Giant Osmotic Pressure in the Forced Wetting of Hydrophobic Nanopores.

The forced intrusion of water in hydrophobic nanoporous pulverulent material is of interest for quick storage of energy. With nanometric pores the energy storage capacity is controlled by interfacial phenomena. With subnanometric pores, we demonstrate that a breakdown occurs with the emergence of molecular exclusion as a leading contribution. This bulk exclusion effect leads to an osmotic contribution to the pressure that can reach levels never previously sustained. We illustrate, on various electrolytes and different microporous materials, that a simple osmotic pressure law accounts quantitatively for the enhancement of the intrusion and extrusion pressures governing the forced wetting and spontaneous drying of the nanopores. Using electrolyte solutions, energy storage and power capacities can be widely enhanced.

Activated drying in hydrophobic nanopores and the line tension of water.

We study the slow dynamics of water evaporation out of hydrophobic cavities by using model porous silica materials grafted with octylsilanes. The cylindrical pores are monodisperse, with a radius in the range of 1-2 nm. Liquid water penetrates in the nanopores at high pressure and empties the pores when the pressure is lowered. The drying pressure exhibits a logarithmic growth as a function of the driving rate over more than three decades, showing the thermally activated nucleation of vapor bubbles. We find that the slow dynamics and the critical volume of the vapor nucleus are quantitatively described by the classical theory of capillarity without adjustable parameter. However, classical capillarity utterly overestimates the critical bubble energy. We discuss the possible influence of surface heterogeneities, long-range interactions, and high-curvature effects, and we show that a classical theory can describe vapor nucleation provided that a negative line tension is taken into account. The drying pressure then provides a determination of this line tension with much higher precision than currently available methods. We find consistent values of the order of -30 pN in a variety of hydrophobic materials.

Clay dispersion and aspect ratios in polymer-clay nanocomposites.

It has clearly been shown in the literature that the properties achieved by polymer clay nanocomposites are often related to their structures and to the states of dispersion of the silicate platelets in the polymer matrices. Unfortunately, up to date most techniques used in a standard procedure do not allow a correct interpretation of polymer-clay nanocomposite structure and dispersion. In a recent work, we proposed an image analysis procedure (I.A.P.) based on TEM/OM observations to characterize the clay dispersion in polymer clay nanocomposites. The I.A.P. allows a very fine description of the nanocomposites microstructure. Nevertheless this analysis method shows some limits like the representativity of the sample analyzed volume. The purpose of this work is to discuss about the accuracy of the parameters extracted from the I.A.P. We propose SAXS experimental developments for evaluating the thickness distribution of the clay tactoids. The good agreement between the results of the two techniques confirms the validity of the I.A.P. methodology. Moreover, other experiments were performed in order to understand the abnormally low platelet lengths and aspect ratios determined from TEM micrographs. Wet-STEM observations revealed that clay platelets were not broken during the extrusion process. And, low platelet lengths and aspect ratios were shown to originate from the preparation of the ultramicrotomed sections and from TEM projection effects induced by the clay platelet wavy shape.

New device to measure dynamic intrusion/extrusion cycles of lyophobic heterogeneous systems.

Lyophobic heterogeneous systems (LHS) are made of mesoporous materials immersed in a non-wetting liquid. One application of LHS is the nonlinear damping of high frequency vibrations. The behaviour of LHS is characterized by P - ΔV cycles, where P is the pressure applied to the system, and ΔV its volume change due to the intrusion of the liquid into the pores of the material, or its extrusion out of the pores. Very few dynamic studies of LHS have been performed until now. We describe here a new apparatus that allows us to carry out dynamic intrusion/extrusion cycles with various liquid/porous material systems, controlling the temperature from ambient to 120 °C and the frequency from 0.01 to 20 Hz. We show that for two LHS: water/MTS and Galinstan/CPG, the energy dissipated during one cycle depends very weakly on the cycle frequency, in strong contrast to conventional dampers.

Characterization of the drastic increase in molecular mobility of a deformed amorphous polymer.

Original experiments of dynamic mechanical analysis and small angle x-ray scattering on a deformed amorphous polymer below its glass transition temperature are reported. The mechanical treatment reveals high mobility zones induced by shearing and leads to a drastic increase in the molecular mobility of the system. These domains are evidenced by small angle x-ray scattering measurements, and their geometrical characteristics are independent of the applied deformation. An experimental procedure is proposed to determine an apparent activation energy associated with high mobility domains. The energy values obtained for intermediate modes rise from the beta to the alpha relaxation ones.