Stability Limit of Water by Metastable Vapor-Liquid Equilibrium with Nanoporous Silicon Membranes.

Liquid can sustain mechanical tension as its pressure drops below the vapor-liquid coexistence line and becomes less than zero, until it reaches the stability limit-the pressure at which cavitation inevitably occurs. For liquid water, its stability limit is still a subject of debate: the results obtained by researchers using a variety of techniques show discrepancies between the values of the stability limit and its temperature dependence as temperature approaches 0 °C. In this work, we present a study of the stability limit of water by the metastable vapor-liquid equilibrium (MVLE) method with nanoporous silicon membranes. We also report on an experimental system which enables tests of the temperature dependence of the stability limit with MVLE. The stability limit we found increases monotonically (larger tension) as temperature approaches 0 °C; this trend contradicts the centrifugal result of Briggs but agrees with the experiments by acoustic cavitation. This result confirms that a quasi-static method can reach stability values similar to that from the dynamic stretching technique, even close to 0 °C. Nevertheless, our results fall in the range of ∼ -20 to -30 MPa, a range that is consistent with the majority of experiments but is far less negative than the limit obtained in experiments involving quartz inclusions and that predicted for homogeneous nucleation.

Drying by cavitation and poroelastic relaxations in porous media with macroscopic pores connected by nanoscale throats.

We investigate the drying dynamics of porous media with two pore diameters separated by several orders of magnitude. Nanometer-sized pores at the edge of our samples prevent air entry, while drying proceeds by heterogeneous nucleation of vapor bubbles--cavitation--in the liquid in micrometer-sized voids within the sample. We show that the dynamics of cavitation and drying are set by the interplay of the deterministic poroelastic mass transport in the porous medium and the stochastic nucleation process. Spatiotemporal patterns emerge in this unusual reaction-diffusion system, with temporal oscillations in the drying rate and variable roughness of the drying front.

A microtensiometer capable of measuring water potentials below -10 MPa.

Tensiometers sense the chemical potential of water (or water potential, Ψw) in an external phase of interest by measuring the pressure in an internal volume of liquid water in equilibrium with that phase. For sub-saturated phases, the internal pressure is below atmospheric and frequently negative; the liquid is under tension. Here, we present the initial characterization of a new tensiometer based on a microelectromechanical pressure sensor and a nanoporous membrane. We explain the mechanism of operation, fabrication, and calibration of this device. We show that these microtensiometers operate stably out to water potentials below -10 MPa, a tenfold extension of the range of current tensiometers. Finally, we present use of the device to perform an accurate measurement of the equation of state of liquid water at pressures down to -14 MPa. We conclude with a discussion of outstanding design considerations, and of the opportunities opened by the extended range of stability and the small form factor in sensing applications, and in fundamental studies of the thermodynamic properties of water.

Exploring water and other liquids at negative pressure.

Water is famous for its anomalies, most of which become dramatic in the supercooled region, where the liquid is metastable with respect to the solid. Another metastable region has been hitherto less studied: the region where the pressure is negative. Here we review the work on the liquid in the stretched state. Characterization of the properties of the metastable liquid before it breaks by nucleation of a vapour bubble (cavitation) is a challenging task. The recent measurement of the equation of state of the liquid at room temperature down to  - 26 MPa opens the way to more detailed information on water at low density. The threshold for cavitation in stretched water has also been studied by several methods. A puzzling discrepancy between experiments and theory remains unexplained. To evaluate how specific this behaviour is to water, we discuss the cavitation data on other liquids. We conclude with a description of the ongoing work in our groups.

Multiple dynamic regimes in concentrated microgel systems.

We investigate dynamical heterogeneities in the collective relaxation of a concentrated microgel system, for which the packing fraction can be conveniently varied by changing the temperature. The packing fraction-dependent mechanical properties are characterized by a fluid-solid transition, where the system properties switch from a viscous to an elastic low-frequency behaviour. Approaching this transition from below, we find that the range xi of spatial correlations in the dynamics increases. Beyond this transition, xi reaches a maximum, extending over the entire observable system size of approximately 5 mm. Increasing the packing fraction even further leads to a second transition, which is characterized by the development of large zones of lower and higher dynamical activity that are well separated from each other; the range of correlation decreases at this point. This striking non-monotonic dependence of xi on volume fraction is reminiscent of the behaviour recently observed at the jamming/rigidity transition in granular systems. We identify this second transition as the transition to 'squeezed' states, where the constituents of the system start to exert direct contact forces on each other, such that the dynamics becomes increasingly determined by imbalanced stresses. Evidence of this transition is also found in the frequency dependence of the storage and loss moduli, which become increasingly coupled as direct friction between the particles starts to contribute to the dissipative losses within the system. To our knowledge, our data provide the first observation of a qualitative change in dynamical heterogeneity as the dynamics switches from purely thermally driven to stress driven.