Yongyun Ji

SELF-ASSEMBLY OF LINEAR TRIBLOCK COPOLYMERS UNDER CYLINDRICAL NANOPORE CONFINEMENTS *

The self-assembly of linear ABC triblock copolymers under cylindrical confinements is investigated in two-dimensional space using the real-space self-consistent field theory. The effects of confinement degrees and preferential strengths on the triblock copolymer phase behaviors with special polymer parameters are first considered. On one hand, different confinement degrees cause different phase behaviors in nanopores with the neutral surfaces. Moreover, the strongly preferential surface fields can surpass the confinement degrees and volume fractions in determing the confined phase behaviors. On the other hand, in contrast, confined morphologies are more sensitive to the variations in the A-preferential surface field strength. Subsequently, the incompatibility degrees between different blocks are systematically varied under cylindrical nanopore confinements. Under cylindrical nanopore confinements, the morphologies are very sensitive to the variations in the incompatibility degrees. Meanwhile, nanopore confinements can affect order-disorder and order-order transition points in the bulk. The corresponding free, internal, and entropic energies as well as the order parameters are also quantificationally examined to deeply investigate the confined phase mechanisms, and a number of morphological transitions are confirmed to be of first-order. These findings may guide the design of novel nanostructures based on triblock copolymers by introducing confinements.

Surface-induced morphologies of ABC star triblock copolymer in spherical cavities

The morphologies and phase diagrams exhibited by symmetric ABC star triblock copolymer nanoparticles are investigated on the basis of real-space self-consistent field theory. The ABC star triblock copolymers were chosen to be tiling-forming with fixed polymer parameter and the spherical boundaries were modeled using the masking technique. We first study a number of examples where the ABC triblock copolymers confined in spherical cavities with neutral surface. Then, two types of spherical cavity distinct preferential surfaces are considered, including both A-block attractive and repulsive preferential surfaces. We aim at the effects due to various spherical cavity diameters and the degree of interactions between the polymer and the spherical surface. A variety of morphologies, such as ring-like structures, concentric sphere, and irregular cylinder, were identified in phase diagrams. The results show that both the degree of interactions and spherical diameters can influence the formation of morphologies so that ring-like structures and other novel structures could be obtained.

Adsorption Behavior of Polymer Chain with Different Topology Structure at the Polymer-Nanoparticle Interface

The effect of the polymer chain topology structure on the adsorption behavior in the polymer-nanoparticle (NP) interface is investigated by employing coarse-grained molecular dynamics simulations in various polymer-NP interaction and chain stiffness. At a weak polymer-NP interaction, ring chain with a closed topology structure has a slight priority to occupy the interfacial region than linear chain. At a strong polymer-NP interaction, the “middle” adsorption mechanism dominates the polymer local packing in the interface. As the increase of chain stiffness, an interesting transition from ring to linear chain preferential adsorption behavior occurs. The semiflexible linear chain squeezes ring chain out of the interfacial region by forming a helical structure and wrapping tightly the surface of NP. In particular, this selective adsorption behavior becomes more dramatic for the case of rigid-like chain, in which 3D tangent conformation of linear chain is absolutely prior to the 2D plane orbital structure of ring chain. The local packing and competitive adsorption behavior of bidisperse matrix in polymer-NP interface can be explained based on the adsorption mechanism of monodisperse (pure ring or linear) case. These investigations may provide some insights into polymer-NP interfacial adsorption behavior and guide the design of high-performance nanocomposites.