Showing papers on "Nucleation published in 2007"

Synthesis of monodisperse spherical nanocrystals.

Abstract: Much progress has been made over the past ten years on the synthesis of monodisperse spherical nanocrystals. Mechanistic studies have shown that monodisperse nanocrystals are produced when the burst of nucleation that enables separation of the nucleation and growth processes is combined with the subsequent diffusion-controlled growth process through which the crystal size is determined. Several chemical methods have been used to synthesize uniform nanocrystals of metals, metal oxides, and metal chalcogenides. Monodisperse nanocrystals of CdSe, Co, and other materials have been generated in surfactant solution by nucleation induced at high temperature, and subsequent aging and size selection. Monodisperse nanocrystals of many metals and metal oxides, including magnetic ferrites, have been synthesized directly by thermal decomposition of metal-surfactant complexes prepared from the metal precursors and surfactants. Nonhydrolytic sol-gel reactions have been used to synthesize various transition-metal-oxide nanocrystals. Monodisperse gold nanocrystals have been obtained from polydisperse samples by digestive-ripening processes. Uniform-sized nanocrystals of gold, silver, platinum, and palladium have been synthesized by polyol processes in which metal salts are reduced by alcohols in the presence of appropriate surfactants.

Nucleation of protein fibrillation by nanoparticles

Abstract: Nanoparticles present enormous surface areas and are found to enhance the rate of protein fibrillation by decreasing the lag time for nucleation. Protein fibrillation is involved in many human diseases, including Alzheimer's, Creutzfeld-Jacob disease, and dialysis-related amyloidosis. Fibril formation occurs by nucleation-dependent kinetics, wherein formation of a critical nucleus is the key rate-determining step, after which fibrillation proceeds rapidly. We show that nanoparticles (copolymer particles, cerium oxide particles, quantum dots, and carbon nanotubes) enhance the probability of appearance of a critical nucleus for nucleation of protein fibrils from human beta(2)-microglobulin. The observed shorter lag (nucleation) phase depends on the amount and nature of particle surface. There is an exchange of protein between solution and nanoparticle surface, and beta(2)-microglobulin forms multiple layers on the particle surface, providing a locally increased protein concentration promoting oligomer formation. This and the shortened lag phase suggest a mechanism involving surface-assisted nucleation that may increase the risk for toxic cluster and amyloid formation. It also opens the door to new routes for the controlled self-assembly of proteins and peptides into novel nanomaterials.

Why does wurtzite form in nanowires of III-V zinc blende semiconductors?

Abstract: We develop a nucleation-based model to explain the formation of the wurtzite phase during the catalyzed growth of freestanding nanowires of zinc blende semiconductors. We show that in vapor-liquid-solid nanowire growth, nucleation generally occurs preferentially at the triple phase line. This entails major differences between zinc blende and wurtzite nuclei. Depending on the pertinent interface energies, wurtzite nucleation is favored at high liquid supersaturation. This explains our systematic observation of zinc blende during early growth of gold-catalyzed GaAs nanowires.

In situ Observations of Catalyst Dynamics during Surface-Bound Carbon Nanotube Nucleation

Abstract: We present atomic-scale, video-rate environmental transmission electron microscopy and in situ time-resolved X-ray photoelectron spectroscopy of surface-bound catalytic chemical vapor deposition of single-walled carbon nanotubes and nanofibers. We observe that transition metal catalyst nanoparticles on SiOx support show crystalline lattice fringe contrast and high deformability before and during nanotube formation. A single-walled carbon nanotube nucleates by lift-off of a carbon cap. Cap stabilization and nanotube growth involve the dynamic reshaping of the catalyst nanocrystal itself. For a carbon nanofiber, the graphene layer stacking is determined by the successive elongation and contraction of the catalyst nanoparticle at its tip.

Toward direct measurement of atmospheric nucleation.

Abstract: Atmospheric aerosol formation is known to occur almost all over the world, and the importance of these particles to climate and air quality has been recognized. Although almost all of the processes driving aerosol formation take place below a particle diameter of 3 nanometers, observations cover only larger particles. We introduce an instrumental setup to measure atmospheric concentrations of both neutral and charged nanometer-sized clusters. By applying the instruments in the field, we come to three important conclusions: (i) A pool of numerous neutral clusters in the sub–3 nanometer size range is continuously present; (ii) the processes initiating atmospheric aerosol formation start from particle sizes of ∼1.5 nanometers; and (iii) neutral nucleation dominates over the ion-induced mechanism, at least in boreal forest conditions.

Spinodal Decomposition and Nucleation and Growth as a Means to Bulk Nanostructured Thermoelectrics: Enhanced Performance in Pb1-xSnxTe-PbS

Abstract: The solid-state transformation phenomena of spinodal decomposition and nucleation and growth are presented as tools to create nanostructured thermoelectric materials with very low thermal conductivity and greatly enhanced figure of merit. The systems (PbTe)1-x(PbS)x and (Pb0.95Sn0.05Te)1-x(PbS)x are not solid solutions but phase separate into PbTe-rich and PbS-rich regions to produce coherent nanoscale heterogeneities that severely depress the lattice thermal conductivity. For x > ∼0.03 the materials are ordered on three submicrometer length scales. Transmission electron microscopy reveals both spinodal decomposition and nucleation and growth phenomena the relative magnitude of which varies with x. We show that the (Pb0.95Sn0.05Te)1-x(PbS)x system, despite its nanostructured nature, maintains a high electron mobility (>100 cm2/V·s at 700 K). At x ∼ 0.08 the material achieves a very low room-temperature lattice thermal conductivity of ∼0.4 W/m·K. This value is only 28% of the PbTe lattice thermal conductiv...

Kinetics of Monodisperse Iron Oxide Nanocrystal Formation by “Heating-Up” Process

Abstract: We studied the kinetics of the formation of iron oxide nanocrystals obtained from the solution-phase thermal decomposition of iron−oleate complex via the “heating-up” process. To obtain detailed information on the thermal decomposition process and the formation of iron oxide nanocrystals in the solution, we performed a thermogravimetric-mass spectrometric analysis (TG-MS) and in-situ magnetic measurements using SQUID. The TG-MS results showed that iron−oleate complex was decomposed at around 320 °C. The in-situ SQUID data revealed that the thermal decomposition of iron−oleate complex generates intermediate species, which seem to act as monomers for the iron oxide nanocrystals. Extensive studies on the nucleation and growth process using size exclusion chromatography, the crystallization yield data, and TEM showed that the sudden increase in the number concentration of the nanocrystals (burst of nucleation) is followed by the rapid narrowing of the size distribution (size focusing). We constructed a theore...

Nucleation : theory and applications to protein solutions and colloidal suspensions

Abstract: The status of our understanding of nucleation is reviewed. Both general aspects of nucleation and those specific to protein solutions and colloidal suspensions are considered. We conclude that although we have what we believe is a quite good understanding of homogeneous nucleation in one simple system, hard-sphere colloids, in other systems there are still basic questions that are unanswered. For example, for even the most studied protein, lysozyme, there is an ongoing debate about whether the observed nucleation is homogeneous or heterogeneous. We review theoretical and simulation work on both homogeneous and heterogeneous nucleation. As heterogeneous nucleation appears to be much more common than homogeneous nucleation, and as earlier reviews have tended to focus more on homogeneous nucleation, we place particular emphasis on heterogeneous nucleation.

The Nature of Water Nucleation Sites on TiO2(110) Surfaces Revealed by Ambient Pressure X-ray Photoelectron Spectroscopy

Abstract: X-ray photoelectron spectroscopy at ambient conditions of pressure (up to 1.5 Torr) and temperature (265K

In situ solid state 11B MAS-NMR studies of the thermal decomposition of ammonia borane: mechanistic studies of the hydrogen release pathways from a solid state hydrogen storage material

Abstract: The mechanism of hydrogen release from solid state ammonia borane (AB) has been investigated via in situ solid state 11B and 11B{1H} MAS-NMR techniques in external fields of 7.1 T and 18.8 T at a decomposition temperature of 88 °C, well below the reported melting point. The decomposition of AB is well described by an induction, nucleation and growth mechanistic pathway. During the induction period, little hydrogen is released from AB; however, a new species identified as a mobile phase of AB is observed in the 11B NMR spectra. Subsequent to induction, at reaction times when hydrogen is initially being released, three additional species are observed: the diammoniate of diborane (DADB), [(NH3)2BH2]+[BH4]−, and two BH2N2 species believed to be the linear (NH3BH2NH2BH3) and cyclic dimer (NH2BH2)2 of aminoborane. At longer reaction times the sharper features are replaced by broad, structureless peaks of a complex polymeric aminoborane (PAB) containing both BH2N2 and BHN3 species. The following mechanistic model for the induction, nucleation and growth for AB decomposition leading to formation of hydrogen is proposed: (i) an induction period that yields a mobile phase of AB caused by disruption of the dihydrogen bonds; (ii) nucleation that yields reactive DADB from the mobile AB; and (iii) growth that includes a bimolecular reaction between DADB and AB to release the stored hydrogen.

Modeling of Formation of Gold Nanoparticles by Citrate Method

Abstract: Properties of nanoparticles are size dependent, and a model to predict particle size is of importance. Gold nanoparticles are commonly synthesized by reducing tetrachloroauric acid with trisodium citrate, a method pioneered by Turkevich et al (Discuss. Faraday Soc. 1951, 11, 55). Data from several investigators that used this method show that when the ratio of initial concentrations of citrate to gold is varied from 0.4 to similar to 2, the final mean size of the particles formed varies by a factor of 7, while subsequent increases in the ratio hardly have any effect on the size. In this paper, a model is developed to explain this widely varying dependence. The steps that lead to the formation of particles are as follows: reduction of Au3+ in solution, disproportionation of Au+ to gold atoms and their nucleation, growth by disproportionation on particle surface, and coagulation. Oxidation of citrate results in the formation of dicarboxy acetone, which aids nucleation but also decomposes into side products. A detailed kinetic model is developed on the basis of these steps and is combined with population balance to predict particle-size distribution. The model shows that, unlike the usual balance between nucleation and growth that determines the particle size, it is the balance between rate of nucleation and degradation of dicarboxy acetone that determines the particle size in the citrate process. It is this feature that is able to explain the unusual dependence of the mean particle size on the ratio of citrate to gold salt concentration. It is also found that coagulation plays an important role in determining the particle size at high concentrations of citrate.

The Nature of Water Nucleation Sites on Tio (2) (110) Surfaces Revealed By Ambient Pressure X-Ray Photoelectron Spectroscopy

Abstract: X-ray photoelectron spectroscopy at ambient conditions of pressure (up to 1.5 Torr) and temperature (265 K < T < 800 K) was used to study the adsorption of water on rutile TiO{sub 2}(110) under conditions of thermodynamic equilibrium. It was found that OH groups in bridging positions, normally present in small amounts due to residual O-vacancies, act as nucleation sites for subsequent water adsorption. The adsorption enthalpy of water binding to these sites is {approx}70 kJ/mol, much stronger than that in the bulk liquid (45 kJ/mol). A model is proposed that relates the structure of the oxide surface to its hydrophilic character.

Nucleation and growth mechanism of ferroelectric domain-wall motion

Abstract: The motion of domain walls is critical to many applications involving ferroelectric materials, such as fast high-density non-volatile random access memory. In memories of this sort, storing a data bit means increasing the size of one polar region at the expense of another, and hence the movement of a domain wall separating these regions. Experimental measurements of domain growth rates in the well-established ferroelectrics PbTiO3 and BaTiO3 have been performed, but the development of new materials has been hampered by a lack of microscopic understanding of how domain walls move. Despite some success in interpreting domain-wall motion in terms of classical nucleation and growth models, these models were formulated without insight from first-principles-based calculations, and they portray a picture of a large, triangular nucleus that leads to unrealistically large depolarization and nucleation energies. Here we use atomistic molecular dynamics and coarse-grained Monte Carlo simulations to analyse these processes, and demonstrate that the prevailing models are incorrect. Our multi-scale simulations reproduce experimental domain growth rates in PbTiO3 and reveal small, square critical nuclei with a diffuse interface. A simple analytic model is also proposed, relating bulk polarization and gradient energies to wall nucleation and growth, and thus rationalizing all experimental rate measurements in PbTiO3 and BaTiO3.

Highly Conductive Coaxial SnO2−In2O3 Heterostructured Nanowires for Li Ion Battery Electrodes

Abstract: Novel SnO(2)-In(2)O(3) heterostructured nanowires were produced via a thermal evaporation method, and their possible nucleation/growth mechanism is proposed. We found that the electronic conductivity of the individual SnO(2)-In(2)O(3) nanowires was 2 orders of magnitude better than that of the pure SnO(2) nanowires, due to the formation of Sn-doped In(2)O(3) caused by the incorporation of Sn into the In(2)O(3) lattice during the nucleation and growth of the In(2)O(3) shell nanostructures. This provides the SnO(2)-In(2)O(3) nanowires with an outstanding lithium storage capacity, making them suitable for promising Li ion battery electrodes.

Synthesis of nanocrystals and morphology control of hydrothermally prepared LiFePO4

Abstract: Lithium transition metal phosphate olivines such as LiFePO4 have been recognized as very promising electrodes for lithium-ion batteries because of their energy storage capacity combined with electrochemical and thermal stability. A key issue in these materials is to determine the synthetic conditions for optimum control of particle size and morphology, and ideally to find those that result in nanocrystalline products. Here, we report a full study that examines the synthesis of the material via hydrothermal methods to give single phase nanocrystalline materials for LiFePO4 and LiMnPO4, and their solid solutions with Mg2+. A reaction mechanism is proposed. Variation of the synthesis parameters showed that increasing reactant concentration strongly favours the formation of nanocrystalline products, but as less defect-free materials are formed at temperatures above 180 °C, and ideally above 200 °C, control of nucleation and growth can (and should) also be effected using polymeric or surfactant additives. The nature of the precursor and carbon-containing additives in the autoclave also have profound effects on morphology and the electrochemical properties.

Nucleation and Growth of GaN Nanowires on Si(111) Performed by Molecular Beam Epitaxy

Abstract: GaN nanowires (NWs) have been grown on Si(111) substrates by plasma-assisted molecular beam epitaxy (PAMBE). The nucleation process of GaN-NWs has been investigated in terms of nucleation density and wire evolution with time for a given set of growth parameters. The wire density increases rapidly with time and then saturates. The growth period until the nucleation of new nanowires is terminated can be defined as the nucleation stage. Coalescence of closely spaced nanowires reduces the density for long deposition times. The average size of the well-nucleated NWs shows linear time dependence in the nucleation stage. High-resolution transmission electron microscopy measurements of alternating GaN and AlN layers give valuable information about the length and radial growth rates for GaN and AlN in NWs.

Evidence of the existence of the low-density liquid phase in supercooled, confined water

Abstract: By confining water in a nanoporous structure so narrow that the liquid could not freeze, it is possible to study properties of this previously undescribed system well below its homogeneous nucleation temperature TH = 231 K. Using this trick, we were able to study, by means of a Fourier transform infrared spectroscopy, vibrational spectra (HOH bending and OH-stretching modes) of deeply supercooled water in the temperature range 183 < T < 273 K. We observed, upon decreasing temperature, the building up of a new population of hydrogen-bonded oscillators centered around 3,120 cm(-1), the contribution of which progressively dominates the spectra as one enters into the deeply supercooled regime. We determined that the fractional weight of this spectral component reaches 50% just at the temperature, TL approximately 225 K, where the confined water shows a fragile-to-strong dynamic cross-over phenomenon [Ito, K., Moynihan, C. T., Angell, C. A. (1999) Nature 398:492-494]. Furthermore, the fact that the corresponding OH stretching spectral peak position of the low-density-amorphous solid water occurs exactly at 3,120 cm(-1) [Sivakumar, T. C., Rice, S. A., Sceats, M. G. (1978) J. Chem. Phys. 69:3468-3476.] strongly suggests that these oscillators originate from existence of the low-density-liquid phase derived from the occurrence of the first-order liquid-liquid (LL) phase transition and the associated LL critical point in supercooled water proposed earlier by a computer molecular dynamics simulation [Poole, P. H., Sciortino, F., Essmann, U., Stanley, H. E. (1992) Nature 360:324-328].

Efficiency of immersion mode ice nucleation on surrogates of mineral dust

Abstract: A differential scanning calorimeter (DSC) was used to explore heterogeneous ice nucleation of emulsified aqueous suspensions of two Arizona test dust (ATD) samples with particle diameters of nominally 0–3 and 0–7 μm, respectively. Aqueous suspensions with ATD concentrations of 0.01–20 wt% have been investigated. The DSC thermograms exhibit a homogeneous and a heterogeneous freezing peak whose intensity ratios vary with the ATD concentration in the aqueous suspensions. Homogeneous freezing temperatures are in good agreement with recent measurements by other techniques. Depending on ATD concentration, heterogeneous ice nucleation occurred at temperatures as high as 256 K or down to the onset of homogeneous ice nucleation (237 K). For ATD-induced ice formation Classical Nucleation Theory (CNT) offers a suitable framework to parameterize nucleation rates as a function of temperature, experimentally determined ATD size, and emulsion droplet volume distributions. The latter two quantities serve to estimate the total heterogeneous surface area present in a droplet, whereas the suitability of an individual heterogeneous site to trigger nucleation is described by the compatibility function (or contact angle) in CNT. The intensity ratio of homogeneous to heterogeneous freezing peaks is in good agreement with the assumption that the ATD particles are randomly distributed amongst the emulsion droplets. The observed dependence of the heterogeneous freezing temperatures on ATD concentrations cannot be described by assuming a constant contact angle for all ATD particles, but requires the ice nucleation efficiency of ATD particles to be (log)normally distributed amongst the particles. Best quantitative agreement is reached when explicitly assuming that high-compatibility sites are rare and that therefore larger particles have on average more and better active sites than smaller ones. This analysis suggests that a particle has to have a diameter of at least 0.1 μm to exhibit on average one active site.

Size- and Phase-Controlled Synthesis of Monodisperse NaYF4:Yb,Er Nanocrystals from a Unique Delayed Nucleation Pathway Monitored with Upconversion Spectroscopy

Abstract: Monodisperse α-NaYF4:Yb,Er and β-NaYF4:Yb,Er nanocrystals with controlled size, chemical composition, and surface state were synthesized from trifluoroacetate precursors in hot surfactant solutions via a unique delayed nucleation pathway. The growth mechanisms of both α- and β-phase nanocrystals and the underlying α→β phase transition process were uncovered by upconversion (UC) spectroscopy, transmission electron microscopy, and X-ray diffraction techniques. The UC emission was sensitive to the growth process of the NaYF4:Yb,Er nanocrystals; that is, the UC intensity is sensitive to the nucleation and phase transition process, and the ratio of green to red emission is also sensitive to the crystallite size and phase, which makes it easy to distinguish various nanocrystal growth stages and phase transition modes with UC spectroscopy. Differently sized monodisperse α-NaYF4:Yb,Er nanopolyhedra (5−14 nm) were readily obtained via only prolonging the reaction time. During the reaction, four consecutive nanocry...

A New Approach to Modeling the Nucleation and Growth Kinetics of Tricalcium Silicate Hydration

Abstract: The hydration kinetics of tricalcium silicate (C3S), the main constituent of portland cement, were analyzed with a mathematical “boundary nucleation” model in which nucleation of the hydration product occurs only on internal boundaries corresponding to the C3S particle surfaces. This model more closely approximates the C3S hydration process than does the widely used Avrami nucleation and growth model. In particular, the boundary model accounts for the important effect of the C3S powder surface area on the hydration kinetics. Both models were applied to isothermal calorimetry data from hydrating C3S pastes in the temperature range of 10°–40°C. The boundary nucleation model provides a better fit to the early hydration rate peak than does the Avrami model, despite having one less varying parameter. The nucleation rate (per unit area) and the linear growth rate of the hydration product were calculated from the fitted values of the rate constants and the independently measured powder surface area. The growth rate follows a simple Arrhenius temperature dependence with a constant activation energy of 31.2 kJ/mol, while the activation energy associated with the nucleation rate increases with increasing temperature. The start of the nucleation and growth process coincides with the time of initial mixing, indicating that the initial slow reaction period known as the “induction period” is not a separate chemical process as has often been hypothesized.

Controlled synthesis and morphology dependent upconversion luminescence of NaYF4 : Yb, Er nanocrystals

Abstract: Size and morphology controlled NaYF4:Yb, Er nanocrystals were synthesized via the hydrothermal method. Polydentate ligands, such as EDTA and citrate, were used in the synthesis of cubic and hexagonal Yb3+, Er3+ codoped NaYF4 nanocrystals as a means of controlling the size and morphology of the nanocrystals. Subsequently, the particle size was found to be dependent on the nucleation rate, which, in turn, was governed by the reactant concentration, molar ratio and choice of ligand. The phase transformation from cubic to hexagonal was found to be sensitive to reaction time and reactant concentration. The upconversion photoluminescence of the nanocrystals demonstrated morphology dependence, which provides a means to characterize their crystalline quality and structure.

In situ nucleation of carbon nanotubes by the injection of carbon atoms into metal particles.

Abstract: The synthesis of carbon nanotubes (CNTs) of desired chiralities and diameters is one of the most important challenges in nanotube science and achieving such selectivity may require a detailed understanding of their growth mechanism. We report the formation of CNTs in an entirely condensed phase process that allows us, for the first time, to monitor the nucleation of a nanotube on the spherical surface of a metal particle. When multiwalled CNTs containing metal particle cores are irradiated with an electron beam, carbon from graphitic shells surrounding the metal particles is ingested into the body of the particle and subsequently emerges as single-walled nanotubes (SWNTs) or multiwalled nanotubes (MWNTs) inside the host nanotubes. These observations, at atomic resolution in an electron microscope, show that there is direct bonding between the tubes and the metal surface from which the tubes sprout and can be readily explained by bulk diffusion of carbon through the body of catalytic particles, with no evidence of surface diffusion.

Probing in situ the nucleation and growth of gold nanoparticles by small-angle X-ray scattering.

Abstract: We probe in situ by synchrotron SAXS/WAXS and UV−visible spectroscopy the nucleation and growth of gold nanoparticles. The use of a fast-mixing stopped-flow device enables the assesment of the whole particle formation process with a 200 ms time resolution. The number of particles, their size distribution, and the yield of the reaction is determined in real time through the quantitative analysis of the SAXS data on an absolute scale. Two ligands exhibit drastically different behaviors: when an alkanoic acid is used, a nucleation phase of 1 s is followed by a growth step whose rate is limited by the reaction of the monomers at the interface; on the other hand, when an alkylamine is used, the nucleation rate is increased by an order of magnitude, thus annealing growth by a lack of monomer and yielding R = 1 nm particles in 2 s, as compared with R = 3.7 nm in 12 s for the acid case.

Material decomposition mechanisms in femtosecond laser interactions with metals

Abstract: A numerical hydrodynamic study of femtosecond laser ablation is presented. A detailed analysis of material decomposition is performed using a thermodynamically complete equation of state with separate stable and metastable phase states and phase boundaries. The lifetime of the metastable liquid state is estimated based on the classical theory of homogeneous nucleation. In addition, mechanical fragmentation of the target material is controlled based on available criteria. As a result, several ablation mechanisms are observed. A major fraction of the ablated material, however, is found to originate from the metastable liquid region, which is decomposed either thermally in the vicinity of the critical point into a liquid-gas-mixture or mechanically at high strain rate and negative pressure into liquid droplets and chunks. The calculation results explain available experimental findings.