Multiple Nucleation Events Research Articles

Birth of NaCl Crystals: Insights from Molecular Simulations.

Molecular dynamics simulations are used to investigate the factors that influence the nucleation of NaCl crystals in a supersaturated aqueous solution. We describe a methodology for detecting solidlike NaCl clusters (potential nuclei) and following their evolution in time until they achieve nucleation (which is very rare) or dissolve back into solution. Through an analysis of cluster lifetimes and multiple nucleation events, we demonstrate that cluster size is not the only property that influences cluster stability and the probability of achieving nucleation. We introduce a parameter called cluster crystallinity, which is a measure of the solidlike order in a particular cluster. We show that cluster order (as measured by this parameter) has a strong influence on the lifetime and nucleation probability of clusters of equal sizes, with the lifetime and probability of nucleation increasing with increasing crystallinity. These observations remain true for clusters as small as six ions, showing that the structural factors are important even at the earliest stages of crystal birth.

Assessing relative contributions of PAHs to soot mass by reversible heterogeneous nucleation and condensation

Given the recent EURO 6 regulations, which include limits on particle number density (and hence size) for soot emissions from land vehicles, soot models must be capable of accurately predicting soot particle sizes. Previous modeling work has demonstrated the importance of the relative strengths of nucleation and condensation in predicting soot primary particle size. Due to this importance, a fundamental reversible model for nucleation and condensation, called the reversible PAH clustering (RPC) model, was developed in previous work through the use of statistical mechanics and the results from several recent works.In the present work, the RPC model is enhanced to include multiple nucleation (or dimerization) events from 6 different PAH size groups, resulting in 21 unique dimer pairs. In addition, a soot PAH tracking model is developed to track the amount of each PAH size group within soot particles. The addition of this model resulted in reduced computation times and the ability to investigate PAH-PAH reactions within soot particles. The results of the enhanced RPC model demonstrate that smaller PAHs are most important for the nucleation process, while small and large PAHs are important for the condensation process. These results are shown to be due to the relatively lower reversibility of condensation versus the nucleation process. These findings are discussed in light of recent experimental results in the literature and are shown to be well supported.

Supercooling, ice nucleation and crystal growth: a systematic study in plant samples

This paper presents an innovative technological platform which is based on infrared video recording and is used for monitoring multiple ice nucleation events and their interactions, as they happen in 96 well microplates. Thousands of freezing curves were obtained during this study and the following freezing parameters were measured: cooling rate, nucleation point, freezing point, solidus point, degree of supercooling, duration of dendritic phase and duration of crystal growth. We demonstrate the use of this platform in the detection of ice nuclei in plant samples. Future applications of this platform may include breeding for frost tolerance, cryopreservation, frozen food technology and atmospheric sciences.

Epitaxial nucleation of garnet on biotite in the polymetamorphic metapelites surrounding the Vedrette di Ries intrusion (Italian Eastern Alps)

Garnet in a metapelite from the aureole of the Vedrette di Ries tonalite, Eastern Alps, is found in two distinctive microstructural settings relative to a large single crystal of biotite: it forms a narrow polycrystalline layer in a reaction zone between plagioclase and biotite, and nearby it occurs in clusters of crystals interspersed with the biotite. In the reaction zone, morphological and microchemical evidence document multiple nucleation events along the interface between biotite and plagioclase, with ilmenite inclusions marking the original plagioclase–biotite boundary. Electron backscatter diffraction analysis shows that for all garnet in both microstructural settings, (110) grt || (001) bt with [100] grt || [100] bt . This single, recurring orientation for all garnet crystals adjacent to the biotite grain implies that nucleation was dominantly epitaxial during crystallization of the garnet. The occurrence is remarkable for the clear genetic relationships revealed by the microstructures and for its preservation of the mica substrate on which the garnet nucleated, which allows unambiguous determination of not only the coincident lattice planes but also the coincident lattice directions involved in the epitaxy.

Formation mechanism of (001) oriented perovskite SrTiO3 microplatelets synthesized by topochemical microcrystal conversion.

To develop a better understanding of the mechanism responsible for topochemical microcrystal conversion (TMC) from Aurivillius SrBi4Ti4O15 precursors to perovskite SrTiO3 microplatelets, compositional/structural evolutions, morphological development, and reaction interface evolution of the (001) oriented SrBi4Ti4O15 microplatelets were investigated during the conversion process. The results show that multiple topotactic nucleation events of SrTiO3 occurred directly on the surfaces of SrBi4Ti4O15 above 700 °C, while reacting zones of intermediate phase(s) with less Bi(3+) contents were observed to form in the interior of SrBi4Ti4O15. Extensive exfoliation of the precursors occurred generally parallel to the (001) surfaces above 775 °C. At 950 °C, the original single-crystal SrBi4Ti4O15 platelet was replaced by a polycrystalline aggregate consisting of (001) aligned SrTiO3 crystallites and poorly crystallized intermediate phase(s). With further increasing the temperature or holding time, the SrTiO3 phase formed from related intermediate phase(s), and the aligned crystallites were sintered to form dense SrTiO3 with strong (001) orientation. The obtained SrTiO3 microplatelets preserved the shape of SrBi4Ti4O15 and show high chemical and phase purity. This TMC mechanism has general applicability to a variety of compounds and will be very useful for the design and synthesis of novel anisotropic perovskite crystals with high quality in the future.

Bubble development in explosive silicic eruptions: insights from pyroclast vesicularity textures from Raoul volcano (Kermadec arc)

Critical to understanding explosive eruptions is establishing how accurately representative pyroclasts are of processes during magma vesiculation and fragmentation. Here, we present data on densities, and vesicle size and number characteristics, for representative pyroclasts from six silicic eruptions of contrasting size and style from Raoul volcano (Kermadec arc). We use these data to evaluate histories of bubble nucleation, coalescence, and growth in explosive eruptions and to provide comparisons with pumiceous dome carapace material. Density/vesicularity distributions show a scarcity of pyroclasts with ∼65–75 % vesicularity; however, pyroclasts closest to this vesicularity range have the highest bubble number density (BND) values regardless of eruptive intensity or style. Clasts with vesicularities greater than this 65–75 % “pivotal” vesicularity range have decreasing BNDs with increasing vesicularities, interpreted to reflect continuing bubble growth and coalescence. Clasts with vesicularities less than the pivotal range have BNDs that decrease with decreasing vesicularity and preserve textures indicative of processes such as stalling and open system degassing prior to vesiculation in a microlite-rich magma, or vesiculation during slow ascent of degassing magma. Bubble size distributions (BSDs) and BNDs show variations consistent with 65–75 % representing the vesicularity at which vesiculating magma is most likely to undergo fragmentation, consistent with the closest packing of spheres. We consider that the observed vesicularity range may reflect the development of permeability in the magma through shearing as it flows through the conduit. These processes can act in concert with multiple nucleation events, generating a situation of heterogeneous bubble populations that permit some regions of the magma to expand and bubbles to coalesce with other regions in which permeable networks are formed. Fragmentation preserves the range in vesicularity seen as well as any post-fragmentation/pre-quenching expansion which may have occurred. We demonstrate that differing density pyroclasts from a single eruption interval can have widely varying BND values corresponding to the degree of bubble maturation that has occurred. The modal density clasts (the usual targets for vesicularity studies) have likely undergone some degree of bubble maturation and are therefore may not be representative of the magma at the onset of fragmentation.

Kinetics of Presynaptic Filament Assembly in the Presence of Single-Stranded DNA Binding Protein and Recombination Mediator Protein

Enzymes of the RecA/Rad51 family catalyze DNA strand exchange reactions that are important for homologous recombination and for the accurate repair of DNA double-strand breaks. RecA/Rad51 recombinases are activated by their assembly into presynaptic filaments on single-stranded DNA (ssDNA), a process that is regulated by ssDNA binding protein (SSB) and mediator proteins. Mediator proteins stimulate strand exchange by accelerating the rate-limiting displacement of SSB from ssDNA by the incoming recombinase. The use of mediators is a highly conserved strategy in recombination, but the precise mechanism of mediator activity is unknown. In this study, the well-defined bacteriophage T4 recombination system (UvsX recombinase, Gp32 SSB, and UvsY mediator) is used to examine the kinetics of presynaptic filament assembly on native ssDNA in vitro. Results indicate that the ATP-dependent assembly of UvsX presynaptic filaments on Gp32-covered ssDNA is limited by a salt-sensitive nucleation step in the absence of mediator. Filament nucleation is selectively enhanced and rendered salt-resistant by mediator protein UvsY, which appears to stabilize a prenucleation complex. This mechanism potentially explains how UvsY promotes presynaptic filament assembly at physiologically relevant ionic strengths and Gp32 concentrations. Other data suggest that presynaptic filament assembly involves multiple nucleation events, resulting in many short UvsX-ssDNA filaments or clusters, which may be the relevant form for recombination in vivo. Together, these findings provide the first detailed kinetic model for presynaptic filament assembly involving all three major protein components (recombinase, mediator, and SSB) on native ssDNA.

Medium pressure hydrate based gas separation (HBGS) process for pre-combustion capture of carbon dioxide employing a novel fixed bed reactor

This work presents an effective medium pressure hydrate based gas separation (HBGS) process for pre-combustion carbon dioxide capture in a novel fixed bed column. 2.5mol% propane was added to the fuel gas mixture as an additive to decrease the operating pressure of the HBGS process. Hydrate formation kinetics was investigated at three different pressures (4.5, 5.5 and 6.0MPa respectively) and at 274.15K. The performance of silica sand and silica gel as a medium was evaluated. In silica sand bed, multiple nucleation events were observed. In silica gel bed, the gas uptake and water conversion to hydrates was significantly low at any given driving force than that obtained in silica sand bed. Experiments at different water saturation levels (50, 75 and 100%) in silica sand bed were investigated at 6.0MPa and 274.15K. It was found that at 50% water saturation, gas consumed for hydrate formation and water conversion to hydrates was almost three times that at 100% saturation. Water to hydrate conversions of up to 64.3% was achieved after 4h of hydrate formation for the 50% water saturated silica sand bed. Our study presents an opportunity to scale up the HBGS process for CO2 capture with enhanced kinetics by employing a fixed bed reactor configuration. Decomposition experiments at a driving force of ΔT of 10K and 23K were carried out to recover the gas consumed for hydrate formation and it was found that ΔT of 23K was sufficient to recover the hydrated gas.

Multiple daytime nucleation events in semi-clean savannah and industrial environments in South Africa: analysis based on observations

Abstract. Recent studies have shown very high frequencies of atmospheric new particle formation in different environments in South Africa. Our aim here was to investigate the causes for two or three consecutive daytime nucleation events, followed by subsequent particle growth during the same day. We analysed 108 and 31 such days observed in a polluted industrial and moderately polluted rural environments, respectively, in South Africa. The analysis was based on two years of measurements at each site. After rejecting the days having notable changes in the air mass origin or local wind direction, i.e. two major reasons for observed multiple nucleation events, we were able to investigate other factors causing this phenomenon. Clouds were present during, or in between most of the analysed multiple particle formation events. Therefore, some of these events may have been single events, interrupted somehow by the presence of clouds. From further analysis, we propose that the first nucleation and growth event of the day was often associated with the mixing of a residual air layer rich in SO2 (oxidized to sulphuric acid) into the shallow surface-coupled layer. The second nucleation and growth event of the day usually started before midday and was sometimes associated with renewed SO2 emissions from industrial origin. However, it was also evident that vapours other than sulphuric acid were required for the particle growth during both events. This was especially the case when two simultaneously growing particle modes were observed. Based on our analysis, we conclude that the relative contributions of estimated H2SO4 and other vapours on the first and second nucleation and growth events of the day varied from day to day, depending on anthropogenic and natural emissions, as well as atmospheric conditions.

Macroscopic kinetics of hydrate formation of mixed hydrates of hydrogen/tetrahydrofuran for hydrogen storage

Hydrogen/Tetrahydrofuran mixed hydrate formation studies were conducted in a stirred tank reactor. Hydrate formation kinetics at driving forces of 2 MPa, 5 MPa and 7 MPa were studied. Tetrahydrofuran (THF) concentration was varied between 1 mol% and 5 mol% and its effect on hydrate formation kinetics was investigated. With an increase in the driving force there was an increase in gas uptake till super saturation. However, the increased driving force had little effect on the reduction of induction time even at high promoter (THF) concentration. 5 mol% THF solutions behave distinctly exhibiting an increased hydrate growth compared to low promoter concentrations due to the occurrence of multiple nucleation events (observed based on temperature spikes and gas uptake). Rate of hydrate formation increased with an increase in driving force for a given concentration of THF promoter. Water conversion to hydrates in the range of 2.8–10.8% was achieved for all the experiments. Addition of Sodium Dodecyl Sulphate (SDS) surfactant had no effect in improving the kinetics of mixed hydrogen/THF hydrates. This study highlights the kinetic challenges that need to be overcome in storing hydrogen as clathrate hydrates.

Multiple nucleation events and local dynamics of poly(ε-caprolactone) (PCL) confined to nanoporous alumina

The crystallization and local dynamics of poly(e-caprolactone) (PCL) confined to self-ordered nanoporous alumina (AAO) were studied as a function of pore size, pore surface functionality, molecular weight and cooling/heating rate by differential scanning calorimetry (DSC), wide-angle X-ray diffraction and dielectric spectroscopy. In contrast to the bulk, PCL located inside nanoporous alumina crystallizes via several distinct nucleation mechanisms. All mechanisms display pronounced rate dependence. At low undercoolings, the usual heterogeneous nucleation of bulk PCL was suppressed at the expense of two additional mechanisms attributed to heterogeneous nucleation initiated at the pore walls. At higher undercoolings a broad peak was observed in DSC which we attribute to crystallization initiated by homogeneous nucleation. At high cooling rates, the critical nucleus size is smaller than the smallest diameter of pores. Thus, PCL is able to crystallize within the smallest pores, despite the lower degree of crystallinity. Inevitably, homogeneous nucleation is strongly coupled to the local viscosity and hence to the local segmental dynamics. Dielectric spectroscopy revealed that confinement affected both the rate of segmental motion with a lowering of the glass temperature as well as a broader distribution of relaxation times.

New strategy of nanolithographyvia controlled block copolymerself-assembly

The self-assembly of block copolymer–homopolymer blends in bulk, as well as under the direction of periodic patterned surfaces, has been investigated by computer simulations of the time-dependent Ginzburg–Landau theory. Specifically, a small amount of homopolymers are added to regulate the spontaneous nucleation rate and substrate patterns are designed to control the position and orientation of the induced nuclei. The mechanism, validity and efficiency of this scheme is examined using 2D and 3D computer simulations of cylinder-forming block copolymer–homopolymer blends, demonstrating that large-scale perfectly ordered patterns can be produced by controlling the position and orientation of induced multiple nucleation events. This scheme, combining the nucleation event of block copolymer self-assembly with the direction of the patterned surface, can be used in the lithography technique of block copolymers to significantly improve the directing efficiency, i.e., the density multiplication.

On Multiple Nucleation Bursts During Solution Crystallization in Pure and Impure Solvent

It is widely accepted that during batch cooling crystallization processes, uncontrolled cooling can produce multiple nucleation events which have detrimental effects on the crystal size distribution (CSD). Controlling the CSD therefore requires mastering nucleation during the whole batch development: this is the starting point of many studies devoted to temperature control during industrial crystallization operations. When nucleation phenomena take place throughout the batch process, the time allocated to every crystal to grow is widespread, which enlarges the width of the final CSD. Successive nucleation phenomena are referred below to as multiple nucleation bursts (MNBs). Oscillatory supersaturation dynamics (OSD) are sometimes assumed to accompany the trend of MNBs, and it is suggested in the following that MNBs should not be misread as oscillatory supersaturation profiles. Experimental results obtained during the crystallization of ammonium oxalate in the presence of impurities (NiSO4) are presented to support and illustrate OSDs crystallizations which, even though they are often presented as a basic pattern of uncontrolled batch crystallization systems, were never observed before. A population balance equations (PBEs) simulation model based on Kubota–Mullin’s pinning mechanism is developed to represent the observed oscillations of supersaturation. The latter are shown to be rather likely when inhibiting impurities are present in solution, but it is suggested that oscillations of supersaturation are unlikely in pure solvents. These latter two results shed some new light on the need to control temperature during batch cooling crystallization processes.

Cirrus cloud-temperature interactions in the tropical tropopause layer: a case study

Abstract. Thin cirrus clouds in the Tropical Tropopause Layer (TTL) have important ramifications for radiative transfer, stratospheric humidity, and vertical transport. A horizontally extensive and vertically thin cirrus cloud in the TTL was detected by the Cloud Aerosol LIDAR and Infrared Pathfinder Satellite Observations (CALIPSO) on 27–29 January 2009 in the Tropical Eastern Pacific region, distant from any regions of deep convection. These observations indicate that the cloud is close to 3000 km in length along the CALIPSO orbit track. Measurements over this three day period indicate that the cloud event extended over a region from approximately 15° S to 10° N and 90° W to 150° W and may be one of the most extensive cirrus events ever observed. Coincident temperature observations from the Constellation of Observing Satellites for Meteorology, Ionosphere, and Climate (COSMIC) suggest that the cloud formed in-situ as a result of a cold anomaly arising from a midlatitude intrusion. The event appears to last for up to 2 days and the temperature observations do not show any indication of the expected infrared heating. It is hypothesized that the cloud could be maintained by either nucleation of numerous small ice crystals that don't sediment or by multiple localized ice nucleation events driven by temperature variability at scales smaller than the overall cloud field, producing small ice-crystal sizes which have sufficiently long residence times (≈53 h) to maintain the cloud. It is possible that the residence times are augmented by vertical motion which could also act to offset the expected infrared heating. Further observations of similar events will be required in order to conclusively explain this curious cloud.

Analysis of an Equiaxed Dendrite Growth Model with Comparisons to <i>In-Situ</i> Results of Equiaxed Dendritic Growth in an Al-Ge Alloy

The Lipton Glicksman Kurz (LGK) growth model is commonly used to predict growth rates for equiaxed dendrites in solidifying mushy zones. However, the original LGK method treats an isolated dendrite growing in an infinite volume of liquid. In an equiaxed mushy zone, with multiple nucleation events, thermal and solutal interactions take place between the equiaxed dendrites. A modified version of the LGK model was developed that allows for measurement of the solute build-up ahead of the dendrites. To investigate the validity of the model, comparisons are made with results obtained from in-situ synchrotron X-ray videomicroscopy of solidification in a Bridgman furnace of an Al-12wt.%Ge alloy inoculated with Al-Ti-B grain refiner. Comparisons between the original LGK and modified LGK models are presented for discussion. The modified LGK model shows realistic tip temperature trends.

Wurtzite to Rocksalt Phase Transformation of Cadmium Selenide Nanocrystals via Laser-Induced Shock Waves: Transition from Single to Multiple Nucleation

The behavior of CdSe nanocrystals shocked to stresses of 2-3.75 GPa has been studied. Above 3 GPa a near-complete disappearance of the first excitonic feature and broadening of the low-energy absorption edge were observed, consistent with a wurtzite to rocksalt structural transformation. The transformation pressure is reduced relative to hydrostatic compression in a diamond anvil cell, and the rate increases, attributed to shock induced shear stress along the reaction coordinate. The especially rapid rate observed for a 3.75 GPa shock suggests multiple nucleation events per particle.

New insights into intragranular ferrite in a low-carbon low-alloy steel

Single and multiple nucleation events on non-metallic inclusions have been observed, leading to the intragranular formation of ferrite as a function of transformation temperature. Three-dimensional shapes have also been characterized. When the ferrite forms at elevated temperatures it is in the form of isolated idiomorphs, whereas larger undercoolings are associated with the multiple nucleation of plates emanating from the inclusions. The plates grow at a fixed orientation to the parent austenite. Nanohardness tests indicate that the idiomorphs are softer when compared with the plates. The formation of intragranular ferrite laths or plates can facilitate the attainment of fine-grained microstructures.

Spatial point pattern analysis applied to bubble nucleation in silicate melts

Experimental bubble nucleation studies are used for determining the nucleation mechanism as a function of experimental conditions, the resulting bubble number density, and can also yield estimates of the melt-vapor surface tension. This provides important information on gas exsolution in silicate melts, which can be applied towards understanding magmatic degassing in volcanic conduits. At present, determination of nucleation processes in tiny experimental samples relies upon visual observations. To improve the characterization of the spatial distribution of bubbles, we present a new application of spatial point pattern analysis. This technique allows the quantitative description of the spatial distribution of nucleation sites and has the potential to distinguish between homogeneous, heterogeneous, and multiple nucleation events. Since point pattern analysis highlights clustering or spatial regularity among objects, it may improve our understanding of the melt structure underlying the spatial distribution of nucleation sites, as well as interactions between bubble populations resulting from different nucleation pulses within a single experimental sample.

Molecular dynamics simulation of the six- to four-coordinate pressure-driven transition inMXnanocrystals: Mechanistic consequences ofΣ3grain boundaries in the high-pressure starting structure

Constant-pressure molecular dynamics has been used to simulate the six- to four-coordinate downstroke pressure-driven phase transition in B1 nanocrystals. The nanocrystals considered have previously been formed in upstroke $\text{B}3\ensuremath{\rightarrow}\text{B}1$ simulations, giving them an amorphous surface region and interior ${\ensuremath{\Sigma}}_{3}$ grain boundaries. Nucleation occurs in the interior of the crystal, with multiple nucleation events observed along grain boundaries, in contrast to previous decompression simulations of single-domain nanocrystals with crystallographically well-defined surfaces. Competing mechanisms give rise to B3, B4, and d-BCT domains in the productstructures. Four distinct mechanisms are observed, including two $\text{B}4\ensuremath{\leftrightarrow}\text{B}1$ mechanisms. The $\text{B}4\stackrel{\text{I}}{\ensuremath{\leftrightarrow}}\text{B}1$ mechanism is the same as seen in previous simulations of single-domain nanocrystalline and bulk systems, while the observed $\text{B}3\ensuremath{\leftrightarrow}\text{B}1$ and $\text{B}4\stackrel{\text{II}}{\ensuremath{\leftrightarrow}}\text{B}1$ display a ${[111]}_{\text{B}3}\ensuremath{\leftrightarrow}{[100]}_{\text{B}1}$ correspondence, in agreement with experimental observations of repeatedly transformed CdSe nanocrystals; both of which are different to those seen in previous upstroke simulations. The interaction between these competing mechanisms determines the domain structure of the product nanocrystals.

Experimental study of bubble growth in Stromboli basalt melts at 1 atm

Volcanic eruptions are characterized by intense degassing, thus it is imperative to have high quality laboratory data to constrain degassing mechanisms. In order to investigate bubble formation and growth at 1 atm, degassing experiments using a Stromboli basalt were performed on the GSECARS X-ray beamline at the Advanced Photon Source. Volatile-bearing glasses were synthesized at 1250 °C and 1000 MPa in a piston cylinder with H 2O or mixtures of H 2O + CO 2; they were then heated in-situ on the X-ray beamline at 1 atm. Bubble growth was observed in-situ using X-ray radiography. The 3D bubble size distributions in the quenched samples and a natural Stromboli pumice were studied by synchrotron X-ray microtomography. The results show that bubble nucleation and growth in basaltic melts are volatile-concentration dependent. Bubbles can easily form in melts initially containing high volatile concentrations. The effect of CO 2 on bubble nucleation and growth becomes significant at large CO 2 concentrations of 880 to 1480 ppm, but is not important at lower concentrations. Multiple nucleation events occur in most of these degassing experiments, and they are more pronounced in more supersaturated melts. Bubble growth is controlled by viscosity near glass transition temperatures and by diffusion at higher temperatures. Bubbles begin to pop 10 to 20 s after a foam is developed at vesicularities of 65% to 83%. Bubble size distributions follow power–law relations at vesicularities of 1% to 65%, and bubble size distributions evolve from power–law relations to exponential relations at vesicularities of 65% to 83%. This evolution is associated with the change from far-from-equilibrium degassing to near-equilibrium degassing. During far-from-equilibrium degassing, multiple nucleation events are pronounced, and possibly account for the generation of power–law relations. When the system reaches near-equilibrium degassing, coalescence is dominant and leads to the formation of bubbles of similar size. Therefore, bubble size distributions are described by exponential relations.