, the competition only exists during the chemical vapor deposition heating process. For non-hydrogen heated samples, oxygen-dominating growth is experienced even though the samples are annealed in hydrogen for a long time after the heating process. With the temperature increases, the role of hydrogen gradually decreases. The balance of hydrogen and oxygen is adjusted by introducing hydrogen gas at a different heating temperatures. The oxygen concentration on the substrate surface is believed to determine the reactions mechanisms based on the secondary ion mass spectrometry test results. This study provides a new method for the controllable synthesis of graphene nucleation during a heating process.

Atomic Scale Imaging of Nucleation and Growth Trajectories of an Interfacial Bismuth Nanodroplet.

PubMed

Li, Yingxuan; Bunes, Benjamin R; Zang, Ling; Zhao, Jie; Li, Yan; Zhu, Yunqing; Wang, Chuanyi

2016-02-23

Because of the lack of experimental evidence, much confusion still exists on the nucleation and growth dynamics of a nanostructure, particularly of metal. The situation is even worse for nanodroplets because it is more difficult to induce the formation of a nanodroplet while imaging the dynamic process with atomic resolution. Here, taking advantage of an electron beam to induce the growth of Bi nanodroplets on a SrBi2Ta2O9 platelet under a high resolution transmission electron microscope (HRTEM), we directly observed the detailed growth pathways of Bi nanodroplets from the earliest stage of nucleation that were previously inaccessible. Atomic scale imaging reveals that the dynamics of nucleation involves a much more complex trajectory than previously predicted based on classical nucleation theory (CNT). The monatomic Bi layer was first formed in the nucleation process, which induced the formation of the prenucleated clusters. Following that, critical nuclei for the nanodroplets formed both directly from the addition of atoms to the prenucleated clusters by the classical growth process and indirectly through transformation of an intermediate liquid film based on the Stranski-Krastanov growth mode, in which the liquid film was induced by the self-assembly of the prenucleated clusters. Finally, the growth of the Bi nanodroplets advanced through the classical pathway and sudden droplet coalescence. This study allows us to visualize the critical steps in the nucleation process of an interfacial nanodroplet, which suggests a revision of the perspective of CNT.

The influence of solution environment on the nucleation kinetics and crystallisability of para-aminobenzoic acid.

PubMed

Turner, T D; Corzo, D M C; Toroz, D; Curtis, A; Dos Santos, M M; Hammond, R B; Lai, X; Roberts, K J

2016-10-05

The influence of solvent type on the solution thermodynamics, nucleation-kinetics and crystal growth of alpha para-aminobenzoic acid (PABA) crystallising from supersaturated ethanol, acetonitrile and water solutions, is examined using poly-thermal analysis of the metastable zone width. Application of a recently proposed model for analysis of crystallisation kinetics (J. Cryst. Growth, 2010, 312, 698-704) indicates a solvent and concentration dependence of the nucleation mechanism and key nucleation parameters for the alpha form of PABA. The mechanism of nucleation is found to change from instantaneous to progressive with decreasing concentration and also when changing the solvent from ethanol to acetonitrile to water. The dependence of the nucleation mechanism is correlated to the kinetic component of the nucleation rate through calculated values of instantaneously nucleated crystallites, which increase from 1.40 × 10 9 m -3 in ethanol to 1.08 × 10 10 m -3 in acetonitrile to 2.58 × 10 10 m -3 in water. This in combination with low calculated number concentrations of interfacial tension between 1.13 and 2.71 mJ m -2 , supports the conclusion that the kinetic component of the nucleation rate is more limiting when crystallising PABA from ethanol solutions in comparison to water solutions. This finding is further supported by molecular dynamics simulations of the solvation free energy of PABA, which is found to be greatest in water, -42.4 kJ mol -1 and lowest in ethanol, -58.5 kJ mol -1 .

Magnetization processes in core/shell exchange-spring structures.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, J. S.

2015-03-27

The magnetization reversal processes in cylindrical and spherical soft core/hard shell exchange-spring structures are investigated via the analytical nucleation theory, and are verified with numerical micromagnetic simulations. At small core sizes, the nucleation of magnetic reversal proceeds via the modified bulging mode, where the transverse component of the magnetization is only semi-coherent in direction and the nucleation field contains a contribution from self-demagnetization. For large core sizes, the modified curling mode, where the magnetization configuration is vortex-like, is favored at nucleation. The preference for the modified curling mode is beneficial in that the fluxclosure allows cylindrical and spherical core/shell exchange-springmore » elements to be densely packed into bulk permanent magnets without affecting the nucleation field, thereby offering the potential for high energy product.« less

Deviation from equilibrium conditions in molecular dynamic simulations of homogeneous nucleation.

PubMed

Halonen, Roope; Zapadinsky, Evgeni; Vehkamäki, Hanna

2018-04-28

We present a comparison between Monte Carlo (MC) results for homogeneous vapour-liquid nucleation of Lennard-Jones clusters and previously published values from molecular dynamics (MD) simulations. Both the MC and MD methods sample real cluster configuration distributions. In the MD simulations, the extent of the temperature fluctuation is usually controlled with an artificial thermostat rather than with more realistic carrier gas. In this study, not only a primarily velocity scaling thermostat is considered, but also Nosé-Hoover, Berendsen, and stochastic Langevin thermostat methods are covered. The nucleation rates based on a kinetic scheme and the canonical MC calculation serve as a point of reference since they by definition describe an equilibrated system. The studied temperature range is from T = 0.3 to 0.65 ϵ/k. The kinetic scheme reproduces well the isothermal nucleation rates obtained by Wedekind et al. [J. Chem. Phys. 127, 064501 (2007)] using MD simulations with carrier gas. The nucleation rates obtained by artificially thermostatted MD simulations are consistently lower than the reference nucleation rates based on MC calculations. The discrepancy increases up to several orders of magnitude when the density of the nucleating vapour decreases. At low temperatures, the difference to the MC-based reference nucleation rates in some cases exceeds the maximal nonisothermal effect predicted by classical theory of Feder et al. [Adv. Phys. 15, 111 (1966)].

Deviation from equilibrium conditions in molecular dynamic simulations of homogeneous nucleation

NASA Astrophysics Data System (ADS)

Halonen, Roope; Zapadinsky, Evgeni; Vehkamäki, Hanna

2018-04-01

We present a comparison between Monte Carlo (MC) results for homogeneous vapour-liquid nucleation of Lennard-Jones clusters and previously published values from molecular dynamics (MD) simulations. Both the MC and MD methods sample real cluster configuration distributions. In the MD simulations, the extent of the temperature fluctuation is usually controlled with an artificial thermostat rather than with more realistic carrier gas. In this study, not only a primarily velocity scaling thermostat is considered, but also Nosé-Hoover, Berendsen, and stochastic Langevin thermostat methods are covered. The nucleation rates based on a kinetic scheme and the canonical MC calculation serve as a point of reference since they by definition describe an equilibrated system. The studied temperature range is from T = 0.3 to 0.65 ɛ/k. The kinetic scheme reproduces well the isothermal nucleation rates obtained by Wedekind et al. [J. Chem. Phys. 127, 064501 (2007)] using MD simulations with carrier gas. The nucleation rates obtained by artificially thermostatted MD simulations are consistently lower than the reference nucleation rates based on MC calculations. The discrepancy increases up to several orders of magnitude when the density of the nucleating vapour decreases. At low temperatures, the difference to the MC-based reference nucleation rates in some cases exceeds the maximal nonisothermal effect predicted by classical theory of Feder et al. [Adv. Phys. 15, 111 (1966)].

Process and Formulation Effects on Protein Structure in Lyophilized Solids using Mass Spectrometric Methods

PubMed Central

Iyer, Lavanya K.; Sacha, Gregory A.; Moorthy, Balakrishnan S.; Nail, Steven L.; Topp, Elizabeth M.

2016-01-01

Myoglobin (Mb) was lyophilized in the absence (Mb-A) and presence (Mb-B) of sucrose in a pilot-scale lyophilizer with or without controlled ice nucleation. Cake morphology was characterized using scanning electron microscopy (SEM) and changes in protein structure were monitored using solid-state Fourier-transform infrared spectroscopy (ssFTIR), solid-state hydrogen-deuterium exchange-mass spectrometry (ssHDX-MS) and solid-state photolytic labeling-mass spectrometry (ssPL-MS). The results showed greater variability in nucleation temperature and irregular cake structure for formulations lyophilized without controlled nucleation. Controlled nucleation resulted in nucleation at ~ −5 °C and uniform cake structure. Formulations containing sucrose showed better retention of protein structure by all measures than formulations without sucrose. Samples lyophilized with and without controlled nucleation were similar by most measures of protein structure. However, ssPL-MS showed the greatest pLeu incorporation and more labeled regions for Mb-B lyophilized with controlled nucleation. The data support the use of ssHDX-MS and ssPL-MS to study formulation and process-induced conformational changes in lyophilized proteins. PMID:27044943

A Geometric Approach to Modeling Microstructurally Small Fatigue Crack Formation. 2; Simulation and Prediction of Crack Nucleation in AA 7075-T651

NASA Technical Reports Server (NTRS)

Hochhalter, Jake D.; Littlewood, David J.; Christ, Robert J., Jr.; Veilleux, M. G.; Bozek, J. E.; Ingraffea, A. R.; Maniatty, Antionette M.

2010-01-01

The objective of this paper is to develop further a framework for computationally modeling microstructurally small fatigue crack growth in AA 7075-T651 [1]. The focus is on the nucleation event, when a crack extends from within a second-phase particle into a surrounding grain, since this has been observed to be an initiating mechanism for fatigue crack growth in this alloy. It is hypothesized that nucleation can be predicted by computing a non-local nucleation metric near the crack front. The hypothesis is tested by employing a combination of experimentation and nite element modeling in which various slip-based and energy-based nucleation metrics are tested for validity, where each metric is derived from a continuum crystal plasticity formulation. To investigate each metric, a non-local procedure is developed for the calculation of nucleation metrics in the neighborhood of a crack front. Initially, an idealized baseline model consisting of a single grain containing a semi-ellipsoidal surface particle is studied to investigate the dependence of each nucleation metric on lattice orientation, number of load cycles, and non-local regularization method. This is followed by a comparison of experimental observations and computational results for microstructural models constructed by replicating the observed microstructural geometry near second-phase particles in fatigue specimens. It is found that orientation strongly influences the direction of slip localization and, as a result, in uences the nucleation mechanism. Also, the baseline models, replication models, and past experimental observation consistently suggest that a set of particular grain orientations is most likely to nucleate fatigue cracks. It is found that a continuum crystal plasticity model and a non-local nucleation metric can be used to predict the nucleation event in AA 7075-T651. However, nucleation metric threshold values that correspond to various nucleation governing mechanisms must be calibrated.

Mechanism of two-step vapour-crystal nucleation in a pore

NASA Astrophysics Data System (ADS)

van Meel, J. A.; Liu, Y.; Frenkel, D.

2015-09-01

We present a numerical study of the effect of hemispherical pores on the nucleation of Lennard-Jones crystals from the vapour phase. As predicted by Page and Sear, there is a narrow range of pore radii, where vapour-liquid nucleation can become a two-step process. A similar observation was made for different pore geometries by Giacomello et al. We find that the maximum nucleation rate depends on both the size and the adsorption strength of the pore. Moreover, a poe can be more effective than a planar wall with the same strength of attraction. Pore-induced vapour-liquid nucleation turns out to be the rate-limiting step for crystal nucleation. This implies that crystal nucleation can be enhanced by a judicious choice of the wetting properties of a microporous nucleating agent.

The Leipzig Ice Nucleation chamber Comparison (LINC): An overview of ice nucleation measurements observed with four on-line ice nucleation devices

NASA Astrophysics Data System (ADS)

Kohn, Monika; Wex, Heike; Grawe, Sarah; Hartmann, Susan; Hellner, Lisa; Herenz, Paul; Welti, André; Stratmann, Frank; Lohmann, Ulrike; Kanji, Zamin A.

2016-04-01

Mixed-phase clouds (MPCs) are found to be the most relevant cloud type leading to precipitation in mid-latitudes. The formation of ice crystals in MPCs is not completely understood. To estimate the effect of aerosol particles on the radiative properties of clouds and to describe ice nucleation in models, the specific properties of aerosol particles acting as ice nucleating particles (INPs) still need to be identified. A number of devices are able to measure INPs in the lab and in the field. However, methods can be very different and need to be tested under controlled conditions with respect to aerosol generation and properties in order to standardize measurement and data analysis approaches for subsequent ambient measurements. Here, we present an overview of the LINC campaign hosted at TROPOS in September 2015. We compare four ice nucleation devices: PINC (Portable Ice Nucleation Chamber, Chou et al., 2011) and SPIN (SPectrometer for Ice Nuclei) are operated in deposition nucleation and condensation freezing mode. LACIS (Leipzig Aerosol Cloud Interaction Simulator, Hartmann et al., 2011) and PIMCA (Portable Immersion Mode Cooling chamber) measure in the immersion freezing mode. PIMCA is used as a vertical extension to PINC and allows activation and droplet growth prior to exposure to the investigated ice nucleation temperature. Size-resolved measurements of multiple aerosol types were performed including pure mineral dust (K-feldspar, kaolinite) and biological particles (Birch pollen washing waters) as well as some of them after treatment with sulfuric or nitric acid prior to experiments. LACIS and PIMCA-PINC operated in the immersion freezing mode showed very good agreement in the measured frozen fraction (FF). For the comparison between PINC and SPIN, which were scanning relative humidity from below to above water vapor saturation, an agreement was found for the obtained INP concentration. However, some differences were observed, which may result from ice detection and data treatment. A difference was observed between FF from LACIS and PIMCA-PINC compared to the ice activated fractions (AF) from PINC and SPIN. This requires further investigations. Acknowledgements Part of this work was funded by the DFG Research Unit FOR 1525 INUIT, grant WE 4722/1-2. References Chou et al. (2011), Atmos. Chem. Phys., 11, 4725-4738. Hartmann et al. (2011), Atmos. Chem. Phys., 11, 1753-1767.

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

Understanding the sensitivity of nucleation free energies: The role of supersaturation and temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keasler, Samuel J., E-mail: samuel.keasler@vcsu.edu; Department of Science, Valley City State University, 101 College Street SW, Valley City, North Dakota 58072; Siepmann, J. Ilja

2015-10-28

Simulations are used to investigate the vapor-to-liquid nucleation of water for several different force fields at various sets of physical conditions. The nucleation free energy barrier is found to be extremely sensitive to the force field at the same absolute conditions. However, when the results are compared at the same supersaturation and reduced temperature or the same metastability parameter and reduced temperature, then the differences in the nucleation free energies of the different models are dramatically reduced. This finding suggests that comparisons of experimental data and computational predictions are most meaningful at the same relative conditions and emphasizes the importancemore » of knowing the phase diagram of a given computational model, but such information is usually not available for models where the interaction energy is determined directly from electronic structure calculations.« less

Champagne experiences various rhythmical bubbling regimes in a flute.

PubMed

Liger-Belair, Gérard; Tufaile, Alberto; Jeandet, Philippe; Sartorelli, José-Carlos

2006-09-20

Bubble trains are seen rising gracefully from a few points on the glass wall (called nucleation sites) whenever champagne is poured into a glass. As time passes during the gas-discharging process, the careful observation of some given bubble columns reveals that the interbubble distance may change suddenly, thus revealing different rhythmical bubbling regimes. Here, it is reported that the transitions between the different bubbling regimes of some nucleation sites during gas discharging is a process which may be ruled by a strong interaction between tiny gas pockets trapped inside the nucleation site and/or also by an interaction between the tiny bubbles just blown from the nucleation site.

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

Influence of solvent polarity and supersaturation on template-induced nucleation of carbamazepine crystal polymorphs

NASA Astrophysics Data System (ADS)

Parambil, Jose V.; Poornachary, Sendhil K.; Tan, Reginald B. H.; Heng, Jerry Y. Y.

2017-07-01

Studies on the use of template surfaces to induce heterogeneous crystal nucleation have gained momentum in recent years-with potential applications in selective crystallisation of polymorphs and in the generation of seed crystals in a continuous crystallisation process. In developing a template-assisted solution crystallisation process, the kinetics of homogeneous versus heterogeneous crystal nucleation could be influenced by solute-solvent, solute-template, and solvent-template interactions. In this study, we report the effect of solvents of varying polarity on the nucleation of carbamazepine (CBZ) crystal polymorphs, a model active pharmaceutical ingredient. The experimental results demonstrate that functionalised template surfaces are effective in promoting crystallisation of either the metastable (form II) or stable (form III) polymorphs of CBZ only in moderately (methanol, ethanol, isopropanol) and low polar (toluene) solvents. A solvent with high polarity (acetonitrile) is thought to mask the template effect on heterogeneous nucleation due to strong solute-solvent and solvent-template interactions. The current study highlights that a quality-by-design (QbD) approach-considering the synergistic effects of solute concentration, solvent type, solution temperature, and template surface chemistry on crystal nucleation-is critical to the development of a template-induced crystallisation process.

A comprehensive laboratory study on the immersion freezing behavior of illite NX particles: a comparison of seventeen ice nucleation measurement techniques

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Augustin-Bauditz, S.; Bingemer, H.; Budke, C.; Curtius, J.; Danielczok, A.; Diehl, K.; Dreischmeier, K.; Ebert, M.; Frank, F.; Hoffmann, N.; Kandler, K.; Kiselev, A.; Koop, T.; Leisner, T.; Möhler, O.; Nillius, B.; Peckhaus, A.; Rose, D.; Weinbruch, S.; Wex, H.; Boose, Y.; DeMott, P. J.; Hader, J. D.; Hill, T. C. J.; Kanji, Z. A.; Kulkarni, G.; Levin, E. J. T.; McCluskey, C. S.; Murakami, M.; Murray, B. J.; Niedermeier, D.; Petters, M. D.; O'Sullivan, D.; Saito, A.; Schill, G. P.; Tajiri, T.; Tolbert, M. A.; Welti, A.; Whale, T. F.; Wright, T. P.; Yamashita, K.

2014-08-01

Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice nucleating particles (INPs). However, an inter-comparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques. Within the framework of INUIT (Ice Nucleation research UnIT), we distributed an illite rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature (T), cooling rate and nucleation time. Seventeen measurement methods were involved in the data inter-comparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while ten other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing dataset was evaluated using the ice nucleation active surface-site density (ns) to develop a representative ns(T) spectrum that spans a wide temperature range (-37 °C < T < -11 °C) and covers nine orders of magnitude in ns. Our inter-comparison results revealed a discrepancy between suspension and dry-dispersed particle measurements for this mineral dust. While the agreement was good below ~ -26 °C, the ice nucleation activity, expressed in ns, was smaller for the wet suspended samples and higher for the dry-dispersed aerosol samples between about -26 and -18 °C. Only instruments making measurement techniques with wet suspended samples were able to measure ice nucleation above -18 °C. A possible explanation for the deviation between -26 and -18 °C is discussed. In general, the seventeen immersion freezing measurement techniques deviate, within the range of about 7 °C in terms of temperature, by three orders of magnitude with respect to ns. In addition, we show evidence that the immersion freezing efficiency (i.e., ns) of illite NX particles is relatively independent on droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature-dependence and weak time- and size-dependence of immersion freezing efficiency of illite-rich clay mineral particles enabled the ns parameterization solely as a function of temperature. We also characterized the ns (T) spectra, and identified a section with a steep slope between -20 and -27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below -27 °C. A multiple exponential distribution fit is expressed as ns(T) = exp(23.82 × exp(-exp(0.16 × (T + 17.49))) + 1.39) based on the specific surface area and ns(T) = exp(25.75 × exp(-exp(0.13 × (T + 17.17))) + 3.34) based on the geometric area (ns and T in m-2 and °C, respectively). These new fits, constrained by using an identical reference samples, will help to compare IN measurement methods that are not included in the present study and, thereby, IN data from future IN instruments.

Nucleation, aggregative growth and detachment of metal nanoparticles during electrodeposition at electrode surfaces.

PubMed

Lai, Stanley C S; Lazenby, Robert A; Kirkman, Paul M; Unwin, Patrick R

2015-02-01

The nucleation and growth of metal nanoparticles (NPs) on surfaces is of considerable interest with regard to creating functional interfaces with myriad applications. Yet, key features of these processes remain elusive and are undergoing revision. Here, the mechanism of the electrodeposition of silver on basal plane highly oriented pyrolytic graphite (HOPG) is investigated as a model system at a wide range of length scales, spanning electrochemical measurements from the macroscale to the nanoscale using scanning electrochemical cell microscopy (SECCM), a pipette-based approach. The macroscale measurements show that the nucleation process cannot be modelled as either truly instantaneous or progressive, and that step edge sites of HOPG do not play a dominant role in nucleation events compared to the HOPG basal plane, as has been widely proposed. Moreover, nucleation numbers extracted from electrochemical analysis do not match those determined by atomic force microscopy (AFM). The high time and spatial resolution of the nanoscale pipette set-up reveals individual nucleation and growth events at the graphite basal surface that are resolved and analysed in detail. Based on these results, corroborated with complementary microscopy measurements, we propose that a nucleation-aggregative growth-detachment mechanism is an important feature of the electrodeposition of silver NPs on HOPG. These findings have major implications for NP electrodeposition and for understanding electrochemical processes at graphitic materials generally.

Nucleation in food colloids

NASA Astrophysics Data System (ADS)

Povey, Malcolm J. W.

2016-12-01

Nucleation in food colloids has been studied in detail using ultrasound spectroscopy. Our data show that classical nucleation theory (CNT) remains a sound basis from which to understand nucleation in food colloids and analogous model systems using n-alkanes. Various interpretations and modifications of CNT are discussed with regard to their relevance to food colloids. Much of the evidence presented is based on the ultrasound velocity spectrometry measurements which has many advantages for the study of nucleating systems compared to light scattering and NMR due to its sensitivity at low solid contents and its ability to measure true solid contents in the nucleation and early crystal growth stages. Ultrasound attenuation spectroscopy also responds to critical fluctuations in the induction region. We show, however, that a periodic pressure fluctuation such as a quasi-continuous (as opposed to a pulse comprising only a few pressure cycles) ultrasound field can alter the nucleation process, even at very low acoustic intensity. Thus care must be taken when using ultrasound techniques that the measurements do not alter the studied processes. Quasi-continuous ultrasound fields may enhance or suppress nucleation and the criteria to determine such effects are derived. The conclusions of this paper are relevant to colloidal systems in foods, pharmaceuticals, agro-chemicals, cosmetics, and personal products.

Overview of TANGENT (Tandem Aerosol Nucleation and Growth ENvironment Tube) 2017 IOP Study

NASA Astrophysics Data System (ADS)

Tiszenkel, L.

2017-12-01

New particle formation consists of two steps: nucleation and growth of nucleated particles. However, most laboratory studies have been conducted under conditions where these two processes are convoluted together, thereby hampering the detailed understanding of the effect of chemical species and atmospheric conditions on two processes. The objective of the Tandem Aerosol Nucleation and Growth ENvironment Tube (TANGENT) laboratory study is to investigate aerosol nucleation and growth properties independently by separating these two processes in two different flow tubes. This research is a collaboration between the University of Alabama in Huntsville and the University of Delaware. In this poster we will present the experimental setup of TANGENT and summarize the key results from the first IOP (intense observation period) experiments undertaken during Summer 2017. Nucleation takes place in a temperature- and RH-controlled fast flow reactor (FT-1) where sulfuric acid forms from OH radicals and sulfur dioxide. Sulfuric acid and impurity base compounds are detected with chemical ionization mass spectrometers (CIMS). Particle sizes and number concentrations of newly nucleated particles are measured with a scanning mobility particle sizer (SMPS) and particle size magnifier (PSM), providing concentrations of particles between 1-100 nm. The nucleation particles are transferred directly to the growth tube (FT-2) where oxidants and biogenic organic precursors are added to grow nucleated nanoparticles. Sizes of particles after growth are analyzed with an additional SMPS and elemental chemical composition of 50 nm and above particles detected with a nano-aerosol mass spectrometer (NAMS). TANGENT provides the unique ability to conduct experiments that can monitor and control reactant concentrations, aerosol size and aerosol chemical composition during nucleation and growth. Experiments during this first IOP study have elucidated the effects of sulfur dioxide, particle size, relative humidity, temperature, oxidants and biogenic organics on nanoparticle formation and growth. In another 3 companion posters, we will discuss findings of these results in detail.

Surface design for controlled crystallization: the role of surface chemistry and nanoscale pores in heterogeneous nucleation.

PubMed

Diao, Ying; Myerson, Allan S; Hatton, T Alan; Trout, Bernhardt L

2011-05-03

Current industrial practice for control of primary nucleation (nucleation from a system without pre-existing crystalline matter) during crystallization from solution involves control of supersaturation generation, impurity levels, and solvent composition. Nucleation behavior remains largely unpredictable, however, due to the presence of container surfaces, dust, dirt, and other impurities that can provide heterogeneous nucleation sites, thus making the control and scale-up of processes that depend on primary nucleation difficult. To develop a basis for the rational design of surfaces to control nucleation during crystallization from solution, we studied the role of surface chemistry and morphology of various polymeric substrates on heterogeneous nucleation using aspirin as a model compound. Nucleation induction time statistics were utilized to investigate and quantify systematically the effectiveness of polymer substrates in inducing nucleation. The nucleation induction time study revealed that poly(4-acryloylmorpholine) and poly(2-carboxyethyl acrylate), each cross-linked by divinylbenzene, significantly lowered the nucleation induction time of aspirin while the other polymers were essentially inactive. In addition, we found the presence of nanoscopic pores on certain polymer surfaces led to order-of-magnitude faster aspirin nucleation rates when compared with surfaces without pores. We studied the preferred orientation of aspirin crystals on polymer films and found the nucleation-active polymer surfaces preferentially nucleated the polar facets of aspirin, guided by hydrogen bonds. A model based on interfacial free energies was also developed which predicted the same trend of polymer surface nucleation activities as indicated by the nucleation induction times.

Nuclear Synthesis of Cytoplasmic Ribonucleic Acid in Amoeba proteus

PubMed Central

Prescott, David M.

1959-01-01

The enucleation technique has been applied to Amoeba proteus by several laboratories in attempts to determine whether the cytoplasm is capable of nucleus-independent ribonucleic acid synthesis. This cell is very convenient for micrurgy, but its use requires a thorough starvation period to eliminate the possibility of metabolic influence by food vacuoles and frequent washings and medium renewal to maintain asepsis. In the experiments described here, amoebae were starved for periods of 24 to 96 hours, cut into nucleated and enucleated halves, and exposed to either C-14 uracil, C-14 adenine, C-14 orotic acid, or a mixture of all three. When the starvation period was short (less than 72 hours), organisms (especially yeast cells) contained within amoeba food vacuoles frequently showed RNA synthesis in both nucleated and enucleated amoebae. When the preperiod of starvation was longer than 72 hours, food vacuole influence was apparently negligible, and a more meaningful comparison between enucleated and nucleated amoebae was possible. Nucleated cells incorporated all three precursors into RNA; enucleated cells were incapable of such incorporation. The experiments indicate a complete dependence on the nucleus for RNA synthesis. The conflict with the experimental results of others on this problem could possibly stem from differences in culture conditions, starvation treatment, or experimental conditions. For an unequivocal answer in experiments of this design, ideally the cells should be capable of growth on an entirely synthetic medium under aseptic conditions. The use of a synthetic medium (experiments with A. proteus are done under starvation conditions) would permit, moreover, a more realistic comparison of metabolic capacities of nucleated and enucleated cells. PMID:14434750

Nuclear synthesis of cytoplasmic ribonucleic acid in Amoeba proteus.

PubMed

PRESCOTT, D M

1959-10-01

The enucleation technique has been applied to Amoeba proteus by several laboratories in attempts to determine whether the cytoplasm is capable of nucleus-independent ribonucleic acid synthesis. This cell is very convenient for micrurgy, but its use requires a thorough starvation period to eliminate the possibility of metabolic influence by food vacuoles and frequent washings and medium renewal to maintain asepsis. In the experiments described here, amoebae were starved for periods of 24 to 96 hours, cut into nucleated and enucleated halves, and exposed to either C-14 uracil, C-14 adenine, C-14 orotic acid, or a mixture of all three. When the starvation period was short (less than 72 hours), organisms (especially yeast cells) contained within amoeba food vacuoles frequently showed RNA synthesis in both nucleated and enucleated amoebae. When the preperiod of starvation was longer than 72 hours, food vacuole influence was apparently negligible, and a more meaningful comparison between enucleated and nucleated amoebae was possible. Nucleated cells incorporated all three precursors into RNA; enucleated cells were incapable of such incorporation. The experiments indicate a complete dependence on the nucleus for RNA synthesis. The conflict with the experimental results of others on this problem could possibly stem from differences in culture conditions, starvation treatment, or experimental conditions. For an unequivocal answer in experiments of this design, ideally the cells should be capable of growth on an entirely synthetic medium under aseptic conditions. The use of a synthetic medium (experiments with A. proteus are done under starvation conditions) would permit, moreover, a more realistic comparison of metabolic capacities of nucleated and enucleated cells.

Dislocation creation and void nucleation in FCC ductile metals under tensile loading: a general microscopic picture.

PubMed

Pang, Wei-Wei; Zhang, Ping; Zhang, Guang-Cai; Xu, Ai-Guo; Zhao, Xian-Geng

2014-11-10

Numerous theoretical and experimental efforts have been paid to describe and understand the dislocation and void nucleation processes that are fundamental for dynamic fracture modeling of strained metals. To date an essential physical picture on the self-organized atomic collective motions during dislocation creation, as well as the essential mechanisms for the void nucleation obscured by the extreme diversity in structural configurations around the void nucleation core, is still severely lacking in literature. Here, we depict the origin of dislocation creation and void nucleation during uniaxial high strain rate tensile processes in face-centered-cubic (FCC) ductile metals. We find that the dislocations are created through three distinguished stages: (i) Flattened octahedral structures (FOSs) are randomly activated by thermal fluctuations; (ii) The double-layer defect clusters are formed by self-organized stacking of FOSs on the close-packed plane; (iii) The stacking faults are formed and the Shockley partial dislocations are created from the double-layer defect clusters. Whereas, the void nucleation is shown to follow a two-stage description. We demonstrate that our findings on the origin of dislocation creation and void nucleation are universal for a variety of FCC ductile metals with low stacking fault energies.

On the discrimination between nucleation and propagation in nanomagnetic logic devices

NASA Astrophysics Data System (ADS)

Ziemys, Grazvydas; Csaba, Gyorgy; Becherer, Markus

2018-05-01

In this paper we present the extensive nucleation and propagation characterization of fabricated nanomagnets by applying ns-range magnetic field pulses. For that, an artificial nucleation center (ANC) is created by focused ion beam irradiation (FIB) of a 50 x 50 nm area at the side of a Co/Pt island as typically used in Nanomagnetic Logic with perpendicular anisotropy (pNML). Laser-Kerr Microscope is applied for statistical evaluation of the switching probability of the whole magnet, while the wide-field-Kerr microscopy is employed to discriminate between the nucleation process (which takes place at the irradiated ANC area) and the domain wall propagation process along the magnet. We show that the nanomagnet can be treated as a single Stoner-Wolfhart particle above 100 ns field-pulse width, as the whole magnetization is switched during the field-pulse. By contrary, for field-pulse width below 100 ns, the domain wall (DW) motion is the limiting process hindering full magnetization reversal on that time-scale. However, the nucleation still follows the Arrhenius law. The results allow precise understanding of the reversal process and highlight the need for faster DW speed in pNML materials.

Snow-borne nanosized particles: Abundance, distribution, composition, and significance in ice nucleation processes

NASA Astrophysics Data System (ADS)

Rangel-Alvarado, Rodrigo Benjamin; Nazarenko, Yevgen; Ariya, Parisa A.

2015-11-01

Physicochemical processes of nucleation constitute a major uncertainty in understanding aerosol-cloud interactions. To improve the knowledge of the ice nucleation process, we characterized physical, chemical, and biological properties of fresh snow using a suite of state-of-the-art techniques based on mass spectrometry, electron microscopy, chromatography, and optical particle sizing. Samples were collected at two North American Arctic sites, as part of international campaigns (2006 and 2009), and in the city of Montreal, Canada, over the last decade. Particle size distribution analyses, in the range of 3 nm to 10 µm, showed that nanosized particles are the most numerous (38-71%) in fresh snow, with a significant portion (11 to 19%) less than 100 nm in size. Particles with diameters less than 200 nm consistently exhibited relatively high ice-nucleating properties (on average ranged from -19.6 ± 2.4 to -8.1 ± 2.6°C). Chemical analysis of the nanosized fraction suggests that they contain bioorganic materials, such as amino acids, as well as inorganic compounds with similar characteristics to mineral dust. The implication of nanoparticle ubiquity and abundance in diverse snow ecosystems are discussed in the context of their importance in understanding atmospheric nucleation processes.

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 active surface site density, which we named ns*, for the investigated feldspar sample. The comparison of these results with those of other studies elucidates the general feasibility of determining such an asymptotic value and also show that the value of ns* strongly depends on the method of the particle surface area determination. Acknowledgement This work is partly funded by the Federal Ministry of Education and Research (BMBF - project CLOUD 12) and by the German Research Foundation (DFG project WE 4722/1-1, part of the research unit INUIT, FOR 1525). D. Niedermeier acknowledges financial support from the Alexander von Humboldt-foundation. References Augustin et al.: Immersion freezing of birch pollen washing water, Atmos. Chem. Phys., 13, 10989-11003, doi:10.5194/acp-13-10989-2013, 2013. Hartmann et al.: Immersion freezing of ice nucleation active protein complexes, Atmos. Chem. Phys., 13, 5751-5766, doi:10.5194/acp-13-5751-2013, 2013. Murray et al.: Ice nucleation by particles immersed in supercooled cloud droplets, Chem. Soc. Rev., 41, 6519-6554, 2012. Wex et al.: Intercomparing different devices for the investigation of ice nucleating particles using Snomax® as test substance, Atmos. Chem. Phys. Discuss., 14, 22321-22384, doi:10.5194/acpd-14-22321-2014, 2014.

Ion-induced nucleation in solution: promotion of solute nucleation in charged levitated droplets.

PubMed

Draper, Neil D; Bakhoum, Samuel F; Haddrell, Allen E; Agnes, George R

2007-09-19

We have investigated the nucleation and growth of sodium chloride in both single quiescent charged droplets and charged droplet populations that were levitated in an electrodynamic levitation trap (EDLT). In both cases, the magnitude of a droplet's net excess charge (ions(DNEC)) influenced NaCl nucleation and growth, albeit in different capacities. We have termed the phenomenon ion-induced nucleation in solution. For single quiescent levitated droplets, an increase in ions(DNEC) resulted in a significant promotion of NaCl nucleation, as determined by the number of crystals observed. For levitated droplet populations, a change in NaCl crystal habit, from regular cubic shapes to dome-shaped dendrites, was observed once a surface charge density threshold of -9 x 10(-4) e.nm(-2) was surpassed. Although promotion of NaCl nucleation was observed for droplet population experiments, this can be attributed in part to the increased rate of solvent evaporation observed for levitated droplet populations having a high net charge. Promotion of nucleation was also observed for two organic acids, 2,4,6-trihydroxyacetophenone monohydrate (THAP) and alpha-cyano-4-hydroxycinnamic acid (CHCA). These results are of direct relevance to processes that occur in both soft-ionization techniques for mass spectrometry and to a variety of industrial processes. To this end, we have demonstrated the use of ion-induced nucleation in solution to form ammonium nitrate particles from levitated droplets to be used in in vitro toxicology studies of ambient particle types.

On the usage of classical nucleation theory in quantification of the impact of bacterial INP on weather and climate

NASA Astrophysics Data System (ADS)

Sahyoun, Maher; Wex, Heike; Gosewinkel, Ulrich; Šantl-Temkiv, Tina; Nielsen, Niels W.; Finster, Kai; Sørensen, Jens H.; Stratmann, Frank; Korsholm, Ulrik S.

2016-08-01

Bacterial ice-nucleating particles (INP) are present in the atmosphere and efficient in heterogeneous ice-nucleation at temperatures up to -2 °C in mixed-phase clouds. However, due to their low emission rates, their climatic impact was considered insignificant in previous modeling studies. In view of uncertainties about the actual atmospheric emission rates and concentrations of bacterial INP, it is important to re-investigate the threshold fraction of cloud droplets containing bacterial INP for a pronounced effect on ice-nucleation, by using a suitable parameterization that describes the ice-nucleation process by bacterial INP properly. Therefore, we compared two heterogeneous ice-nucleation rate parameterizations, denoted CH08 and HOO10 herein, both of which are based on classical-nucleation-theory and measurements, and use similar equations, but different parameters, to an empirical parameterization, denoted HAR13 herein, which considers implicitly the number of bacterial INP. All parameterizations were used to calculate the ice-nucleation probability offline. HAR13 and HOO10 were implemented and tested in a one-dimensional version of a weather-forecast-model in two meteorological cases. Ice-nucleation-probabilities based on HAR13 and CH08 were similar, in spite of their different derivation, and were higher than those based on HOO10. This study shows the importance of the method of parameterization and of the input variable, number of bacterial INP, for accurately assessing their role in meteorological and climatic processes.

Heterogeneous Nucleation of Trichloroethylene Ozonation Products in the Formation of New Fine Particles

NASA Astrophysics Data System (ADS)

Wang, Ning; Sun, Xiaomin; Chen, Jianmin; Li, Xiang

2017-02-01

Free radicals in atmosphere have played an important role in the atmospheric chemistry. The chloro-Criegee free radicals are produced easily in the decomposition of primary ozonide (POZ) of the trichloroethylene, and can react with O2, NO, NO2, SO2 and H2O subsequently. Then the inorganic salts, polar organic nitrogen and organic sulfur compounds, oxygen-containing heterocyclic intermediates and polyhydroxy compounds can be obtained. The heterogeneous nucleation of oxidation intermediates in the formation of fine particles is investigated using molecular dynamics simulation. The detailed nucleation processes are reported. According to molecular dynamics simulation, the nucleation with a diameter of 2 nm is formed in the Organic Compounds-(NH4)2SO4-H2O system. The spontaneous nucleation is an important process in the formation of fine particles in atmosphere. The model study gives a good example from volatile organic compounds to new fine particles.

Correlation of Solubility with the Metastable Limit of Nucleation Using Gauge-Cell Monte Carlo Simulations.

PubMed

Clark, Michael D; Morris, Kenneth R; Tomassone, Maria Silvina

2017-09-12

We present a novel simulation-based investigation of the nucleation of nanodroplets from solution and from vapor. Nucleation is difficult to measure or model accurately, and predicting when nucleation should occur remains an open problem. Of specific interest is the "metastable limit", the observed concentration at which nucleation occurs spontaneously, which cannot currently be estimated a priori. To investigate the nucleation process, we employ gauge-cell Monte Carlo simulations to target spontaneous nucleation and measure thermodynamic properties of the system at nucleation. Our results reveal a widespread correlation over 5 orders of magnitude of solubilities, in which the metastable limit depends exclusively on solubility and the number density of generated nuclei. This three-way correlation is independent of other parameters, including intermolecular interactions, temperature, molecular structure, system composition, and the structure of the formed nuclei. Our results have great potential to further the prediction of nucleation events using easily measurable solute properties alone and to open new doors for further investigation.

Insight into Nucleation Mechanisms of Tetrahedral Materials from Advanced Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Bi, Yuanfei

This dissertation studies the nucleation mechanisms of ice, clathrate hydrate and silicon clathrate which all belong to tetrahedral materials and carry significant importance to modern society. Because of the stochastic nature and the ultra-fine scale of nucleation, the mechanisms through which these important tetrahedral materials form from liquid remain poorly understood. Our goal is to address the current knowledge gap between experiment and theory on the nucleation mechanisms by conducting molecular dynamics (MD) studies. To overcome the rare event nature of nucleation, an advanced sampling method Forward Flux Sampling (FFS) is integrated with classical MD simulations. This integration allows obtaining not only nucleation rate explicitly but also an ensemble of nucleation trajectories with their correct statistical weights. By analyzing the ensemble of trajectories obtained from FFS, we reveal the important details of nucleation at the molecular level, particular at the early stage of nucleation. By combining Backward Flux Sampling (BFS) with FFS, we can also compute the free energy profile of nucleation explicitly, which allows a comparison against the classical nucleation theory (CNT). We began our investigation by studying heterogeneous ice nucleation, which is the most relevant form of ice formation. In this part of study, we aim to understand the key microscopic factors that control ice formation, including surface hydrophilicity, surface crystallinity, and surface geometry. Our simulations reveal that heterogeneous ice nucleation on graphitic surfaces is controlled by the coupling of surface crystallinity and surface hydrophilicity. In particular, our analysis shows that the crystalline graphitic lattice with an appropriate hydrophilicity may indeed template ice basal plane by forming a strained ice layer, thus significantly enhance its ice nucleation efficiency. The templating effect is further found to transit from within the first contact layer of water to the second as the surface hydrophilicity increases, which yields an oscillating distinction between the crystalline and amorphous graphitic surfaces in their ice nucleation efficiency. With this understanding, we then shifted our focus on the role of surface geometry, where we find that an atomically sharp, concave wedge can further promote ice nucleation. Remarkably, our molecular analysis shows a significant enhancement of ice nucleation can emerge both when the geometry of a wedge matches the ice lattice and when such lattice match does not exist. We then investigated the nucleation of gas hydrate, a binary compound composed of water and natural gas, e.g., methane. To facilitate the application of FFS in studying gas hydrate nucleation, we proposed a new order parameter: Half-Cage Order Parameter (H-COP), based on the topological signature of hydrate structure, and conducted a pB histogram analysis to verify the effectiveness of the H-COP order parameter. Our analyses show that the nucleation of M-hydrate (M can be methane or carbon dioxide) starts in the vicinity of water-M interface, and gradually transit from amorphous to crystalline structures. This is the direct support to the proposed two-step nucleation mechanism of methane hydrate. However, within the ensemble of nucleation trajectories, we also identified some direct crystallization pathways without going through a amorphous phase in the nucleation of both M-hydrate and L-hydrate. Remarkably the free energy profile of L-hydrate nucleation, which is obtained independent of nucleation theory, is found to fit well against the CNT, albeit with noticeable differences when the nucleus is small. Therefore, the CNT-like free energy profile and the existence of multiple nucleation pathways indicate the near degeneracy of these pathways in their free energy profiles and highlight the complexity of hydrate nucleation. On the basis of these results, we further proposed a new perspective of gas hydrate nucleation, which can be considered to be an entropically driven, kinetic process that proceeds via multiple pathways that have similar free energy profiles. Finally, inspired by our insight gained in studying gas hydrate nucleation, we proposed a novel synthesis route to obtain inert gas silicon clathrate, which has an attractive opto-electronic property for energy application, but remains as an experimental challenge for synthesis. We thoroughly examined this proposal through high-throughput computational studies that show the novel phases of silicon could form spontaneously from liquid silicon in the presence of noble gases under high pressure and high temperature. In particular, our results show that a medium size of noble gas, e.g., Ar, can trigger the nucleation and growth of inert-gas silicon clathrate, whereas a small noble gas such as He is able to induce the formation of an unconventional, inclusion-type compound Si2He. Our findings, along with the gained molecular insights, thus strongly suggest it is viable to experimentally synthesize novel silicon phases with noble gas through high pressure and high temperature. (Abstract shortened by ProQuest.).

A master equation approach to actin polymerization applied to endocytosis in yeast.

PubMed

Wang, Xinxin; Carlsson, Anders E

2017-12-01

We present a Master Equation approach to calculating polymerization dynamics and force generation by branched actin networks at membranes. The method treats the time evolution of the F-actin distribution in three dimensions, with branching included as a directional spreading term. It is validated by comparison with stochastic simulations of force generation by actin polymerization at obstacles coated with actin "nucleation promoting factors" (NPFs). The method is then used to treat the dynamics of actin polymerization and force generation during endocytosis in yeast, using a model in which NPFs form a ring around the endocytic site, centered by a spot of molecules attaching the actin network strongly to the membrane. We find that a spontaneous actin filament nucleation mechanism is required for adequate forces to drive the process, that partial inhibition of branching and polymerization lead to different characteristic responses, and that a limited range of polymerization-rate values provide effective invagination and obtain correct predictions for the effects of mutations in the active regions of the NPFs.

A master equation approach to actin polymerization applied to endocytosis in yeast

PubMed Central

Wang, Xinxin

2017-01-01

We present a Master Equation approach to calculating polymerization dynamics and force generation by branched actin networks at membranes. The method treats the time evolution of the F-actin distribution in three dimensions, with branching included as a directional spreading term. It is validated by comparison with stochastic simulations of force generation by actin polymerization at obstacles coated with actin “nucleation promoting factors” (NPFs). The method is then used to treat the dynamics of actin polymerization and force generation during endocytosis in yeast, using a model in which NPFs form a ring around the endocytic site, centered by a spot of molecules attaching the actin network strongly to the membrane. We find that a spontaneous actin filament nucleation mechanism is required for adequate forces to drive the process, that partial inhibition of branching and polymerization lead to different characteristic responses, and that a limited range of polymerization-rate values provide effective invagination and obtain correct predictions for the effects of mutations in the active regions of the NPFs. PMID:29240771

Kinetics of binary nucleation of vapors in size and composition space.

PubMed

Fisenko, Sergey P; Wilemski, Gerald

2004-11-01

We reformulate the kinetic description of binary nucleation in the gas phase using two natural independent variables: the total number of molecules g and the molar composition x of the cluster. The resulting kinetic equation can be viewed as a two-dimensional Fokker-Planck equation describing the simultaneous Brownian motion of the clusters in size and composition space. Explicit expressions for the Brownian diffusion coefficients in cluster size and composition space are obtained. For characterization of binary nucleation in gases three criteria are established. These criteria establish the relative importance of the rate processes in cluster size and composition space for different gas phase conditions and types of liquid mixtures. The equilibrium distribution function of the clusters is determined in terms of the variables g and x. We obtain an approximate analytical solution for the steady-state binary nucleation rate that has the correct limit in the transition to unary nucleation. To further illustrate our description, the nonequilibrium steady-state cluster concentrations are found by numerically solving the reformulated kinetic equation. For the reformulated transient problem, the relaxation or induction time for binary nucleation was calculated using Galerkin's method. This relaxation time is affected by processes in both size and composition space, but the contributions from each process can be separated only approximately.

Uncovering molecular processes in crystal nucleation and growth by using molecular simulation.

PubMed

Anwar, Jamshed; Zahn, Dirk

2011-02-25

Exploring nucleation processes by molecular simulation provides a mechanistic understanding at the atomic level and also enables kinetic and thermodynamic quantities to be estimated. However, whilst the potential for modeling crystal nucleation and growth processes is immense, there are specific technical challenges to modeling. In general, rare events, such as nucleation cannot be simulated using a direct "brute force" molecular dynamics approach. The limited time and length scales that are accessible by conventional molecular dynamics simulations have inspired a number of advances to tackle problems that were considered outside the scope of molecular simulation. While general insights and features could be explored from efficient generic models, new methods paved the way to realistic crystal nucleation scenarios. The association of single ions in solvent environments, the mechanisms of motif formation, ripening reactions, and the self-organization of nanocrystals can now be investigated at the molecular level. The analysis of interactions with growth-controlling additives gives a new understanding of functionalized nanocrystals and the precipitation of composite materials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic control of heterogeneous ice nucleation with nanophase magnetite: Biophysical and agricultural implications.

PubMed

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

2018-05-22

In supercooled water, ice nucleation is a stochastic process that requires ∼250-300 molecules to transiently achieve structural ordering before an embryonic seed crystal can nucleate. This happens most easily on crystalline surfaces, in a process termed heterogeneous nucleation; without such surfaces, water droplets will supercool to below -30 °C before eventually freezing homogeneously. A variety of fundamental processes depends on heterogeneous ice nucleation, ranging from desert-blown dust inducing precipitation in clouds to frost resistance in plants. Recent experiments have shown that crystals of nanophase magnetite (Fe 3 O 4 ) are powerful nucleation sites for this heterogeneous crystallization of ice, comparable to other materials like silver iodide and some cryobacterial peptides. In natural materials containing magnetite, its ferromagnetism offers the possibility that magneto-mechanical motion induced by external oscillating magnetic fields could act to disrupt the water-crystal interface, inhibiting the heterogeneous nucleation process in subfreezing water and promoting supercooling. For this to act, the magneto-mechanical rotation of the particles should be higher than the magnitude of Brownian motions. We report here that 10-Hz precessing magnetic fields, at strengths of 1 mT and above, on ∼50-nm magnetite crystals dispersed in ultrapure water, meet these criteria and do indeed produce highly significant supercooling. Using these rotating magnetic fields, we were able to elicit supercooling in two representative plant and animal tissues (celery and bovine muscle), both of which have detectable, natural levels of ferromagnetic material. Tailoring magnetic oscillations for the magnetite particle size distribution in different tissues could maximize this supercooling effect. Copyright © 2018 the Author(s). Published by PNAS.

Towards establishing a combined rate law of nucleation and crystal growth - The case study of gypsum precipitation

NASA Astrophysics Data System (ADS)

Rendel, Pedro M.; Gavrieli, Ittai; Wolff-Boenisch, Domenik; Ganor, Jiwchar

2018-03-01

The main obstacle in the formulation of a quantitative rate-model for mineral precipitation is the absence of a rigorous method for coupling nucleation and growth processes. In order to link both processes, we conducted a series of batch experiments in which gypsum nucleation was followed by crystal growth. Experiments were carried out using various stirring methods in several batch vessels made of different materials. In the experiments, the initial degree of supersaturation of the solution with respect to gypsum (Ωgyp) was set between 1.58 and 1.82. Under these conditions, heterogeneous nucleation is the dominant nucleation mode. Based on changes in SO42- concentration with time, the induction time of gypsum nucleation and the following rate of crystal growth were calculated for each experiment. The induction time (6-104 h) was found to be a function of the vessel material, while the rates of crystal growth, which varied over three orders of magnitude, were strongly affected by the stirring speed and its mode (i.e. rocking, shaking, magnetic stirrer, and magnetic impeller). The SO42- concentration data were then used to formulate a forward model that couples the simple rate laws for nucleation and crystal growth of gypsum into a single kinetic model. Accordingly, the obtained rate law is based on classical nucleation theory and heterogeneous crystal growth.

Taking directions: the role of microtubule-bound nucleation in the self-organization of the plant cortical array

NASA Astrophysics Data System (ADS)

Deinum, Eva E.; Tindemans, Simon H.; Mulder, Bela M.

2011-10-01

The highly aligned cortical microtubule array of interphase plant cells is a key regulator of anisotropic cell expansion. Recent computational and analytical work has shown that the non-equilibrium self-organization of this structure can be understood on the basis of experimentally observed collisional interactions between dynamic microtubules attached to the plasma membrane. Most of these approaches assumed that new microtubules are homogeneously and isotropically nucleated on the cortical surface. Experimental evidence, however, shows that nucleation mostly occurs from other microtubules and under specific relative angles. Here, we investigate the impact of directed microtubule-bound nucleations on the alignment process using computer simulations. The results show that microtubule-bound nucleations can increase the degree of alignment achieved, decrease the timescale of the ordering process and widen the regime of dynamic parameters for which the system can self-organize. We establish that the major determinant of this effect is the degree of co-alignment of the nucleations with the parent microtubule. The specific role of sideways branching nucleations appears to allow stronger alignment while maintaining a measure of overall spatial homogeneity. Finally, we investigate the suggestion that observed persistent rotation of microtubule domains can be explained through a handedness bias in microtubule-bound nucleations, showing that this is possible only for an extreme bias and over a limited range of parameters.

Cavitation in a metallic liquid: Homogeneous nucleation and growth of nanovoids

NASA Astrophysics Data System (ADS)

Cai, Y.; Wu, H. A.; Luo, S. N.

2014-06-01

Large-scale molecular dynamics (MD) simulations are performed to investigate homogeneous nucleation and growth of nanovoids during cavitation in liquid Cu. We characterize in detail the atomistic cavitation processes by following the temporal evolution of cavities or voids, analyze the nucleation behavior with the mean first-passage time (MFPT) and survival probability (SP) methods, and discuss the results against classical nucleation theory (CNT), the Tolman equation for surface energy, independent calculation of surface tension via integrating the stress profiles, the Johnson-Mehl-Avrami (JMA) growth law, and the power law for nucleus size distributions. Cavitation in this representative metallic liquid is a high energy barrier Poisson processes, and the steady-state nucleation rates obtained from statistical runs with the MFPT and SP methods are in agreement. The MFPT method also yields the critical nucleus size and the Zeldovich factor. Fitting with the Tolman's equation to the MD simulations yields the surface energy of a planar interface (˜0.9 J {m}^{-2}) and the Tolman length (0.4-0.5 Å), and those values are in accord with those from integrating the stress profiles of a planar interface. Independent CNT predictions of the nucleation rate (1033 - 34 s-1 m-3) and critical size (3-4 Å in radius) are in agreement with the MFPT and SP results. The JMA law can reasonably describe the nucleation and growth process. The size distribution of subcritical nuclei appears to follow a power law with an exponent decreasing with increasing tension owing to coupled nucleation and growth, and that of the supercritical nuclei becomes flattened during further stress relaxation due to void coalescence.

Cavitation in a metallic liquid: homogeneous nucleation and growth of nanovoids.

PubMed

Cai, Y; Wu, H A; Luo, S N

2014-06-07

Large-scale molecular dynamics (MD) simulations are performed to investigate homogeneous nucleation and growth of nanovoids during cavitation in liquid Cu. We characterize in detail the atomistic cavitation processes by following the temporal evolution of cavities or voids, analyze the nucleation behavior with the mean first-passage time (MFPT) and survival probability (SP) methods, and discuss the results against classical nucleation theory (CNT), the Tolman equation for surface energy, independent calculation of surface tension via integrating the stress profiles, the Johnson-Mehl-Avrami (JMA) growth law, and the power law for nucleus size distributions. Cavitation in this representative metallic liquid is a high energy barrier Poisson processes, and the steady-state nucleation rates obtained from statistical runs with the MFPT and SP methods are in agreement. The MFPT method also yields the critical nucleus size and the Zeldovich factor. Fitting with the Tolman's equation to the MD simulations yields the surface energy of a planar interface (~0.9 J m⁻²) and the Tolman length (0.4-0.5 Å), and those values are in accord with those from integrating the stress profiles of a planar interface. Independent CNT predictions of the nucleation rate (10(33 - 34) s(-1) m(-3)) and critical size (3-4 Å in radius) are in agreement with the MFPT and SP results. The JMA law can reasonably describe the nucleation and growth process. The size distribution of subcritical nuclei appears to follow a power law with an exponent decreasing with increasing tension owing to coupled nucleation and growth, and that of the supercritical nuclei becomes flattened during further stress relaxation due to void coalescence.

Cavitation in a metallic liquid: Homogeneous nucleation and growth of nanovoids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Y.; The Peac Institute of Multiscale Sciences, Chengdu, Sichuan 610207; Wu, H. A., E-mail: wuha@ustc.edu.cn

2014-06-07

Large-scale molecular dynamics (MD) simulations are performed to investigate homogeneous nucleation and growth of nanovoids during cavitation in liquid Cu. We characterize in detail the atomistic cavitation processes by following the temporal evolution of cavities or voids, analyze the nucleation behavior with the mean first-passage time (MFPT) and survival probability (SP) methods, and discuss the results against classical nucleation theory (CNT), the Tolman equation for surface energy, independent calculation of surface tension via integrating the stress profiles, the Johnson-Mehl-Avrami (JMA) growth law, and the power law for nucleus size distributions. Cavitation in this representative metallic liquid is a high energymore » barrier Poisson processes, and the steady-state nucleation rates obtained from statistical runs with the MFPT and SP methods are in agreement. The MFPT method also yields the critical nucleus size and the Zeldovich factor. Fitting with the Tolman's equation to the MD simulations yields the surface energy of a planar interface (∼0.9 J m{sup −2}) and the Tolman length (0.4–0.5 Å), and those values are in accord with those from integrating the stress profiles of a planar interface. Independent CNT predictions of the nucleation rate (10{sup 33−34} s{sup −1} m{sup −3}) and critical size (3–4 Å in radius) are in agreement with the MFPT and SP results. The JMA law can reasonably describe the nucleation and growth process. The size distribution of subcritical nuclei appears to follow a power law with an exponent decreasing with increasing tension owing to coupled nucleation and growth, and that of the supercritical nuclei becomes flattened during further stress relaxation due to void coalescence.« less

Immersion freezing in concentrated solution droplets for a variety of ice nucleating particles

NASA Astrophysics Data System (ADS)

Wex, Heike; Kohn, Monika; Grawe, Sarah; Hartmann, Susan; Hellner, Lisa; Herenz, Paul; Welti, Andre; Lohmann, Ulrike; Kanji, Zamin; Stratmann, Frank

2016-04-01

The measurement campaign LINC (Leipzig Ice Nucleation counter Comparison) was conducted in September 2015, during which ice nucleation measurements as obtained with the following instruments were compared: - LACIS (Leipzig Aerosol Cloud Interaction Simulator, see e.g. Wex et al., 2014) - PIMCA-PINC (Portable Immersion Mode Cooling Chamber together with PINC) - PINC (Portable Ice Nucleation Chamber, Chou et al., 2011) - SPIN (SPectrometer for Ice Nuclei, Droplet Measurement Technologies) While LACIS and PIMCA-PINC measured immersion freezing, PINC and SPIN varied the super-saturation during the measurements and collected data also for relative humidities below 100% RHw. A suite of different types of ice nucleating particles were examined, where particles were generated from suspensions, subsequently dried and size selected. For the following samples, data for all four instruments are available: K-feldspar, K-feldspar treated with nitric acid, Fluka-kaolinite and birch pollen. Immersion freezing measurements by LACIS and PIMCA-PINC were in excellent agreement. Respective parameterizations from these measurement were used to model the ice nucleation behavior below water vapor saturation, assuming that the process can be described as immersion freezing in concentrated solutions. This is equivalent to simply including a concentration dependent freezing point depression in the immersion freezing parameterization, as introduced for coated kaolinite particles in Wex et al. (2014). Overall, measurements performed below water vapor saturation were reproduced by the model, and it will be discussed in detail, why deviations were observed in some cases. Acknowledgement: Part of this work was funded by the DFG Research Unit FOR 1525 INUIT, grant WE 4722/1-2. Literature: Chou, C., O. Stetzer, E. Weingartner, Z. Juranyi, Z. A. Kanji, and U. Lohmann (2011), Ice nuclei properties within a Saharan dust event at the Jungfraujoch in the Swiss Alps, Atmos. Chem. Phys., 11(10), 4725-4738, doi:10.5194/acp-11-4725-2011. Wex, H., P. J. DeMott, Y. Tobo, S. Hartmann, M. Rösch, T. Clauss, L. Tomsche, D. Niedermeier, and F. Stratmann (2014), Kaolinite particles as ice nuclei: learning from the use of different kaolinite samples and different coatings, Atmos. Chem. Phys., 14, doi:10.5194/acp-14-5529-2014.

Effect of nitrogen oxides (NO and NO2) and toluene on SO2 photooxidation, nucleation and growth: A smog chamber study

NASA Astrophysics Data System (ADS)

Li, Kangwei; Chen, Linghong; White, Stephen J.; Han, Ke; Lv, Biao; Bao, Kaiji; Wu, Xuecheng; Gao, Xiang; Azzi, Merched; Cen, Kefa

2017-08-01

The formation and growth of new particles has recently been shown to have a significant influence on Chinese haze pollution, and sulfuric acid has long been recognized as a major contributor to new particle formation. In this study, four comparison groups of experiments related to SO2 photooxidation, as well as aerosol nucleation and growth, have been conducted in the CAPS-ZJU (Complex Air Pollution Study-Zhejiang University) smog chamber. These were conducted either under SO2/NOx or SO2/toluene gas-phase environments in the absence of seed particles. During aerosol nucleation and growth process, several physical properties such as mass, size and effective density were measured simultaneously by Scanning Mobility Particle Sizer (SMPS) and Differential Mobility Analyzer-Aerosol Particle Mass Analyzer-Condensation Particle Counter (DMA-APM-CPC). The effective density of new particles decreased from 1.8 to 1.35 g/cm3 as the particle size increased from 20 to 65 nm. The single particle mass showed good power-law relationship with mobility diameter, with an average mass-mobility exponent of 2.885. A new algorithm and a reference density of 1.38 g/cm3 based on size-resolved single particle mass (SPM) were proposed to calculate the mass concentration of new particles. Two methods based on Log Normal and Max Concentration were applied to derive particle growth rate (GR), and data merging from both methods was implemented to decrease calculation uncertainty. Meanwhile, both continuous nucleation and inhibition of further growth in sub-20 nm size range were observed in different experiments depending on composition, and possible reasons were analyzed. The presence of NO was found to suppress nucleation and subsequent aerosol growth; while the presence of NO2 or toluene promoted it. It was concluded that decreasing NOx (NO or NO2) or increasing toluene may promote SO2 photooxidation, nucleation and subsequent aerosol growth, all of which is significant for deeper understanding of complex air pollution in China.

Properties of the seismic nucleation phase

USGS Publications Warehouse

Beroza, G.C.; Ellsworth, W.L.

1996-01-01

Near-source observations show that earthquakes begin abruptly at the P-wave arrival, but that this beginning is weak, with a low moment rate relative to the rest of the main shock. We term this initial phase of low moment rate the seismic nucleation phase. We have observed the seismic nucleation phase for a set of 48 earthquakes ranging in magnitude from 1.1-8.1. The size and duration of the seismic nucleation phase scale with the total seismic moment of the earthquake, suggesting that the process responsible for the seismic nucleation phase carries information about the eventual size of the earthquake. The seismic nucleation phase is characteristically followed by quadratic growth in the moment rate, consistent with self-similar rupture at constant stress drop. In this paper we quantify the properties of the seismic nucleation phase and offer several possible explanations for it.

Solute Nucleation and Growth in Supercritical Fluid Mixtures

NASA Technical Reports Server (NTRS)

Smedley, Gregory T.; Wilemski, Gerald; Rawlins, W. Terry; Joshi, Prakash; Oakes, David B.; Durgin, William W.

1996-01-01

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

Novel polypropylene/inorganic fullerene-like WS2 nanocomposites containing a β-nucleating agent: dynamic crystallization and melting behavior.

PubMed

Naffakh, Mohammed; Marco, Carlos; Ellis, Gary

2011-09-22

The dynamic crystallization and melting behavior of isotactic polypropylene-tungsten disulfide (iPP/IF-WS(2)) nanocomposites incorporating a β-nucleating agent is investigated by X-ray diffraction and differential scanning calorimetry. A conventional melt-processing strategy is employed to generate new materials that exhibit variable α and β polymorphism under the appropriate kinetic conditions. The results show that when the dual additive system is employed the nucleation ability on isotactic polypropylene not only depends on the nucleation efficiency (NE) and relative content of the individual α and β-nucleating agents, but also on the cooling rates employed. The nucleating behavior of the additives is explained by competitive nucleation, and the correlation between crystallization and melting temperatures and relative content of α and β-crystals of iPP in the nanocomposites is discussed.

Overview: Nucleation of clathrate hydrates

NASA Astrophysics Data System (ADS)

Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

2016-12-01

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

Overview: Nucleation of clathrate hydrates.

PubMed

Warrier, Pramod; Khan, M Naveed; Srivastava, Vishal; Maupin, C Mark; Koh, Carolyn A

2016-12-07

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

A comparison of manual and electronic counting for total nucleated cell counts on synovial fluid from canine stifle joints.

PubMed

Atilola, M A; Lumsden, J H; Rooke, F

1986-04-01

Synovial fluids collected from the stifle joints of 20 physically normal adult dogs were subjected to cytological examination. A total nucleated cell count was performed on each sample using both an electronic cell counter and a hemocytometer. The mean of the total counts done with the electronic counter was significantly higher (1008 cells/microL) than that obtained manually with the hemocytometer (848 cells/microL).

Nucleation and condensational growth to CCN sizes during a sustained pristine biogenic SOA event in a forested mountain valley

NASA Astrophysics Data System (ADS)

Liggio, J.; Pierce, J. R.; Leaitch, R.; Macdonald, A.; Whistler Aerosol; Cloud Study (WACS2010) Team

2011-12-01

The Whistler Aerosol and Cloud Study (WACS 2010), included intensive measurements of trace gases and particles at two sites on Whistler Mountain. Between July 6-11, 2010 there was a sustained high-pressure system over the region with cloud-free and higher-temperature conditions. During this period, the organic aerosol concentrations rose from <1 to 6 μ g m-3. Precursor gas and aerosol composition measurements show that these organics were almost entirely of secondary biogenic nature. Throughout July 6-11, the anthropogenic influence was minimal with sulfate concentrations < 0.2 μ g m-3 and SO2 mixing ratios ≈ 0.5 ppbv. Although SO2 mixing ratios were relatively low, companion box-model simulations show that nucleation and growth may be modeled accurately if Jnuc=3x10-7[H2SO4] and the organics are treated as effectively non-volatile. Due to the low condensation sink and the fast rate of condensing organics, the nucleated particles grew rapidly (2-5 nm hr-1) with a high probability of growing to CCN sizes before being scavenged by coagulation with larger particles (>10% growing to 100 nm in the first two days). The particles were observed to ultimately grow to ~200 nm after three days. Comparisons of SMPS with DMT CCN data show that particle hygroscopicity was generally around 0.1-0.11. The concentration of particles with diameters larger than 100 nm as well as CCN at 3% supersaturation rise from about 300 cm-3 to 1200 cm-3 during the 5 days due entirely to nucleation and growth. Relatively little SO2 is necessary to generate nucleation and growth to CCN sizes when biogenic SOA is abundant. This case offers a unique look at processes that may have controlled CCN formation in the pristine pre-industrial forested continental atmosphere.

Molecular beam epitaxial growth and structural characterization of ZnS on (001) GaAs

NASA Technical Reports Server (NTRS)

Benz, R. G., II; Huang, P. C.; Stock, S. R.; Summers, C. J.

1988-01-01

The effect of surface nucleation processes on the quality of ZnS layers grown on (001) GaAs substrates by molecular beam epitaxy is reported. Reflection high energy electron diffraction indicated that nucleation at high temperatures produced more planar surfaces than nucleation at low temperatures, but the crystalline quality as assessed by X-ray double crystal diffractometry is relatively independent of nucleation temperature. A critical factor in layer quality was the initial roughness of the GaAs surfaces.

Dislocation creation and void nucleation in FCC ductile metals under tensile loading: A general microscopic picture

PubMed Central

Pang, Wei-Wei; Zhang, Ping; Zhang, Guang-Cai; Xu, Ai-Guo; Zhao, Xian-Geng

2014-01-01

Numerous theoretical and experimental efforts have been paid to describe and understand the dislocation and void nucleation processes that are fundamental for dynamic fracture modeling of strained metals. To date an essential physical picture on the self-organized atomic collective motions during dislocation creation, as well as the essential mechanisms for the void nucleation obscured by the extreme diversity in structural configurations around the void nucleation core, is still severely lacking in literature. Here, we depict the origin of dislocation creation and void nucleation during uniaxial high strain rate tensile processes in face-centered-cubic (FCC) ductile metals. We find that the dislocations are created through three distinguished stages: (i) Flattened octahedral structures (FOSs) are randomly activated by thermal fluctuations; (ii) The double-layer defect clusters are formed by self-organized stacking of FOSs on the close-packed plane; (iii) The stacking faults are formed and the Shockley partial dislocations are created from the double-layer defect clusters. Whereas, the void nucleation is shown to follow a two-stage description. We demonstrate that our findings on the origin of dislocation creation and void nucleation are universal for a variety of FCC ductile metals with low stacking fault energies. PMID:25382029

The Nucleation of Protein Aggregates - From Crystals to Amyloid Fibrils.

PubMed

Buell, Alexander K

2017-01-01

The condensation and aggregation of individual protein molecules into dense insoluble phases is of relevance in such diverse fields as materials science, medicine, structural biology and pharmacology. A common feature of these condensation phenomena is that they usually are nucleated processes, i.e. the first piece of the condensed phase is energetically costly to create and hence forms slowly compared to its subsequent growth. Here we give a compact overview of the differences and similarities of various protein nucleation phenomena, their theoretical description in the framework of colloid and polymer science and their experimental study. Particular emphasis is put on the nucleation of a specific type of filamentous protein aggregates, amyloid fibrils. The current experimentally derived knowledge on amyloid fibril nucleation is critically assessed, and we argue that it is less advanced than is generally believed. This is due to (I) the lack of emphasis that has been put on the distinction between homogeneous and heterogeneous nucleation in experimental studies (II) the use of oversimplifying and/or inappropriate theoretical frameworks for the analysis of kinetic data of amyloid fibril nucleation. A strategy is outlined and advocated of how our understanding of this important class of processes can be improved in the future. © 2017 Elsevier Inc. All rights reserved.

Controlled ice nucleation using freeze-dried Pseudomonas syringae encapsulated in alginate beads.

PubMed

Weng, Lindong; Tessier, Shannon N; Swei, Anisa; Stott, Shannon L; Toner, Mehmet

2017-04-01

The control of ice nucleation is of fundamental significance in many process technologies related to food and pharmaceutical science and cryobiology. Mechanical perturbation, electromagnetic fields and ice-nucleating agents (INAs) have been known to induce ice nucleation in a controlled manner. But these ice-nucleating methods may suffer from cumbersome manual operations, safety concerns of external fields, and biocompatibility and recovery issues of INA particles, especially when used in living systems. Given the automatic ice-seeding nature of INAs, a promising solution to overcome some of the above limitations is to engineer a biocomposite that accommodates the INA particles but minimizes their interactions with biologics, as well as enabling the recovery of used particles. In this study, freeze-dried Pseudomonas syringae, a model ice-nucleating agent, was encapsulated into microliter-sized alginate beads. We evaluated the performance of the bacterial hydrogel beads to initiate ice nucleation in water and aqueous glycerol solution by investigating factors including the size and number of the beads and the local concentration of INA particles. In the aqueous sample of a fixed volume, the total mass of the INA particles (m) was found to be the governing parameter that is solely responsible for determining the ice nucleation performance of the bacterial hydrogel beads. The freezing temperature has a strong positive linear correlation with log 10 m. The findings in this study provide an effective, predictable approach to control ice nucleation, which can improve the outcome and standardization of many ice-assisted process technologies. Copyright © 2017 Elsevier Inc. All rights reserved.

What experiments on pinned nanobubbles can tell about the critical nucleus for bubble nucleation.

PubMed

Xiao, Qianxiang; Liu, Yawei; Guo, Zhenjiang; Liu, Zhiping; Frenkel, Daan; Dobnikar, Jure; Zhang, Xianren

2017-12-22

The process of homogeneous bubble nucleation is almost impossible to probe experimentally, except near the critical point or for liquids under large negative tension. Elsewhere in the phase diagram, the bubble nucleation barrier is so high as to be effectively insurmountable. Consequently, there is a severe lack of experimental studies of homogenous bubble nucleation under conditions of practical importance (e.g., cavitation). Here we use a simple geometric relation to show that we can obtain information about the homogeneous nucleation process from Molecular Dynamics studies of bubble formation in solvophobic nanopores on a solid surface. The free energy of pinned nanobubbles has two extrema as a function of volume: one state corresponds to a free-energy maximum ("the critical nucleus"), the other corresponds to a free-energy minimum (the metastable, pinned nanobubble). Provided that the surface tension does not depend on nanobubble curvature, the radius of the curvature of the metastable surface nanobubble is independent of the radius of the pore and is equal to the radius of the critical nucleus in homogenous bubble nucleation. This observation opens the way to probe the parameters that determine homogeneous bubble nucleation under experimentally accessible conditions, e.g. with AFM studies of metastable nanobubbles. Our theoretical analysis also indicates that a surface with pores of different sizes can be used to determine the curvature corrections to the surface tension. Our conclusions are not limited to bubble nucleation but suggest that a similar approach could be used to probe the structure of critical nuclei in crystal nucleation.

Kinetic Monte Carlo simulations of electrodeposition: Crossover from continuous to instantaneous homogeneous nucleation within Avrami’s law

NASA Astrophysics Data System (ADS)

Frank, Stefan; Rikvold, Per Arne

2006-06-01

The influence of lateral adsorbate diffusion on the dynamics of the first-order phase transition in a two-dimensional Ising lattice gas with attractive nearest-neighbor interactions is investigated by means of kinetic Monte Carlo simulations. For example, electrochemical underpotential deposition proceeds by this mechanism. One major difference from adsorption in vacuum surface science is that under control of the electrode potential and in the absence of mass-transport limitations, local adsorption equilibrium is approximately established. We analyze our results using the theory of Kolmogorov, Johnson and Mehl, and Avrami (KJMA), which we extend to an exponentially decaying nucleation rate. Such a decay may occur due to a suppression of nucleation around existing clusters in the presence of lateral adsorbate diffusion. Correlation functions prove the existence of such exclusion zones. By comparison with microscopic results for the nucleation rate I and the interface velocity of the growing clusters v, we can show that the KJMA theory yields the correct order of magnitude for Iv2. This is true even though the spatial correlations mediated by diffusion are neglected. The decaying nucleation rate causes a gradual crossover from continuous to instantaneous nucleation, which is complete when the decay of the nucleation rate is very fast on the time scale of the phase transformation. Hence, instantaneous nucleation can be homogeneous, producing negative minima in the two-point correlation functions. We also present in this paper an n-fold way Monte Carlo algorithm for a square lattice gas with adsorption/desorption and lateral diffusion.

Heteroepitaxial growth of GaAs on (100) Ge/Si using migration enhanced epitaxy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tanoto, H.; Loke, W. K.; Yoon, S. F.

In this paper, heteroepitaxial growth of GaAs on nominal (100) Ge/Si substrate was investigated. The root-mean square surface roughness of the sample where the first few monolayers of the GaAs were nucleated by migration enhanced epitaxy (MEE) is four times smaller compared to the sample without such a process, indicating better surface planarity. From the (004) x-ray diffraction rocking curve measurement, the full width at half maximum of the GaAs layer nucleated by MEE is 40% lower compared to that of the GaAs layer without such a process, indicating better crystal quality. Furthermore, it was found that the sample wheremore » the GaAs layer was nucleated by MEE experienced early relaxation. As the MEE process promotes two-dimensional growth, the GaAs layer where nucleation was initiated by such a process has fewer islandlike formations. This leads to a pseudomorphically grown GaAs layer, which experiences higher strain compared to the GaAs layer with more islandlike formations, where most relaxation occurs on the free surface of the islands. Therefore, for the same layer thickness, the GaAs layer on (100) Ge/Si substrate where nucleation was initiated by MEE relaxed first.« less

Electrochemical synthesis of copper nanoparticles using cuprous oxide as a precursor in choline chloride-urea deep eutectic solvent: nucleation and growth mechanism.

PubMed

Zhang, Q B; Hua, Y X

2014-12-28

The electrochemical nucleation and growth kinetics of copper nanoparticles on a Ni electrode have been studied with cyclic voltammetry and chronoamperometry in the choline chloride (ChCl)-urea based deep eutectic solvent (DES). The copper source was introduced into the solvent by the dissolution of Cu(I) oxide (Cu2O). Cyclic voltammetry indicates that the electroreduction of Cu(I) species in the DES is a diffusion-controlled quasi-reversible process. The analysis of the chronoamperometric transient behavior during electrodeposition suggests that the deposition of copper on the Ni electrode at low temperatures follows a progressive nucleation and three-dimensional growth controlled by diffusion. The effect of temperature on the diffusion coefficient of Cu(I) species that is present in the solvent and electron transfer rate constant obeys the Arrhenius law, according to which the activation energies are estimated to be 49.20 and 21.72 kJ mol(-1), respectively. The initial stage of morphological study demonstrates that both electrode potential and temperature play important roles in controlling the nucleation and growth kinetics of the nanocrystals during the electrodeposition process. Electrode potential is observed to affect mainly the nucleation process, whereas temperature makes a major contribution to the growth process.

Initial stage of nucleation-mediated crystallization of a supercooled melt

NASA Astrophysics Data System (ADS)

Chernov, A. A.; Pil'nik, A. A.; Islamov, D. R.

2016-09-01

The kinetic model of nucleation-mediated crystallization of a supercooled melt is presented in this work. It correctly takes into account the change in supercooling of the initial phase in the process of formation and evolution of a new phase. The model makes it possible to find the characteristic time of the process, time course of the crystal phase volume, solidified material microstructure. The distinctive feature of the model is the use of the "forbidden" zones in the volume where the formation of new nucleation centers is suppressed.

Ice nucleation activity of diesel soot particles at Cirrus relevant conditions: Effects of hydration, secondary organics coating, hydration, soot morphology, and coagulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulkarni, Gourihar R.; China, Swarup; Liu, Shang

The role of atmospheric relevant soot particles that are processed in the atmosphere toward ice nucleation at cirrus cloud condition is poorly understood. In this study, the ice nucleating properties of diesel soot particles subjected to various physical and chemical aging treatments were investigated at temperatures ranging from -40 to -50 °C. We show that bare soot particles nucleate ice in deposition mode, but coating with secondary organics suppresses the heterogeneous ice nucleation potential of soot particles requiring homogeneous freezing threshold conditions. However, the ice nucleation efficiency of soot particles coated with an aqueous organic layer was similar to baremore » soot particles. Hydration of bare soot particles slightly enhanced the ice nucleation efficiency, and the IN abilities of compact soot particles (roundness = ~ 0.6) were similar to bare lacey soot particles (roundness = ~ 0.4). These results indicate that ice nucleation properties are sensitive to the various aging treatments.« less

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

Nucleation of protein crystals under the influence of solution shear flow.

PubMed

Penkova, Anita; Pan, Weichun; Hodjaoglu, Feyzim; Vekilov, Peter G

2006-09-01

Several recent theories and simulations have predicted that shear flow could enhance, or, conversely, suppress the nucleation of crystals from solution. Such modulations would offer a pathway for nucleation control and provide a novel explanation for numerous mysteries in nucleation research. For experimental tests of the effects of shear flow on protein crystal nucleation, we found that if a protein solution droplet of approximately 5 microL (2-3 mm diameter at base) is held on a hydrophobic substrate in an enclosed environment and in a quasi-uniform constant electric field of 2 to 6 kV cm(-1), a rotational flow with a maximum rate at the droplet top of approximately 10 microm s(-1) is induced. The shear rate varies from 10(-3) to 10(-1) s(-1). The likely mechanism of the rotational flow involves adsorption of the protein and amphiphylic buffer molecules on the air-water interface and their redistribution in the electric field, leading to nonuniform surface tension of the droplet and surface tension-driven flow. Observations of the number of nucleated crystals in 24- and 72-h experiments with the proteins ferritin, apoferritin, and lysozyme revealed that the crystals are typically nucleated at a certain radius of the droplet, that is, at a preferred shear rate. Variations of the rotational flow velocity resulted in suppression or enhancement of the total number of nucleated crystals of ferritin and apoferritin, while all solution flow rates were found to enhance lysozyme crystal nucleation. These observations show that shear flow may strongly affect nucleation, and that for some systems, an optimal flow velocity, leading to fastest nucleation, exists. Comparison with the predictions of theories and simulations suggest that the formation of ordered nuclei in a "normal" protein solution cannot be affected by such low shear rates. We conclude that the flow acts by helping or suppressing the formation of ordered nuclei within mesoscopic metastable dense liquid clusters. Such clusters were recently shown to exist in protein solutions and to constitute the first step in the nucleation mechanism of many protein and nonproteinsystems.

Quantum chemical molecular dynamics simulation of single-walled carbon nanotube cap nucleation on an iron particle.

PubMed

Ohta, Yasuhito; Okamoto, Yoshiko; Page, Alister J; Irle, Stephan; Morokuma, Keiji

2009-11-24

The atomic scale details of single-walled carbon nanotube (SWNT) nucleation on metal catalyst particles are elusive to experimental observations. Computer simulation of metal-catalyzed SWNT nucleation is a challenging topic but potentially of great importance to understand the factors affecting SWNT diameters, chirality, and growth efficiency. In this work, we use nonequilibrium density functional tight-binding molecular dynamics simulations and report nucleation of sp(2)-carbon cap structures on an iron particle consisting of 38 atoms. One C(2) molecule was placed every 1.0 ps around an Fe(38) cluster for 30 ps, after which a further 410 ps of annealing simulation without carbon supply was performed. We find that sp(2)-carbon network nucleation and annealing processes occur in three sequential and repetitive stages: (A) polyyne chains on the metal surface react with each other to evolve into a Y-shaped polyyne junction, which preferentially form a five-membered ring as a nucleus; (B) polyyne chains on the first five-membered ring form an additional fused five- or six-membered ring; and (C) pentagon-to-hexagon self-healing rearrangement takes place with the help of short-lived polyyne chains, stabilized by the mobile metal atoms. The observed nucleation process resembles the formation of a fullerene cage. However, the metal particle plays a key role in differentiating the nucleation process from fullerene cage formation, most importantly by keeping the growing cap structure from closing into a fullerene cage and by keeping the carbon edge "alive" for the addition of new carbon material.

Branching microtubule nucleation in Xenopus egg extracts mediated by augmin and TPX2

PubMed Central

Petry, Sabine; Groen, Aaron C.; Ishihara, Keisuke; Mitchison, Timothy J.; Vale, Ronald D.

2013-01-01

Summary The microtubules that comprise mitotic spindles in animal cells are nucleated at centrosomes and by spindle assembly factors that are activated in the vicinity of chromatin. Indirect evidence also has suggested that microtubules might be nucleated from pre-existing microtubules throughout the spindle, but this process has not been observed directly. Here, we demonstrate microtubule nucleation from the sides of existing microtubules in meiotic Xenopus egg extracts. Daughter microtubules grow at a low branch angle and with the same polarity as mother filaments. Branching microtubule nucleation requires gamma-tubulin and augmin and is stimulated by GTP-bound Ran and its effector TPX2, factors previously implicated in chromatin-stimulated nucleation. Because of the rapid amplification of microtubule numbers and the preservation of microtubule polarity, microtubule-dependent microtubule nucleation is well suited for spindle assembly and maintenance. PMID:23415226

Microtubule array reorientation in response to hormones does not involve changes in microtubule nucleation modes at the periclinal cell surface

PubMed Central

Atkinson, Samantha; Kirik, Angela; Kirik, Viktor

2014-01-01

Aligned microtubule arrays spatially organize cell division, trafficking, and determine the direction of cell expansion in plant cells. In response to changes in environmental and developmental signals, cells reorganize their microtubule arrays into new configurations. Here, we tested the role of microtubule nucleation during hormone-induced microtubule array reorientation. We have found that in the process of microtubule array reorientation the ratios between branching, parallel, and de-novo nucleations remained constant, suggesting that the microtubule reorientation mechanism does not involve changes in nucleation modes. In the ton2/fass mutant, which has reduced microtubule branching nucleation frequency and decreased nucleation activity of the γ-tubulin complexes, microtubule arrays were able to reorient. Presented data suggest that reorientation of microtubules into transverse arrays in response to hormones does not involve changes in microtubule nucleation at the periclinal cell surface PMID:25135522

Comparing the ice nucleation efficiencies of ice nucleating substrates to natural mineral dusts

NASA Astrophysics Data System (ADS)

Steinke, Isabelle; Funk, Roger; Höhler, Kristina; Haarig, Moritz; Hoffmann, Nadine; Hoose, Corinna; Kiselev, Alexei; Möhler, Ottmar; Leisner, Thomas

2014-05-01

Mineral dust particles in the atmosphere may act as efficient ice nuclei over a wide range of temperature and relative humidity conditions. The ice nucleation capability of dust particles mostly depends on the particle surface area and the associated physico-chemical surface properties. It has been observed that the surface-related ice nucleation efficiency of different dust particles and mineral species can vary by several orders of magnitude. However, the relation between aerosol surface properties and observed ice nucleation efficiency is still not completely understood due to the large variability of chemical compositions and morphological features. In order to gain a better understanding of small scale freezing processes, we investigated the freezing of several hundreds of small droplets (V=0.4 nl) deposited on materials with reasonably well defined surfaces such as crystalline silicon wafers, graphite and freshly cleaved mica sheets under atmospherically relevant conditions. These substrates are intended to serve as simple model structures compared to the surface of natural aerosol particles. To learn more about the impact of particle morphology on ice nucleation processes, we also investigated micro-structured silicon wafers with prescribed trenches. The ice nucleation efficiencies deduced from these experiments are expressed as ice nucleation active surface site density values. With this approach, the freezing properties of the above-described substrates could be compared to those of natural mineral dusts such as agricultural soil dusts, volcanic ash and fossil diatoms, which have been investigated in AIDA cloud chamber experiments. All tested ice nucleating substrates were consistently less efficient at nucleating ice than the natural mineral dusts. Crystalline silicon only had a negligible influence on the freezing of small droplets, leading to freezing near the homogeneous freezing temperature threshold. Applying surface structures to silicon led to a shift towards heterogeneous freezing. However, the measured ice nucleation active surface site densities were still smaller than those of mineral dusts.

Nonclassical nucleation pathways in protein crystallization

NASA Astrophysics Data System (ADS)

Zhang, Fajun

2017-11-01

Classical nucleation theory (CNT), which was established about 90 years ago, has been very successful in many research fields, and continues to be the most commonly used theory in describing the nucleation process. For a fluid-to-solid phase transition, CNT states that the solute molecules in a supersaturated solution reversibly form small clusters. Once the cluster size reaches a critical value, it becomes thermodynamically stable and favored for further growth. One of the most important assumptions of CNT is that the nucleation process is described by one reaction coordinate and all order parameters proceed simultaneously. Recent studies in experiments, computer simulations and theory have revealed nonclassical features in the early stage of nucleation. In particular, the decoupling of order parameters involved during a fluid-to-solid transition leads to the so-called two-step nucleation mechanism, in which a metastable intermediate phase (MIP) exists between the initial supersaturated solution and the final crystals. Depending on the exact free energy landscapes, the MIPs can be a high density liquid phase, mesoscopic clusters, or a pre-ordered state. In this review, we focus on the studies of nonclassical pathways in protein crystallization and discuss the applications of the various scenarios of two-step nucleation theory. In particular, we focus on protein solutions in the presence of multivalent salts, which serve as a model protein system to study the nucleation pathways. We wish to point out the unique features of proteins as model systems for further studies.

Nonclassical nucleation pathways in protein crystallization.

PubMed

Zhang, Fajun

2017-11-08

Classical nucleation theory (CNT), which was established about 90 years ago, has been very successful in many research fields, and continues to be the most commonly used theory in describing the nucleation process. For a fluid-to-solid phase transition, CNT states that the solute molecules in a supersaturated solution reversibly form small clusters. Once the cluster size reaches a critical value, it becomes thermodynamically stable and favored for further growth. One of the most important assumptions of CNT is that the nucleation process is described by one reaction coordinate and all order parameters proceed simultaneously. Recent studies in experiments, computer simulations and theory have revealed nonclassical features in the early stage of nucleation. In particular, the decoupling of order parameters involved during a fluid-to-solid transition leads to the so-called two-step nucleation mechanism, in which a metastable intermediate phase (MIP) exists between the initial supersaturated solution and the final crystals. Depending on the exact free energy landscapes, the MIPs can be a high density liquid phase, mesoscopic clusters, or a pre-ordered state. In this review, we focus on the studies of nonclassical pathways in protein crystallization and discuss the applications of the various scenarios of two-step nucleation theory. In particular, we focus on protein solutions in the presence of multivalent salts, which serve as a model protein system to study the nucleation pathways. We wish to point out the unique features of proteins as model systems for further studies.

FTIR absorption reflection study of biomimetic growth of phosphates on titanium implants

NASA Astrophysics Data System (ADS)

Stoch, A.; Jastrzębski, W.; Brożek, A.; Stoch, J.; Szaraniec, J.; Trybalska, B.; Kmita, G.

2000-11-01

Titanium has been used for many medical applications; however, its joining to a living bone still is not satisfactorily good, challenging appropriate investigations. The aim of this work was to generate chemical modifications at its surface such that in vivo conditions, heterogeneous nucleation, and then growth of apatite from the body fluid could be easily induced and successfully performed. For this purpose, on the titanium samples, the oxide sublayers containing titanium, calcium and silicon (TCS) were deposited from a suitable solution using the sol-gel deep-coating procedure. Dried samples were heated at 400°C then cooled and thermostatically held in synthetic body fluids (SBF, SBFIII) under physiological conditions to mimic the natural process of apatite formation. Changes in surface composition of TCS sublayers caused by the heating were studied with XPS. Infrared spectroscopy and scanning electron microscopy monitored successive steps of apatite growth. It was found that in SBF, at the precoated titanium surface, nucleation and growth of the apatite containing carbonate took place. In SBFIII, for a higher concentration of calcium ions in comparison with SBF, a much-enhanced growth of the apatite free of carbonate was observed. TCS precoatings applied on stainless steel and Cr-Co-Mo alloy (Micromed) act also as bioactive interfaces with high ability to nucleation of biologically equivalent apatite. Biomimetic formation of this apatite on biologically inactive materials can be an important step in implant surgery.

Comparison of aftershock sequences between 1975 Haicheng earthquake and 1976 Tangshan earthquake

NASA Astrophysics Data System (ADS)

Liu, B.

2017-12-01

The 1975 ML 7.3 Haicheng earthquake and the 1976 ML 7.8 Tangshan earthquake occurred in the same tectonic unit. There are significant differences in spatial-temporal distribution, number of aftershocks and time duration for the aftershock sequence followed by these two main shocks. As we all know, aftershocks could be triggered by the regional seismicity change derived from the main shock, which was caused by the Coulomb stress perturbation. Based on the rate- and state- dependent friction law, we quantitative estimated the possible aftershock time duration with a combination of seismicity data, and compared the results from different approaches. The results indicate that, aftershock time durations from the Tangshan main shock is several times of that form the Haicheng main shock. This can be explained by the significant relationship between aftershock time duration and earthquake nucleation history, normal stressand shear stress loading rateon the fault. In fact the obvious difference of earthquake nucleation history from these two main shocks is the foreshocks. 1975 Haicheng earthquake has clear and long foreshocks, while 1976 Tangshan earthquake did not have clear foreshocks. In that case, abundant foreshocks may mean a long and active nucleation process that may have changed (weakened) the rocks in the source regions, so they should have a shorter aftershock sequences for the reason that stress in weak rocks decay faster.

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.

Steering a crystallization process to reduce crystal polydispersity; case study of insulin crystallization

NASA Astrophysics Data System (ADS)

Nanev, Christo N.; Petrov, Kostadin P.

2017-12-01

The use of the classical nucleation-growth-separation principle (NGSP) was restricted hitherto to nucleation kinetics studies only. A novel application of the NGSP is proposed. To reduce crystal polydispersity internal seeding of equally-sized crystals is suggested, the advantage being avoidance of crystal grinding, sieving and any introduction of impurities. In the present study, size distributions of grown insulin crystals are interpreted retrospectively to select the proper nucleation stage parameters. The conclusion is that when steering a crystallization process aimed at reducing crystal polydispersity, the shortest possible nucleation stage duration has to be chosen because it renders the closest size distribution of the nucleated crystal seeds. Causes of inherent propensity to increasing crystal polydispersity during prolonged growth are also explored. Step sources of increased activity, present in some crystals while absent in others, are pointed as the major polydispersity cause. Insulin crystal morphology is also considered since it determines the dissolution rate of a crystalline medicine.

Electrochemical processes of nucleation and growth of hydroxyapatite on titanium supported by real-time electrochemical atomic force microscopy.

PubMed

Eliaz, Noam; Eliyahu, Moshe

2007-03-01

Recently, interest in electrochemical formation of hydroxyapatite has evolved. In this work, highly crystalline hydroxyapatite is electrodeposited on pure titanium and Ti-6Al-4V alloy. In situ and ex situ imaging, coupled with potentiostatic and potentiodynamic measurements, is conducted by means of electrochemical atomic force microscopy. This allows for a study of the nucleation and growth of hydroxyapatite as well as of its near-atomic structure. Electrodeposition of hydroxyapatite is shown to result from precipitation in solution, following two stages: (1) instantaneous nucleation, two-dimensional growth; (2) progressive nucleation, three-dimensional growth. Although some nucleation occurs already at -842 mV, potentials that are more negative than -1.26 V versus SCE are required for enhanced growth. Mass transport is found to have only secondary effect on the deposition process. The conclusions of this work have implications in optimization of coatings on implants as well as in enhancement of the understanding of bone mineralization in vivo.

Reducing the nucleation barrier in magnetocaloric Heusler alloys by nanoindentation

NASA Astrophysics Data System (ADS)

Niemann, R.; Hahn, S.; Diestel, A.; Backen, A.; Schultz, L.; Nielsch, K.; Wagner, M. F.-X.; Fähler, S.

2016-06-01

Magnetocaloric materials are promising as solid state refrigerants for more efficient and environmentally friendly cooling devices. The highest effects have been observed in materials that exhibit a first-order phase transition. These transformations proceed by nucleation and growth which lead to a hysteresis. Such irreversible processes are undesired since they heat up the material and reduce the efficiency of any cooling application. In this article, we demonstrate an approach to decrease the hysteresis by locally changing the nucleation barrier. We created artificial nucleation sites and analyzed the nucleation and growth processes in their proximity. We use Ni-Mn-Ga, a shape memory alloy that exhibits a martensitic transformation. Epitaxial films serve as a model system, but their high surface-to-volume ratio also allows for a fast heat transfer which is beneficial for a magnetocaloric regenerator geometry. Nanoindentation is used to create a well-defined defect. We quantify the austenite phase fraction in its proximity as a function of temperature which allows us to determine the influence of the defect on the transformation.

Early nucleation events in the polymerization of actin, probed by time-resolved small-angle x-ray scattering

PubMed Central

Oda, Toshiro; Aihara, Tomoki; Wakabayashi, Katsuzo

2016-01-01

Nucleators generating new F-actin filaments play important roles in cell activities. Detailed information concerning the events involved in nucleation of actin alone in vitro is fundamental to understanding these processes, but such information has been hard to come by. We addressed the early process of salt-induced polymerization of actin using the time-resolved synchrotron small-angle X-ray scattering (SAXS). Actin molecules in low salt solution maintain a monomeric state by an electrostatic repulsive force between molecules. On mixing with salts, the repulsive force was rapidly screened, causing an immediate formation of many of non-polymerizable dimers. SAXS kinetic analysis revealed that tetramerization gives the highest energetic barrier to further polymerization, and the major nucleation is the formation of helical tetramers. Filaments start to grow rapidly with the formation of pentamers. These findings suggest an acceleration mechanism of actin assembly by a variety of nucleators in cells. PMID:27775032

Ice nucleation by particles immersed in supercooled cloud droplets.

PubMed

Murray, B J; O'Sullivan, D; Atkinson, J D; Webb, M E

2012-10-07

The formation of ice particles in the Earth's atmosphere strongly affects the properties of clouds and their impact on climate. Despite the importance of ice formation in determining the properties of clouds, the Intergovernmental Panel on Climate Change (IPCC, 2007) was unable to assess the impact of atmospheric ice formation in their most recent report because our basic knowledge is insufficient. Part of the problem is the paucity of quantitative information on the ability of various atmospheric aerosol species to initiate ice formation. Here we review and assess the existing quantitative knowledge of ice nucleation by particles immersed within supercooled water droplets. We introduce aerosol species which have been identified in the past as potentially important ice nuclei and address their ice-nucleating ability when immersed in a supercooled droplet. We focus on mineral dusts, biological species (pollen, bacteria, fungal spores and plankton), carbonaceous combustion products and volcanic ash. In order to make a quantitative comparison we first introduce several ways of describing ice nucleation and then summarise the existing information according to the time-independent (singular) approximation. Using this approximation in combination with typical atmospheric loadings, we estimate the importance of ice nucleation by different aerosol types. According to these estimates we find that ice nucleation below about -15 °C is dominated by soot and mineral dusts. Above this temperature the only materials known to nucleate ice are biological, with quantitative data for other materials absent from the literature. We conclude with a summary of the challenges our community faces.

Single-fluorophore monitoring of DNA hybridization for investigating the effect of secondary structure on the nucleation step.

PubMed

Jo, Joon-Jung; Kim, Min-Ji; Son, Jung-Tae; Kim, Jandi; Shin, Jong-Shik

2009-07-17

Nucleic acid hybridization is one of the essential biological processes involved in storage and transmission of genetic information. Here we quantitatively determined the effect of secondary structure on the hybridization activation energy using structurally defined oligonucleotides. It turned out that activation energy is linearly proportional to the length of a single-stranded region flanking a nucleation site, generating a 0.18 kcal/mol energy barrier per nucleotide. Based on this result, we propose that the presence of single-stranded segments available for non-productive base pairing with a nucleation counterpart extends the searching process for nucleation sites to find a perfect match. This result may provide insights into rational selection of a target mRNA site for siRNA and antisense gene silencing.

Effects of gaseous sulphuric acid on diesel exhaust nanoparticle formation and characteristics.

PubMed

Rönkkö, Topi; Lähde, Tero; Heikkilä, Juha; Pirjola, Liisa; Bauschke, Ulrike; Arnold, Frank; Schlager, Hans; Rothe, Dieter; Yli-Ojanperä, Jaakko; Keskinen, Jorma

2013-10-15

Diesel exhaust gaseous sulphuric acid (GSA) concentrations and particle size distributions, concentrations, and volatility were studied at four driving conditions with a heavy duty diesel engine equipped with oxidative exhaust after-treatment. Low sulfur fuel and lubricant oil were used in the study. The concentration of the exhaust GSA was observed to vary depending on the engine driving history and load. The GSA affected the volatile particle fraction at high engine loads; higher GSA mole fraction was followed by an increase in volatile nucleation particle concentration and size as well as increase of size of particles possessing nonvolatile core. The GSA did not affect the number of nonvolatile particles. At low and medium loads, the exhaust GSA concentration was low and any GSA driven changes in particle population were not observed. Results show that during the exhaust cooling and dilution processes, besides critical in volatile nucleation particle formation, GSA can change the characteristics of all nucleation mode particles. Results show the dual nature of the nucleation mode particles so that the nucleation mode can include simultaneously volatile and nonvolatile particles, and fulfill the previous results for the nucleation mode formation, especially related to the role of GSA in formation processes.

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.

Non-equilibrium Quasi-Chemical Nucleation Model

NASA Astrophysics Data System (ADS)

Gorbachev, Yuriy E.

2018-04-01

Quasi-chemical model, which is widely used for nucleation description, is revised on the basis of recent results in studying of non-equilibrium effects in reacting gas mixtures (Kolesnichenko and Gorbachev in Appl Math Model 34:3778-3790, 2010; Shock Waves 23:635-648, 2013; Shock Waves 27:333-374, 2017). Non-equilibrium effects in chemical reactions are caused by the chemical reactions themselves and therefore these contributions should be taken into account in the corresponding expressions for reaction rates. Corrections to quasi-equilibrium reaction rates are of two types: (a) spatially homogeneous (caused by physical-chemical processes) and (b) spatially inhomogeneous (caused by gas expansion/compression processes and proportional to the velocity divergency). Both of these processes play an important role during the nucleation and are included into the proposed model. The method developed for solving the generalized Boltzmann equation for chemically reactive gases is applied for solving the set of equations of the revised quasi-chemical model. It is shown that non-equilibrium processes lead to essential deviation of the quasi-stationary distribution and therefore the nucleation rate from its traditional form.

Role of filament annealing in the kinetics and thermodynamics of nucleated polymerization.

PubMed

Michaels, Thomas C T; Knowles, Tuomas P J

2014-06-07

The formation of nanoscale protein filaments from soluble precursor molecules through nucleated polymerization is a common form of supra-molecular assembly phenomenon. This process underlies the generation of a range of both functional and pathological structures in nature. Filament breakage has emerged as a key process controlling the kinetics of the growth reaction since it increases the number of filament ends in the system that can act as growth sites. In order to ensure microscopic reversibility, however, the inverse process of fragmentation, end-to-end annealing of filaments, is a necessary component of a consistent description of such systems. Here, we combine Smoluchowski kinetics with nucleated polymerization models to generate a master equation description of protein fibrillization, where filamentous structures can undergo end-to-end association, in addition to elongation, fragmentation, and nucleation processes. We obtain self-consistent closed-form expressions for the growth kinetics and discuss the key physics that emerges from considering filament fusion relative to current fragmentation only models. Furthermore, we study the key time scales that describe relaxation to equilibrium.

Microstructure development in Kolmogorov, Johnson-Mehl, and Avrami nucleation and growth kinetics

NASA Astrophysics Data System (ADS)

Pineda, Eloi; Crespo, Daniel

1999-08-01

A statistical model with the ability to evaluate the microstructure developed in nucleation and growth kinetics is built in the framework of the Kolmogorov, Johnson-Mehl, and Avrami theory. A populational approach is used to compute the observed grain-size distribution. The impingement process which delays grain growth is analyzed, and the effective growth rate of each population is estimated considering the previous grain history. The proposed model is integrated for a wide range of nucleation and growth protocols, including constant nucleation, pre-existing nuclei, and intermittent nucleation with interface or diffusion-controlled grain growth. The results are compared with Monte Carlo simulations, giving quantitative agreement even in cases where previous models fail.

Transient nucleate pool boiling in microgravity: Some initial results

NASA Technical Reports Server (NTRS)

Merte, Herman, Jr.; Lee, H. S.; Ervin, J. S.

1994-01-01

Variable gravity provides an opportunity to test the understanding of phenomena which are considered to depend on buoyancy, such as nucleate pool boiling. The active fundamental research in nucleate boiling has sought to determine the mechanisms or physical processes responsible for its high effectiveness, manifested by the high heat flux levels possible with relatively low temperature differences. Earlier research on nucleate pool boiling at high gravity levels under steady conditions demonstrated quantitatively that the heat transfer is degraded as the buoyancy normal to the heater surfaced increases. Correspondingly, it was later shown, qualitatively for short periods of time only, that nucleate boiling heat transfer is enhanced as the buoyancy normal to the heater surface is reduced. It can be deduced that nucleate pool boiling can be sustained as a quasi-steady process provided that some means is available to remove the vapor generated from the immediate vicinity of the heater surface. One of the objectives of the research, the initial results of which are presented here, is to quantify the heat transfer associated with boiling in microgravity. Some quantitative results of nucleate pool boiling in high quality microgravity (a/g approximately 10(exp -5)) of 5s duration, obtained in an evacuated drop tower, are presented here. These experiments were conducted as precursors of longer term space experiments. A transient heating technique is used, in which the heater surface is a transparent gold film sputtered on a qua rtz substrate, simultaneously providing the mean surface temperature from resistance thermometry and viewing of the boiling process both from beneath and across the surface. The measurement of the transient mean heater surface temperature permits the computation, by numerical means, of the transient mean heat transfer coefficient. The preliminary data obtained demonstrates that a quasi-steady boiling process can occur in microgravity if the bulk liquid subcooling is sufficiently high and if the imposed heat flux is sufficiently low. This is attributed to suface tension effects at the liquid-vapor-solid junction causing rewetting to take place, sustaining the nucleate boiling. Otherwise, dryout at the heater surface will occur, as observed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Bingbing; Knopf, Daniel A.; China, Swarup

Heterogeneous ice nucleation is a physical chemistry process of critical relevance to a range of topics in the fundamental and the applied sciences and technologies. Heterogeneous ice nucleation remains insufficiently understood. This is in part due to the lack of experimental methods capable of in situ visualization of ice formation over nucleating substrates with microscopically characterized morphology and composition. We present development, validation and first applications of a novel electron microscopy platform allowing observation of individual ice nucleation events at temperature and relative humidity (RH) relevant for ice formation in a broad range of environmental and applied technology processes. Themore » approach utilizes a custom-built ice nucleation cell, interfaced with an Environmental Scanning Electron Microscope (IN-ESEM system). The IN-ESEM system allows dynamic observations of individual ice formation events over particles of atmospheric relevance and determination of the ice nucleation mechanisms. Additional IN-ESEM experiments allow examination of the location of ice formation on the surface of individual particles and micro-spectroscopy analysis of the ice nucleating particles (INPs). This includes elemental composition detected by the energy dispersed analysis of X-rays (EDX), speciation of the organic content in particles using scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS), and Helium ion microscopy (HeIM). The capabilities of the IN-ESEM experimental platform are demonstrated first on laboratory standards and then by chemical imaging of INPs using a complex sample of ambient particles.« less

Introducing uncertainty analysis of nucleation and crystal growth models in Process Analytical Technology (PAT) system design of crystallization processes.

PubMed

Samad, Noor Asma Fazli Abdul; Sin, Gürkan; Gernaey, Krist V; Gani, Rafiqul

2013-11-01

This paper presents the application of uncertainty and sensitivity analysis as part of a systematic model-based process monitoring and control (PAT) system design framework for crystallization processes. For the uncertainty analysis, the Monte Carlo procedure is used to propagate input uncertainty, while for sensitivity analysis, global methods including the standardized regression coefficients (SRC) and Morris screening are used to identify the most significant parameters. The potassium dihydrogen phosphate (KDP) crystallization process is used as a case study, both in open-loop and closed-loop operation. In the uncertainty analysis, the impact on the predicted output of uncertain parameters related to the nucleation and the crystal growth model has been investigated for both a one- and two-dimensional crystal size distribution (CSD). The open-loop results show that the input uncertainties lead to significant uncertainties on the CSD, with appearance of a secondary peak due to secondary nucleation for both cases. The sensitivity analysis indicated that the most important parameters affecting the CSDs are nucleation order and growth order constants. In the proposed PAT system design (closed-loop), the target CSD variability was successfully reduced compared to the open-loop case, also when considering uncertainty in nucleation and crystal growth model parameters. The latter forms a strong indication of the robustness of the proposed PAT system design in achieving the target CSD and encourages its transfer to full-scale implementation. Copyright © 2013 Elsevier B.V. All rights reserved.

Using the Binary Phase-Field Crystal Model to Describe Non-Classical Nucleation Pathways in Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Smith, Nathan; Provatas, Nikolas

Recent experimental work has shown that gold nanoparticles can precipitate from an aqueous solution through a non-classical, multi-step nucleation process. This multi-step process begins with spinodal decomposition into solute-rich and solute-poor liquid domains followed by nucleation from within the solute-rich domains. We present a binary phase-field crystal theory that shows the same phenomology and examine various cross-over regimes in the growth and coarsening of liquid and solid domains. We'd like to the thank Canada Research Chairs (CRC) program for funding this work.

Electron microscopy studies of the morphological evolution in hydrothermally derived lead titanate

NASA Astrophysics Data System (ADS)

Ye, Zhiyuan

Hydrothermal processing is a promising technique to synthesize perovskite ceramic powders. Understanding the reaction mechanisms and the factors that affect the particle morphologies is essential to optimize the hydrothermal processing. In this dissertation, the reaction mechanisms and nucleation processes in hydrothermally derived lead titanate (PbTiO3) are examined and established by morphological studies. The initial concentration of potassium hydroxide [KOH]i had a strong influence on the reaction. As [KOH] i increased from 0.01 M to 0.1 M to 1.0 M, the resultant morphology changed from irregular spherical to dendritic to faceted rectangular platelet morphology. The morphological evolution was well explained in the context of a supersaturation-nucleation relation. As the [KOH]i increased, the supersaturation increased and the nucleation mechanism changed from weak heterogeneous nucleation to strong heterogeneous nucleation or even homogeneous nucleation. These different nucleation mechanisms resulted in the different morphologies. Kinetic and morphological studies suggest that the reaction starting from nanocrystalline titania is dominated by dissolution-precipitation. The titanium precursors strongly affected the reaction. Increasing the particle size of precursors significantly reduced the reaction rate, especially at the low [KOH]i case. In situ transformations play important roles under the conditions of low [KOH] i and/or large particle size of precursors. Investigation using amorphous titania indicated that the nucleation of lead titanate at low and intermediate [KOH]i is via a in situ transformation while at high [KOH]i a dissolution-precipitation mechanism dominates. Ferro electricity of PbTiO3 also affects the particle morphology. The hydrothermal lead titanate particles could grow as a single domain during the processing. The ferroelectric polarization of PbTiO3 induced different local ionic environment between the positively and negatively charged surfaces, resulting a one-sided dendritic morphology at intermediate [KOH] i. The platelet morphology at high [KOH]i gave rise to a new type of size effect. For platelets with size less than a critical size of ˜70 nm, the domain polarization reoriented from perpendicular to the platelet during the processing, to parallel to the platelet after the particles were washed and dried (so that the depolarization energy builds up). This domain reorientation is attributed to strong depolarization effects and anisotropic geometry factors.

Doubled heterogeneous crystal nucleation in sediments of hard sphere binary-mass mixtures

NASA Astrophysics Data System (ADS)

Löwen, Hartmut; Allahyarov, Elshad

2011-10-01

Crystallization during the sedimentation process of a binary colloidal hard spheres mixture is explored by Brownian dynamics computer simulations. The two species are different in buoyant mass but have the same interaction diameter. Starting from a completely mixed system in a finite container, gravity is suddenly turned on, and the crystallization process in the sample is monitored. If the Peclet numbers of the two species are both not too large, crystalline layers are formed at the bottom of the cell. The composition of lighter particles in the sedimented crystal is non-monotonic in the altitude: it is first increasing, then decreasing, and then increasing again. If one Peclet number is large and the other is small, we observe the occurrence of a doubled heterogeneous crystal nucleation process. First, crystalline layers are formed at the bottom container wall which are separated from an amorphous sediment. At the amorphous-fluid interface, a secondary crystal nucleation of layers is identified. This doubled heterogeneous nucleation can be verified in real-space experiments on colloidal mixtures.

Black holes as bubble nucleation sites

NASA Astrophysics Data System (ADS)

Gregory, Ruth; Moss, Ian G.; Withers, Benjamin

2014-03-01

We consider the effect of inhomogeneities on the rate of false vacuum decay. Modelling the inhomogeneity by a black hole, we construct explicit Euclidean instantons which describe the nucleation of a bubble of true vacuum centred on the inhomogeneity. We find that inhomogeneity significantly enhances the nucleation rate over that of the Coleman-de Luccia instanton — the black hole acts as a nucleation site for the bubble. The effect is larger than previously believed due to the contributions to the action from conical singularities. For a sufficiently low initial mass, the original black hole is replaced by flat space during this process, as viewed by a single causal patch observer. Increasing the initial mass, we find a critical value above which a black hole remnant survives the process. This resulting black hole can have a higher mass than the original black hole, but always has a lower entropy. We compare the process to bubble-to-bubble transitions, where there is a semi-classical Lorentzian description in the WKB approximation.

Sensitivity Studies of Dust Ice Nuclei Effect on Cirrus Clouds with the Community Atmosphere Model CAM5

NASA Technical Reports Server (NTRS)

Liu, Xiaohong; Zhang, Kai; Jensen, Eric J.; Gettelman, Andrew; Barahona, Donifan; Nenes, Athanasios; Lawson, Paul

2012-01-01

In this study the effect of dust aerosol on upper tropospheric cirrus clouds through heterogeneous ice nucleation is investigated in the Community Atmospheric Model version 5 (CAM5) with two ice nucleation parameterizations. Both parameterizations consider homogeneous and heterogeneous nucleation and the competition between the two mechanisms in cirrus clouds, but differ significantly in the number concentration of heterogeneous ice nuclei (IN) from dust. Heterogeneous nucleation on dust aerosol reduces the occurrence frequency of homogeneous nucleation and thus the ice crystal number concentration in the Northern Hemisphere (NH) cirrus clouds compared to simulations with pure homogeneous nucleation. Global and annual mean shortwave and longwave cloud forcing are reduced by up to 2.0+/-0.1Wm (sup-2) (1 uncertainty) and 2.4+/-0.1Wm (sup-2), respectively due to the presence of dust IN, with the net cloud forcing change of -0.40+/-0.20W m(sup-2). Comparison of model simulations with in situ aircraft data obtained in NH mid-latitudes suggests that homogeneous ice nucleation may play an important role in the ice nucleation at these regions with temperatures of 205-230 K. However, simulations overestimate observed ice crystal number concentrations in the tropical tropopause regions with temperatures of 190- 205 K, and overestimate the frequency of occurrence of high ice crystal number concentration (greater than 200 L(sup-1) and underestimate the frequency of low ice crystal number concentration (less than 30 L(sup-1) at NH mid-latitudes. These results highlight the importance of quantifying the number concentrations and properties of heterogeneous IN (including dust aerosol) in the upper troposphere from the global perspective.

Nucleation and growth constraints and outcome in the natural gas hydrate system

NASA Astrophysics Data System (ADS)

Osegovic, J. P.; Max, M. D.

2016-12-01

Hydrate formation processes are functions of energy distribution constrained by physical and kinetic parameters. The generation of energy and energy derivative plots of a constrained growth crucible are used to demonstrate nucleation probability zones (phase origin(s)). Nucleation sets the stage for growth by further constraining the pathways through changes in heat capacity, heat flow coefficient, and enthalpy which in turn modify the mass and energy flow into the hydrate formation region. Nucleation events result from the accumulation of materials and energy relative to pressure, temperature, and composition. Nucleation induction is predictive (a frequency parameter) rather than directly dependent on time. Growth, as mass tranfer into a new phase, adds time as a direct parameter. Growth has direct feedback on phase transfer, energy dynamics, and mass export/import rates. Many studies have shown that hydrate growth is largely an equilibrium process controlled by either mass or energy flows. Subtle changes in the overall energy distribution shift the equilibrium in a predictable fashion. We will demonstrate the localization of hydrate nucleation in a reservoir followed by likely evolution of growth in a capped, sand filled environment. The gas hydrate stability zone (GHSZ) can be characterized as a semi-batch crystallizer in which nucleation and growth of natural gas hydrate (NGH) is a continuous process that may result in very large concentrations of NGH. Gas flux, or the relative concentration of hydrate-forming gas is the critical factor in a GHSZ. In an open groundwater system in which flow rate exceeds diffusion transport rate, dissolved natural gas is transported into and through the GHSZ. In a closed system, such as a geological trap, diffusion of hydrate-forming gas from a free gas zone below the GHSZ is the primary mechanism for movement of gas reactants. Because of the lower molecular weight of methane, where diffusion is the principal transport mechanism, the natural system can be a purification process for formation of increasingly pure NGH from a mixed gas solution over time.

Time-evolution of grain size distributions in random nucleation and growth crystallization processes

NASA Astrophysics Data System (ADS)

Teran, Anthony V.; Bill, Andreas; Bergmann, Ralf B.

2010-02-01

We study the time dependence of the grain size distribution N(r,t) during crystallization of a d -dimensional solid. A partial differential equation, including a source term for nuclei and a growth law for grains, is solved analytically for any dimension d . We discuss solutions obtained for processes described by the Kolmogorov-Avrami-Mehl-Johnson model for random nucleation and growth (RNG). Nucleation and growth are set on the same footing, which leads to a time-dependent decay of both effective rates. We analyze in detail how model parameters, the dimensionality of the crystallization process, and time influence the shape of the distribution. The calculations show that the dynamics of the effective nucleation and effective growth rates play an essential role in determining the final form of the distribution obtained at full crystallization. We demonstrate that for one class of nucleation and growth rates, the distribution evolves in time into the logarithmic-normal (lognormal) form discussed earlier by Bergmann and Bill [J. Cryst. Growth 310, 3135 (2008)]. We also obtain an analytical expression for the finite maximal grain size at all times. The theory allows for the description of a variety of RNG crystallization processes in thin films and bulk materials. Expressions useful for experimental data analysis are presented for the grain size distribution and the moments in terms of fundamental and measurable parameters of the model.

Role of clusters in nonclassical nucleation and growth of protein crystals

PubMed Central

Sleutel, Mike; Van Driessche, Alexander E. S.

2014-01-01

The development of multistep nucleation theory has spurred on experimentalists to find intermediate metastable states that are relevant to the solidification pathway of the molecule under interest. A great deal of studies focused on characterizing the so-called “precritical clusters” that may arise in the precipitation process. However, in macromolecular systems, the role that these clusters might play in the nucleation process and in the second stage of the precipitation process, i.e., growth, remains to a great extent unknown. Therefore, using biological macromolecules as a model system, we have studied the mesoscopic intermediate, the solid end state, and the relationship that exists between them. We present experimental evidence that these clusters are liquid-like and stable with respect to the parent liquid and metastable compared with the emerging crystalline phase. The presence of these clusters in the bulk liquid is associated with a nonclassical mechanism of crystal growth and can trigger a self-purifying cascade of impurity-poisoned crystal surfaces. These observations demonstrate that there exists a nontrivial connection between the growth of the macroscopic crystalline phase and the mesoscopic intermediate which should not be ignored. On the other hand, our experimental data also show that clusters existing in protein solutions can significantly increase the nucleation rate and therefore play a relevant role in the nucleation process. PMID:24449867

Collaborative Research: failure of RockMasses from Nucleation and Growth of Microscopic Defects and Disorder

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, William

Over the 21 years of funding we have pursued several projects related to earthquakes, damage and nucleation. We developed simple models of earthquake faults which we studied to understand Gutenburg-Richter scaling, foreshocks and aftershocks, the effect of spatial structure of the faults and its interaction with underlying self organization and phase transitions. In addition we studied the formation of amorphous solids via the glass transition. We have also studied nucleation with a particular concentration on transitions in systems with a spatial symmetry change. In addition we investigated the nucleation process in models that mimic rock masses. We obtained the structuremore » of the droplet in both homogeneous and heterogeneous nucleation. We also investigated the effect of defects or asperities on the nucleation of failure in simple models of earthquake faults.« less

New particle formation in rural areas - what is behind the story?

NASA Astrophysics Data System (ADS)

Boy, M.; Sihto, S. L.-; Lauros, J.; Bonn, B.; Guenther, A.

2009-04-01

New particle formation in rural areas - what's behind it? M. Boy(1), S.-L. Sihto(1), J. Lauros(1), B. Bonn(2) and A. Guenther(3) (1) Department of Physical Sciences, P.O. Box 64, 00014 University of Helsinki, Finland. (2) Institute of Atmospherical and Environmental Sciences, J. W. Goethe University, Altenhöferallee 1, D-60438 Frankfurt/Main, Germany (3) ACD, NCAR, P.O. Box 3000, 80305 Boulder, Colorado, USA. New particle formation has been observed at almost all sites, where both particle number concentrations and size distributions have been measured. Although many field campaigns, laboratory experiments and new modelling approaches have led to increased understanding, detailed mechanisms responsible for the formation of new particles in the troposphere have still not been completely elucidated. In MALTE (Model to predict new Aerosol formation in the Lower Troposphere) individually developed codes from different institutes around the globe merged into a one-dimensional model including aerosol dynamics, boundary layer meteorology, biology and chemistry in order to investigate the formation and growth processes of Secondary Organic Aerosols (SOA) under realistic atmospheric conditions. Our knowledge concerning the formation of very small particles or clusters is still limited. The question of which molecules are involved in the atmospheric nucleation processes remains controversial within the aerosol community. MALTE takes several hypothetical nucleation theories into account for the formation of secondary aerosols. To test the different hypothesis concerning atmospheric nucleation we used data from several field stations in Europe, USA, Africa and Australia. Furthermore, we investigated the role of certain organic vapours in the particle formation processes during intensive laboratory chamber experiments at NCAR - National Centre for Atmospheric Research in Boulder, Colorado, USA. Initial model simulations performed with the activation or kinetic nucleation mechanism predict nucleation rates that are strongly correlated with observed nucleation rates at background areas like boreal forest in Finland or somewhat more polluted areas east of Leipzig, Germany. In addition, many chamber experiments raise the possibility that organic vapours may form new particles by organic nucleation. Regarding the possibility that organic vapours can nucleate, as apparently observed in several chamber experiments, we estimated with MALTE that even with low SO2 concentrations, sufficient sulphuric acid is generated to explain observed particle number concentrations via the activation or kinetic nucleation mechanism alone. To investigate the possibility for nucleation of organic vapours we included in MALTE a parameterization developed by Bonn et al. (2008). Calculated nucleation rates with the organic nucleation code for data achieved during a field campaign in USA and the chamber experiments at NCAR showed high agreement with the measurements. It is currently not possible to draw a final conclusion if nucleation of organic vapours in the real atmosphere is present and if yes how important it is compared to other nucleation mechanisms.

Detailed observations of California foreshock sequences: Implications for the earthquake initiation process

USGS Publications Warehouse

Dodge, D.A.; Beroza, G.C.; Ellsworth, W.L.

1996-01-01

We find that foreshocks provide clear evidence for an extended nucleation process before some earthquakes. In this study, we examine in detail the evolution of six California foreshock sequences, the 1986 Mount Lewis (ML, = 5.5), the 1986 Chalfant (ML = 6.4), the. 1986 Stone Canyon (ML = 4.7), the 1990 Upland (ML = 5.2), the 1992 Joshua Tree (MW= 6.1), and the 1992 Landers (MW = 7.3) sequence. Typically, uncertainties in hypocentral parameters are too large to establish the geometry of foreshock sequences and hence to understand their evolution. However, the similarity of location and focal mechanisms for the events in these sequences leads to similar foreshock waveforms that we cross correlate to obtain extremely accurate relative locations. We use these results to identify small-scale fault zone structures that could influence nucleation and to determine the stress evolution leading up to the mainshock. In general, these foreshock sequences are not compatible with a cascading failure nucleation model in which the foreshocks all occur on a single fault plane and trigger the mainshock by static stress transfer. Instead, the foreshocks seem to concentrate near structural discontinuities in the fault and may themselves be a product of an aseismic nucleation process. Fault zone heterogeneity may also be important in controlling the number of foreshocks, i.e., the stronger the heterogeneity, the greater the number of foreshocks. The size of the nucleation region, as measured by the extent of the foreshock sequence, appears to scale with mainshock moment in the same manner as determined independently by measurements of the seismic nucleation phase. We also find evidence for slip localization as predicted by some models of earthquake nucleation. Copyright 1996 by the American Geophysical Union.

Bubble nucleation in simple and molecular liquids via the largest spherical cavity method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gonzalez, Miguel A., E-mail: m.gonzalez12@imperial.ac.uk; Department of Chemistry, Imperial College London, London SW7 2AZ; Abascal, José L. F.

2015-04-21

In this work, we propose a methodology to compute bubble nucleation free energy barriers using trajectories generated via molecular dynamics simulations. We follow the bubble nucleation process by means of a local order parameter, defined by the volume of the largest spherical cavity (LSC) formed in the nucleating trajectories. This order parameter simplifies considerably the monitoring of the nucleation events, as compared with the previous approaches which require ad hoc criteria to classify the atoms and molecules as liquid or vapor. The combination of the LSC and the mean first passage time technique can then be used to obtain themore » free energy curves. Upon computation of the cavity distribution function the nucleation rate and free-energy barrier can then be computed. We test our method against recent computations of bubble nucleation in simple liquids and water at negative pressures. We obtain free-energy barriers in good agreement with the previous works. The LSC method provides a versatile and computationally efficient route to estimate the volume of critical bubbles the nucleation rate and to compute bubble nucleation free-energies in both simple and molecular liquids.« less

Sulfur driven nucleation mode formation in diesel exhaust under transient driving conditions.

PubMed

Karjalainen, Panu; Rönkkö, Topi; Pirjola, Liisa; Heikkilä, Juha; Happonen, Matti; Arnold, Frank; Rothe, Dieter; Bielaczyc, Piotr; Keskinen, Jorma

2014-02-18

Sulfur driven diesel exhaust nucleation particle formation processes were studied in an aerosol laboratory, on engine dynamometers, and on the road. All test engines were equipped with a combination of a diesel oxidation catalyst (DOC) and a partial diesel particulate filter (pDPF). At steady operating conditions, the formation of semivolatile nucleation particles directly depended on SO2 conversion in the catalyst. The nucleation particle emission was most significant after a rapid increase in engine load and exhaust gas temperature. Results indicate that the nucleation particle formation at transient driving conditions does not require compounds such as hydrocarbons or sulfated hydrocarbons, however, it cannot be explained only by the nucleation of sulfuric acid. A real-world exhaust study with a heavy duty diesel truck showed that the nucleation particle formation occurs even with ultralow sulfur diesel fuel, even at downhill driving conditions, and that nucleation particles can contribute 60% of total particle number emissions. In general, due to sulfur storage and release within the exhaust aftertreatment systems and transients in driving, emissions of nucleation particles can even be the dominant part of modern diesel vehicle exhaust particulate number emissions.

A simple model for heterogeneous nucleation of isotactic polypropylene

NASA Astrophysics Data System (ADS)

Howard, Michael; Milner, Scott

2013-03-01

Flow-induced crystallization (FIC) is of interest because of its relevance to processes such as injection molding. It has been suggested that flow increases the homogeneous nucleation rate by reducing the melt state entropy. However, commercial polypropylene (iPP) exhibits quiescent nucleation rates that are much too high to be consistent with homogeneous nucleation in carefully purified samples. This suggests that heterogeneous nucleation is dominant for typical samples used in FIC experiments. We describe a simple model for heterogeneous nucleation of iPP, in terms of a cylindrical nucleus on a flat surface with the critical size and barrier set by the contact angle. Analysis of quiescent crystallization data with this model gives reasonable values for the contact angle. We have also employed atomistic simulations of iPP crystals to determine surface energies with vacuum and with Hamaker-matched substrates, and find values consistent with the contact angles inferred from heterogeneous nucleation experiments. In future work, these results combined with calculations from melt rheology of entropy reduction due to flow can be used to estimate the heterogeneous nucleation barrier reduction due to flow, and hence the increase in nucleation rate due to FIC for commecial iPP.

Interpreting activity in H(2)O-H(2)SO(4) binary nucleation.

PubMed

Bein, Keith J; Wexler, Anthony S

2007-09-28

Sulfuric acid-water nucleation is thought to be a key atmospheric mechanism for forming new condensation nuclei. In earlier literature, measurements of sulfuric acid activity were interpreted as the total (monomer plus hydrate) concentration above solution. Due to recent reinterpretations, most literature values for H(2)SO(4) activity are thought to represent the number density of monomers. Based on this reinterpretation, the current work uses the most recent models of H(2)O-H(2)SO(4) binary nucleation along with perturbation analyses to predict a decrease in critical cluster mole fraction, increase in critical cluster diameter, and orders of magnitude decrease in nucleation rate. Nucleation rate parameterizations available in the literature, however, give opposite trends. To resolve these discrepancies, nucleation rates were calculated for both interpretations of H(2)SO(4) activity and directly compared to the available parameterizations as well as the perturbation analysis. Results were in excellent agreement with older parameterizations that assumed H(2)SO(4) activity represents the total concentration and duplicated the predicted trends from the perturbation analysis, but differed by orders of magnitude from more recent parameterizations that assume H(2)SO(4) activity represents only the monomer. Comparison with experimental measurements available in the literature revealed that the calculations of the current work assuming a(a) represents the total concentration are most frequently in agreement with observations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhukhovitskii, D. I., E-mail: dmr@ihed.ras.ru

The vapor–liquid nucleation in a dense Lennard-Jones system is studied analytically and numerically. A solution of the nucleation kinetic equations, which includes the elementary processes of condensation/evaporation involving the lightest clusters, is obtained, and the nucleation rate is calculated. Based on the equation of state for the cluster vapor, the pre-exponential factor is obtained. The latter diverges as a spinodal is reached, which results in the nucleation enhancement. The work of critical cluster formation is calculated using the previously developed two-parameter model (TPM) of small clusters. A simple expression for the nucleation rate is deduced and it is shown thatmore » the work of cluster formation is reduced for a dense vapor. This results in the nucleation enhancement as well. To verify the TPM, a simulation is performed that mimics a steady-state nucleation experiments in the thermal diffusion cloud chamber. The nucleating vapor with and without a carrier gas is simulated using two different thermostats for the monomers and clusters. The TPM proves to match the simulation results of this work and of other studies.« less

The effect of solute on the homogeneous crystal nucleation frequency in metallic melts

NASA Technical Reports Server (NTRS)

Thompson, C. V.; Spaepen, F.

1982-01-01

A complete calculation that extends the classical theory for crystal nucleation in pure melts to binary alloys has been made. Using a regular solution model, approximate expressions have been developed for the free energy change upon crystallization as a function of solute concentration. They are used, together with model-based estimates of the interfacial tension, to calculate the nucleation frequency. The predictions of the theory for the maximum attainable undercooling are compared with existing experimental results for non-glass forming alloys. The theory is also applied to several easy glass-forming alloys (Pd-Si, Au-Si, Fe-B) for qualitative comparison with the present experimental experience on the ease of glass formation, and for assessment of the potential for formation of the glass in bulk.

A Discrete Fracture Network Model with Stress-Driven Nucleation and Growth

NASA Astrophysics Data System (ADS)

Lavoine, E.; Darcel, C.; Munier, R.; Davy, P.

2017-12-01

The realism of Discrete Fracture Network (DFN) models, beyond the bulk statistical properties, relies on the spatial organization of fractures, which is not issued by purely stochastic DFN models. The realism can be improved by injecting prior information in DFN from a better knowledge of the geological fracturing processes. We first develop a model using simple kinematic rules for mimicking the growth of fractures from nucleation to arrest, in order to evaluate the consequences of the DFN structure on the network connectivity and flow properties. The model generates fracture networks with power-law scaling distributions and a percentage of T-intersections that are consistent with field observations. Nevertheless, a larger complexity relying on the spatial variability of natural fractures positions cannot be explained by the random nucleation process. We propose to introduce a stress-driven nucleation in the timewise process of this kinematic model to study the correlations between nucleation, growth and existing fracture patterns. The method uses the stress field generated by existing fractures and remote stress as an input for a Monte-Carlo sampling of nuclei centers at each time step. Networks so generated are found to have correlations over a large range of scales, with a correlation dimension that varies with time and with the function that relates the nucleation probability to stress. A sensibility analysis of input parameters has been performed in 3D to quantify the influence of fractures and remote stress field orientations.

Elucidating Key Motifs Required for Arp2/3-Dependent and Independent Actin Nucleation by Las17/WASP

PubMed Central

Urbanek, Agnieszka N.; Smaczynska-de Rooij, Iwona I.

2016-01-01

Actin nucleation is the key rate limiting step in the process of actin polymerization, and tight regulation of this process is critical to ensure actin filaments form only at specific times and at defined regions of the cell. Arp2/3 is a well-characterised protein complex that can promote nucleation of new filaments, though its activity requires additional nucleation promotion factors (NPFs). The best recognized of these factors are the WASP family of proteins that contain binding motifs for both monomeric actin and for Arp2/3. Previously we demonstrated that the yeast WASP homologue, Las17, in addition to activating Arp2/3 can also nucleate actin filaments de novo, independently of Arp2/3. This activity is dependent on its polyproline rich region. Through biochemical and in vivo analysis we have now identified key motifs within the polyproline region that are required for nucleation and elongation of actin filaments, and have addressed the role of the WH2 domain in the context of actin nucleation without Arp2/3. We have also demonstrated that full length Las17 is able to bind liposomes giving rise to the possibility of direct linkage of nascent actin filaments to specific membrane sites to which Las17 has been recruited. Overall, we propose that Las17 functions as the key initiator of de novo actin filament formation at endocytic sites by nucleating, elongating and tethering nascent filaments which then serve as a platform for Arp2/3 recruitment and function. PMID:27637067

Monomer-dependent secondary nucleation in amyloid formation.

PubMed

Linse, Sara

2017-08-01

Secondary nucleation of monomers on the surface of an already existing aggregate that is formed from the same kind of monomers may lead to autocatalytic amplification of a self-assembly process. Such monomer-dependent secondary nucleation occurs during the crystallization of small molecules or proteins and self-assembled materials, as well as in protein self-assembly into fibrous structures. Indications of secondary nucleation may come from analyses of kinetic experiments starting from pure monomers or monomers supplemented with a low concentration of pre-formed aggregates (seeds). More firm evidence requires additional experiments, for example those employing isotope labels to distinguish new aggregates arising from the monomer from those resulting from fragmentation of the seed. In cases of amyloid formation, secondary nucleation leads to the formation of toxic oligomers, and inhibitors of secondary nucleation may serve as starting points for therapeutic developments. Secondary nucleation displays a high degree of structural specificity and may be enhanced by mutations or screening of electrostatic repulsion.

Homogeneous crystal nucleation in Ni droplets

NASA Astrophysics Data System (ADS)

Kožíšek, Zdeněk; Demo, Pavel

2017-10-01

Crystal nucleation kinetics is often represented by induction times or metastable zone widths (Kulkarni et al., 2013; Bokeloh et al., 2011). Repeating measurements of supercooling or time delay, at which phase transition is detected, are statistically processed to determine the so-called survivorship function, from which nucleation rate is computed. The size distribution of nuclei is difficult to measure near the critical size directly, and it is not clear which amount of nuclei is formed at the moment when the phase transition is detected. In the present paper, kinetic nucleation equations are solved for the crystal nucleation in Ni liquid droplet to determine the number of nuclei formed within a considered system. Analysis of supercooling experimental data, based on the classical nucleation theory CNT), computes appropriate values of the nucleation rate. However, CNT underestimates the number of nuclei F (F ≪ 1 for supercritical sizes). Taking into account the dependence of the surface energy on nucleus size to data analysis overcomes this discrepancy and leads to reasonable values of the size distribution of nuclei.

Influence of the supersaturation on the nucleation-growth process of scale electrodeposition by in situ observation through a transparent quartz crystal microbalance.

PubMed

Devos, O; Gabrielli, C; Tribollet, B

2004-01-01

An original technique allowed three in situ measurements to be obtained simultaneously, i.e. electrochemical and mass measurements and a microscope image of the interface between electrode and solution. The nucleation-growth process of CaCO3 deposition was investigated by varying different parameters which influenced the supersaturation coefficient, the Ca2+ concentration, pH and convection of the carbonically pure water near the substrate. The results showed that the variation of the scaling rate was due, for the two first cases, to an influence of the nucleation process whereas for the last case, the kinetics of scale deposition were modified by a shift of the growth rate.

FORMULATION OF NON-STEADY-STATE DUST FORMATION PROCESS IN ASTROPHYSICAL ENVIRONMENTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nozawa, Takaya; Kozasa, Takashi, E-mail: takaya.nozawa@ipmu.jp

2013-10-10

The non-steady-state formation of small clusters and the growth of grains accompanied by chemical reactions are formulated under the consideration that the collision of key gas species (key molecule) controls the kinetics of dust formation process. The formula allows us to evaluate the size distribution and condensation efficiency of dust formed in astrophysical environments. We apply the formulation to the formation of C and MgSiO{sub 3} grains in the ejecta of supernovae, as an example, to investigate how the non-steady effect influences the formation process, condensation efficiency f{sub con,{sub ∞}}, and average radius a{sub ave,{sub ∞}} of newly formed grainsmore » in comparison with the results calculated with the steady-state nucleation rate. We show that the steady-state nucleation rate is a good approximation if the collision timescale of key molecule τ{sub coll} is much smaller than the timescale τ{sub sat} with which the supersaturation ratio increases; otherwise the effect of the non-steady state becomes remarkable, leading to a lower f{sub con,{sub ∞}} and a larger a{sub ave,{sub ∞}}. Examining the results of calculations, we reveal that the steady-state nucleation rate is applicable if the cooling gas satisfies Λ ≡ τ{sub sat}/τ{sub coll} ∼> 30 during the formation of dust, and find that f{sub con,{sub ∞}} and a{sub ave,{sub ∞}} are uniquely determined by Λ{sub on} at the onset time t{sub on} of dust formation. The approximation formulae for f{sub con,{sub ∞}} and a{sub ave,{sub ∞}} as a function of Λ{sub on} could be useful in estimating the mass and typical size of newly formed grains from observed or model-predicted physical properties not only in supernova ejecta but also in mass-loss winds from evolved stars.« less

Why are some Interfaces in Materials Stronger than others?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fensin, Saryu J.; Cerreta, Ellen K.; Gray, George T.

2014-06-26

Grain boundaries (GBs) are often the preferred sites for void nucleation in ductile metals. However, it has been observed that all boundaries do not contribute equally to this process. We present a mechanistic rationale for the role of GBs in damage nucleation in copper, along with a quantitative map for predicting preferred void nucleation at GBs based on molecular dynamics simulations in copper. Simulations show a direct correlation between the void nucleation stress and the ability of a grain boundary to plastically deform by emitting dislocations, during shock compression. Plastic response of a GB, affects the development of stress concentrationsmore » believed to be responsible for void nucleation by acting as a dissipation mechanism for the applied stress.« less

Surface nucleation in complex rheological systems

NASA Astrophysics Data System (ADS)

Herfurth, J.; Ulrich, J.

2017-07-01

Forced nucleation induced by suitable foreign seeds is an important tool to control the production of defined crystalline products. The quality of a surface provided by seed materials represents an important variable in the production of crystallizing layers that means for the nucleation process. Parameters like shape and surface structure, size and size distribution of the seed particles as well as the ability to hold up the moisture (the solvent), can have an influence on the nucleation process of different viscous supersaturated solutions. Here the properties of different starch powders as seeds obtained from corn, potato, rice, tapioca and wheat were tested. It could be found, that the best nucleation behavior of a sugar solution could be reached with the use of corn starch as seed material. Here the surface of the crystallized sugar layer is smooth, crystallization time is short (<3 h) and the shape of the product is easily reproducible. Beneficial properties of seed materials are therefore an edged, uneven surface, small particle sizes as well as low moisture content at ambient conditions within the seed materials.

Optical nucleation of bubble clouds in a high pressure spherical resonator.

PubMed

Anderson, Phillip; Sampathkumar, A; Murray, Todd W; Gaitan, D Felipe; Glynn Holt, R

2011-11-01

An experimental setup for nucleating clouds of bubbles in a high-pressure spherical resonator is described. Using nanosecond laser pulses and multiple phase gratings, bubble clouds are optically nucleated in an acoustic field. Dynamics of the clouds are captured using a high-speed CCD camera. The images reveal cloud nucleation, growth, and collapse and the resulting emission of radially expanding shockwaves. These shockwaves are reflected at the interior surface of the resonator and then reconverge to the center of the resonator. As the shocks reconverge upon the center of the resonator, they renucleate and grow the bubble cloud. This process is repeated over many acoustic cycles and with each successive shock reconvergence, the bubble cloud becomes more organized and centralized so that subsequent collapses give rise to stronger, better defined shockwaves. After many acoustic cycles individual bubbles cannot be distinguished and the cloud is then referred to as a cluster. Sustainability of the process is ultimately limited by the detuning of the acoustic field inside the resonator. The nucleation parameter space is studied in terms of laser firing phase, laser energy, and acoustic power used.

Time-Resolved In Situ Liquid-Phase Atomic Force Microscopy and Infrared Nanospectroscopy during the Formation of Metal-Organic Framework Thin Films.

PubMed

Mandemaker, Laurens D B; Filez, Matthias; Delen, Guusje; Tan, Huanshu; Zhang, Xuehua; Lohse, Detlef; Weckhuysen, Bert M

2018-04-19

Metal-organic framework (MOF) thin films show unmatched promise as smart membranes and photocatalytic coatings. However, their nucleation and growth resulting from intricate molecular assembly processes are not well understood yet are crucial to control the thin film properties. Here, we directly observe the nucleation and growth behavior of HKUST-1 thin films by real-time in situ AFM at different temperatures in a Cu-BTC solution. In combination with ex situ infrared (nano)spectroscopy, synthesis at 25 °C reveals initial nucleation of rapidly growing HKUST-1 islands surrounded by a continuously nucleating but slowly growing HKUST-1 carpet. Monitoring at 13 and 50 °C shows the strong impact of temperature on thin film formation, resulting in (partial) nucleation and growth inhibition. The nucleation and growth mechanisms as well as their kinetics provide insights to aid in future rational design of MOF thin films.

Dynamic Light Scattering Analysis of the Effect of Phosphorylated Osteopontin Peptides on Mineral Formation

NASA Astrophysics Data System (ADS)

Mozaffari, Maryam; Goiko, Maria; de Bruyn, John; Goldberg, Harvey

2015-03-01

Biomineralization is the process by which living organisms synthesize minerals. Osteopontin (OPN), a mineral-associated protein, has been shown to be a potent inhibitor of mineral formation, a process that is dependent on phosphorylation. To gain a better understanding of the mechanism of inhibition, dynamic light scattering (DLS) was used to monitor the initial stages of nucleation, providing information about the size and relative concentration of the growing crystals as a function of time. DLS was used to investigate the effect of phosphorylated (P3, pOPAR) and non-phosphorylated (P0, OPAR) OPN peptides on the formation and growth of hydroxyapatite (HA) crystals from supersaturated solutions of calcium and phosphate ions. The non-phosphorylated P0 had a limited effect on HA nucleation and growth, while its thrice-phosphorylated isoform, P3, was a potent inhibitor of HA nucleation. The aspartic acid-rich OPAR was found to moderately inhibit nucleation but not growth, while its singly-phosphorylated isoform, pOPAR, inhibited HA nucleation more effectively, with some effect on HA crystal growth. The order of the inhibitory potential of these peptides was pOPAR>OPAR>P3>P0. This work confirms that highly acidic and phosphorylated peptides can inhibit the nucleation of HA more effectively.

Atmospheric aging of dust ice nucleating particles - a combined laboratory and field approach

NASA Astrophysics Data System (ADS)

Boose, Yvonne; Rodríguez, Sergio; García, M. Isabel; Linke, Claudia; Schnaiter, Martin; Zipori, Assaf; Crawford, Ian; Lohmann, Ulrike; Kanji, Zamin A.; Sierau, Berko

2016-04-01

We present INP data measured in-situ at two mostly free tropospheric locations: the High Altitude Research Station Jungfraujoch (JFJ) in the Swiss Alps, located at 3580 m above sea level (asl) and the Izaña observatory on Tenerife, off the West African shore (2373 m asl). INP concentrations were measured online with the Portable Ice Nucleation Chamber, PINC, at the Jungfraujoch in the winters of 2012, 2013 and 2014 and at Izaña in the summers of 2013 and 2014. Each measurement period lasted between 2 to 6 weeks. During summer, Izaña is frequently within the Saharan Air Layer and thus often exposed to Saharan dust events. Saharan dust also reaches the Jungfraujoch mainly during spring. For offline ice nucleation analysis in the laboratory under similar thermodynamic conditions, airborne dust was collected a) at Izaña with a cyclone directly from the air and b) collected from the surface of the Aletsch glacier close to the JFJ after deposition. Supporting measurements of aerosol particle size distributions and fluorescence were conducted at both locations, as well as cloud water isotope analysis at the Jungfraujoch and aerosol chemistry at Izaña. For both locations the origin of the INPs was investigated with a focus on dust and biological particles using back trajectories and chemical signature. Results show that dust aerosol is the dominant INP type at both locations at a temperature of 241 K. In addition to Saharan dust, also more local, basaltic dust is found at the Jungfraujoch. Biological particles are not observed to play a role for ice nucleation in clouds during winter at Jungfraujoch but are enriched in INP compared to the total aerosol at Izaña also during dust events. The comparison of the laboratory and the field measurements at Izaña indicates a good reproducibility of the field data by the collected dust samples. Field and laboratory data of the dust samples from both locations show that the dust arriving at JFJ is less ice nucleation active than the rather fresh dust at Izaña. This suggests that atmospheric aging and processing decreases the ice nucleation efficiency of Saharan dust during advection to Central Europe.

A novel optical freezing array for the examination of cooling rate dependence in heterogeneous ice nucleation

NASA Astrophysics Data System (ADS)

Budke, Carsten; Dreischmeier, Katharina; Koop, Thomas

2014-05-01

Homogeneous ice nucleation is a stochastic process, implying that it is not only temperature but also time dependent. For heterogeneous ice nucleation it is still under debate whether there is a significant time dependence or not. In case of minor time dependence it is probably sufficient to use a singular or slightly modified singular approach, which mainly supposes temperature dependence and just small stochastic variations. We contribute to this discussion using a novel optical freezing array termed BINARY (Bielefeld Ice Nucleation ARraY). The setup consists of an array of microliter-sized droplets on a Peltier cooling stage. The droplets are separated from each other with a polydimethylsiloxane (PDMS) spacer to prevent a Bergeron-Findeisen process, in which the first freezing droplets grow at the expense of the remaining liquid ones due to their vapor pressure differences. An automatic detection of nucleation events is realized optically by the change in brightness during freezing. Different types of ice nucleating agents were tested with the presented setup, e. g. pollen and clay mineral dust. Exemplarily, cooling rate dependent measurements are shown for the heterogeneous ice nucleation induced by Snomax®. The authors gratefully acknowledge funding by the German Research Foundation (DFG) through the project BIOCLOUDS (KO 2944/1-1) and through the research unit INUIT (FOR 1525) under KO 2944/2-1. We particularly thank our INUIT partners for fruitful collaboration and sharing of ideas and IN samples.

Biological ice nucleation initiates hailstone formation

NASA Astrophysics Data System (ADS)

Michaud, Alexander B.; Dore, John E.; Leslie, Deborah; Lyons, W. Berry; Sands, David C.; Priscu, John C.

2014-11-01

Cloud condensation and ice nuclei in the troposphere are required precursors to cloud and precipitation formation, both of which influence the radiative balance of Earth. The initial stage of hailstone formation (i.e., the embryo) and the subsequent layered growth allow hail to be used as a model for the study of nucleation processes in precipitation. By virtue of the preserved particle and isotopic record captured by hailstones, they represent a unique form of precipitation that allows direct characterization of the particles present during atmospheric ice nucleation. Despite the ecological and economic consequences of hail storms, the dynamics of hailstone nucleation, and thus their formation, are not well understood. Our experiments show that hailstone embryos from three Rocky Mountain storms contained biological ice nuclei capable of freezing water at warm, subzero (°C) temperatures, indicating that biological particles can act as nucleation sites for hailstone formation. These results are corroborated by analysis of δD and δ18O from melted hailstone embryos, which show that the hailstones formed at similarly warm temperatures in situ. Low densities of ice nucleation active abiotic particles were also present in hailstone embryos, but their low concentration indicates they were not likely to have catalyzed ice formation at the warm temperatures determined from water stable isotope analysis. Our study provides new data on ice nucleation occurring at the bottom of clouds, an atmospheric region whose processes are critical to global climate models but which has challenged instrument-based measurements.

A review of phosphate mineral nucleation in biology and geobiology.

PubMed

Omelon, Sidney; Ariganello, Marianne; Bonucci, Ermanno; Grynpas, Marc; Nanci, Antonio

2013-10-01

Relationships between geological phosphorite deposition and biological apatite nucleation have often been overlooked. However, similarities in biological apatite and phosphorite mineralogy suggest that their chemical formation mechanisms may be similar. This review serves to draw parallels between two newly described phosphorite mineralization processes, and proposes a similar novel mechanism for biologically controlled apatite mineral nucleation. This mechanism integrates polyphosphate biochemistry with crystal nucleation theory. Recently, the roles of polyphosphates in the nucleation of marine phosphorites were discovered. Marine bacteria and diatoms have been shown to store and concentrate inorganic phosphate (Pi) as amorphous, polyphosphate granules. Subsequent release of these P reserves into the local marine environment as Pi results in biologically induced phosphorite nucleation. Pi storage and release through an intracellular polyphosphate intermediate may also occur in mineralizing oral bacteria. Polyphosphates may be associated with biologically controlled apatite nucleation within vertebrates and invertebrates. Historically, biological apatite nucleation has been attributed to either a biochemical increase in local Pi concentration or matrix-mediated apatite nucleation control. This review proposes a mechanism that integrates both theories. Intracellular and extracellular amorphous granules, rich in both calcium and phosphorus, have been observed in apatite-biomineralizing vertebrates, protists, and atremate brachiopods. These granules may represent stores of calcium-polyphosphate. Not unlike phosphorite nucleation by bacteria and diatoms, polyphosphate depolymerization to Pi would be controlled by phosphatase activity. Enzymatic polyphosphate depolymerization would increase apatite saturation to the level required for mineral nucleation, while matrix proteins would simultaneously control the progression of new biological apatite formation.

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.

TONNEAU2/FASS Regulates the Geometry of Microtubule Nucleation and Cortical Array Organization in Interphase Arabidopsis Cells[C][W

PubMed Central

Kirik, Angela; Ehrhardt, David W.; Kirik, Viktor

2012-01-01

Organization of microtubules into ordered arrays involves spatial and temporal regulation of microtubule nucleation. Here, we show that acentrosomal microtubule nucleation in plant cells involves a previously unknown regulatory step that determines the geometry of microtubule nucleation. Dynamic imaging of interphase cortical microtubules revealed that the ratio of branching to in-bundle microtubule nucleation on cortical microtubules is regulated by the Arabidopsis thaliana B′′ subunit of protein phosphatase 2A, which is encoded by the TONNEAU2/FASS (TON2) gene. The probability of nucleation from γ-tubulin complexes localized at the cell cortex was not affected by a loss of TON2 function, suggesting a specific role of TON2 in regulating the nucleation geometry. Both loss of TON2 function and ectopic targeting of TON2 to the plasma membrane resulted in defects in cell shape, suggesting the importance of TON2-mediated regulation of the microtubule cytoskeleton in cell morphogenesis. Loss of TON2 function also resulted in an inability for cortical arrays to reorient in response to light stimulus, suggesting an essential role for TON2 and microtubule branching nucleation in reorganization of microtubule arrays. Our data establish TON2 as a regulator of interphase microtubule nucleation and provide experimental evidence for a novel regulatory step in the process of microtubule-dependent nucleation. PMID:22395485

Stochastic kinetics reveal imperative role of anisotropic interfacial tension to determine morphology and evolution of nucleated droplets in nematogenic films

NASA Astrophysics Data System (ADS)

Bhattacharjee, Amit Kumar

2017-01-01

For isotropic fluids, classical nucleation theory predicts the nucleation rate, barrier height and critical droplet size by ac- counting for the competition between bulk energy and interfacial tension. The nucleation process in liquid crystals is less understood. We numerically investigate nucleation in monolayered nematogenic films using a mesoscopic framework, in par- ticular, we study the morphology and kinetic pathway in spontaneous formation and growth of droplets of the stable phase in the metastable background. The parameter κ that quantifies the anisotropic elastic energy plays a central role in determining the geometric structure of the droplets. Noncircular nematic droplets with homogeneous director orientation are nucleated in a background of supercooled isotropic phase for small κ. For large κ, noncircular droplets with integer topological charge, accompanied by a biaxial ring at the outer surface, are nucleated. The isotropic droplet shape in a superheated nematic background is found to depend on κ in a similar way. Identical growth laws are found in the two cases, although an unusual two-stage mechanism is observed in the nucleation of isotropic droplets. Temporal distributions of successive events indi- cate the relevance of long-ranged elasticity-mediated interactions within the isotropic domains. Implications for a theoretical description of nucleation in anisotropic fluids are discussed.

Simple improvements to classical bubble nucleation models.

PubMed

Tanaka, Kyoko K; Tanaka, Hidekazu; Angélil, Raymond; Diemand, Jürg

2015-08-01

We revisit classical nucleation theory (CNT) for the homogeneous bubble nucleation rate and improve the classical formula using a correct prefactor in the nucleation rate. Most of the previous theoretical studies have used the constant prefactor determined by the bubble growth due to the evaporation process from the bubble surface. However, the growth of bubbles is also regulated by the thermal conduction, the viscosity, and the inertia of liquid motion. These effects can decrease the prefactor significantly, especially when the liquid pressure is much smaller than the equilibrium one. The deviation in the nucleation rate between the improved formula and the CNT can be as large as several orders of magnitude. Our improved, accurate prefactor and recent advances in molecular dynamics simulations and laboratory experiments for argon bubble nucleation enable us to precisely constrain the free energy barrier for bubble nucleation. Assuming the correction to the CNT free energy is of the functional form suggested by Tolman, the precise evaluations of the free energy barriers suggest the Tolman length is ≃0.3σ independently of the temperature for argon bubble nucleation, where σ is the unit length of the Lennard-Jones potential. With this Tolman correction and our prefactor one gets accurate bubble nucleation rate predictions in the parameter range probed by current experiments and molecular dynamics simulations.

Protein Polymerization into Fibrils from the Viewpoint of Nucleation Theory.

PubMed

Kashchiev, Dimo

2015-11-17

The assembly of various proteins into fibrillar aggregates is an important phenomenon with wide implications ranging from human disease to nanoscience. Using general kinetic results of nucleation theory, we analyze the polymerization of protein into linear or helical fibrils in the framework of the Oosawa-Kasai (OK) model. We show that while within the original OK model of linear polymerization the process does not involve nucleation, within a modified OK model it is nucleation-mediated. Expressions are derived for the size of the fibril nucleus, the work for fibril formation, the nucleation barrier, the equilibrium and stationary fibril size distributions, and the stationary fibril nucleation rate. Under otherwise equal conditions, this rate decreases considerably when the short (subnucleus) fibrils lose monomers much more frequently than the long (supernucleus) fibrils, a feature that should be born in mind when designing a strategy for stymying or stimulating fibril nucleation. The obtained dependence of the nucleation rate on the concentration of monomeric protein is convenient for experimental verification and for use in rate equations accounting for nucleation-mediated fibril formation. The analysis and the results obtained for linear fibrils are fully applicable to helical fibrils whose formation is describable by a simplified OK model. Copyright © 2015 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Dynamics of protein aggregation and oligomer formation governed by secondary nucleation

NASA Astrophysics Data System (ADS)

Michaels, Thomas C. T.; Lazell, Hamish W.; Arosio, Paolo; Knowles, Tuomas P. J.

2015-08-01

The formation of aggregates in many protein systems can be significantly accelerated by secondary nucleation, a process where existing assemblies catalyse the nucleation of new species. In particular, secondary nucleation has emerged as a central process controlling the proliferation of many filamentous protein structures, including molecular species related to diseases such as sickle cell anemia and a range of neurodegenerative conditions. Increasing evidence suggests that the physical size of protein filaments plays a key role in determining their potential for deleterious interactions with living cells, with smaller aggregates of misfolded proteins, oligomers, being particularly toxic. It is thus crucial to progress towards an understanding of the factors that control the sizes of protein aggregates. However, the influence of secondary nucleation on the time evolution of aggregate size distributions has been challenging to quantify. This difficulty originates in large part from the fact that secondary nucleation couples the dynamics of species distant in size space. Here, we approach this problem by presenting an analytical treatment of the master equation describing the growth kinetics of linear protein structures proliferating through secondary nucleation and provide closed-form expressions for the temporal evolution of the resulting aggregate size distribution. We show how the availability of analytical solutions for the full filament distribution allows us to identify the key physical parameters that control the sizes of growing protein filaments. Furthermore, we use these results to probe the dynamics of the populations of small oligomeric species as they are formed through secondary nucleation and discuss the implications of our work for understanding the factors that promote or curtail the production of these species with a potentially high deleterious biological activity.

Dynamics of protein aggregation and oligomer formation governed by secondary nucleation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michaels, Thomas C. T., E-mail: tctm3@cam.ac.uk; Lazell, Hamish W.; Arosio, Paolo

2015-08-07

The formation of aggregates in many protein systems can be significantly accelerated by secondary nucleation, a process where existing assemblies catalyse the nucleation of new species. In particular, secondary nucleation has emerged as a central process controlling the proliferation of many filamentous protein structures, including molecular species related to diseases such as sickle cell anemia and a range of neurodegenerative conditions. Increasing evidence suggests that the physical size of protein filaments plays a key role in determining their potential for deleterious interactions with living cells, with smaller aggregates of misfolded proteins, oligomers, being particularly toxic. It is thus crucial tomore » progress towards an understanding of the factors that control the sizes of protein aggregates. However, the influence of secondary nucleation on the time evolution of aggregate size distributions has been challenging to quantify. This difficulty originates in large part from the fact that secondary nucleation couples the dynamics of species distant in size space. Here, we approach this problem by presenting an analytical treatment of the master equation describing the growth kinetics of linear protein structures proliferating through secondary nucleation and provide closed-form expressions for the temporal evolution of the resulting aggregate size distribution. We show how the availability of analytical solutions for the full filament distribution allows us to identify the key physical parameters that control the sizes of growing protein filaments. Furthermore, we use these results to probe the dynamics of the populations of small oligomeric species as they are formed through secondary nucleation and discuss the implications of our work for understanding the factors that promote or curtail the production of these species with a potentially high deleterious biological activity.« less

Nucleation of ordered solid phases of proteins via a disordered high-density state: Phenomenological approach

NASA Astrophysics Data System (ADS)

Pan, Weichun; Kolomeisky, Anatoly B.; Vekilov, Peter G.

2005-05-01

Nucleation of ordered solid phases of proteins triggers numerous phenomena in laboratory, industry, and in healthy and sick organisms. Recent simulations and experiments with protein crystals suggest that the formation of an ordered crystalline nucleus is preceded by a disordered high-density cluster, akin to a droplet of high-density liquid that has been observed with some proteins; this mechanism allowed a qualitative explanation of recorded complex nucleation kinetics curves. Here, we present a simple phenomenological theory that takes into account intermediate high-density metastable states in the nucleation process. Nucleation rate data at varying temperature and protein concentration are reproduced with high fidelity using literature values of the thermodynamic and kinetic parameters of the system. Our calculations show that the growth rate of the near-critical and supercritical ordered clusters within the dense intermediate is a major factor for the overall nucleation rate. This highlights the role of viscosity within the dense intermediate for the formation of the ordered nucleus. The model provides an understanding of the action of additives that delay or accelerate nucleation and presents a framework within which the nucleation of other ordered protein solid phases, e.g., the sickle cell hemoglobin polymers, can be analyzed.

Nucleation and hysteresis of vapor-liquid phase transitions in confined spaces: effects of fluid-wall interaction.

PubMed

Men, Yumei; Yan, Qingzhao; Jiang, Guangfeng; Zhang, Xianren; Wang, Wenchuan

2009-05-01

In this work, we propose a method to stabilize a nucleus in the framework of lattice density-functional theory (LDFT) by imposing a suitable constraint. Using this method, the shape of critical nucleus and height of the nucleation barrier can be determined without using a predefined nucleus as input. As an application of this method, we study the nucleation behavior of vapor-liquid transition in nanosquare pores with infinite length and relate the observed hysteresis loop on an adsorption isotherm to the nucleation mechanism. According to the dependence of hysteresis and the nucleation mechanism on the fluid-wall interaction, w , in this work, we have classified w into three regions ( w>0.9 , 0.1< or =w< or =0.9 , and w<0.1 ), which are denoted as strongly, moderately, and weakly attractive fluid-wall interaction, respectively. The dependence of hysteresis on the fluid-wall interaction is interpreted by the different nucleation mechanisms. Our constrained LDFT calculations also show that the different transition paths may induce different nucleation behaviors. The transition path dependence should be considered if morphological transition of nuclei exists during a nucleation process.

Partitioning the primary ice formation modes in large eddy simulations of mixed-phase clouds

NASA Astrophysics Data System (ADS)

Hande, Luke B.; Hoose, Corinna

2017-11-01

State-of-the-art aerosol-dependent parameterisations describing each heterogeneous ice nucleation mode (contact, immersion, and deposition ice nucleation), as well as homogeneous nucleation, were incorporated into a large eddy simulation model. Several cases representing commonly occurring cloud types were simulated in an effort to understand which ice nucleation modes contribute the most to total concentrations of ice crystals. The cases include a completely idealised warm bubble, semi-idealised deep convection, an orographic cloud, and a stratiform case. Despite clear differences in thermodynamic conditions between the cases, the results are remarkably consistent between the different cloud types. In all the investigated cloud types and under normal aerosol conditions, immersion freezing dominates and contact freezing also contributes significantly. At colder temperatures, deposition nucleation plays only a small role, and homogeneous freezing is important. To some extent, the temporal evolution of the cloud determines the dominant freezing mechanism and hence the subsequent microphysical processes. Precipitation is not correlated with any one ice nucleation mode, instead occurring simultaneously when several nucleation modes are active. Furthermore, large variations in the aerosol concentration do affect the dominant ice nucleation mode; however, they have only a minor influence on the precipitation amount.

Adsorption of dysprosium on the graphite (0001) surface: Nucleation and growth at 300 K

DOE PAGES

Kwolek, Emma J.; Lei, Huaping; Lii-Rosales, Ann; ...

2016-06-13

We have studied nucleation and growth of Dy islands on the basal plane of graphite at 300 K using scanning tunneling microscopy, density functional theory (DFT) in a form that includes van der Waals interactions, and analytic theory. The interaction of atomic Dy with graphite is strong, while the diffusion barrier is small. Experiment shows that at 300 K, the density of nucleated islands is close to the value predicted for homogeneous nucleation, using critical nucleus size of 1 and the DFT-derived diffusion barrier. Homogeneous nucleation is also supported by the monomodal shape of the island size distributions. Comparison withmore » the published island density of Dy on graphene shows that the value is about two orders of magnitude smaller on graphite, which can be attributed to more effective charge screening in graphite. The base of each island is 3 atomic layers high and atomically ordered, forming a coincidence lattice with the graphite. Islands resist coalescence, probably due to multiple rotational orientations associated with the coincidence lattice. Upper levels grow as discernible single-atom layers. Analysis of the level populations reveals significant downward interlayer transport, which facilitates growth of the base. As a result, this island shape is metastable, since more compact three-dimensional islands form at elevated growth temperature.« less

Molecular dynamics simulation study of the early stages of nucleation of iron oxyhydroxide nanoparticles in aqueous solutions

DOE PAGES

Zhang, Hengzhong; Waychunas, Glenn A.; Banfield, Jillian F.

2015-07-29

Nucleation is a fundamental step in crystal growth. Of environmental and materials relevance are reactions that lead to nucleation of iron oxyhydroxides in aqueous solutions. These reactions are difficult to study experimentally due to their rapid kinetics. Here, we used classical molecular dynamics simulations to investigate nucleation of iron hydroxide/oxyhydroxide nanoparticles in aqueous solutions. Results show that in a solution containing ferric ions and hydroxyl groups, iron–hydroxyl molecular clusters form by merging ferric monomers, dimers, and other oligomers, driven by strong affinity of ferric ions to hydroxyls. When deprotonation reactions are not considered in the simulations, these clusters aggregate tomore » form small iron hydroxide nanocrystals with a six-membered ring-like layered structure allomeric to gibbsite. By comparison, in a solution containing iron chloride and sodium hydroxide, the presence of chlorine drives cluster assembly along a different direction to form long molecular chains (rather than rings) composed of Fe–O octahedra linked by edge sharing. Further, in chlorine-free solutions, when deprotonation reactions are considered, the simulations predict ultimate formation of amorphous iron oxyhydroxide nanoparticles with local atomic structure similar to that of ferrihydrite nanoparticles. Overall, our simulation results reveal that nucleation of iron oxyhydroxide nanoparticles proceeds via a cluster aggregation-based nonclassical pathway.« less

Adsorption of dysprosium on the graphite (0001) surface: Nucleation and growth at 300 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwolek, Emma J.; Lii-Rosales, Ann; Department of Chemistry, Iowa State University, Ames, Iowa 50011

2016-12-07

We have studied nucleation and growth of Dy islands on the basal plane of graphite at 300 K using scanning tunneling microscopy, density functional theory (DFT) in a form that includes van der Waals interactions, and analytic theory. The interaction of atomic Dy with graphite is strong, while the diffusion barrier is small. Experiment shows that at 300 K, the density of nucleated islands is close to the value predicted for homogeneous nucleation, using critical nucleus size of 1 and the DFT-derived diffusion barrier. Homogeneous nucleation is also supported by the monomodal shape of the island size distributions. Comparison withmore » the published island density of Dy on graphene shows that the value is about two orders of magnitude smaller on graphite, which can be attributed to more effective charge screening in graphite. The base of each island is 3 atomic layers high and atomically ordered, forming a coincidence lattice with the graphite. Islands resist coalescence, probably due to multiple rotational orientations associated with the coincidence lattice. Upper levels grow as discernible single-atom layers. Analysis of the level populations reveals significant downward interlayer transport, which facilitates growth of the base. This island shape is metastable, since more compact three-dimensional islands form at elevated growth temperature.« less

Numerical Simulation and Experimental Casting of Nickel-Based Single-Crystal Superalloys by HRS and LMC Directional Solidification Processes

NASA Astrophysics Data System (ADS)

Yan, Xuewei; Wang, Run'nan; Xu, Qingyan; Liu, Baicheng

2017-04-01

Mathematical models for dynamic heat radiation and convection boundary in directional solidification processes are established to simulate the temperature fields. Cellular automaton (CA) method and Kurz-Giovanola-Trivedi (KGT) growth model are used to describe nucleation and growth. Primary dendritic arm spacing (PDAS) and secondary dendritic arm spacing (SDAS) are calculated by the Ma-Sham (MS) and Furer-Wunderlin (FW) models respectively. The mushy zone shape is investigated based on the temperature fields, for both high-rate solidification (HRS) and liquid metal cooling (LMC) processes. The evolution of the microstructure and crystallographic orientation are analyzed by simulation and electron back-scattered diffraction (EBSD) technique, respectively. Comparison of the simulation results from PDAS and SDAS with experimental results reveals a good agreement with each other. The results show that LMC process can provide both dendritic refinement and superior performance for castings due to the increased cooling rate and thermal gradient.

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.

Morphology and mixing state of atmospheric particles: Links to optical properties and cloud processing

NASA Astrophysics Data System (ADS)

China, Swarup

Atmospheric particles are ubiquitous in Earth's atmosphere and impact the environment and the climate while affecting human health and Earth's radiation balance, and degrading visibility. Atmospheric particles directly affect our planet's radiation budget by scattering and absorbing solar radiation, and indirectly by interacting with clouds. Single particle morphology (shape, size and internal structure) and mixing state (coating by organic and inorganic material) can significantly influence the particle optical properties as well as various microphysical processes, involving cloud-particle interactions and including heterogeneous ice nucleation and water uptake. Conversely, aerosol cloud processing can affect the morphology and mixing of the particles. For example, fresh soot has typically an open fractal-like structure, but aging and cloud processing can restructure soot into more compacted shapes, with different optical and ice nucleation properties. During my graduate research, I used an array of electron microscopy and image analysis tools to study morphology and mixing state of a large number of individual particles collected during several field and laboratory studies. To this end, I investigated various types of particles such as tar balls (spherical carbonaceous particles emitted during biomass burning) and dust particles, but with a special emphasis on soot particles. In addition, I used the Stony Brook ice nucleation cell facility to investigate heterogeneous ice nucleation and water uptake by long-range transported particles collected at the Pico Mountain Observatory, in the Archipelago of the Azores. Finally, I used ice nucleation data from the SAAS (Soot Aerosol Aging Study) chamber study at the Pacific Northwest National Laboratory to understand the effects that ice nucleation and supercooled water processing has on the morphology of residual soot particles. Some highlights of our findings and implications are discussed next. We found that the morphology of fresh soot emitted by vehicles depends on the driving conditions (i.e.; the vehicle specific power). Soot emitted by biomass burning is often heavily coated by other materials while processing of soot in urban environment exhibits complex mixing. We also found that long-range transported soot over the ocean after atmospheric processing is very compacted. In addition, our results suggest that freezing process can facilitate restructuring of soot and results into collapsed soot. Furthermore, numerical simulations showed strong influence on optical properties when fresh open fractal-like soot evolved to collapsed soot. Further investigation of long-range transported aged particles exhibits that they are efficient in water uptake and can induce ice nucleation in colder temperature. Our results have implications for assessing the impact of the morphology and mixing state of soot particles on human health, environment and climate. Our findings can provide guidance to numerical models such as particle-resolved mixing state models to account for, and better understand, vehicular emissions and soot evolution since its emission to atmospheric processing in urban environment and finally in remote regions after long-range transport. Morphology and mixing state information can be used to model observational-constrained optical properties. The details of morphology and mixing state of soot particles are crucial to assess the accuracy of climate models in describing the contribution of soot radiative forcing and their direct and indirect climate effects. Finally, our observations of ice nucleation ability by aged particles show that nucleated particles are internally mixed and coated with several materials.

Observation of end-vortex nucleation in individual ferromagnetic nanotubes

NASA Astrophysics Data System (ADS)

Mehlin, A.; Gross, B.; Wyss, M.; Schefer, T.; Tütüncüoglu, G.; Heimbach, F.; Fontcuberta i Morral, A.; Grundler, D.; Poggio, M.

2018-04-01

The reversal of uniform axial magnetization in a ferromagnetic nanotube (FNT) has been predicted to occur through the nucleation and propagation of vortex domains forming at the ends. We provide experimental evidence for this behavior through dynamic cantilever magnetometry measurements of individual FNTs. In particular, we identify the nucleation of the vortex end domains as a function of applied magnetic field and show that they mark the onset of magnetization reversal. We find that the nucleation field depends sensitively on the angle between the end surface of the FNT and the applied field. Micromagnetic simulations substantiate the experimental results and highlight the importance of the ends in determining the reversal process. The control over end-vortex nucleation enabled by our findings is promising for the production of FNTs with tailored reversal properties.

Nucleation and growth mechanisms of nano magnesium hydride from the hydrogen sorption kinetics.

PubMed

Mooij, Lennard; Dam, Bernard

2013-07-21

We use a combination of hydrogenography and Johnson-Mehl-Avrami-Kolmogorov (JMAK) analyses to identify (1) the driving force dependence of the nucleation and growth mechanism of MgH2 in thin film multilayers of Mg (10 nm) and (2) the nucleation and growth mechanism of Mg in the earlier formed MgH2, i.e. the hydrogen desorption process. We conclude that JMAK may be successfully applied to obtain the nucleation and growth mechanism of hydrogen absorption. The desorption mechanism, however, is not simply the reverse of the absorption mechanism. We find evidence that the barrier for nucleation of Mg is small. The dehydrogenation probably involves the formation of voids, which is energetically more favorable than elastic and plastic deformation of the multilayer.

Distinct thermodynamic signatures of oligomer generation in the aggregation of the amyloid-β peptide

NASA Astrophysics Data System (ADS)

Cohen, Samuel I. A.; Cukalevski, Risto; Michaels, Thomas C. T.; Šarić, Andela; Törnquist, Mattias; Vendruscolo, Michele; Dobson, Christopher M.; Buell, Alexander K.; Knowles, Tuomas P. J.; Linse, Sara

2018-05-01

Mapping free-energy landscapes has proved to be a powerful tool for studying reaction mechanisms. Many complex biomolecular assembly processes, however, have remained challenging to access using this approach, including the aggregation of peptides and proteins into amyloid fibrils implicated in a range of disorders. Here, we generalize the strategy used to probe free-energy landscapes in protein folding to determine the activation energies and entropies that characterize each of the molecular steps in the aggregation of the amyloid-β peptide (Aβ42), which is associated with Alzheimer's disease. Our results reveal that interactions between monomeric Aβ42 and amyloid fibrils during fibril-dependent secondary nucleation fundamentally reverse the thermodynamic signature of this process relative to primary nucleation, even though both processes generate aggregates from soluble peptides. By mapping the energetic and entropic contributions along the reaction trajectories, we show that the catalytic efficiency of Aβ42 fibril surfaces results from the enthalpic stabilization of adsorbing peptides in conformations amenable to nucleation, resulting in a dramatic lowering of the activation energy for nucleation.

Distinct thermodynamic signatures of oligomer generation in the aggregation of the amyloid-β peptide.

PubMed

Cohen, Samuel I A; Cukalevski, Risto; Michaels, Thomas C T; Šarić, Anđela; Törnquist, Mattias; Vendruscolo, Michele; Dobson, Christopher M; Buell, Alexander K; Knowles, Tuomas P J; Linse, Sara

2018-05-01

Mapping free-energy landscapes has proved to be a powerful tool for studying reaction mechanisms. Many complex biomolecular assembly processes, however, have remained challenging to access using this approach, including the aggregation of peptides and proteins into amyloid fibrils implicated in a range of disorders. Here, we generalize the strategy used to probe free-energy landscapes in protein folding to determine the activation energies and entropies that characterize each of the molecular steps in the aggregation of the amyloid-β peptide (Aβ42), which is associated with Alzheimer's disease. Our results reveal that interactions between monomeric Aβ42 and amyloid fibrils during fibril-dependent secondary nucleation fundamentally reverse the thermodynamic signature of this process relative to primary nucleation, even though both processes generate aggregates from soluble peptides. By mapping the energetic and entropic contributions along the reaction trajectories, we show that the catalytic efficiency of Aβ42 fibril surfaces results from the enthalpic stabilization of adsorbing peptides in conformations amenable to nucleation, resulting in a dramatic lowering of the activation energy for nucleation.

The Nucleation and Growth of Protein Crystals

NASA Technical Reports Server (NTRS)

Pusey, Marc

2004-01-01

Obtaining crystals of suitable size and high quality continues to be a major bottleneck in macromolecular crystallography. Currently, structural genomics efforts are achieving on average about a 10% success rate in going from purified protein to a deposited crystal structure. Growth of crystals in microgravity was proposed as a means of overcoming size and quality problems, which subsequently led to a major NASA effort in microgravity crystal growth, with the agency also funding research into understanding the process. Studies of the macromolecule crystal nucleation and growth process were carried out in a number of labs in an effort to understand what affected the resultant crystal quality on Earth, and how microgravity improved the process. Based upon experimental evidence, as well as simple starting assumptions, we have proposed that crystal nucleation occurs by a series of discrete self assembly steps, which 'set' the underlying crystal symmetry. This talk will review the model developed, and its origins, in our laboratory for how crystals nucleate and grow, and will then present, along with preliminary data, how we propose to use this model to improve the success rate for obtaining crystals from a given protein.

Nanoscale plasma chemistry enables fast, size-selective nanotube nucleation.

PubMed

Ostrikov, Kostya Ken; Mehdipour, Hamid

2012-03-07

The possibility of fast, narrow-size/chirality nucleation of thin single-walled carbon nanotubes (SWCNTs) at low, device-tolerant process temperatures in a plasma-enhanced chemical vapor deposition (CVD) is demonstrated using multiphase, multiscale numerical experiments. These effects are due to the unique nanoscale reactive plasma chemistry (NRPC) on the surfaces and within Au catalyst nanoparticles. The computed three-dimensional process parameter maps link the nanotube incubation times and the relative differences between the incubation times of SWCNTs of different sizes/chiralities to the main plasma- and precursor gas-specific parameters and explain recent experimental observations. It is shown that the unique NRPC leads not only to much faster nucleation of thin nanotubes at much lower process temperatures, but also to better selectivity between the incubation times of SWCNTs with different sizes and chiralities, compared to thermal CVD. These results are used to propose a time-programmed kinetic approach based on fast-responding plasmas which control the size-selective, narrow-chirality nucleation and growth of thin SWCNTs. This approach is generic and can be used for other nanostructure and materials systems. © 2012 American Chemical Society

Molecular dynamics simulations investigating consecutive nucleation, solidification and grain growth in a twelve-million-atom Fe-system

NASA Astrophysics Data System (ADS)

Okita, Shin; Verestek, Wolfgang; Sakane, Shinji; Takaki, Tomohiro; Ohno, Munekazu; Shibuta, Yasushi

2017-09-01

Continuous processes of homogeneous nucleation, solidification and grain growth are spontaneously achieved from an undercooled iron melt without any phenomenological parameter in the molecular dynamics (MD) simulation with 12 million atoms. The nucleation rate at the critical temperature is directly estimated from the atomistic configuration by cluster analysis to be of the order of 1034 m-3 s-1. Moreover, time evolution of grain size distribution during grain growth is obtained by the combination of Voronoi and cluster analyses. The grain growth exponent is estimated to be around 0.3 from the geometric average of the grain size distribution. Comprehensive understanding of kinetic properties during continuous processes is achieved in the large-scale MD simulation by utilizing the high parallel efficiency of a graphics processing unit (GPU), which is shedding light on the fundamental aspects of production processes of materials from the atomistic viewpoint.

Current state of aerosol nucleation parameterizations for air-quality and climate modeling

NASA Astrophysics Data System (ADS)

Semeniuk, Kirill; Dastoor, Ashu

2018-04-01

Aerosol nucleation parameterization models commonly used in 3-D air quality and climate models have serious limitations. This includes classical nucleation theory based variants, empirical models and other formulations. Recent work based on detailed and extensive laboratory measurements and improved quantum chemistry computation has substantially advanced the state of nucleation parameterizations. In terms of inorganic nucleation involving BHN and THN including ion effects these new models should be considered as worthwhile replacements for the old models. However, the contribution of organic species to nucleation remains poorly quantified. New particle formation consists of a distinct post-nucleation growth regime which is characterized by a strong Kelvin curvature effect and is thus dependent on availability of very low volatility organic species or sulfuric acid. There have been advances in the understanding of the multiphase chemistry of biogenic and anthropogenic organic compounds which facilitate to overcome the initial aerosol growth barrier. Implementation of processes influencing new particle formation is challenging in 3-D models and there is a lack of comprehensive parameterizations. This review considers the existing models and recent innovations.

Continuum analysis of the nucleus growth of reverse domains in large ferroelectric crystals

NASA Astrophysics Data System (ADS)

Neumeister, Peter; Balke, Herbert; Lupascu, Doru C.

2009-04-01

Polarization reversal in ferroelectrics arises due to domain nucleation and domain wall motion. The nucleation of reverse domains at crystal boundaries is the fundamental initiation process observed in single crystals. The classical continuum approach by Landauer determines an insurmountable energy barrier to extrinsic domain nucleation. We rediscuss the continuum approach. Predetermined surface states are found to be a misleading concept. Alternate energy contributions, for example, due to a dead layer or due to charge injection as well as reduced domain wall energy and anisotropy of domain wall energy, have to be included into a convincing picture of domain nucleation.

Importance of Chemical Composition of Ice Nuclei on the Formation of Arctic Ice Clouds

NASA Astrophysics Data System (ADS)

Keita, Setigui Aboubacar; Girard, Eric

2016-09-01

Ice clouds play an important role in the Arctic weather and climate system but interactions between aerosols, clouds and radiation remain poorly understood. Consequently, it is essential to fully understand their properties and especially their formation process. Extensive measurements from ground-based sites and satellite remote sensing reveal the existence of two Types of Ice Clouds (TICs) in the Arctic during the polar night and early spring. TICs-1 are composed by non-precipitating small (radar-unseen) ice crystals of less than 30 μm in diameter. The second type, TICs-2, are detected by radar and are characterized by a low concentration of large precipitating ice crystals ice crystals (>30 μm). To explain these differences, we hypothesized that TIC-2 formation is linked to the acidification of aerosols, which inhibits the ice nucleating properties of ice nuclei (IN). As a result, the IN concentration is reduced in these regions, resulting to a lower concentration of larger ice crystals. Water vapor available for deposition being the same, these crystals reach a larger size. Current weather and climate models cannot simulate these different types of ice clouds. This problem is partly due to the parameterizations implemented for ice nucleation. Over the past 10 years, several parameterizations of homogeneous and heterogeneous ice nucleation on IN of different chemical compositions have been developed. These parameterizations are based on two approaches: stochastic (that is nucleation is a probabilistic process, which is time dependent) and singular (that is nucleation occurs at fixed conditions of temperature and humidity and time-independent). The best approach remains unclear. This research aims to better understand the formation process of Arctic TICs using recently developed ice nucleation parameterizations. For this purpose, we have implemented these ice nucleation parameterizations into the Limited Area version of the Global Multiscale Environmental Model (GEM-LAM) and use them to simulate ice clouds observed during the Indirect and Semi-Direct Aerosol Campaign (ISDAC) in Alaska. Simulation results of the TICs-2 observed on April 15th and 25th (acidic cases) and TICs-1 observed on April 5th (non-acidic cases) are presented. Our results show that the stochastic approach based on the classical nucleation theory with the appropriate contact angle is better. Parameterizations of ice nucleation based on the singular approach tend to overestimate the ice crystal concentration in TICs-1 and TICs-2. The classical nucleation theory using the appropriate contact angle is the best approach to use to simulate the ice clouds investigated in this research.

Evaluating aerosol influence on cloud models using in-situ measurements during the INUPIAQ campaign

NASA Astrophysics Data System (ADS)

Farrington, R.; Connolly, P.; Choularton, T.; Bower, K.; Lloyd, G.; Flynn, M.; Crosier, J.; Field, P.

2014-12-01

At temperatures between -35°C and 0°C, the presence of insoluble aerosols acting as ice nuclei (IN) initiate the nucleation of ice under atmospheric conditions. Previous field and laboratory campaigns have suggested that mineral dust present in the atmosphere act as IN at temperatures around -20°C (e.g. Sassen et al. 2003), however the cause of ice nucleation at temperatures of around -5°C is less certain. Coupled with the limited representation of aerosol and cloud processes in large-scale weather and climate models, the need for improved in-situ measurements of aerosol properties and cloud micro-physical processes to drive the improvement of aerosol-clouds processes in models is evident. As part of the Ice NUcleation Process Investigation and Quantification (INUPIAQ) project, two field campaigns were conducted in early 2013 and early 2014. Both campaigns included measurements of cloud micro-physical properties at the summit of Jungfraujoch in Switzerland (3580m asl). Using data from the 2013 campaign and modelling simulations from the Weather Research and Forecasting model (WRF), an upwind site, located at Schilthorn (2970m asl), was determined for measuring aerosol properties out of cloud during the 2014 campaign. Further measurements of the cloud and aerosols properties were taken remotely using a doppler LiDAR located at Kleine Scheidegg (2061m asl). The aim of this project is to determine whether detailed aerosol information is important to determining cloud and precipitation properties downwind. To this end WRF was run using the aerosol number concentrations and size distributions measured at the Schilthorn site to compare modelled ice number concentrations with measurements taken at Jungfraujoch using state of the science cloud ice probes, including the Three-View Cloud Particle Imager (3V-CPI) and the Cloud Aerosol Spectrometer with Depolarization (CAS-DPOL), with the results of the comparison presented and discussed at this meeting. ReferencesSassen, K., et al, 2003: Saharan dust storms and indirect aerosol effects on clouds: Crystal-face results. Geophys. Res. Lett., 30(12), 1633-1636.

A nacre protein forms mesoscale hydrogels that “hijack” the biomineralization process within a seawater environment

DOE PAGES

Pendola, Martin; Jain, Gaurav; Davidyants, Anastasia; ...

2016-09-26

We examined the mineralization performance of a nacre protein, AP7, within seawater mineralization assays that form aragonite and magnesium calcite. Under these conditions AP7 forms hydrogel particles that vary in size and complexity depending upon ionic conditions. These hydrogels “hijack” the mineralization process by limiting nucleation in bulk solution and promoting nucleation within the hydrogels.

The effects of ice on methane hydrate nucleation: a microcanonical molecular dynamics study.

PubMed

Zhang, Zhengcai; Guo, Guang-Jun

2017-07-26

Although ice powders are widely used in gas hydrate formation experiments, the effects of ice on hydrate nucleation and what happens in the quasi-liquid layer of ice are still not well understood. Here, we used high-precision constant energy molecular dynamics simulations to study methane hydrate nucleation from vapor-liquid mixtures exposed to the basal, prismatic, and secondary prismatic planes of hexagonal ice (ice Ih). Although no significant difference is observed in hydrate nucleation processes for these different crystal planes, it is found, more interestingly, that methane hydrate can nucleate either on the ice surface heterogeneously or in the bulk solution phase homogeneously. Several factors are mentioned to be able to promote the heterogeneous nucleation of hydrates, including the adsorption of methane molecules at the solid-liquid interface, hydrogen bonding between hydrate cages and the ice structure, the stronger ability of ice to transfer heat than that of the aqueous solution, and the higher occurrence probability of hydrate cages in the vicinity of the ice surface than in the bulk solution. Meanwhile, however, the other factors including the hydrophilicity of ice and the ice lattice mismatch with clathrate hydrates can inhibit heterogeneous nucleation on the ice surface and virtually promote homogeneous nucleation in the bulk solution. Certainly, the efficiency of ice as a promoter and as an inhibitor for heterogeneous nucleation is different. We estimate that the former is larger than the latter under the working conditions. Additionally, utilizing the benefit of ice to absorb heat, the NVE simulation of hydrate formation with ice can mimic the phenomenon of ice shrinking during the heterogeneous nucleation of hydrates and lower the overly large temperature increase during homogeneous nucleation. These results are helpful in understanding the nucleation mechanism of methane hydrate in the presence of ice.

Genome-Wide siRNA Screen Identifies Complementary Signaling Pathways Involved in Listeria Infection and Reveals Different Actin Nucleation Mechanisms during Listeria Cell Invasion and Actin Comet Tail Formation

PubMed Central

Kühbacher, Andreas; Emmenlauer, Mario; Rämo, Pauli; Kafai, Natasha; Dehio, Christoph

2015-01-01

ABSTRACT Listeria monocytogenes enters nonphagocytic cells by a receptor-mediated mechanism that is dependent on a clathrin-based molecular machinery and actin rearrangements. Bacterial intra- and intercellular movements are also actin dependent and rely on the actin nucleating Arp2/3 complex, which is activated by host-derived nucleation-promoting factors downstream of the cell receptor Met during entry and by the bacterial nucleation-promoting factor ActA during comet tail formation. By genome-wide small interfering RNA (siRNA) screening for host factors involved in bacterial infection, we identified diverse cellular signaling networks and protein complexes that support or limit these processes. In addition, we could precise previously described molecular pathways involved in Listeria invasion. In particular our results show that the requirements for actin nucleators during Listeria entry and actin comet tail formation are different. Knockdown of several actin nucleators, including SPIRE2, reduced bacterial invasion while not affecting the generation of comet tails. Most interestingly, we observed that in contrast to our expectations, not all of the seven subunits of the Arp2/3 complex are required for Listeria entry into cells or actin tail formation and that the subunit requirements for each of these processes differ, highlighting a previously unsuspected versatility in Arp2/3 complex composition and function. PMID:25991686

Improvements in the Formation of Boron-Doped Diamond Coatings on Platinum Wires Using the Novel Nucleation Process (NNP)

PubMed Central

Fhaner, Mathew; Zhao, Hong; Bian, Xiaochun; Galligan, James J.; Swain, Greg M.

2010-01-01

In order to increase the initial nucleation density for the growth of boron-doped diamond on platinum wires, we employed the novel nucleation process (NNP) originally developed by Rotter et al. and discussed by others [1–3]. This pretreatment method involves (i) the initial formation of a thin carbon layer over the substrate followed by (ii) ultrasonic seeding of this “soft” carbon layer with nanoscale particles of diamond. This two-step pretreatment is followed by the deposition of boron-doped diamond by microwave plasma-assisted CVD. Both the diamond seed particles and sites on the carbon layer itself function as the initial nucleation zones for diamond growth from an H2-rich source gas mixture. We report herein on the characterization of the pre-growth carbon layer formed on Pt as well as boron-doped films grown for 2, 4 and 6 h post NNP pretreatment. Results from scanning electron microscopy, Raman spectroscopy and electrochemical studies are reported. The NNP method increases the initial nucleation density on Pt and leads to the formation of a continuous diamond film in a shorter deposition time than is typical for wires pretreated by conventional ultrasonic seeding. The results indicate that the pregrowth layer itself consists of nanoscopic domains of diamond and functions well to enhance the initial nucleation of diamond without any diamond powder seeding. PMID:21617759

The enhancement and suppression of immersion mode heterogeneous ice-nucleation by solutes.

PubMed

Whale, Thomas F; Holden, Mark A; Wilson, Theodore W; O'Sullivan, Daniel; Murray, Benjamin J

2018-05-07

Heterogeneous nucleation of ice from aqueous solutions is an important yet poorly understood process in multiple fields, not least the atmospheric sciences where it impacts the formation and properties of clouds. In the atmosphere ice-nucleating particles are usually, if not always, mixed with soluble material. However, the impact of this soluble material on ice nucleation is poorly understood. In the atmospheric community the current paradigm for freezing under mixed phase cloud conditions is that dilute solutions will not influence heterogeneous freezing. By testing combinations of nucleators and solute molecules we have demonstrated that 0.015 M solutions (predicted melting point depression <0.1 °C) of several ammonium salts can cause suspended particles of feldspars and quartz to nucleate ice up to around 3 °C warmer than they do in pure water. In contrast, dilute solutions of certain alkali metal halides can dramatically depress freezing points for the same nucleators. At 0.015 M, solutes can enhance or deactivate the ice-nucleating ability of a microcline feldspar across a range of more than 10 °C, which corresponds to a change in active site density of more than a factor of 10 5 . This concentration was chosen for a survey across multiple solutes-nucleant combinations since it had a minimal colligative impact on freezing and is relevant for activating cloud droplets. Other nucleators, for instance a silica gel, are unaffected by these 'solute effects', to within experimental uncertainty. This split in response to the presence of solutes indicates that different mechanisms of ice nucleation occur on the different nucleators or that surface modification of relevance to ice nucleation proceeds in different ways for different nucleators. These solute effects on immersion mode ice nucleation may be of importance in the atmosphere as sea salt and ammonium sulphate are common cloud condensation nuclei (CCN) for cloud droplets and are internally mixed with ice-nucleating particles in mixed-phase clouds. In addition, we propose a pathway dependence where activation of CCN at low temperatures might lead to enhanced ice formation relative to pathways where CCN activation occurs at higher temperatures prior to cooling to nucleation temperature.

The enhancement and suppression of immersion mode heterogeneous ice-nucleation by solutes

PubMed Central

Holden, Mark A.; Wilson, Theodore W.; O'Sullivan, Daniel; Murray, Benjamin J.

2018-01-01

Heterogeneous nucleation of ice from aqueous solutions is an important yet poorly understood process in multiple fields, not least the atmospheric sciences where it impacts the formation and properties of clouds. In the atmosphere ice-nucleating particles are usually, if not always, mixed with soluble material. However, the impact of this soluble material on ice nucleation is poorly understood. In the atmospheric community the current paradigm for freezing under mixed phase cloud conditions is that dilute solutions will not influence heterogeneous freezing. By testing combinations of nucleators and solute molecules we have demonstrated that 0.015 M solutions (predicted melting point depression <0.1 °C) of several ammonium salts can cause suspended particles of feldspars and quartz to nucleate ice up to around 3 °C warmer than they do in pure water. In contrast, dilute solutions of certain alkali metal halides can dramatically depress freezing points for the same nucleators. At 0.015 M, solutes can enhance or deactivate the ice-nucleating ability of a microcline feldspar across a range of more than 10 °C, which corresponds to a change in active site density of more than a factor of 105. This concentration was chosen for a survey across multiple solutes–nucleant combinations since it had a minimal colligative impact on freezing and is relevant for activating cloud droplets. Other nucleators, for instance a silica gel, are unaffected by these ‘solute effects’, to within experimental uncertainty. This split in response to the presence of solutes indicates that different mechanisms of ice nucleation occur on the different nucleators or that surface modification of relevance to ice nucleation proceeds in different ways for different nucleators. These solute effects on immersion mode ice nucleation may be of importance in the atmosphere as sea salt and ammonium sulphate are common cloud condensation nuclei (CCN) for cloud droplets and are internally mixed with ice-nucleating particles in mixed-phase clouds. In addition, we propose a pathway dependence where activation of CCN at low temperatures might lead to enhanced ice formation relative to pathways where CCN activation occurs at higher temperatures prior to cooling to nucleation temperature. PMID:29780544

Nucleation, aggregative growth and detachment of metal nanoparticles during electrodeposition at electrode surfaces† †Electronic supplementary information (ESI) available: S1 Scharifker–Hills model, S2 tapping mode-atomic force microscopy (TM-AFM) image of AM grade HOPG, after exposure to a droplet of 50 mM KNO3, S3 distribution of induction times, S4 results of the modified Cottrell fits at different potentials, S5 FE-SEM images of HOPG after control tip breaking, S6 extended current–time trace. See DOI: 10.1039/c4sc02792b Click here for additional data file.

PubMed Central

Lazenby, Robert A.; Kirkman, Paul M.

2015-01-01

The nucleation and growth of metal nanoparticles (NPs) on surfaces is of considerable interest with regard to creating functional interfaces with myriad applications. Yet, key features of these processes remain elusive and are undergoing revision. Here, the mechanism of the electrodeposition of silver on basal plane highly oriented pyrolytic graphite (HOPG) is investigated as a model system at a wide range of length scales, spanning electrochemical measurements from the macroscale to the nanoscale using scanning electrochemical cell microscopy (SECCM), a pipette-based approach. The macroscale measurements show that the nucleation process cannot be modelled as either truly instantaneous or progressive, and that step edge sites of HOPG do not play a dominant role in nucleation events compared to the HOPG basal plane, as has been widely proposed. Moreover, nucleation numbers extracted from electrochemical analysis do not match those determined by atomic force microscopy (AFM). The high time and spatial resolution of the nanoscale pipette set-up reveals individual nucleation and growth events at the graphite basal surface that are resolved and analysed in detail. Based on these results, corroborated with complementary microscopy measurements, we propose that a nucleation-aggregative growth-detachment mechanism is an important feature of the electrodeposition of silver NPs on HOPG. These findings have major implications for NP electrodeposition and for understanding electrochemical processes at graphitic materials generally. PMID:29560200

In-situ observations of bubble growth in basaltic, andesitic and rhyodacitic melts

NASA Astrophysics Data System (ADS)

Masotta, M.; Ni, H.; Keppler, H.

2013-12-01

Bubble growth strongly affects the physical properties of degassing magmas and their eruption dynamics. Natural samples and products from quench experiments provide only a snapshot of the final state of volatile exsolution, leaving the processes occurring during its early stages unconstrained. In order to fill this gap, we present in-situ high-temperature observations of bubble growth in magmas of different compositions (basalt, andesite and rhyodacite) at 1100 to 1240 °C and 1 bar, obtained using a moissanite cell apparatus. The data show that nucleation occurs at very small degrees of supersaturaturation (<20 MPa in basalt and andesite, ca. 100 MPa in rhyodacite), probably due to heterogeneous nucleation of bubbles occurring simultaneously with the nucleation of crystals. During the early stages of exsolution, melt degassing is the driving mechanism of bubble growth, with coalescence becoming increasingly important as exsolution progresses. Ostwald ripening occurs only at the end of the process and only in basaltic melt. The average bubble growth rate (GR) ranges from 3.4*10-6 to 5.2*10-7 mm/s, with basalt and andesite showing faster growth rates than rhyodacite. The bubble number density (NB) at nucleation ranges from 1.8*108 to 7.9*107 cm-3 and decreases exponentially over time. While the rhyodacite melt maintained a well-sorted bubble-size distribution (BSD) through time, the BSD's of basalt and andesite are much more inhomogeneous. Our experimental observations demonstrate that bubble growth cannot be ascribed to a single mechanism but is rather a combination of many processes, which depend on the physical properties of the melt. Depending on coalescence rate, annealing of bubbles following a single nucleation event can produce complex bubble size distributions. In natural samples, such BSD's may be misinterpreted as resulting from several separate nucleation events. Incipient crystallization upon cooling of a magma may allow bubble nucleation already at very small degrees of supersaturation and could therefore be an important trigger for volatile release and explosive eruptions.

Cellulose and Their Characteristic Ice Nucleation Activity- Freezing on a Chip

NASA Astrophysics Data System (ADS)

Häusler, Thomas; Felgitsch, Laura; Grothe, Hinrich

2016-04-01

The influence of clouds on the Earth's climate system is well known (IPCC, 2013). Cloud microphysics determines for example cloud lifetime and precipitation properties. Clouds are cooling the climate system by reflecting incoming solar radiation and warm its surface by trapping outgoing infrared radiation (Baker and Peter, 2008). In all these processes, aerosol particles play a crucial role by acting as cloud condensation nuclei (CCN) for liquid droplets and as an ice nucleation particle (INP) for the formation of ice particles. Freezing processes at higher temperatures than -38°C occur heterogeneously (Pruppacher and Klett 1997). Therefore aerosol particles act like a catalyst, which reduces the energy barrier for nucleation. The nucleation mechanisms, especially the theory of functional sites are not entirely understood. It remains unclear which class of compound nucleates ice. Here we present a unique technique to perform drop- freezing experiments in a more efficient way. A self-made freezing- chip will be presented. Measurements done to proof the efficiency of our setup as well as advantages compared with other setups will be discussed. Furthermore we present a proxy for biological INPs, microcrystalline cellulose. Cellulose is the main component of herbal cell walls (about 50 wt%). It is a polysaccharide consisting of a linear chain of several hundred to many thousands of β(1→4) linked D-glucose units. Cellulose can contribute to the diverse spectrum of ice nucleation particles. We present results of the nucleation activity measurements of MCCs as well as the influence of concentration, preparation or chemical modification.

Evaluation of safety of hypobaric decompressions and EVA from positions of probabilistic theory

NASA Astrophysics Data System (ADS)

Nikolaev, V. P.

Formation and subsequent evolution of gas bubbles in blood and tissues of subjects exposed to decompression are casual processes in their nature. Such character of bubbling processes in a body predetermines probabilistic character of decompression sickness (DCS) incidence in divers, aviators and astronauts. Our original probabilistic theory of decompression safety is based on stochastic models of these processes and on the concept of critical volume of a free gas phase in body tissues. From positions of this theory, the probability of DCS incidence during single-stage decompressions and during hypobaric decompressions under EVA in particular, is defined by the distribution of possible values of nucleation efficiency in "pain" tissues and by its critical significance depended on the parameters of a concrete decompression. In the present study the following is shown: 1) the dimensionless index of critical nucleation efficiency for "pain" body tissues is a more adequate index of decompression stress in comparison with Tissue Ratio, TR; 2) a priory the decompression under EVA performed according to the Russian protocol is more safe than decompression under EVA performed in accordance with the U.S. protocol; 3) the Russian space suit operated at a higher pressure and having a higher "rigidity" induces a stronger inhibition of mechanisms of cavitation and gas bubbles formation in tissues of a subject located in it, and by that provides a more considerable reduction of the DCS risk during real EVA performance.

Numerical Modeling of Nanocellular Foams Using Classical Nucleation Theory and Influence Volume Approach

NASA Astrophysics Data System (ADS)

Khan, Irfan; Costeux, Stephane; Bunker, Shana; Moore, Jonathan; Kar, Kishore

2012-11-01

Nanocellular porous materials present unusual optical, dielectric, thermal and mechanical properties and are thus envisioned to find use in a variety of applications. Thermoplastic polymeric foams show considerable promise in achieving these properties. However, there are still considerable challenges in achieving nanocellular foams with densities as low as conventional foams. Lack of in-depth understanding of the effect of process parameters and physical properties on the foaming process is a major obstacle. A numerical model has been developed to simulate the simultaneous nucleation and bubble growth during depressurization of thermoplastic polymers saturated with supercritical blowing agents. The model is based on the popular ``Influence Volume Approach,'' which assumes a growing boundary layer with depleted blowing agent surrounds each bubble. Classical nucleation theory is used to predict the rate of nucleation of bubbles. By solving the mass balance, momentum balance and species conservation equations for each bubble, the model is capable of predicting average bubble size, bubble size distribution and bulk porosity. The model is modified to include mechanisms for Joule-Thompson cooling during depressurization and secondary foaming. Simulation results for polymer with and without nucleating agents will be discussed and compared with experimental data.

Early stages of zeolite growth

NASA Astrophysics Data System (ADS)

Kumar, Sandeep

Zeolites are crystalline nonporous aluminosilicates with important applications in separation, purification, and adsorption of liquid and gaseous molecules. However, an ability to tailor the zeolite microstructure, such as particle size/shape and pore-size, to make it benign for specific application requires control over nucleation and particle growth processes. But, the nucleation and crystallization mechanisms of zeolites are not fully understood. In this context, the synthesis of an all-silica zeolite with MFI-type framework has been studied extensively as a model system. Throughout chapters 2, 4 and 5, MFI growth process has been investigated by small-angle x-ray scattering (SAXS) and transmission electron microscopy (TEM). Of fundamental importance is the role of nanoparticles (~5 nm), which are present in the precursor sol, in MFI nucleation and crystallization. Formation of amorphous aggregates and their internal restructuring are concluded as essential steps in MFI nucleation. Early stage zeolite particles have disordered and less crystalline regions within, which indicates the role of structurally distributed population of nanoparticles in growth. Faceting occurs after the depletion of nanoparticles. The chapter 6 presents growth studies in silica sols prepared by using a dimer of tertaprpylammonium (TPA) and reports that MFI nucleation and crystallization are delayed with a more pronounced delay in crystal growth.

A general perspective on the magnetization reversal in cylindrical soft magnetic nanowires with dominant shape anisotropy

NASA Astrophysics Data System (ADS)

Kuncser, A.; Antohe, S.; Kuncser, V.

2017-02-01

Peculiarities of the magnetization reversal process in cylindrical Ni-Cu soft magnetic nanowires with dominant shape anisotropy are analyzed via both static and time dependent micromagnetic simulations. A reversible process involving a coherent-like spin rotation is always observed for magnetic fields applied perpendicularly to the easy axis whereas nucleation of domain walls is introduced for fields applied along the easy axis. Simple criteria for making distinction between a Stoner-Wohlfarth type rotation and a nucleation mechanism in systems with uniaxial magnetic anisotropy are discussed. Superposed reversal mechanisms can be in action for magnetic fields applied at arbitrary angles with respect to the easy axis within the condition of an enough strong axial component required by the nucleation. The dynamics of the domain wall, involving two different stages (nucleation and propagation), is discussed with respect to initial computing conditions and orientations of the magnetic field. A nucleation time of about 3 ns and corkscrew domain walls propagating with a constant velocity of about 150 m/s are obtained in case of Ni-Cu alloy (Ni rich side) NWs with diameters of 40 nm and high aspect ratio.

Estimation of the nucleation kinetics for the anti-solvent crystallisation of paracetamol in methanol/water solutions

NASA Astrophysics Data System (ADS)

Ó'Ciardhá, Clifford T.; Frawley, Patrick J.; Mitchell, Niall A.

2011-08-01

In this work the primary nucleation kinetics have been estimated for the anti-solvent crystallisation of paracetamol in methanol-water solutions from metastable zone widths (MSZW) and induction times at 25 °C. Laser back-scattering via a focused beam reflectance Measurement (FBRM ®) is utilised to detect the onset of nucleation. The theoretical approach of Kubota was employed to estimate the nucleation kinetics, which accounts for the sensitivity of the nucleation detection technique. This approach is expanded in this work to analyse the induction time for an anti-solvent crystallisation process. Solvent composition is known to have a significant impact on the measured induction times and MSZW. The induction time in this paper was measured from 40% to 70% mass water and the MSZW is measured from 40% to 60% mass water. The primary focus of the paper was to gauge the extent of how solvent composition affects nucleation kinetics so that this effect may be incorporated into a population balance model. Furthermore, the effects of solvent composition on the estimated nucleation rates are investigated. The primary nucleation rates were found to decrease with dynamic solvent composition, with the extent of their reduction linked to the gradient of the solubility curve. Finally, both MSZW and induction time methods have been found to produce similar estimates for the nucleation parameters.

Homogeneous nucleation and microstructure evolution in million-atom molecular dynamics simulation

PubMed Central

Shibuta, Yasushi; Oguchi, Kanae; Takaki, Tomohiro; Ohno, Munekazu

2015-01-01

Homogeneous nucleation from an undercooled iron melt is investigated by the statistical sampling of million-atom molecular dynamics (MD) simulations performed on a graphics processing unit (GPU). Fifty independent instances of isothermal MD calculations with one million atoms in a quasi-two-dimensional cell over a nanosecond reveal that the nucleation rate and the incubation time of nucleation as functions of temperature have characteristic shapes with a nose at the critical temperature. This indicates that thermally activated homogeneous nucleation occurs spontaneously in MD simulations without any inducing factor, whereas most previous studies have employed factors such as pressure, surface effect, and continuous cooling to induce nucleation. Moreover, further calculations over ten nanoseconds capture the microstructure evolution on the order of tens of nanometers from the atomistic viewpoint and the grain growth exponent is directly estimated. Our novel approach based on the concept of “melting pots in a supercomputer” is opening a new phase in computational metallurgy with the aid of rapid advances in computational environments. PMID:26311304

Ice-nucleating bacteria control the order and dynamics of interfacial water

DOE PAGES

Pandey, Ravindra; Usui, Kota; Livingstone, Ruth A.; ...

2016-04-22

Ice-nucleating organisms play important roles in the environment. With their ability to induce ice formation at temperatures just below the ice melting point, bacteria such as Pseudomonas syringae attack plants through frost damage using specialized ice-nucleating proteins. Besides the impact on agriculture and microbial ecology, airborne P. syringae can affect atmospheric glaciation processes, with consequences for cloud evolution, precipitation, and climate. Biogenic ice nucleation is also relevant for artificial snow production and for biomimetic materials for controlled interfacial freezing. We use interface-specific sum frequency generation (SFG) spectroscopy to show that hydrogen bonding at the water-bacteria contact imposes structural ordering onmore » the adjacent water network. Experimental SFG data and molecular dynamics simulations demonstrate that ice active sites within P. syringae feature unique hydrophilic-hydrophobic patterns to enhance ice nucleation. Finally, the freezing transition is further facilitated by the highly effective removal of latent heat from the nucleation site, as apparent from time-resolved SFG spectroscopy.« less

Ice-nucleating bacteria control the order and dynamics of interfacial water

PubMed Central

Pandey, Ravindra; Usui, Kota; Livingstone, Ruth A.; Fischer, Sean A.; Pfaendtner, Jim; Backus, Ellen H. G.; Nagata, Yuki; Fröhlich-Nowoisky, Janine; Schmüser, Lars; Mauri, Sergio; Scheel, Jan F.; Knopf, Daniel A.; Pöschl, Ulrich; Bonn, Mischa; Weidner, Tobias

2016-01-01

Ice-nucleating organisms play important roles in the environment. With their ability to induce ice formation at temperatures just below the ice melting point, bacteria such as Pseudomonas syringae attack plants through frost damage using specialized ice-nucleating proteins. Besides the impact on agriculture and microbial ecology, airborne P. syringae can affect atmospheric glaciation processes, with consequences for cloud evolution, precipitation, and climate. Biogenic ice nucleation is also relevant for artificial snow production and for biomimetic materials for controlled interfacial freezing. We use interface-specific sum frequency generation (SFG) spectroscopy to show that hydrogen bonding at the water-bacteria contact imposes structural ordering on the adjacent water network. Experimental SFG data and molecular dynamics simulations demonstrate that ice-active sites within P. syringae feature unique hydrophilic-hydrophobic patterns to enhance ice nucleation. The freezing transition is further facilitated by the highly effective removal of latent heat from the nucleation site, as apparent from time-resolved SFG spectroscopy. PMID:27152346

Preferential nucleation during polymorphic transformations

DOE PAGES

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

2016-08-03

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 thereforemore » nucleation more probable - with increasing number of special OR’s. As a result, 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.« less

Time-Resolved In Situ Liquid-Phase Atomic Force Microscopy and Infrared Nanospectroscopy during the Formation of Metal–Organic Framework Thin Films

PubMed Central

2018-01-01

Metal–organic framework (MOF) thin films show unmatched promise as smart membranes and photocatalytic coatings. However, their nucleation and growth resulting from intricate molecular assembly processes are not well understood yet are crucial to control the thin film properties. Here, we directly observe the nucleation and growth behavior of HKUST-1 thin films by real-time in situ AFM at different temperatures in a Cu-BTC solution. In combination with ex situ infrared (nano)spectroscopy, synthesis at 25 °C reveals initial nucleation of rapidly growing HKUST-1 islands surrounded by a continuously nucleating but slowly growing HKUST-1 carpet. Monitoring at 13 and 50 °C shows the strong impact of temperature on thin film formation, resulting in (partial) nucleation and growth inhibition. The nucleation and growth mechanisms as well as their kinetics provide insights to aid in future rational design of MOF thin films. PMID:29595980

Ice nucleation by cellulose and its potential impact on clouds and climate

NASA Astrophysics Data System (ADS)

Hiranuma, Naruki; Möhler, Ottmar; Yamashita, Katsuya; Tajiri, Takuya; Saito, Atsushi; Kiselev, Alexei; Hoose, Corinna; Murakami, Masataka

2014-05-01

Biological aerosol particles have recently been accentuated by their efficient ice nucleating activity as well as potential impact on clouds and global climate. Despite their potential importance, little is known about the abundance of biological particles in the atmosphere and their role compared to non-biological material and, consequently, their potential role in the cloud-hydrology and climate system is also poorly constrained. However, field observations show that the concentration of airborne cellulose, which is one of the most important derivatives of glucose and atmospherically relevant biopolymers, is consistently prevalent (>10 ng per cubic meter) throughout the whole year even at remote- and elevated locations. Here we use a novel cloud simulation chamber in Tsukuba, Japan to demonstrate that airborne cellulose of biological origin can act as efficient ice nucleating particles in super-cooled clouds of the lower and middle troposphere. In specific, we measured the surface-based ice nucleation activity of microcrystalline cellulose particles immersed in cloud droplets, which may add crucial importance to further quantify the role of biological particles as ice nuclei in the troposphere. Our results suggest that the concentration of ice nucleating cellulose to become significant (>0.1 per liter) below about -17 °C and nearly comparable to other known ice nucleating clay mineral particles (e.g., illite rich clay mineral - INUIT comparisons are also presented). An important and unique characteristic of microcrystalline cellulose compared to other particles of biological origin is its high molecular packing density, enhancing resistance to hydrolysis degradation. More in-depth microphysical understandings as well as quantitative observations of ice nucleating cellulose particles in the atmosphere are necessary to allow better estimates of their effects on clouds and the global climate. Acknowledgement: We acknowledge support by German Research Society (DfG) and Ice Nucleation research UnIT (FOR 1525 INUIT).

Study on optimizing ultrasonic irradiation period for thick polycrystalline PZT film by hydrothermal method.

PubMed

Ohta, Kanako; Isobe, Gaku; Bornmann, Peter; Hemsel, Tobias; Morita, Takeshi

2013-04-01

The hydrothermal method utilizes a solution-based chemical reaction to synthesize piezoelectric thin films and powders. This method has a number of advantages, such as low-temperature synthesis, and high purity and high quality of the product. In order to promote hydrothermal reactions, we developed an ultrasonic assisted hydrothermal method and confirmed that it produces dense and thick lead-zirconate-titanate (PZT) films. In the hydrothermal method, a crystal growth process follows the nucleation process. In this study, we verified that ultrasonic irradiation is effective for the nucleation process, and there is an optimum irradiation period to obtain thicker PZT films. With this optimization, a 9.2-μm-thick PZT polycrystalline film was obtained in a single deposition process. For this film, ultrasonic irradiation was carried out from the beginning of the reaction for 18 h, followed by a 6 h deposition without ultrasonic irradiation. These results indicate that the ultrasonic irradiation mainly promotes the nucleation process. Copyright © 2012 Elsevier B.V. All rights reserved.

Nucleation in the presence of long-range interactions. [performed on ferroelectric barium titanate

NASA Technical Reports Server (NTRS)

Chandra, P.

1989-01-01

Unlike droplet nucleation near a liquid-gas critical point, the decay of metastable phases in crystalline materials is strongly affected by the presence of long-range forces. Field quench experiments performed on the ferroelectric barium titanate indicate that nucleation in this material is markedly different from that observed in liquids. In this paper, a theory for nucleation at a first-order phase transition in which the mediating forces are long range is presented. It is found that the long-range force induces cooperative nucleation and growth processes, and that this feedback mechanism produces a well-defined delay time with a sharp onset in the transformation to the stable phase. Closed-form expressions for the characteristic onset time and width of the transition are developed, in good agreement with numerical and experimental results.

Quantification of dislocation nucleation stress in TiN through high-resolution in situ indentation experiments and first principles calculations

DOE PAGES

Li, N.; Yadav, S. K.; Liu, X. -Y.; ...

2015-11-05

Using the in situ indentation of TiN in a high-resolution transmission electron microscope, the nucleation of full as well as partial dislocations has been observed from {001} and {111} surfaces, respectively. The critical elastic strains associated with the nucleation of the dislocations were analyzed from the recorded atomic displacements, and the nucleation stresses corresponding to the measured critical strains were computed using density functional theory. The resolved shear stress was estimated to be 13.8 GPa for the partial dislocation 1/6 <110> {111} and 6.7 GPa for the full dislocation ½ <110> {110}. Moreover, such an approach of quantifying nucleation stressesmore » for defects via in situ high-resolution experiment coupled with density functional theory calculation may be applied to other unit processes.« less

Incubation behavior of silicon nanowire growth investigated by laser-assisted rapid heating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryu, Sang-gil; Kim, Eunpa; Grigoropoulos, Costas P., E-mail: cgrigoro@berkeley.edu

2016-08-15

We investigate the early stage of silicon nanowire growth by the vapor-liquid-solid mechanism using laser-localized heating combined with ex-situ chemical mapping analysis by energy-filtered transmission electron microscopy. By achieving fast heating and cooling times, we can precisely determine the nucleation times for nanowire growth. We find that the silicon nanowire nucleation process occurs on a time scale of ∼10 ms, i.e., orders of magnitude faster than the times reported in investigations using furnace processes. The rate-limiting step for silicon nanowire growth at temperatures in the vicinity of the eutectic temperature is found to be the gas reaction and/or the silicon crystalmore » growth process, whereas at higher temperatures it is the rate of silicon diffusion through the molten catalyst that dictates the nucleation kinetics.« less

Tellurium nano-structure based NO gas sensor.

PubMed

Kumar, Vivek; Sen, Shashwati; Sharma, M; Muthe, K P; Jagannath; Gaur, N K; Gupta, S K

2009-09-01

Tellurium nanotubes were grown on bare and silver/gold nanoparticle (nucleation centers) deposited silicon substrates by vacuum deposition technique at a substrate temperature of 100 degrees C under high vacuum conditions. Silver and gold nanoparticles prepared on (111) oriented silicon substrates were found to act as nucleation centers for growth of Tellurium nanostructures. Density of nanotubes was found to increase while their diameter reduced when grown using metallic nanoparticle template. These Te nanostructures were investigated for their gas sensitivity. Tellurium nanotubes on Ag templates showed better response to NO in comparison to H2S and NH3 gases. Selectivity in response to NO was improved in comparison to Te thin film sensors reported earlier. The gas sensing mechanism was investigated using Raman and X-ray photoelectron spectroscopy techniques. The interaction of NO is seen to yield increased adsorption of oxygen that in turn increases hole density and conductivity in the material.

Spatiotemporal complexity of 2-D rupture nucleation process observed by direct monitoring during large-scale biaxial rock friction experiments

NASA Astrophysics Data System (ADS)

Fukuyama, Eiichi; Tsuchida, Kotoyo; Kawakata, Hironori; Yamashita, Futoshi; Mizoguchi, Kazuo; Xu, Shiqing

2018-05-01

We were able to successfully capture rupture nucleation processes on a 2-D fault surface during large-scale biaxial friction experiments using metagabbro rock specimens. Several rupture nucleation patterns have been detected by a strain gauge array embedded inside the rock specimens as well as by that installed along the edge walls of the fault. In most cases, the unstable rupture started just after the rupture front touched both ends of the rock specimen (i.e., when rupture front extended to the entire width of the fault). In some cases, rupture initiated at multiple locations and the rupture fronts coalesced to generate unstable ruptures, which could only be detected from the observation inside the rock specimen. Therefore, we need to carefully examine the 2-D nucleation process of the rupture especially when analyzing the data measured only outside the rock specimen. At least the measurements should be done at both sides of the fault to identify the asymmetric rupture propagation on the fault surface, although this is not perfect yet. In the present experiment, we observed three typical types of the 2-D rupture propagation patterns, two of which were initiated at a single location either close to the fault edge or inside the fault. This initiation could be accelerated by the free surface effect at the fault edge. The third one was initiated at multiple locations and had a rupture coalescence at the middle of the fault. These geometrically complicated rupture initiation patterns are important for understanding the earthquake nucleation process in nature.

Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations

PubMed Central

2016-01-01

The nucleation of crystals in liquids is one of nature’s most ubiquitous phenomena, playing an important role in areas such as climate change and the production of drugs. As the early stages of nucleation involve exceedingly small time and length scales, atomistic computer simulations can provide unique insights into the microscopic aspects of crystallization. In this review, we take stock of the numerous molecular dynamics simulations that, in the past few decades, have unraveled crucial aspects of crystal nucleation in liquids. We put into context the theoretical framework of classical nucleation theory and the state-of-the-art computational methods by reviewing simulations of such processes as ice nucleation and the crystallization of molecules in solutions. We shall see that molecular dynamics simulations have provided key insights into diverse nucleation scenarios, ranging from colloidal particles to natural gas hydrates, and that, as a result, the general applicability of classical nucleation theory has been repeatedly called into question. We have attempted to identify the most pressing open questions in the field. We believe that, by improving (i) existing interatomic potentials and (ii) currently available enhanced sampling methods, the community can move toward accurate investigations of realistic systems of practical interest, thus bringing simulations a step closer to experiments. PMID:27228560

Ice nucleation in nature: supercooling point (SCP) measurements and the role of heterogeneous nucleation.

PubMed

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

2003-02-01

In biological systems, nucleation of ice from a supercooled aqueous solution is a stochastic process and always heterogeneous. The average time any solution may remain supercooled is determined only by the degree of supercooling and heterogeneous nucleation sites it encounters. Here we summarize the many and varied definitions of the so-called "supercooling point," also called the "temperature of crystallization" and the "nucleation temperature," and exhibit the natural, inherent width associated with this quantity. We describe a new method for accurate determination of the supercooling point, which takes into account the inherent statistical fluctuations of the value. We show further that many measurements on a single unchanging sample are required to make a statistically valid measure of the supercooling point. This raises an interesting difference in circumstances where such repeat measurements are inconvenient, or impossible, for example for live organism experiments. We also discuss the effect of solutes on this temperature of nucleation. Existing data appear to show that various solute species decrease the nucleation temperature somewhat more than the equivalent melting point depression. For non-ionic solutes the species appears not to be a significant factor whereas for ions the species does affect the level of decrease of the nucleation temperature.

The influence of dopants on the nucleation of semiconductor nanocrystals from homogeneous solution.

PubMed

Bryan, J Daniel; Schwartz, Dana A; Gamelin, Daniel R

2005-09-01

The influence of Co2+ ions on the homogeneous nucleation of ZnO is examined. Using electronic absorption spectroscopy as a dopant-specific in-situ spectroscopic probe, Co2+ ions are found to be quantitatively excluded from the ZnO critical nuclei but incorporated nearly statistically in the subsequent growth layers, resulting in crystallites with pure ZnO cores and Zn(1-x)Co(x)O shells. Strong inhibition of ZnO nucleation by Co2+ ions is also observed. These results are explained using the classical nucleation model. Statistical analysis of nucleation inhibition data allows estimation of the critical nucleus size as 25 +/- 4 Zn2+ ions. Bulk calorimetric data allow the activation barrier for ZnO nucleation containing a single Co2+ impurity to be estimated as 5.75 kcal/mol cluster greater than that of pure ZnO, corresponding to a 1.5 x 10(4)-fold reduction in the ZnO nucleation rate constant upon introduction of a single Co2+ impurity. These data and analysis offer a rare view into the role of composition in homogeneous nucleation processes, and specifically address recent experiments targeting formation of semiconductor quantum dots containing single magnetic impurity ions at their precise centers.

Nucleation mode particles with a nonvolatile core in the exhaust of a heavy duty diesel vehicle.

PubMed

Rönkkö, Topi; Virtanen, Annele; Kannosto, Jonna; Keskinen, Jorma; Lappi, Maija; Pirjola, Liisa

2007-09-15

The characteristics of the nucleation mode particles of a Euro IV heavy-duty diesel vehicle exhaust were studied. The NOx and PM emissions of the vehicle were controlled through the use of cooled EGR and high-pressure fuel injection techniques; no exhaust gas after-treatment was used. Particle measurements were performed in vehicle laboratory and on road. Nucleation mode dominated the particle number size distribution in all the tested driving conditions. According to the on-road measurements, the nucleation mode was already formed after 0.7 s residence time in the atmosphere and no significant changes were observed for longer residence times. The nucleation mode was insensitive to the fuel sulfur content, dilution air temperature, and relative humidity. An increase in the dilution ratio decreased the size of the nucleation mode particles. This behavior was observed to be linked to the total hydrocarbon concentration in the diluted sample. In volatility measurements, the nucleation mode particles were observed to have a nonvolatile core with volatile species condensed on it. The results indicate that the nucleation mode particles have a nonvolatile core formed before the dilution process. The core particles have grown because of the condensation of semivolatile material, mainly hydrocarbons, during the dilution.

Non-monotonic variations of the nucleation free energy in a glass-forming ultra-soft particles fluid.

PubMed

Desgranges, Caroline; Delhommelle, Jerome

2018-06-18

Using molecular dynamics simulation, we study the impact of the degree of supercooling on the crystal nucleation of ultra-soft particles, modeled with the Gaussian core potential. Focusing on systems with a high number density, our simulations reveal dramatically different behaviors as the degree of supercooling is varied. In the moderate supercooling regime, crystal nucleation proceeds as expected from classical nucleation theory, with a decrease in the free energy of nucleation, as well as in the size of the critical nucleus, as supercooling is increased. On the other hand, in the large supercooling regime, we observe an unusual reversal of behavior with an increase in the free energy of nucleation and in the critical size, as supercooling is increased. This unexpected result is analyzed in terms of the interplay between the glass transition and the crystal nucleation process. Specifically, medium range order crystal-like domains, with structural features different from that of the crystal nucleus, are found to form throughout the system when the supercooling is very large. These, in turn, play a pivotal role in the increase in the free energy of nucleation, as well as in the critical size, as the temperature gets closer to the glass transition.

Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations.

PubMed

Sosso, Gabriele C; Chen, Ji; Cox, Stephen J; Fitzner, Martin; Pedevilla, Philipp; Zen, Andrea; Michaelides, Angelos

2016-06-22

The nucleation of crystals in liquids is one of nature's most ubiquitous phenomena, playing an important role in areas such as climate change and the production of drugs. As the early stages of nucleation involve exceedingly small time and length scales, atomistic computer simulations can provide unique insights into the microscopic aspects of crystallization. In this review, we take stock of the numerous molecular dynamics simulations that, in the past few decades, have unraveled crucial aspects of crystal nucleation in liquids. We put into context the theoretical framework of classical nucleation theory and the state-of-the-art computational methods by reviewing simulations of such processes as ice nucleation and the crystallization of molecules in solutions. We shall see that molecular dynamics simulations have provided key insights into diverse nucleation scenarios, ranging from colloidal particles to natural gas hydrates, and that, as a result, the general applicability of classical nucleation theory has been repeatedly called into question. We have attempted to identify the most pressing open questions in the field. We believe that, by improving (i) existing interatomic potentials and (ii) currently available enhanced sampling methods, the community can move toward accurate investigations of realistic systems of practical interest, thus bringing simulations a step closer to experiments.

Terminating DNA Tile Assembly with Nanostructured Caps.

PubMed

Agrawal, Deepak K; Jiang, Ruoyu; Reinhart, Seth; Mohammed, Abdul M; Jorgenson, Tyler D; Schulman, Rebecca

2017-10-24

Precise control over the nucleation, growth, and termination of self-assembly processes is a fundamental tool for controlling product yield and assembly dynamics. Mechanisms for altering these processes programmatically could allow the use of simple components to self-assemble complex final products or to design processes allowing for dynamic assembly or reconfiguration. Here we use DNA tile self-assembly to develop general design principles for building complexes that can bind to a growing biomolecular assembly and terminate its growth by systematically characterizing how different DNA origami nanostructures interact with the growing ends of DNA tile nanotubes. We find that nanostructures that present binding interfaces for all of the binding sites on a growing facet can bind selectively to growing ends and stop growth when these interfaces are presented on either a rigid or floppy scaffold. In contrast, nucleation of nanotubes requires the presentation of binding sites in an arrangement that matches the shape of the structure's facet. As a result, it is possible to build nanostructures that can terminate the growth of existing nanotubes but cannot nucleate a new structure. The resulting design principles for constructing structures that direct nucleation and termination of the growth of one-dimensional nanostructures can also serve as a starting point for programmatically directing two- and three-dimensional crystallization processes using nanostructure design.

Nucleation and growth of chimney pores during electron-beam additive manufacturing

DOE PAGES

Cordero, Zachary C.; Dinwiddie, Ralph B.; Immel, David; ...

2016-12-05

The nucleation and growth of chimney pores during powder-bed, electron-beam additive manufacturing is investigated using in-situ infrared thermography as well as microcomputed tomography of as-printed parts. The pores are found to nucleate at dimples on the part s surface, clearly demonstrating how process parameters can affect surface roughness, which can in turn affect the internal defect structure in an additive manufactured part. Based on the results of this study, several strategies for suppressing the formation of chimney pores are discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shin, Swanee J.; Kozioziemski, Bernard J.

In this work, we performed a series of experiments to elucidate the characteristics of a good template for solid hydrogen nucleation. Zinc stands out among several materials with comparable size and shape. Nucleation could be observed to occur on top of sharp features, such as grain boundaries and cracks, but our attempts proved unsuccessful to fabricate or replicate such features. The variations of the supercooling (ΔT) values measured for comparable samples and the dependence of ΔT on the cell temperature cycling revealed that templated nucleation of solid hydrogen is a very delicate process.

The ice nucleation temperature determines the primary drying rate of lyophilization for samples frozen on a temperature-controlled shelf.

PubMed

Searles, J A; Carpenter, J F; Randolph, T W

2001-07-01

The objective of this study was to determine the influence of ice nucleation temperature on the primary drying rate during lyophilization for samples in vials that were frozen on a lyophilizer shelf. Aqueous solutions of 10% (w/v) hydroxyethyl starch were frozen in vials with externally mounted thermocouples and then partially lyophilized to determine the primary drying rate. Low- and high-particulate-containing samples, ice-nucleating additives silver iodide and Pseudomonas syringae, and other methods were used to obtain a wide range of nucleation temperatures. In cases where the supercooling exceeded 5 degrees C, freezing took place in the following three steps: (1) primary nucleation, (2) secondary nucleation encompassing the entire liquid volume, and (3) final solidification. The primary drying rate was dependent on the ice nucleation temperature, which is stochastic in nature but is affected by particulate content and the presence of ice nucleators. Sample cooling rates of 0.05 to 1 degrees C/min had no effect on nucleation temperatures and drying rate. We found that the ice nucleation temperature is the primary determinant of the primary drying rate. However, the nucleation temperature is not under direct control, and its stochastic nature and sensitivity to difficult-to-control parameters result in drying rate heterogeneity. Nucleation temperature heterogeneity may also result in variation in other morphology-related parameters such as surface area and secondary drying rate. Overall, these results document that factors such as particulate content and vial condition, which influence ice nucleation temperature, must be carefully controlled to avoid, for example, lot-to-lot variability during cGMP production. In addition, if these factors are not controlled and/or are inadvertently changed during process development and scaleup, a lyophilization cycle that was successful on the research scale may fail during large-scale production.

The ice nucleation activity of biological aerosols

NASA Astrophysics Data System (ADS)

Grothe, H.; Pummer, B.; Bauer, H.; Bernardi, J.

2012-04-01

Primary Biological Aerosol Particles (PBAPs), including bacteria, spores and pollen may be important for several atmospheric processes. Particularly, the ice nucleation caused by PBAPs is a topic of growing interest, since their impact on ice cloud formation and thus on radiative forcing, an important parameter in global climate is not yet fully understood. In laboratory model studies we investigated the ice nucleation activity of selected PBAPs. We studied the immersion mode freezing using water-oil emulsion, which we observed by optical microscopy. We particularly focused on pollen. We show that pollen of different species strongly differ in their ice nucleation behavior. The average freezing temperatures in laboratory experiments range from 240 K to 255 K. As the most efficient nuclei (silver birch, Scots pine and common juniper pollen) have a distribution area up to the Northern timberline, their ice nucleation activity might be a cryoprotective mechanism. For comparison the ice nucleation activity of Snomax, fungal spores, and mushrooms will be discussed as well. In the past, pollen have been rejected as important atmospheric IN, as they are not as abundant in the atmosphere as bacteria or mineral dust and are too heavy to reach higher altitudes. However, in our experiments (Pummer et al. 2011) it turned out that water, which had been in contact with pollen and then been separated from the bodies, nucleates as good as the pollen grains themselves. So the ice nuclei have to be easily-suspendable macromolecules (100-300 kDa) located on the pollen. Once extracted, they can be distributed further through the atmosphere than the heavy pollen grains and so augment the impact of pollen on ice cloud formation even in the upper troposphere. It is widely known, that material from the pollen, like allergens and sugars, can indeed leave the pollen body and be distributed independently. The most probable mechanism is the pollen grain bursting by rain, which releases material, like allergens (Schäppi et al., 1999). As a consequence allergenic material was found in aerosol particles smaller than 5 µm, which contained no pollen or bigger fragments (Solomon et al., 1983). The release of material by bursting of wet pollen has been observed by electron microscopy (Swoboda et al., 2001). Not only allergens, but also sugars originating from pollen can be detected in the atmosphere (Yttri et al., 2007). These authors see pollen rupture and wood burning as their main sources in the atmosphere. The contrast between the hydrophilic properties of many of the surface components and the relative hydrophobia of the sporopollenin boosts the suspension of surface components in water droplets. According to that we conclude that the impact of pollen on the global atmosphere might have been underestimated. Additionally, our experiments lead to the conclusion that pollen ice nuclei, in contrast to bacterial and fungal ice nucleating proteins, are non-proteinaceous compounds.

Heterogeneous nucleation of polymorphs on polymer surfaces: polymer-molecule interactions using a heterogeneous dielectric solvation model.

PubMed

Wahlberg, Nanna; Madsen, Anders Ø; Mikkelsen, Kurt V

2018-06-09

We have investigated the mechanism of the nucleation of acetaminophen on poly(methyl-methacrylate) and poly(vinyl-acetate) utilizing a combination of quantum mechanical computations and electrostatic models. We have used a heterogeneous dielectric solvation model to determine the stability of different orientations of acetaminophen on polymer surfaces. We find that for the nucleation of acetaminophen on the polymer surfaces in vacuum, the most stable orientation is a flat orientation. For the nucleation process in solution where acetaminophen and the polymer surface are surrounded by a solvent, we find that the heterogeneous dielectric solvation model predicts that a sideways orientation is the most stable orientation.

Quantification of asymmetric microtubule nucleation at sub-cellular structures

PubMed Central

Zhu, Xiaodong; Kaverina, Irina

2012-01-01

Cell polarization is important for multiple physiological processes. In polarized cells, microtubules (MTs) are organized into a spatially polarized array. Generally, in non-differentiated cells, it is assumed that MTs are symmetrically nucleated exclusively from centrosome (microtubule organizing center, MTOC) and then reorganized into the asymmetric array. We have recently identified the Golgi complex as an additional MTOC that asymmetrically nucleates MTs toward one side of the cell. Methods used for alternative MTOC identification include microtubule re-growth after complete drug-induced depolymerization and tracking of growing microtubules using fluorescence labeled MT +TIP binding proteins in living cells. These approaches can be used for quantification of MT nucleation sites at diverse sub-cellular structures. PMID:21773933

Acyl-CoA synthetase 3 promotes lipid droplet biogenesis in ER microdomains

PubMed Central

Kassan, Adam; Herms, Albert; Fernández-Vidal, Andrea; Bosch, Marta; Schieber, Nicole L.; Reddy, Babu J.N.; Fajardo, Alba; Gelabert-Baldrich, Mariona; Tebar, Francesc; Enrich, Carlos; Gross, Steven P.

2013-01-01

Control of lipid droplet (LD) nucleation and copy number are critical, yet poorly understood, processes. We use model peptides that shift from the endoplasmic reticulum (ER) to LDs in response to fatty acids to characterize the initial steps of LD formation occurring in lipid-starved cells. Initially, arriving lipids are rapidly packed in LDs that are resistant to starvation (pre-LDs). Pre-LDs are restricted ER microdomains with a stable core of neutral lipids. Subsequently, a first round of “emerging” LDs is nucleated, providing additional lipid storage capacity. Finally, in proportion to lipid concentration, new rounds of LDs progressively assemble. Confocal microscopy and electron tomography suggest that emerging LDs are nucleated in a limited number of ER microdomains after a synchronized stepwise process of protein gathering, lipid packaging, and recognition by Plin3 and Plin2. A comparative analysis demonstrates that the acyl-CoA synthetase 3 is recruited early to the assembly sites, where it is required for efficient LD nucleation and lipid storage. PMID:24368806

Water condensation: a multiscale phenomenon.

PubMed

Jensen, Kasper Risgaard; Fojan, Peter; Jensen, Rasmus Lund; Gurevich, Leonid

2014-02-01

The condensation of water is a phenomenon occurring in multiple situations in everyday life, e.g., when fog is formed or when dew forms on the grass or on windows. This means that this phenomenon plays an important role within the different fields of science including meteorology, building physics, and chemistry. In this review we address condensation models and simulations with the main focus on heterogeneous condensation of water. The condensation process is, at first, described from a thermodynamic viewpoint where the nucleation step is described by the classical nucleation theory. Further, we address the shortcomings of the thermodynamic theory in describing the nucleation and emphasize the importance of nanoscale effects. This leads to the description of condensation from a molecular viewpoint. Also presented is how the nucleation can be simulated by use of molecular models, and how the condensation process is simulated on the macroscale using computational fluid dynamics. Finally, examples of hybrid models combining molecular and macroscale models for the simulation of condensation on a surface are presented.

Simulation studies of nucleation of ferroelectric polarization reversal.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brennecka, Geoffrey L.; Winchester, Benjamin Michael

2014-08-01

Electric field-induced reversal of spontaneous polarization is the defining characteristic of a ferroelectric material, but the process(es) and mechanism(s) associated with the initial nucleation of reverse-polarity domains are poorly understood. This report describes studies carried out using phase field modeling of LiTaO 3, a relatively simple prototype ferroelectric material, in order to explore the effects of either mechanical deformation or optically-induced free charges on nucleation and resulting domain configuration during field-induced polarization reversal. Conditions were selected to approximate as closely as feasible those of accompanying experimental work in order to provide not only support for the experimental work but alsomore » ensure that additional experimental validation of the simulations could be carried out in the future. Phase field simulations strongly support surface mechanical damage/deformation as effective for dramatically reducing the overall coercive field (Ec) via local field enhancements. Further, optically-nucleated polarization reversal appears to occur via stabilization of latent nuclei via the charge screening effects of free charges.« less

Accelerated nucleation of the 2014 Iquique, Chile Mw 8.2 Earthquake.

PubMed

Kato, Aitaro; Fukuda, Jun'ichi; Kumazawa, Takao; Nakagawa, Shigeki

2016-04-25

The earthquake nucleation process has been vigorously investigated based on geophysical observations, laboratory experiments, and theoretical studies; however, a general consensus has yet to be achieved. Here, we studied nucleation process for the 2014 Iquique, Chile Mw 8.2 megathrust earthquake located within the current North Chile seismic gap, by analyzing a long-term earthquake catalog constructed from a cross-correlation detector using continuous seismic data. Accelerations in seismicity, the amount of aseismic slip inferred from repeating earthquakes, and the background seismicity, accompanied by an increasing frequency of earthquake migrations, started around 270 days before the mainshock at locations up-dip of the largest coseismic slip patch. These signals indicate that repetitive sequences of fast and slow slip took place on the plate interface at a transition zone between fully locked and creeping portions. We interpret that these different sliding modes interacted with each other and promoted accelerated unlocking of the plate interface during the nucleation phase.

Accelerated nucleation of the 2014 Iquique, Chile Mw 8.2 Earthquake

NASA Astrophysics Data System (ADS)

Kato, Aitaro; Fukuda, Jun'Ichi; Kumazawa, Takao; Nakagawa, Shigeki

2016-04-01

The earthquake nucleation process has been vigorously investigated based on geophysical observations, laboratory experiments, and theoretical studies; however, a general consensus has yet to be achieved. Here, we studied nucleation process for the 2014 Iquique, Chile Mw 8.2 megathrust earthquake located within the current North Chile seismic gap, by analyzing a long-term earthquake catalog constructed from a cross-correlation detector using continuous seismic data. Accelerations in seismicity, the amount of aseismic slip inferred from repeating earthquakes, and the background seismicity, accompanied by an increasing frequency of earthquake migrations, started around 270 days before the mainshock at locations up-dip of the largest coseismic slip patch. These signals indicate that repetitive sequences of fast and slow slip took place on the plate interface at a transition zone between fully locked and creeping portions. We interpret that these different sliding modes interacted with each other and promoted accelerated unlocking of the plate interface during the nucleation phase.

Accelerated nucleation of the 2014 Iquique, Chile Mw 8.2 Earthquake

PubMed Central

Kato, Aitaro; Fukuda, Jun’ichi; Kumazawa, Takao; Nakagawa, Shigeki

2016-01-01

The earthquake nucleation process has been vigorously investigated based on geophysical observations, laboratory experiments, and theoretical studies; however, a general consensus has yet to be achieved. Here, we studied nucleation process for the 2014 Iquique, Chile Mw 8.2 megathrust earthquake located within the current North Chile seismic gap, by analyzing a long-term earthquake catalog constructed from a cross-correlation detector using continuous seismic data. Accelerations in seismicity, the amount of aseismic slip inferred from repeating earthquakes, and the background seismicity, accompanied by an increasing frequency of earthquake migrations, started around 270 days before the mainshock at locations up-dip of the largest coseismic slip patch. These signals indicate that repetitive sequences of fast and slow slip took place on the plate interface at a transition zone between fully locked and creeping portions. We interpret that these different sliding modes interacted with each other and promoted accelerated unlocking of the plate interface during the nucleation phase. PMID:27109362

Role of stacking disorder in ice nucleation

NASA Astrophysics Data System (ADS)

Lupi, Laura; Hudait, Arpa; Peters, Baron; Grünwald, Michael; Gotchy Mullen, Ryan; Nguyen, Andrew H.; Molinero, Valeria

2017-11-01

The freezing of water affects the processes that determine Earth’s climate. Therefore, accurate weather and climate forecasts hinge on good predictions of ice nucleation rates. Such rate predictions are based on extrapolations using classical nucleation theory, which assumes that the structure of nanometre-sized ice crystallites corresponds to that of hexagonal ice, the thermodynamically stable form of bulk ice. However, simulations with various water models find that ice nucleated and grown under atmospheric temperatures is at all sizes stacking-disordered, consisting of random sequences of cubic and hexagonal ice layers. This implies that stacking-disordered ice crystallites either are more stable than hexagonal ice crystallites or form because of non-equilibrium dynamical effects. Both scenarios challenge central tenets of classical nucleation theory. Here we use rare-event sampling and free energy calculations with the mW water model to show that the entropy of mixing cubic and hexagonal layers makes stacking-disordered ice the stable phase for crystallites up to a size of at least 100,000 molecules. We find that stacking-disordered critical crystallites at 230 kelvin are about 14 kilojoules per mole of crystallite more stable than hexagonal crystallites, making their ice nucleation rates more than three orders of magnitude higher than predicted by classical nucleation theory. This effect on nucleation rates is temperature dependent, being the most pronounced at the warmest conditions, and should affect the modelling of cloud formation and ice particle numbers, which are very sensitive to the temperature dependence of ice nucleation rates. We conclude that classical nucleation theory needs to be corrected to include the dependence of the crystallization driving force on the size of the ice crystallite when interpreting and extrapolating ice nucleation rates from experimental laboratory conditions to the temperatures that occur in clouds.

Pre-ordering of interfacial water in the pathway of heterogeneous ice nucleation does not lead to a two-step crystallization mechanism.

PubMed

Lupi, Laura; Peters, Baron; Molinero, Valeria

2016-12-07

According to Classical Nucleation Theory (CNT), the transition from liquid to crystal occurs in a single activated step with a transition state controlled by the size of the crystal embryo. This picture has been challenged in the last two decades by several reports of two-step crystallization processes in which the liquid first produces pre-ordered or dense domains, within which the crystal nucleates in a second step. Pre-ordering preceding crystal nucleation has been recently reported in simulations of ice crystallization, raising the question of whether the mechanism of ice nucleation involves two steps. In this paper, we investigate the heterogeneous nucleation of ice on carbon surfaces. We use molecular simulations with efficient coarse-grained models combined with rare event sampling methods and free energy calculations to elucidate the role of pre-ordering of liquid water at the carbon surface in the reaction coordinate for heterogeneous nucleation. We find that ice nucleation proceeds through a classical mechanism, with a single barrier between liquid and crystal. The reaction coordinate that determines the crossing of the nucleation barrier is the size of the crystal nucleus, as predicted by CNT. Wetting of the critical ice nuclei within pre-ordered domains decreases the nucleation barrier, increasing the nucleation rates. The preferential pathway for crystallization involves the early creation of pre-ordered domains that are the birthplace of the ice crystallites but do not represent a minimum in the free energy pathway from liquid to ice. We conclude that a preferential pathway through an intermediate-order precursor does not necessarily result in a two-step mechanism.

Role of stacking disorder in ice nucleation.

PubMed

Lupi, Laura; Hudait, Arpa; Peters, Baron; Grünwald, Michael; Gotchy Mullen, Ryan; Nguyen, Andrew H; Molinero, Valeria

2017-11-08

The freezing of water affects the processes that determine Earth's climate. Therefore, accurate weather and climate forecasts hinge on good predictions of ice nucleation rates. Such rate predictions are based on extrapolations using classical nucleation theory, which assumes that the structure of nanometre-sized ice crystallites corresponds to that of hexagonal ice, the thermodynamically stable form of bulk ice. However, simulations with various water models find that ice nucleated and grown under atmospheric temperatures is at all sizes stacking-disordered, consisting of random sequences of cubic and hexagonal ice layers. This implies that stacking-disordered ice crystallites either are more stable than hexagonal ice crystallites or form because of non-equilibrium dynamical effects. Both scenarios challenge central tenets of classical nucleation theory. Here we use rare-event sampling and free energy calculations with the mW water model to show that the entropy of mixing cubic and hexagonal layers makes stacking-disordered ice the stable phase for crystallites up to a size of at least 100,000 molecules. We find that stacking-disordered critical crystallites at 230 kelvin are about 14 kilojoules per mole of crystallite more stable than hexagonal crystallites, making their ice nucleation rates more than three orders of magnitude higher than predicted by classical nucleation theory. This effect on nucleation rates is temperature dependent, being the most pronounced at the warmest conditions, and should affect the modelling of cloud formation and ice particle numbers, which are very sensitive to the temperature dependence of ice nucleation rates. We conclude that classical nucleation theory needs to be corrected to include the dependence of the crystallization driving force on the size of the ice crystallite when interpreting and extrapolating ice nucleation rates from experimental laboratory conditions to the temperatures that occur in clouds.

Computational investigation of surface freezing in a molecular model of water.

PubMed

Haji-Akbari, Amir; Debenedetti, Pablo G

2017-03-28

Water freezes in a wide variety of low-temperature environments, from meteors and atmospheric clouds to soil and biological cells. In nature, ice usually nucleates at or near interfaces, because homogenous nucleation in the bulk can only be observed at deep supercoolings. Although the effect of proximal surfaces on freezing has been extensively studied, major gaps in understanding remain regarding freezing near vapor-liquid interfaces, with earlier experimental studies being mostly inconclusive. The question of how a vapor-liquid interface affects freezing in its vicinity is therefore still a major open question in ice physics. Here, we address this question computationally by using the forward-flux sampling algorithm to compute the nucleation rate in a freestanding nanofilm of supercooled water. We use the TIP4P/ice force field, one of the best existing molecular models of water, and observe that the nucleation rate in the film increases by seven orders of magnitude with respect to bulk at the same temperature. By analyzing the nucleation pathway, we conclude that freezing in the film initiates not at the surface, but within an interior region where the formation of double-diamond cages (DDCs) is favored in comparison with the bulk. This, in turn, facilitates freezing by favoring the formation of nuclei rich in cubic ice, which, as demonstrated by us earlier, are more likely to grow and overcome the nucleation barrier. The films considered here are ultrathin because their interior regions are not truly bulk-like, due to their subtle structural differences with the bulk.

Computational investigation of surface freezing in a molecular model of water

PubMed Central

Haji-Akbari, Amir; Debenedetti, Pablo G.

2017-01-01

Water freezes in a wide variety of low-temperature environments, from meteors and atmospheric clouds to soil and biological cells. In nature, ice usually nucleates at or near interfaces, because homogenous nucleation in the bulk can only be observed at deep supercoolings. Although the effect of proximal surfaces on freezing has been extensively studied, major gaps in understanding remain regarding freezing near vapor–liquid interfaces, with earlier experimental studies being mostly inconclusive. The question of how a vapor–liquid interface affects freezing in its vicinity is therefore still a major open question in ice physics. Here, we address this question computationally by using the forward-flux sampling algorithm to compute the nucleation rate in a freestanding nanofilm of supercooled water. We use the TIP4P/ice force field, one of the best existing molecular models of water, and observe that the nucleation rate in the film increases by seven orders of magnitude with respect to bulk at the same temperature. By analyzing the nucleation pathway, we conclude that freezing in the film initiates not at the surface, but within an interior region where the formation of double-diamond cages (DDCs) is favored in comparison with the bulk. This, in turn, facilitates freezing by favoring the formation of nuclei rich in cubic ice, which, as demonstrated by us earlier, are more likely to grow and overcome the nucleation barrier. The films considered here are ultrathin because their interior regions are not truly bulk-like, due to their subtle structural differences with the bulk. PMID:28292905

Invasive advance of an advantageous mutation: nucleation theory.

PubMed

O'Malley, Lauren; Basham, James; Yasi, Joseph A; Korniss, G; Allstadt, Andrew; Caraco, Thomas

2006-12-01

For sedentary organisms with localized reproduction, spatially clustered growth drives the invasive advance of a favorable mutation. We model competition between two alleles where recurrent mutation introduces a genotype with a rate of local propagation exceeding the resident's rate. We capture ecologically important properties of the rare invader's stochastic dynamics by assuming discrete individuals and local neighborhood interactions. To understand how individual-level processes may govern population patterns, we invoke the physical theory for nucleation of spatial systems. Nucleation theory discriminates between single-cluster and multi-cluster dynamics. A sufficiently low mutation rate, or a sufficiently small environment, generates single-cluster dynamics, an inherently stochastic process; a favorable mutation advances only if the invader cluster reaches a critical radius. For this mode of invasion, we identify the probability distribution of waiting times until the favored allele advances to competitive dominance, and we ask how the critical cluster size varies as propagation or mortality rates vary. Increasing the mutation rate or system size generates multi-cluster invasion, where spatial averaging produces nearly deterministic global dynamics. For this process, an analytical approximation from nucleation theory, called Avrami's Law, describes the time-dependent behavior of the genotype densities with remarkable accuracy.

Emerging techniques for assisting and accelerating food freezing processes: A review of recent research progresses.

PubMed

Cheng, Lina; Sun, Da-Wen; Zhu, Zhiwei; Zhang, Zi

2017-03-04

Freezing plays an important role in food preservation and the emergence of rapid freezing technologies can be highly beneficial to the food industry. This paper reviews some novel food freezing technologies, including high-pressure freezing (HPF), ultrasound-assisted freezing (UAF), electrically disturbed freezing (EF) and magnetically disturbed freezing (MF), microwave-assisted freezing (MWF), and osmo-dehydro-freezing (ODF). HPF and UAF can initiate ice nucleation rapidly, leading to uniform distribution of ice crystals and the control of their size and shape. Specifically, the former is focused on increasing the degree of supercooling, whereas the latter aims to decrease it. Direct current electric freezing (DC-EF) and alternating current electric freezing (AC-EF) exhibit different effects on ice nucleation. DC-EF can promote ice nucleation and AC-EF has the opposite effect. Furthermore, ODF has been successfully used for freezing various vegetables and fruit. MWF cannot control the nucleation temperature, but can decrease supercooling degree, thus decreasing the size of ice crystals. The heat and mass transfer processes during ODF have been investigated experimentally and modeled mathematically. More studies should be carried out to understand the effects of these technologies on food freezing process.

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).

Electrodeposition of CuZn Alloys from the Non-Cyanide Alkaline Baths

NASA Astrophysics Data System (ADS)

Li, Minggang; Wei, Guoying; Hu, Shuangshuang; Xu, Shuhan; Yang, Yejiong; Miao, Qinfang

2015-10-01

Effect of copper sulfate on CuZn alloys electroplating from non-cyanide baths are investigated by different electrochemical methods. Cyclic voltammetry and current transient measurements are used to characterize the CuZn alloys electroplating system in order to analyze the nucleation and growth mechanism. The reduction of Cu and CuZn alloy on sheet iron substrates shows an instantaneous nucleation process. However, the reduction of Zn on sheet iron substrates shows a progressive nucleation process. The structure and surface morphology of CuZn alloys are analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The morphology of CuZn alloys obtained with 50 g L-1 copper sulfate presents a smooth and compact deposit and the size of crystal particle is uniform.

Grain boundary oxidation and its effects on high temperature fatigue life

NASA Technical Reports Server (NTRS)

Liu, H. W.; Oshida, Yoshiki

1986-01-01

Fatigue lives at elevated temperatures are often shortened by creep and/or oxidation. Creep causes grain boundary void nucleation and grain boundary cavitation. Grain boundary voids and cavities will accelerate fatigue crack nucleation and propagation, and thereby shorten fatigue life. The functional relationships between the damage rate of fatigue crack nucleation and propagation and the kinetic process of oxygen diffusion depend on the detailed physical processes. The kinetics of grain boundary oxidation penetration was investigated. The statistical distribution of grain boundary penetration depth was analyzed. Its effect on high temperature fatigue life are discussed. A model of intermittent micro-ruptures of grain boundary oxide was proposed for high temperature fatigue crack growth. The details of these studies are reported.

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

PubMed Central

Wills, Lindsay A.; Qu, Xiaohui; Chang, I-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-01-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions. PMID:28643782

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

NASA Astrophysics Data System (ADS)

Wills, Lindsay A.; Qu, Xiaohui; Chang, I.-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-06-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 existsmore » 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.« less

Energy dispersive-EXAFS of Pd nucleation at a liquid/liquid interface

NASA Astrophysics Data System (ADS)

Chang, S.-Y.; Booth, S. G.; Uehara, A.; Mosselmans, J. F. W.; Cibin, G.; Pham, V.-T.; Nataf, L.; Dryfe, R. A. W.; Schroeder, S. L. M.

2016-05-01

Energy dispersive extended X-ray absorption fine structure (EDE) has been applied to Pd nanoparticle nucleation at a liquid/liquid interface under control over the interfacial potential and thereby the driving force for nucleation. Preliminary analysis focusing on Pd K edge-step height determination shows that under supersaturated conditions the concentration of Pd near the interface fluctuate over a period of several hours, likely due to the continuous formation and dissolution of sub-critical nuclei. Open circuit potential measurements conducted ex-situ in a liquid/liquid electrochemical cell support this view, showing that the fluctuations in Pd concentration are also visible as variations in potential across the liquid/liquid interface. By decreasing the interfacial potential through inclusion of a common ion (tetraethylammonium, TEA+) the Pd nanoparticle growth rate could be slowed down, resulting in a smooth nucleation process. Eventually, when the TEA+ ions reached an equilibrium potential, Pd nucleation and particle growth were inhibited.

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pandey, Ravindra; Usui, Kota; Livingstone, Ruth A.

Ice-nucleating organisms play important roles in the environment. With their ability to induce ice formation at temperatures just below the ice melting point, bacteria such as Pseudomonas syringae attack plants through frost damage using specialized ice-nucleating proteins. Besides the impact on agriculture and microbial ecology, airborne P. syringae can affect atmospheric glaciation processes, with consequences for cloud evolution, precipitation, and climate. Biogenic ice nucleation is also relevant for artificial snow production and for biomimetic materials for controlled interfacial freezing. We use interface-specific sum frequency generation (SFG) spectroscopy to show that hydrogen bonding at the water-bacteria contact imposes structural ordering onmore » the adjacent water network. Experimental SFG data and molecular dynamics simulations demonstrate that ice active sites within P. syringae feature unique hydrophilic-hydrophobic patterns to enhance ice nucleation. Finally, the freezing transition is further facilitated by the highly effective removal of latent heat from the nucleation site, as apparent from time-resolved SFG spectroscopy.« less

Hysteresis and the role of nucleation and growth in the hydrogenation of Mg nanolayers.

PubMed

Mooij, Lennard; Dam, Bernard

2013-02-28

We investigated the hydrogenation of 3 and 10 nm Mg layers sandwiched between Ti using an optical transmission technique (hydrogenography). We observe in situ the two dimensional nucleation and growth of single hydride domains of up to several millimeters in diameter. The low density of nuclei points to preferential nucleation at heterogeneous sites. From an analysis of the growth kinetics we deduce an extremely large edge boundary energy, which we relate to the plastic deformations inherent to the 30% volume expansion of the MgH(2). We find that the nucleation and growth process affects the hysteresis between absorption and desorption. Especially, the absorption branch can be lowered when nucleation barriers are removed. Our results show that when discussing the effect of nano-structuring on hydrogenation it may be quite complex to distinguish the thermodynamic and kinetic effects involved.

Applicability of the Fokker-Planck equation to the description of diffusion effects on nucleation

NASA Astrophysics Data System (ADS)

Sorokin, M. V.; Dubinko, V. I.; Borodin, V. A.

2017-01-01

The nucleation of islands in a supersaturated solution of surface adatoms is considered taking into account the possibility of diffusion profile formation in the island vicinity. It is shown that the treatment of diffusion-controlled cluster growth in terms of the Fokker-Planck equation is justified only provided certain restrictions are satisfied. First of all, the standard requirement that diffusion profiles of adatoms quickly adjust themselves to the actual island sizes (adiabatic principle) can be realized only for sufficiently high island concentration. The adiabatic principle is essential for the probabilities of adatom attachment to and detachment from island edges to be independent of the adatom diffusion profile establishment kinetics, justifying the island nucleation treatment as the Markovian stochastic process. Second, it is shown that the commonly used definition of the "diffusion" coefficient in the Fokker-Planck equation in terms of adatom attachment and detachment rates is justified only provided the attachment and detachment are statistically independent, which is generally not the case for the diffusion-limited growth of islands. We suggest a particular way to define the attachment and detachment rates that allows us to satisfy this requirement as well. When applied to the problem of surface island nucleation, our treatment predicts the steady-state nucleation barrier, which coincides with the conventional thermodynamic expression, even though no thermodynamic equilibrium is assumed and the adatom diffusion is treated explicitly. The effect of adatom diffusional profiles on the nucleation rate preexponential factor is also discussed. Monte Carlo simulation is employed to analyze the applicability domain of the Fokker-Planck equation and the diffusion effect beyond it. It is demonstrated that a diffusional cloud is slowing down the nucleation process for a given monomer interaction with the nucleus edge.

From Aβ Filament to Fibril: Molecular Mechanism of Surface-Activated Secondary Nucleation from All-Atom MD Simulations.

PubMed

Schwierz, Nadine; Frost, Christina V; Geissler, Phillip L; Zacharias, Martin

2017-02-02

Secondary nucleation pathways in which existing amyloid fibrils catalyze the formation of new aggregates and neurotoxic oligomers are of immediate importance for the onset and progression of Alzheimer's disease. Here, we apply extensive all-atom molecular dynamics simulations in explicit water to study surface-activated secondary nucleation pathways at the extended lateral β-sheet surface of a preformed Aβ 9-40 filament. Calculation of free-energy profiles allows us to determine binding free energies and conformational intermediates for nucleation complexes consisting of 1-4 Aβ peptides. In addition, we combine the free-energy profiles with position-dependent diffusion profiles to extract complementary kinetic information and macroscopic growth rates. Single monomers bind to the β-sheet surface in a disordered, hydrophobically collapsed conformation, whereas dimers and larger oligomers can retain a cross-β conformation resembling a more ordered fibril structure. The association processes during secondary nucleation follow a dock/lock mechanism consisting of a fast initial encounter phase (docking) and a slow structural rearrangement phase (locking). The major driving forces for surface-activated secondary nucleation are the release of a large number of hydration water molecules and the formation of hydrophobic interface contacts, the latter being in contrast to the elongation process at filament tips, which is dominated by the formation of stable and highly specific interface hydrogen bonds. The calculated binding free energies and the association rates for the attachment of Aβ monomers and oligomers to the extended lateral β-sheet surface of the filament seed are higher compared to those for elongation at the filament tips, indicating that secondary nucleation pathways can become important once a critical concentration of filaments has formed.

Inferring the effects of compositional boundary layers on crystal nucleation, growth textures, and mineral chemistry in natural volcanic tephras through submicron-resolution imaging

NASA Astrophysics Data System (ADS)

Zellmer, Georg; Sakamoto, Naoya; Hwang, Shyh-Lung; Matsuda, Nozomi; Iizuka, Yoshiyuki; Moebis, Anja; Yurimoto, Hisayoshi

2016-09-01

Crystal nucleation and growth are first order processes captured in volcanic rocks and record important information about the rates of magmatic processes and chemical evolution of magmas during their ascent and eruption. We have studied glass-rich andesitic tephras from the Central Plateau of the Southern Taupo Volcanic Zone by electron- and ion-microbeam imaging techniques to investigate down to sub-micrometre scale the potential effects of compositional boundary layers (CBLs) of melt around crystals on the nucleation and growth of mineral phases and the chemistry of crystal growth zones. We find that CBLs may influence the types of mineral phases nucleating and growing, and growth textures such as the development of swallowtails. The chemistry of the CBLs also has the capacity to trigger intermittent overgrowths of nanometre-scale bands of different phases in rapidly growing crystals, resulting in what we refer to as cryptic phase zoning. The existence of cryptic phase zoning has implications for the interpretation of microprobe compositional data, and the resulting inferences made on the conditions of magmatic evolution. Identification of cryptic phase zoning may in future lead to more accurate thermobarometric estimates and thus geospeedometric constraints. In future, a more quantitative characterization of CBL formation and its effects on crystal nucleation and growth may contribute to a better understanding of melt rheology and magma ascent processes at the onset of explosive volcanic eruptions, and will likely be of benefit to hazard mitigation efforts.

Investigation of the effect of power ultrasound on the nucleation of water during freezing of agar gel samples in tubing vials.

PubMed

Kiani, Hossein; Sun, Da-Wen; Delgado, Adriana; Zhang, Zhihang

2012-05-01

Nucleation, as an important stage of freezing process, can be induced by the irradiation of power ultrasound. In this study, the effect of irradiation temperature (-2 °C, -3 °C, -4 °C and -5 °C), irradiation duration (0s, 1s, 3s, 5s, 10s or 15s) and ultrasound intensity (0.07 W cm(-2), 0.14 W cm(-2), 0.25 W cm(-2), 0.35 W cm(-2) and 0.42 W cm(-2)) on the dynamic nucleation of ice in agar gel samples was studied. The samples were frozen in an ethylene glycol-water mixture (-20 °C) in an ultrasonic bath system after putting them into tubing vials. Results indicated that ultrasound irradiation is able to initiate nucleation at different supercooled temperatures (from -5 °C to -2 °C) in agar gel if optimum intensity and duration of ultrasound were chosen. Evaluation of the effect of 0.25 W cm(-2) ultrasound intensity and different durations of ultrasound application on agar gels showed that 1s was not long enough to induce nucleation, 3s induced the nucleation repeatedly but longer irradiation durations resulted in the generation of heat and therefore nucleation was postponed. Investigation of the effect of ultrasound intensity revealed that higher intensities of ultrasound were effective when a shorter period of irradiation was used, while lower intensities only resulted in nucleation when a longer irradiation time was applied. In addition to this, higher intensities were not effective at longer irradiation times due to the heat generated in the samples by the heating effect of ultrasound. In conclusion, the use of ultrasound as a means to control the crystallization process offers promising application in freezing of solid foods, however, optimum conditions should be selected. Copyright © 2011 Elsevier B.V. All rights reserved.

Thermodynamic Derivation of the Activation Energy for Ice Nucleation

NASA Technical Reports Server (NTRS)

Barahona, D.

2015-01-01

Cirrus clouds play a key role in the radiative and hydrological balance of the upper troposphere. Their correct representation in atmospheric models requires an understanding of the microscopic processes leading to ice nucleation. A key parameter in the theoretical description of ice nucleation is the activation energy, which controls the flux of water molecules from the bulk of the liquid to the solid during the early stages of ice formation. In most studies it is estimated by direct association with the bulk properties of water, typically viscosity and self-diffusivity. As the environment in the ice-liquid interface may differ from that of the bulk, this approach may introduce bias in calculated nucleation rates. In this work a theoretical model is proposed to describe the transfer of water molecules across the ice-liquid interface. Within this framework the activation energy naturally emerges from the combination of the energy required to break hydrogen bonds in the liquid, i.e., the bulk diffusion process, and the work dissipated from the molecular rearrangement of water molecules within the ice-liquid interface. The new expression is introduced into a generalized form of classical nucleation theory. Even though no nucleation rate measurements are used to fit any of the parameters of the theory the predicted nucleation rate is in good agreement with experimental results, even at temperature as low as 190 K, where it tends to be underestimated by most models. It is shown that the activation energy has a strong dependency on temperature and a weak dependency on water activity. Such dependencies are masked by thermodynamic effects at temperatures typical of homogeneous freezing of cloud droplets; however, they may affect the formation of ice in haze aerosol particles. The new model provides an independent estimation of the activation energy and the homogeneous ice nucleation rate, and it may help to improve the interpretation of experimental results and the development of parameterizations for cloud formation.

Studies of cavitation and ice nucleation in 'doubly-metastable' water: time-lapse photography and neutron diffraction.

PubMed

Barrow, Matthew S; Williams, P Rhodri; Chan, Hoi-Houng; Dore, John C; Bellissent-Funel, Marie-Claire

2012-10-14

High-speed photographic studies and neutron diffraction measurements have been made of water under tension in a Berthelot tube. Liquid water was cooled below the normal ice-nucleation temperature and was in a doubly-metastable state prior to a collapse of the liquid state. This transition was accompanied by an exothermic heat release corresponding with the rapid production of a solid phase nucleated by cavitation. Photographic techniques have been used to observe the phase transition over short time scales in which a solidification front is observed to propagate through the sample. Significantly, other images at a shorter time interval reveal the prior formation of cavitation bubbles at the beginning of the process. The ice-nucleation process is explained in terms of a mechanism involving hydrodynamically-induced changes in tension in supercooled water in the near vicinity of an expanding cavitation bubble. Previous explanations have attributed the nucleation of the solid phase to the production of high positive pressures. Corresponding results are presented which show the initial neutron diffraction pattern after ice-nucleation. The observed pattern does not exhibit the usual crystalline pattern of hexagonal ice [I(h)] that is formed under ambient conditions, but indicates the presence of other ice forms. The composite features can be attributed to a mixture of amorphous ice, ice-I(h)/I(c) and the high-pressure form, ice-III, and the diffraction pattern continues to evolve over a time period of about an hour.

Immersion freezing by SnomaxTM particles: Comparison of results from different instruments

NASA Astrophysics Data System (ADS)

Wex, Heike; Stratmann, Frank; Rösch, Michael; Niedermeier, Dennis; Nilius, Björn; Möhler, Ottmar; Mitra, Subir K.; Koop, Thomas; Jantsch, Evelyn; Hiranuma, Naruki; Diehl, Karoline; Curtius, Joachim; Budke, Carsten; Boose, Yvonne; Augustin, Stefanie

2014-05-01

Within the DFG funded research unit INUIT (Ice Nucleation research UnIT, FOR 1525), an effort was made to compare results on immersion freezing from a suite of different instruments. Besides mineral dusts, SnomaxTM was picked as one of the substances that were examined by all participating groups. Here, the comparison of the results for SnomaxTM is presented. Every participating group used SnomaxTM from the same batch and, as far as possible, the same particle generation set-up. Instruments participating in the comparison were, in alphabetical order, an acoustic levitator (Diehl et al., 2009), AIDA (Connolly et al., 2009), BINARY (Budke et al., 2013), FINCH (Bundke et al., 2008), LACIS (Hartmann et al., 2011), PINC (Chou et al., 2011) and the Mainz vertical windtunnel (Diehl et al., 2011). Some of the instruments examined droplets directly produced from SnomaxTM suspensions, where the suspensions could have a wide range of concentrations. Other instruments used size segregated particles which were generated via atomization from a SnomaxTM suspension and subsequent drying, followed by size selection with a DMA (Differential Mobility Analyzer). These particles were then activated to droplets and cooled subsequently. For these, the number of ice nucleation active protein complexes present in the droplets depended on the original particle size (for details see e.g. Hartmann et al., 2013). Also, the different measurements spanned a range of different time scales. The shortest residence time of roughly 1 second was used for LACIS measurements, and the longest one was about 6 seconds used in the BINARY setup with a cooling rate of 1 K/min. All data were evaluated using two different approaches: 1) a time dependent approach following Classical Nucleation Theory which included the use of a contact angle distribution (see Niedermeier et al., 2014); 2) a singular approach using an active site density per mass (see Vali, 1971, Murray et al., 2012). Both approaches were found to work equally well, hence freezing by SnomaxTM can be considered to show no time dependence. Particularly data from LACIS and BINARY, i.e. from the "fastest" and "slowest" measurements, were found to agree very well. Acknowledgement: This work was done within the framework of the DFG funded Ice Nucleation research UnIT (INUIT, FOR 1525). Literature Budke et al. (2013), Investigation of Heterogeneous Ice Nucleation Using a Novel Optical Freezing Array, AIP Conference Proceedings, 1527, 949-951, doi: 10.1064/1.4803429. Bundke et al. (2008), The fast Ice Nucleus chamber FINCH, Atmos. Res. 90, 180-186. Chou et al. (2011), Ice nuclei properties within a Saharan dust event at the Jungfraujoch in the Swiss Alps, Atmos. Chem. Phys., 11, 4725-4738. Connolly, et al. (2009), Studies of heterogeneous freezing by three different desert dust samples, Atmos. Chem. Phys., 9, 2805-2824. Diehl et al. (2011), The Mainz vertical wind tunnel facility: A review of 25 years of laboratory experiments on cloud physics and chemistry. In: J.D. Pereira (Ed.), Wind tunnels: Aerodynamics, models, and experiments. Nova Science Publishers, Inc., Chapter 2. Diehl et al. (2009), Homogeneous freezing of single sulfuric and nitric acid solution drops levitated in an acoustic trap, Atm. Res., 94, 356-361, doi:10.1016/j.atmosres.2009.06.001. Hartmann et al. (2011), Homogeneous and heterogeneous ice nucleation at LACIS: Operating principle and theoretical studies, Atmos. Chem. Phys., 11, 1753-1767. Hartmann et al. (2013), Immersion freezing of ice nucleating active protein complexes, Atmos. Chem. Phys., 13, 5751-5766. Murray et al. (2012), Ice nucleation by particles immersed in supercooled cloud droplets, Chem. Soc. Rev., 41, 6519-6554. Niedermeier et al. (2014), A computationally-efficient description of heterogeneous freezing: A simplified version of the Soccer ball model, Geophys. Res. Lett., 10.1002/2013GL058684. Vali, G. (1971), Quantitative evaluation of experimental results on heterogeneous freezing nucleation of supercooled liquids, J. Atmos. Sci., 28(3), 402-409.

Supersaturation Control using Analytical Crystal Size Distribution Estimator for Temperature Dependent in Nucleation and Crystal Growth Phenomena

NASA Astrophysics Data System (ADS)

Zahari, Zakirah Mohd; Zubaidah Adnan, Siti; Kanthasamy, Ramesh; Saleh, Suriyati; Samad, Noor Asma Fazli Abdul

2018-03-01

The specification of the crystal product is usually given in terms of crystal size distribution (CSD). To this end, optimal cooling strategy is necessary to achieve the CSD. The direct design control involving analytical CSD estimator is one of the approaches that can be used to generate the set-point. However, the effects of temperature on the crystal growth rate are neglected in the estimator. Thus, the temperature dependence on the crystal growth rate needs to be considered in order to provide an accurate set-point. The objective of this work is to extend the analytical CSD estimator where Arrhenius expression is employed to cover the effects of temperature on the growth rate. The application of this work is demonstrated through a potassium sulphate crystallisation process. Based on specified target CSD, the extended estimator is capable of generating the required set-point where a proposed controller successfully maintained the operation at the set-point to achieve the target CSD. Comparison with other cooling strategies shows a reduction up to 18.2% of the total number of undesirable crystals generated from secondary nucleation using linear cooling strategy is achieved.

Heterogeneous nucleation and growth of nanoparticles at environmental interfaces

DOE PAGES

Jun, Young -Shin; Kim, Doyoon; Neil, Chelsea W.

2016-08-11

Here, mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth’s crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolutionmore » of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of water chemistry and substrate identity on heterogeneously and homogeneously formed nanoscale precipitate size dimensions and total particle volume. Using this technique, we also provided a new platform for quantitatively comparing between heterogeneous and homogeneous nucleation and growth of nanoparticles and obtaining undiscovered interfacial energies between nuclei and surfaces. In addition, nanoscale surface characterization tools, such as in situ atomic force microscopy (AFM), were utilized to support and complement our findings. With these powerful nanoscale tools, we systematically evaluated the influences of environmentally abundant (oxy)anions and cations and the properties of environmental surfaces, such as surface charge and hydrophobicity. The findings, significantly enhanced by in situ observations, can lead to a more accurate prediction of the behaviors of nanoparticles in the environment and enable better control of the physicochemical properties of nanoparticles in engineered systems, such as catalytic reactions and energy storage.« less

Heterogeneous Nucleation and Growth of Nanoparticles at Environmental Interfaces.

PubMed

Jun, Young-Shin; Kim, Doyoon; Neil, Chelsea W

2016-09-20

Mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth's crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolution of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of water chemistry and substrate identity on heterogeneously and homogeneously formed nanoscale precipitate size dimensions and total particle volume. Using this technique, we also provided a new platform for quantitatively comparing between heterogeneous and homogeneous nucleation and growth of nanoparticles and obtaining undiscovered interfacial energies between nuclei and surfaces. In addition, nanoscale surface characterization tools, such as in situ atomic force microscopy (AFM), were utilized to support and complement our findings. With these powerful nanoscale tools, we systematically evaluated the influences of environmentally abundant (oxy)anions and cations and the properties of environmental surfaces, such as surface charge and hydrophobicity. The findings, significantly enhanced by in situ observations, can lead to a more accurate prediction of the behaviors of nanoparticles in the environment and enable better control of the physicochemical properties of nanoparticles in engineered systems, such as catalytic reactions and energy storage.

Real-time synchrotron x-ray observations of equiaxed solidification of aluminium alloys and implications for modelling

NASA Astrophysics Data System (ADS)

Prasad, A.; Liotti, E.; McDonald, S. D.; Nogita, K.; Yasuda, H.; Grant, P. S.; StJohn, D. H.

2015-06-01

Recently, in-situ observations were carried out by synchrotron X-ray radiography to observe the nucleation and growth in Al alloys during solidification. The nucleation and grain formation of a range of Al-Si and Al-Cu binary alloys were studied. When grain refiner was added to the alloys, the location of the nucleation events was readily observed. Once nucleation began it continued to occur in a wave of events with the movement of the temperature gradient across the field of view due to cooling. Other features observed were the settling of the primary phase grains in the Al-Si alloys and floating in the Al-Cu alloys, the effects of convection with marked fluctuation of the growth rate of the solid-liquid interface in the Al-Si alloys, and an absence of fragmentation. The microstructures are typical of those produced in the equiaxed zone of actual castings. These observations are compared with predictions arising from the Interdependence model. The results from this comparison have implications for further refinement of the model and simulation and modelling approaches in general. These implications will be discussed.

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.

PubMed

Abdelsayed, Victor; El-Shall, M Samy

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 correlation is found between the seed nanoparticle's size and the degree of the supersaturation of the condensing vapor. This result and the agreement among the calculated Kelvin diameters and the size of the nucleating Al nanoparticles determined by transmission electron microscopy provide strong proof for the development of a new approach for the separation and characterization of heterogeneous nuclei formed in organic vapors. These processes can take place in the atmosphere by a combination of several organic species including polar compounds which could be very efficient in activating charged nanoparticles and cluster ions of atmospheric relevance.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abdelsayed, Victor; Samy El-Shall, M., E-mail: mselshal@vcu.edu

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 indicatesmore » 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 correlation is found between the seed nanoparticle's size and the degree of the supersaturation of the condensing vapor. This result and the agreement among the calculated Kelvin diameters and the size of the nucleating Al nanoparticles determined by transmission electron microscopy provide strong proof for the development of a new approach for the separation and characterization of heterogeneous nuclei formed in organic vapors. These processes can take place in the atmosphere by a combination of several organic species including polar compounds which could be very efficient in activating charged nanoparticles and cluster ions of atmospheric relevance.« less

Understanding the crystallization behavior of as-deposited Ti-Sb-Te alloys through real-time radial distribution functions.

PubMed

Zhu, Min; Xia, Mengjiao; Song, Zhitang; Cheng, Yan; Wu, Liangcai; Rao, Feng; Song, Sannian; Wang, Miao; Lu, Yegang; Feng, Songlin

2015-06-07

Phase change materials, successfully used in optical data-storage and non-volatile electronic memory, are well-known for their ultrafast crystallization speed. However, the fundamental understanding of their crystallization behavior, especially the nucleation process, is limited by present experimental techniques. Here, real-time radial distribution functions (RDFs), derived from the selected area electron diffractions, are employed as structural probes to comprehensively study both nucleation and subsequent growth stages of Ti-doped Sb2Te3 (TST) materials in the electron-irradiation crystallization process. It can be found that the incorporation of Ti atoms in Sb2Te3 forms wrong bonds such as Ti-Te, Ti-Sb, breaks the originally ordered atomic arrangement and diminishes the initial nucleus size of the as-deposited films, which results in better thermal stability. But these nuclei hardly grow until their sizes exceed a critical value, and then a rapid growth period starts. This means that an extended nucleation time is required to form the supercritical nuclei of TST alloys with higher concentration. Also, the increasing formation of four-membered rings, which served as nucleation sites, after doping excessive Ti is responsible for the change of the crystallization behavior from growth-dominated to nucleation-dominated.

Controlled ice nucleation in cryopreservation--a review.

PubMed

Morris, G John; Acton, Elizabeth

2013-04-01

We review here for the first time, the literature on control of ice nucleation in cryopreservation. Water and aqueous solutions have a tendency to undercool before ice nucleation occurs. Control of ice nucleation has been recognised as a critical step in the cryopreservation of embryos and oocytes but is largely ignored for other cell types. We review the processes of ice nucleation and crystal growth in the solution around cells and tissues during cryopreservation with an emphasis on non IVF applications. The extent of undercooling that is encountered during the cooling of various cryocontainers is defined and the methods that have been employed to control the nucleation of ice are examined. The effects of controlled ice nucleation on the structure of the sample and the outcome of cryopreservation of a range of cell types and tissues are presented and the physical events which define the cellular response are discussed. Nucleation of ice is the most significant uncontrolled variable in conventional cryopreservation leading to sample to sample variation in cell recovery, viability and function and should be controlled to allow standardisation of cryopreservation protocols for cells for biobanking, cell based assays or clinical application. This intervention allows a way of increasing viability of cells and reducing variability between samples and should be included as standard operating procedures are developed. Copyright © 2012 Elsevier Inc. All rights reserved.

SUCCESS Evidence for Cirrus Cloud Ice Nucleation Mechanisms

NASA Technical Reports Server (NTRS)

Jensen, Eric; Gore, Warren J. Y. (Technical Monitor)

1997-01-01

During the SUCCESS mission, several measurements were made which should improve our understanding of ice nucleation processes in cirrus clouds. Temperature and water vapor concentration were made with a variety of instruments on the NASA DC-8. These observations should provide accurate upper tropospheric humidities. In particular, we will evaluate what humidities are required for ice nucleation. Preliminary results suggest that substantial supersaturations frequently exist in the upper troposphere. The leading-edge region of wave-clouds (where ice nucleation occurs) was sampled extensively at temperatures near -40 and -60C. These observations should give precise information about conditions required for ice nucleation. In addition, we will relate the observed aerosol composition and size distributions to the ice formation observed to evaluate the role of soot or mineral particles on ice nucleation. As an alternative technique for determining what particles act as ice nuclei, numerous samples of aerosols inside ice crystals were taken. In some cases, large numbers of aerosols were detected in each crystal, indicating that efficient scavenging occurred. Analysis of aerosols in ice crystals when only one particle per crystal was detected should help with the ice nucleation issue. Direct measurements of the ice nucleating activity of ambient aerosols drawn into airborne cloud chambers were also made. Finally, measurements of aerosols and ice crystals in contrails should indicate whether aircraft exhaust soot particles are effective ice nuclei.

Investigation of nucleation processes during dynamic recrystallization of ice using cryo-EBSD.

PubMed

Chauve, T; Montagnat, M; Barou, F; Hidas, K; Tommasi, A; Mainprice, D

2017-02-13

Nucleation mechanisms occurring during dynamic recrystallization play a crucial role in the evolution of microstructures and textures during high temperature deformation. In polycrystalline ice, the strong viscoplastic anisotropy induces high strain heterogeneities between grains which control the recrystallization mechanisms. Here, we study the nucleation mechanisms occurring during creep tests performed on polycrystalline columnar ice at high temperature and stress (T=-5°C;σ=0.5 MPa) by post-mortem analyses of deformation microstructures using cryogenic electron backscatter diffraction. The columnar geometry of the samples enables discrimination of the nuclei from the initial grains. Various nucleation mechanisms are deduced from the analysis of the nuclei relations with the dislocation sub-structures within grains and at grain boundaries. Tilt sub-grain boundaries and kink bands are the main structures responsible for development of polygonization and mosaic sub-structures. Nucleation by bulging at serrated grain boundaries is also an efficient nucleation mechanism near the grain boundaries where strain incompatibilities are high. Observation of nuclei with orientations not related to the 'parent' ones suggests the possibility of 'spontaneous' nucleation driven by the relaxation of the dislocation-related internal stress field. The complexity of the nucleation mechanisms observed here emphasizes the impact of stress and strain heterogeneities on dynamic recrystallization mechanisms.This article is part of the themed issue 'Microdynamics of ice'. © 2016 The Author(s).

Investigation of nucleation processes during dynamic recrystallization of ice using cryo-EBSD

PubMed Central

Barou, F.; Hidas, K.; Tommasi, A.; Mainprice, D.

2017-01-01

Nucleation mechanisms occurring during dynamic recrystallization play a crucial role in the evolution of microstructures and textures during high temperature deformation. In polycrystalline ice, the strong viscoplastic anisotropy induces high strain heterogeneities between grains which control the recrystallization mechanisms. Here, we study the nucleation mechanisms occurring during creep tests performed on polycrystalline columnar ice at high temperature and stress (T=−5°C;σ=0.5 MPa) by post-mortem analyses of deformation microstructures using cryogenic electron backscatter diffraction. The columnar geometry of the samples enables discrimination of the nuclei from the initial grains. Various nucleation mechanisms are deduced from the analysis of the nuclei relations with the dislocation sub-structures within grains and at grain boundaries. Tilt sub-grain boundaries and kink bands are the main structures responsible for development of polygonization and mosaic sub-structures. Nucleation by bulging at serrated grain boundaries is also an efficient nucleation mechanism near the grain boundaries where strain incompatibilities are high. Observation of nuclei with orientations not related to the ‘parent’ ones suggests the possibility of ‘spontaneous’ nucleation driven by the relaxation of the dislocation-related internal stress field. The complexity of the nucleation mechanisms observed here emphasizes the impact of stress and strain heterogeneities on dynamic recrystallization mechanisms. This article is part of the themed issue ‘Microdynamics of ice’. PMID:28025294

Crack Nucleation in β Titanium Alloys under High Cycle Fatigue Conditions - A Review

NASA Astrophysics Data System (ADS)

Benjamin, Rohit; Nageswara Rao, M.

2017-05-01

Beta titanium (β-Ti) alloys have emerged over the last 3 to 4 decades as an important class of titanium alloys. Many of the applications that they found, particularly in aerospace sector, are such that their high cycle fatigue (HCF) behavior becomes critical. In HCF regime, crack nucleation accounts for major part of the life. Consequently it becomes important to understand the mechanisms underlying the nucleation of cracks under HCF type loading conditions. The purpose of this review is to document the best understanding we have on date on crack nucleation in β-Ti alloys under HCF conditions. Role of various microstructural features encountered in β-Ti alloys in influencing the crack nucleation under HCF conditions has been reviewed. It has been brought out that changes in processing can result in changes in microstructure which in turn influence the time for crack nucleation/fatigue life and fatigue limit. While majority of fatigue failures originate at the surface, subsurface cracking is not uncommon with β-Ti alloys and the factors leading to subsurface cracking have been discussed in this review.

3D Study of the Morphology and Dynamics of Zeolite Nucleation.

PubMed

Melinte, Georgian; Georgieva, Veselina; Springuel-Huet, Marie-Anne; Nossov, Andreï; Ersen, Ovidiu; Guenneau, Flavien; Gedeon, Antoine; Palčić, Ana; Bozhilov, Krassimir N; Pham-Huu, Cuong; Qiu, Shilun; Mintova, Svetlana; Valtchev, Valentin

2015-12-07

The principle aspects and constraints of the dynamics and kinetics of zeolite nucleation in hydrogel systems are analyzed on the basis of a model Na-rich aluminosilicate system. A detailed time-series EMT-type zeolite crystallization study in the model hydrogel system was performed to elucidate the topological and temporal aspects of zeolite nucleation. A comprehensive set of analytical tools and methods was employed to analyze the gel evolution and complement the primary methods of transmission electron microscopy (TEM) and nuclear magnetic resonance (NMR) spectroscopy. TEM tomography reveals that the initial gel particles exhibit a core-shell structure. Zeolite nucleation is topologically limited to this shell structure and the kinetics of nucleation is controlled by the shell integrity. The induction period extends to the moment when the shell is consumed and the bulk solution can react with the core of the gel particles. These new findings, in particular the importance of the gel particle shell in zeolite nucleation, can be used to control the growth process and properties of zeolites formed in hydrogels. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microtubule nucleation and organization in dendrites

PubMed Central

Delandre, Caroline; Amikura, Reiko; Moore, Adrian W.

2016-01-01

ABSTRACT Dendrite branching is an essential process for building complex nervous systems. It determines the number, distribution and integration of inputs into a neuron, and is regulated to create the diverse dendrite arbor branching patterns characteristic of different neuron types. The microtubule cytoskeleton is critical to provide structure and exert force during dendrite branching. It also supports the functional requirements of dendrites, reflected by differential microtubule architectural organization between neuron types, illustrated here for sensory neurons. Both anterograde and retrograde microtubule polymerization occur within growing dendrites, and recent studies indicate that branching is enhanced by anterograde microtubule polymerization events in nascent branches. The polarities of microtubule polymerization events are regulated by the position and orientation of microtubule nucleation events in the dendrite arbor. Golgi outposts are a primary microtubule nucleation center in dendrites and share common nucleation machinery with the centrosome. In addition, pre-existing dendrite microtubules may act as nucleation sites. We discuss how balancing the activities of distinct nucleation machineries within the growing dendrite can alter microtubule polymerization polarity and dendrite branching, and how regulating this balance can generate neuron type-specific morphologies. PMID:27097122

Vapor-liquid nucleation: the solid touch.

PubMed

Yarom, Michal; Marmur, Abraham

2015-08-01

Vapor-liquid nucleation is a ubiquitous process that has been widely researched in many disciplines. Yet, case studies are quite scattered in the literature, and the implications of some of its basic concepts are not always clearly stated. This is especially noticeable for heterogeneous nucleation, which involves a solid surface in touch with the liquid and vapor. The current review attempts to offer a comprehensive, though concise, thermodynamic discussion of homogeneous and heterogeneous nucleation in vapor-liquid systems. The fundamental concepts of nucleation are detailed, with emphasis on the role of the chemical potential, and on intuitive explanations whenever possible. We review various types of nucleating systems and discuss the effect of the solid geometry on the characteristics of the new phase formation. In addition, we consider the effect of mixing on the vapor-liquid equilibrium. An interesting sub-case is that of a non-volatile solute that modifies the chemical potential of the liquid, but not of the vapor. Finally, we point out topics that need either further research or more exact, accurate presentation. Copyright © 2014 Elsevier B.V. All rights reserved.

Representation of Nucleation Mode Microphysics in a Global Aerosol Model with Sectional Microphysics

NASA Technical Reports Server (NTRS)

Lee, Y. H.; Pierce, J. R.; Adams, P. J.

2013-01-01

In models, nucleation mode (1 nm

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.

Collaborative Project: Understanding the Chemical Processes tat Affect Growth rates of Freshly Nucleated Particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

McMurry, Peter; Smuth, James

This final technical report describes our research activities that have, as the ultimate goal, the development of a model that explains growth rates of freshly nucleated particles. The research activities, which combine field observations with laboratory experiments, explore the relationship between concentrations of gas-phase species that contribute to growth and the rates at which those species are taken up. We also describe measurements of the chemical composition of freshly nucleated particles in a variety of locales, as well as properties (especially hygroscopicity) that influence their effects on climate.

Materials and Morphology Study for Templated Hydrogen Solidification

DOE PAGES

Shin, Swanee J.; Kozioziemski, Bernard J.

2017-11-29

In this work, we performed a series of experiments to elucidate the characteristics of a good template for solid hydrogen nucleation. Zinc stands out among several materials with comparable size and shape. Nucleation could be observed to occur on top of sharp features, such as grain boundaries and cracks, but our attempts proved unsuccessful to fabricate or replicate such features. The variations of the supercooling (ΔT) values measured for comparable samples and the dependence of ΔT on the cell temperature cycling revealed that templated nucleation of solid hydrogen is a very delicate process.

Coarse-grained models of key self-assembly processes in HIV-1

NASA Astrophysics Data System (ADS)

Grime, John

Computational molecular simulations can elucidate microscopic information that is inaccessible to conventional experimental techniques. However, many processes occur over time and length scales that are beyond the current capabilities of atomic-resolution molecular dynamics (MD). One such process is the self-assembly of the HIV-1 viral capsid, a biological structure that is crucial to viral infectivity. The nucleation and growth of capsid structures requires the interaction of large numbers of capsid proteins within a complicated molecular environment. Coarse-grained (CG) models, where degrees of freedom are removed to produce more computationally efficient models, can in principle access large-scale phenomena such as the nucleation and growth of HIV-1 capsid lattice. We report here studies of the self-assembly behaviors of a CG model of HIV-1 capsid protein, including the influence of the local molecular environment on nucleation and growth processes. Our results suggest a multi-stage process, involving several characteristic structures, eventually producing metastable capsid lattice morphologies that are amenable to subsequent capsid dissociation in order to transmit the viral infection.

Nano scale dynamics of bubble nucleation in confined liquid subjected to rapid cooling: Effect of solid-liquid interfacial wettability

NASA Astrophysics Data System (ADS)

Hasan, Mohammad Nasim; Rabbi, Kazi Fazle; Mukut, K. M.; Tamim, Saiful Islam; Faisal, A. H. M.

2017-06-01

This study focuses on the occurrence of bubble nucleation in a liquid confined in a nano scale confinement and subjected to rapid cooling at one of its wall. Due to the very small size scale of the present problem, we adopt the molecular dynamics (MD) approach. The liquid (Argon) is confined within two solid (Platinum) walls. The temperature of the upper wall of the confinement is maintained at 90 K while the lower wall is being cooled rapidly to 50 K from initial equilibrium temperature of 90 K within 0.1 ns. This results in the nucleation and formation of nanobubbles in the liquid. The pattern of bubble nucleation has been studied for three different conditions of solid-liquid interfacial wettability such as hydrophilic, hydrophobic and neutral. Behavior of bubble nucleation is significantly different in the three case of solid-liquid interfacial wettability. In case of the hydrophobic confinement (weakly adsorbing), the liquid cannot achieve deeper metastability; vapor layers appear immediately on the walls. In case of the neutral confinement (moderately adsorbing), bubble nucleation is promoted by the walls where the nucleation is heterogeneous. In case of the hydrophilic walls (strongly adsorbing) bubbles are developed inside the liquid; that is the nucleation process is homogeneous. The variation in bubble nucleation under different conditions of surface wettability has been studied by the analysis of number density distribution, spatial temperature distribution, spatial number density distribution and heat flux through the upper and lower walls of the confinement. The present study indicates that the variation of heat transfer efficiency due to different surface wettability has significant effect on the size, shape and location of bubble nucleation in case rapid cooling of liquid in nano confinement.

Critical Nuclei Size, Rate, and Activation Energy of H2 Gas Nucleation.

PubMed

German, Sean R; Edwards, Martin A; Ren, Hang; White, Henry S

2018-03-21

Electrochemical measurements of the nucleation rate of individual H 2 bubbles at the surface of Pt nanoelectrodes (radius = 7-41 nm) are used to determine the critical size and geometry of H 2 nuclei leading to stable bubbles. Precise knowledge of the H 2 concentration at the electrode surface, C H 2 surf , is obtained by controlled current reduction of H + in a H 2 SO 4 solution. Induction times of single-bubble nucleation events are measured by stepping the current, to control C H 2 surf , while monitoring the voltage. We find that gas nucleation follows a first-order rate process; a bubble spontaneously nucleates after a stochastic time delay, as indicated by a sudden voltage spike that results from impeded transport of H + to the electrode. Hundreds of individual induction times, at different applied currents and using different Pt nanoelectrodes, are used to characterize the kinetics of phase nucleation. The rate of bubble nucleation increases by four orders of magnitude (0.3-2000 s -1 ) over a very small relative change in C H 2 surf (0.21-0.26 M, corresponding to a ∼0.025 V increase in driving force). Classical nucleation theory yields thermodynamic radii of curvature for critical nuclei of 4.4 to 5.3 nm, corresponding to internal pressures of 330 to 270 atm, and activation energies for nuclei formation of 14 to 26 kT, respectively. The dependence of nucleation rate on H 2 concentration indicates that nucleation occurs by a heterogeneous mechanism, where the nuclei have a contact angle of ∼150° with the electrode surface and contain between 35 and 55 H 2 molecules.

Aerosol nucleation and its role for clouds and Earth's radiative forcing in the aerosol-climate model ECHAM5-HAM

NASA Astrophysics Data System (ADS)

Kazil, J.; Stier, P.; Zhang, K.; Quaas, J.; Kinne, S.; O'Donnell, D.; Rast, S.; Esch, M.; Ferrachat, S.; Lohmann, U.; Feichter, J.

2010-05-01

Nucleation from the gas phase is an important source of aerosol particles in the Earth's atmosphere, contributing to the number of cloud condensation nuclei, which form cloud droplets. We have implemented in the aerosol-climate model ECHAM5-HAM a new scheme for neutral and charged nucleation of sulfuric acid and water based on laboratory data, and nucleation of an organic compound and sulfuric acid using a parametrization of cluster activation based on field measurements. We give details of the implementation, compare results with observations, and investigate the role of the individual aerosol nucleation mechanisms for clouds and the Earth's radiative budget. The results of our simulations are most consistent with observations when neutral and charged nucleation of sulfuric acid proceed throughout the troposphere and nucleation due to cluster activation is limited to the forested boundary layer. The globally averaged annual mean contributions of the individual nucleation processes to total absorbed solar short-wave radiation via the direct, semi-direct, indirect cloud-albedo and cloud-lifetime effects in our simulations are -1.15 W/m2 for charged H2SO4/H2O nucleation, -0.235 W/m2 for cluster activation, and -0.05 W/m2 for neutral H2SO4/H2O nucleation. The overall effect of nucleation is -2.55 W/m2, which exceeds the sum of the individual terms due to feedbacks and interactions in the model. Aerosol nucleation contributes over the oceans with -2.18 W/m2 to total absorbed solar short-wave radiation, compared to -0.37 W/m2 over land. We explain the higher effect of aerosol nucleation on Earth's radiative budget over the oceans with the larger area covered by ocean clouds, due to the larger contrast in albedo between clouds and the ocean surface compared to continents, and the larger susceptibility of pristine clouds owing to the saturation of effects. The large effect of charged nucleation in our simulations is not in contradiction with small effects seen in local measurements: over southern Finland, where cluster activation proceeds efficiently, we find that charged nucleation of sulfuric acid and water contributes on average less than 10% to ultrafine aerosol concentrations, in good agreement with observations.

Aerosol nucleation and its role for clouds and Earth's radiative forcing in the aerosol-climate model ECHAM5-HAM

NASA Astrophysics Data System (ADS)

Kazil, J.; Stier, P.; Zhang, K.; Quaas, J.; Kinne, S.; O'Donnell, D.; Rast, S.; Esch, M.; Ferrachat, S.; Lohmann, U.; Feichter, J.

2010-11-01

Nucleation from the gas phase is an important source of aerosol particles in the Earth's atmosphere, contributing to the number of cloud condensation nuclei, which form cloud droplets. We have implemented in the aerosol-climate model ECHAM5-HAM a new scheme for neutral and charged nucleation of sulfuric acid and water based on laboratory data, and nucleation of an organic compound and sulfuric acid using a parametrization of cluster activation based on field measurements. We give details of the implementation, compare results with observations, and investigate the role of the individual aerosol nucleation mechanisms for clouds and the Earth's radiative forcing. The results of our simulations are most consistent with observations when neutral and charged nucleation of sulfuric acid proceed throughout the troposphere and nucleation due to cluster activation is limited to the forested boundary layer. The globally averaged annual mean contributions of the individual nucleation processes to total absorbed solar short-wave radiation via the direct, semi-direct, indirect cloud-albedo and cloud-lifetime effects in our simulations are -1.15 W/m2 for charged H2SO4/H2O nucleation, -0.235 W/m2 for cluster activation, and -0.05 W/m2 for neutral H2SO4/H2O nucleation. The overall effect of nucleation is -2.55 W/m2, which exceeds the sum of the individual terms due to feedbacks and interactions in the model. Aerosol nucleation contributes over the oceans with -2.18 W/m2 to total absorbed solar short-wave radiation, compared to -0.37 W/m2 over land. We explain the higher effect of aerosol nucleation on Earth's radiative forcing over the oceans with the larger area covered by ocean clouds, due to the larger contrast in albedo between clouds and the ocean surface compared to continents, and the larger susceptibility of pristine clouds owing to the saturation of effects. The large effect of charged nucleation in our simulations is not in contradiction with small effects seen in local measurements: over southern Finland, where cluster activation proceeds efficiently, we find that charged nucleation of sulfuric acid and water contributes on average less than 10% to ultrafine aerosol concentrations, in good agreement with observations.

Impact of the Bergeron-Findeisen process on the release of aerosol particles during the evolution of cloud ice

NASA Astrophysics Data System (ADS)

Schwarzenböck, A.; Mertes, S.; Heintzenberg, J.; Wobrock, W.; Laj, P.

The paper focuses on the redistribution of aerosol particles (APs) during the artificial nucleation and subsequent growth of ice crystals in a supercooled cloud. A significant number of the supercooled cloud droplets during icing periods (seeding agents: C 3H 8, CO 2) did not freeze as was presumed prior to the experiment but instead evaporated. The net mass flux of water vapour from the evaporating droplets to the nucleating ice crystals (Bergeron-Findeisen mechanism) led to the release of residual particles that simultaneously appeared in the interstitial phase. The strong decrease of the droplet residuals confirms the nucleation of ice particles on seeding germs without natural aerosol particles serving as ice nuclei. As the number of residual particles during the seedings did not drop to zero, other processes such as heterogeneous ice nucleation, spontaneous freezing, entrainment of supercooled droplets and diffusion to the created particle-free ice germs must have contributed to the experimental findings. During the icing periods, residual mass concentrations in the condensed phase dropped by a factor of 1.1-6.7, as compared to the unperturbed supercooled cloud. As the Bergeron-Findeisen process also occurs without artificial seeding in the atmosphere, this study demonstrated that the hydrometeors in mixed-phase clouds might be much cleaner than anticipated for the simple freezing process of supercooled droplets in tropospheric mid latitude clouds.

In situ observations of bubble growth in basaltic, andesitic and rhyodacitic melts

NASA Astrophysics Data System (ADS)

Masotta, M.; Ni, H.; Keppler, H.

2014-02-01

Bubble growth strongly affects the physical properties of degassing magmas and their eruption dynamics. Natural samples and products from quench experiments provide only a snapshot of the final state of volatile exsolution, leaving the processes occurring during its early stages unconstrained. In order to fill this gap, we present in situ high-temperature observations of bubble growth in magmas of different compositions (basalt, andesite and rhyodacite) at 1,100 to 1,240 °C and 0.1 MPa (1 bar), obtained using a moissanite cell apparatus. The data show that nucleation occurs at very small degrees of supersaturaturation (<60 MPa in basalt and andesite, 200 MPa in rhyodacite), probably due to heterogeneous nucleation of bubbles occurring simultaneously with the nucleation of crystals. During the early stages of exsolution, melt degassing is the driving mechanism of bubble growth, with coalescence becoming increasingly important as exsolution progresses. Ostwald ripening occurs only at the end of the process and only in basaltic melt. The average bubble growth rate ( G R) ranges from 3.4 × 10-6 to 5.2 × 10-7 mm/s, with basalt and andesite showing faster growth rates than rhyodacite. The bubble number density ( N B) at nucleation ranges from 7.9 × 104 mm-3 to 1.8 × 105 mm-3 and decreases exponentially over time. While the rhyodacite melt maintained a well-sorted bubble size distribution (BSD) through time, the BSDs of basalt and andesite are much more inhomogeneous. Our experimental observations demonstrate that bubble growth cannot be ascribed to a single mechanism but is rather a combination of many processes, which depend on the physical properties of the melt. Depending on coalescence rate, annealing of bubbles following a single nucleation event can produce complex bubble size distributions. In natural samples, such BSDs may be misinterpreted as resulting from several separate nucleation events. Incipient crystallization upon cooling of a magma may allow bubble nucleation already at very small degrees of supersaturation and could therefore be an important trigger for volatile release and explosive eruptions.

Numerical Investigation of Earthquake Nucleation on a Laboratory-Scale Heterogeneous Fault with Rate-and-State Friction

NASA Astrophysics Data System (ADS)

Higgins, N.; Lapusta, N.

2014-12-01

Many large earthquakes on natural faults are preceded by smaller events, often termed foreshocks, that occur close in time and space to the larger event that follows. Understanding the origin of such events is important for understanding earthquake physics. Unique laboratory experiments of earthquake nucleation in a meter-scale slab of granite (McLaskey and Kilgore, 2013; McLaskey et al., 2014) demonstrate that sample-scale nucleation processes are also accompanied by much smaller seismic events. One potential explanation for these foreshocks is that they occur on small asperities - or bumps - on the fault interface, which may also be the locations of smaller critical nucleation size. We explore this possibility through 3D numerical simulations of a heterogeneous 2D fault embedded in a homogeneous elastic half-space, in an attempt to qualitatively reproduce the laboratory observations of foreshocks. In our model, the simulated fault interface is governed by rate-and-state friction with laboratory-relevant frictional properties, fault loading, and fault size. To create favorable locations for foreshocks, the fault surface heterogeneity is represented as patches of increased normal stress, decreased characteristic slip distance L, or both. Our simulation results indicate that one can create a rate-and-state model of the experimental observations. Models with a combination of higher normal stress and lower L at the patches are closest to matching the laboratory observations of foreshocks in moment magnitude, source size, and stress drop. In particular, we find that, when the local compression is increased, foreshocks can occur on patches that are smaller than theoretical critical nucleation size estimates. The additional inclusion of lower L for these patches helps to keep stress drops within the range observed in experiments, and is compatible with the asperity model of foreshock sources, since one would expect more compressed spots to be smoother (and hence have lower L). In this heterogeneous rate-and-state fault model, the foreshocks interact with each other and with the overall nucleation process through their postseismic slip. The interplay amongst foreshocks, and between foreshocks and the larger-scale nucleation process, is a topic of our future work.

Crystal growth in a microgravity environment

NASA Technical Reports Server (NTRS)

Kroes, Roger L. (Inventor); Reiss, Donald A. (Inventor); Lehoczky, Sandor L. (Inventor)

1992-01-01

Gravitational phenomena, including convection, sedimentation, and interactions of materials with their containers all affect the crystal growth process. If they are not taken into consideration they can have adverse effects on the quantity and quality of crystals produced. As a practical matter, convection, and sedimentation can be completely eliminated only under conditions of low gravity attained during orbital flight. There is, then, an advantage to effecting crystallization in space. In the absence of convection in a microgravity environment cooling proceeds by thermal diffusion from the walls to the center of the solution chamber. This renders control of nucleation difficult. Accordingly, there is a need for a new improved nucleation process in space. Crystals are nucleated by creating a small localized region of high relative supersaturation in a host solution at a lower degree of supersaturation.

A size-composition resolved aerosol model for simulating the dynamics of externally mixed particles: SCRAM (v 1.0)

NASA Astrophysics Data System (ADS)

Zhu, S.; Sartelet, K. N.; Seigneur, C.

2015-06-01

The Size-Composition Resolved Aerosol Model (SCRAM) for simulating the dynamics of externally mixed atmospheric particles is presented. This new model classifies aerosols by both composition and size, based on a comprehensive combination of all chemical species and their mass-fraction sections. All three main processes involved in aerosol dynamics (coagulation, condensation/evaporation and nucleation) are included. The model is first validated by comparison with a reference solution and with results of simulations using internally mixed particles. The degree of mixing of particles is investigated in a box model simulation using data representative of air pollution in Greater Paris. The relative influence on the mixing state of the different aerosol processes (condensation/evaporation, coagulation) and of the algorithm used to model condensation/evaporation (bulk equilibrium, dynamic) is studied.

Microstructure evolution and texture development in a friction stir-processed AISI D2 tool steel

NASA Astrophysics Data System (ADS)

Yasavol, N.; Abdollah-zadeh, A.; Vieira, M. T.; Jafarian, H. R.

2014-02-01

Crystallographic texture developments during friction stir processing (FSP) of AISI D2 tool were studied with respect to grain sizes in different tool rotation rates. Comparison of the grain sizes in various rotation rates confirmed that grain refinement occurred progressively in higher rotation rates by severe plastic deformation. It was found that the predominant mechanism during FSP should be dynamic recovery (DRV) happened concurrently with continuous dynamic recrystallization (CDRX) caused by particle-stimulated nucleation (PSN). The developed shear texture relates to the ideal shear textures of D1 and D2 in bcc metals. The prevalence of highly dense arrangement of close-packed planes of bcc and the lowest Taylor factor showed the lowest compressive residual stress which is responsible for better mechanical properties compared with the grain-precipitate refinement.

Landscapes with megabasins: Polyamorphism in liquids and biopolymers and the role of nucleation in folding and folding diseases

NASA Astrophysics Data System (ADS)

Angell, C. A.

1997-02-01

We show how energy landscape concepts can rationalize the observations on glassforming liquids over the whole range of behavior, strong to fragile. In particular, we show how the existence of landscapes with both strong and fragile megabasins can provide a basis for understanding the nature of quasi-first-order transitions between amorphous states such as those observed to occur in the glassy states of “strong” glassformers. We show how this propensity originates in the liquid state and then emphasize the analogy provided, at the mesoscopic level, by the folding transition in proteins. Recognition that the folding transition is an equilibrium first-order transition between polyamorphic forms of a complex system implies recognition of the need for a nucleation step in the process. When nucleated phase transitions are kinetically retarded, their probability can be influenced by time-temperature history and by the presence of nucleating agents. Nucleation events are statistically rare in mesoscopic systems, hence the ability to fold rapidly should require special features in the folding molecular structure or the presence of nucleating agents. We propose that the unwanted folding events leading to pathogenic forms of certain proteins (prions) can be stimulated by nucleating agents, which thus may be the unidentified infectious agents in “mad cow” disease and related maladies.

Mechanisms for Ductile Rupture - FY16 ESC Progress Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boyce, Brad L.; Carroll, Jay D.; Noell, Phillip

2017-01-01

Ductile rupture in metals is generally a multi-step process of void nucleation, growth, and coalescence. Particle decohesion and particle fracture are generally invoked as the primary microstructural mechanisms for room-temperature void nucleation. However, because high-purity materials also fail by void nucleation and coalescence, other microstructural features must also act as sites for void nucleation. Early studies of void initiation in high-purity materials, which included post-mortem fracture surface characterization using scanning electron microscopy (SEM) and high-voltage electron microscopy (HVEM) and in-situ HVEM observations of fracture, established the presence of dislocation cell walls as void initiation sites in high-purity materials. Direct experimentalmore » evidence for this contention was obtained during in-situ HVEM tensile tests of Be single crystals. Voids between 0.2 and 1 μm long appeared suddenly along dislocation cell walls during tensile straining. However, subsequent attempts to replicate these results in other materials, particularly α -Fe single crystals, were unsuccessful because of the small size of the dislocation cells, and these remain the only published in-situ HVEM observations of void nucleation at dislocation cell walls in the absence of a growing macrocrack. Despite this challenge, other approaches to studying void nucleation in high-purity metals also indicate that dislocation cell walls are nucleation sites for voids.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mishchenko, L; Khan, M; Aizenberg, J

Certain natural organisms use micro-patterned surface chemistry, or ice-nucleating species, to control water condensation and ice nucleation for survival under extreme conditions. As an analogy to these biological approaches, it is shown that functionalized, hydrophilic polymers and particles deposited on the tips of superhydrophobic posts induce precise topographical control over water condensation and freezing at the micrometer scale. A bottom-up deposition process is used to take advantage of the limited contact area of a non-wetting aqueous solution on a superhydrophobic surface. Hydrophilic polymer deposition on the tips of these geometrical structures allows spatial control over the nucleation, growth, and coalescencemore » of micrometer-scale water droplets. The hydrophilic tips nucleate water droplets with extremely uniform nucleation and growth rates, uniform sizes, an increased stability against coalescence, and asymmetric droplet morphologies. Control of freezing behavior is also demonstrated via deposition of ice-nucleating AgI nanoparticles on the tips of these structures. This combination of the hydrophilic polymer and AgI particles on the tips was used to achieve templating of ice nucleation at the micrometer scale. Preliminary results indicate that control over ice crystal size, spatial symmetry, and position might be possible with this method. This type of approach can serve as a platform for systematically analyzing micrometer-scale condensation and freezing phenomena, and as a model for natural systems.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mishchenko, Lidiya; Khan, M.; Aizenberg, Joanna

Certain natural organisms use micro-patterned surface chemistry, or ice-nucleating species, to control water condensation and ice nucleation for survival under extreme conditions. As an analogy to these biological approaches, it is shown that functionalized, hydrophilic polymers and particles deposited on the tips of superhydrophobic posts induce precise topographical control over water condensation and freezing at the micrometer scale. A bottom-up deposition process is used to take advantage of the limited contact area of a non-wetting aqueous solution on a superhydrophobic surface. Hydrophilic polymer deposition on the tips of these geometrical structures allows spatial control over the nucleation, growth, and coalescencemore » of micrometer-scale water droplets. The hydrophilic tips nucleate water droplets with extremely uniform nucleation and growth rates, uniform sizes, an increased stability against coalescence, and asymmetric droplet morphologies. Furthermore, control of freezing behavior is also demonstrated via deposition of ice-nucleating AgI nanoparticles on the tips of these structures. The combination of the hydrophilic polymer and AgI particles on the tips was used to achieve templating of ice nucleation at the micrometer scale. Preliminary results indicate that control over ice crystal size, spatial symmetry, and position might be possible with this method. This type of approach can serve as a platform for systematically analyzing micrometer-scale condensation and freezing phenomena, and as a model for natural systems.« less

In vivo bubble nucleation probability in sheep brain tissue.

PubMed

Gateau, J; Aubry, J-F; Chauvet, D; Boch, A-L; Fink, M; Tanter, M

2011-11-21

Gas nuclei exist naturally in living bodies. Their activation initiates cavitation activity, and is possible using short ultrasonic excitations of high amplitude. However, little is known about the nuclei population in vivo, and therefore about the rarefaction pressure required to form bubbles in tissue. A novel method dedicated to in vivo investigations was used here that combines passive and active cavitation detection with a multi-element linear ultrasound probe (4-7 MHz). Experiments were performed in vivo on the brain of trepanated sheep. Bubble nucleation was induced using a focused single-element transducer (central frequency 660 kHz, f-number = 1) driven by a high power (up to 5 kW) electric burst of two cycles. Successive passive recording and ultrafast active imaging were shown to allow detection of a single nucleation event in brain tissue in vivo. Experiments carried out on eight sheep allowed statistical studies of the bubble nucleation process. The nucleation probability was evaluated as a function of the peak negative pressure. No nucleation event could be detected with a peak negative pressure weaker than -12.7 MPa, i.e. one order of magnitude higher than the recommendations based on the mechanical index. Below this threshold, bubble nucleation in vivo in brain tissues is a random phenomenon.

Microbial production of ice crystals in clouds as a novel atmospheric biosignature

NASA Astrophysics Data System (ADS)

Santl-Temkiv, T.; Sahyoun, M.; Kjeldsen, H.; Ling, M.; Boesen, T.; Karlson, U. G.; Finster, K.

2014-03-01

A diverse assembly of exoplanets has been discovered during recent decades (Howard 2013), their atmospheres providing some of the most accessible evidence for the presence of biological activity on these planets. Metabolic gases have been commonly proposed as atmospheric biosignatures (Seager et al 2012). However, airborne microbes are also involved in cloud- and precipitation formation on Earth. Thus, meteorological phenomena may serve as alternative atmospheric biosignatures, for which appropriate observational techniques have yet to be developed. The atmospheric part of the Earth's water cycle heavily relies on the presence of nucleating particles, which promote the condensation and freezing of atmospheric water, both potentially leading to precipitation. While cloud condensation nuclei are diverse and relatively common, ice nuclei are poorly understood and comparably rare airborne particles. According to current knowledge, most ice nucleation below ñ15∞C is driven by the presence of inorganic dust particles, which are considered inactive at higher temperatures. Biogenic IN are the only reported particles that promote ice formation above ñ10∞C. Some bacteria, e.g. Pseudomonas syringae, produce Ice Nucleation Active (INA) proteins that are most efficient ice nuclei currently known. These INA bacteria are common in the atmosphere, and may thus be involved in precipitation processes of mixed phase clouds (Möhler et al 2007). We investigate the relevance of bacterial INA proteins for atmospheric processes using three approaches: (i) study of the presence of INA bacteria and their INA proteins in the atmosphere, (ii) a detailed molecular and physical study of isolated INA proteins, and finally (iii) a modeling study of the importance of INA proteins for ice-path in clouds as well as their importance for precipitation. During 14 precipitation events, we observed that 12% of isolated bacteria carried INA genes. INA bacteria had likely been emitted to the atmosphere from terrestrial surfaces, e.g. by convective transport. Additionally, we found INA biological fragments <220 nm in two precipitation samples (199, 482 INA per L), which indicates that in addition to intact cells, bacterial fragments that are more abundant than cells could also impact atmospheric processes. In order to study isolated INA proteins, we sequenced the INA gene from one of the isolated bacteria, Pseudomonas sp. R10.79. The INA gene will be expressed, purified and introduced into nano-discs. These INA nano-discs will facilitate a detailed molecular and physical study of INA proteins and its ice active properties. Most of modeling approaches rely on parameterizations based on classical nucleation theory, e.g. CH08 (Chen et al 2008), when introducing INA bacteria into climate models. Instead, we used an experimentally derived parameterization HAR13 (Hartmann et al 2013), when introducing bacteria into a 1-d operational weather forecast model HIRLAM (Unden et al 2002). By comparison HAR13 yields more ice and is more sensitive to the change of bacterial densities than CH08. While CH08 is a function of the size of the ice nuclei, HAR13 is a function of the number of INA protein complexes. INA protein complexes are the locations where the nucleation occurs and their number appears to be a more important parameter than cell size. We suggest that the study of individual INA proteins complexes both alone and on cell surfaces will lead to a better understanding of ice nucleation by INA bacteria.

Nucleation speed limit on remote fluid induced earthquakes

USGS Publications Warehouse

Parsons, Thomas E.; Akinci, Aybige; Malignini, Luca

2017-01-01

Earthquakes triggered by other remote seismic events are explained as a response to long-traveling seismic waves that temporarily stress the crust. However, delays of hours or days after seismic waves pass through are reported by several studies, which are difficult to reconcile with the transient stresses imparted by seismic waves. We show that these delays are proportional to magnitude and that nucleation times are best fit to a fluid diffusion process if the governing rupture process involves unlocking a magnitude-dependent critical nucleation zone. It is well established that distant earthquakes can strongly affect the pressure and distribution of crustal pore fluids. Earth’s crust contains hydraulically isolated, pressurized compartments in which fluids are contained within low-permeability walls. We know that strong shaking induced by seismic waves from large earthquakes can change the permeability of rocks. Thus, the boundary of a pressurized compartment may see its permeability rise. Previously confined, overpressurized pore fluids may then diffuse away, infiltrate faults, decrease their strength, and induce earthquakes. Magnitude-dependent delays and critical nucleation zone conclusions can also be applied to human-induced earthquakes.

Nucleation speed limit on remote fluid-induced earthquakes.

PubMed

Parsons, Tom; Malagnini, Luca; Akinci, Aybige

2017-08-01

Earthquakes triggered by other remote seismic events are explained as a response to long-traveling seismic waves that temporarily stress the crust. However, delays of hours or days after seismic waves pass through are reported by several studies, which are difficult to reconcile with the transient stresses imparted by seismic waves. We show that these delays are proportional to magnitude and that nucleation times are best fit to a fluid diffusion process if the governing rupture process involves unlocking a magnitude-dependent critical nucleation zone. It is well established that distant earthquakes can strongly affect the pressure and distribution of crustal pore fluids. Earth's crust contains hydraulically isolated, pressurized compartments in which fluids are contained within low-permeability walls. We know that strong shaking induced by seismic waves from large earthquakes can change the permeability of rocks. Thus, the boundary of a pressurized compartment may see its permeability rise. Previously confined, overpressurized pore fluids may then diffuse away, infiltrate faults, decrease their strength, and induce earthquakes. Magnitude-dependent delays and critical nucleation zone conclusions can also be applied to human-induced earthquakes.

Nucleation speed limit on remote fluid-induced earthquakes

PubMed Central

Parsons, Tom; Malagnini, Luca; Akinci, Aybige

2017-01-01

Earthquakes triggered by other remote seismic events are explained as a response to long-traveling seismic waves that temporarily stress the crust. However, delays of hours or days after seismic waves pass through are reported by several studies, which are difficult to reconcile with the transient stresses imparted by seismic waves. We show that these delays are proportional to magnitude and that nucleation times are best fit to a fluid diffusion process if the governing rupture process involves unlocking a magnitude-dependent critical nucleation zone. It is well established that distant earthquakes can strongly affect the pressure and distribution of crustal pore fluids. Earth’s crust contains hydraulically isolated, pressurized compartments in which fluids are contained within low-permeability walls. We know that strong shaking induced by seismic waves from large earthquakes can change the permeability of rocks. Thus, the boundary of a pressurized compartment may see its permeability rise. Previously confined, overpressurized pore fluids may then diffuse away, infiltrate faults, decrease their strength, and induce earthquakes. Magnitude-dependent delays and critical nucleation zone conclusions can also be applied to human-induced earthquakes. PMID:28845448

Anvil Glaciation in a Deep Cumulus Updraught over Florida Simulated with the Explicit Microphysics Model. I: Impact of Various Nucleation Processes

NASA Technical Reports Server (NTRS)

Phillips, Vaughan T. J.; Andronache, Constantin; Sherwood, Steven C.; Bansemer, Aaron; Conant, William C.; Demott, Paul J.; Flagan, Richard C.; Heymsfield, Andy; Jonsson, Haflidi; Poellot, Micheal;

Regiospecific Nucleation and Growth of Silane Coupling Agent Droplets onto Colloidal Particles

PubMed Central

2017-01-01

Nucleation-and-growth processes are used extensively in the synthesis of spherical colloids, and more recently regiospecific nucleation-and-growth processes have been exploited to prepare more complex colloids such as patchy particles. We demonstrate that surface geometry alone can be made to play the dominant role in determining the final particle geometry in such syntheses, meaning that intricate chemical surface patternings are not required. We present a synthesis method for “lollipop”-shaped colloidal heterodimers (patchy particles), combining a recently published nucleation-and-growth technique with our recent findings that particle geometry influences the locus of droplet adsorption onto anisotropic template particles. Specifically, 3-methacryloxypropyl trimethoxysilane (MPTMS) is nucleated and grown onto bullet-shaped and nail-shaped colloids. The shape of the template particle can be chosen such that the MPTMS adsorbs regiospecifically onto the flat ends. In particular, we find that particles with a wider base increase the range of droplet volumes for which the minimum in the free energy of adsorption is located at the flat end of the particle compared with bullet-shaped particles of the same aspect ratio. We put forward an extensive analysis of the synthesis mechanism and experimentally determine the physical properties of the heterodimers, supported by theoretical simulations. Here we numerically optimize, for the first time, the shape of finite-sized droplets as a function of their position on the rod-like silica particle surface. We expect that our findings will give an impulse to complex particle creation by regiospecific nucleation and growth. PMID:29057028

Numerical Issues Associated with Compensating and Competing Processes in Climate Models: an Example from ECHAM-HAM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wan, Hui; Rasch, Philip J.; Zhang, Kai

2013-06-26

The purpose of this paper is to draw attention to the need for appropriate numerical techniques to represent process interactions in climate models. In two versions of the ECHAM-HAM model, different time integration methods are used to solve the sulfuric acid (H2SO4) gas evolution equation, which lead to substantially different results in the H2SO4 gas concentration and the aerosol nucleation rate. Using convergence tests and sensitivity simulations performed with various time stepping schemes, it is confirmed that numerical errors in the second model version are significantly smaller than those in version one. The use of sequential operator splitting in combinationmore » with long time step is identified as the main reason for the large systematic biases in the old model. The remaining errors in version two in the nucleation rate, related to the competition between condensation and nucleation, have a clear impact on the simulated concentration of cloud condensation nuclei in the lower troposphere. These errors can be significantly reduced by employing an implicit solver that handles production, condensation and nucleation at the same time. Lessons learned in this work underline the need for more caution when treating multi-time-scale problems involving compensating and competing processes, a common occurrence in current climate models.« less

Numerical determination of the interfacial energy and nucleation barrier of curved solid-liquid interfaces in binary systems

NASA Astrophysics Data System (ADS)

Kundin, Julia; Choudhary, Muhammad Ajmal

2016-07-01

The phase-field crystal (PFC) technique is a widely used approach for modeling crystal growth phenomena with atomistic resolution on mesoscopic time scales. We use a two-dimensional PFC model for a binary system based on the work of Elder et al. [Phys. Rev. B 75, 064107 (2007), 10.1103/PhysRevB.75.064107] to study the effect of the curved, diffuse solid-liquid interface on the interfacial energy as well as the nucleation barrier. The calculation of the interfacial energy and the nucleation barrier certainly depends on the proper definition of the solid-liquid dividing surface and the corresponding nucleus size. We define the position of the sharp interface at which the interfacial energy is to be evaluated by using the concept of equimolar dividing surface (re) and the minimization of the interfacial energy (rs). The comparison of the results based on both radii shows that the difference re-rs is always positive and has a limit for large cluster sizes which is comparable to the Tolman length. Furthermore, we found the real nucleation barrier for small cluster sizes, which is defined as a function of the radius rs, and compared it with the classical nucleation theory. The simulation results also show that the extracted interfacial energy as function of both radii is independent of system size, and this dependence can be reasonably described by the nonclassical Tolman formula with a positive Tolman length.

Controllable Magnetization Processes Induced by Nucleation Sites in Permalloy Rings

NASA Astrophysics Data System (ADS)

Chen, Ying-Jiun; Hsu, Chia-Jung; Liao, Chun-Neng; Huang, Hao-Ting; Lee, Chiun-Peng; Chiu, Yi-Hsun; Tung, Tzu-Yun; Lai, Mei-Feng

2010-02-01

Different arrangements of notches as nucleation sites are demonstrated experimentally and numerically to effectively control the magnetization processes of permalloy rings. In the ring with notches at the same side with respect to field direction, two same-helicity vortex domain walls in the onion state lead to two-step switching going through flux-closure state; in the ring with diagonal notches two opposite-helicity vortex domain walls lead to one-step switching skipping flux-closure state. The switching processes are repeatable in contrast to rings without notches where helicites of two vortex domain walls are random so the switching processes can not be controlled.

Homogeneous nucleation in supersaturated vapors of methane, ethane, and carbon dioxide predicted by brute force molecular dynamics.

PubMed

Horsch, Martin; Vrabec, Jadran; Bernreuther, Martin; Grottel, Sebastian; Reina, Guido; Wix, Andrea; Schaber, Karlheinz; Hasse, Hans

2008-04-28

Molecular dynamics (MD) simulation is applied to the condensation process of supersaturated vapors of methane, ethane, and carbon dioxide. Simulations of systems with up to a 10(6) particles were conducted with a massively parallel MD program. This leads to reliable statistics and makes nucleation rates down to the order of 10(30) m(-3) s(-1) accessible to the direct simulation approach. Simulation results are compared to the classical nucleation theory (CNT) as well as the modification of Laaksonen, Ford, and Kulmala (LFK) which introduces a size dependence of the specific surface energy. CNT describes the nucleation of ethane and carbon dioxide excellently over the entire studied temperature range, whereas LFK provides a better approach to methane at low temperatures.

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.

Experimental approaches to well controlled studies of thin-film nucleation and growth.

NASA Technical Reports Server (NTRS)

Poppa, H.; Moorhead, R. D.; Heinemann, K.

1972-01-01

Particular features and the performance of two experimental systems are described for quantitative studies of thin-film nucleation and growth processes including epitaxial depositions. System I consists of a modified LEED-Auger instrument combined with high-resolution electron microscopy. System II is a UHV electron microscope adapted for in-situ deposition studies. The two systems complement each other ideally, and the combined use of both can result in a comprehensive investigation of vapor deposition processes not obtainable with any other known method.

Experimental Study of the Low Supersaturation Nucleation in Crystal Growth by Contactless Physical Vapor Transport

NASA Technical Reports Server (NTRS)

Grasza, K.; Palosz, W.; Trivedi, S. B.

1998-01-01

The process of the development of the nuclei and of subsequent seeding in 'contactless' physical vapor transport is investigated experimentally. Consecutive stages of the Low Supersaturation Nucleation in 'contactless' geometry for growth of CdTe crystals from the vapor are shown. The effects of the temperature field, geometry of the system, and experimental procedures on the process are presented and discussed. The experimental results are found to be consistent with our earlier numerical modeling results.

Divorced Eutectic Solidification of Mg-Al Alloys

NASA Astrophysics Data System (ADS)

Monas, Alexander; Shchyglo, Oleg; Kim, Se-Jong; Yim, Chang Dong; Höche, Daniel; Steinbach, Ingo

2015-08-01

We present simulations of the nucleation and equiaxed dendritic growth of the primary hexagonal close-packed -Mg phase followed by the nucleation of the -phase in interdendritic regions. A zoomed-in region of a melt channel under eutectic conditions is investigated and compared with experiments. The presented simulations allow prediction of the final properties of an alloy based on process parameters. The obtained results give insight into the solidification processes governing the microstructure formation of Mg-Al alloys, allowing their targeted design for different applications.

Advances in heterogeneous ice nucleation research: Theoretical modeling and measurements

NASA Astrophysics Data System (ADS)

Beydoun, Hassan

In the atmosphere, cloud droplets can remain in a supercooled liquid phase at temperatures as low as -40 °C. Above this temperature, cloud droplets freeze via heterogeneous ice nucleation whereby a rare and poorly understood subset of atmospheric particles catalyze the ice phase transition. As the phase state of clouds is critical in determining their radiative properties and lifetime, deficiencies in our understanding of heterogeneous ice nucleation poses a large uncertainty on our efforts to predict human induced global climate change. Experimental challenges in properly simulating particle-induced freezing processes under atmospherically relevant conditions have largely contributed to the absence of a well-established model and parameterizations that accurately predict heterogeneous ice nucleation. Conversely, the sparsity of reliable measurement techniques available struggle to be interpreted by a single consistent theoretical or empirical framework, which results in layers of uncertainty when attempting to extrapolate useful information regarding ice nucleation for use in atmospheric cloud models. In this dissertation a new framework for describing heterogeneous ice nucleation is developed. Starting from classical nucleation theory, the surface of an ice nucleating particle is treated as a continuum of heterogeneous ice nucleating activity and a particle specific distribution of this activity g is derived. It is hypothesized that an individual particle species exhibits a critical surface area. Above this critical area the ice nucleating activity of a particle species can be described by one g distribution, g, while below it g expresses itself expresses externally resulting in particle to particle variability in ice nucleating activity. The framework is supported by cold plate droplet freezing measurements for dust and biological particles in which the total surface area of particle material available is varied. Freezing spectra above a certain surface area are shown to be successfully fitted with g while a process of random sampling from g can predict the freezing behavior below the identified critical surface area threshold. The framework is then extended to account for droplets composed of multiple particle species and successfully applied to predict the freezing spectra of a mixed proxy for an atmospheric dust-biological particle system. The contact freezing mode of ice nucleation, whereby a particle induces freezing upon collision with a droplet, is thought to be more efficient than particle initiated immersion freezing from within the droplet bulk. However, it has been a decades' long challenge to accurately measure this ice nucleation mode, since it necessitates reliably measuring the rate at which particles hit a droplet surface combined with direct determination of freezing onset. In an effort to remedy this longstanding deficiency a temperature controlled chilled aerosol optical tweezers capable of stably isolating water droplets in air at subzero temperatures has been designed and implemented. The new temperature controlled system retains the powerful capabilities of traditional aerosol optical tweezers: retrieval of a cavity enhanced Raman spectrum which could be used to accurately determine the size and refractive index of a trapped droplet. With these capabilities, it is estimated that the design can achieve ice supersaturation conditions at the droplet surface. It was also found that a KCl aqueous droplet simultaneously cooling and evaporating exhibited a significantly higher measured refractive index at its surface than when it was held at a steady state temperature. This implies the potential of a "salting out" process. Sensitivity of the cavity enhanced Raman spectrum as well as the visual image of a trapped droplet to dust particle collisions is shown, an important step in measuring collision frequencies of dust particles with a trapped droplet. These results may pave the way for future experiments of the exceptionally poorly understood contact freezing mode of ice nucleation.

Controlled nucleation in freeze-drying: effects on pore size in the dried product layer, mass transfer resistance, and primary drying rate.

PubMed

Konstantinidis, Alex K; Kuu, Wei; Otten, Lori; Nail, Steven L; Sever, Robert R

2011-08-01

A novel and scalable method has been developed to enable control of the ice nucleation step for the freezing process during lyophilization. This method manipulates the chamber pressure of the freeze dryer to simultaneously induce nucleation in all product vials at a desired temperature. The effects of controlled nucleation on the drying rate of various formulations including 5% (w/w) mannitol, 5% (w/w) sucrose, and a mixture of 3% (w/w) mannitol and 2% (w/w) sucrose were studied. For a 5% (w/w) mannitol, uncontrolled ice nucleation occurred randomly at product temperatures between -8.0°C and -15.9°C as the vials were cooled to -40°C. Controlled ice nucleation was achieved at product temperatures between -2.3°C and -3.7°C. The effect of nucleation control on the effective pore radius (r(e) ) of the cake was determined from the product temperature profiles using a pore diffusion model in combination with a nonlinear parameter estimation approach reported earlier. Results show that the value of r(e) for 5% (w/w) mannitol was enlarged from 13 to 27 μm by uniformly inducing nucleation at higher temperatures. Applying the resistance parameters obtained from the pore diffusion model for 5% (w/w) mannitol, optimized cycles were theoretically generated and experimentally tested, resulting in a 41% reduction in primary drying time. Copyright © 2011 Wiley-Liss, Inc.

Magnetic vortex nucleation modes in static magnetic fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vanatka, Marek; Urbanek, Michal; Jira, Roman

The magnetic vortex nucleation process in nanometer- and micrometer-sized magnetic disks undergoes several phases with distinct spin configurations called the nucleation states. Before formation of the final vortex state, small submicron disks typically proceed through the so-called C-state while the larger micron-sized disks proceed through the more complicated vortex-pair state or the buckling state. This work classifies the nucleation states using micromagnetic simulations and provides evidence for the stability of vortex-pair and buckling states in static magnetic fields using magnetic imaging techniques and electrical transport measurements. Lorentz Transmission Electron Microscopy and Magnetic Transmission X-ray Microscopy are employed to reveal themore » details of spin configuration in each of the nucleation states. We further show that it is possible to unambiguously identify these states by electrical measurements via the anisotropic magnetoresistance effect. Combination of the electrical transport and magnetic imaging techniques confirms stability of a vortex-antivortex-vortex spin configuration which emerges from the buckling state in static magnetic fields.« less

Magnetic vortex nucleation modes in static magnetic fields

DOE PAGES

Vanatka, Marek; Urbanek, Michal; Jira, Roman; ...

2017-10-03

The magnetic vortex nucleation process in nanometer- and micrometer-sized magnetic disks undergoes several phases with distinct spin configurations called the nucleation states. Before formation of the final vortex state, small submicron disks typically proceed through the so-called C-state while the larger micron-sized disks proceed through the more complicated vortex-pair state or the buckling state. This work classifies the nucleation states using micromagnetic simulations and provides evidence for the stability of vortex-pair and buckling states in static magnetic fields using magnetic imaging techniques and electrical transport measurements. Lorentz Transmission Electron Microscopy and Magnetic Transmission X-ray Microscopy are employed to reveal themore » details of spin configuration in each of the nucleation states. We further show that it is possible to unambiguously identify these states by electrical measurements via the anisotropic magnetoresistance effect. Combination of the electrical transport and magnetic imaging techniques confirms stability of a vortex-antivortex-vortex spin configuration which emerges from the buckling state in static magnetic fields.« less

Cirrus Susceptibility to Changes in Ice Nuclei: Physical Processes, Model Uncertainties, and Measurement Needs

NASA Technical Reports Server (NTRS)

Jensen, Eric

2017-01-01

In this talk, I will begin by discussing the physical processes that govern the competition between heterogeneous and homogeneous ice nucleation in upper tropospheric cirrus clouds. Next, I will review the current knowledge of low-temperature ice nucleation from laboratory experiments and field measurements. I will then discuss the uncertainties and deficiencies in representations of cirrus processes in global models used to estimate the climate impacts of changes in cirrus clouds. Lastly, I will review the critical field measurements needed to advance our understanding of cirrus and their susceptibility to changes in aerosol properties.

Surface or internal nucleation and crystallization of glass-ceramics

NASA Astrophysics Data System (ADS)

Höland, W.; Rheinberger, V. M.; Ritzberger, C.; Apel, E.

2013-07-01

Fluoroapatite (Ca5(PO4)3F) was precipitated in glass-ceramics via internal crystallization of base glasses. The crystals grew with a needle-like morphology in the direction of the crystallographic c-axis. Two different reaction mechanisms were analyzed: precipitation via a disordered primary apatite crystals and a solid state parallel reaction to rhenanite (NaCaPO4) precipitation. In contrast to the internal nucleation used in the formation of fluoroapatite, surface crystallization was induced to precipitate a phosphate-free oxyapatite of NaY9(SiO4)6O2-type. Internal nucleation and crystallization have been shown to be a very useful tool for developing high-strength lithium disilicate (Li2Si2O5) glass-ceramics. A very controlled process was conducted to transform the lithium metasilicate glass-ceramic precursor material into the final product of the lithium disilicate glass-ceramic without the major phase of the precursor material. The combination of all these methods allowed the driving forces of the internal nucleation and crystallization mechanisms to be explained. An amorphous phosphate primary phase was discovered in the process. Nucleation started at the interface between the amorphous phosphate phase and the glass matrix. The final products of all these glass-ceramics are biomaterials for dental restoration showing special optical properties, e.g. translucence and color close to dental teeth.

Geometrical Dependence of Domain-Wall Propagation and Nucleation Fields in Magnetic-Domain-Wall Sensors

NASA Astrophysics Data System (ADS)

Borie, B.; Kehlberger, A.; Wahrhusen, J.; Grimm, H.; Kläui, M.

2017-08-01

We study the key domain-wall properties in segmented nanowire loop-based structures used in domain-wall-based sensors. The two reasons for device failure, namely, distribution of the domain-wall propagation field (depinning) and the nucleation field are determined with magneto-optical Kerr effect and giant-magnetoresistance (GMR) measurements for thousands of elements to obtain significant statistics. Single layers of Ni81 Fe19 , a complete GMR stack with Co90 Fe10 /Ni81Fe19 as a free layer, and a single layer of Co90 Fe10 are deposited and industrially patterned to determine the influence of the shape anisotropy, the magnetocrystalline anisotropy, and the fabrication processes. We show that the propagation field is influenced only slightly by the geometry but significantly by material parameters. Simulations for a realistic wire shape yield a curling-mode type of magnetization configuration close to the nucleation field. Nonetheless, we find that the domain-wall nucleation fields can be described by a typical Stoner-Wohlfarth model related to the measured geometrical parameters of the wires and fitted by considering the process parameters. The GMR effect is subsequently measured in a substantial number of devices (3000) in order to accurately gauge the variation between devices. This measurement scheme reveals a corrected upper limit to the nucleation fields of the sensors that can be exploited for fast characterization of the working elements.

Practical physics behind growing crystals of biological macromolecules.

PubMed

Candoni, Nadine; Grossier, Romain; Hammadi, Zoubida; Morin, Roger; Veesler, Stéphane

2012-07-01

The aim of this review is to provide biocrystallographers who intend to tackle protein-crystallization with theory and practical examples. Crystallization involves two separate processes, nucleation and growth, which are rarely completely unconnected. Here we give theoretical background and concrete examples illustrating protein crystallization. We describe the nucleation of a new phase, solid or liquid, and the growth and transformation of existing crystals obtained by primary or secondary nucleation or by seeding. Above all, we believe that a thorough knowledge of the phase diagram is vital to the selection of starting position and path for any crystallization experiment.

Initial Growth of Single-Crystalline Nanowires: From 3D Nucleation to 2D Growth.

PubMed

Huang, Xh; Li, Gh; Sun, Gz; Dou, Xc; Li, L; Zheng, Lx

2010-04-17

The initial growth stage of the single-crystalline Sb and Co nanowires with preferential orientation was studied, which were synthesized in porous anodic alumina membranes by the pulsed electrodeposition technique. It was revealed that the initial growth of the nanowires is a three-dimensional nucleation process, and then gradually transforms to two-dimensional growth via progressive nucleation mechanism, which resulting in a structure transition from polycrystalline to single crystalline. The competition among the nuclei inside the nanoscaled-confined channel and the growth kinetics is responsible for the structure transition of the initial grown nanowires.

Effects of solutes on dislocation nucleation from grain boundaries

DOE PAGES

Borovikov, Valery; Mendelev, Mikhail I.; King, Alexander H.

2016-12-27

When grain sizes are reduced to the nanoscale, grain boundaries (GB) become the dominant sources of the dislocations that enable plastic deformation. Here, we present the first molecular dynamics (MD) study of the effect of substitutional solutes on the dislocation nucleation process from GBs during uniaxial tensile deformation. A simple bi-crystal geometry is utilized in which the nucleation and propagation of dislocations away from a GB is the only active mechanism of plastic deformation. Solutes with atomic radii both larger and smaller than the solvent atomic radius were considered. Although the segregation sites are different for the two cases, bothmore » produce increases in the stress required to nucleate a dislocation. MD simulations at room temperature revealed that this increase in the nucleation stress is associated with changes of the GB structure at the emission site caused by dislocation emission, leading to increases in the heats of segregation of the solute atoms, which cannot diffuse to lower-energy sites on the timescale of the nucleation event. These results contribute directly to understanding the strength of nanocrystalline materials, and suggest suitable directions for nanocrystalline alloy design leading toward structural applications.« less

The role of ultrasound in controlling the liquid-liquid phase separation and nucleation of vanillin polymorphs I and II

NASA Astrophysics Data System (ADS)

Parimaladevi, P.; Supriya, S.; Srinivasan, K.

2018-02-01

The influence of ultrasound on liquid-liquid phase separation (LLPS) and polymorphism of vanillin in aqueous solution has been investigated for the first time by varying the ultrasonic parameters such as power, pulse rate and insonation time at ambient condition. Results reveal that the application of ultrasound controls the impact of LLPS and accelerates the nucleation of vanillin within a short period at lower levels of ultrasonic process parameters, and also enhances the quality of the nucleated crystals. Moreover, the application of ultrasound induces the nucleation of rare and metastable polymorph of vanillin Form II in aqueous solution. But, at higher levels of power, pulse rate and insonation time, the rate of LLPS is found increased and the quality of the crystals becomes deteriorated. Morphology of the nucleated polymorphs were identified through optical microscopy and confirmed by optical goniometry. The internal structure and thermal stability of the grown stable Form I and metastable Form II of vanillin were confirmed through powder X-ray diffraction (PXRD) and differential scanning calorimetry (DSC) analyses. Further, results suggest that the ultrasound has profound effect in controlling the LLPS and nucleation of vanillin polymorphs in aqueous solution.

Pool Boiling Experiment Has Five Successful Flights

NASA Technical Reports Server (NTRS)

Chiaramonte, Fran

1997-01-01

The Pool Boiling Experiment (PBE) is designed to improve understanding of the fundamental mechanisms that constitute nucleate pool boiling. Nucleate pool boiling is a process wherein a stagnant pool of liquid is in contact with a surface that can supply heat to the liquid. If the liquid absorbs enough heat, a vapor bubble can be formed. This process occurs when a pot of water boils. On Earth, gravity tends to remove the vapor bubble from the heating surface because it is dominated by buoyant convection. In the orbiting space shuttle, however, buoyant convection has much less of an effect because the forces of gravity are very small. The Pool Boiling Experiment was initiated to provide insight into this nucleate boiling process, which has many earthbound applications in steamgeneration power plants, petroleum plants, and other chemical plants. In addition, by using the test fluid R-113, the Pool Boiling Experiment can provide some basic understanding of the boiling behavior of cryogenic fluids without the large cost of an experiment using an actual cryogen.

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.

Analysis of isothermal and cooling-rate-dependent immersion freezing by a unifying stochastic ice nucleation model

NASA Astrophysics Data System (ADS)

Alpert, Peter A.; Knopf, Daniel A.

2016-02-01

Immersion freezing is an important ice nucleation pathway involved in the formation of cirrus and mixed-phase clouds. Laboratory immersion freezing experiments are necessary to determine the range in temperature, T, and relative humidity, RH, at which ice nucleation occurs and to quantify the associated nucleation kinetics. Typically, isothermal (applying a constant temperature) and cooling-rate-dependent immersion freezing experiments are conducted. In these experiments it is usually assumed that the droplets containing ice nucleating particles (INPs) all have the same INP surface area (ISA); however, the validity of this assumption or the impact it may have on analysis and interpretation of the experimental data is rarely questioned. Descriptions of ice active sites and variability of contact angles have been successfully formulated to describe ice nucleation experimental data in previous research; however, we consider the ability of a stochastic freezing model founded on classical nucleation theory to reproduce previous results and to explain experimental uncertainties and data scatter. A stochastic immersion freezing model based on first principles of statistics is presented, which accounts for variable ISA per droplet and uses parameters including the total number of droplets, Ntot, and the heterogeneous ice nucleation rate coefficient, Jhet(T). This model is applied to address if (i) a time and ISA-dependent stochastic immersion freezing process can explain laboratory immersion freezing data for different experimental methods and (ii) the assumption that all droplets contain identical ISA is a valid conjecture with subsequent consequences for analysis and interpretation of immersion freezing. The simple stochastic model can reproduce the observed time and surface area dependence in immersion freezing experiments for a variety of methods such as: droplets on a cold-stage exposed to air or surrounded by an oil matrix, wind and acoustically levitated droplets, droplets in a continuous-flow diffusion chamber (CFDC), the Leipzig aerosol cloud interaction simulator (LACIS), and the aerosol interaction and dynamics in the atmosphere (AIDA) cloud chamber. Observed time-dependent isothermal frozen fractions exhibiting non-exponential behavior can be readily explained by this model considering varying ISA. An apparent cooling-rate dependence of Jhet is explained by assuming identical ISA in each droplet. When accounting for ISA variability, the cooling-rate dependence of ice nucleation kinetics vanishes as expected from classical nucleation theory. The model simulations allow for a quantitative experimental uncertainty analysis for parameters Ntot, T, RH, and the ISA variability. The implications of our results for experimental analysis and interpretation of the immersion freezing process are discussed.

Experimental studies of nucleation and growth processes related to the formation of presolar grains

NASA Technical Reports Server (NTRS)

Berg, Otto E.

1992-01-01

An understanding was sought for the mechanisms of nucleation of refractory materials, and the relative importance of factors controlling the rate of cluster formation and growth for astrophysically important species. The structure and composition of the condensates is being studied, with the goal of characterizing the grains present in the primitive solar nebula.

High-definition infrared thermography of ice nucleation and propagation in wheat under natural frost conditions and controlled freezing

USDA-ARS?s Scientific Manuscript database

Infrared thermography has been used to visualize the freezing process in plants and has greatly enhanced our knowledge of ice nucleation and propagation in plants. The majority of IR analyses have been conducted under controlled rather than natural conditions and often on plant parts instead of wh...

Stabilization of X–Au–X complexes on the Au(111) surface: A theoretical investigation and comparison of X = S, Cl, CH 3S, and SiH 3S

DOE PAGES

Lee, Jiyoung; Boschen, Jeffery S.; Windus, Theresa L.; ...

2017-01-27

Alnico alloys have long been used as strong permanent magnets because of their ferromagnetism and high coercivity. Understanding their structural details allows for better prediction of the resulting magnetic properties. However, quantitative three-dimensional characterization of the phase separation in these alloys is still challenged by the spatial quantification of nanoscale phases. Herein, we apply a dual tomography approach, where correlative scanning transmission electron microscopy (STEM) energy-dispersive X-ray spectroscopic (EDS) tomography and atom probe tomography (APT) are used to investigate the initial phase separation process of an alnico 8 alloy upon non-magnetic annealing. STEM-EDS tomography provides information on the morphology andmore » volume fractions of Fe–Co-rich and Νi–Al-rich phases after spinodal decomposition in addition to quantitative information of the composition of a nanoscale volume. Subsequent analysis of a portion of the same specimen by APT offers quantitative chemical information of each phase at the sub-nanometer scale. Furthermore, APT reveals small, 2–4 nm Fe-rich α 1 phases that are nucleated in the Ni-rich α 2 matrix. From this information, we show that phase separation of the alnico 8 alloy consists of both spinodal decomposition and nucleation and growth processes. The complementary benefits and challenges associated with correlative STEM-EDS and APT are discussed.« less

Ice formation on kaolinite: Insights from molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Sosso, Gabriele C.; Tribello, Gareth A.; Zen, Andrea; Pedevilla, Philipp; Michaelides, Angelos

2016-12-01

The formation of ice affects many aspects of our everyday life as well as important technologies such as cryotherapy and cryopreservation. Foreign substances almost always aid water freezing through heterogeneous ice nucleation, but the molecular details of this process remain largely unknown. In fact, insight into the microscopic mechanism of ice formation on different substrates is difficult to obtain even if state-of-the-art experimental techniques are used. At the same time, atomistic simulations of heterogeneous ice nucleation frequently face extraordinary challenges due to the complexity of the water-substrate interaction and the long time scales that characterize nucleation events. Here, we have investigated several aspects of molecular dynamics simulations of heterogeneous ice nucleation considering as a prototypical ice nucleating material the clay mineral kaolinite, which is of relevance in atmospheric science. We show via seeded molecular dynamics simulations that ice nucleation on the hydroxylated (001) face of kaolinite proceeds exclusively via the formation of the hexagonal ice polytype. The critical nucleus size is two times smaller than that obtained for homogeneous nucleation at the same supercooling. Previous findings suggested that the flexibility of the kaolinite surface can alter the time scale for ice nucleation within molecular dynamics simulations. However, we here demonstrate that equally flexible (or non flexible) kaolinite surfaces can lead to very different outcomes in terms of ice formation, according to whether or not the surface relaxation of the clay is taken into account. We show that very small structural changes upon relaxation dramatically alter the ability of kaolinite to provide a template for the formation of a hexagonal overlayer of water molecules at the water-kaolinite interface, and that this relaxation therefore determines the nucleation ability of this mineral.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2013-05-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2 : 1 mixtures of organic polyols (1,2,6-hexanetriol and 1 : 1 1,2,6-hexanetriol + 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicate that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase-separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2012-12-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2:1 mixtures of organic polyols (1,2,6-hexanetriol, and 1:1 1,2,6-hexanetriol +2,2,6,6-tetrakis(hydroxymethyl)cycohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicates that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Subtle charge balance controls surface-nucleated self-assembly of designed biopolymers.

PubMed

Charbonneau, Céline; Kleijn, J Mieke; Cohen Stuart, Martien A

2014-03-25

We report the surface-nucleated self-assembly into fibrils of a biosynthetic amino acid polymer synthesized by the yeast Pichia pastoris. This polymer has a block-like architecture, with a central silk-like block labeled SH, responsible for the self-assembly into fibrils, and two collagen-like random coil end blocks (C) that colloidally stabilize the fibers in aqueous solution. The silk-like block contains histidine residues (pKa≈6) that are positively charged in the low pH region, which hinders self-assembly. In aqueous solution, CSHC self-assembles into fibers above a pH-dependent critical nucleation concentration Ccb. Below Ccb, where no self-assembly occurs in solution, fibril formation can be induced by a negatively charged surface (silica) in the pH range of 3.5-7. The density of the fibers at the surface and their length are controlled by a subtle balance in charge between the protein polymer and the silica surface, which is evidenced from the dependence on pH. With increasing number density of the fibers at the surface, their average length decreases. The results can be explained on the basis of a nucleation-and-growth mechanism: the surface density of fibers depends on the rate of nucleation, while their growth rate is limited by transport of proteins from solution. Screening of the charges on the surface and histidine units by adding NaCl influences the nucleation-and-growth process in a complicated fashion: at low pH, the growth is improved, while at high pH, the nucleation is limited. Under conditions where nucleation in the bulk solution is not possible, growth of the surface-nucleated fibers into the solution--away from the surface--can still occur.

The Effect of Solution Chemistry on Nucleation of Nesquehonite

NASA Astrophysics Data System (ADS)

Zhao, L.; Zhu, C.; Wang, Z.

2016-12-01

The interfaces between minerals and aqueous solutions are key to important Earth surface processes, including chemical weathering, mineral dissolution/precipitation, and pollutant absorption/release. Mineral surface properties, such as the surface structure and the surface energy, determine the outcomes of many geochemical reactions. Several factors could affect surface energy, but the effect of solution chemistry, particularly the solution stoichiometry, on the surface energy and nucleation process is poorly understood. The goal of this study is to understand the effect of solution chemistry on the nucleation of nesquehonite. Nesquehonite nucleation experiments were conducted in aqueous solutions having similar Mg2+/ CO32- activity ratios, but different saturation states and solution pH. The experimental results show that induction-time estimates from our precipitation experiments with similar Mg2+/CO32- activity ratios are consistent with classical nucleation theory (CNT), while the surface energy derived from CNT varies with Mg2+/CO32- activity ratios. Our observations can be explained by the different absorption behaviors of Mg2+ and CO32- and and/or reduced Gibbs free energies through better screening of the electric double layer. A surface energy model involving solution composition is developed that combines surface complexation with electrostatic models. The new model takes into account how surface charge may affect surface energy. It implies that the highest surface energy may occur around the point of zero charge (p.z.c), where the nucleation is fastest (or conversely, where the induction time is shortest) under low saturation states, but not under high saturation states. An accelerated attachment rate of monomers at the p.z.c. is consistent with high surface energy, since it represents higher reactivity of surface ions and less work needed to break the solvated water molecules. This study provides deeper insights into mechanisms of nesquehonite nucleation in nature, and guidelines for accelerating the precipitation rates of nesquehonite.

Evaporation rate of nucleating clusters.

PubMed

Zapadinsky, Evgeni

2011-11-21

The Becker-Döring kinetic scheme is the most frequently used approach to vapor liquid nucleation. In the present study it has been extended so that master equations for all cluster configurations are included into consideration. In the Becker-Döring kinetic scheme the nucleation rate is calculated through comparison of the balanced steady state and unbalanced steady state solutions of the set of kinetic equations. It is usually assumed that the balanced steady state produces equilibrium cluster distribution, and the evaporation rates are identical in the balanced and unbalanced steady state cases. In the present study we have shown that the evaporation rates are not identical in the equilibrium and unbalanced steady state cases. The evaporation rate depends on the number of clusters at the limit of the cluster definition. We have shown that the ratio of the number of n-clusters at the limit of the cluster definition to the total number of n-clusters is different in equilibrium and unbalanced steady state cases. This causes difference in evaporation rates for these cases and results in a correction factor to the nucleation rate. According to rough estimation it is 10(-1) by the order of magnitude and can be lower if carrier gas effectively equilibrates the clusters. The developed approach allows one to refine the correction factor with Monte Carlo and molecular dynamic simulations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jun, Young -Shin; Kim, Doyoon; Neil, Chelsea W.

Here, mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth’s crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolutionmore » of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of water chemistry and substrate identity on heterogeneously and homogeneously formed nanoscale precipitate size dimensions and total particle volume. Using this technique, we also provided a new platform for quantitatively comparing between heterogeneous and homogeneous nucleation and growth of nanoparticles and obtaining undiscovered interfacial energies between nuclei and surfaces. In addition, nanoscale surface characterization tools, such as in situ atomic force microscopy (AFM), were utilized to support and complement our findings. With these powerful nanoscale tools, we systematically evaluated the influences of environmentally abundant (oxy)anions and cations and the properties of environmental surfaces, such as surface charge and hydrophobicity. The findings, significantly enhanced by in situ observations, can lead to a more accurate prediction of the behaviors of nanoparticles in the environment and enable better control of the physicochemical properties of nanoparticles in engineered systems, such as catalytic reactions and energy storage.« less

The Nucleation Rate of Single O2 Nanobubbles at Pt Nanoelectrodes.

PubMed

Soto, Álvaro Moreno; German, Sean R; Ren, Hang; van der Meer, Devaraj; Lohse, Detlef; Edwards, Martin A; White, Henry S

2018-06-13

Nanobubble nucleation is a problem that affects efficiency in electrocatalytic reactions since those bubbles can block the surface of the catalytic sites. In this article, we focus on the nucleation rate of O 2 nanobubbles resulting from the electrooxidation of H 2 O 2 at Pt disk nanoelectrodes. Bubbles form almost instantaneously when a critical peak current, i nb p , is applied, but for lower currents, bubble nucleation is a stochastic process in which the nucleation (induction) time, t ind , dramatically decreases as the applied current approaches i nb p , a consequence of the local supersaturation level, ζ, increasing at high currents. Here, by applying different currents below i nb p , nanobubbles take some time to nucleate and block the surface of the Pt electrode at which the reaction occurs, providing a means to measure the stochastic t ind . We study in detail the different conditions in which nanobubbles appear, concluding that the electrode surface needs to be preconditioned to achieve reproducible results. We also measure the activation energy for bubble nucleation, E a , which varies in the range from (6 to 30) kT, and assuming a spherically cap-shaped nanobubble nucleus, we determine the footprint diameter L = 8-15 nm, the contact angle to the electrode surface θ = 135-155°, and the number of O 2 molecules contained in the nucleus (50 to 900 molecules).

Sensitivity of Cirrus Properties to Ice Nuclei Abundance

NASA Technical Reports Server (NTRS)

Jensen, Eric

2014-01-01

The relative importance of heterogeneous and homogeneous ice nucleation for cirrus formation remains an active area of debate in the cloud physics community. From a theoretical perspective, a number of modeling studies have investigated the sensitivity of ice number concentration to the nucleation mechanism and the abundance of ice nuclei. However, these studies typically only addressed ice concentration immediately after ice nucleation. Recent modeling work has shown that the high ice concentrations produced by homogeneous freezing may not persist very long, which is consistent with the low frequency of occurrence of high ice concentrations indicated by cirrus measurements. Here, I use idealized simulations to investigate the impact of ice nucleation mechanism and ice nuclei abundance on the full lifecycle of cirrus clouds. The primary modeling framework used includes different modes of ice nucleation, deposition growth/sublimation, aggregation, sedimentation, and radiation. A limited number of cloud-resolving simulations that treat radiation/dynamics interactions will also been presented. I will show that for typical synoptic situations with mesoscale waves present, the time-averaged cirrus ice crystal size distributions and bulk cloud properties are less sensitive to ice nucleation processes than might be expected from the earlier simple ice nucleation calculations. I will evaluate the magnitude of the ice nuclei impact on cirrus for a range of temperatures and mesoscale wave specifications, and I will discuss the implications for cirrus aerosol indirect effects in general.

A classical view on nonclassical nucleation.

PubMed

Smeets, Paul J M; Finney, Aaron R; Habraken, Wouter J E M; Nudelman, Fabio; Friedrich, Heiner; Laven, Jozua; De Yoreo, James J; Rodger, P Mark; Sommerdijk, Nico A J M

2017-09-19

Understanding and controlling nucleation is important for many crystallization applications. Calcium carbonate (CaCO 3 ) is often used as a model system to investigate nucleation mechanisms. Despite its great importance in geology, biology, and many industrial applications, CaCO 3 nucleation is still a topic of intense discussion, with new pathways for its growth from ions in solution proposed in recent years. These new pathways include the so-called nonclassical nucleation mechanism via the assembly of thermodynamically stable prenucleation clusters, as well as the formation of a dense liquid precursor phase via liquid-liquid phase separation. Here, we present results from a combined experimental and computational investigation on the precipitation of CaCO 3 in dilute aqueous solutions. We propose that a dense liquid phase (containing 4-7 H 2 O per CaCO 3 unit) forms in supersaturated solutions through the association of ions and ion pairs without significant participation of larger ion clusters. This liquid acts as the precursor for the formation of solid CaCO 3 in the form of vaterite, which grows via a net transfer of ions from solution according to z Ca 2+ + z CO 3 2- → z CaCO 3 The results show that all steps in this process can be explained according to classical concepts of crystal nucleation and growth, and that long-standing physical concepts of nucleation can describe multistep, multiphase growth mechanisms.

Nucleation, Growth, Annealing, and Coagulation of Refractory Oxides and Metals: Recent Experimental Progress and Applications to Astrophysical Systems

NASA Technical Reports Server (NTRS)

Nuth, J. A.; Rietmeijer, F. J. M.; Hallenbeck, S. L.; Withey, P. A.

1999-01-01

Starting with cooling, refractory vapors diluted in significant quantities of H and He there are four processes that most natural systems will undergo: nucleation, growth, annealing, and coagulation. Nucleation is the processes by which the first stable refractory nuclei form in the vapor. These are the seeds onto which the remaining vapors will condense during the growth stage. Solids of any composition will try to arrange themselves into the least energetic configuration, provided that there is sufficient energy available to support such processes as diffusion and the breaking of chemical bonds. There is a significant activation energy associated with the annealing process in refractory solids due to the relatively high energy of the chemical bonds in solids. The grains formed in most cosmochemical systems are extremely small and often tightly coupled to the gas. Because of their small physical cross sections coagulation may be a very slow process unless there is another driving force involved in addition to normal Brownian motion. In what follows we will briefly cover each of these four stages for refractory oxide and metal grains, although in inverse order.

Unraveling Mixed Hydrate Formation: Microscopic Insights into Early Stage Behavior.

PubMed

Hall, Kyle Wm; Zhang, Zhengcai; Kusalik, Peter G

2016-12-29

The molecular-level details of mixed hydrate nucleation remain unclear despite the broad implications of this process for a variety of scientific domains. Through analysis of mixed hydrate nucleation in a prototypical CH 4 /H 2 S/H 2 O system, we demonstrate that high-level kinetic similarities between mixed hydrate systems and corresponding pure hydrate systems are not a reliable basis for estimating the composition of early stage mixed hydrate nuclei. Moreover, we show that solution compositions prior to and during nucleation are not necessarily effective proxies for the composition of early stage mixed hydrate nuclei. Rather, microscopic details, (e.g., guest-host interactions and previously neglected cage types) apparently play key roles in determining early stage behavior of mixed hydrates. This work thus provides key foundational concepts and insights for understanding mixed hydrate nucleation.

Mixed-mode singularity and temperature effects on dislocation nucleation in strained interconnects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Jinhaeng; Gao, Yanfei

2011-01-01

Dislocations can be nucleated from sharp geometric features in strained interconnects due to thermal expansion coefficient mismatch, lattice mismatch, or stresses that arise during material processing. The asymptotic stress fields near the edge root can be described by mixed-mode singularities, which depend on the dihedral angle and material properties, and a transverse T-stress, which depends on how residual stress is realized in the interconnects. The critical condition for stress nucleation can be determined when an appropriate measure of the stress intensity factors (SIFs) reaches a critical value. Such a method, however, does not offer an explicit picture of the dislocationmore » nucleation process so that it has difficulties in studying complicated structures, mode mixity effects, and more importantly the temperature effects. Based on the Peierls concept, a dislocation can be described by a continuous slip field, and the dislocation nucleation condition corresponds when the total potential energy reaches a stationary state. Through implementing this ad hoc interface model into a finite element framework, it is found that dislocation nucleation becomes more difficult with the increase of mode mixity and T-stress, or the decrease of the width-to-height ratio of the surface pad, while the shape of the surface pad, being a square or a long line, plays a less important role. The Peierls dislocation model also allows us to determine the activation energy, which is the energy needed for the thermal activation of a dislocation when the applied load is lower than the athermal critical value. The calculated saddle point configuration compares favorably the molecular simulations in literature. Suggestions on making immortal strained interconnects are provided.« less

Differences in ice nucleation behavior of arable and desert soil dust in deposition nucleation regime

NASA Astrophysics Data System (ADS)

Ullrich, Romy; Vogel, Franziska; Möhler, Ottmar; Höhler, Kristina; Schiebel, Thea

2017-04-01

Soil dust from arid and semi-arid regions is one of the most abundant aerosol types in the atmosphere with emission rates of about 1600 Tg per year (Andreae et al. (2009)). Therewith, soil dust plays an important role for the atmospheric radiative transfer and also for the formation of clouds. Soil dust refers to dust sampled from agricultural used areas, to dust from bare soil as well as to dust from desert regions. By mass-spectrometric measurements of the chemical composition of ice residuals, mineral dust as component of soil dust was found to be the major heterogeneous ice nucleating particle (INP) type (e.g. Cziczo et al. (2013)), in particular in the upper troposphere. Also in laboratory studies the ice nucleation efficiency of the different soil dusts was investigated. It was shown that desert dusts (Ullrich et al. (2017)) as well as soil dusts from arable regions (O'Sullivan et al. (2014), Tobo et al. (2014)) are efficient INP. However, there is still a lack of data for ice nucleation on soil dusts for temperatures below about 220 K. With the AIDA (Aerosol Interactions and Dynamics in the Atmosphere) cloud chamber, we are able to characterize the ice nucleation efficiency for different aerosol types to temperatures down to 180 K and high ice supersaturations. In order to extend the already existing AIDA data base for deposition nucleation on desert dusts and agricultural soil dusts, new experiments were done in the upper tropospheric temperature regime. This contribution will show the results of the new experiments with desert dust in comparison to existing data for higher temperatures. The first data analysis confirms the temperature dependent trend of the ice nucleation activity as discussed and parameterized in a recent paper by Ullrich et al. (2017). Furthermore, the update and extension of the recently published parameterization of deposition nucleation for desert dust to lower temperatures will be discussed. The experiments with agricultural soil dust will be compared to existing AIDA experiments at higher temperatures published by Steinke et al. (2016). Finally, the ice nucleation activity of both desert dust and agricultural soil dust will be compared for the upper tropospheric temperature regime. Andreae et al. (2009), Sources and Nature of Atmospheric Aerosols, in Aerosol Pollution Impact on Precipitation - A Scientific Review, Ch.3, Springer Netherlands, 45-89 Cziczo et al. (2013), Clarifying the Dominant Sources and Mechanisms of Cirrus Cloud Formation, Science, 340, 1320-1324 O'Sullivan et al. (2014), Ice nucleation by fertile soil dusts: relative importance of mineral and biogenic components, Atmos. Chem. Phys., 14, 1853-1867 Steinke et al. (2016), Ice nucleation activity of agricultural soil dust aerosols from Mongolia, Argentina and Germany, J. Geophys. Res., 121 Tobo et al. (2014), Organic matter matters for ice nuclei of agricultural soil origin, Atmos. Chem. Phys., 14, 8521-8531 Ullrich et al. (2017), A new ice nucleation active site parametrization for desert dust and soot, J. Atmos. Sci., in press

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.

2014-06-01

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 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 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 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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hiranuma, Naruki; Paukert, Marco; Steinke, Isabelle

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 n s, 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 (RH ice) in the chamber. Our measurementsmore » showed several different pathways to nucleate ice depending on T and RH ice conditions. For instance, almost independent freezing was observed at -60 °C < T < -50 °C, where RH ice explicitly controlled ice nucleation efficiency, while both T and RH ice 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 n s, whereas T may have played a significant role in ice nucleation at T warmer than -50 °C. We implemented new n s 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.« less

How does bone sialoprotein promote the nucleation of hydroxyapatite? A molecular dynamics study using model peptides of different conformations.

PubMed

Yang, Yang; Cui, Qiang; Sahai, Nita

2010-06-15

Bone sialoprotein (BSP) is a highly phosphorylated, acidic, noncollagenous protein in bone matrix. Although BSP has been proposed to be a nucleator of hydroxyapatite (Ca(5)(PO(4))(3)OH), the major mineral component of bone, no detailed mechanism for the nucleation process has been elucidated at the atomic level to date. In the present work, using a peptide model, we apply molecular dynamics (MD) simulations to study the conformational effect of a proposed nucleating motif of BSP (a phosphorylated, acidic, 10 amino-acid residue sequence) on controlling the distributions of Ca(2+) and inorganic phosphate (Pi) ions in solution, and specifically, we explore whether a nucleating template for orientated hydroxyapatite could be formed in different peptide conformations. Both the alpha-helical conformation and the random coil structure have been studied, and inorganic solutions without the peptide are simulated as reference. Ca(2+) distributions around the peptide surface and interactions between Ca(2+) and Pi in the presence of the peptide are examined in detail. From the MD simulations, although in some cases for the alpha-helical conformation, we observe that a Ca(2+) equilateral triangle forms around the surface of peptide, which matches the distribution of Ca(2+) ions on the (001) face of the hydroxyapatite crystal, we do not consistently find a stable nucleating template formation in general for either the helical conformation or the random coil structure. Therefore, independent of conformations, the BSP nucleating motif is more likely to help nucleate an amorphous calcium phosphate cluster, which ultimately converts to crystalline hydroxyapatite.

Dynamic observations of vesiculation reveal the role of silicate crystals in bubble nucleation and growth in andesitic magmas

NASA Astrophysics Data System (ADS)

Pleše, P.; Higgins, M. D.; Mancini, L.; Lanzafame, G.; Brun, F.; Fife, J. L.; Casselman, J.; Baker, D. R.

2018-01-01

Bubble nucleation and growth control the explosivity of volcanic eruptions, and the kinetics of these processes are generally determined from examinations of natural samples and quenched experimental run products. These samples, however, only provide a view of the final state, from which the initial conditions of a time-evolving magmatic system are then inferred. The interpretations that follow are inexact due to the inability of determining the exact conditions of nucleation and the potential detachment of bubbles from their nucleation sites, an uncertainty that can obscure their nucleation location - either homogeneously within the melt or heterogeneously at the interface between crystals and melts. We present results of a series of dynamic, real-time 4D X-ray tomographic microscopy experiments where we observed the development of bubbles in crystal bearing silicate magmas. Experimentally synthesized andesitic glasses with 0.25-0.5 wt% H2O and seed silicate crystals were heated at 1 atm to induce bubble nucleation and track bubble growth and movement. In contrast to previous studies on natural and experimentally produced samples, we found that bubbles readily nucleated on plagioclase and clinopyroxene crystals, that their contact angle changes during growth and that they can grow to sizes many times that of the silicate on whose surface they originated. The rapid heterogeneous nucleation of bubbles at low degrees of supersaturation in the presence of silicate crystals demonstrates that silicates can affect when vesiculation ensues, influencing subsequent permeability development and effusive vs. explosive transition in volcanic eruptions.

On the thermodynamic path enabling a room-temperature, laser-assisted graphite to nanodiamond transformation

NASA Astrophysics Data System (ADS)

Gorrini, F.; Cazzanelli, M.; Bazzanella, N.; Edla, R.; Gemmi, M.; Cappello, V.; David, J.; Dorigoni, C.; Bifone, A.; Miotello, A.

2016-10-01

Nanodiamonds are the subject of active research for their potential applications in nano-magnetometry, quantum optics, bioimaging and water cleaning processes. Here, we present a novel thermodynamic model that describes a graphite-liquid-diamond route for the synthesis of nanodiamonds. Its robustness is proved via the production of nanodiamonds powders at room-temperature and standard atmospheric pressure by pulsed laser ablation of pyrolytic graphite in water. The aqueous environment provides a confinement mechanism that promotes diamond nucleation and growth, and a biologically compatible medium for suspension of nanodiamonds. Moreover, we introduce a facile physico-chemical method that does not require harsh chemical or temperature conditions to remove the graphitic byproducts of the laser ablation process. A full characterization of the nanodiamonds by electron and Raman spectroscopies is reported. Our model is also corroborated by comparison with experimental data from the literature.

Photochemistry, Ion Chemistry, and Haze Formation in Pluto’s Atmosphere

NASA Astrophysics Data System (ADS)

Summers, Michael E.; Stern, S. A.; Gladstone, G. Randal; Young, Leslie A.; Olkin, C. B.; Weaver, H. A.; Cheng, A. F.; Strobel, D. F.; Ennico, K. A.; Kammer, J. A.; Parker, A. H.; Retherford, K. D.; Schindhelm, E.; Singer, K. N.; Steffl, A. J.; Tsang, C. C.; Versteeg, M. H.; Greathouse, T. K.; Linscott, I. R.; Tyler, L. G.; Woods, W. W.; Hinson, D. P.; Parker, J. W.; Renaud, J. P.; Ewell, M.; Lisse, Cary M.

2015-11-01

The detection of ethylene (C2H4) and acetylene (C2H2) in Pluto’s atmosphere provides important ground-truth observations for validating photochemical models of Pluto’s atmosphere. Their detection also confirms the production of precursor chemical compounds involved in the formation of tholins, which are thought to give Pluto’s surface its reddish color. Photochemical models predict many other hydrocarbon and nitrile products, currently undetected, which may also be participants in tholin production on Pluto’s surface or on atmospheric haze particles. The observed atmospheric haze layer extending to altitudes of ~140 km above Pluto’s surface, suggests a global and very robust process of atmospheric particle nucleation, growth, and sedimentation onto Pluto’s surface. The high altitude extent of the haze layer suggests that the nucleation process begins above the expected altitude range where hydrocarbons become supersaturated (below ~30 km altitude). This situation may be analogous to that in Titan’s atmosphere, wherein nucleation and aerosol growth is directly related to large negative ion production. In the case of Pluto, this means that nucleation may occur at altitudes as high as 1200 km altitude where ionization in Pluto’s atmosphere peaks. In this paper we discuss these processes and their implications for haze formation in Pluto’s atmosphere and its deposition onto Pluto’s surface. This work was supported by NASA's New Horizons project.

Nucleation and growth of hydroxyapatite on arc-deposited TiO2 surfaces studied by quartz crystal microbalance with dissipation

NASA Astrophysics Data System (ADS)

Lilja, Mirjam; Butt, Umer; Shen, Zhijian; Bjöörn, Dorota

2013-11-01

Understanding of nucleation and growth kinetics of biomimetically deposited hydroxyapatite (HA) on crystalline TiO2 surfaces is important with respect to the application and performance of HA as functional implant coatings. Arc-evaporation was used to deposit TiO2 coatings dominated by anatase phase, rutile phase or their mixtures. Subsequent formation of HA from phosphate buffered saline solution (PBS) was investigated in real-time using in situ quartz crystal microbalance with dissipation technique (QCM-D). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were employed to characterize the presence, morphology and crystal structure of TiO2 coatings and the formed HA. Increasing temperature of the PBS, increasing flow rate and applying a higher ion concentration in solution were found to accelerate HA nucleation process and hence affect growth kinetics. Lower PBS temperature resulted in the formation of HA coatings with flake-like morphology and increasing HA porosity. All TiO2 coatings under study enabled HA formation at body temperature, while in contrast Ti reference surfaces only supported HA nucleation and growth at elevated temperatures. QCM-D technique is a powerful tool for studying the impact of process parameters during biomimetic coating deposition on coating structure evolution in real time and provides valuable information for understanding, optimizing as well as tailoring the biomimetic HA growth processes.

Water-assisted compounding of cellulose nanocrystals into polyamide 6 for use as a nucleating agent for microcellular foaming

Treesearch

Jun Peng; Philip J. Walsh; Ronald C. Sabo; Lih-Sheng Turng; Craig M. Clemons

2016-01-01

Cellulose nanocrystals (CNCs) are a biorenewable filler and can be an excellent nucleating agent for the development of microcellular foamed polymeric nanocomposites. However, their relatively low degradation temperature limits their use with engineering resins like polyamide 6 (PA6) in typical melt processing techniques such as injection molding, compounding, and...

Kinetics modeling of precipitation with characteristic shape during post-implantation annealing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Kun-Dar, E-mail: kundar@mail.nutn.edu.tw; Chen, Kwanyu

2015-11-15

In this study, we investigated the precipitation with characteristic shape in the microstructure during post-implantation annealing via a theoretical modeling approach. The processes of precipitates formation and evolution during phase separation were based on a nucleation and growth mechanism of atomic diffusion. Different stages of the precipitation, including the nucleation, growth and coalescence, were distinctly revealed in the numerical simulations. In addition, the influences of ion dose, temperature and crystallographic symmetry on the processes of faceted precipitation were also demonstrated. To comprehend the kinetic mechanism, the simulation results were further analyzed quantitatively by the Kolmogorov-Johnson-Mehl-Avrami (KJMA) equation. The Avrami exponentsmore » obtained from the regression curves varied from 1.47 to 0.52 for different conditions. With the increase of ion dose and temperature, the nucleation and growth of precipitations were expedited in accordance with the shortened incubation time and the raised coefficient of growth rate. A miscellaneous shape of precipitates in various crystallographic symmetry systems could be simulated through this anisotropic model. From the analyses of the kinetics, more fundamental information about the nucleation and growth mechanism of faceted precipitation during post-implantation annealing was acquired for future application.« less

Ice Nucleation Activity of Graphene and Graphene Oxides

PubMed Central

2018-01-01

Aerosols can act as cloud condensation nuclei and/or ice-nucleating particles (INPs), influencing cloud properties. In particular, INPs show a variety of different and complex mechanisms when interacting with water during the freezing process. To gain a fundamental understanding of the heterogeneous freezing mechanisms, studies with proxies for atmospheric INPs must be performed. Graphene and its derivatives offer suitable model systems for soot particles, which are ubiquitous aerosols in the atmosphere. In this work, we present an investigation of the ice nucleation activity (INA) of different types of graphene and graphene oxides. Immersion droplet freezing experiments as well as additional analytical analyses, such as X-ray photoelectron spectroscopy, Raman spectroscopy, and transmission electron microscopy, were performed. We show within a group of samples that a highly ordered graphene lattice (Raman G band intensity >50%) can support ice nucleation more effectively than a lowly ordered graphene lattice (Raman G band intensity <20%). Ammonia-functionalized graphene revealed the highest INA of all samples. Atmospheric ammonia is known to play a primary role in the formation of secondary particulate matter, forming ammonium-containing aerosols. The influence of functionalization on interactions between the particle interface and water molecules, as well as on hydrophobicity and agglomeration processes, is discussed. PMID:29707097

Microphysical processes affecting stratospheric aerosol particles

NASA Technical Reports Server (NTRS)

Hamill, P.; Toon, O. B.; Kiang, C. S.

1977-01-01

Physical processes which affect stratospheric aerosol particles include nucleation, condensation, evaporation, coagulation and sedimentation. Quantitative studies of these mechanisms to determine if they can account for some of the observed properties of the aerosol are carried out. It is shown that the altitude range in which nucleation of sulfuric acid-water solution droplets can take place corresponds to that region of the stratosphere where the aerosol is generally found. Since heterogeneous nucleation is the dominant nucleation mechanism, the stratospheric solution droplets are mainly formed on particles which have been mixed up from the troposphere or injected into the stratosphere by volcanoes or meteorites. Particle growth by heteromolecular condensation can account for the observed increase in mixing ratio of large particles in the stratosphere. Coagulation is important in reducing the number of particles smaller than 0.05 micron radius. Growth by condensation, applied to the mixed nature of the particles, shows that available information is consistent with ammonium sulfate being formed by liquid phase chemical reactions in the aerosol particles. The upper altitude limit of the aerosol layer is probably due to the evaporation of sulfuric acid aerosol particles, while the lower limit is due to mixing across the tropopause.

Crystalline nucleation in undercooled liquids: a Bayesian data-analysis approach for a nonhomogeneous Poisson process.

PubMed

Filipponi, A; Di Cicco, A; Principi, E

2012-12-01

A Bayesian data-analysis approach to data sets of maximum undercooling temperatures recorded in repeated melting-cooling cycles of high-purity samples is proposed. The crystallization phenomenon is described in terms of a nonhomogeneous Poisson process driven by a temperature-dependent sample nucleation rate J(T). The method was extensively tested by computer simulations and applied to real data for undercooled liquid Ge. It proved to be particularly useful in the case of scarce data sets where the usage of binned data would degrade the available experimental information.

Interfacial microstructure in a B{sub 4}C/Al composite fabricated by pressureless infiltration.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Z.; Song, Y.; Zhang, S.

In this work, B{sub 4}C particulate-reinforced Al composite was fabricated by a pressureless infiltration technique, and its interfacial microstructure was studied in detail by X-ray diffraction as well as by scanning and transmission electron microscopy. The B{sub 4}C phase was unstable in Al melt during the infiltration process, forming AlB{sub 10}-type AlB{sub 24}C{sub 4} or Al{sub 2.1}B{sub 51}C{sub 8} as a major reactant phase. The Al matrix was large grains (over 10 {micro}m), which had no definite orientation relationships (ORs) with the randomly orientated B{sub 4}C or its reactant particles, except for possible nucleation sites with {l_brace}011{r_brace}{sub B{sub 4}C} almostmore » parallel to {l_brace}111{r_brace}{sub Al} at a deviation angle of 1.5 deg. Both B{sub 4}C-Al and reactant-Al interfaces are semicoherent and free of other phases. A comparison was made with the SiC/Al composite fabricated similarly by the pressureless infiltration. It was suggested that the lack of ORs between the Al matrix and reinforced particles, except for possible nucleation sites, is the common feature of the composites prepared by the infiltration method.« less

Suppressing Ice Nucleation of Supercooled Condensate with Biphilic Topography

NASA Astrophysics Data System (ADS)

Hou, Youmin; Yu, Miao; Shang, Yuhe; Zhou, Peng; Song, Ruyuan; Xu, Xiaonan; Chen, Xuemei; Wang, Zuankai; Yao, Shuhuai

2018-02-01

Preventing or minimizing ice formation in supercooled water is of prominent importance in many infrastructures, transportation, and cooling systems. The overall phase change heat transfer on icephobic surfaces, in general, is intentionally sacrificed to suppress the nucleation of water and ice. However, in a condensation frosting process, inhibiting freezing without compromising the water condensation has been an unsolved challenge. Here we show that this conflict between anti-icing and efficient condensation cooling can be resolved by utilizing biphilic topography with patterned high-contrast wettability. By creating a varying interfacial thermal barrier underneath the supercooled condensate, the biphilic structures tune the nucleation rates of water and ice in the sequential condensation-to-freezing process. Our experimental and theoretical investigation of condensate freezing dynamics further unravels the correlation between the onset of droplet freezing and its characteristic radius, offering a new insight for controlling the multiphase transitions among vapor, water, and ice in supercooled conditions.

Suppressing Ice Nucleation of Supercooled Condensate with Biphilic Topography.

PubMed

Hou, Youmin; Yu, Miao; Shang, Yuhe; Zhou, Peng; Song, Ruyuan; Xu, Xiaonan; Chen, Xuemei; Wang, Zuankai; Yao, Shuhuai

2018-02-16

Preventing or minimizing ice formation in supercooled water is of prominent importance in many infrastructures, transportation, and cooling systems. The overall phase change heat transfer on icephobic surfaces, in general, is intentionally sacrificed to suppress the nucleation of water and ice. However, in a condensation frosting process, inhibiting freezing without compromising the water condensation has been an unsolved challenge. Here we show that this conflict between anti-icing and efficient condensation cooling can be resolved by utilizing biphilic topography with patterned high-contrast wettability. By creating a varying interfacial thermal barrier underneath the supercooled condensate, the biphilic structures tune the nucleation rates of water and ice in the sequential condensation-to-freezing process. Our experimental and theoretical investigation of condensate freezing dynamics further unravels the correlation between the onset of droplet freezing and its characteristic radius, offering a new insight for controlling the multiphase transitions among vapor, water, and ice in supercooled conditions.

Reflection high energy electron diffraction observation of surface mass transport at the two- to three-dimensional growth transition of InAs on GaAs(001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patella, F.; Arciprete, F.; Fanfoni, M.

2005-12-19

We have followed by reflection high-energy electron diffraction the nucleation of InAs quantum dots on GaAs(001), grown by molecular-beam epitaxy with growth interruptions. Surface mass transport gives rise, at the critical InAs thickness, to a huge nucleation of three-dimensional islands within 0.2 monolayers (ML). Such surface mass diffusion has been evidenced by observing the transition of the reflection high-energy electron diffraction pattern from two- to three-dimensional during the growth interruption after the deposition of 1.59 ML of InAs. It is suggested that the process is driven by the As{sub 2} adsorption-desorption process and by the lowering of the In bindingmore » energy due to compressive strain. The last condition is met first in the region surrounding dots at step edges where nucleation predominantly occurs.« less

Bioactive and Porous Metal Coatings for Improved Tissue Regeneration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campbell, A. A.

Our first objective was to develop the SIM process for the deposition of calcium phosphate films. This process is based on the observation that, in nature, living organisms use macromolecules to control the nucleation and growth of mineral phases. These macromolecules act as templates where various charged functional groups, contained within the molecule, can interact with the ions in the surrounding media, thus stimulating crystal nucleation and growth. Rather than using complex proteins or biopolymers, surface modification schemes were developed to place simple functional groups on the underlying substrate using self-assembling monolayers. Once the substrate was chemically modified, it wasmore » then placed into an aqueous solution containing soluble precursors of the desired mineral coating. Solution pH, ionic concentration and temperature is maintained in a regime where the solution is supersaturated with respect to the desired mineral phase, thereby creating the driving force for nucleation and growth.« less

Crystallization of aqueous ammonium sulfate particles internally mixed with soot and kaolinite: crystallization relative humidities and nucleation rates.

PubMed

Pant, Atul; Parsons, Matthew T; Bertram, Allan K

2006-07-20

Using optical microscopy, we investigated the crystallization of aqueous ammonium sulfate droplets containing soot and kaolinite, as well as the crystallization of aqueous ammonium sulfate droplets free of solid material. Our results show that soot did not influence the crystallization RH of aqueous ammonium sulfate particles under our experimental conditions. In contrast, kaolinite increased the crystallization RH of the aqueous ammonium sulfate droplets by approximately 10%. In addition, our results show that the crystallization RH of aqueous ammonium sulfate droplets free of solid material does not depend strongly on particle size. This is consistent with conclusions made previously in the literature, based on comparisons of results from different laboratories. From the crystallization results we determined the homogeneous nucleation rates of crystalline ammonium sulfate in aqueous ammonium sulfate droplets and the heterogeneous nucleation rates of crystalline ammonium sulfate in aqueous ammonium sulfate particles containing kaolinite. Using classical nucleation theory and our experimental data, we determined that the interfacial tension between an ammonium sulfate critical nucleus and an aqueous ammonium sulfate solution is 0.064 +/- 0.003 J m(-2) (in agreement with our previous measurements), and the contact angle between an ammonium sulfate critical nucleus and a kaolinite surface is 59 +/- 2 degrees. On the basis of our results, we argue that soot will not influence the crystallization RH of aqueous ammonium sulfate droplets in the atmosphere, but kaolinite can significantly modify the crystallization RH of atmospheric ammonium sulfate droplets. As an example, the CRH50 (the relative humidity at which 50% of the droplets crystallize) ranges from about 41 to 51% RH when the diameter of the kaolinite inclusion ranges from 0.1 to 5 microm. For comparison, the CRH50 of aqueous ammonium sulfate droplets (0.5 microm diameter) free of solid material is approximately 34.3% RH under atmospheric conditions.

Controls of ionic strength and macromolecule chemistry on calcite nucleation: Salinity and ion hydration as levers for regulating biomineralization

NASA Astrophysics Data System (ADS)

Dove, P. M.; Giuffre, A. J.; Mergelsberg, S. T.; Han, N.; De Yoreo, J. J.

2016-12-01

Organisms form shells and skeletons with remarkable fidelity by controlling the timing and placement of the minerals that nucleate and subsequently grow. An extensive effort has identified features of the organic matrix that regulate this process. Recent measurements from our group show the energy barrier to nucleation onto polysaccharide (PS) substrates is dependent upon hydrophilicity through functional group chemistry and suggest that free energy of the macromolecule-liquid interface influences where and when mineral nucleation occurs (Giuffre et al., 2013, PNAS). The importance of interfacial free energy in regulating nucleation raises the question of whether local changes in salinity or electrolyte composition can be tuned to further modulate the onset of calcite nucleation. Using alginate (negatively charged by carboxyl groups) and chitosan (small positive charge by amine groups), the rate of calcite nucleation was measured at controlled supersaturations and pH as a function of NaCl concentration (65-600 mM). Analyses of the data show the thermodynamic barrier to calcite nucleation onto both types of PS increases with ionic strength. The evidence suggests this effect arises from an increasing concentration of solvated ions at the PS-water interface while also increasing the hydrophilic character of that interface; thus decreasing the substrate-liquid interfacial free energy. To test this explanation, a second group of nucleation experiments used a suite of electrolytes (alkali chlorides for alginate and sodium halides for chitosan) while holding ionic strength constant. Indeed, the nucleation barriers for calcite formation are electrolyte-specific and correlated with the hydration free energy of the ion. This suggests solvated electrolyte ions indirectly regulate calcite nucleation onto substrates through their competition with the substrate for water thereby influencing net interfacial free energy. These effects are consistent with the long-established salting-in phenomena of the Hofmeister series. The new insights from this experimental study reiterate the importance of electrolytes in reactions involving mineral-water interfaces and suggest a role for seemingly inert `spectator' ions in regulating the local timing and placement of minerals during biomineralization.

Nanoparticle Nucleation Is Termolecular in Metal and Involves Hydrogen: Evidence for a Kinetically Effective Nucleus of Three {Ir3H2x·P2W15Nb3O62}6- in Ir(0)n Nanoparticle Formation From [(1,5-COD)IrI·P2W15Nb3O62]8- Plus Dihydrogen.

PubMed

Özkar, Saim; Finke, Richard G

2017-04-19

The nucleation process yielding Ir(0) ∼300 nanoparticles from (Bu 4 N) 5 Na 3 [(1,5-COD)Ir·P 2 W 15 Nb 3 O 62 ] (abbreviated hereafter as (COD)Ir·POM 8- , where POM 9- = the polyoxometalate, P 2 W 15 Nb 3 O 62 9- ) under H 2 is investigated to learn the true molecularity, and hence the associated kinetically effective nucleus (KEN), for nanoparticle formation for the first time. Recent work with this prototype transition-metal nanoparticle formation system ( J. Am. Chem. Soc. 2014 , 136 , 17601 - 17615 ) revealed that nucleation in this system is an apparent second-order in the precatalyst, A = (COD)Ir·POM 8- , not the higher order implied by classic nucleation theory and its nA ⇌ A n , "critical nucleus", A n concept. Herein, the three most reasonable more intimate mechanisms of nucleation are tested: bimolecular nucleation, termolecular nucleation, and a mechanism termed "alternative termolecular nucleation" in which 2(COD)Ir + and 1(COD)Ir·POM 8- yield the transition state of the rate-determining step of nucleation. The results obtained definitively rule out a simple bimolecular nucleation mechanism and provide evidence for the alternative termolecular mechanism with a KEN of 3, Ir 3 . All higher molecularity nucleation mechanisms were also ruled out. Further insights into the KEN and its more detailed composition involving hydrogen, {Ir 3 H 2x POM} 6- , are also obtained from the established role of H 2 in the Ir(0) ∼300 formation balanced reaction stoichiometry, from the p(H 2 ) dependence of the kinetics, and from a D 2 /H 2 kinetic isotope effect of 1.2(±0.3). Eight insights and conclusions are presented. A section covering caveats in the current work, and thus needed future studies, is also included.

Physical origin of the incubation time of self-induced GaN nanowires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Consonni, V.; Trampert, A.; Geelhaar, L.

2011-07-18

The nucleation process of self-induced GaN nanowires grown by molecular beam epitaxy has been investigated by reflection high-energy electron diffraction measurements. It is found that stable nuclei in the form of spherical cap-shaped islands develop only after an incubation time that is strongly dependent upon the growth conditions. Its evolution with the growth temperature and gallium rate has been described within standard island nucleation theory, revealing a nucleation energy of 4.9 {+-} 0.1 eV and a very small nucleus critical size. The consideration of the incubation time is critical for the control of the nanowire morphology.

Nucleate pool boiling in subcooled liquid under microgravity: Results of TEXUS experimental investigations

NASA Astrophysics Data System (ADS)

Zell, M.; Straub, J.; Weinzierl, A.

1984-12-01

Experiments on subcooled nucleate pool boiling in microgravity were carried out to separate gravity driven effects on heat transfer within the boiling process. A ballistic trajectory by sounding rocket flight (TEXUS 5 and 10) achieved a gravity level of a/g = 0.0001 for 360 sec. For determination of geometrical effects on heat transport two different experimental configurations (platinum wire and flat plate) were employed. Boiling curves and bubble dynamics recorded by cinematography lead to gravity independent modelling of the boiling phenomena. The results ensure the applicability and high efficiency of nucleate pool boiling for heat exchangers in space laboratories.

Mechanisms of single-walled carbon nanotube nucleation, growth, and healing determined using QM/MD methods.

PubMed

Page, Alister J; Ohta, Yasuhito; Irle, Stephan; Morokuma, Keiji

2010-10-19

Since their discovery in the early 1990s, single-walled carbon nanotubes (SWNTs) have spawned previously unimaginable commercial and industrial technologies. Their versatility stems from their unique electronic, physical/chemical, and mechanical properties, which set them apart from traditional materials. Many researchers have investigated SWNT growth mechanisms in the years since their discovery. The most prevalent of these is the vapor-liquid-solid (VLS) mechanism, which is based on experimental observations. Within the VLS mechanism, researchers assume that the formation of a SWNT starts with co-condensation of carbon and metal atoms from vapor to form liquid metal carbide. Once the liquid reaches supersaturation, the solid phase nanotubes begin to grow. The growth process is partitioned into three distinct stages: nucleation of a carbon "cap-precursor," "cap-to-tube" transformation, and continued SWNT growth. In recent years, molecular dynamics (MD) simulations have come to the fore with respect to SWNT growth. MD simulations lead to spatial and temporal resolutions of these processes that are superior to those possible using current experimental techniques, and so provide valuable information regarding the growth process that researchers cannot obtain experimentally. In this Account, we review our own recent efforts to simulate SWNT nucleation, growth, and healing phenomena on transition-metal catalysts using quantum mechanical molecular dynamics (QM/MD) methods. In particular, we have validated each stage of the SWNT condensation mechanism using a self-consistent-charge density-functional tight-binding (SCC-DFTB) methodology. With respect to the nucleation of a SWNT cap-precursor (stage 1), we have shown that the presence of a transition-metal carbide particle is not a necessary prerequisite for SWNT nucleation, contrary to conventional experimental presumptions. The formation and coalescence of polyyne chains on the metal surface occur first, followed by the formation of the SWNT cap-precursor, "ring condensation", and the creation of an sp(2)-hybridized carbon structure. In our simulations, the nucleation process takes approximately 400 ps. This first step occurs over a much longer time scale than the second stage of SWNT condensation (approximately 50 ps). We therefore observe SWNT nucleation to be akin to the rate-limiting step of the SWNT formation process. In addition to the QM/MD simulation of various stages of SWNT nucleation, growth, and healing processes, we have determined the effects of temperature, catalyst composition, and catalyst size on the kinetics and mechanism of SWNT growth. With respect to temperature dependence, we observe a "sweet-spot" with respect to the efficiency of SWNT growth. In addition, Ni-catalyzed SWNT growth is observed to be 70-100% faster compared to Fe-catalyzed SWNT growth, depending on the catalyst particle size. We also observe a noticeable increase in SWNT growth rates using smaller catalyst particles. Finally, we review our recent QM/MD investigation of SWNT healing. In particular, we recount mechanisms by which adatom defects, monovacancy defects, and a "5-7 defect" are removed from a nascent SWNT. The effectiveness of these healing mechanisms depends on the rate at which carbon moieties are incorporated into the growing SWNT. Explicitly, we observe that healing is promoted using a slower carbon supply rate. From this rudimentary control of SWNT healing, we propose a route towards chirality-controlled SWNT growth.

Growth and melting of droplets in cold vapors.

PubMed

L'Hermite, Jean-Marc

2009-11-01

A model has been developed to investigate the growth of droplets in a supersaturated cold vapor taking into account their possible solid-liquid phase transition. It is shown that the solid-liquid phase transition is nontrivially coupled, through the energy released in attachment, to the nucleation process. The model is based on the one developed by J. Feder, K. C. Russell, J. Lothe, and G. M. Pound [Adv. Phys. 15, 111 (1966)], where the nucleation process is described as a thermal diffusion motion in a two-dimensional field of force given by the derivatives of a free-energy surface. The additional dimension accounts for droplets internal energy. The solid-liquid phase transition is introduced through a bimodal internal energy distribution in a Gaussian approximation derived from small clusters physics. The coupling between nucleation and melting results in specific nonequilibrium thermodynamical properties, exemplified in the case of water droplets. Analyzing the free-energy landscapes gives an insight into the nucleation dynamics. This landscape can be complex but generally exhibits two paths: the first one can generally be ascribed to the solid state, while the other to the liquid state. Especially at high supersaturation, the growth in the liquid state is often favored, which is not unexpected since in a supersaturated vapor the droplets can stand higher internal energy than at equilibrium. From a given critical temperature that is noticeably lower than the bulk melting temperature, nucleation may end in very large liquid droplets. These features can be qualitatively generalized to systems other than water.

Unified risk analysis of fatigue failure in ductile alloy components during all three stages of fatigue crack evolution process.

PubMed

Patankar, Ravindra

2003-10-01

Statistical fatigue life of a ductile alloy specimen is traditionally divided into three stages, namely, crack nucleation, small crack growth, and large crack growth. Crack nucleation and small crack growth show a wide variation and hence a big spread on cycles versus crack length graph. Relatively, large crack growth shows a lesser variation. Therefore, different models are fitted to the different stages of the fatigue evolution process, thus treating different stages as different phenomena. With these independent models, it is impossible to predict one phenomenon based on the information available about the other phenomenon. Experimentally, it is easier to carry out crack length measurements of large cracks compared to nucleating cracks and small cracks. Thus, it is easier to collect statistical data for large crack growth compared to the painstaking effort it would take to collect statistical data for crack nucleation and small crack growth. This article presents a fracture mechanics-based stochastic model of fatigue crack growth in ductile alloys that are commonly encountered in mechanical structures and machine components. The model has been validated by Ray (1998) for crack propagation by various statistical fatigue data. Based on the model, this article proposes a technique to predict statistical information of fatigue crack nucleation and small crack growth properties that uses the statistical properties of large crack growth under constant amplitude stress excitation. The statistical properties of large crack growth under constant amplitude stress excitation can be obtained via experiments.

Three-dimensional GaN/AlN nanowire heterostructures by separating nucleation and growth processes.

PubMed

Carnevale, Santino D; Yang, Jing; Phillips, Patrick J; Mills, Michael J; Myers, Roberto C

2011-02-09

Bottom-up nanostructure assembly has been a central theme of materials synthesis over the past few decades. Semiconductor quantum dots and nanowires provide additional degrees of freedom for charge confinement, strain engineering, and surface sensitivity-properties that are useful to a wide range of solid state optical and electronic technologies. A central challenge is to understand and manipulate nanostructure assembly to reproducibly generate emergent structures with the desired properties. However, progress is hampered due to the interdependence of nucleation and growth phenomena. Here we show that by dynamically adjusting the growth kinetics, it is possible to separate the nucleation and growth processes in spontaneously formed GaN nanowires using a two-step molecular beam epitaxy technique. First, a growth phase diagram for these nanowires is systematically developed, which allows for control of nanowire density over three orders of magnitude. Next, we show that by first nucleating nanowires at a low temperature and then growing them at a higher temperature, height and density can be independently selected while maintaining the target density over long growth times. GaN nanowires prepared using this two-step procedure are overgrown with three-dimensionally layered and topologically complex heterostructures of (GaN/AlN). By adjusting the growth temperature in the second growth step either vertical or coaxial nanowire superlattices can be formed. These results indicate that a two-step method allows access to a variety of kinetics at which nanowire nucleation and adatom mobility are adjustable.

Magnetization mechanisms in ordered arrays of polycrystalline Fe100-xCox nanowires

NASA Astrophysics Data System (ADS)

Viqueira, M. S.; Bajales, N.; Urreta, S. E.; Bercoff, P. G.

2015-05-01

Magnetization reversal processes and coercivity mechanisms in polycrystalline Fe100-xCox nanowire arrays, resulting from an AC electrodeposition process, are investigated. The array coercivity is described on the basis of polarization reversal mechanisms operating in individual wires, under the effect of inter-wire dipolar interactions described by a mean field approximation. For individual wires, a reversal mechanism involving the nucleation and further expansion of domain-wall like spin configuration is considered. The wires have a mean grain size larger than both the nanowire diameter and the exchange length, so localized and non-cooperative nucleation modes are considered. As the Co content increases, the alloy saturation polarization gradually decreases, but the coercive field and the relative remanence of the arrays increase, indicating that they are not controlled by the shape anisotropy in all the composition range. The coercive field dependence on the angle between the applied field and the wire long axis is not well described by reversal mechanisms involving nucleation and further displacement of neither vortex nor transverse ideal domain walls. On the contrary, the angular dependence of the coercive field observed at room temperature is well predicted by a model considering nucleation of inverse domains by localized curling, in regions smaller than the grain size, exhibiting quite small aspect ratios as compared to those of the entire nanowire. In arrays with higher Co contents, a transition from an initial (small angle) localized curling nucleation mechanism to another one, involving localized coherent rotation is observed at about π/4.

Actin kinetics shapes cortical network structure and mechanics

PubMed Central

Fritzsche, Marco; Erlenkämper, Christoph; Moeendarbary, Emad; Charras, Guillaume; Kruse, Karsten

2016-01-01

The actin cortex of animal cells is the main determinant of cellular mechanics. The continuous turnover of cortical actin filaments enables cells to quickly respond to stimuli. Recent work has shown that most of the cortical actin is generated by only two actin nucleators, the Arp2/3 complex and the formin Diaph1. However, our understanding of their interplay, their kinetics, and the length distribution of the filaments that they nucleate within living cells is poor. Such knowledge is necessary for a thorough comprehension of cellular processes and cell mechanics from basic polymer physics principles. We determined cortical assembly rates in living cells by using single-molecule fluorescence imaging in combination with stochastic simulations. We find that formin-nucleated filaments are, on average, 10 times longer than Arp2/3-nucleated filaments. Although formin-generated filaments represent less than 10% of all actin filaments, mechanical measurements indicate that they are important determinants of cortical elasticity. Tuning the activity of actin nucleators to alter filament length distribution may thus be a mechanism allowing cells to adjust their macroscopic mechanical properties to their physiological needs. PMID:27152338

Quasiconvexity at the Boundary and the Nucleation of Austenite

NASA Astrophysics Data System (ADS)

Ball, J. M.; Koumatos, K.

2016-01-01

Motivated by experimental observations of H. Seiner et al., we study the nucleation of austenite in a single crystal of a CuAlNi shape-memory alloy stabilized as a single variant of martensite. In the experiments the nucleation process was induced by localized heating and it was observed that, regardless of where the localized heating was applied, the nucleation points were always located at one of the corners of the sample—a rectangular parallelepiped in the austenite. Using a simplified nonlinear elasticity model, we propose an explanation for the location of the nucleation points by showing that the martensite is a local minimizer of the energy with respect to localized variations in the interior, on faces and edges of the sample, but not at some corners, where a localized microstructure, involving austenite and a simple laminate of martensite, can lower the energy. The result for the interior, faces and edges is established by showing that the free-energy function satisfies a set of quasiconvexity conditions at the stabilized variant in the interior, faces and edges, respectively, provided the specimen is suitably cut.

Actin kinetics shapes cortical network structure and mechanics.

PubMed

Fritzsche, Marco; Erlenkämper, Christoph; Moeendarbary, Emad; Charras, Guillaume; Kruse, Karsten

2016-04-01

The actin cortex of animal cells is the main determinant of cellular mechanics. The continuous turnover of cortical actin filaments enables cells to quickly respond to stimuli. Recent work has shown that most of the cortical actin is generated by only two actin nucleators, the Arp2/3 complex and the formin Diaph1. However, our understanding of their interplay, their kinetics, and the length distribution of the filaments that they nucleate within living cells is poor. Such knowledge is necessary for a thorough comprehension of cellular processes and cell mechanics from basic polymer physics principles. We determined cortical assembly rates in living cells by using single-molecule fluorescence imaging in combination with stochastic simulations. We find that formin-nucleated filaments are, on average, 10 times longer than Arp2/3-nucleated filaments. Although formin-generated filaments represent less than 10% of all actin filaments, mechanical measurements indicate that they are important determinants of cortical elasticity. Tuning the activity of actin nucleators to alter filament length distribution may thus be a mechanism allowing cells to adjust their macroscopic mechanical properties to their physiological needs.

Investigation of nucleation and growth processes of diamond films by atomic force microscopy

NASA Technical Reports Server (NTRS)

George, M. A.; Burger, A.; Collins, W. E.; Davidson, J. L.; Barnes, A. V.; Tolk, N. H.

1994-01-01

The nucleation and growth of plasma-enhanced chemical-vapor deposited polycrystalline diamond films were studied using atomic force microscopy (AFM). AFM images were obtained for (1) nucleated diamond films produced from depositions that were terminated during the initial stages of growth, (2) the silicon substrate-diamond film interface side of diamond films (1-4 micrometers thick) removed from the original surface of the substrate, and (3) the cross-sectional fracture surface of the film, including the Si/diamond interface. Pronounced tip effects were observed for early-stage diamond nucleation attributed to tip convolution in the AFM images. AFM images of the film's cross section and interface, however, were not highly affected by tip convolution, and the images indicate that the surface of the silicon substrate is initially covered by a small grained polycrystalline-like film and the formation of this precursor film is followed by nucleation of the diamond film on top of this layer. X-ray photoelectron spectroscopy spectra indicate that some silicon carbide is present in the precursor layer.

Analytical solutions of mushy layer equations describing directional solidification in the presence of nucleation

NASA Astrophysics Data System (ADS)

Alexandrov, Dmitri V.; Ivanov, Alexander A.; Alexandrova, Irina V.

2018-01-01

The processes of particle nucleation and their evolution in a moving metastable layer of phase transition (supercooled liquid or supersaturated solution) are studied analytically. The transient integro-differential model for the density distribution function and metastability level is solved for the kinetic and diffusionally controlled regimes of crystal growth. The Weber-Volmer-Frenkel-Zel'dovich and Meirs mechanisms for nucleation kinetics are used. We demonstrate that the phase transition boundary lying between the mushy and pure liquid layers evolves with time according to the following power dynamic law: , where Z1(t)=βt7/2 and Z1(t)=βt2 in cases of kinetic and diffusionally controlled scenarios. The growth rate parameters α, β and ε are determined analytically. We show that the phase transition interface in the presence of crystal nucleation and evolution propagates slower than in the absence of their nucleation. This article is part of the theme issue `From atomistic interfaces to dendritic patterns'.

Global Simulations of Ice nucleation and Ice Supersaturation with an Improved Cloud Scheme in the Community Atmosphere Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gettelman, A.; Liu, Xiaohong; Ghan, Steven J.

2010-09-28

A process-based treatment of ice supersaturation and ice-nucleation is implemented in the National Center for Atmospheric Research (NCAR) Community Atmosphere Model (CAM). The new scheme is designed to allow (1) supersaturation with respect to ice, (2) ice nucleation by aerosol particles and (3) ice cloud cover consistent with ice microphysics. The scheme is implemented with a 4-class 2 moment microphysics code and is used to evaluate ice cloud nucleation mechanisms and supersaturation in CAM. The new model is able to reproduce field observations of ice mass and mixed phase cloud occurrence better than previous versions of the model. Simulations indicatemore » heterogeneous freezing and contact nucleation on dust are both potentially important over remote areas of the Arctic. Cloud forcing and hence climate is sensitive to different formulations of the ice microphysics. Arctic radiative fluxes are sensitive to the parameterization of ice clouds. These results indicate that ice clouds are potentially an important part of understanding cloud forcing and potential cloud feedbacks, particularly in the Arctic.« less

Anisotropic toughness and strength in graphene and its atomistic origin

NASA Astrophysics Data System (ADS)

Hossain, M. Zubaer; Ahmed, Tousif; Silverman, Benjamin; Khawaja, M. Shehroz; Calderon, Justice; Rutten, Andrew; Tse, Stanley

2018-01-01

This paper presents the implication of crystallographic orientation on toughness and ideal strength in graphene under lattice symmetry-preserving and symmetry-breaking deformations. In symmetry-preserving deformation, both toughness and strength are isotropic, regardless of the chirality of the lattice; whereas, in symmetry-breaking deformation they are strongly anisotropic, even in the presence of vacancy defects. The maximum and minimum of toughness or strength occur for loading along the zigzag direction and the armchair direction, respectively. The anisotropic behavior is governed by a complex interplay among bond-stretching deformation, bond-bending deformation, and the chirality of the lattice. Nevertheless, the condition for crack-nucleation is dictated by the maximum bond-force required for bond rupture, and it is independent of the chiral angle of the lattice or loading direction. At the onset of crack-nucleation a localized nucleation zone is formed, wherein the bonds rupture locally satisfying the maximum bond-force criterion. The nucleation zone acts as the physical origin in triggering the fracture nucleation process, but its presence is undetectable from the macroscopic stress-strain data.

Effect of CaCO3(S) nucleation modes on algae removal from alkaline water.

PubMed

Choi, Jin Yong; Kinney, Kerry A; Katz, Lynn E

2016-02-29

The role of calcite heterogeneous nucleation was studied in a particle coagulation treatment process for removing microalgae from water. Batch experiments were conducted with Scenedesmus sp. and Chlorella sp. in the presence and absence of carbonate and in the presence and absence of Mg to delineate the role of CaCO 3(S) nucleation on microalgae removal. The results indicate that effective algae coagulation (e.g., up to 81 % algae removal efficiency) can be achieved via heterogeneous nucleation with CaCO 3(S) ; however, supersaturation ratios between 120 and 200 are required to achieve at least 50% algae removal, depending on ion concentrations. Algae removal was attributed to adsorption of Ca 2+ onto the cell surface which provides nucleation sites for CaCO 3(S) precipitation. Bridging of calcite particles between the algal cells led to rapid aggregation and formation of larger flocs. However, at higher supersaturation conditions, algae removal was diminished due to the dominance of homogeneous nucleation of CaCO 3(S) . Removal of algae in the presence of Ca 2+ and Mg 2+ required higher supersaturation values; however, the shift from heteronucleation to homonucleation with increasing supersaturation was still evident. The results suggest that water chemistry, pH, ionic strength, alkalinity and Ca 2+ concentration can be optimized for algae removal via coagulation-sedimentation.

Nucleation and Epitaxy-Mediated Phase Transformation of a Precursor Cadmium Carbonate Phase at the Calcite/Water Interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riechers, Shawn L.; Rosso, Kevin M.; Kerisit, Sebastien N.

Mineral nucleation can be catalyzed by the presence of mineral substrates; however, the mechanisms of heterogeneous nucleation remain poorly understood. A combination of in situ time-sequenced measurements and nano-manipulation experiments were performed using atomic force microscopy (AFM) to probe the mechanisms of heteroepitaxial nucleation of otavite (CdCO3) on calcite (CaCO3) single crystals that exposed the (10-14) surface. Otavite and calcite are isostructural carbonates that display a 4% lattice mismatch, based on their (10-14) surface areas. AFM observations revealed a two-stage process in the nucleation of cadmium carbonate surface precipitates. As evidenced by changes in height, shape, growth behavior, and frictionmore » signal of the precipitates, a precursor phase was observed to initially form on the surface and subsequently undergo an epitaxy-mediated phase transformation to otavite, which then grew epitaxially. Nano-manipulation experiments, in which the applied force was increased progressively until precipitates were removed from the surface, showed that adhesion of the precursor phase to the substrate was distinctively weaker than that of the epitaxial phase, consistent with that of an amorphous phase. These findings demonstrate for the first time that heterogeneous mineral nucleation can follow a non-classical pathway like that found in homogenous aqueous conditions.« less

Engineering Surfaces for Enhanced Nucleation and Droplet Removal During Dropwise Condensation

NASA Astrophysics Data System (ADS)

Dutta, Sanmitra; Khan, Sameera; Anand, Sushant

2017-11-01

Condensation plays critical role in numerous industrial applications, such as condensers, HVAC,etc In the most applications, fast formation (i.e. high nucleation) and subsequent removal of water droplets is critical for enhancing the efficiencies of their associated systems. Significant focus has been placed on the aspect of droplet removal from surfaces. This has led to, development of superhydrophobic surfaces with special textures on which droplets are self-removed after coalescence. However,because of their inherent low surface energy, nucleation energy barriers are also high on such surfaces. In contrast to conventional superhydrophobic surfaces, here we show that surfaces can be engineered such that the simultaneous benefits of high nucleation rates and fast droplet removal can be obtained during the condensation process.These benefits are obtained by impregnating a superhydrophobic surface with an oil that despite its defect-free interface provides low nucleation energy barrier during condensation. At the same time, the oil facilitates high droplet shedding rates by providing a lubricating layer below the droplets due to which droplets have negligible contact angle hysteresis. We provide a guide to choose oils that lead to enhanced nucleation, and provide experimental evidence supporting the proposed guide. We discuss the importance of different oil properties in affecting the droplet growth and subsequent removal of water droplets.

Identification and quantification of ice nucleation active microorganisms by digital droplet PCR (ddPCR)

NASA Astrophysics Data System (ADS)

Linden, Martin; Pöschl, Ulrich; Fröhlich-Nowoisky, Janine

2015-04-01

Several bioaerosol types, including bacteria, fungi, pollen and lichen, have been identified as sources of biological ice nucleators (IN) which induce ice formation already at temperatures as high as -10 °C or above. Accordingly, they potentially contribute widely to environmental ice nucleation in the atmosphere and are of great interest in the study of natural heterogenous ice nucleation processes. Ice nucleation active microorganisms have been found and studied among bacteria (Proteobacteria) and fungi (phyla Basidiomycota and Ascomycota). The mechanisms enabling the microorganisms to ice nucleation are subject to ongoing research. While it has been demonstrated that whole cells can act as ice nucleators in the case of bacteria due to the presence of specific membrane proteins, cell-free ice nucleation active particles seem to be responsible for this phenomenon in fungi and lichen. The identification and quantification of these ice nucleation active microorganisms and their IN in atmospheric samples is crucial to understand their contribution to the pool of atmospheric IN. This is not a trivial task since the respective microorganisms are often prevalent in lowest concentrations and a variety of states, be it viable cells, spores or cell debris from dead cells. Molecular biology provides tools to identify and quantify ice nucleation active microorganisms independent of their state by detecting genetic markers specific for the organism of interest. Those methods are not without their drawbacks in terms of sample material concentration required or reliable standardization. Digital Droplet Polymerase Chain Reaction (ddPCR) was chosen for our demands as a more elegant, quick and specific method in the investigation of ice nucleation active microorganisms in atmospheric samples. The advantages of ddPCR lie in the simultaneous detection and quantification of genetic markers and their original copy numbers in a sample. This is facilitated by the fractionation of the PCR reaction volumes containing template DNA of ice nucleation active microorganisms from atmospheric samples in thousands of identical droplets. Each droplet encapsulates the reagents necessary for DNA amplification. With template DNA concentrations low enough, the droplets will statistically contain either no template molecules or one molecule. A molecule of template DNA corresponds to exactly one cell of an ice nucleation active microorganism in the original sample provided the genetic marker on the template is present in a single copy. Successful amplification in the presence of template DNA is coupled to a measurable fluorescence signal. The original template DNA concentration is automatically derived from the fraction of fluorescence positive droplets to total droplet number. This far, molecular probes against single-copy genetic markers for ice nucleation active fungi Mortierella alpina, Acremonium implicatum, Isaria farinosa and the ice nucleation active bacterium Pseudomonas syringae have been successfully designed and tested by our group.

Continuous microcellular foaming of polylactic acid/natural fiber composites

NASA Astrophysics Data System (ADS)

Diaz-Acosta, Carlos A.

Poly(lactic acid) (PLA), a biodegradable thermoplastic derived from renewable resources, stands out as a substitute to petroleum-based plastics. In spite of its excellent properties, commercial applications are limited because PLA is more expensive and more brittle than traditional petroleum-based resins. PLA can be blended with cellulosic fibers to reduce material cost. However, the lowered cost comes at the expense of flexibility and impact strength, which can be enhanced through the production of microcellular structures in the composite. Microcellular foaming uses inert gases (e.g., carbon dioxide) as physical blowing agents to make cellular structures with bubble sizes of less than 10 microm and cell-population densities (number of bubbles per unit volume) greater than 109 cells/cm³. These unique characteristics result in a significant increase in toughness and elongation at break (ductility) compared with unfoamed parts because the presence of small bubbles can blunt the crack-tips increasing the energy needed to propagate the crack. Microcellular foams have been produced through a two step batch process. First, large amounts of gas are dissolved in the solid plastic under high pressure (sorption process) to form a single-phase solution. Second, a thermodynamic instability (sudden drop in solubility) triggers cell nucleation and growth as the gas diffuses out of the plastic. Batch production of microcellular PLA has addressed some of the drawbacks of PLA. Unfortunately, the batch foaming process is not likely to be implemented in the industrial production of foams because it is not cost-effective. This study investigated the continuous microcellular foaming process of PLA and PLA/wood-fiber composites. The effects of the processing temperature and material compositions on the melt viscosity, pressure drop rate, and cell-population density were examined in order to understand the nucleation mechanisms in neat and filled PLA foams. The results indicated that the processing temperature had a strong effect of the rheology of the melt and cell morphology. Processing at a lower temperature significantly increased the cell nucleation rate of neat PLA (amorphous and semi-crystalline) because of the fact that a high melt viscosity induced a high pressure drop rate in the polymer/gas solution. The presence of nanoclay did not affect the homogeneous nucleation but increased the heterogeneous nucleation, allowing both nucleation mechanisms to occur during the foaming process. The effect of wood-flour (0-30 wt.%) and rheology modifier contents on the melt viscosity and cell morphology of microcellular foamed composites was investigated. The viscosity of the melt increased with wood-flour content and decreased with rheology modifier content, affecting the processing conditions (i.e., pressure drop and pressure drop rate) and foamability of the composites. Matching the viscosity of the composites with that of neat PLA resulted in the best cell morphologies. Physico-mechanical characterization of microcellular foamed PLA as a function of cell morphology was performed to establish process-morphology-property relationships. The processing variables, i.e., amount of gas injected, flow rate, and processing temperature affected the development of the cellular structure and mechanical properties of the foams.

New twinning route in face-centered cubic nanocrystalline metals.

PubMed

Wang, Lihua; Guan, Pengfei; Teng, Jiao; Liu, Pan; Chen, Dengke; Xie, Weiyu; Kong, Deli; Zhang, Shengbai; Zhu, Ting; Zhang, Ze; Ma, Evan; Chen, Mingwei; Han, Xiaodong

2017-12-15

Twin nucleation in a face-centered cubic crystal is believed to be accomplished through the formation of twinning partial dislocations on consecutive atomic planes. Twinning should thus be highly unfavorable in face-centered cubic metals with high twin-fault energy barriers, such as Al, Ni, and Pt, but instead is often observed. Here, we report an in situ atomic-scale observation of twin nucleation in nanocrystalline Pt. Unlike the classical twinning route, deformation twinning initiated through the formation of two stacking faults separated by a single atomic layer, and proceeded with the emission of a partial dislocation in between these two stacking faults. Through this route, a three-layer twin was nucleated without a mandatory layer-by-layer twinning process. This route is facilitated by grain boundaries, abundant in nanocrystalline metals, that promote the nucleation of separated but closely spaced partial dislocations, thus enabling an effective bypassing of the high twin-fault energy barrier.

Oxidative Processing Lowers the Ice Nucleation Activity of Birch and Alder Pollen

NASA Astrophysics Data System (ADS)

Gute, Ellen; Abbatt, Jonathan P. D.

2018-02-01

Pollen carry water extractable compounds with ice nucleating (IN) activity. This study investigates whether the hydroxyl radical, as the major atmospheric oxidant, can affect the IN activity of silver birch and grey alder subpollen particles under in-cloud conditions for deposition freezing mode conditions at 234 K. It is found that oxidation increases the supersaturation ratio with respect to ice necessary for the onset of ice nucleation and decreases the fraction of particles which initiate ice nucleation. This reduction of IN activity under equivalent oxidation conditions does not occur with a mineral dust sample (Arizona Test Dust). Chemical analysis of fresh and oxidized pollen material indicates a change of molecular structure with a loss of conjugation and an increase in oxidized functional groups, such as carbonyls. This is the first demonstration that in-cloud oxidation may lower the IN abilities of biological particles such as pollen.

Potentiostatic controlled nucleation and growth modes of electrodeposited cobalt thin films on n-Si(1 1 1)

NASA Astrophysics Data System (ADS)

Mechehoud, Fayçal; Khelil, Abdelbacet; Eddine Hakiki, Nour; Bubendorff, Jean-Luc

2016-08-01

The nucleation and growth of Co electrodeposits on n-Si(1 1 1) substrate have been investigated as a function of the applied potential in a large potential range using electrochemical techniques (voltammetry and chrono-amperometry) and surface imaging by atomic force microscopy (AFM). The surface preparation of the sample is crucial and we achieve a controlled n-Si(1 1 1) surface with mono-atomic steps and flat terraces. Using Scharifker-Hills models for fitting the current-time transients, we show that a transition from an instantaneous nucleation process to a progressive one occurs when the overpotential increases. A good agreement between the nucleation and growth parameters extracted from the models and the AFM data's is observed. The growth is of the Volmer-Weber type with a roughness and a spatial extension in the substrate plane of the deposited islands that increase with thickness.

Capture zone area distributions for nucleation and growth of islands during submonolayer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Yong; Li, Maozhi; Evans, James W.

2016-12-07

A fundamental evolution equation is developed to describe the distribution of areas of capture zones (CZs) associated with islands formed by homogeneous nucleation and growth during submonolayer deposition on perfect flat surfaces. This equation involves various quantities which characterize subtle spatial aspects of the nucleation process. These quantities in turn depend on the complex stochastic geometry of the CZ tessellation of the surface, and their detailed form determines the CZ area distribution (CZD) including its asymptotic features. For small CZ areas, behavior of the CZD reflects the critical island size, i. For large CZ areas, it may reflect the probabilitymore » for nucleation near such large CZs. Predictions are compared with kinetic Monte Carlo simulation data for models with two-dimensional compact islands with i = 1 (irreversible island formation by diffusing adatom pairs) and i = 0 (adatoms spontaneously convert to stable nuclei, e.g., by exchange with the substrate).« less

Ice nucleation activity of diesel soot particles at cirrus relevant temperature conditions: Effects of hydration, secondary organics coating, soot morphology, and coagulation

NASA Astrophysics Data System (ADS)

Kulkarni, Gourihar; China, Swarup; Liu, Shang; Nandasiri, Manjula; Sharma, Noopur; Wilson, Jacqueline; Aiken, Allison C.; Chand, Duli; Laskin, Alexander; Mazzoleni, Claudio; Pekour, Mikhail; Shilling, John; Shutthanandan, Vaithiyalingam; Zelenyuk, Alla; Zaveri, Rahul A.

2016-04-01

Ice formation by diesel soot particles was investigated at temperatures ranging from -40 to -50°C. Size-selected soot particles were physically and chemically aged in an environmental chamber, and their ice nucleating properties were determined using a continuous flow diffusion type ice nucleation chamber. Bare (freshly formed), hydrated, and compacted soot particles, as well as α-pinene secondary organic aerosol (SOA)-coated soot particles at high relative humidity conditions, showed ice formation activity at subsaturation conditions with respect to water but below the homogeneous freezing threshold conditions. However, SOA-coated soot particles at dry conditions were observed to freeze at homogeneous freezing threshold conditions. Overall, our results suggest that heterogeneous ice nucleation activity of freshly emitted diesel soot particles are sensitive to some of the aging processes that soot can undergo in the atmosphere.

An investigation of voids formation mechanisms and their effects on freeze and thaw processes of lithium and lithium fluoride

NASA Technical Reports Server (NTRS)

El-Genk, Mohamed S.; Yang, Jae-Young

1991-01-01

The mechanisms of void formation during the cooldown and freezing of lithium coolant within the primary loop of SP-100 type systems are investigated. These mechanisms are: (1) homogeneous nucleation; (2) heterogeneous nucleation; (3) normal segregation of helium gas dissolved in liquid lithium; and (4) shrinkage of lithium during freezing. To evaluate the void formation potential due to segregation, a numerical scheme that couples the freezing and mass diffusion processes in both the solid and liquid regions is developed. The results indicated that the formation of He bubbles is unlikely by either homogeneous or heterogeneous nucleation during the cooldown process. However, homogeneous nucleation of He bubbles following the segregation of dissolved He in liquid lithium ahead of the solid-liquid interface is likely to occur. Results also show that total volume of He void is insignificant when compared to that of shrinkage voids. In viewing this, the subsequent research focuses on the effects of shrinkage void forming during freezing of lithium on subsequent thaw processes are investigated using a numerical scheme that is based on a single (solid/liquid) cell approach. The cases of lithium-fluoride are also investigated to show the effect of larger volume shrinkage upon freezing on the freeze and thaw processes. Results show that a void forming at the wall appreciably reduces the solid-liquid interface velocity, during both freeze and thaw, and causes a substantial rise in the wall temperature during thaw. However, in the case of Li, the maximum wall temperature was much lower than the melting temperature of PWC-11, which is used as the structure material in the SP-100 system. Hence, it is included that a formation of hot spots is unlikely during the startup or restart of the SP-100 system.

Size Exclusion Chromatography Studies of the Initial Self-Association Steps of Chicken Egg White Lysozyme Nucleation

NASA Technical Reports Server (NTRS)

Ewing, Felecia; Donovan, David; Pusey, Marc

2000-01-01

Nucleation is one of the least understood aspects of crystallogenesis. In the case of macromolecule nucleation, this understanding is further hampered by uncertainty over what precisely is being discussed. We define the process of solute self-association (aggregation, oligomerization, interaction, clustering, etc.) whereby n-mers (n > or = 2) having a crystallographic or nascent crystallographic arrangement leading to the critical nucleus reversibly form in the solution, to be part of the nucleation process. This reversible self-association process is a fundamental part of the nucleation process, and occurs as a function of the solute concentration. In the case of chicken egg white lysozyme, a considerable body of experimental evidence leads us to the conclusion that it also forms the crystal growth units. Size exclusion chromatography is a simple and direct method for determining the equilibrium constants for the self-association process. A Pharmacia FPLC system was used to provide accurate solution flow rates. The column, injection valve, and sample loop were all mounted within a temperature-controlled chamber. Chromatographically re-purified lysozyme was first dialyzed against the column equilibration buffer, with injection onto the column after several hours pre-incubation at the running temperature. Preliminary experiments, were carried out using a Toyopearl HW-50F column (1 x 50cm), equilibrated with 0.1 M sodium acetate, 5% sodium chloride, pH 4.6, at 15C. Protein concentrations from 0.1 to 4 mg/ml were employed (C(sub sat) = 1.2 mg/ml). The data from several different protein preparations consistently shows a progressively decreasing elution volume with increasing protein concentration, indicating that reversible self-association is occurring. The dotted line indicates the monomeric lysozyme elution volume. However, lysozyme interacts with the column matrix in these experiments, which complicates data analysis.Accordingly, we are testing silica-based HPLC columns in an effort to eliminate this problem and substantially reduce the column volume and experimental run time. The results and data analysis from these and subsequent experiments will be presented.

Nonthermal ice nucleation observed at distorted contact lines of supercooled water drops

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Fan; Cruikshank, Owen; He, Weilue

Ice nucleation is the crucial step for ice formation in atmospheric clouds and therefore underlies climatologically relevant precipitation and radiative properties. Some progress has been made in understanding the roles of temperature, supersaturation, and material properties, but an explanation for the efficient ice nucleation occurring when a particle contacts a supercooled water drop has been elusive for over half a century. Here, we explore ice nucleation initiated at constant temperature and observe that mechanical agitation induces freezing of supercooled water drops at distorted contact lines. Results show that symmetric motion of supercooled water on a vertically oscillating substrate does notmore » freeze, no matter how we agitate it. However, when the moving contact line is distorted with the help of trace amounts of oil or inhomogeneous pinning on the substrate, freezing can occur at temperatures much higher than in a static droplet, equivalent to ~1010 increase in nucleation rate. Several possible mechanisms are proposed to explain the observations. One plausible explanation among them, decreased pressure due to interface curvature, is explored theoretically and compared with the observational results quasiquantitatively. Indeed, the observed freezing-temperature increase scales with contact line speed in a manner consistent with the pressure hypothesis. Whatever the mechanism, the experiments demonstrate a strong preference for ice nucleation at three-phase contact lines compared to the two-phase interface, and they also show that movement and distortion of the contact line are necessary contributions to stimulating the nucleation process.« less

Nonthermal ice nucleation observed at distorted contact lines of supercooled water drops

DOE PAGES

Yang, Fan; Cruikshank, Owen; He, Weilue; ...

2018-02-06

Ice nucleation is the crucial step for ice formation in atmospheric clouds and therefore underlies climatologically relevant precipitation and radiative properties. Some progress has been made in understanding the roles of temperature, supersaturation, and material properties, but an explanation for the efficient ice nucleation occurring when a particle contacts a supercooled water drop has been elusive for over half a century. Here, we explore ice nucleation initiated at constant temperature and observe that mechanical agitation induces freezing of supercooled water drops at distorted contact lines. Results show that symmetric motion of supercooled water on a vertically oscillating substrate does notmore » freeze, no matter how we agitate it. However, when the moving contact line is distorted with the help of trace amounts of oil or inhomogeneous pinning on the substrate, freezing can occur at temperatures much higher than in a static droplet, equivalent to ~1010 increase in nucleation rate. Several possible mechanisms are proposed to explain the observations. One plausible explanation among them, decreased pressure due to interface curvature, is explored theoretically and compared with the observational results quasiquantitatively. Indeed, the observed freezing-temperature increase scales with contact line speed in a manner consistent with the pressure hypothesis. Whatever the mechanism, the experiments demonstrate a strong preference for ice nucleation at three-phase contact lines compared to the two-phase interface, and they also show that movement and distortion of the contact line are necessary contributions to stimulating the nucleation process.« less

Nucleation of stoichiometric compounds from liquid: Role of the kinetic factor

DOE PAGES

Song, H.; Sun, Y.; Zhang, F.; ...

2018-02-02

The nucleation rate depends on the free-energy barrier and the kinetic factor. While the role of the free energy barrier is a text-book subject, the importance of the kinetic factor is frequently underestimated. Here in this study, we applied the mean first-passage time method, to obtain the free-energy landscape and kinetic factor directly from the molecular dynamics (MD) simulations of the nucleation of the face-centered cubic (fcc) phase in the pure Ni and the B2 phases in the Ni 50Al 50 and Cu 50Zr 50 alloys. The obtained data show that while the free-energy barrier for nucleation is higher inmore » pure Ni the nucleation rate is considerably lower in the Ni 50Al 50 alloy. This result can be explained by the slow attachment kinetics in the N i 50 A l 50 alloy, which was related to the ordered nature of the B2 phase. Even smaller fraction of the antisite defects in the C u 50 Z r 50 alloy leads to such a slow attachment kinetics that the nucleation is never observed for this alloy in the course of the MD simulation. Finally, this is consistent with the experimental facts that the Cu 50Zr 50 alloy is a good glass forming alloy and the Ni 50Al 50 alloy is not. Thus the present study demonstrates that the atom attachment rate can be the critical factor that controls the nucleation process under certain conditions.« less

Nonthermal ice nucleation observed at distorted contact lines of supercooled water drops

NASA Astrophysics Data System (ADS)

Yang, Fan; Cruikshank, Owen; He, Weilue; Kostinski, Alex; Shaw, Raymond A.

2018-02-01

Ice nucleation is the crucial step for ice formation in atmospheric clouds and therefore underlies climatologically relevant precipitation and radiative properties. Progress has been made in understanding the roles of temperature, supersaturation, and material properties, but an explanation for the efficient ice nucleation occurring when a particle contacts a supercooled water drop has been elusive for over half a century. Here, we explore ice nucleation initiated at constant temperature and observe that mechanical agitation induces freezing of supercooled water drops at distorted contact lines. Results show that symmetric motion of supercooled water on a vertically oscillating substrate does not freeze, no matter how we agitate it. However, when the moving contact line is distorted with the help of trace amounts of oil or inhomogeneous pinning on the substrate, freezing can occur at temperatures much higher than in a static droplet, equivalent to ˜1010 increase in nucleation rate. Several possible mechanisms are proposed to explain the observations. One plausible explanation among them, decreased pressure due to interface curvature, is explored theoretically and compared with the observational results quasiquantitatively. Indeed, the observed freezing-temperature increase scales with contact line speed in a manner consistent with the pressure hypothesis. Whatever the mechanism, the experiments demonstrate a strong preference for ice nucleation at three-phase contact lines compared to the two-phase interface, and they also show that movement and distortion of the contact line are necessary contributions to stimulating the nucleation process.

Nucleation of stoichiometric compounds from liquid: Role of the kinetic factor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, H.; Sun, Y.; Zhang, F.

The nucleation rate depends on the free-energy barrier and the kinetic factor. While the role of the free energy barrier is a text-book subject, the importance of the kinetic factor is frequently underestimated. Here in this study, we applied the mean first-passage time method, to obtain the free-energy landscape and kinetic factor directly from the molecular dynamics (MD) simulations of the nucleation of the face-centered cubic (fcc) phase in the pure Ni and the B2 phases in the Ni 50Al 50 and Cu 50Zr 50 alloys. The obtained data show that while the free-energy barrier for nucleation is higher inmore » pure Ni the nucleation rate is considerably lower in the Ni 50Al 50 alloy. This result can be explained by the slow attachment kinetics in the N i 50 A l 50 alloy, which was related to the ordered nature of the B2 phase. Even smaller fraction of the antisite defects in the C u 50 Z r 50 alloy leads to such a slow attachment kinetics that the nucleation is never observed for this alloy in the course of the MD simulation. Finally, this is consistent with the experimental facts that the Cu 50Zr 50 alloy is a good glass forming alloy and the Ni 50Al 50 alloy is not. Thus the present study demonstrates that the atom attachment rate can be the critical factor that controls the nucleation process under certain conditions.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pleše, P.; Higgins, M. D.; Mancini, L.

Bubble nucleation and growth control the explosivity of volcanic eruptions, and the kinetics of these processes are generally determined from examinations of natural samples and quenched experimental run products. These samples, however, only provide a view of the final state, from which the initial conditions of a time-evolving magmatic system are then inferred. The interpretations that follow are inexact due to the inability of determining the exact conditions of nucleation and the potential detachment of bubbles from their nucleation sites, an uncertainty that can obscure their nucleation location – either homogeneously within the melt or heterogeneously at the interface betweenmore » crystals and melts. We present results of a series of dynamic, real-time 4D X-ray tomographic microscopy experiments where we observed the development of bubbles in crystal bearing silicate magmas. Experimentally synthesized andesitic glasses with 0.25–0.5 wt% H2O and seed silicate crystals were heated at 1 atm to induce bubble nucleation and track bubble growth and movement. In contrast to previous studies on natural and experimentally produced samples, we found that bubbles readily nucleated on plagioclase and clinopyroxene crystals, that their contact angle changes during growth and that they can grow to sizes many times that of the silicate on whose surface they originated. The rapid heterogeneous nucleation of bubbles at low degrees of supersaturation in the presence of silicate crystals demonstrates that silicates can affect when vesiculation ensues, influencing subsequent permeability development and effusive vs. explosive transition in volcanic eruptions.« less

Nonthermal ice nucleation observed at distorted contact lines of supercooled water drops.

PubMed

Yang, Fan; Cruikshank, Owen; He, Weilue; Kostinski, Alex; Shaw, Raymond A

2018-02-01

Ice nucleation is the crucial step for ice formation in atmospheric clouds and therefore underlies climatologically relevant precipitation and radiative properties. Progress has been made in understanding the roles of temperature, supersaturation, and material properties, but an explanation for the efficient ice nucleation occurring when a particle contacts a supercooled water drop has been elusive for over half a century. Here, we explore ice nucleation initiated at constant temperature and observe that mechanical agitation induces freezing of supercooled water drops at distorted contact lines. Results show that symmetric motion of supercooled water on a vertically oscillating substrate does not freeze, no matter how we agitate it. However, when the moving contact line is distorted with the help of trace amounts of oil or inhomogeneous pinning on the substrate, freezing can occur at temperatures much higher than in a static droplet, equivalent to ∼10^{10} increase in nucleation rate. Several possible mechanisms are proposed to explain the observations. One plausible explanation among them, decreased pressure due to interface curvature, is explored theoretically and compared with the observational results quasiquantitatively. Indeed, the observed freezing-temperature increase scales with contact line speed in a manner consistent with the pressure hypothesis. Whatever the mechanism, the experiments demonstrate a strong preference for ice nucleation at three-phase contact lines compared to the two-phase interface, and they also show that movement and distortion of the contact line are necessary contributions to stimulating the nucleation process.

Plagioclase nucleation and growth kinetics in a hydrous basaltic melt by decompression experiments

NASA Astrophysics Data System (ADS)

Arzilli, Fabio; Agostini, C.; Landi, P.; Fortunati, A.; Mancini, L.; Carroll, M. R.

2015-12-01

Isothermal single-step decompression experiments (at temperature of 1075 °C and pressure between 5 and 50 MPa) were used to study the crystallization kinetics of plagioclase in hydrous high-K basaltic melts as a function of pressure, effective undercooling (Δ T eff) and time. Single-step decompression causes water exsolution and a consequent increase in the plagioclase liquidus, thus imposing an effective undercooling (Δ T eff), accompanied by increased melt viscosity. Here, we show that the decompression process acts directly on viscosity and thermodynamic energy barriers (such as interfacial-free energy), controlling the nucleation process and favoring the formation of homogeneous nuclei also at high pressure (low effective undercoolings). In fact, this study shows that similar crystal number densities ( N a) can be obtained both at low and high pressure (between 5 and 50 MPa), whereas crystal growth processes are favored at low pressures (5-10 MPa). The main evidence of this study is that the crystallization of plagioclase in decompressed high-K basalts is more rapid than that in rhyolitic melts on similar timescales. The onset of the crystallization process during experiments was characterized by an initial nucleation event within the first hour of the experiment, which produced the largest amount of plagioclase. This nucleation event, at short experimental duration, can produce a dramatic change in crystal number density ( N a) and crystal fraction ( ϕ), triggering a significant textural evolution in only 1 h. In natural systems, this may affect the magma rheology and eruptive dynamics on very short time scales.

Fault growth and acoustic emissions in confined granite

USGS Publications Warehouse

Lockner, David A.; Byerlee, James D.

1992-01-01

The failure process in a brittle granite was studied by using acoustic emission techniques to obtain three dimensional locations of the microfracturing events. During a creep experiment the nucleation of faulting coincided with the onset of tertiary creep, but the development of the fault could not be followed because the failure occurred catastrophically. A technique has been developed that enables the failure process to be stabilized by controlling the axial stress to maintain a constant acoustic emission rate. As a result the post-failure stress-strain curve has been followed quasi-statically, extending to hours the fault growth process that normally would occur violently in a fraction of a second. The results from the rate-controlled experiments show that the fault plane nucleated at a point on the sample surface after the stress-strain curve reached its peak. Before nucleation, the microcrack growth was distributed throughout the sample. The fault plane then grew outward from the nucleation site and was accompanied by a gradual drop in stress. Acoustic emission locations showed that the fault propagated as a fracture front (process zone) with dimensions of 1 to 3 cm. As the fracture front passed by a given fixed point on the fault plane, the subsequent acoustic emission would drop. When growth was allowed to progress until the fault bisected the sample, the stress dropped to the frictional strength. These observations are in accord with the behavior predicted by Rudnicki and Rice's bifurcation analysis but conflict with experiments used to infer that shear localization would occur in brittle rock while the material is still hardening.

Analysis of isothermal and cooling-rate-dependent immersion freezing by a unifying stochastic ice nucleation model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alpert, Peter A.; Knopf, Daniel A.

Immersion freezing is an important ice nucleation pathway involved in the formation of cirrus and mixed-phase clouds. Laboratory immersion freezing experiments are necessary to determine the range in temperature, T, and relative humidity, RH, at which ice nucleation occurs and to quantify the associated nucleation kinetics. Typically, isothermal (applying a constant temperature) and cooling-rate-dependent immersion freezing experiments are conducted. In these experiments it is usually assumed that the droplets containing ice nucleating particles (INPs) all have the same INP surface area (ISA); however, the validity of this assumption or the impact it may have on analysis and interpretation of the experimentalmore » data is rarely questioned. Descriptions of ice active sites and variability of contact angles have been successfully formulated to describe ice nucleation experimental data in previous research; however, we consider the ability of a stochastic freezing model founded on classical nucleation theory to reproduce previous results and to explain experimental uncertainties and data scatter. A stochastic immersion freezing model based on first principles of statistics is presented, which accounts for variable ISA per droplet and uses parameters including the total number of droplets, N tot, and the heterogeneous ice nucleation rate coefficient, J het( T). This model is applied to address if (i) a time and ISA-dependent stochastic immersion freezing process can explain laboratory immersion freezing data for different experimental methods and (ii) the assumption that all droplets contain identical ISA is a valid conjecture with subsequent consequences for analysis and interpretation of immersion freezing. The simple stochastic model can reproduce the observed time and surface area dependence in immersion freezing experiments for a variety of methods such as: droplets on a cold-stage exposed to air or surrounded by an oil matrix, wind and acoustically levitated droplets, droplets in a continuous-flow diffusion chamber (CFDC), the Leipzig aerosol cloud interaction simulator (LACIS), and the aerosol interaction and dynamics in the atmosphere (AIDA) cloud chamber. Observed time-dependent isothermal frozen fractions exhibiting non-exponential behavior can be readily explained by this model considering varying ISA. An apparent cooling-rate dependence of J het is explained by assuming identical ISA in each droplet. When accounting for ISA variability, the cooling-rate dependence of ice nucleation kinetics vanishes as expected from classical nucleation theory. Finally, the model simulations allow for a quantitative experimental uncertainty analysis for parameters N tot, T, RH, and the ISA variability. We discuss the implications of our results for experimental analysis and interpretation of the immersion freezing process.« less

Analysis of isothermal and cooling-rate-dependent immersion freezing by a unifying stochastic ice nucleation model

DOE PAGES

Alpert, Peter A.; Knopf, Daniel A.

2016-02-24

Immersion freezing is an important ice nucleation pathway involved in the formation of cirrus and mixed-phase clouds. Laboratory immersion freezing experiments are necessary to determine the range in temperature, T, and relative humidity, RH, at which ice nucleation occurs and to quantify the associated nucleation kinetics. Typically, isothermal (applying a constant temperature) and cooling-rate-dependent immersion freezing experiments are conducted. In these experiments it is usually assumed that the droplets containing ice nucleating particles (INPs) all have the same INP surface area (ISA); however, the validity of this assumption or the impact it may have on analysis and interpretation of the experimentalmore » data is rarely questioned. Descriptions of ice active sites and variability of contact angles have been successfully formulated to describe ice nucleation experimental data in previous research; however, we consider the ability of a stochastic freezing model founded on classical nucleation theory to reproduce previous results and to explain experimental uncertainties and data scatter. A stochastic immersion freezing model based on first principles of statistics is presented, which accounts for variable ISA per droplet and uses parameters including the total number of droplets, N tot, and the heterogeneous ice nucleation rate coefficient, J het( T). This model is applied to address if (i) a time and ISA-dependent stochastic immersion freezing process can explain laboratory immersion freezing data for different experimental methods and (ii) the assumption that all droplets contain identical ISA is a valid conjecture with subsequent consequences for analysis and interpretation of immersion freezing. The simple stochastic model can reproduce the observed time and surface area dependence in immersion freezing experiments for a variety of methods such as: droplets on a cold-stage exposed to air or surrounded by an oil matrix, wind and acoustically levitated droplets, droplets in a continuous-flow diffusion chamber (CFDC), the Leipzig aerosol cloud interaction simulator (LACIS), and the aerosol interaction and dynamics in the atmosphere (AIDA) cloud chamber. Observed time-dependent isothermal frozen fractions exhibiting non-exponential behavior can be readily explained by this model considering varying ISA. An apparent cooling-rate dependence of J het is explained by assuming identical ISA in each droplet. When accounting for ISA variability, the cooling-rate dependence of ice nucleation kinetics vanishes as expected from classical nucleation theory. Finally, the model simulations allow for a quantitative experimental uncertainty analysis for parameters N tot, T, RH, and the ISA variability. We discuss the implications of our results for experimental analysis and interpretation of the immersion freezing process.« less

Self-assembled growth of GaN nanowires on amorphous Al x O y : from nucleation to the formation of dense nanowire ensembles.

PubMed

Sobanska, M; Fernández-Garrido, S; Zytkiewicz, Z R; Tchutchulashvili, G; Gieraltowska, S; Brandt, O; Geelhaar, L

2016-08-12

We present a comprehensive description of the self-assembled nucleation and growth of GaN nanowires (NWs) by plasma-assisted molecular beam epitaxy on amorphous Al x O y buffers (a-Al x O y ) prepared by atomic layer deposition. The results are compared with those obtained on nitridated Si(111). Using line-of-sight quadrupole mass spectrometry, we analyze in situ the incorporation of Ga starting from the incubation and nucleation stages till the formation of the final nanowire ensemble and observe qualitatively the same time dependence for the two types of substrates. However, on a-Al x O y the incubation time is shorter and the nucleation faster than on nitridated Si. Moreover, on a-Al x O y we observe a novel effect of decrease in incorporated Ga flux for long growth durations which we explain by coalescence of NWs leading to reduction of the GaN surface area where Ga may reside. Dedicated samples are used to analyze the evolution of surface morphology. In particular, no GaN nuclei are detected when growth is interrupted during the incubation stage. Moreover, for a-Al x O y , the same shape transition from spherical cap-shaped GaN crystallites to the NW-like geometry is found as it is known for nitridated Si. However, while the critical radius for this transition is only slightly larger for a-Al x O y than for nitridated Si, the critical height is more than six times larger for a-Al x O y . Finally, we observe that in fully developed NW ensembles, the substrate no longer influences growth kinetics and the same N-limited axial growth rate is measured on both substrates. We conclude that the same nucleation and growth processes take place on a-Al x O y as on nitridated Si and that these processes are of a general nature. Quantitatively, nucleation proceeds somewhat differently, which indicates the influence of the substrate, but once shadowing limits growth processes to the upper part of the NW ensemble, they are not affected anymore by the type of substrate.

Applying shot boundary detection for automated crystal growth analysis during in situ transmission electron microscope experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moeglein, W. A.; Griswold, R.; Mehdi, B. L.

In-situ (scanning) transmission electron microscopy (S/TEM) is being developed for numerous applications in the study of nucleation and growth under electrochemical driving forces. For this type of experiment, one of the key parameters is to identify when nucleation initiates. Typically the process of identifying the moment that crystals begin to form is a manual process requiring the user to perform an observation and respond accordingly (adjust focus, magnification, translate the stage etc.). However, as the speed of the cameras being used to perform these observations increases, the ability of a user to “catch” the important initial stage of nucleation decreasesmore » (there is more information that is available in the first few milliseconds of the process). Here we show that video shot boundary detection (SBD) can automatically detect frames where a change in the image occurs. We show that this method can be applied to quickly and accurately identify points of change during crystal growth. This technique allows for automated segmentation of a digital stream for further analysis and the assignment of arbitrary time stamps for the initiation of processes that are independent of the user’s ability to observe and react.« less

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.

Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kürten, Andreas; Bianchi, Federico; Almeida, Joao

Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia are thought to be the dominant processes responsible for new particle formation (NPF) in the cold temperatures of the middle and upper troposphere. Ions are also thought to be important for particle nucleation in these regions. However, global models presently lack experimentally measured NPF rates under controlled laboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here with data obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we present the first experimental survey of NPF ratesmore » spanning free tropospheric conditions. The conditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrations between 5 × 10 5 and 1 × 10 9cm -3, and ammonia mixing ratios from zero added ammonia, i.e., nominally pure binary, to a maximumof ~1400 parts per trillion by volume (pptv).We performed nucleation studies under pure neutral conditions with zero ions being present in the chamber and at ionization rates of up to 75 ion pairs cm -3 s -1 to study neutral and ion-induced nucleation. We found that the contribution from ion-induced nucleation is small at temperatures between 208 and 248 K when ammonia is present at several pptv or higher. However, the presence of charges significantly enhances the nucleation rates, especially at 248 K with zero added ammonia, and for higher temperatures independent of NH 3 levels. In conclusion, we compare these experimental data with calculated cluster formation rates from the Atmospheric Cluster Dynamics Code with cluster evaporation rates obtained from quantum chemistry.« less

Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

DOE PAGES

Kürten, Andreas; Bianchi, Federico; Almeida, Joao; ...

2016-10-27

Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia are thought to be the dominant processes responsible for new particle formation (NPF) in the cold temperatures of the middle and upper troposphere. Ions are also thought to be important for particle nucleation in these regions. However, global models presently lack experimentally measured NPF rates under controlled laboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here with data obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we present the first experimental survey of NPF ratesmore » spanning free tropospheric conditions. The conditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrations between 5 × 10 5 and 1 × 10 9cm -3, and ammonia mixing ratios from zero added ammonia, i.e., nominally pure binary, to a maximumof ~1400 parts per trillion by volume (pptv).We performed nucleation studies under pure neutral conditions with zero ions being present in the chamber and at ionization rates of up to 75 ion pairs cm -3 s -1 to study neutral and ion-induced nucleation. We found that the contribution from ion-induced nucleation is small at temperatures between 208 and 248 K when ammonia is present at several pptv or higher. However, the presence of charges significantly enhances the nucleation rates, especially at 248 K with zero added ammonia, and for higher temperatures independent of NH 3 levels. In conclusion, we compare these experimental data with calculated cluster formation rates from the Atmospheric Cluster Dynamics Code with cluster evaporation rates obtained from quantum chemistry.« less

Effect of photochemical ageing on the ice nucleation properties of diesel and wood burning particles

NASA Astrophysics Data System (ADS)

Chou, C.; Kanji, Z. A.; Stetzer, O.; Tritscher, T.; Chirico, R.; Heringa, M. F.; Weingartner, E.; Prévôt, A. S. H.; Baltensperger, U.; Lohmann, U.

2013-01-01

A measurement campaign (IMBALANCE) conducted in 2009 was aimed at characterizing the physical and chemical properties of freshly emitted and photochemically aged combustion particles emitted from a log wood burner and diesel vehicles: a EURO3 Opel Astra with a diesel oxidation catalyst (DOC) but no particle filter and a EURO2 Volkswagen Transporter TDI Syncro without emission aftertreatment. Ice nucleation experiments in the deposition and condensation freezing modes were conducted with the Portable Ice Nucleation Chamber (PINC) at three nominal temperatures, -30 °C, -35 °C and -40 °C. Freshly emitted diesel particles showed ice formation only at -40 °C in the deposition mode at 137% relative humidity with respect to ice (RHi) and 92% relative humidity with respect to water (RHw), and photochemical ageing did not play a role in modifying their ice nucleation behaviour. Only one diesel experiment where α-pinene was added for the ageing process, showed an ice nucleation enhancement at -35 °C. Wood burning particles also act as ice nuclei (IN) at -40 °C in the deposition mode at the same conditions as for diesel particles and photochemical ageing also did not alter the ice formation properties of the wood burning particles. Unlike diesel particles, wood burning particles form ice via condensation freezing at -35 °C whereas no ice nucleation was observed at -30 °C. Photochemical ageing did not affect the ice nucleation ability of the diesel and wood burning particles at the three different temperatures investigated but a broader range of temperatures below -40 °C need to be investigated in order to draw an overall conclusion on the effect of photochemical ageing on deposition/condensation ice nucleation across the entire temperature range relevant to cold clouds.

Effect of Immersion Time on Corrosion Behavior of Single-Phase Alloy and Nanocomposite Bismuth Telluride-Based Thermoelectrics in NaCl Solution

NASA Astrophysics Data System (ADS)

Keshavarz, Mohsen K.; Fattah-Alhosseini, Arash

2018-05-01

The corrosiveness of bismuth telluride-based thermoelectric materials (n-type single-phase alloy and a nanocomposite with MoS2 nanoinclusions), in 0.1 molar solution of sodium chloride (NaCl), was investigated. The electrochemical impedance spectroscopy curves obtained after 1, 24, 48 and 72 h immersion time revealed the enhancement of the corrosion resistance of the nanocomposite specimen in a 0.1 molar NaCl solution in comparison with the single-phase bismuth telluride-based alloys, and the passivity increased by immersion time up to 72 h. The nanocomposite sample with submicron grains provided suitable nucleation sites for passive film nucleation that led to higher protective behavior.

Nominal vs. actual supersaturation of solutions

NASA Astrophysics Data System (ADS)

Borisenko, Alexander

2018-03-01

Following the formalism of the Classical Nucleation Theory beyond the dilute solution approximation, this paper considers a difference between the actual solute supersaturation (given by the present-to-saturated solute activity ratio) and the nominal supersaturation (given by the present-to-saturated solute concentration ratio) due to formation of subcritical transient solute clusters, called heterophase fluctuations. Based on their distribution function, we introduce an algebraic equation of supersaturation that couples the nominal supersaturation of a binary metastable solution with its actual supersaturation and a function of the specific interface energy and temperature. The applicability of this approach is validated by comparison to simulation data [(Clouet et al., Phys. Rev. B 69, 064109 (2004)] on nucleation of Al3Zr and Al3Sc in model binary Al alloys.

A Study of Nucleate Boiling with Forced Convection in Microgravity

NASA Technical Reports Server (NTRS)

Merte, Herman, Jr.

1996-01-01

Boiling is a rather imprecise term applied to the process of evaporation in which the rate of liquid-vapor phase change is large. In seeking to determine the role and significance of body forces on the process, of which buoyancy or gravity is just one agent, it becomes necessary to define the term more precisely. It is generally characterized by the formation and growth of individual vapor bubbles arising from heat transfer to the liquid, either at a solid/liquid or liquid/liquid interface, or volumetrically. The terms 'bubble' boiling and 'nucleate' boiling are frequently used, in recognition of the interactions of surface tension and other forces in producing discrete bubbles at distinctive locations (although not always). Primary considerations are that evaporation can occur only at existing liquid-vapor interfaces, so that attention must be given to the formation of an interface (the nucleation process), and that the latent heat for this evaporation can come only from the superheated liquid, so that attention must also be given to the temperature distributions in the liquid.

The impact of dissolved fluorine on bubble nucleation in hydrous rhyolite melts

NASA Astrophysics Data System (ADS)

Gardner, James E.; Hajimirza, Sahand; Webster, James D.; Gonnermann, Helge M.

2018-04-01

Surface tension of hydrous rhyolitic melt is high enough that large degrees of supersaturation are needed to homogeneously nucleate H2O bubbles during eruptive magma ascent. This study examines whether dissolved fluorine lowers surface tension of hydrous rhyolite, and thus lowers the supersaturation required for bubble nucleation. Fluorine was targeted because it, like H2O, changes melt properties and is highly soluble, unlike all other common magmatic volatiles. Rhyolite melts were saturated at Ps = 245 MPa with H2O fluid that contained F, generating rhyolite with 6.7 ± 0.4 wt.% H2O and 1.1-1.3 wt.% F. When these melts were decompressed rapidly to Pf = 149-202 MPa and quenched after 60 s, bubbles nucleated at supersaturations of ΔP = Ps - Pf ≥52 MPa, and reached bubble number densities of NB = 1012-13 m-3 at ΔP = 78-101 MPa. In comparison, rhyolite saturated with 6.34 ± 0.09 wt.% H2O, but only 0.25 wt.% F, did not nucleate bubbles until ΔP ≥ 100-116 MPa, and even then, at significantly lower NB (<1010 m-3). Numerical modeling of bubble nucleation and growth was used to estimate the values of surface tension required to generate the observed values of NB. Slight differences in melt compositions (i.e., alkalinity and H2O content), H2O diffusivity, or melt viscosity cannot explain the observed differences in NB. Instead, surface tension of F-rich rhyolite must be lower by approximately 4% than that of F-poor rhyolite. This difference in surface tension is significant and, for example, exceeds that found between hydrous basaltic andesite and hydrous rhyolite. These results suggest that is likely that surface tension for F-rich magmas, such as topaz rhyolite, is significantly lower than for F-poor magmas.

Refreeze experiments with water droplets containing different types of ice nuclei interpreted by classical nucleation theory

NASA Astrophysics Data System (ADS)

Kaufmann, Lukas; Marcolli, Claudia; Luo, Beiping; Peter, Thomas

2017-03-01

Homogeneous nucleation of ice in supercooled water droplets is a stochastic process. In its classical description, the growth of the ice phase requires the emergence of a critical embryo from random fluctuations of water molecules between the water bulk and ice-like clusters, which is associated with overcoming an energy barrier. For heterogeneous ice nucleation on ice-nucleating surfaces both stochastic and deterministic descriptions are in use. Deterministic (singular) descriptions are often favored because the temperature dependence of ice nucleation on a substrate usually dominates the stochastic time dependence, and the ease of representation facilitates the incorporation in climate models. Conversely, classical nucleation theory (CNT) describes heterogeneous ice nucleation as a stochastic process with a reduced energy barrier for the formation of a critical embryo in the presence of an ice-nucleating surface. The energy reduction is conveniently parameterized in terms of a contact angle α between the ice phase immersed in liquid water and the heterogeneous surface. This study investigates various ice-nucleating agents in immersion mode by subjecting them to repeated freezing cycles to elucidate and discriminate the time and temperature dependences of heterogeneous ice nucleation. Freezing rates determined from such refreeze experiments are presented for Hoggar Mountain dust, birch pollen washing water, Arizona test dust (ATD), and also nonadecanol coatings. For the analysis of the experimental data with CNT, we assumed the same active site to be always responsible for freezing. Three different CNT-based parameterizations were used to describe rate coefficients for heterogeneous ice nucleation as a function of temperature, all leading to very similar results: for Hoggar Mountain dust, ATD, and larger nonadecanol-coated water droplets, the experimentally determined increase in freezing rate with decreasing temperature is too shallow to be described properly by CNT using the contact angle α as the only fit parameter. Conversely, birch pollen washing water and small nonadecanol-coated water droplets show temperature dependencies of freezing rates steeper than predicted by all three CNT parameterizations. Good agreement of observations and calculations can be obtained when a pre-factor β is introduced to the rate coefficient as a second fit parameter. Thus, the following microphysical picture emerges: heterogeneous freezing occurs at ice-nucleating sites that need a minimum (critical) surface area to host embryos of critical size to grow into a crystal. Fits based on CNT suggest that the critical active site area is in the range of 10-50 nm2, with the exact value depending on sample, temperature, and CNT-based parameterization. Two fitting parameters are needed to characterize individual active sites. The contact angle α lowers the energy barrier that has to be overcome to form the critical embryo at the site compared to the homogeneous case where the critical embryo develops in the volume of water. The pre-factor β is needed to adjust the calculated slope of freezing rate increase with temperature decrease. When this slope is steep, this can be interpreted as a high frequency of nucleation attempts, so that nucleation occurs immediately when the temperature is low enough for the active site to accommodate a critical embryo. This is the case for active sites of birch pollen washing water and for small droplets coated with nonadecanol. If the pre-factor is low, the frequency of nucleation attempts is low and the increase in freezing rate with decreasing temperature is shallow. This is the case for Hoggar Mountain dust, the large droplets coated with nonadecanol, and ATD. Various hypotheses why the value of the pre-factor depends on the nature of the active sites are discussed.

The Effect of Solution Thermal History on Chicken Egg White Lysozyme Nucleation

NASA Technical Reports Server (NTRS)

Burke, Michael W.; Judge, Russell A.; Pusey, Marc L.

2001-01-01

Proteins are highly flexible molecules and often exhibit defined conformational changes in response to changes in the ambient temperature. Chicken egg white lysozyme has been previously shown to undergo an apparent structural change when warmed above the tetragonal/orthorhombic phase transition temperature. This is reflected by a change in the habit of the tetragonal and orthorhombic crystals so formed. In this study, we show that possible conformational changes induced by heating are stable and apparently non-reversible by simple cooling. Exposure of protein solutions to temperatures above the phase change transition temperature, before combining with precipitant solution to begin crystallization, reduces final crystal numbers. Protein that is briefly warmed to 37 C, then cooled shows no sign of reversal to the unheated nucleation behavior even after storage for four weeks at 4 C. The change in nucleation behavior of tetragonal lysozyme crystals, attributed to a structural shift, occurs faster the greater the exposure to temperature above the equi-solubility point for the two phases. Heating for 2 hours at 48 C reduces crystal numbers by 20 fold in comparison to the same solution heated for the same time at 30 C. Thermal treatment of solutions is therefore a possible tool to reduce crystal numbers and increase crystal size. The effects of a protein's previous thermal history are now shown to be a potentially critical factor in subsequent macromolecule crystal nucleation and growth studies.

The Effect of Solution Thermal History on Chicken Egg White Lysozyme Nucleation

NASA Technical Reports Server (NTRS)

Burke, Michael W.; Judge, Russell A.; Pusey, Marc L.; Rose, M. Franklin (Technical Monitor)

2000-01-01

Proteins are highly flexible molecules and often exhibit defined conformational changes in response to changes in the ambient temperature. Chicken egg white lysozyme has been previously shown to undergo an apparent structural change when warmed above the tetragonal/orthorhombic phase transition temperature. This is reflected by a change in the habit of the tetragonal and orthorhombic crystals so formed. In this study we show that possible conformational changes induced by heating are stable and apparently non- reversible by simple cooling. Exposure of protein solutions to temperatures above the phase change transition temperature, before combining with precipitant solution to begin crystallization, reduces final crystal numbers. Protein that is briefly warmed to 37 C, then cooled shows no sign of reversal to the unheated nucleation behavior even after storage for 4 weeks at 4 C. The change in nucleation behavior of tetragonal lysozyme crystals, attributed to a structural shift, occurs faster the greater the exposure to temperature above the equi-solubility point for the two phases. Heating for 2 h at 48 C reduces crystal numbers by 20 fold in comparison to the same solution heated for the same time at 30 C. Thermal treatment of solutions is therefore a possible tool to reduce crystal numbers and increase crystal size. The effects of a protein's previous thermal history are now shown to be a potentially critical factor in subsequent macromolecule crystal nucleation and growth studies.

Ice nucleation of bioaerosols - a resumee

NASA Astrophysics Data System (ADS)

Pummer, Bernhard G.; Atanasova, Lea; Bauer, Heidi; Bernardi, Johannes; Chazallon, Bertrand; Druzhinina, Irina S.; Grothe, Hinrich

2013-04-01

The role of biological particles for ice nucleation (IN) is still debated. Here, we present a summary of investigation and comparison of different ice nuclei. Apart from the bacterial ice nucleation proteins in Snomax, we further investigated a broad spectrum of pollen and fungal spores in the search for ice nucleation activity. Apart from Snomax, only few samples showed vital IN activity, like Fusarium avenaceum spores and Betula pendula pollen. Chemical characterization accentuated the differences between bacterial and pollen ice nuclei. Exposure to natural stresses, like UV and NOx, led to a significant decrease in IN activity. Furthermore, the releasable fraction of the pollen material, which includes the ice nuclei, was extracted with water and dried up. These residues were investigated with Raman spectroscopy and compared with the spectra of whole pollen grains. Measurements clearly demonstrated that the aqueous fraction contained mainly saccharides, lipids and proteins, but no sporopollenin, which is the bulk material of the outer pollen wall. Fungal spores of ecologically, economically or otherwise relevant species were also investigated. Most species showed no significant IN activity at all. A few species showed a slight increase in freezing temperature, but still significantly below the activity of the most active pollen or mineral dusts. Only Fusarium avenaceum showed strong IN activity. Cultivation of Fusarium and Trichoderma (close relatives of Fusarium) at different temperatures showed changes in total protein expression, but no impact on the IN activity.

Model simulations with COSMO-SPECS: impact of heterogeneous freezing modes and ice nucleating particle types on ice formation and precipitation in a deep convective cloud

NASA Astrophysics Data System (ADS)

Diehl, Karoline; Grützun, Verena

2018-03-01

In deep convective clouds, heavy rain is often formed involving the ice phase. Simulations were performed using the 3-D cloud resolving model COSMO-SPECS with detailed spectral microphysics including parameterizations of homogeneous and three heterogeneous freezing modes. The initial conditions were selected to result in a deep convective cloud reaching 14 km of altitude with strong updrafts up to 40 m s-1. At such altitudes with corresponding temperatures below -40 °C the major fraction of liquid drops freezes homogeneously. The goal of the present model simulations was to investigate how additional heterogeneous freezing will affect ice formation and precipitation although its contribution to total ice formation may be rather low. In such a situation small perturbations that do not show significant effects at first sight may trigger cloud microphysical responses. Effects of the following small perturbations were studied: (1) additional ice formation via immersion, contact, and deposition modes in comparison to solely homogeneous freezing, (2) contact and deposition freezing in comparison to immersion freezing, and (3) small fractions of biological ice nucleating particles (INPs) in comparison to higher fractions of mineral dust INP. The results indicate that the modification of precipitation proceeds via the formation of larger ice particles, which may be supported by direct freezing of larger drops, the growth of pristine ice particles by riming, and by nucleation of larger drops by collisions with pristine ice particles. In comparison to the reference case with homogeneous freezing only, such small perturbations due to additional heterogeneous freezing rather affect the total precipitation amount. It is more likely that the temporal development and the local distribution of precipitation are affected by such perturbations. This results in a gradual increase in precipitation at early cloud stages instead of a strong increase at later cloud stages coupled with approximately 50 % more precipitation in the cloud center. The modifications depend on the active freezing modes, the fractions of active INP, and the composition of the internal mixtures in the drops.

Effect of controlled ice nucleation on primary drying stage and protein recovery in vials cooled in a modified freeze-dryer.

PubMed

Passot, Stéphanie; Tréléa, Ioan Cristian; Marin, Michèle; Galan, Miquel; Morris, G John; Fonseca, Fernanda

2009-07-01

The freezing step influences lyophilization efficiency and protein stability. The main objective of this work was to investigate the impact on the primary drying stage of an ultrasound controlled ice nucleation technology, compared with usual freezing protocols. Lyophilization cycles involving different freezing protocols (applying a constant shelf cooling rate of 1 degrees C/min or 0.2 degrees C/min, putting vials on a precooled shelf, and controlling nucleation by ultrasounds or by addition of a nucleating agent) were performed in a prototype freeze-dryer. Three protective media including sucrose or maltodextrin and differing by their thermal properties and their ability to preserve a model protein (catalase) were used. The visual aspect of the lyophilized cake, residual water content, and enzymatic activity recovery of catalase were assessed after each lyophilization cycle and after 1 month of storage of the lyophilized product at 4 degrees C and 25 degrees C. The freezing protocols allowing increasing nucleation temperature (precooled shelf and controlled nucleation by using ultrasounds or a nucleating agent) induced a faster sublimation step and higher sublimation rate homogeneity. Whatever the composition of the protective medium, applying the ultrasound technology made it possible to decrease the sublimation time by 14%, compared with the freezing method involving a constant shelf cooling rate of 1 degrees C/min. Concerning the enzyme activity recovery, the impact of the freezing protocol was observed only for the protective medium involving maltodextrin, a less effective protective agent than sucrose. Higher activity recovery results were obtained after storage when the ultrasound technology or the precooled shelf method was applied. Controlling ice nucleation during the freezing step of the lyophilization process improved the homogeneity of the sublimation rates, which will, in turn, reduce the intervial heterogeneity. The freeze-dryer prototype including the system of controlled nucleation by ultrasounds appears to be a promising tool in accelerating sublimation and improving intrabatch homogeneity.

Heterogeneous nucleation from a supercooled ionic liquid on a carbon surface

NASA Astrophysics Data System (ADS)

He, Xiaoxia; Shen, Yan; Hung, Francisco R.; Santiso, Erik E.

2016-12-01

Classical molecular dynamics simulations were used to study the nucleation of the crystal phase of the ionic liquid [dmim+][Cl-] from its supercooled liquid phase, both in the bulk and in contact with a graphitic surface of D = 3 nm. By combining the string method in collective variables [Maragliano et al., J. Chem. Phys. 125, 024106 (2006)], with Markovian milestoning with Voronoi tessellations [Maragliano et al., J. Chem. Theory Comput. 5, 2589-2594 (2009)] and order parameters for molecular crystals [Santiso and Trout, J. Chem. Phys. 134, 064109 (2011)], we computed minimum free energy paths, the approximate size of the critical nucleus, the free energy barrier, and the rates involved in these nucleation processes. For homogeneous nucleation, the subcooled liquid phase has to overcome a free energy barrier of ˜85 kcal/mol to form a critical nucleus of size ˜3.6 nm, which then grows into the monoclinic crystal phase. This free energy barrier becomes about 42% smaller (˜49 kcal/mol) when the subcooled liquid phase is in contact with a graphitic disk, and the critical nucleus formed is about 17% smaller (˜3.0 nm) than the one observed for homogeneous nucleation. The crystal formed in the heterogeneous nucleation scenario has a structure that is similar to that of the bulk crystal, with the exception of the layers of ions next to the graphene surface, which have larger local density and the cations lie with their imidazolium rings parallel to the graphitic surface. The critical nucleus forms near the graphene surface separated only by these layers of ions. The heterogeneous nucleation rate (˜4.8 × 1011 cm-3 s-1) is about one order of magnitude faster than the homogeneous rate (˜6.6 × 1010 cm-3 s-1). The computed free energy barriers and nucleation rates are in reasonable agreement with experimental and simulation values obtained for the homogeneous and heterogeneous nucleation of other systems (ice, urea, Lennard-Jones spheres, and oxide glasses).

Heterogeneous nucleation from a supercooled ionic liquid on a carbon surface.

PubMed

He, Xiaoxia; Shen, Yan; Hung, Francisco R; Santiso, Erik E

2016-12-07

Classical molecular dynamics simulations were used to study the nucleation of the crystal phase of the ionic liquid [dmim + ][Cl - ] from its supercooled liquid phase, both in the bulk and in contact with a graphitic surface of D = 3 nm. By combining the string method in collective variables [Maragliano et al., J. Chem. Phys. 125, 024106 (2006)], with Markovian milestoning with Voronoi tessellations [Maragliano et al., J. Chem. Theory Comput. 5, 2589-2594 (2009)] and order parameters for molecular crystals [Santiso and Trout, J. Chem. Phys. 134, 064109 (2011)], we computed minimum free energy paths, the approximate size of the critical nucleus, the free energy barrier, and the rates involved in these nucleation processes. For homogeneous nucleation, the subcooled liquid phase has to overcome a free energy barrier of ∼85 kcal/mol to form a critical nucleus of size ∼3.6 nm, which then grows into the monoclinic crystal phase. This free energy barrier becomes about 42% smaller (∼49 kcal/mol) when the subcooled liquid phase is in contact with a graphitic disk, and the critical nucleus formed is about 17% smaller (∼3.0 nm) than the one observed for homogeneous nucleation. The crystal formed in the heterogeneous nucleation scenario has a structure that is similar to that of the bulk crystal, with the exception of the layers of ions next to the graphene surface, which have larger local density and the cations lie with their imidazolium rings parallel to the graphitic surface. The critical nucleus forms near the graphene surface separated only by these layers of ions. The heterogeneous nucleation rate (∼4.8 × 10 11 cm -3 s -1 ) is about one order of magnitude faster than the homogeneous rate (∼6.6 × 10 10 cm -3 s -1 ). The computed free energy barriers and nucleation rates are in reasonable agreement with experimental and simulation values obtained for the homogeneous and heterogeneous nucleation of other systems (ice, urea, Lennard-Jones spheres, and oxide glasses).

Urediospores of Puccinia spp. and other rusts are warm-temperature ice nucleators and harbor ice nucleation active bacteria

NASA Astrophysics Data System (ADS)

Morris, C. E.; Sands, D. C.; Glaux, C.; Samsatly, J.; Asaad, S.; Moukahel, A. R.; Gonçalves, F. L. T.; Bigg, E. K.

2012-10-01

In light of various features of the biology of the rust fungi and of the epidemiology of the plant diseases they cause that illustrate the important role of rainfall in their life history, we have characterized the ice nucleation activity (INA) of the aerially disseminated spores (urediospores) of this group of fungi. Urediospores of this obligate plant parasite were collected from natural infections from 7 species of weeds in France, from coffee in Brazil and from field and greenhouse-grown wheat in France, the USA, Turkey and Syria. Immersion freezing was used to determine freezing onset temperatures and the abundance of ice nuclei in suspensions of washed spores. Microbiological analyses of spores and subsequent tests of the ice nucleation activity of the bacteria associated with spores were deployed to quantify the contribution of bacteria to the ice nucleation activity of the spores. All samples of spores were ice nucleation active having freezing onset temperatures as warm as -4 °C. Spores in most of the samples carried cells of ice nucleation-active strains of the bacterium Pseudomonas syringae (at rates of less than 1 bacterial cell per 100 urediospores), but bacterial INA accounted for only a small fraction of the INA observed in spore suspensions. Changes in the INA of spore suspensions after treatment with lysozyme suggest that the INA of urediospores involves a polysaccharide. Based on data from the literature, we have estimated the concentrations of urediospores in air at cloud height and in rainfall. These quantities are very similar to those reported for other biological ice nucleators in these same substrates. We suggest that air sampling techniques have ignored the spatial and temporal variability of atmospheric concentrations that occur under conditions propitious for precipitation that could increase their local abundance intermittently. Nevertheless, we propose that the relative low abundance of warm-temperature biological ice nucleators in the atmosphere corresponds to optimal conditions for the processes of evolution to positively select for INA.

Ambient in-situ immersion freezing measurements - findings from the ZAMBIS 2014 field campaign for three ice nucleation techniques

NASA Astrophysics Data System (ADS)

Kohn, Monika; Atkinson, James D.; Lohmann, Ulrike; Kanji, Zamin A.

2015-04-01

To estimate the influence of clouds on the Earth's radiation budget, it is crucial to understand cloud formation processes in the atmosphere. A key process, which significantly affects cloud microphysical properties and the initiation of precipitation thus contributing to the hydrological cycle, is the prevailing type of ice nucleation mechanism. In mixed-phase clouds immersion freezing is the dominant ice crystal forming mechanism, whereby ice nucleating particles (INP) first act as cloud condensation nuclei (CCN) and are activated to cloud droplets followed by freezing upon supercooling. There are a number of experimental methods and techniques to investigate the ice nucleating ability in the immersion mode, however most techniques are offline for field sampling or only suitable for laboratory measurements. In-situ atmospheric studies are needed to understand the ice formation processes of 'real world' particles. Laboratory experiments simulate conditions of atmospheric processes like ageing or coating but are still idealized. Our method is able to measure ambient in-situ immersion freezing on single immersed aerosol particles. The instrumental setup consists of the recently developed portable immersion mode cooling chamber (PIMCA) as a vertical extension to the portable ice nucleation chamber (PINC, [1]), where the frozen fraction of activated aerosol particles are detected by the ice optical depolarization detector (IODE, [2]). Two additional immersion freezing techniques based on a droplet freezing array [3,4] are used to sample ambient aerosol particles either in a suspension (fraction larger ~0.6 μm) or on PM10-filters to compare different ice nucleation techniques. Here, we present ambient in-situ measurements at an urban forest site in Zurich, Switzerland held during the Zurich ambient immersion freezing study (ZAMBIS) in spring 2014. We investigated the ice nucleating ability of natural atmospheric aerosol with the PIMCA/PINC immersion freezing setup as well as a droplet freezing method on aerosol particles either collected in a suspension or on PM10-filters to obtain atmospheric IN concentrations based on the measured ambient aerosol. Investigation of physical properties (number and size distribution) and chemical composition as well as the meteorological conditions provide supplementary information that help to understand the nature of particles and air masses that contribute to immersion freezing. Acknowledgements We thank Hannes Wydler and Hansjörg Frei from ETH Zurich for their technical support. Furthermore, the authors want thank Franz Conen from the University of Basel for sharing equipment and training in the drop freezing experiment. References [1] Chou et al. (2011), Atmos. Chem. Phys., 11, 4725-4738. [2] Nicolet et al. (2010), Atmos. Chem. Phys., 10, 313-325. [3] Conen et al. (2012), Atmos. Meas. Tech., 5, 321-327. [4] Stopelli et al. (2014), Atmos. Meas. Tech., 7, 129-134.

Evidence from mixed hydrate nucleation for a funnel model of crystallization.

PubMed

Hall, Kyle Wm; Carpendale, Sheelagh; Kusalik, Peter G

2016-10-25

The molecular-level details of crystallization remain unclear for many systems. Previous work has speculated on the phenomenological similarities between molecular crystallization and protein folding. Here we demonstrate that molecular crystallization can involve funnel-shaped potential energy landscapes through a detailed analysis of mixed gas hydrate nucleation, a prototypical multicomponent crystallization process. Through this, we contribute both: (i) a powerful conceptual framework for exploring and rationalizing molecular crystallization, and (ii) an explanation of phenomenological similarities between protein folding and crystallization. Such funnel-shaped potential energy landscapes may be typical of broad classes of molecular ordering processes, and can provide a new perspective for both studying and understanding these processes.

Evidence from mixed hydrate nucleation for a funnel model of crystallization

PubMed Central

Hall, Kyle Wm.; Carpendale, Sheelagh; Kusalik, Peter G.

2016-01-01

The molecular-level details of crystallization remain unclear for many systems. Previous work has speculated on the phenomenological similarities between molecular crystallization and protein folding. Here we demonstrate that molecular crystallization can involve funnel-shaped potential energy landscapes through a detailed analysis of mixed gas hydrate nucleation, a prototypical multicomponent crystallization process. Through this, we contribute both: (i) a powerful conceptual framework for exploring and rationalizing molecular crystallization, and (ii) an explanation of phenomenological similarities between protein folding and crystallization. Such funnel-shaped potential energy landscapes may be typical of broad classes of molecular ordering processes, and can provide a new perspective for both studying and understanding these processes. PMID:27790987

Measurements to Fill Knowledge Gaps on Ice Nucleating Particle Sources over Oceans

NASA Astrophysics Data System (ADS)

DeMott, P. J.; Hill, T. C.; Ruppel, M. J.; Prather, K. A.; Collins, D. B.; Axson, J. L.; Lee, T.; Hwang, C. Y.; Sullivan, R. C.; McMeeking, G. R.; Mason, R.; Bertram, A. K.; Mayol-Bracero, O. L.; Lewis, E. R.

2013-12-01

Measurements of the temperature spectrum of ice nucleating particle concentrations by two methods in recent specialized laboratory sea spray studies and field campaigns in the Northern Hemisphere will be discussed and compared with historical data from over Southern Oceans. In general, new measurements of the condensation/immersion freezing activation spectra of realistically-generated laboratory sea spray particles (by wave generation or plunging water bubble production) are consistent with previous measurements made over oceans. The number concentrations of ice nuclei tend to be lower than are measured over land regions, at least for modestly supercooled cloud conditions. Certain but complex connections of ice nucleating particle production to ocean microbiological processes affecting the chemical composition of the sea surface microlayer are seen, but the nature of the ice nucleating units of particles remains to be identified. Associations of ice nucleating particle concentrations with heterotrophic bacterial concentrations were noted in some experiments, while correlation with chlorophyll-a concentration in seawater was clearly identified in laboratory simulations of phytoplankton blooms. These data may ultimately serve as the basis for parameterization development for ice initiation in numerical model simulations of mixed-phase clouds. Atmospheric measurements have been made at island sites, via aircraft, and from ship-based filter collections in the Northern Hemisphere. The immersion freezing spectra of these particles are similar to those found in recent laboratory studies and historical measurements, but show the expected natural variability by location. The majority of particles detected thus far as ice nuclei from sea spray and in marine air show minimal or episodic/variable direct participation of biological ice nucleating organisms on the basis of sensitivity to high temperatures (95°C). However, assembled measurements are still sparse, the nuclei could be a product of biological processes, and ship-collected particles from the Bering Sea showed a high labile fraction associated with the presence of a high proportion, based on pyrosequencing of DNA extracted from the collected particles, of species from the Gammaproteobacteria, the same class that contains the ice nucleating bacteria. These studies are ongoing, and new measurement plans, including ship-based aerosol collections over Southern Oceans, will be described.

Cyclic voltammetric study of Co-Ni-Fe alloys electrodeposition in sulfate medium

NASA Astrophysics Data System (ADS)

Hanafi, I.; Daud, A. R.; Radiman, S.

2013-11-01

Electrochemical technique has been used to study the electrodeposition of cobalt, nickel, iron and Co-Ni-Fe alloy on indium tin oxide (ITO) coated glass substrate. To obtain the nucleation mechanism, cyclic voltammetry is used to characterize the Co-Ni-Fe system. The scanning rate effect on the deposition process was investigated. Deposition of single metal occurs at potential values more positive than that estimated stability potential. Based on the cyclic voltammetry results, the electrodeposition of cobalt, nickel, iron and Co-Ni-Fe alloy clearly show that the process of diffusion occurs is controlled by the typical nucleation mechanism.

A review on radiation-induced nucleation and growth of colloidal metallic nanoparticles

PubMed Central

2013-01-01

This review presents an introduction to the synthesis of metallic nanoparticles by radiation-induced method, especially gamma irradiation. This method offers some benefits over the conventional methods because it provides fully reduced and highly pure nanoparticles free from by-products or chemical reducing agents, and is capable of controlling the particle size and structure. The nucleation and growth mechanism of metallic nanoparticles are also discussed. The competition between nucleation and growth process in the formation of nanoparticles can determine the size of nanoparticles which is influenced by certain parameters such as the choice of solvents and stabilizer, the precursor to stabilizer ratio, pH during synthesis, and absorbed dose. PMID:24225302

Buckyball Nucleation of HiPco Tubes

NASA Technical Reports Server (NTRS)

Smalley, Richard E.

2012-01-01

The purpose of this innovation is to enhance nucleation of single-wall nanotubes (SWNTs) in the HiPco process, selectively producing 10,10 tubes, something which until now has not been thought possible. This is accomplished by injecting C60, or a derivative of C60, solubilized in supercritical CO2 together with a transition metal carboneal cocatalyst into the HiPco reactor. This is a variant on the supercritical disclosure. C60 has never been used to nucleate carbon nanotubes in the gas phase. C60 itself may not have adequate solubility in supercritical CO2. However, fluorinated C60, e.g., C60F36, is easy to make cheaply and should have much enhanced solubility.

Soot Formation in Hydrocarbon/Air Laminar Jet Diffusion Flames

NASA Technical Reports Server (NTRS)

Sunderland, P. B.; Faeth, G. M.

1994-01-01

Soot processes within hydrocarbon/air diffusion flames are important because they affect the durability and performance of propulsion systems, the hazards of unwanted fires, the pollutant and particulate emissions from combustion processes, and the potential for developing computational combustion. Motivated by these observations, this investigation involved an experimental study of the structure and soot properties of round laminar jet diffusion flames, seeking an improved understanding of soot formation (growth and nucleation) within diffusion flames. The present study extends earlier work in this laboratory concerning laminar smoke points (l) and soot formation in acetylene/air laminar jet diffusion flames (2), emphasizing soot formation in hydrocarbon/air laminar jet diffusion flames for fuels other than acetylene. In the flame system, acetylene is the dominant gas species in the soot formation region and both nucleation and growth were successfully attributed to first-order reactions of acetylene, with nucleation exhibiting an activation energy of 32 kcal/gmol while growth involved negligible activation energy and a collision efficiency of O.53%. In addition, soot growth in the acetylene diffusion flames was comparable to new soot in premixed flame (which also has been attributed to first-order acetylene reactions). In view of this status, a major issue is the nature of soot formation processes in diffusion flame involving hydrocarbon fuels other than acetylene. In particular, information is needed about th dominant gas species in the soot formation region and the impact of gas species other than acetylene on soot nucleation and growth.

Nucleation mechanisms of epitaxial GaN nanowires: Origin of their self-induced formation and initial radius

NASA Astrophysics Data System (ADS)

Consonni, V.; Knelangen, M.; Geelhaar, L.; Trampert, A.; Riechert, H.

2010-02-01

The formation mechanisms of epitaxial GaN nanowires grown within a self-induced approach by molecular-beam epitaxy have been investigated at the onset of the nucleation process by combining in situ reflection high-energy electron-diffraction measurements and ex situ high-resolution transmission electron microscopy imaging. It is shown that the self-induced growth of GaN nanowires on the AlN buffer layer is initially governed by the nucleation of dislocation-free coherent islands. These coherent islands develop through a series of shape transitions from spherical caps through truncated to full pyramids in order to elastically relieve the lattice-mismatch-induced strain. A strong correlation between the subsequent process of plastic relaxation and the final shape transition from full pyramids toward the very first nanowires is found. The experimental critical radius at which the misfit dislocation nucleates is in very good agreement with the theoretical critical radius for the formation of the misfit dislocation in full pyramids, showing that the plastic relaxation process does take place within full pyramids: this critical size corresponds to the initial radius of the very first nanowires. We associate the plastic relaxation of the lattice-mismatch-induced strain occurring within full pyramids with a drastic change in their total free energy: this gives rise to a driving force for the shape transition toward the very first nanowires, which is mainly due to the anisotropy of surface energy.

Traffic and nucleation events as main sources of ultrafine particles in high-insolation developed world cities

NASA Astrophysics Data System (ADS)

Brines, M.; Dall'Osto, M.; Beddows, D. C. S.; Harrison, R. M.; Gómez-Moreno, F.; Núñez, L.; Artíñano, B.; Costabile, F.; Gobbi, G. P.; Salimi, F.; Morawska, L.; Sioutas, C.; Querol, X.

2015-05-01

Road traffic emissions are often considered the main source of ultrafine particles (UFP, diameter smaller than 100 nm) in urban environments. However, recent studies worldwide have shown that - in high-insolation urban regions at least - new particle formation events can also contribute to UFP. In order to quantify such events we systematically studied three cities located in predominantly sunny environments: Barcelona (Spain), Madrid (Spain) and Brisbane (Australia). Three long-term data sets (1-2 years) of fine and ultrafine particle number size distributions (measured by SMPS, Scanning Mobility Particle Sizer) were analysed. Compared to total particle number concentrations, aerosol size distributions offer far more information on the type, origin and atmospheric evolution of the particles. By applying k-means clustering analysis, we categorized the collected aerosol size distributions into three main categories: "Traffic" (prevailing 44-63% of the time), "Nucleation" (14-19%) and "Background pollution and Specific cases" (7-22%). Measurements from Rome (Italy) and Los Angeles (USA) were also included to complement the study. The daily variation of the average UFP concentrations for a typical nucleation day at each site revealed a similar pattern for all cities, with three distinct particle bursts. A morning and an evening spike reflected traffic rush hours, whereas a third one at midday showed nucleation events. The photochemically nucleated particles' burst lasted 1-4 h, reaching sizes of 30-40 nm. On average, the occurrence of particle size spectra dominated by nucleation events was 16% of the time, showing the importance of this process as a source of UFP in urban environments exposed to high solar radiation. Nucleation events lasting for 2 h or more occurred on 55% of the days, this extending to > 4 h in 28% of the days, demonstrating that atmospheric conditions in urban environments are not favourable to the growth of photochemically nucleated particles. In summary, although traffic remains the main source of UFP in urban areas, in developed countries with high insolation urban nucleation events are also a main source of UFP. If traffic-related particle concentrations are reduced in the future, nucleation events will likely increase in urban areas, due to the reduced urban condensation sinks.

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.

Microstructure study of a severely plastically deformed Mg-Zn-Y alloy by application of low angle annular dark field diffraction contrast imaging.

PubMed

Basha, Dudekula Althaf; Rosalie, Julian M; Somekawa, Hidetoshi; Miyawaki, Takashi; Singh, Alok; Tsuchiya, Koichi

2016-01-01

Microstructural investigation of extremely strained samples, such as severely plastically deformed (SPD) materials, by using conventional transmission electron microscopy techniques is very challenging due to strong image contrast resulting from the high defect density. In this study, low angle annular dark field (LAADF) imaging mode of scanning transmission electron microscope (STEM) has been applied to study the microstructure of a Mg-3Zn-0.5Y (at%) alloy processed by high pressure torsion (HPT). LAADF imaging advantages for observation of twinning, grain fragmentation, nucleation of recrystallized grains and precipitation on second phase particles in the alloy processed by HPT are highlighted. By using STEM-LAADF imaging with a range of incident angles, various microstructural features have been imaged, such as nanoscale subgrain structure and recrystallization nucleation even from the thicker region of the highly strained matrix. It is shown that nucleation of recrystallized grains starts at a strain level of revolution [Formula: see text] (earlier than detected by conventional bright field imaging). Occurrence of recrystallization of grains by nucleating heterogeneously on quasicrystalline particles is also confirmed. Minimizing all strain effects by LAADF imaging facilitated grain size measurement of [Formula: see text] nm in fully recrystallized HPT specimen after [Formula: see text].

Shock induced crystallization of amorphous Nickel powders

NASA Astrophysics Data System (ADS)

Cherukara, Mathew; Strachan, Alejandro

2015-06-01

Recent experimental work has shown the efficacy of amorphous Ni/crystalline Al composites as energetic materials, with flame velocities twice that of a comparable crystalline Ni/crystalline Al system. Of further interest is the recrystallization mechanisms in the pure amorphous Ni powders, both thermally induced and mechanically induced. We present large-scale molecular dynamics simulations of shock-induced recrystallization in loosely packed amorphous Nickel powders. We study the time dependent nucleation and growth processes by holding the shocked samples at the induced pressures and temperatures for extended periods following the passage of the shock (up to 6 ns). We find that the nanostructure of the recrystallized Ni and time scales of recrystallization are dependent on the piston velocity. At low piston velocities, nucleation events are rare, leading to long incubation times and a relatively coarse nanostructure. At higher piston velocities, local variations in temperature due to jetting phenomena and void collapse, give rise to multiple nucleation events on time scales comparable to the passage of the shock wave, leading to the formation of a fine-grained nanostructure. Interestingly, we observe that the nucleation and growth process occurs in two steps, with the first nuclei crystallizing into the BCC structure, before evolving over time into the expected FCC structure. U.S. Defense Threat Reduction Agency, HDTRA1-10-1-0119 (Program Manager Suhithi Peiris).