Slow Kinetics of Capillary Condensation in Confined Geometry: Experiment and Theory

When two solid surfaces are brought in contact, water vapor present in the ambient air may condense in the region of the contact to form a liquid bridge connecting the two surfaces : this is the so-called capillary condensation. This phenomenon has drastic consequences on the contact between solids, modifying the macroscopic adhesion and friction properties. In this paper, we present a survey of the work we have performed both experimentally and theoretically to understand the microscopic foundations of the kinetics of capillary condensation. From the theoretical point of view, we have computed the free energy barrier associated with the condensation of the liquid from the gas in a confined system. These calculations allow to understand the existence of very large hysteresis, which is often associated with capillary condensation. This results are compatible with experimental results obtained with a surface forces apparatus in a vapor atmosphere, showing a large hysteris of the surface energy of two parallel planes as a function of their distance. In the second part, we present some experiments on the influence of humidity on the avalanche angle of granular media. We show that the ageing in time of this avalanche angle can be explained by the slow kinetics of capillary condensation in a random confined geometry.Comment: Special Volume of Colloids and Surfaces A,Proceedings of Nanocapillarity: Wetting of Heterogeneous Surfaces and Porous Solids,June 25-27, 2001, TRI/Princeton International Workshop, Editor: Alexander V. Neimar

Experimental velocity fields and forces for a cylinder penetrating into a granular medium

We present here a detailed granular flow characterization together with force measurements for the quasi-bidimensional situation of a horizontal cylinder penetrating vertically at a constant velocity in dry granular matter between two parallel glass walls. In the velocity range studied here, the drag force on the cylinder does not depend on the velocity V_0 and is mainly proportional to the cylinder diameter d. Whereas the force on the cylinder increases with its penetration depth, the granular velocity profile around the cylinder is found stationary with fluctuations around a mean value leading to the granular temperature profile. Both mean velocity profile and temperature profile exhibit strong localization near the cylinder. The mean flow perturbation induced by the cylinder decreases exponentially away from the cylinder on a characteristic length \lambda, that is mainly governed by the cylinder diameter for large enough cylinder/grain size ratio d/d_g: \lambda ~ d/4 + 2d_g. The granular temperature exhibits a constant plateau value T_0 in a thin layer close to the cylinder of extension \delta_{T_0} ~ \lambda/2 and decays exponentially far away with a characteristic length \lambda_T of a few grain diameters (\lambda_T ~ 3d_g). The granular temperature plateau T_0 that scales as (V_0^2 d_g/d) is created by the flow itself from the balance between the "granular heat" production by the shear rate V_0/\lambda over \delta_{T_0} close to the cylinder and the granular dissipation far away

Nanorheology : an Investigation of the Boundary Condition at Hydrophobic and Hydrophilic Interfaces

t has been shown that the flow of a simple liquid over a solid surface can violate the so-called no-slip boundary condition. We investigate the flow of polar liquids, water and glycerol, on a hydrophilic Pyrex surface and a hydrophobic surface made of a Self-Assembled Monolayer of OTS (octadecyltrichlorosilane) on Pyrex. We use a Dynamic Surface Force Apparatus (DSFA) which allows one to study the flow of a liquid film confined between two surfaces with a nanometer resolution. No-slip boundary conditions are found for both fluids on hydrophilic surfaces only. Significant slip is found on the hydrophobic surfaces, with a typical length of one hundred nanometers.Comment: 8 pages, 7 figures, 2 tables. Accepted for European Physical Journal E - Sofr Mate

Thermally Activated Dynamics of the Capillary Condensation

This paper is devoted to the thermally activated dynamics of the capillary condensation. We present a simple model which enables us to identify the critical nucleus involved in the transition mechanism. This simple model is then applied to calculate the nucleation barrier from which we can obtain informations on the nucleation time. We present a simple estimation of the nucleation barrier in slab geometry both in the two dimensional case and in the three dimensional case. We extend the model in the case of rough surfaces which is closer to the experimental case and allows comparison with experimental datas.Comment: 6 pages, 3 figures, Submitted to J. Phys. : Condens. Matter, Proceedings of the IV Liquid Matter Conference - Grenada(Spain) july 199

Mixing and condensation in a wet granular medium

We have studied the effect of small amounts of added liquid on the dynamic behavior of a granular system consisting of a mixture of glass beads of two different sizes. Segregation of the large beads to the top of the sample is found to depend in a nontrivial way on the liquid content. A transition to viscoplastic behavior occurs at a critical liquid content, which depends upon the bead size. We show that this transition can be interpreted as a condensation due to the hysteretic liquid bridge forces connecting the beads, and provide the corresponding phase diagram.Comment: submitted to PR

Modelling microgels with controlled structure across the volume phase transition

Thermoresponsive microgels are soft colloids that find widespread use as model systems for soft matter physics. Their complex internal architecture, made of a disordered and heterogeneous polymer network, has been so far a major challenge for computer simulations. In this work we put forward a coarse-grained model of microgels whose structural properties are in quantitative agreement with results obtained with small-angle X-ray scattering experiments across a wide range of temperatures, encompassing the volume phase transition. These results bridge the gap between experiments and simulations of individual microgel particles, paving the way to theoretically address open questions about their bulk properties with unprecedented nano and microscale resolution

Quantifying the Reversible Association of Thermosensitive Nanoparticles

Under many conditions, biomolecules and nanoparticles associate by means of attractive bonds, due to hydrophobic attraction. Extracting the microscopic association or dissociation rates from experimental data is complicated by the dissociation events and by the sensitivity of the binding force to temperature (T). Here we introduce a theoretical model that combined with light-scattering experiments allows us to quantify these rates and the reversible binding energy as a function of T. We apply this method to the reversible aggregation of thermoresponsive polystyrene/poly(N-isopropylacrylamide) core-shell nanoparticles, as a model system for biomolecules. We find that the binding energy changes sharply with T, and relate this remarkable switchable behavior to the hydrophobic-hydrophilic transition of the thermosensitive nanoparticles

Flow curves of colloidal dispersions close to the glass transition: Asymptotic scaling laws in a schematic model of mode coupling theory

The flow curves, viz. the curves of stationary stress under steady shearing, are obtained close to the glass transition in dense colloidal dispersions using asymptotic expansions in a schematic model of mode coupling theory. The shear thinning of the viscosity in fluid states and the yielding of glassy states is discussed. At the transition between fluid and shear-molten glass, simple and generalized Herschel-Bulkley laws are derived with power law exponents that can be computed for different particle interactions from the equilibrium structure factor.Comment: 14 pages, 14 figures, 4 tables, Eur. Phys. J. E (submitted

Acid/base-triggered switching of circularly polarized luminescence and electronic circular dichroism in organic and organometallic helicenes.

Electronic circular dichroism and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene-bipyridine proligand 1 a and in its “rollover” cycloplatinated derivative 2 a. Whereas proligand 1 a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2 a displays slightly stronger emission. This strikingly different behavior between singlet emission in the organic helicene and triplet emission in the organometallic derivative has been rationalized by using quantum-chemical calculations. The very large bathochromic shift of the emission observed upon protonation of azahelicene-bipyridine 1 a has been attributed to the decrease in aromaticity (promoting a charge-transfer-type transition rather than a π–π* transition) as well as an increase in the HOMO–LUMO character of the transition and stabilization of the LUMO level upon protonation