Pore Morphology Determines Spontaneous Liquid Extrusion from Nanopores.

In this contribution we explore by means of experiments, theory, and molecular dynamics the effect of pore morphology on the spontaneous extrusion of nonwetting liquids from nanopores. Understanding and controlling this phenomenon is central for manipulating nanoconfined liquids, e. g., in nanofluidic applications, drug delivery, and oil extraction. Qualitatively different extrusion behaviors were observed in high-pressure water intrusion-extrusion experiments on porous materials with similar nominal diameter and hydrophobicity: macroscopic capillary models and molecular dynamics simulations revealed that the very presence or absence of extrusion is connected to the internal morphology of the pores and, in particular, to the presence of small-scale roughness or pore interconnections. Additional experiments with mercury confirmed that this mechanism is generic for nonwetting liquids and is rooted in the pore topology. The present results suggest a rational way to engineer heterogeneous systems for energy and nanofluidic applications in which the extrusion behavior can be controlled via the pore morphology.

Self-Recovery Superhydrophobic Surfaces: Modular Design.

Superhydrophobicity, the enhanced hydrophobicity of surfaces decorated with textures of suitable size, is associated with a layer of gas trapped within surface roughness. The reduced liquid/solid contact makes superhydrophobicity attractive for many technological applications. This gas layer, however, can break down with the liquid completely wetting the surface. Experiments have shown that the recovery of the "suspended" superhydrophobic state from the wet one is difficult. Self-recovery-the spontaneous restoring of the gas layer at ambient conditions-is one of the dreams of research in superhydrophobicity as it would allow to overcome the fragility of superhydrophobicity. In this work we have performed a theoretical investigation of the wetting and recovery processes on a set of surfaces characterized by textures of different dimensions and morphology in order to elucidate the optimal parameters for avoiding wetting and achieving self-recovery. Results show that texture size in the nanometer range is a necessary but not sufficient condition for self-recovery: the geometry plays a crucial role, nanopillars prevent self-recovery, while surfaces with square pores exhibit self-recovery even at large positive pressures. However, the optimal morphology for self-recovery, the square pore, is suboptimal for the functional properties of the surface, for example, high slippage. Our calculations show that these two properties are related to regions of the texture separated in space: self-recovery is controlled by the characteristics of the bottom surface, while wetting and slip are controlled by the cavity mouth. We thus propose a modular design strategy which combines self-recovery and good functional properties: Square pores surmounted by ridges achieve self-recovery even at 2 MPa and have a very small liquid/solid contact area. The macroscopic calculations, which allowed us to efficiently devise design criteria, have been validated by atomistic simulations, with the optimal texture showing self-recovery on atomic time scales, τ ∼ 2 ns.

Wetting and cavitation pathways on nanodecorated surfaces.

In this contribution we study the wetting and nucleation of vapor bubbles on nanodecorated surfaces via free energy molecular dynamics simulations. The results shed light on the stability of superhydrophobicity in submerged surfaces with nanoscale corrugations. The re-entrant geometry of the cavities under investigation is capable of sustaining a confined vapor phase within the surface roughness (Cassie state) both for hydrophobic and hydrophilic combinations of liquid and solid. The atomistic system is of nanometric size; on this scale thermally activated events can play an important role ultimately determining the lifetime of the Cassie state. Such a superhydrophobic state can break down by full wetting of the texture at large pressures (Cassie-Wenzel transition) or by nucleating a vapor bubble at negative pressures (cavitation). Specialized rare event techniques show that several pathways for wetting and cavitation are possible, due to the complex surface geometry. The related free energy barriers are of the order of 100kBT and vary with pressure. The atomistic results are found to be in semi-quantitative accord with macroscopic capillarity theory. However, the latter is not capable of capturing the density fluctuations, which determine the destabilization of the confined liquid phase at negative pressures (liquid spinodal).