Properties of argon liquid-vapor interface

The short-wave cutoff boundary of the capillary wave spectrum is established. Effective thickness L _b of the “bare” density profile in the interfacial layer is calculated according to experimental data on the ellipticity ratio of reflected light. The free parameters of the extended van der Waals theory of capillarity are determined. The positions of the equimolecular dividing surface and tension surface are calculated, as well as the temperature dependence of the Tolman parameter.     

Attainable superheating of solutions of cryogenic liquids

The kinetics of spontaneous boiling-up of superheated binary solutions of cryogenic liquids is studied. Within the framework of the Kramers-Zeldovich method, an expression is obtained for the steady state rate of homogeneous nucleation in a solution that takes into account free-molecular and diffusion regimes of the substance supply to a growing bubble. Viscous and inertial forces are also taken into account in the study of the nucleus growth dynamics. The work of critical nucleus formation is determined within the framework of the Gibbs and van der Waals capillarity theories. The dependence of the surface tension of critical bubbles in the solution on their size is investigated. The temperature of attainable superheating and nucleation rates in superheated solutions of cryogenic liquids with complete or partial solubility of the components are determined by a method of lifetime measurement. The experiments were conducted in a wide range of pressures and solution concentrations. The measurement results are compared with the theory of homogeneous nucleation taking or not taking into account the size effect in nucleation. It has been found that, by taking into account the size dependence of the surface tension of a nucleus, better agreement between the theory and experiment is obtained. The boundary of essential instability of the solution, that is, the diffusion spinodal, is computed.     

Cavitation and crystallization in a metastable Lennard-Jones liquid at negative pressures and low temperatures

Molecular dynamics simulations have been used to investigate the kinetics of spontaneous cavitation and crystallization in a Lennard-Jones liquid at negative pressures in the temperature range where these processes compete with each other. The nucleation rate has been calculated in NVE and NpT ensembles by the method of mean lifetime and the transition interface sampling method with parallel path swapping. The data obtained have been used to determine in the framework of classical nucleation theory the value of the ratio of the solid-liquid and the liquid-void interfacial free energy for critical crystals and cavities and the values of their volumes at points where the cavitation rate of the liquid is equal to the rate of its crystallization.     

Explosive cavitation in superheated liquid argon

The kinetics of explosive boiling-up of liquid argon has been investigated at negative pressures created by the reflection of a compression pulse 3-5 mus long from the free surface of a liquid by the method of liquid pulse heating on a thin platinum wire (with a rate of temperature increase of about 1 Kmus). The limiting superheats T(*) (stretches p(*)), the effective nucleation rate J(*), and the derivative G(T)=(d ln JdT)(T=T(*) ) have been determined by experimental data on the thermal perturbation of a wire probe and the results of solution of the problem on the initial stage of explosive boiling-up of a liquid. The experimental data are compared with homogeneous nucleation theory.     

Homogeneous nucleation in liquid nitrogen at negative pressures

The kinetics of spontaneous cavitation in liquid nitrogen at positive and negative pressures has been studied in a tension wave formed by a compression pulse reflected from the liquid–vapor interface on a thin platinum wire heated by a current pulse. The limiting tensile stresses (Δp = p_s–p, where p_s is the saturation pressure), the corresponding bubble nucleation frequencies J (10²⁰–10²² s^–1 m^–3), and temperature induced nucleation frequency growth rate G_T = dlnJ/dT have been experimentally determined. At T = 90 K, the limiting tensile stress was Δp = 8.3 MPa, which was 4.9 MPa lower than the value corresponding to the boundary of thermodynamic stability of the liquid phase (spinodal). The measurement results were compared to classical (homogeneous) nucleation theory (CNT) with and without neglect of the dependence of the surface tension of critical bubbles on their dimensions. In the latter case, the properties of new phase nuclei were described in terms of the Van der Waals theory of capillarity. The experimental data agree well with the CNT theory when it takes into account the “size effect.”     

Computer simulation of nucleation in a gas-saturated liquid

Molecular dynamics methods have been used to investigate the kinetics of the liquid-gas phase transition in a two-component Lennard-Jones system at negative pressures and elastic stretches of the liquid to values close to spinodal ones. The molecular dynamics system consists of 2048 interacting particles with parameters of the Lennard-Jones potential for argon and neon. Density dependences of pressure and internal energy have been calculated for stable and metastable states of the mixture at a temperature T* approximately 0.7+/-0.01 and three values of the concentration. The location of mechanical and the diffusion spinodals has been determined. It has been established that a gas-saturated mixture retains its stability against finite variations of state variables up to stretches close to the values near the diffusion spinodal. The statistic laws of the process of destruction of the metastable state have been investigated. The lifetimes of the metastable phase have been determined. It is shown that owing to the small height of the potential barrier that separates the microheterogeneous from the homogeneous state a system of finite size has a possibility to make the reverse transition from the microheterogeneous into the homogeneous state. The lifetimes of the system in the microheterogeneous state, as well as the expectation times of the occurrence of a critical nucleus, are described by Poissonian distributions.     

The attainable superheating of nitrogen-helium solutions

The nucleation of the vapor phase in superheated nitrogen-helium liquid solutions was studied by lifetime measurements. The temperature dependences of the mean lifetime of metastable solutions were obtained at p = 0.5 and 1.0 MPa and several concentrations. The nucleation rate J was found to vary from 10⁴ to 10⁸ s⁻¹ m⁻³. The adsorption of the high-volatility component on the metastable liquid-critical bubble boundary was shown to play a determining role in decreasing the temperature of the attainable solution super-heating as the solution concentration increased. The experimental data were compared with homogeneous nucleation theory. Systematic discrepancies were obtained; these discrepancies were related to the influence of the size effect on the surface tension of a nucleus and the work of its formation     

Tensile strength of two-dimensional Lennard-Jones crystals. 2. Dynamic aspect

The failure of a two-dimensional crystal at negative pressures and at temperatures lower than the triple point is studied in a molecular-dynamics experiment. The dynamics of the failure is analyzed by visualizing the evolution of a net of interparticle bonds and the particle trajectories and by determining the time dependence of rms displacements of particles in the states before the failure and after crack relaxation. Institute of Thermal Physics, Ural Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 36, No. 1, pp. 50–57, January–February, 1995. Translated by I. Izvekova