Yuhua Yin

Simulated annealing study of morphological transitions of diblock copolymers in solution

The simulated annealing method was applied to study the self-assembling process of diblock copolymers in selective solvents for one block. The simulation results illustrated that the morphologies of the copolymer aggregates strongly depend on the interactions between the core-forming blocks and the solvents and on the length of the corona-forming blocks. Multiple morphological transitions were observed in one system. The transition sequence (disordered state-spherical micelles-short rodlike micelles-long rodlike micelles-onionlike aggregates) was observed for copolymers with increasing core-solvent interaction. Similar transitions were observed with the decrease of the length of the corona-forming blocks. The mechanisms of these transitions are investigated. The simulation results are compared with experiments and other simulations.

Simulated annealing study of asymmetric diblock copolymer thin films

We report a simulated annealing study of the morphology of asymmetric diblock copolymer thin films confined between two homogeneous and identical surfaces. We have focused on copolymers that form a gyroidal morphology in the bulk. The morphological dependence of the confined films on the film thickness and the surface-polymer interaction has been systematically investigated. From the simulations it is found that much richer morphologies can form for the gyroid-forming asymmetric diblock copolymer thin films, in contrast to the lamella-forming symmetric and cylinder-forming asymmetric diblock copolymer films. Multiple morphological transitions induced by changing the film thickness and polymer-surface interactions are observed.

Self-assembly of grafted Y-shaped ABC triblock copolymers in solutions

Self-assembled morphologies of grafted Y-shaped ABC triblock copolymers are investigated using a simulated annealing method. The block copolymers are composed of two incompatible arms (A and B) and a short stem (C), with the C-stems grafted onto a flat surface. A rich array of novel morphologies is discovered. The formation of these morphologies is controlled by polymer grafting density, the incompatibility between the A-B-blocks, as well as the quality and selectivity of the solvents. In particular, it is observed that solvent selectivity drives lateral and/or perpendicular microphase separation. A phase diagram for systems with low grafting density is constructed. It is predicted that multiple morphological transitions, such as these from mixed or core-shell micelles to internally segregated micelles, to hamburger-like micelles, to segmented wormlike micelles, to connected micelles, and to split micelles, can be induced by varying either the incompatibility between the two arms or the quality of the solvents. These results are consistent with previous experiments and theories.

Effects of compositional polydispersity on gradient copolymer melts

The phase behavior of gradient copolymers is studied theoretically using random phase approximation (RPA) and self-consistent field theory (SCFT), focusing on the effects of monomer sequence distribution, or compositional polydispersity, of the polymer chains. The stability of the disordered phase is examined using RPA analysis, whereas the ordered phases of the system are studied using SCFT calculations. It is discovered that the critical domain spacing increases and the disorder-order transition temperature moves to higher values with the increase of the compositional polydispersity. SCFT results reveal that, depending on the value of the degree of segregation, structural change due to the different chain-to-chain monomer sequence distribution is controlled by two different mechanisms.

Influence of Grafting Point Distribution on the Surface Structures of Y-Shaped Polymer Brushes in Solution

We report a simulated annealing study of surface structures of the Y-shaped copolymers grafted onto a planar substrate in nonselective solvents. The influences of the lateral size of the grafting surface and the distribution manner of the grafting point on the order degree of the ripple structures are investigated. Under uniformly distribution conditions, it is found that the well-defined ripple structures can be formed when the lateral size less than a threshold which depends on the solvent quality and grafting density. However, introducing a density fluctuation into the uniformly distribution grafting points in different ways, the defects with different degrees are observed in the ripple structures. The influence of the density fluctuations on the ripple phase are studied quantitatively. Furthermore, the possibility of the formation of surface structures with long-range order induced by directed self-assembly is investigated. The findings provide guidelines for fabricating patterned surfaces with highly ordered structures.

Effect of Chain Architecture on Self-Assembled Aggregates from Cyclic AB Diblock and Linear ABA Triblock Copolymers in Solution

The self-assembly behaviors of two block copolymers with the same chain length but different chain architectures (cyclic AB, linear ABA) in B-selective solvents are investigated using Monte Carlo simulations. A morphological transition sequence, from spherical micelles to cylindrical micelles, to vesicles and then to multicompartment vesicles, is observed for both copolymer systems when the interaction between the solvophobic A-block and the solvent is increased. In particular, toroidal micelles could be formed in triblock systems due to the presence of the bridging chains at the parameter region between cylindrical micelles and vesicles whereas disklike micelles are formed in cyclic systems. The simulation results demonstrated that the architecture of block copolymers could be used to regulate the structural characteristics and thermal stability of these self-assembled aggregates.

Phase behavior of ABC-type triple-hydrophilic block copolymers in aqueous solutions.

Abstract.The phase behavior of symmetric ABC triple-hydrophilic triblock copolymers in concentrated aqueous solutions is investigated using a simulated annealing technique. Two typical cases, in which the hydrophilicity of the middle B-block is either stronger or weaker than that of the end A- and C-blocks, are studied. In these two cases, a variety of phase diagrams are constructed as a function of the volume fraction of the B-block and the copolymer concentration (

A Simulated Annealing Study of Diblock Copolymer Brushes in Selective Solvents

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Simulated annealing study of diblock copolymer thin films confined between two homogeneous surfaces.

for both non-frustrated and frustrated copolymers. Structures, such as two-color alternatingly packed cylinders or gyroid, and lamellae-in-lamellae etc. that do not occur in the melt system, are obtained in solutions. Rich phase transition sequences, especially re-entrant phase transitions involving complex continuous networks of alternating gyroid and alternating diamond are observed for a given copolymer with decreasing

Fast off-lattice Monte Carlo simulations with “soft” repulsive potentials

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