Self-Consistent-Field and Hybrid Particle-Field Theory Simulation of Confined Copolymer and Nanoparticle Mixtures

Abstract

In this paper, we used combined self-consistent-field and hybrid particle-field theory to explore the self-assembly behavior of diblock copolymer-nanoparticle mixtures confined between two concentric circular walls. The simulation reveals that the structural frustration, the loss of conformational entropy of the copolymer, and the radii of the two concentric circles have great influence on the morphologies of the system. We also discuss the underlying mechanism of controlling the self-assembly of such a system in terms of enthalpic interaction between particles and copolymers, steric repulsive interactions between particles, and the conformational entropy of copolymers, and a representative phase diagram in terms of block ratio and the particle volume fraction is constructed. This study suggests a route to help experimentalists better create high-performance nanodevices.

Design principles for metamorphic block copolymer assemblies

“…For example, morphology transitions can be induced by changing the size of the solvent molecules, 14 varying the solution temperature 15 or by the addition of nanoparticles when the block copolymer chains are under confinement. 16 Numerical self-consistent field methods are appealing for their low computational cost and, unlike full computer simulations, are suitable for extensive systematic studies using a wide range of parameters. In this work, the metamorphic self-assembly of AB diblock copolymers is studied using Scheutjens-Fleer Self-Consistent Field (SF-SCF) theory.…”

Effect of selective nanoparticles on phase separation of copolymer–nanoparticle composites confined between two neutral surfaces

“…There are several theoretical and experimental studies on block copolymer nanocomposites conned in a lm, [19][20][21][22][23][24][25][26] nanopore, 27,28 and between two concentric circular walls. 29 In the conned state, the orientation of the microstructure and frustration-induced structural deformation are unique, which do not exist in the unconned system. As reported by Lee et al, 30 the conned copolymer nanocomposites can theoretically exhibit a rich phase behavior, which results from the interplay of entropic and enthalpic interactions among the constituents of conned composites.…”

Atomistic and mesoscopic simulations of the interfacial dynamics of polymer melts

“…Over the years, several hybrid particle-field (HPF) simulation schemes [197][198][199][200][201][202][203][204][205] have been developed with applications in homopolymers, 197,198,200 in self-assembly processes of diblock copolymers [198][199][200][201]203 , nanoparticles, 199,203 biophysics, 202,205 and more. There are many types of HPF approaches such as single chain mean field (SCMF), 197,198 Helmholtz energy density functional depending on the local density and derived from an equation of state that is consistent with the equilibrium volumetric properties of the melt.…”

“…117 The ability of the mesoscopic simulation scheme to converge to each of these stable nanophase-separated states is assessed. This is the first time that a HPF approach [197][198][199][200][201][202][203][204][205] or a slip-link / slip-spring approach 57,62-64 is employed to describe free polymer surfaces in conjunction with a realistic EoS and square gradient theory. Furthermore, in contrast to other HPF studies, [197][198][199][200][201][202][203][204][205] besides the prediction of equilibrium structure and phase transitions the approach allows for the prediction of viscoelastic and rheological properties under equilibrium 58,105 and nonequilibrium 105 conditions.…”

“…This is the first time that a HPF approach [197][198][199][200][201][202][203][204][205] or a slip-link / slip-spring approach 57,62-64 is employed to describe free polymer surfaces in conjunction with a realistic EoS and square gradient theory. Furthermore, in contrast to other HPF studies, [197][198][199][200][201][202][203][204][205] besides the prediction of equilibrium structure and phase transitions the approach allows for the prediction of viscoelastic and rheological properties under equilibrium 58,105 and nonequilibrium 105 conditions. The evolution of the entanglement network is tracked via a kMC simulation scheme operating on the slip-springs, which runs in parallel with the Brownian Dynamics of the beads.…”