We present a computer simulation study of a (6,12)-Lennard-Jones fluid confined to a slit pore, formed by two uniform planes. These interact via (3,9)-Lennard-Jones potential with the fluid particles. When the fluid approaches the liquid-to-solid transition we first observe layering parallel to the walls. In order to investigate the nature of the freezing transition we performed a detailed analysis of the bond-orientational order parameter in the layers. We found no signs of hexatic order which would indicate a melting scenario of the Kosterlitz-Thouless type. An analysis of the mean-square displacement shows that the particles can easily move between the layers, making the crystallization a 3d-like process. This is consistent with the fact that we observe a considerable hysteresis in the heating-freezing curves, showing that the crystallization transition proceeds as an activated process.
It is demonstrated that properly reduced transport coefficients (self-diffusion, shear viscosity, and thermal conductivity) of Lennard-Jones fluids along isotherms exhibit quasi-universal scaling on the density divided by its value at the freezing point. Moreover, this scaling is closely related to the density scaling of transport coefficients of hard-sphere fluids. The Stokes-Einstein relation without the hydrodynamic diameter is valid in the dense fluid regime. The lower density boundary of its validity can serve as a practical demarcation line between gas-like and liquid-like regimes.
In a recent paper [S. Khrapak, Molecules {\bf 25}, 3498 (2000)] the longitudinal and transverse sound velocities of conventional Lennard-Jones systems at the liquid-solid coexistence were calculated. It was shown that the sound velocities remain almost invariant along the liquid-solid coexistence boundary lines and that their magnitudes are comparable with those of repulsive soft sphere and hard sphere models at the fluid-solid phase transition. This implies that attraction does not affect the magnitude of sound velocities at the fluid-solid phase transition. This paper provides further eviden…
Adsorption-Induced Deformation of a Nanoporous Material: Influence of the Fluid-Adsorbent Interaction and Surface Freezing on the Pore-Load Modulus Measurement
It is demonstrated that the crossover between gas- and liquid-like regions on the phase diagram of the Lennard-Jones system occurs at a fixed value of the density divided by its value at the freezing point, $ρ/ρ_{\rm fr}\simeq 0.35$. This definition is consistent with other definitions proposed recently. As a result a very simple practical expression for the gas-to-liquid crossover line emerges.
We present a computer simulation study of influence of the confinement on the density anomaly in the system with isotropic core-softened potential which is used for a qualitative description of the anomalous behavior of water and some other liquids. We have found that a maximum temperature of the density anomaly region along an isochor $ρ=0.5$ does not depend on the pore width. We have shown that a decrease in the width of the confining slit pore leads to an increase in the crystallization temperature and as a result the local density distribution is mostly controlled by the particle-wall inte…
It is shown that porous spherical particles can be obtained via the freezing of silica nanoparticle aqueous suspensions emulsified in a continuous oil phase. After two freeze-thaw cycles, nanoparticles turn aggregated into flocculated objects with microstructure that depends upon emulsion volume fraction and droplet size. For low volume fractions, regular microspheres are produced while for large ones, irregular beads with several tens of micrometer radius are formed. Electronic microscopy, mercury porosimetry and nitrogen adsorption are used to get insights into these porous particles typical…
Formation mechanism of speed-dependent ice bandings in freezing colloidal suspensions, of significance in frost heaving and materials science, remains a mystery. With quantitative experiments, we propose a possible mechanism of speed-dependent ice bandings by focusing on the particle packing density and dynamic interface undercooling. The particle packing density ahead of the freezing interface decreases with increasing pulling speeds, attributed to the speed-dependent packing of particles. Through affecting the curvature undercooling of pore ices, the speed-dependent packing of particles can …
In the present work, we employ broadband dielectric spectroscopy to study the molecular dynamics of the prototypical glass former glycerol confined in two microporous zeolitic imidazolate frameworks (ZIF-8 and ZIF-11) with well-defined pore diameters of 1.16 and 1.46 nm, respectively. The spectra reveal information on the modified alpha relaxation of the confined supercooled liquid, whose temperature dependence exhibits clear deviations from the typical super-Arrhenius temperature dependence of the bulk material, depending on temperature and pore size. This allows assigning well-defined cooper…
Ice-templating is a well-established processing route for porous ceramics. Because of the structure/properties relationships, it is essential to better understand and control the solidification microstructures. Ice-templating is based on the segregation and concentration of particles by growing ice crystals. What we understand so far of the process is based on either observations by optical or X-ray imaging techniques, or on the characterization of ice-templated materials. However, in situ observations at particle-scale are still missing. Here we show that confocal microscopy can provide multi…
Nanoconfinement can drastically change the behavior of liquids, puzzling us with counterintuitive properties. Moreover, it is relevant in applications, including decontamination and crystallization control. It still lacks a systematic analysis for fluids with different bulk properties. Here we fill this gap. We compare, by molecular dynamics simulations, three different liquids in a graphene slit pore: (A) A simple fluid, such as argon, described by a Lennard-Jones potential; (B) An anomalous fluid, such as a liquid metal, modeled with an isotropic core-softened potential; (C) Water, the proto…
Within the so-called "no-man's land" between about 150 and 235 K, crystallization of bulk water is inevitable. The glasslike freezing and a liquid-to-liquid transition of water, predicted to occur in this region, can be investigated by confining water in nanometer-sized pores. Here we report the molecular dynamics of water within the pores of a metal-organic framework using dielectric spectroscopy. The detected temperature-dependent dynamics of supercooled water matches that of bulk water as reported outside the borders of the no-man's land. In confinement, a different type of water is formed,…
Fluids confined in nanopores are ubiquitous in nature and technology. In recent years, the interest in confined fluids has grown, driven by research on unconventional hydrocarbon resources -- shale gas and shale oil, much of which are confined in nanopores. When fluids are confined in nanopores, many of their properties differ from those of the same fluid in the bulk. These properties include density, freezing point, transport coefficients, thermal expansion coefficient, and elastic properties. The elastic moduli of a fluid confined in the pores contribute to the overall elasticity of the flui…
