Biomedical subjects

Dimo Kashchiev

Publications and source records attributed to Dimo Kashchiev.

7 recordsLinked to original sources

PubMed2006

Analysis of experimental data for the nucleation rate of water droplets.

A formula for the stationary nucleation rate J is proposed and used for analysis of experimental data for the dependence of J on the supersaturation ratio S in isothermal homogeneous nucleation of water droplets in vapors. It is found that the experimental data are described quite successfully by the proposed formula which is based on (i) the Gibbs presentation of the nucleation work in terms of overpressure, (ii) the Girshick-Chiu [J. Chem. Phys. 93, 1273 (1990); 94, 826 (1991)] self-consistency correction to the equilibrium cluster size distribution, and (iii) the Reguera-Rubi [J. Chem. Phys. 115, 7100 (2001)] kinetic accounting of the nucleus translational-rotational motion. The formula, like that of Wolk and Strey [J. Phys. Chem. B 105, 11683 (2001)], could be used as a semiempirical relation describing the J(S) dependence for nucleation in vapors of single-component droplets or crystals of substances with insufficiently well known equations of state.

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PubMed2006

Forms and applications of the nucleation theorem.

The nucleation theorem is a general relation between the nucleation work, the nucleus size, and the supersaturation or other thermodynamic parameters of the old phase. The theorem appears in different forms, depending not only on the chosen set of independent variables describing the nucleation work but also on which of these variables is changed while the others are held fixed. This paper gives a rigorous, systematic, and comprehensive presentation of various forms of the nucleation theorem and shows how some of them can be applied to concrete cases of nucleation. Both theoretical and experimental applications of the theorem to nucleation in unary, binary, or ternary phases are considered.

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PubMed2005

Determining the nucleation rate from the dimer growth probability.

A new method is proposed for the determination of the stationary one-component nucleation rate J with the help of data for the growth probability P2 of a dimer which is the smallest cluster of the nucleating phase. The method is based on an exact formula relating J and P2, and is readily applicable to computer simulations of nucleation. Using the method, the dependence of J on the supersaturation s is determined by kinetic Monte Carlo simulations of two-dimensional (2D) nucleation of monolayers on the (100) face of Kossel crystal. The change of J over nearly 11 orders of magnitude is followed and it is found that the classical nucleation theory overestimates the simulation J values by an s-dependent factor. The 2D nucleus size evaluated via the nucleation theorem is described satisfactorily by the classical Gibbs-Thomson equation and its corrected version accounting for the spinodal limit of 2D nucleation.

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PubMed2005

Kinetics of two-step nucleation of crystals.

When the nucleation of a stable crystalline phase directly in a supersaturated old phase is greatly retarded, the crystal nuclei might nucleate within faster-forming particles of an intermediate phase. Here we present a theoretical investigation of the kinetics of this two-step nucleation of crystals and derive general expressions for the time dependence of the number of crystals nucleated within the particles of the intermediate phase. The results reveal that crystal nucleation can be strongly delayed by the slow growth of the particles and/or by the slow nucleation of the crystals in them. Furthermore, the linear part of the time dependence of the number of nucleated crystals is determined by the formation rate of the intermediate particles. This is in contrast with the one-step nucleation of crystals when this linear part is determined by the rate of crystal nucleation directly in the old phase. Criteria are proposed for distinction between the one- and two-step nucleation mechanisms, based on the supersaturation dependence of the delay time for nucleation. The application of the theoretical approach to the analysis of experimental data on the nucleation of crystals and other ordered aggregates of protein and other soluble materials is discussed.

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PubMed2005

Moments of the rate of nonstationary nucleation.

The zeroth, first, and reduced moments of the rate of nonstationary nucleation at constant supersaturation are parameters in the description of the variation of this rate with time. The dependence of the reduced moment M(r) on the nucleus size n(*) and the supersaturation Deltamu is analyzed and it is found that under typical conditions this moment decreases from about 1.9 to 1.1 with increasing n(*) or, alternatively, decreasing Deltamu. Expressions for the M(r)(n(*)) and M(r)(Deltamu) dependences are given which allow approximate calculation of the reduced moment in different cases of one-component nucleation.

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PubMed2004

Phase diagrams of nonionic foam films: construction by means of disjoining pressure versus thickness curves.

The thickness h of foam films can be measured as a function of the disjoining pressure Pi using a thin film pressure balance. Experimental Pi-h curves of foam films stabilized with nonionic surfactants measured at various concentrations resemble the p-V(m) isotherms of real gases measured at various temperatures (p is the pressure and V(m) is the molar volume of the gas). This observation led us to adopt the van der Waals approach for describing real gases to thin foam films, where the thickness h takes the role of V(m) and the disjoining pressure Pi replaces the ordinary pressure p. Our analysis results in a phase diagram for a thin foam film with spinodal, binodal as well as a critical point. The thicker common black film corresponds to the gas phase and the compact Newton black film for which the two surfaces are in direct contact corresponds to the dense liquid. We show that the tuning parameter for the phase behavior of the film is the surface charge density, which means that Pi-h curves should not be referred to as isotherms. In addition to the equilibrium properties the driving force for the phase transition from a common black film to a Newton black film or vice versa is calculated. We discuss how this transition can be controlled experimentally.

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PubMed2004

Multicomponent nucleation: thermodynamically consistent description of the nucleation work.

A thermodynamically consistent formula is derived for the nucleation work in multicomponent homogeneous nucleation. The derivation relies on the conservative dividing surface which defines the nucleus as having specific surface energy equal to the specific surface energy sigma0 of the interface between the macroscopically large new and old phases at coexistence. Expressions are given for the radius of the nucleus defined by the conservative dividing surface and by the surface of tension. As a side result, the curvature dependence of the surface tension sigmaT of the nucleus defined by the surface of tension is also determined. The analysis is valid for nuclei of any size, i.e., for nucleation in the whole range of conditions between the binodal and the spinodal of the metastable old phase provided the inequality sigmaT < or = sigma0 is satisfied. It is found that under the conditions of validity of the analysis the nucleation rate is higher than the nucleation rate given by the classical nucleation theory. The general results are applied to nucleation of unary liquids or solids in binary gaseous, liquid or solid mixtures.

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