Molecular insights into fluid-solid interfacial tensions in water + gas + solid systems at various temperatures and pressures

The fluid-solid interfacial tension is of great importance to many applications including the geological storage of greenhouse gases and enhancing the recovery of geo-resources, but it is rarely studied. Extensive molecular dynamics simulations are conducted to calculate fluid-solid interfacial properties in H2O + gas (H2, N2, CH4, and CO2) + rigid solid three-phase systems at various temperatures (298-403 K), pressures (0-100 MPa), and wettabilities (hydrophilic, neutral, and hydrophobic). Our results on the H2O + solid system show that vapor-solid interfacial tension should not be ignored in cases where the fluid-solid interaction energy is strong or the contact angle is close to 90°. As the temperature rises, the magnitude of H2O's liquid-solid interfacial tension declines because the oscillation of the interfacial density/pressure profile weakens at high temperatures. However, the magnitude of H2O vapor-solid interfacial tension is enhanced with temperature due to the stronger adsorption of H2O. Moreover, the H2O-solid interfacial tension in H2O + gas (H2 or N2) + solid systems is weakly dependent on pressure, while the pressure effects on H2O-solid interfacial tensions in systems with CH4 or CO2 are significant. We show that the assumption of pressure independent H2O-solid interfacial tensions should be cautiously applied to Neumann's method for systems containing non-hydrophilic surfaces with strong gas-solid interaction. Meanwhile, the magnitude of gas-solid interfacial tension increases with pressure and gas-solid interaction. High temperatures generally decrease the magnitude of gas-solid interfacial tensions. Further, we found that the increment of contact angle due to the presence of gases follows this order: H2 < N2 < CH4 < CO2.