Interpreting contact angle results under air, water and oil for the same surfaces

Abstract

Under-water and under-oil superhydropobicity and superhydrophilicity have gained significant attention over the last few years. In this study, contact angles on five flat surfaces (polypropylene, poly(methyl methacrylate), polycarbonate, TEFLON-FEP and glass slide) were measured in water drop-in-air, air bubble-under-water, oil drop-in-air, air bubble-under-oil, oil drop-under-water and water drop-under-oil conditions. Heptane, octane, nonane, decane, dodecane, and hexadecane hydrocarbons were used as oils. Immiscible water/oil pairs were previously mutually saturated to provide thermodynamical equilibrium conditions and their surface and interfacial tensions were determined experimentally. These pairs were used in the two-liquid contact angle measurements. Surface free energies of the solid surfaces in air were determined independently by using the van Oss Good method, using the contact angle results of pure water, ethylene glycol, formamide, methylene iodide and alpha-bromonaphalene. In addition, Zisman's 'critical surface tension' values were also determined for comparison. In theory, the summation of contact angle results in a complementary case would give a total of 180 degrees for ideal surfaces. However, it was determined that there are large deviations from this rule in practical cases and these deviations depend on surface free energies of solids. Three complementary cases of (water-in-air with air bubble-under-water); (oil-in-air with air bubble-under oil); and (oil-under-water with water-under-oil) were investigated in particular to determine the deviations from ideality. A novel approach, named 'complementary hysteresis' [gamma(WA)(cos theta(1) - cos theta(2)) and gamma(OW)(cos theta(6) - cos theta(5)) was developed where gamma(WA) and gamma(OW) represent the interfacial tensions of water/air and oil/water, and theta(1), theta(2), theta(5), and theta(6) were the contact angles of water/air, air bubble/water, oil/water and water/oil respectively. It was experimentally determined that complementary hysteresis varies almost linearly with the surface free energy of the flat solid samples. This is the first report showing the relation of the surface free energy of a solid which is determined under-air with the contact angles obtained on the same solid in different three-phase systems.