Showing papers on "Nucleation published in 2013"

Vapour phase growth and grain boundary structure of molybdenum disulphide atomic layers

Abstract: Single-layered molybdenum disulphide with a direct bandgap is a promising two-dimensional material that goes beyond graphene for the next generation of nanoelectronics. Here, we report the controlled vapour phase synthesis of molybdenum disulphide atomic layers and elucidate a fundamental mechanism for the nucleation, growth, and grain boundary formation in its crystalline monolayers. Furthermore, a nucleation-controlled strategy is established to systematically promote the formation of large-area, single- and few-layered films. Using high-resolution electron microscopy imaging, the atomic structure and morphology of the grains and their boundaries in the polycrystalline molybdenum disulphide atomic layers are examined, and the primary mechanisms for grain boundary formation are evaluated. Grain boundaries consisting of 5- and 7- member rings are directly observed with atomic resolution, and their energy landscape is investigated via first-principles calculations. The uniformity in thickness, large grain sizes, and excellent electrical performance signify the high quality and scalable synthesis of the molybdenum disulphide atomic layers.

Vapor Phase Growth and Grain Boundary Structure of Molybdenum Disulfide Atomic Layers

Abstract: Single layered molybdenum disulfide with a direct bandgap is a promising two-dimensional material that goes beyond graphene for next generation nanoelectronics. Here, we report the controlled vapor phase synthesis of molybdenum disulfide atomic layers and elucidate a fundamental mechanism for the nucleation, growth, and grain boundary formation in its crystalline monolayers. Furthermore, a nucleation-controlled strategy is established to systematically promote the formation of large-area single- and few-layered films. The atomic structure and morphology of the grains and their boundaries in the polycrystalline molybdenum disulfide atomic layers are examined and first-principles calculations are applied to investigate their energy landscape. The electrical properties of the atomic layers are examined and the role of grain boundaries is evaluated. The uniformity in thickness, large grain sizes, and excellent electrical performance of these materials signify the high quality and scalable synthesis of the molybdenum disulfide atomic layers.

Proliferation of amyloid-β42 aggregates occurs through a secondary nucleation mechanism

Abstract: The generation of toxic oligomers during the aggregation of the amyloid-β (Aβ) peptide Aβ42 into amyloid fibrils and plaques has emerged as a central feature of the onset and progression of Alzheimer’s disease, but the molecular pathways that control pathological aggregation have proved challenging to identify. Here, we use a combination of kinetic studies, selective radiolabeling experiments, and cell viability assays to detect directly the rates of formation of both fibrils and oligomers and the resulting cytotoxic effects. Our results show that once a small but critical concentration of amyloid fibrils has accumulated, the toxic oligomeric species are predominantly formed from monomeric peptide molecules through a fibril-catalyzed secondary nucleation reaction, rather than through a classical mechanism of homogeneous primary nucleation. This catalytic mechanism couples together the growth of insoluble amyloid fibrils and the generation of diffusible oligomeric aggregates that are implicated as neurotoxic agents in Alzheimer’s disease. These results reveal that the aggregation of Aβ42 is promoted by a positive feedback loop that originates from the interactions between the monomeric and fibrillar forms of this peptide. Our findings bring together the main molecular species implicated in the Aβ aggregation cascade and suggest that perturbation of the secondary nucleation pathway identified in this study could be an effective strategy to control the proliferation of neurotoxic Aβ42 oligomers.

Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere

Abstract: Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei(1). Aerosols can cause a net cooling of climate by scattering sun ...

Ion-association complexes unite classical and non-classical theories for the biomimetic nucleation of calcium phosphate

Abstract: Despite its importance in many industrial, geological and biological processes, the mechanism of crystallization from supersaturated solutions remains a matter of debate. Recent discoveries show that in many solution systems nanometre-sized structural units are already present before nucleation. Still little is known about the structure and role of these so-called pre-nucleation clusters. Here we present a combination of in situ investigations, which show that for the crystallization of calcium phosphate these nanometre-sized units are in fact calcium triphosphate complexes. Under conditions in which apatite forms from an amorphous calcium phosphate precursor, these complexes aggregate and take up an extra calcium ion to form amorphous calcium phosphate, which is a fractal of Ca(2)(HPO(4))(3)(2-) clusters. The calcium triphosphate complex also forms the basis of the crystal structure of octacalcium phosphate and apatite. Finally, we demonstrate how the existence of these complexes lowers the energy barrier to nucleation and unites classical and non-classical nucleation theories.

Nucleation and growth of magnetite from solution.

Abstract: The formation of crystalline materials from solution is usually described by the nucleation and growth theory, where atoms or molecules are assumed to assemble directly from solution. For numerous systems, the formation of the thermodynamically stable crystalline phase is additionally preceded by metastable intermediates . More complex pathways have recently been proposed, such as aggregational processes of nanoparticle precursors or pre-nucleation clusters, which seem to contradict the classical theory. Here we show by cryogenic transmission electron microscopy that the nucleation and growth of magnetite-a magnetic iron oxide with numerous bio- and nanotechnological applications-proceed through rapid agglomeration of nanometric primary particles and that in contrast to the nucleation of other minerals, no intermediate amorphous bulk precursor phase is involved. We also demonstrate that these observations can be described within the framework of classical nucleation theory.

Microscopic Evidence for Liquid-Liquid Separation in Supersaturated CaCO3 Solutions

Abstract: Recent experimental observations of the onset of calcium carbonate (CaCO3) mineralization suggest the emergence of a population of clusters that are stable rather than unstable as predicted by classical nucleation theory. This study uses molecular dynamics simulations to probe the structure, dynamics, and energetics of hydrated CaCO3 clusters and lattice gas simulations to explore the behavior of cluster populations before nucleation. Our results predict formation of a dense liquid phase through liquid-liquid separation within the concentration range in which clusters are observed. Coalescence and solidification of nanoscale droplets results in formation of a solid phase, the structure of which is consistent with amorphous CaCO3. The presence of a liquid-liquid binodal enables a diverse set of experimental observations to be reconciled within the context of established phase-separation mechanisms.

Nucleation of Organic Crystals—A Molecular Perspective

Abstract: The outcome of synthetic procedures for crystalline organic materials strongly depends on the first steps along the molecular self-assembly pathway, a process we know as crystal nucleation. New experimental techniques and computational methodologies have spurred significant interest in understanding the detailed molecular mechanisms by which nuclei form and develop into macroscopic crystals. Although classical nucleation theory (CNT) has served well in describing the kinetics of the processes involved, new proposed nucleation mechanisms are additionally concerned with the evolution of structure and the competing nature of crystallization in polymorphic systems. In this Review, we explore the extent to which CNT and nucleation rate measurements can yield molecular-scale information on this process and summarize current knowledge relating to molecular self-assembly in nucleating systems.

The Vitreous State: Thermodynamics, Structure, Rheology, and Crystallization

Abstract: Introduction.- States of Aggregation, Thermodynamic Phases, and the Vitreous State.- Non-Equilibrium Thermodynamics and the Kinetics of Glass Transition and Stabilization.- General Approaches to the Description of the Structure of Glasses.- Statistical Physics of Under-Cooled Melts and Glasses.- Nucleation in Glass-Forming Systems.- Catalyzed Crystallization of Glass-Forming Melts.- Theory of Crystal Growth and Dissolution in Under-cooled Melts.- Growth of Clusters. Ostwald's Rule of Stages.- Kinetics of Overall Crystallization.- Liquid Phase Separation in Glass-Forming Melts.- Rheology of Glass-Forming Melts.- Concluding Remarks.

Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

Abstract: Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiala boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions.

The Filler Effect: The Influence of Filler Content and Surface Area on Cementitious Reaction Rates

Abstract: Finely ground mineral powders are known to accelerate cement hydration rates. This “filler effect” has been attributed to the effects of dilution (w/c increase) when the cement content is reduced or to the provision of additional surface area by fine powders. The latter contribution (i.e., surface area increase) is speculated to provide additional sites for the nucleation of the hydration products, which accelerates reactions. Through extensive experimentation and simulation this study describes the influence of surface area and mineral type (e.g., quartz or limestone) on cement reaction rates. Simulations using a boundary nucleation and growth (BNG) model and a multiphase reaction ensemble (MRE) indicate that the extent of the acceleration is linked to the: (1) magnitude of surface area increase and (2a) capacity of the filler's surface to offer favorable nucleation sites for hydration products. Other simulations using a kinetic cellular automaton model (HydratiCA) suggest that accelerations are linked to: (2b) the interfacial properties of the filler that alters (increases or decreases) its tendency to serve as a nucleant, and (3) the chemical composition of the filler and the tendency for its dissociated ions to participate in exchange reactions with the calcium silicate hydrate product. The simulations are correlated with accelerations observed using isothermal calorimetry when fillers partially replace cement. The research correlates and unifies the fundamental parameters that drive the filler effect and provides a mechanistic understanding of the influence of filler agents on cementitious reaction rates.

Inhibition of ice nucleation by slippery liquid-infused porous surfaces (SLIPS)

Abstract: Ice repellent coatings have been studied and keenly sought after for many years, where any advances in the durability of such coatings will result in huge energy savings across many fields. Progress in creating anti-ice and anti-frost surfaces has been particularly rapid since the discovery and development of slippery, liquid infused porous surfaces (SLIPS). Here we use SLIPS-coated differential scanning calorimeter (DSC) pans to investigate the effects of the surface modification on the nucleation of supercooled water. This investigation is inherently different from previous studies which looked at the adhesion of ice to SLIPS surfaces, or the formation of ice under high humidity conditions. Given the stochastic nature of nucleation of ice from supercooled water, multiple runs on the same sample are needed to determine if a given surface coating has a real and statistically significant effect on the nucleation temperature. We have cycled supercooling to freezing and then thawing of deionized water in hydrophilic (untreated aluminum), hydrophobic, superhydrophobic, and SLIPS-treated DSC pans multiple times to determine the effects of surface treatment on the nucleation and subsequent growth of ice. We find that SLIPS coatings lower the nucleation temperature of supercooled water in contact with statistical significance and show no deterioration or change in the coating performance even after 150 freeze–thaw cycles.

Mechanisms of Morphological Evolution of Li2O2 Particles during Electrochemical Growth

Abstract: Li-O2 batteries, wherein solid Li2O2 is formed at the porous air cathode during discharge, are candidates for high gravimetric energy (3212 Wh/kgLi2O2) storage for electric vehicles. Understanding and controlling the nucleation and morphological evolution of Li2O2 particles upon discharge is key to achieving high volumetric energy densities. Scanning and transmission electron microscopy were used to characterize the discharge product formed in Li-O2 batteries on electrodes composed of carpets of aligned carbon nanotubes. At low discharge rates, Li2O2 particles form first as stacked thin plates, ∼10 nm in thickness, which spontaneously splay so that secondary nucleation of new plates eventually leads to the development of a particle with a toroidal shape. Li2O2 crystallites have large (001) crystal faces consistent with the theoretical Wulff shape and appear to grow by a layer-by-layer mechanism. In contrast, at high discharge rates, copious nucleation of equiaxed Li2O2 particles precedes growth of discs and toroids.

Chemical Solution Deposition of Functional Oxide Thin Films

Abstract: Introduction.-Solution Chemistry Simple alkoxide based precursor systems Carboxylate based precursor systems Single-source precursors Acqueos Precursor Systems Solution Synthesis Strategies.-Analytical Methods Introduction Thermal Analysis NMR Sepctroscopy EXAFS Other Methods (XRM, SEM,TEM scattering methods at nanocrystalline films) Spin-Coating Dip Coating Inkjet Printing and Other Direct Writing Methods(dip point and imprint techniques) Chemical Bath Deposition Polymer Assisted Deposition.-Processing and Crystallization Thermodynamics and Heating Processes Material Systems Dominated by Heterogeneous Nucleation Material Systems Dominated by Homogeneous Nucleation Low Temperature Processing Epitaxial Films Powder Assisted Film Fabrication UV-and E-Beam Direct Patterning of Photosensitive CSD Films Template Controlled Growth.-Functions and Applications Introduction Integrated Capacitors Base Metal Electrodes Polar Oxide Films for MEMS Applications Conducting Films and Electrodes Transparent conducting oxides Superconducting Films Porous Films for Gas Sensors Luminescent Fims.-Appendix Synthesis for Standard material Systems.

Homogeneous ice nucleation at moderate supercooling from molecular simulation.

Abstract: Among all of the freezing transitions, that of water into ice is probably the most relevant to biology, physics, geology, or atmospheric science. In this work, we investigate homogeneous ice nucleation by means of computer simulations. We evaluate the size of the critical cluster and the nucleation rate for temperatures ranging between 15 and 35 K below melting. We use the TIP4P/2005 and the TIP4P/ice water models. Both give similar results when compared at the same temperature difference with the model’s melting temperature. The size of the critical cluster varies from ∼8000 molecules (radius = 4 nm) at 15 K below melting to ∼600 molecules (radius = 1.7 nm) at 35 K below melting. We use Classical Nucleation Theory (CNT) to estimate the ice–water interfacial free energy and the nucleation free-energy barrier. We obtain an interfacial free energy of 29(3) mN/m from an extrapolation of our results to the melting temperature. This value is in good agreement both with experimental measurements and with previo...

Growth of Adlayer Graphene on Cu Studied by Carbon Isotope Labeling

Abstract: The growth of bilayer and multilayer graphene on copper foils was studied by isotopic labeling of the methane precursor. Isotope-labeled graphene films were characterized by micro-Raman mapping and time-of-flight secondary ion mass spectrometry. Our investigation shows that during growth at high temperature, the adlayers formed simultaneously and beneath the top, continuous layer of graphene and the Cu substrate. Additionally, the adlayers share the same nucleation center and all adlayers nucleating in one place have the same edge termination. These results suggest that adlayer growth proceeds by catalytic decomposition of methane (or CHx, x < 4) trapped in a “nano-chemical vapor deposition” chamber between the first layer and the substrate. On the basis of these results, submillimeter bilayer graphene was synthesized by applying a much lower growth rate.

HfO2 on MoS2 by Atomic Layer Deposition: Adsorption Mechanisms and Thickness Scalability

Abstract: We report our investigation of the atomic layer deposition (ALD) of HfO2 on the MoS2 surface. In contrast to previous reports of conformal growth on MoS2 flakes, we find that ALD on MoS2 bulk material is not uniform. No covalent bonding between the HfO2 and MoS2 is detected. We highlight that individual precursors do not permanently adsorb on the clean MoS2 surface but that organic and solvent residues can dramatically change ALD nucleation behavior. We then posit that prior reports of conformal ALD deposition on MoS2 flakes that had been exposed to such organics and solvents likely rely on contamination-mediated nucleation. These results highlight that surface functionalization will be required before controllable and low defect density high-κ/MoS2 interfaces will be realized. The band structure of the HfO2/MoS2 system is experimentally derived with valence and conduction band offsets found to be 2.67 and 2.09 eV, respectively.

Near-ideal theoretical strength in gold nanowires containing angstrom scale twins

Abstract: Low-dimensional materials containing defects such as twin boundaries are known to fail well below their theoretical strength due to surface imperfections. Here, Wang et al. observe strengths close to the ideal limit in gold nanowires with angstrom scale twins, where homogeneous dislocation nucleation controls deformation.

Turning off hydrogen to realize seeded growth of subcentimeter single-crystal graphene grains on copper.

Abstract: Subcentimeter single-crystalline graphene grains, with diameter up to 5.9 mm, have been successfully synthesized by tuning the nucleation density during atmospheric pressure chemical vapor deposition. Morphology studies show the existence of a single large nanoparticle (>∼20 nm in diameter) at the geometric center of those graphene grains. Similar size particles were produced by slightly oxidizing the copper surface to obtain oxide nanoparticles in Ar-only environments, followed by reduction into large copper nanoparticles under H2/Ar environment, and are thus explained to be the main constituent nuclei for graphene growth. On this basis, we were able to control the nanoparticle density by adjusting the degree of oxidation and hydrogen annealing duration, thereby controlling nucleation density and consequently controlling graphene grain sizes. In addition, we found that hydrogen plays dual roles on copper morphology during the whole growth process, that is, removing surface irregularities and, at the same...

Nucleation and growth of thin films of rod-like conjugated molecules.

Abstract: Thin films formed from small molecules are rapidly gaining importance in different technological fields. To explain their growth, methods developed for zero-dimensional atoms as the film-forming particles are applied. However, in organic thin-film growth the dimensionality of the building blocks comes into play. Using the special case of the model molecule para-Sexiphenyl, we will emphasize the challenges that arise from the anisotropic and one-dimensional nature of building blocks. Differences or common features with other rod-like molecules will be discussed. The typical morphologies encountered for this group of molecules and the relevant growth modes will be investigated. Special attention is given to the transition between a flat-lying and upright orientation of the building blocks during nucleation. We will further discuss methods to control the molecular orientation and describe the involved diffusion processes qualitatively and quantitatively.

Modelling amyloid fibril formation kinetics: mechanisms of nucleation and growth.

Abstract: Amyloid and amyloid-like fibrils are self-assembling protein nanostructures, of interest for their robust material properties and inherent biological compatibility as well as their putative role in a number of debilitating mammalian disorders. Understanding fibril formation is essential to the development of strategies to control, manipulate or prevent fibril growth. As such, this area of research has attracted significant attention over the last half century. This review describes a number of different models that have been formulated to describe the kinetics of fibril assembly. We describe the macroscopic implications of mechanisms in which secondary processes such as secondary nucleation, fragmentation or branching dominate the assembly pathway, compared to mechanisms dominated by the influence of primary nucleation. We further describe how experimental data can be analysed with respect to the predictions of kinetic models.

Immersion Condensation on Oil-Infused Heterogeneous Surfaces for Enhanced Heat Transfer

Abstract: Enhancing condensation heat transfer is important for broad applications from power generation to water harvesting systems Significant efforts have focused on easy removal of the condensate, yet the other desired properties of low contact angles and high nucleation densities for high heat transfer performance have been typically neglected In this work, we demonstrate immersion condensation on oil-infused micro and nanostructured surfaces with heterogeneous coatings, where water droplets nucleate immersed within the oil The combination of surface energy heterogeneity, reduced oil-water interfacial energy, and surface structuring enabled drastically increased nucleation densities while maintaining easy condensate removal and low contact angles Accordingly, on oil-infused heterogeneous nanostructured copper oxide surfaces, we demonstrated approximately 100% increase in heat transfer coefficient compared to state-of-the-art dropwise condensation surfaces in the presence of non-condensable gases This work offers a distinct approach utilizing surface chemistry and structuring together with liquid-infusion for enhanced condensation heat transfer

van der Waals epitaxial growth of graphene on sapphire by chemical vapor deposition without a metal catalyst.

Abstract: van der Waals epitaxial growth of graphene on c-plane (0001) sapphire by CVD without a metal catalyst is presented. The effects of CH4 partial pressure, growth temperature, and H2/CH4 ratio were investigated and growth conditions optimized. The formation of monolayer graphene was shown by Raman spectroscopy, optical transmission, grazing incidence X-ray diffraction (GIXRD), and low voltage transmission electron microscopy (LVTEM). Electrical analysis revealed that a room temperature Hall mobility above 2000 cm2/V·s was achieved, and the mobility and carrier type were correlated to growth conditions. Both GIXRD and LVTEM studies confirm a dominant crystal orientation (principally graphene [10–10] || sapphire [11–20]) for about 80–90% of the material concomitant with epitaxial growth. The initial phase of the nucleation and the lateral growth from the nucleation seeds were observed using atomic force microscopy. The initial nuclei density was ∼24 μm–2, and a lateral growth rate of ∼82 nm/min was determined....