Nucleation Rate (nucleation + rate)

Distribution by Scientific Domains
Distribution within Polymers and Materials Science


Selected Abstracts


On slow protein crystal nucleation: cluster-cluster aggregation on diffusional encounters

CRYSTAL RESEARCH AND TECHNOLOGY, Issue 1 2009
C. N. NanevArticle first published online: 7 NOV 200
Abstract With a view to experimental results on protein crystal nucleation the effects of cluster coalescence are probed semi-quantitatively. The steric association restriction, which stems from the patchy surface of the protein molecules, explains both experimentally measured low crystal nucleation rate and coalescence limitations for crystalline clusters of protein molecules. The conclusion is that due to its action, and the impact of rotational diffusion, the coalescence of critical (and/or supercritical) clusters should be rejected as a conceivable alternative for explaining the slow nucleation of protein crystals. Besides, the analysis of cluster-cluster aggregation on diffusional encounters may be of more general interest; it may be helpful by considering the coalescence of structured bio-nano-particles. ( 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]


An Atomic and Mesoscopic Study of Precipitation Kinetics in Al-Zr-Sc Alloys,

ADVANCED ENGINEERING MATERIALS, Issue 12 2006
E. Clouet
This study illustrates how a quantitative multiscale modelling of the precipitation kinetics can be performed. Using a very limited number of experimental data and ab-initio calculations, we built for the Al-Zr-Sc alloy an atomic model from which mesoscopic quantities like the interface free energy or the nucleation free energy could be deduced. For the two binary Al-Zr and Al-Sc alloys, it was shown that a good agreement can be obtained between the KMC simulations, different mesoscopic models (CD and CNT) and experimental data. For the ternary alloy, CNT could be extended leading to predictions of an increase of the nucleation rate in agreement with atomic simulations and with experimental data. [source]


Architecture of Supramolecular Soft Functional Materials: From Understanding to Micro-/Nanoscale Engineering

ADVANCED FUNCTIONAL MATERIALS, Issue 19 2010
Jing-Liang Li
Abstract This article gives an overview of the current progress of a class of supramolecular soft materials consisting of fiber networks and the trapped liquid. After discussing the up-to-date knowledge on the types of fiber networks and the correlation to the rheological properties, the gelation mechanism turns out to be one of the key subjects for this review. In this concern, the following two aspects will be focused upon: the single fiber network formation and the multi-domain fiber network formation of this type of material. Concerning the fiber network formation, taking place via nucleation, and the nucleation-mediated growth and branching mechanism, the theoretical basis of crystallographic mismatch nucleation that governs fiber branching and formation of three-dimensional fiber networks is presented. In connection to the multi-domain fiber network formation, which is governed by the primary nucleation and the subsequent formation of single fiber networks from nucleation centers, the control of the primary nucleation rate will be considered. Based on the understanding on the the gelation mechanism, the engineering strategies of soft functional materials of this type will be systematically discussed. These include the control of the nucleation and branching-controlled fiber network formation in terms of tuning the thermodynamic driving force of the gelling system and introducing suitable additives, as well as introducing ultrasound. Finally, a summary and the outlook of future research on the basis of the nucleation-growth-controlled fiber network formation are given. [source]


Architecture of Supramolecular Soft Functional Materials: From Understanding to Micro-/Nanoscale Engineering

ADVANCED FUNCTIONAL MATERIALS, Issue 19 2010
Jing-Liang Li
Abstract This article gives an overview of the current progress of a class of supramolecular soft materials consisting of fiber networks and the trapped liquid. After discussing the up-to-date knowledge on the types of fiber networks and the correlation to the rheological properties, the gelation mechanism turns out to be one of the key subjects for this review. In this concern, the following two aspects will be focused upon: the single fiber network formation and the multi-domain fiber network formation of this type of material. Concerning the fiber network formation, taking place via nucleation, and the nucleation-mediated growth and branching mechanism, the theoretical basis of crystallographic mismatch nucleation that governs fiber branching and formation of three-dimensional fiber networks is presented. In connection to the multi-domain fiber network formation, which is governed by the primary nucleation and the subsequent formation of single fiber networks from nucleation centers, the control of the primary nucleation rate will be considered. Based on the understanding on the the gelation mechanism, the engineering strategies of soft functional materials of this type will be systematically discussed. These include the control of the nucleation and branching-controlled fiber network formation in terms of tuning the thermodynamic driving force of the gelling system and introducing suitable additives, as well as introducing ultrasound. Finally, a summary and the outlook of future research on the basis of the nucleation-growth-controlled fiber network formation are given. [source]


Population balance modeling of aggregation kinetics of recombinant human interleukin-1 receptor antagonist

JOURNAL OF PHARMACEUTICAL SCIENCES, Issue 12 2005
Eva Y. Chi
Abstract The kinetics of benzyl alcohol-induced nonnative aggregation of recombinant human interleukin-1 receptor antagonist (rhIL-1ra) were investigated using a population balance model. Steady-state size distributions of rhIL-1ra aggregates formed in a continuous mixed suspension, mixed product removal (MSMPR) reactor were measured and used to extrapolate aggregate nucleation and growth rates parameters. Aggregate growth rate was size-dependent and a linear growth rate model was used to derive a population density function. Addition of 0.9 wt/v% benzyl alcohol increased the nucleation rate by approximately four orders of magnitude. The growth rate for aggregates, however, changed little as a function of benzyl alcohol concentration in the range of 0,0.9%. The addition of sucrose to buffer containing 0.9% benzyl alcohol decreased rhIL1-ra nucleation rate by orders of magnitude and had little impact on growth rate kinetics. The simplicity of the population balance model and the physical relevance of the information obtained from this model render it a useful tool to study protein aggregation kinetics and the effects of excipients on this process. 2005 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 94:2735,2748, 2005 [source]


Nucleation and Crystallization of a Lead Halide Phosphate Glass by Differential Thermal Analysis

JOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 4 2002
Hongsheng Zhao
The nucleation and crystallization mechanisms of a lead halide phosphate glass [40P2O530PbBr230PbF2 (mol%)] were investigated by differential thermal analysis (DTA) and X-ray diffraction analysis. There were two crystalline phases in the crystallized samples: the major phase was PbP2O4, and the minor phase was PbP2O6. The average activation energy for crystallization, E, for two different particle sizes of this glass was determined to be 119 4 kJ/mol by the Kissinger method and 124 4 kJ/mol by the Augis,Bennett method. The Avrami constants were determined to be 1.6 and 2.5 for particle sizes of 203 and 1040 ,m, respectively, by the Ozawa equation, and 1.7 and 2.4 for particle sizes of 203 and 1040 ,m, respectively, by the Augis,Bennett equation. The decrease in the crystallization peak height in the DTA curve with increasing particle size suggested that the particles crystallize primarily by surface crystallization. A nucleation-rate type curve was determined by plotting either the reciprocal of the temperature corresponding to the crystallization peak maximum, 1/Tp, or the height of the crystallization peak, (,T)p, as a function of nucleation temperature, Tn. The temperature where nucleation can occur for this glass ranges from 360,450C and the maximum nucleation rate is at 420 10C. [source]


Microemulsion Polymerization Modeling Based on the Experimental Conversion Trend and its Derivative

MACROMOLECULAR SYMPOSIA, Issue 1 2008
F. Lpez-Serrano
Abstract In this work, the microemulsion polymerization modeling problem is addressed with an integrodifferential approach. The procedure was applied to experimental data, previously presented, on the microemulsion polymerization of hexyl methacrylate (C6MA) and styrene (STY). It was found that: (i) the nucleation rate is not linear with time, as assumed before, (ii) a vitreous effect is observed even in reactions where the polymer's glass transition temperature is lower than the reaction temperature, (iii) radical entry to polymer particles and coagulation among particles are negligible, (iv) the rate decrease interval is also caused by a reduction of active sites, (v) a mechanism in which micelles provide monomer to living particles was detected, and (vi) a simple three-parameter mechanistic model was obtained, capable of describing the studied systems. [source]


Non-local thermodynamic equilibrium dust nucleation in subsaturated vapours

MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 1 2008
Davide Lazzati
ABSTRACT We use the kinetic theory of nucleation to explore the properties of dust nucleation in subsaturated vapours. Due to radiation losses, the subcritical clusters have a smaller temperature compared to their vapour. This alters the dynamical balance between the attachment and detachment of monomers, allowing for stable nucleation of grains in vapours that are subsaturated for their temperature. We find this effect particularly important at low densities and in the absence of a strong background radiation field. We find new conditions for stable nucleation in the n,T phase diagram. The nucleation in the non-local thermodynamic equilibrium (non-LTE) regions is likely to be at much slower rate than in the supersaturated vapours. We evaluate the nucleation rate, warning the reader that it does depend on poorly substantiated properties of the macro-molecules assumed in the computation. On the other hand, the conditions for nucleation depend only on the properties of the large stable grains and are more robust. We finally point out that this mechanism may be relevant in the early Universe as an initial dust pollution mechanism, since once the interstellar medium is polluted with dust, mantle growth is likely to be dominant over non-LTE nucleation in the diffuse medium. [source]


Influence of wurtzite,zinc-blende interfacial energy on growth and crystal phase of the III-V nanowires

PHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 2 2010
Maxim Lubov
Abstract Influence of wurtzite,zinc-blende energy on nucleation rate and growth kinetics is studied. The physical model of III-V nanowires growth is proposed. We show that wurtzite,zinc-blende interfacial energy caused formation of the zinc-blende structure on the initial stage of nanowires growth. Role of the fluctuations in quasi-periodic crystal structure formation representing alternating layers of wurtzite and zinc-blende phase is revealed. Calculations of the growth of the nanowire growth accounting fluctuations in the droplet alloy are carried out. The results of the calculations are in a good agreement with available experimental data. ( 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]


Effect of die temperature on the morphology of microcellular foams

POLYMER ENGINEERING & SCIENCE, Issue 6 2003
Xiangmin Han
A study on the extrusion of microcellular polystyrene foams at different foaming temperatures was carried out using CO2 as the foaming agent. The contraction flow in the extrusion die was simulated with FLUENT computational fluid dynamics code at two temperatures (150C and 175C) to predict pressure and temperature profiles in the die. The location of nucleation onset was determined based on the pressure profile and equilibrium solubility. The relative importance of pressure and temperature in determining the nucleation rate was compared using calculations based on classical homogeneous nucleation theory. Experimentally, the effects of die temperature (i.e., the foaming temperature) on the pressure profile in the die, cell size, cell density, and cell morphology were investigated at different screw rotation speeds (10 , 30 rpm). Experimental results were compared with simulations to gain insight into the foaming process. Although the foaming temperature was found to be less significant than the pressure drop or the pressure drop rate in deciding the cell size and cell density, it affects the cell morphology dramatically. Open and closed cell structures can be generated by changing the foaming temperature. Microcellular foams of PS (with cell sizes smaller than 10 ,m and cell densities greater than 10 cells/cm3) are created experimentally when the die temperature is 160C, the pressure drop through the die is greater than 16 MPa, and the pressure drop rate is higher than 109 Pa/sec. [source]


Evaluation of a large-eddy model simulation of a mixed-phase altocumulus cloud using microwave radiometer, lidar and Doppler radar data

THE QUARTERLY JOURNAL OF THE ROYAL METEOROLOGICAL SOCIETY, Issue 618 2006
J. H. Marsham
Abstract Using the Met Office large-eddy model (LEM) we simulate a mixed-phase altocumulus cloud that was observed from Chilbolton in southern England by a 94 GHz Doppler radar, a 905 nm lidar, a dual-wavelength microwave radiometer and also by four radiosondes. It is important to test and evaluate such simulations with observations, since there are significant differences between results from different cloud-resolving models for ice clouds. Simulating the Doppler radar and lidar data within the LEM allows us to compare observed and modelled quantities directly, and allows us to explore the relationships between observed and unobserved variables. For general-circulation models, which currently tend to give poor representations of mixed-phase clouds, the case shows the importance of using: (i) separate prognostic ice and liquid water, (ii) a vertical resolution that captures the thin layers of liquid water, and (iii) an accurate representation the subgrid vertical velocities that allow liquid water to form. It is shown that large-scale ascents and descents are significant for this case, and so the horizontally averaged LEM profiles are relaxed towards observed profiles to account for these. The LEM simulation then gives a reasonable cloud, with an ice-water path approximately two thirds of that observed, with liquid water at the cloud top, as observed. However, the liquid-water cells that form in the updraughts at cloud top in the LEM have liquid-water paths (LWPs) up to half those observed, and there are too few cells, giving a mean LWP five to ten times smaller than observed. In reality, ice nucleation and fallout may deplete ice-nuclei concentrations at the cloud top, allowing more liquid water to form there, but this process is not represented in the model. Decreasing the heterogeneous nucleation rate in the LEM increased the LWP, which supports this hypothesis. The LEM captures the increase in the standard deviation in Doppler velocities (and so vertical winds) with height, but values are 1.5 to 4 times smaller than observed (although values are larger in an unforced model run, this only increases the modelled LWP by a factor of approximately two). The LEM data show that, for values larger than approximately 12 cm s,1, the standard deviation in Doppler velocities provides an almost unbiased estimate of the standard deviation in vertical winds, but provides an overestimate for smaller values. Time-smoothing the observed Doppler velocities and modelled mass-squared-weighted fallspeeds shows that observed fallspeeds are approximately two-thirds of the modelled values. Decreasing the modelled fallspeeds to those observed increases the modelled IWC, giving an IWP 1.6 times that observed. Copyright 2006 Royal Meteorological Society [source]


Protein crystallization in hydrogel beads

ACTA CRYSTALLOGRAPHICA SECTION D, Issue 9 2005
Ronnie Willaert
The use of hydrogel beads for the crystallization of proteins is explored in this contribution. The dynamic behaviour of the internal precipitant, protein concentration and relative supersaturation in a gel bead upon submerging the bead in a precipitant solution is characterized theoretically using a transient diffusion model. Agarose and calcium alginate beads have been used for the crystallization of a low-molecular-weight (14.4,kDa, hen egg-white lysozyme) and a high-molecular-weight (636.0,kDa, alcohol oxidase) protein. Entrapment of the protein in the agarose-gel matrix was accomplished using two methods. In the first method, a protein solution is mixed with the agarose sol solution. Gel beads are produced by immersing drops of the protein,agarose sol mixture in a cold paraffin solution. In the second method (which was used to produce calcium alginate and agarose beads), empty gel beads are first produced and subsequently filled with protein by diffusion from a bulk solution into the bead. This latter method has the advantage that a supplementary purification step is introduced (for protein aggregates and large impurities) owing to the diffusion process in the gel matrix. Increasing the precipitant, gel concentration and protein loading resulted in a larger number of crystals of smaller size. Consequently, agarose as well as alginate gels act as nucleation promoters. The supersaturation in a gel bead can be dynamically controlled by changing the precipitant and/or the protein concentration in the bulk solution. Manipulation of the supersaturation allowed the nucleation rate to be varied and led to the production of large crystals which were homogeneously distributed in the gel bead. [source]


Osmolyte controlled fibrillation kinetics of insulin: New insight into fibrillation using the preferential exclusion principle

BIOTECHNOLOGY PROGRESS, Issue 5 2009
Arpan Nayak
Abstract Amyloid proteins are converted from their native-fold to long ,-sheet-rich fibrils in a typical sigmoidal time-dependent protein aggregation curve. This reaction process from monomer or dimer to oligomer to nuclei and then to fibrils is the subject of intense study. The main results of this work are based on the use of a well-studied model amyloid protein, insulin, which has been used in vitro by others. Nine osmolyte molecules, added during the protein aggregation process for the production of amyloid fibrils, slow-down or speed up the process depending on the molecular structure of each osmolyte. Of these, all stabilizing osmolytes (sugars) slow down the aggregation process in the following order: tri > di > monosaccharides, whereas destabilizing osmolytes (urea, guanidium hydrochloride) speed up the aggregation process in a predictable way that fits the trend of all osmolytes. With respect to kinetics, we illustrate, by adapting our earlier reaction model to the insulin system, that the intermediates (trimers, tetramers, pentamers, etc.) are at very low concentrations and that nucleation is orders of magnitude slower than fibril growth. The results are then collated into a cogent explanation using the preferential exclusion and accumulation of osmolytes away from and at the protein surface during nucleation, respectively. Both the heat of solution and the neutral molecular surface area of the osmolytes correlate linearly with two fitting parameters of the kinetic rate model, that is, the lag time and the nucleation rate prior to fibril formation. These kinetic and thermodynamic results support the preferential exclusion model and the existence of oligomers including nuclei and larger structures that could induce toxicity. 2009 American Institute of Chemical Engineers Biotechnol. Prog., 2009 [source]


Analysis of supersaturation and nucleation in a moving solution droplet with flowing supercritical carbon dioxide

JOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 4 2005
Mamata Mukhopadhyay
Abstract A supercritical antisolvent (SAS) process is employed for production of solid nanoparticles from atomized droplets of dilute solution in a flowing supercritical carbon dioxide (SC CO2) stream by attaining extremely high, very rapid, and uniform supersaturation. This is facilitated by a two-way mass transfer of CO2 and solvent, to and from the droplet respectively, rendering rapid reduction in equilibrium solubility of the solid solute in the ternary solution. The present work analyses the degree of supersaturation and nucleation kinetics in a single droplet of cholesterol solution in acetone during its flight in a flowing SC CO2 stream. Both temperature and composition are assumed to be uniform within the droplet, and their variations with time are calculated by balancing the heat and mass transfer fluxes to and from the droplet. The equilibrium solubility of cholesterol with CO2 dissolution has been predicted as being directly proportional to the Partial Molar Volume Fraction (PMVF) of acetone in the binary (CO2,acetone) system. The degree of supersaturation has been simulated up to the time required to attain almost zero cholesterol solubility in the droplet for evaluating the rate of nucleation and the size of the stable critical nuclei formed. The effects of process parameters have been analysed in the pressure range of 7.1,35.0 MPa, temperature range of 313,333 K, SC CO2 flow rate of 0.1136,1.136 mol s,1, the ratio of the volumetric flow rates of CO2 -to-solution in the range of 100,1000, and the initial mole fraction of cholesterol in acetone solution in the range of 0.0025,0.010. The results confirm an extremely high and rapid increase in degree of supersaturation, very high nucleation rates and stable critical nucleus diameter of the order of a nanometre. Copyright 2005 Society of Chemical Industry [source]


Modeling the crystallization of proteins and small organic molecules in nanoliter drops

AICHE JOURNAL, Issue 1 2010
Richard D. Dombrowski
Abstract Drop-based crystallization techniques are used to achieve a high degree of control over crystallization conditions in order to grow high-quality protein crystals for X-ray diffraction or to produce organic crystals with well-controlled size distributions. Simultaneous crystal growth and stochastic nucleation makes it difficult to predict the number and size of crystals that will be produced in a drop-based crystallization process. A mathematical model of crystallization in drops is developed using a Monte Carlo method. The model incorporates key phenomena in drop-based crystallization, including stochastic primary nucleation and growth rate dispersion (GRD) and can predict distributions of the number of crystals per drop and full crystal size distributions (CSD). Key dimensionless parameters are identified to quickly screen for crystallization conditions that are expected to yield a high fraction of drops containing one crystal and a narrow CSD. Using literature correlations for the solubilities, growth, and nucleation rates of lactose and lysozyme, the model is able to predict the experimentally observed crystallization behavior over a wide range of conditions. Model-based strategies for use in the design and optimization of a drop-based crystallization process for producing crystals of well-controlled CSD are identified. 2009 American Institute of Chemical Engineers AIChE J, 2010 [source]


Mineralogical and Geochemical Characterization of Beryl-Bearing Granitoids, Eastern Desert, Egypt: Metallogenic and Exploration Constraints

RESOURCE GEOLOGY, Issue 2 2009
Hamdy M. Abdalla
Abstract Mineral chemistry and geochemical characteristics of beryl-bearing granitoids in Eastern Desert of Egypt, were examined in order to identify the metallogenetic processes of the host granitoids. The investigated Be-bearing granitoids and type occurrences are classified into two groups: (i) peraluminous, Ta , Nb + Sn + Be W-enriched, Li-albite granite (e.g. Nuweibi and Abu Dabbab); and (ii) metasomatized, Nb >> Ta + Sn + Be W Mo-enriched alkali feldspar granite (i.e. apogranite; e.g. Homr Akarem, Homr Mikpid and Qash Amir). In these two groups, beryl occurs as stockwork greisen veins, greisen bodies, beryl-bearing cassiterite wolframite quartz veins, dissemination, and miarolitic pegmatites. Beryl of the Be-granitoids, particularly those of miarolitic pegmatites, contains appreciable contents of Fe, Na, and H2O. An important feature of the Be-apogranites is the occurrence of white mica as the sole mafic mineral in the unaltered alkali feldspar granite in lower zones. Presence of white mica as volatile-rich pockets suggests that the melt underwent disequilibrium crystallization, rapid nucleation rates, and exsolving and expulsion of volatiles. [source]