Showing papers on "Nucleation published in 2001"

Real-space imaging of nucleation and growth in colloidal crystallization.

Abstract: Crystallization of concentrated colloidal suspensions was studied in real space with laser scanning confocal microscopy. Direct imaging in three dimensions allowed identification and observation of both nucleation and growth of crystalline regions, providing an experimental measure of properties of the nucleating crystallites. By following their evolution, we identified critical nuclei, determined nucleation rates, and measured the average surface tension of the crystal-liquid interface. The structure of the nuclei was the same as the bulk solid phase, random hexagonal close-packed, and their average shape was rather nonspherical, with rough rather than faceted surfaces.

Prediction of absolute crystal-nucleation rate in hard-sphere colloids

Abstract: Crystal nucleation is a much-studied phenomenon, yet the rate at which it occurs remains difficult to predict. Small crystal nuclei form spontaneously in supersaturated solutions, but unless their size exceeds a critical value--the so-called critical nucleus--they will re-dissolve rather than grow. It is this rate-limiting step that has proved difficult to probe experimentally. The crystal nucleation rate depends on Pcrit, the (very small) probability that a critical nucleus forms spontaneously, and on a kinetic factor (kappa) that measures the rate at which critical nuclei subsequently grow. Given the absence of a priori knowledge of either quantity, classical nucleation theory is commonly used to analyse crystal nucleation experiments, with the unconstrained parameters adjusted to fit the observations. This approach yields no 'first principles' prediction of absolute nucleation rates. Here we approach the problem from a different angle, simulating the nucleation process in a suspension of hard colloidal spheres, to obtain quantitative numerical predictions of the crystal nucleation rate. We find large discrepancies between the computed nucleation rates and those deduced from experiments: the best experimental estimates of Pcrit seem to be too large by several orders of magnitude.

Evidence for Seed-Mediated Nucleation in the Chemical Reduction of Gold Salts to Gold Nanoparticles

Abstract: Central to the concept of seed-mediated growth of nanoparticles is that small nanoparticle seeds serve as nucleation centers to grow nanoparticles to a desired size. We have examined this common assumption in a model system, the wet chemical synthesis of gold nanoparticles via reduction of a gold salt, by transmission electron microscopy and electronic absorption spectroscopy. We find that changing the seed concentration does affect the size of the product nanoparticles, but the method of reagent addition drastically affects the outcome even more. For fast addition of reducing agent, the presence of seeds appears to promote the formation of more seeds instead of growth. The observed nucleations are drastically enhanced (99%) compared to particle growth. For slow addition of reducing agent, the seeds do grow, but the product nanoparticle's degree of homogeneity in shape is compromised. For higher concentrations of seeds, nanoparticle growth is better controlled for slow addition of reducing agent compared ...

Dewetting patterns and molecular forces: a reconciliation.

Abstract: We studied the dewetting of thin liquid polymer films from solid surfaces. Our experimental results lead to a consistent picture demonstrating the interplay between short- and long-range interfacial forces. Observations comprise nucleation and spinodal dewetting, as well as thermal nucleation of holes. The effective interface potential of the system, as reconstructed from the morphology of the dewetting patterns, agrees quantitatively with what is computed from the optical properties of the system. This shows that the assumption of additivity of dispersion potentials in multilayer systems yields good results.

On the formation, growth and composition of nucleation mode particles

Abstract: Taking advantage of only the measured aerosol particles spectral evolution as a function of time, a new analytical tool is developed to derive formation and growth properties of nucleation mode aerosols. This method, when used with hygroscopic growth-factors, can also estimate basic composition properties of these recently-formed particles. From size spectra the diameter growth-rate can be obtained, and aerosol condensation and coagulation sinks can be calculated. Using this growth-rate and condensation sink, the concentration of condensable vapours and their source rate can be estimated. Then, combining the coagulation sink together with measured number concentrations and apparent source rates of 3 nm particles, 1 nm particle nucleation rates and concentration can be estimated. To estimate nucleation rates and vapour concentration source rates producing new particle bursts over the Boreal forest regions, three cases from the BIOFOR project were examined using this analytical tool. In this environment, the nucleation mode growth-rate was observed to be 2–3 nm hour −1 , which required a condensable vapour concentration of 2.5–4×10 7 cm −3 and a source rate of approximately 7.5–11×10 4 cm −3 s −1 to be sustained. The formation rate of 3 nm particles was ≈1 particle cm −3 s −1 in all three cases. The estimated formation rate of 1 nm particles was 10–100 particles cm −3 s −1 , while their concentration was estimated to be between 10,000 and 100,000 particles cm −3 . Using hygroscopicity data and mass flux expressions, the mass flux of insoluble vapour is estimated to be of the same order of magnitude as that of soluble vapour, with a soluble to insoluble vapour flux ratio ranging from 0.7 to 1.4 during these nucleation events. DOI: 10.1034/j.1600-0889.2001.530411.x

Controlled Aqueous Chemical Growth of Oriented Three-Dimensional Crystalline Nanorod Arrays: Application to Iron(III) Oxides

Abstract: The ability to create thin films of highly oriented anisotropic nanoparticles of transition metal oxides onto polycrystalline and single-crystalline substrates is demonstrated by the fabrication of large three-dimensional arrays of perpendicularly oriented nanorods of crystalline iron(III) oxides onto tin oxide and sapphire substrates. An enchanced control of the thermodynamics and kinetics of nucleation and growth processes allows one to grow such novel materials directly onto substrates from a simple aqueous solution of metal salts.

Surface Step Effects on Nanoindentation

Abstract: Atomistic simulation is used to examine nanoindentation of a Au(111) crystal both near and far from a surface step. While the load needed to nucleate dislocations decreases significantly when indenting close to the step, the extent of the step's influence is not as great as seen experimentally. This behavior is explained by measuring the contact area from the simulation data. A new metric, the slip vector, shows material slip coinciding with the directions of a lowest unstable stacking fault barrier. The slip vector is used to calculate an atomic critical resolved shear stress, which is shown to be a good dislocation nucleation criterion.

Observation of a bi-domain state and nucleation free switching in mesoscopic ring magnets.

Abstract: We present the results of a study of the magnetic properties of an array of 34-nm thick Co(100) epitaxial ring magnets, with inner and outer diameters of d(in) = 1.3 microm and d(out) = 1.6 microm, respectively. Magnetic measurements and micromagnetic simulations show that a two step switching process occurs at high fields, indicating the existence of two different stable states. In addition to the vortex state, which occurs at intermediate fields, we have identified a new bi-domain state, which we term the onion state, corresponding to opposite circulation of the magnetization in each half of the ring. The onion state is stable at remanence and undergoes a simple and well characterized nucleation free switching.

Nanofiber-reinforced thermoplastic composites. I. Thermoanalytical and mechanical analyses

Abstract: This article is a portion of a comprehensive study on carbon nanofiber–reinforced thermoplastic composites. The thermal behavior and dynamic and tensile mechanical properties of polypropylene–carbon nanofibers composites are discussed. Carbon nanofibers are those produced by the vapor-grown carbon method and have an average diameter of 100 nm. These hollow-core nanofibers are an ideal precursor system to working with multiwall and single-wall nanotubes for composite development. Composites were prepared by conventional Banbury-type plastic-processing methods ideal for low-cost composite development. Nanofiber agglomerates were eliminated because of shear working conditions, resulting in isotropic compression-molded composites. Incorporation of carbon nanofibers raised the working temperature range of the thermoplastic by 100°C. The nanofiber additions led to an increase in the rate of polymer crystallization with no change in the nucleation mechanism, as analyzed by the Avrami method. Although the tensile strength of the composite was unaltered with increasing nanofiber composition, the dynamic modulus increased by 350%. The thermal behavior of the composites was not significantly altered by the functionalization of the nanofibers since chemical alteration is associated with the defect structure of the chemical vapor deposition (CVD) layer on the nanofibers. Composite strength was limited by the enhanced crystallization of the polymer brought on by nanofiber interaction as additional nucleation sites. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 125–133, 2001

From molecular clusters to nanoparticles: Role of ambient ionization in tropospheric aerosol formation

Abstract: We investigate the role of background ionization, associated mainly with galactic cosmic radiation, in the generation and evolution of ultrafine particles in the marine boundary layer. We follow the entire course of aerosol evolution, from the initial buildup of molecular clusters (charged and uncharged) through their growth into stable nanoparticles. The model used for this purpose is based on a unified collisional (kinetic) mechanism that treats the interactions between vapors, neutral and charged clusters, and particles at all sizes. We show that air ions are likely to play a central role in the formation of new ultrafine particles. The nucleation of aerosols under atmospheric conditions involves a series of competing processes, including molecular aggregation, evaporation, and scavenging by preexisting particles. In this highly sensitive nonlinear system, electrically charged embryos have a competitive advantage over similar neutral embryos. The charged clusters experience enhanced growth and stability as a consequence of electrostatic interactions. Simulations of a major nucleation event observed during the Pacific Exploratory Mission (PEM) Tropics-A can explain most of the observed features in the ultrafine particle behavior. The key parameters controlling this behavior are the concentrations of precursor vapors and the surface area of preexisting particles, as well as the background ionization rate. We find that systematic variations in ionization levels due to the modulation of galactic cosmic radiation by the solar cycle are sufficient to cause a notable variation in aerosol production. This effect is greatest when the ambient nucleation rate is limited principally by the availability of ions. Hence we conclude that the greatest influence of such ionization is likely to occur in and above the marine boundary layer. While a systematic change in the ultrafine particle production rate is likely to affect the population of cloud condensation nuclei and hence cloud optical properties, the magnitude of the effect cannot be directly inferred from the present analysis, and requires additional analysis based on specific aerosol-cloud interactions.

Suppression of crystal nucleation in polydisperse colloids due to increase of the surface free energy

Abstract: The formation of small crystallites is governed by two competing factors: the free energy gained upon transferring constituent atoms, molecules or colloidal particles from the metastable liquid to the more stable solid, and the free energy needed to create the surface area of the crystallite. Because the ratio of surface area to bulk is large for small particles, small crystallites dissolve spontaneously under conditions where larger crystallites are stable and macroscopic crystal growth occurs only if spontaneously formed crystallites exceed a critical minimum size. On theoretical grounds, the probability of forming such critical crystal nuclei is expected to increase rapidly with supersaturation. However, experiments show that the rate of crystal nucleation in many systems goes through a maximum as the supersaturation is increased. It is commonly assumed that the nucleation rate peaks because, even though the probability of forming critical nuclei increases with increasing concentration, the rate of growth of such nuclei decreases. Here we report simulations of crystal nucleation in suspensions of colloidal spheres with varying size distributions that show that the probability that critical nuclei will form itself goes through a maximum as the supersaturation is increased. We find that this effect, which is strongest for systems with the broadest particle size distribution, results from an increase with supersaturation of the solid-liquid interfacial free energy. The magnitude of this effect suggests that vitrification at high supersaturations should yield colloidal glasses that are truly amorphous, rather than nano-crystalline.

Melting mechanisms at the limit of superheating

Abstract: The atomic-scale details during melting of a surface-free Lennard-Jones crystal were monitored using molecular dynamics simulations. Melting occurs when the superheated crystal spontaneously generates a sufficiently large number of spatially correlated destabilized particles that simultaneously satisfy the Lindemann and Born instability criteria. The accumulation and coalescence of these internal local lattice instabilities constitute the primary mechanism for homogeneous melt nucleation inside the crystal, in lieu of surface nucleation for equilibrium melting. The vibrational and elastic lattice instability criteria as well as the homogeneous nucleation theory all coincide in determining the superheating limit.

Overview of the international project on biogenic aerosol formation in the boreal forest (BIOFOR)

Abstract: Aerosol formation and subsequent particle growth in ambient air have been frequently observed at a boreal forest site (SMEAR II station) in Southern Finland. The EU funded project BIOFOR (Biogenic aerosol formation in the boreal forest) has focused on: (a) determination of formation mechanisms of aerosol particles in the boreal forest site; (b) verification of emissions of secondary organic aerosols from the boreal forest site; and (c) quantification of the amount of condensable vapours produced in photochemical reactions of biogenic volatile organic compounds (BVOC) leading to aerosol formation. The approach of the project was to combine the continuous measurements with a number of intensive field studies. These field studies were organised in three periods, two of which were during the most intense particle production season and one during a non-event season. Although the exact formation route for 3 nm particles remains unclear, the results can be summarised as follows: Nucleation was always connected to Arctic or Polar air advecting over the site, giving conditions for a stable nocturnal boundary layer followed by a rapid formation and growth of a turbulent convective mixed layer closely followed by formation of new particles. The nucleation seems to occur in the mixed layer or entrainment zone. However two more prerequisites seem to be necessary. A certain threshold of high enough sulphuric acid and ammonia concentrations is probably needed as the number of newly formed particles was correlated with the product of the sulphuric acid production and the ammonia concentrations. No such correlation was found with the oxidation products of terpenes. The condensation sink, i.e., effective particle area, is probably of importance as no nucleation was observed at high values of the condensation sink. From measurement of the hygroscopic properties of the nucleation particles it was found that inorganic compounds and hygroscopic organic compounds contributed both to the particle growth during daytime while at night time organic compounds dominated. Emissions rates for several gaseous compounds was determined. Using four independent ways to estimate the amount of the condensable vapour needed for observed growth of aerosol particles we get an estimate of 2–10×10 7 vapour molecules cm −3 . The estimations for source rate give 7.5–11×10 4 cm −3 s −1 . These results lead to the following conclusions: The most probable formation mechanism is ternary nucleation (water-sulphuric acid-ammonia). After nucleation, growth into observable sizes (∼3 nm) is required before new particles appear. The major part of this growth is probably due to condensation of organic vapours. However, there is lack of direct proof of this phenomenon because the composition of 1–5 nm size particles is extremely difficult to determine using the present state-of-art instrumentation DOI: 10.1034/j.1600-0889.2001.530402.x

Vortex nucleation in a stirred Bose-Einstein condensate.

Abstract: We studied the nucleation of vortices in a Bose-Einstein condensate stirred by a laser beam The vortex cores were observed using time-of-flight absorption imaging Depending on the stirrer size, either discrete resonances or a broad response was visible as the stir frequency was varied Stirring beams small compared to the condensate size generated vortices below the critical rotation frequency for the nucleation of surface modes, suggesting a local mechanism of generation In addition, we observed the centrifugal distortion of the condensate due to the rotating vortex lattice and found evidence for bent vortices

Polylactide stereocomplex crystallites as nucleating agents for isotactic polylactide

Abstract: A nucleation efficiency scale for isotactic poly(L-lactide) (PLLA) was obtained with self-nucleation and nonisothermal differential scanning calorimetry experiments. The maximum nucleation efficiency occurred at the highest concentration of self-nucleating sites, and the minimum efficiency occurred in the absence of these sites (pure PLLA polymer melt). Blends of PLLA and isotactic poly(D-lactide) (PDLA) led to the formation of a 1/1 stereocomplex. In comparison with the homopolymer (PLLA), the stereocomplex had a higher melting temperature and crystallized at higher temperatures from the melt. Small stereocomplex crystallites were formed in PLLA/PDLA blends containing low concentrations of PDLA. These crystallites acted as heterogeneous nucleation sites for subsequent PLLA crystallization. Using the PLLA nucleation efficiency scale, we evaluated a series of PLLA/PDLA blends (0.25–15 wt % PDLA). A maximum nucleation efficiency of 66% was observed at 15 wt % PDLA. The nucleation efficiency was largely dependent on the thermal treatment of the sample. The nucleating ability of the stereocomplex was most efficient when it was formed well before PLLA crystallization. According to the efficiency scale, the stereocomplex was far superior to talc, a common nucleating agent for PLLA, in its ability to enhance the rate of PLLA crystallization. In comparison with the PLLA homopolymer, the addition of PDLA led to reduced spherulite sizes and a reduction in the overall extent of PLLA crystallization. The decreased extent of crystallization was attributed to the hindered mobility of the PLLA chains due to tethering by the stereocomplex. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 300–313, 2001

Magnetization reversal due to vortex nucleation, displacement, and annihilation in submicron ferromagnetic dot arrays

Abstract: Magnetization processes are analytically described for the arrays of soft ferromagnetic polycrystalline circular dots with submicron dimensions, wherein the magnetization reversal accompanied by nucleation, displacement, and annihilation of magnetic vortices. Magnetostatic, exchange, and Zeeman energies are taken into account for the analysis. The magnetic state of each dot in an applied magnetic field is treated as an off-centered rigid vortex structure; i.e., the vortex keeps its spin distribution while being displaced. This rigid vortex model yields analytical expressions for the size-dependent initial susceptibility, the vortex nucleation, and the annihilation fields. The interdot magnetostatic interaction plays an important role in the magnetization reversal for the arrays when the interdot distance is smaller than the disk radius, where the initial susceptibility increases and both the nucleation and annihilation fields decrease. The analytical predictions are compared to the micromagnetic calculations, and limitations of the model are discussed.

Copper interconnect barrier layer structure and formation method

Abstract: A method for forming a tungsten-containing copper interconnect barrier layer (e.g., a tungsten [W] or tungsten-nitride [WxN] copper interconnect barrier layer) on a substrate with a high (e.g., greater than 30%) sidewall step coverage and ample adhesion to underlying dielectric layers. The method includes first depositing a thin titanium-nitride (TiN) or tantalum nitride (TaN) nucleation layer (12) on the substrate, followed by the formation of a tungsten-containing copper interconnect barrier layer (20) (e.g., a W orWxN copper interconnect barrier layer) overlying the substrate. The tungsten-containing copper interconnect barrier layer can, for example, be formed using a Chemical Vapor Deposition (CVD) technique that employs a fluorine-free tungsten-containing gas (e.g., tungsten hexacarbonyl [W(CO)6]) or a WF6-based Atomic Layer Deposition (ALD) technique. The presence of a thin TiN (or TaN) nucleation layer facilitates the formation of a tungsten-­containing copper interconnect barrier layer with a sidewall step coverage of greater than 30% and ample adhesion to dielectric layers. A copper interconnect barrier layer structure includes a thin titanium-nitride (TiN) (or tantalum nitride [TAN]) nucleation layer disposed directly on the dielectric substrate (e.g., a single or dual-damascene copper interconnect dielectric substrate). The copper interconnect barrier layer structure also includes a tungsten-­containing copper interconnect barrier layer (e.g., a W or WxN copper interconnect barrier layer) formed on the thin TiN (or TaN) nucleation layer using, for example, a CVD technique that employs a fluorine-free tungsten-containing gas (e.g., [W(CO)6]) or a WF6-based ALD technique.

Polymer crystallization confined in one, two, or three dimensions

Abstract: We examine the crystallization behavior of polyethylene-b-poly(vinylcyclohexane) diblock copolymers, E/VCH, using a combination of transmission electron microscopy (TEM), dilatometry, and time-resolved small-angle X-ray scattering (SAXS). The glassy VCH matrix effectively restricts E crystallization to within the spheres, cylinders, gyroid channels, or lamellae formed by microphase separation in the melt. The VCH matrix can contract in response to crystallization of the E microdomains, so crystallization proceeds without cavitation. The crystallization kinetics strongly reflect the connectivity of the E microdomains: homogeneous nucleation and first-order crystallization kinetics for spheres or cylinders of E; conventional sigmoidal kinetics for the highly interconnected gyroid structure. Lamellar materials show an interesting two-step crystallization behavior: at higher temperature, heterogeneous nucleation permits the crystallization of lamellae interconnected through grain boundaries or defects, and ...

Stress and piezoelectric properties of aluminum nitride thin films deposited onto metal electrodes by pulsed direct current reactive sputtering

Abstract: Polycrystalline aluminum nitride thin films were deposited onto platinum, aluminum, and titanium electrodes by reactive magnetron sputtering in the pulsed direct current mode. The films exhibited all a columnar microstructure and a c-axis texture. The built-in stress and the piezoelectric properties of these films were studied as a function of both the processing conditions and the electrode material. Stress was found to be very much dependent on the growth conditions, and values ranging from strong compression to high tension were observed. The piezoelectric d33,f coefficient was shown to rely on substrate quality and ionic bombardment: The nucleation surface must be stable with regard to the nitrogen plasma and present a hexagonal symmetry and, on the other hand, enough energy must be delivered to the growing film through ionic bombardment.

Control of Crystal Nucleation and Growth of Calcium Carbonate by Synthetic Substrates

Abstract: Construction of organic−inorganic hybrid materials with controlled mineralization analogous to those produced by nature is now of current interest for both organic and inorganic chemists to understand the mechanism of the natural biomineralization process as well as to seek industrial and technological applications. This review provides a general survey of recent research on control of crystal nucleation and growth of calcium carbonate by synthetic substrates from the viewpoint of organic and polymer chemistry. Model systems in which low-molecular-weight, linear polymeric, and dendritic organic additives are used to study the effect of molecular properties such as charge and functionality on inorganic crystallization are providing insights into the possible mechanisms operating in biology. To probe the organic−inorganic interface and resolve some of the molecular events mediating template-directed crystal nucleation and growth, a simple model surface, that is, compressed monolayers at the air/water interf...

Model of Formation of Monodispersed Colloids

Abstract: Ample experimental evidence has been accumulated demonstrating that the formation of monodispersed colloids proceeds through a more complex mechanism than the generally excepted diffusional “burst nucleation” process. Instead, the synthesis of narrow-size-distribution colloidal dispersions involves two distinct stages. Nanosize primary particles are nucleated in a supersaturated solution. They then aggregate to form much larger uniform secondary particles. To explain the size selection in such a process, a kinetic model has been developed which couples the two growth/aggregation stages. Our earlier study has shown the burst-nucleation growth of the primary particles to depend strongly on the value of the effective surface tension entering the surface term in the free energy of the subcritical embryos. The aim of the present work has been to identify an appropriate control parameter in the process of secondary particle formation. We tried modifications of the aggregation rates to account for singlet size a...

Stationary States of a Rotating Bose-Einstein Condensate: Routes to Vortex Nucleation

Abstract: Using a focused laser beam we stir a ${}^{87}\mathrm{Rb}$ Bose-Einstein condensate confined in a magnetic trap. We observe that the steady states of the condensate correspond to an elliptic cloud, stationary in the rotating frame. These steady states depend nonlinearly on the stirring parameters (amplitude and frequency), and various solutions can be reached experimentally depending on the path followed in this parameter space. These states can be dynamically unstable and we observe that such instabilities lead to vortex nucleation in the condensate.

Driving Bose-Einstein-Condensate Vorticity with a Rotating Normal Cloud

Abstract: We have developed an evaporative cooling technique that accelerates the rotation of an ultracold 87Rb gas, confined in a static harmonic potential. As a normal gas is evaporatively spun up and cooled below quantum degeneracy, it is found to nucleate vorticity in a Bose-Einstein condensate. Measurements of the condensate's aspect ratio and surface-wave excitations are consistent with effective rigid-body rotation. Rotation rates of up to 94% of the centrifugal limit are inferred. A threshold in the normal cloud's rotation is observed for the intrinsic nucleation of the first vortex. The threshold value lies below the prediction for a nucleation mechanism involving the excitation of surface waves of the condensate.