Non-monotonic effect of confinement on the glass transition

Abstract

The relaxation dynamics of glass forming liquids and their structure are influenced in the vicinity of confining walls. In view of the great potential of this effect for applications in those fields of science and industry, where liquids occur under strong confinement (e.g., nano-technology), the number of researchers studying various aspects and consequences of this non-monotonic behaviour has been rapidly growing. This review aims at providing an overview of the research activity in this newly emerging field. We first briefly discuss how competing mechanisms such as packing effects and short-range attraction may lead to a non-monotonic glass transition scenario in the bulk. We then analyse confinement effects on the dynamics of fluids using a thermodynamic route which relates the single particle dynamics to the excess entropy. Moreover, relating the diffusive dynamics to the Widom's insertion probability, the oscillations of the local dynamics with density at moderate densities are fairly well described. At high densities belonging to the supercooled regime, however, this approach breaks down signaling the onset of strongly collective effects. Indeed, confinement introduces a new length scale which in the limit of high densities and small pore sizes competes with the short-range local order of the fluid. This gives rise to a non-monotonic dependence of the packing structure on confinement, with a corresponding effect on the dynamics of structural relaxation. This non-monotonic effect occurs also in the case of a cone-plate type channel, where the degree of confinement varies with distance from the apex. This is a very promising issue for future research with the possibility of uncovering the existence of alternating glassy and liquid-like domains.

49 pages,20 figures, topical review

References in corpus (32)

• Inhomogeneous Mode-Coupling Theory and Growing Dynamic Length in Supercooled Liquids
• Crystallization of hard-sphere glasses
• Density functional theory for hard-sphere mixtures: the White-Bear version Mark II
• Layering and position-dependent diffusive dynamics of confined fluids
• Phase behavior of hard spheres confined between parallel hard plates: Manipulation of colloidal crystal structures by confinement
• Liquid-glass transition of a fluid confined in a disordered porous matrix: A mode-coupling theory
• Evidence for a Superglass State in Solid 4He
• Crystallization kinetics of colloidal model suspensions: recent achievements and new perspectives
• Structural relaxation of polydisperse hard spheres: comparison of the mode-coupling theory to a Langevin dynamics simulation
• Glass Transition in Confined Geometry
• Mixing effects for the structural relaxation in binary hard-sphere liquids
• Mode-coupling theory for the slow collective dynamics of fluids adsorbed in disordered porous media
• Slow Relaxation, Spatial Mobility Gradients and Vitrification in Confined Films
• Single-particle and collective slow dynamics of colloids in porous confinement
• Dynamic Glass Transition in Two Dimensions
• Tuning density profiles and mobility of inhomogeneous fluids
• Multiple reentrant glass transitions in confined hard-sphere glasses
• Mode-coupling theory of the glass transition for confined fluids
• Phase behavior and far-from-equilibrium gelation of charged attractive colloids
• Theory of the superglass phase
• Fluids in Extreme Confinement
• Transport properties of dense fluid argon
• Phase behavior and structure of model colloid-polymer mixtures confined between two parallel planar walls
• Available states and available space: Static properties that predict dynamics of confined fluids
• Cofinement, entropy, and single-particle dynamics of equilibrium hard-sphere mixtures
• New Members in the $0^{+}$ ($0^{++})$ Family
• Tagged-particle motion in a dense confined liquid
• Structural quantities of quasi-two-dimensional fluids
• Glassy dynamics in confinement: Planar and bulk limit of the mode-coupling theory
• Long-time limit of correlation functions
• Local structure-mobility relationships of confined fluids reverse upon supercooling
• Packing frustration in dense confined fluids

Cited by in corpus (8)

• Diverging time scale in the dimensional crossover for liquids in strong confinement
• Nonergodicity parameters of confined hard-sphere glasses
• Motility-induced clustering of active particles under soft confinement
• Mode-coupling theory of the glass transition for colloidal liquids in slit geometry
• Static properties of quasi-confined hard-sphere fluids
• Dynamical properties of densely packed confined hard-sphere fluids
• Structural properties of liquids in extreme confinement
• Dynamic properties of quasi-confined colloidal hard-sphere liquids near the glass transition