Curvature as a Guiding Field for Patterns in Thin Block Copolymer Films
Experimental data on thin films of cylinder-forming block copolymers (BC)—free-standing BCmembranes as well as supported BC films—strongly suggest that the local orientation of the BC patternsis coupled to the geometry in which the patterns are embedded. We analyze this phenomenon using generalsymmetry considerations and numerical self-consistent field studies of curved BC films in cylindricalgeometry. The stability of the films against curvature-induced dewetting is also analyzed. In goodagreement with experiments, we find that the BC cylinders tend to align along the direction of curvature athigh curvatures. At low curvatures, we identify a transition from perpendicular to parallel alignm…
Order-Order Phase Transitions Induced by Supercritical Carbon Dioxide in Triblock Copolymer Thin Films
We study the influence of supercritical carbon dioxide (scCO2) on the phase behavior of a cylinder-forming polystyrene-block-polybutadiene-b-polystyrenetriblock copolymer thin film. Solvent annealing with scCO2 can produce patterns with long-range order but these structures become unstable for thin films with small thicknesses. These results are in good agreement with self-consistent mean field calculations, which indicate that a drying transition occurs for thicknesses below the radius of gyration of the molecule.After decompression and solvent extraction, the initially swollen polymer nanostructure suffers a strong reduction in the average domain spacing, which has a deleterious effect on…
Semiflexible Polymers in Spherical Confinement: Bipolar Orientational Order Versus Tennis Ball States
Densely packed semiflexible polymers with contour length L confined in spheres with radius R of the same order as L cannot exhibit uniform nematic order. Depending on the chain stiffness (which we vary over a wide range), highly distorted structures form with topological defects on the sphere surface. These structures are completely different from previously observed ones of very long chains winding around the inner surface of spheres and from nematic droplets. At high densities, a thin shell of polymers close to the sphere surface exhibits a tennis ball texture due to the confinement-induced gradual bending of polymer bonds. In contrast, when the contour length of the chains is significant…
Shear-aligned block copolymer monolayers as seeds to control the orientational order in cylinder-forming block copolymer thin films
We study the dynamics of coarsening of a cylinder-forming block copolymer thin film deposited on a prepatterned substrate made of a well-ordered block copolymer monolayer. During thermal annealing the shear-aligned bottom layer drives extinction of the disclinations and promotes a strong orientational correlation, disturbed only by dislocations and undulations along the cylinders of the minority phase. The thin film bilayer system remains stable during annealing, in agreement with self-consistent field theory results that indicate that although the thickness of a stack of two monolayers is not at the optimum thickness condition, it is very close to equilibrium. Phase field simulations indic…
Anomalous Slowdown of Polymer Detachment Dynamics on Carbon Nanotubes
The "wrapping" of polymer chains on the surface of carbon nanotubes allows one to obtain multifunctional hybrid materials with unique properties for a wide range of applications in biomedicine, electronics, nanocomposites, biosensors, and solar cell technologies. We study by means of molecular dynamics simulations the force-assisted desorption kinetics of a polymer from the surface of a carbon nanotube. We find that, due to the geometric coupling between the adsorbing surface and the conformation of the macromolecule, the process of desorption slows down dramatically upon increasing the windings around the nanotube. This behavior can be rationalized in terms of an overdamped dynamics with a…
Densely packed semiflexible macromolecules in a rigid spherical capsule
The ordering of semiflexible polymers with persistence length lp and contour length L confined in a sphere of radius R is studied by molecular dynamics simulations of a coarse-grained model. Monomer densities are chosen where the corresponding bulk lyotropic solution or melt is a well-ordered nematic, and purely repulsive walls of the rigid confining sphere are considered. It is found that polymers close to the walls are bent according to the curvature of the confining spheres with all their monomers in a few layers parallel to the sphere surface, whereas the remaining macromolecules closer to the sphere center have one chain end and their center of mass far from the surface. The latter cha…