Temperature-actuated changes in wettability at elastomer/water interfaces.

Surface modification of 1,4-polybutadiene and cis-1,4-polyisoprene to introduce polar functional groups provided surfaces that reconstructed reversibly against water as a function of temperature. These surfaces became hydrophobic in contact with hot water, but their original hydrophilicity returned upon equilibration against cold water. Repeated cycling between hot and cold water, however, led to a damping of this reversibility. A series of parallel experiments on both the interfacial and bulk behavior of these elastomers strongly indicated that this damping was due to the alignment of extended interfacial chains during temperature cycling and to a decay of the restoring force on the interfacial chains under extension. These studies thus demonstrate that the interfacial behavior of elastomers can display close analogies to the bulk viscoelastic properties of the solid.