Residual patterns of alkyl polyoxyethylene surfactant droplets after water evaporation

Using a nonionic, alkyl polyoxyethylene surfactant (X-77) in aqueous solutions, sessile droplet spreading, pinning, evaporation, contraction, and post-evaporation deposits are characterized. X-77 is widely used in the agricultural field as a spreader/adherent, intended to optimize pathenogenic agent coverage. Using a single droplet size under monitored temperature conditions, we control humidity, substrate hydrophobicity, and surfactant concentration to mimic varying agricultural conditions. For hydrophilic surfaces, the droplet spreads, reaching and retaining a maximum, stationary size. At this stage, a ring accretion occurs at the maximum spread diameter. During the final stage, the water film retracts, resulting in deposition of small islands of surfactant residue inside the ring. At lower concentrations of surfactant, we discover ring formations that break-up into "ring islands" at late-stage evaporation, accompanied by a distribution of the smaller islands in the interior portion of the substrate contact area. These are promoted by higher relative humidity. At higher concentrations, only a solid ring of surfactant remains, post-evaporation. Increasing surfactant concentration tends to increase the mean of the interior island size and to broaden the overall island size distribution. On sufficiently hydrophobic surfaces, surfactant-laden droplets do not evidence pinning, ring formations, or post-evaporation interior islands. Interestingly, lower humidity increases spreading at higher surfactant concentrations. Such pattern formations of surfactant deposit are reported for the first time and are of significance in projecting how surfactants such as X-77 distribute pesticides or other chemicals on leaf surfaces.