Synergic Swelling of Interactive Network Support and Block Copolymer Films during Solvent Vapor Annealing.

We report the effect of "interactive" polymer network (PN) supports on the solvent-vapor processing of thin polymer films. Densely cross-linked surface-attached network exhibits under experimental time scale a glassy swelling behavior with the conformational states and solvent-uptake clearly sensitive to the degree of solvent vapor saturation in the atmosphere. Pretreatment of the thermally cured PN films by complete immersion or by swelling in saturated chloroform vapors facilitates relaxation of the residual stresses and induces irreversible changes to the network structure as revealed by the swelling/deswelling tests. The presence of a polymer film on top of the PN support results in a mutual influence of the layers on the respective swelling kinetics, steady-state solvent uptake, and chain dynamics. Using UV-vis ellipsometry, we revealed a significantly faster swelling and higher solvent uptake of glassy PN layer below a polymer film as compared to a single PN layer on silicon substrate. Remarkably, the swelling of the network support continues to increase even when the overall swelling of the bilayer is in a steady-state regime. Block copolymer films on PN supports exhibit a faster ordering dynamics and exceptional stability toward dewetting as compared to similar films on silicon wafers. The mechanical stress produced by continuously swelling PN is suggested to account for the enhanced segmental dynamics even at low solvent concentration in the block copolymer film. Apart from novel insights into dynamics of solvent uptake by heterogeneous polymer films, these results might be useful in developing novel approaches toward fast-processing/annealing of functional polymer films and fibers.

Morphology-Controlled Kinetics of Solvent Uptake by Block Copolymer Films in Nonselective Solvent Vapors.

We compare the swelling behavior of a compositionally symmetric diblock copolymer in films with nonbulk micellar morphology and with vertically oriented lamellae. The morphologies preformed by spin-coating from selective/nonselective solvents differ in shape and total area of the AB interfaces between incompatible units. Experimental measurements and dissipative particle dynamics (DPD) simulations demonstrate that AB interfaces dominate as the diffusion pathways of nonselective solvent molecules in strongly segregated films. In experiments, the lamellar films swell about 20× faster as compared to densely packed micellar structures, while the degrees of swelling at saturation are equal for the two types of morphologies. The difference in the kinetics of solvent uptake vanishes as soon as the solvent plasticizing effect allows for micelles-to-lamellae transition. DPD simulations confirm the inhomogeneous distribution of the solvent inside the film, with the higher fraction of the solvent localized at the AB interface and reveal morphology-dependent kinetics of the solvent uptake. The effect of dissimilar abilities of the nanodomains and of AB interface to serve as diffusion pathways for small molecules may find potential in designing nanosensors and heterogeneous barrier layers.