No Arabic abstract
We study Ostwald ripening of two-dimensional adatom and advacancy islands on a crystal surface by means of kinetic Monte Carlo simulations. At large bond energies the islands are square-shaped, which qualitatively changes the coarsening kinetics. The Gibbs--Thomson chemical potential is violated: the coarsening proceeds through a sequence of `magic sizes corresponding to square or rectangular islands. The coarsening becomes attachment-limited, but Wagners asymptotic law is reached after a very long transient time. The unusual coarsening kinetics obtained in Monte Carlo simulations are well described by the Becker--Doring equations of nucleation kinetics. These equations can be applied to a wide range of coarsening problems.
The phenomenon of Ostwald Ripening is generally considered a limiting factor in the monodisperse production of nanoparticles. However, by analysing the free energy of a binary AB solution with precipitated A particles we show that there is a region in the parameter space of component concentrations and interaction energies where smaller particles are more stable than bigger ones. The strong binding of B species to surfaces of A particles significantly decreases the particle effective surface energy, making it negative. The global minimum of free energy in such a system is thus reached when mass is transferred from bigger particles to the smaller ones, such that all particles become identical in size. The process of mass transfer is opposite to Ostwald ripening, and can be used for generating monodisperse arrays of nanoparticles.
Applicability of classical Lifshitz-Slyozov theory of Ostwald ripening is analyzed and found limited by relatively large cluster sizes due to restrictions imposed by theoretical assumptions. An assumption about the steady state ripening regime poses an upper limit, while another, implicit assumption of continuous description poses a cluster size-dependent lower limit on the supersaturation level. These two limits mismatch for the clusters under certain size in the nanometer scale making the theory inapplicable. We present a more generic, molecular theory of Ostwald ripening, which reproduces classical Lifshitz-Slyozov and Wagner theories in appropriate extreme cases. This theory has a wider applicability than classical theories, especially at lower supersaturation levels, and is more suitable for nanoscale systems.
In this work we perform an ab-initio study of an ideal two-dimensional sample of 4He atoms, a model for 4He films adsorbed on several kinds of substrates. Starting from a realistic hamiltonian we face the microscopic study of the excitation phonon-roton spectrum of the system at zero temperature. Our approach relies on Path Integral Ground State Monte Carlo projection methods, allowing to evaluate exactly the dynamical density correlation functions in imaginary time, and this gives access to the dynamical structure factor of the system S(q,omega), containing information about the excitation spectrum E(q), resulting in sharp peaks in S(q,omega). The actual evaluation of S(q,omega) requires the inversion of the Laplace transform in ill-posed conditions, which we face via the Genetic Inversion via Falsification of Theories technique. We explore the full density range from the region of spinodal decomposition to the freezing density, i.e. 0.0321 A^-2 - 0.0658 A^-2. In particular we follow the density dependence of the excitation spectrum, focusing on the low wave--vector behavior of E(q), the roton dispersion, the strength of single quasi--particle peak, Z(q), and the static density response function, chi(q). As the density increases, the dispersion E(q) at low wave--vector changes from a super-linear (anomalous dispersion) trend to a sub-linear (normal dispersion) one, anticipating the crystallization of the system; at the same time the maxon-roton structure, which is barely visible at low density, becomes well developed at high densities and the roton wave vector has a strong density dependence. Connection is made with recent inelastic neutron scattering results from highly ordered silica nanopores partially filled with 4He.
The Ostwald ripening phenomenon for gas bubbles in a liquid consists mainly in gas transfer from smaller bubbles to larger bubbles. An experiment was carried out in which the Ostwald ripening for air bubbles, in a liquid fluid with some rheological parameters of the human blood, is reproduced. There it has been measured time evolution of bubbles mean radius, number of bubbles and radius size distribution, where the initial bubbles radii normalized distribution behaves like a Tsallis ($q$-Weibull) distribution. One of the main results shows that, while the number of bubbles decreases in time the bubbles mean radius increases, therefore smaller bubbles disappear whereas the, potentially dangerous for the diver, larger bubbles grow up. Consequently, it is presumed that such a bubble broadening effect could contribute, even minimally, to decompression illness: decompression sickness and arterial gas embolism. This conjecture is reinforced by the preliminary results of Ostwald broadening to RGBM (Reduced Gradient Bubble Model) decompression schedules for a closed circuit rebreather (CCR) dive to 420fsw (128m) with 21/79 Heliox gas mixture.
The two-body (pair) contribution to the entropy of two-dimensional Yukawa systems is calculated and analyzed. It is demonstrated that in the vicinity of the fluid-solid (freezing) phase transition the pair entropy exhibits an abrupt jump in a narrow temperature range and this can be used to identify the freezing point. Relations to the full excess entropy and some existing freezing indicators are briefly discussed.