The contact angle (CA) formed at equilibrium at the three‐phase line of contact between a liquid, a solid, and a gas may be expressed as a function of both the interfacial and surface tensions. Young first derived this thermodynamic relationship in 1805. In practice, multiple CA values are observed due to kinetic phenomena induced by evaporation, vapour adsorption, or swelling, and thermodynamic ones induced by roughness and surface chemical heterogeneities, even at molecular‐scale. These non‐ideal conditions result into an hysteresis, i.e., a difference between wetting and dewetting behaviours, and Young's equation rarely applies. Three measuring methods stand out for their applicability and reliability. In the sessile drop method, a syringe deposits a liquid drop on a flat surface and the contact angle is measured through optical means based on the drop shape. In the Wilhelmy balance method, the force required to immerse a solid plate in a bath of liquid is indirectly related to the contact angle. In the Washburn capillary rise method, the contact angle is derived from the rate at which a liquid rises by capillarity through a packed bed of powder. Employing probe liquids of various polarities, the free surface energy of the solid may be estimated. Over the last two years, ∼8600 published articles mentioned “contact angle” in their topic. Their main focus was either to develop the fundamental understanding of wetting science, or to assess the success of surface modification methods for the production of novel surfaces, composites, and membranes with enhanced wetting, adhesive, and filtration properties.

Cellulose nanocrystal (CNC)-based materials display apparently erratic wetting behaviors with contact angle (CA) variations as large as 30°from sample to sample. This work hypothesizes that it is the orientation of CNC amphiphilic functionalities at the interface with air that causes the variability in CA. By exploiting relationships with the Hansen solubility parameter theory, a set of surface tension parameters is proposed for both the polar and the non-polar surfaces of cellulose I β nanocrystals. These coefficients elucidate the wettability of CNC materials by establishing a correlation between the wetting properties of the air/sample interface and its chemical composition in terms of non-polar moieties. Advancing/receding CA experiments suggest that, while spin-coating CNC suspensions yield purely polar films, oven-casting them produces amphiphilic surfaces. We proposed a mechanism where the state of dispersion (individual or agglomerated) in which CNCs reach the air/water interface during casting is the determining factor: while individual nanocrystals find it more stable to orient their non-polar surfaces toward the interface, the aspect ratio of CNC agglomerates favors an orientation of their polar surfaces. This represents the first compelling evidence of CNC orientation at an interface and can be applied to Pickering emulsions and nanocomposites and to the production of CNC materials with tuned wettability.