Contact angle hysteresis on fluoropolymer surfaces.

Contact angle hysteresis of liquids with different molecular and geometrical properties on high quality films of four fluoropolymers was studied. A number of different causes are identified for hysteresis. With n-alkanes as probe liquids, contact angle hysteresis is found to be strongly related to the configuration of polymer chains. The largest hysteresis is obtained with amorphous polymers whereas the smallest hysteresis occurs for polymers with ordered molecular chains. This is explained in terms of sorption of liquid by the solid and penetration of liquid into the polymer film. Correlation of contact angle hysteresis with the size of n-alkane molecules supports this conclusion. On the films of two amorphous fluoropolymers with different molecular configurations, contact angle hysteresis of one and the same liquid with "bulky" molecules is shown to be quite different. On the surfaces of Teflon AF 1600, with stiff molecular chains, the receding angles of the probe liquids are independent of contact time between solid and liquid and similar hysteresis is obtained for all the liquids. Retention of liquid molecules on the solid surface is proposed as the most likely cause of hysteresis in these systems. On the other hand, with EGC-1700 films that consist of flexible chains, the receding angles are strongly time-dependent and the hysteresis is large. Contact angle hysteresis increases even further when liquids with strong dipolar intermolecular forces are used. In this case, major reorganization of EGC-1700 chains due to contact with the test liquids is suggested as the cause. The effect of rate of motion of the three-phase line on the advancing and receding contact angles, and therefore contact angle hysteresis, is investigated. For low viscous liquids, contact angles are independent of the drop front velocity up to approximately 10 mm/min. This agrees with the results of an earlier study that showed that the rate-dependence of the contact angles is an issue only for liquids with high viscosity.