No abstract

To address the high salinity of flow-back water during hydraulic fracturing, we have studied the equilibrium partitioning of NaCl and water between the bulk phase and clay pores. In shale rocks, such a partitioning can occur between fractures with a bulk-like phase and clay pores. We use an advanced Grand Canonical Monte Carlo (GCMC) technique based on fractional exchanges of dissolved ions and water molecules. We consider a typical shale gas reservoir condition of a temperature of 365 K and pressure of 275 bar, and we represent clay pores by pyrophyllite and Na-montmorillonite slits of a width ranging from about 7 to 28 Å, covering clay pores from dry clay to clay pores with a bulk-like layer in the middle of the pore. We employ the Joung-Cheatham model for ions, SPC/E model for water and CLAYFF for the clay pores. We first determine the chemical potentials for NaCl and water in the bulk phase using Osmotic Ensemble Monte Carlo simulations. The chemical potentials are then used in GCMC to simulate the adsorption of ions and water molecules in the clay pores, and in turn to predict the salt solubility in confined solutions. Besides the thermodynamic properties, we evaluate the structure and in-plane diffusion of the adsorbed fluids, and ion conductivities.

We employ molecular dynamics simulations to study the wettability of nanoscale rough surfaces in systems governed by Lennard-Jones (LJ) interactions. We consider both smooth and molecularly rough planar surfaces. Solid substrates are modeled as a static collection of LJ particles arranged in a face-centered cubic lattice with the (100) surface exposed to the LJ fluid. Molecularly rough solid surfaces are prepared by removing several strips of LJ atoms from the external layers of the substrate, i.e., forming parallel nanogrooves on the surface. We vary the solid-fluid interactions to investigate strongly and weakly wettable surfaces. We determine the wetting properties by measuring the equilibrium droplet profiles that are in turn used to evaluate the contact angles. Macroscopic arguments, such as those leading to Wenzel's law, suggest that surface roughness always amplifies the wetting properties of a lyophilic surface. However, our results indicate the opposite effect from roughness for microscopically corrugated surfaces, i.e., surface roughness deteriorates the substrate wettability. Adding the roughness to a strongly wettable surface shrinks the surface area wet with the liquid, and it either increases or only marginally affects the contact angle, depending on the degree of liquid adsorption into the nanogrooves. For a weakly wettable surface, the roughness changes the surface character from lyophilic to lyophobic due to a weakening of the solid-fluid interactions by the presence of the nanogrooves and the weaker adsorption of the liquid into the nanogrooves.

No abstract