Decay of isolated surface features driven by the Gibbs-Thomson effect in analytic model and simulation

A theory based on the thermodynamic Gibbs-Thomson relation is presented which provides the framework for understanding the time evolution of isolated nanoscale features (i.e., islands and pits) on surfaces. Two limiting cases are predicted, in which either diffusion or interface transfer is the limiting process. These cases correspond to similar regimes considered in previous works addressing the Ostwald ripening of ensembles of features. A third possible limiting case is noted for the special geometry of "stacked" islands. In these limiting cases, isolated features are predicted to decay in size with a power law scaling in time: A is proportional to (t0-t)^n, where A is the area of the feature, t0 is the time at which the feature disappears, and n=2/3 or 1. The constant of proportionality is related to parameters describing both the kinetic and equilibrium properties of the surface. A continuous time Monte Carlo simulation is used to test the application of this theory to generic surfaces with atomic scale features. A new method is described to obtain macroscopic kinetic parameters describing interfaces in such simulations. Simulation and analytic theory are compared directly, using measurements of the simulation to determine the constants of the analytic theory. Agreement between the two is very good over a range of surface parameters, suggesting that the analytic theory properly captures the necessary physics. It is anticipated that the simulation will be useful in modeling complex surface geometries often seen in experiments on physical surfaces, for which application of the analytic model is not straightforward.Comment: RevTeX (with .bbl file), 25 pages, 7 figures from 9 Postscript files embedded using epsf. Submitted to Phys. Rev. B A few minor changes made on 9/24/9

Direct Observations of Oxygen-induced Platinum Nanoparticle Ripening Studied by In Situ TEM

This study addresses the sintering mechanism of Pt nanoparticles dispersed on a planar, amorphous Al2O3 support as a model system for a catalyst for automotive exhaust abatement. By means of in situ transmission electron microscopy (TEM), the model catalyst was monitored during the exposure to 10 mbar air at 650 degrees C. Time-resolved image series unequivocally reveal that the sintering of Pt nanoparticles was mediated by an Ostwald ripening process. A statistical analysis of an ensemble of Pt nanoparticles shows that the particle size distributions change shape from an initial Gaussian distribution via a log-normal distribution to a Lifshitz-Slyozov-Wagner (LSW) distribution. Furthermore, the time-dependency of the ensemble-averaged particle size and particle density is determined. A mean field kinetic description captures the main trends in the observed behavior. However, at the individual nanoparticle level, deviations from the model are observed suggesting in part that the local environment influences the atom exchange process

PRODUCTION OF CARBON PRODUCTS USING A COAL EXTRACTION PROCESS

This Department of Energy National Energy Technology Laboratory sponsored project developed carbon products, using mildly hydrogenated solvents to extract the organic portion of coal to create synthetic pitches, cokes, carbon foam and carbon fibers. The focus of this effort was on development of lower cost solvents, milder hydrogenation conditions and improved yield in order to enable practical production of these products. This technology is needed because of the long-term decline in production of domestic feedstocks such as petroleum pitch and coal tar pitch. Currently, carbon products represents a market of roughly 5 million tons domestically, and 19 million tons worldwide. Carbon products are mainly derived from feedstocks such as petroleum pitch and coal tar pitch. The domestic supply of petroleum pitch is declining because of the rising price of liquid fuels, which has caused US refineries to maximize liquid fuel production. As a consequence, the long term trend has a decline in production of petroleum pitch over the past 20 years. The production of coal tar pitch, as in the case of petroleum pitch, has likewise declined significantly over the past two decades. Coal tar pitch is a byproduct of metallurgical grade coke (metcoke) production. In this industry, modern metcoke facilities are recycling coal tar as fuel in order to enhance energy efficiency and minimize environmental emissions. Metcoke production itself is dependent upon the production requirements for domestic steel. Hence, several metcoke ovens have been decommissioned over the past two decades and have not been replaced. As a consequence sources of coal tar are being taken off line and are not being replaced. The long-term trend is a reduction in coal tar pitch production. Thus import of feedstocks, mainly from Eastern Europe and China, is on the rise despite the relatively large transportation cost. To reverse this trend, a new process for producing carbon products is needed. The process must be economically competitive with current processes, and yet be environmentally friendly as well. The solvent extraction process developed uses mild hydrogenation of low cost oils to create powerful solvents that can dissolve the organic portion of coal. The insoluble portion, consisting mainly of mineral matter and fixed carbon, is removed via centrifugation or filtration, leaving a liquid solution of coal chemicals and solvent. This solution can be further refined via distillation to meet specifications for products such as synthetic pitches, cokes, carbon foam and fibers. The most economical process recycles 85% of the solvent, which itself is obtained as a low-cost byproduct from industrial processes such as coal tar or petroleum refining. Alternatively, processes have been developed that can recycle 100% of the solvent, avoiding any need for products derived from petroleum or coal tar