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Arrested spinodal decomposition in polymer brush collapsing in poor solvent

Accepted version
Peer-reviewed

Repository DOI


Type

Article

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Authors

Lappala, A 
Mendiratta, S 
Terentjev, EM 

Abstract

We study the Brownian dynamics of flexible and semiflexible polymer chains densely grafted on a flat substrate, upon rapid quenching of the system when the quality of solvent becomes poor and chains attempt collapse into a globular state. The collapse process of such a polymer brush differs from individual chains, both in its kinetics and its structural morphology. We find that the resulting collapsed brush does not form a homogeneous dense layer, in spite of all chain monomers equally attracting each other via a model Lennard-Jones potential. Instead, a very distinct inhomogeneous density distribution in the plane forms, with a characteristic length scale dependent on the quenching depth (or equivalently, the strength of monomer attraction) and the geometric parameters of the brush. This structure is identical to the spinodal-decomposition structure, however, due to the grafting constraint we find no subsequent coarsening: the established random bundling with characteristic periodicity remains as the apparently equilibrium structure. We compare this finding with a recent field-theoretical model of bundling in a semiflexible polymer brush.

Description

Keywords

cond-mat.soft, cond-mat.soft

Journal Title

Macromolecules

Conference Name

Journal ISSN

0024-9297
1520-5835

Volume Title

48

Publisher

American Chemical Society (ACS)
Sponsorship
Engineering and Physical Sciences Research Council (EP/F032773/1)
Engineering and Physical Sciences Research Council (EP/J017639/1)
This work was funded by the Osk. Huttunen Foundation (Finland) and the Cambridge Theory of Condensed Matter Grant from EPSRC. Simulations were performed using the Darwin supercomputer of the University of Cambridge High Performance Computing Service provided by Dell Inc. using Strategic Research Infrastructure funding from the Higher Education Funding Council for England.