Assessment of Kerogen Wettability from Contact Angle Goniometry

Understanding the wetting properties of shale reservoirs can benefit their development for energy-related purposes and their potential for long-term carbon dioxide injection and storage. Given its potential volumetric abundance and high surface area, the wetting behavior of kerogen in shale requires assessment. Despite their known limitations, wettability studies are commonly limited to static contact angle (θ) measurements. In this Article, the conflicting factors related to the analysis and interpretation of kerogen wetting via static contact angle measurements are discussed. Contact angle data for deionized water, brine (5% NaCl), and n-dodecane are presented for seven paleomarine type-II kerogens spanning a wide range of thermal maturities (vitrinite reflectance, R_o: 0.55 to 2.75%) and chemical composition (aromatic carbon content, H/C ratio, O/C ratio). Droplets of n-dodecane instantaneously absorbed (θ* ≈ 0°) upon contact with all kerogen pellet surfaces, showing the oleophilic nature of kerogen for all maturities tested. Apparent contact angles of water with kerogen surfaces were positively correlated with H/C ratios and inversely correlated with aromatic carbon content, while the bulk and surface oxygen concentrations did not strongly correlate with the measured data. Kerogen exhibited hydrophobic (θ_water > 90°) behavior, except at the highest thermal maturities. For example, the least thermally mature and most thermally mature samples studied presented apparent contact angles for water of 123 ± 15 and 59 ± 10°, respectively. Profilometry analyses showed roughness average values ranging from 0.4 ± 0.1 to 3.9 ± 0.7 μm, with the indication that sample topology can affect measured contact angles, albeit in second order as compared to sample chemistry in this study. We recommend caution when associating contact angle data alone with wetting behavior, as data obtained through sessile droplet analysis are subject to known but not always considered, caveats.