Process-directed self-assembly of multiblock copolymers: Solvent casting vs spray coating*
Institut für Theoretische Physik, Georg-August-Universität, 37077 Göttingen, Germany
Received: 15 April 2016
Revised: 9 June 2016
Published online: 18 July 2016
Using computer simulation of a soft, coarse-grained model and self-consistent field theory we investigate how collapsed, globular chain conformations in the initial stages of structure formation, which are produced by spray-coating, affect the single-chain structure and morphology of microphase-separated multiblock copolymers. Comparing spray-coated films with films that start from a disordered state of Gaussian chains, we observe that the collapsed molecular conformations in the initial stage give rise to (1) a smaller fraction of blocks that straddle domains (bridges), (2) a significant reduction of the molecular extension normal to the internal interfaces, and (3) a slightly larger lamellar domain spacing in the final morphology. The relaxation of molecular conformations towards equilibrium is very protracted for both processes – solvent casting and spray coating. These findings illustrate that the process conditions of the copolymer materials may significantly affect materials properties (such as mechanical properties) because the system does not reach thermal equilibrium on the relevant time scales.
© EDP Sciences, Springer-Verlag, 2016