Christiane Alba-Simionesco

Effects of confinement on freezing and melting

We present a review of experimental, theoretical, and molecular simulation studies of confinement effects on freezing and melting. We consider both simple and more complex adsorbates that are confined in various environments (slit or cylindrical pores and also disordered porous materials). The most commonly used molecular simulation, theoretical and experimental methods are first presented. We also provide a brief description of the most widely used porous materials. The current state of knowledge on the effects of confinement on structure and freezing temperature, and the appearance of new surface-driven and confinement-driven phases are then discussed. We also address how confinement affects the glass transition.

Supercooled liquids and the glass transition: Temperature as the control variable

It has long been appreciated that both temperature and density play roles in determining the extremely super-Arrhenius, low-temperature behavior of the viscosity and long α-relaxation times that characterize fragile supercooled liquids. But what has not been generally appreciated, and what we believe we have established (by focusing on a model-free analysis in terms of temperature and density, rather than upon temperature and pressure) is that over the range of densities and temperatures spanned by the experiments carried out at 1 atm pressure, temperature is the dominant control variable. This information is essential input to the formulation of a theory or model of the long-time dynamics of low-temperature fragile liquids, and it suggests a focus on activated dynamics rather than on free volume. This work indicates that, except possibly at very high densities (very high pressures), the glass transition is not a result of congestion due to a lack of free volume.

Spatial correlations in the dynamics of glassforming liquids : Experimental determination of their temperature dependence

We use recently introduced three-point dynamic susceptibilities to obtain an experimental determination of the temperature evolution of the number of molecules Ncorr that are dynamically correlated during the structural relaxation of supercooled liquids. We first discuss in detail the physical content of three-point functions that relate the sensitivity of the averaged two-time dynamics to external control parameters (such as temperature or density), as well as their connection to the more standard four-point dynamic susceptibility associated with dynamical heterogeneities. We then demonstrate that these functions can be experimentally determined with good precision. We gather available data to obtain the temperature dependence of Ncorr for a large number of supercooled liquids over a wide range of relaxation time scales from the glass transition up to the onset of slow dynamics. We find that Ncorr systematically grows when approaching the glass transition. It does so in a modest manner close to the glass transition, which is consistent with an activation-based picture of the dynamics in glassforming materials. For higher temperatures, there appears to be a regime where Ncorr behaves as a power-law of the relaxation time. Finally, we find that the dynamic response to density, while being smaller than the dynamic response to temperature, behaves similarly, in agreement with theoretical expectations.

Finite-size and surface effects on the glass transition of liquid toluene confined in cylindrical mesopores

Some of the most regular porous silicates (MCM-41 and SBA-15), with several different pore diameters from 2.4 to 8.7 nm, are used to study the van der Waals fragile liquid toluene in confined geometry. We measure two major macroscopic signatures of a glass transition, i.e., a discontinuous change in the heat capacity and in the thermal expansion, by adiabatic calorimetry and neutron scattering experiments. A nontrivial size dependence of the glass transition features, most notably a nonmonotonic variation of the mean glass transition temperature, is observed. The range of the glass transition is found extremely broad. This supports the notion of competition between surface boundary conditions and cutoff or finite-size effects.

THERMODYNAMIC ASPECTS OF THE GLASS TRANSITION PHENOMENON. II. MOLECULAR LIQUIDS WITH VARIABLE INTERACTIONS

As a contribution to the understanding of the thermodynamics of the glass transition phenomenon a series of molecules having the same steric character, but differing in the strength and nature of intermolecular interactions, has been investigated. The series is based on systematic changes of substituents on disubstituted benzene ring compounds, the simplest example of which is meta-xylene. Meta-isomers are chosen in each instance because of their greater tendency to supercool. In particular, m-fluoroaniline cannot be crystallized at ambient pressure. The principal measurements performed were of heat capacity and enthalpy change, using the technique of differential scanning calorimetry, and these have been examined in the light of literature data on the liquid viscosities and some recent data for dielectric relaxation. As the strength of hydrogen-bonding interactions between the ring substituents on adjacent molecules increases, the glass transition temperature Tg increases by almost 100 degrees from the l...

Hydrogen-bond-induced clustering in the fragile glass-forming liquid m-toluidine: Experiments and simulations

We study the “prepeak” appearing in the static structure factor of the molecular glass-former m-toluidine by means of neutron scattering experiments and Monte Carlo simulations. The occurrence of this prepeak is interpreted as resulting from spatial organization of the molecules that goes beyond the usual short range liquid order and has a typical length scale of several molecular diameters. The origin of this phenomenon, as well as its specific temperature and density dependence, is explained by the competition between hydrogen-bonding interactions that tend to favor clustering and steric hindrance between aromatic rings that limits the extension of the H-bond network. Finally, effects of such clustering on the relaxational properties of the liquid and on the glass transition are discussed.

Temperature, density, and pressure dependence of relaxation times in supercooled liquids

We have examined experimental and simulation data on the relaxation times (τα) and the viscosities in liquids and supercooled liquids as functions of temperature (T), density (ρ), and pressure (p). We achieve a data collapse by placing the data on master curves that depend only on a single density- and species-dependent (but T independent) effective interaction energy, E∞(ρ).We have examined experimental and simulation data on the relaxation times (τα) and the viscosities in liquids and supercooled liquids as functions of temperature (T), density (ρ), and pressure (p). We achieve a data collapse by placing the data on master curves that depend only on a single density- and species-dependent (but T independent) effective interaction energy, E∞(ρ).

Liquids in confined geometry: How to connect changes in the structure factor to modifications of local order

The recent advances in the syntheses of mesostructured porous silicates (MCM-41 and SBA-15) allow us to study liquids confined in highly regular geometry. Hence, one might get to a better understanding of the structure and the dynamics of confined fluids. In this paper, we address the problem of the interpretation of the structure factor of a confined phase. Distortions due to geometric effects—so-called “excluded volume effects” and “cross-correlation terms”—may dominate the observed features and cannot be ignored. We present a generalization of the formalism introduced by Soper et al. It is applied in the case of a honeycomb-type lattice of parallel cylindrical pores, which corresponds to the topology of these novel porous materials. It shows that the large variations of the experimental structure factor of confined liquid benzene at room temperature are essentially attributed to an “excluded volume effect” that does not reflect different local ordering of the confined phase.

Structure of liquid and glassy methanol confined in cylindrical pores

We present a neutron scattering analysis of the density and the static structure factor of confined methanol at various temperatures. Confinement is performed in the cylindrical pores of MCM-41 silicates with pore diameters D=24 and 35 A. A change of the thermal expansivity of confined methanol at low temperature is the signature of a glass transition, which occurs at higher temperature for the smallest pore. This is evidence of a surface induced slowing down of the dynamics of the fluid. The structure factor presents a systematic evolution with the pore diameter, which has been analyzed in terms of excluded volume effects and fluid-matrix cross correlation. Conversely to the case of Van der Waals fluids, it shows that stronger fluid-matrix correlations must be invoked most probably in relation with the H-bonding character of both methanol and silicate surface.

Adsorption and Structure of Benzene on Silica Surfaces and in Nanopores

Grand canonical Monte Carlo simulations are used to study the adsorption of benzene on atomistic silica surfaces and in cylindrical nanopores. The effect of temperature and surface chemistry is addressed by studying the adsorption of benzene at 293 and 323 K on both fully and partially hydroxylated silica surfaces or nanopores. We also consider the adsorption of benzene in a cylindrical nanopore of diameter D=3.6 nm and compare our results with those obtained for planar surfaces. The structure of benzene in the vicinity of the planar surface and confined in the cylindrical nanopore is determined by calculating orientational order parameters and examining positional pair correlation functions. The density profiles of adsorbed benzene reveal the strong layering of the adsorbate, which decays with the distance from the silica surface. At a given temperature and at low pressures, the film adsorbed at the fully hydroxylated silica surface is larger than that for the partially hydroxylated silica surface. This result is due to an increase in the density of silanol groups that induces an increase in the polarity of the silica surface, which becomes more attractive for the adsorbate. Our results also suggest that the benzene molecules prefer an orientation in which their ring is nearly perpendicular to the surface when fully hydroxylated surfaces are considered. When partially hydroxylated surfaces are considered, a second preferential orientation is observed where the benzene ring forms an angle of approximately 50 degrees with the silica surface. In this case, the average orientation of the benzene molecules appears disordered as in the bulk phase. These results suggest that determining the experimental orientation of benzene in the vicinity of a silica surface is a difficult task even when the surface chemistry is known. Capillary condensation in the nanopores involves a transition from a partially filled pore (a thin film adsorbed at the pore surface) to a completely filled pore configuration where the confined liquid coexists at equilibrium with the external gas phase. The disordered orientation of the adsorbed benzene molecules in the case of the partially hydroxylated surface favors the condensation of benzene molecules (the condensation pressure for this substrate is lower than that for the fully hydroxylated surface). Finally, these results are consistent with the structural analysis, showing that (1) benzene tends to relax its liquid structure a little in order to optimize its molecular arrangement near the pore wall and (2) the disordering of the liquid structure induced by the surface becomes stronger as the interaction with the pore wall increases.