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Journal ArticleDOI

Thermodynamic Free Energy Behavior of Diblock Copolymer Chains Confined Between Planar Surfaces Having End-Tethered Flexible Polymer Molecules

10 May 2012-Journal of Macromolecular Science, Part B (Taylor & Francis Group)-Vol. 51, Iss: 7, pp 1282-1302
TL;DR: In this article, a molecular model for the free energy of a confined system of diblock copolymer chains within a 2D slit with the interior surfaces having end-tethered chains is presented, based on a combined lattice and scaling theory approach.
Abstract: A molecular model for the free energy of a confined system of diblock copolymer chains within a 2D slit with the interior surfaces having end-tethered chains is presented, based on a combined lattice and scaling theory approach. The thermodynamics of a model system, based on a constrained minimization of free energy, is explored as a function of the intermolecular energy parameters for interaction between the segments of block copolymer chains, end-tethered chains, and the surfaces. The effects of chain length and the block length ratio are investigated over a wide range of values. The results obtained are qualitative in nature; however, the model can be implemented to real systems provided appropriate parameterization of the model parameters to real systems can be performed. The phase diagrams obtained here provide ways for designing thermodynamically stable systems within the physical parametric variable space.
Citations
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01 Mar 2000
TL;DR: In this paper, a simulation of the flow of a symmetric diblock copolymer from a bulk melt into a slit whose surfaces are modified by grafted surfactant chains, and whose walls are maintained at a constant pressure to permit the slit to open as polymer intercalates, is presented.
Abstract: Polymer-layered silicate nanocomposites may be formed by annealing layered silicate particles with a polymer melt. Polymer molecules flow from a bulk melt into the galleries between silicate sheets, swelling the silicate structure. The use of an amphiphilic intercalant raises possibilities of forming novel structures and enhancing the intercalation kinetics relative to the case of homopolymer intercalants. We perform molecular dynamics simulations of the flow of a symmetric diblock copolymer from a bulk melt into a slit whose surfaces are modified by grafted surfactant chains, and whose walls are maintained at a constant pressure to permit the slit to open as polymer intercalates. Intercalation kinetics are examined for a variety of polymer–surface and interblock interactions and for thermodynamic states in which the bulk polymer occupies either a lamellar or disordered phase. Comparison to previous simulations of homopolymer intercalation demonstrates that diblock copolymers may be used to intercalate a block that would not spontaneously intercalate as a homopolymer.

34 citations

References
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Journal ArticleDOI
TL;DR: It is found that on decreasing the copolymer concentration, a reentrant structural transformation between hexagonal --> lamellar --> hexagonal phases occurs as a result of the competition between the wetting effect of the brush surface and the bulk phase behavior of the asymmetricCopolymer driven by the A-B interfacial tension.
Abstract: We study the equilibrium morphology of an asymmetric A-B diblock copolymer solution film confined between homopolymer-grafted substrates by using self-consistent-field calculations. We find that on decreasing the copolymer concentration, a reentrant structural transformation between hexagonal --> lamellar --> hexagonal phases occurs as a result of the competition between the wetting effect of the brush surface and the bulk phase behavior of the asymmetric copolymer driven by the A-B interfacial tension.

10 citations

Journal ArticleDOI
TL;DR: In this article, scaling analyses were used to study the adsorption of A-B diblock copolymers on spherical colloidal particles of finite sizes in a selective solvent good for the B-block and poor for the A-block.

10 citations


Additional excerpts

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Journal ArticleDOI

8 citations

Journal ArticleDOI
TL;DR: The theoretical predictions on the density profiles of the polymer and the solvent molecules are found to agree quite well with the Monte Carlo simulation results for varying densities, chain lengths, wall separations, and different sets of interaction potentials.
Abstract: A density functional theory is presented to study the effect of attractions on the structure of polymer solutions confined between surfaces. The polymer molecules have been modeled as a pearl necklace of freely jointed hard spheres and the solvent as hard spheres, both having Yukawa-type attractions and the mixture being confined between attractive Yukawa-type surfaces. The present theory treats the ideal gas free energy functional exactly and uses weighted density approximation for the hard chain and hard sphere contributions to the excess free energy functional. The attractive interactions are calculated using the direct correlation function obtained from the polymer reference interaction site model theory along with the mean spherical approximation closure. The theoretical predictions on the density profiles of the polymer and the solvent molecules are found to agree quite well with the Monte Carlo simulation results for varying densities, chain lengths, wall separations, and different sets of interaction potentials.

6 citations

Journal ArticleDOI
TL;DR: In this article, the properties of simple models of linear and star-branched polymer chains confined in a slit were studied and Monte Carlo simulations with a sampling algorithm based on chain's local changes of conformation were carried out.
Abstract: We studied the properties of simple models of linear and star-branched polymer chains confined in a slit. The polymer chains were built of united atoms and were restricted to a simple cubic lattice. Two macromolecular architectures of the chain: linear and star-branched with three branches (of equal length) were studied. The excluded volume was the only potential introduced into the model and thus, the system was athermal. The chains were put between two parallel and impenetrable surfaces. Monte Carlo simulations with a sampling algorithm based on chain’s local changes of conformation were carried out. The differences and similarities in the global size and the structure and of linear and star-branched chains were shown and discussed.

6 citations