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Defect-Mediated Rheology of Block Copolymers

Published online by Cambridge University Press:  29 November 2013

Steven D. Hudson ,
Karl R. Amundson ,
Hong G. Jeon  and
Steven D. Smith
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Block copolymer melts with a near-symmetric composition can microphase-separate to form a lamellar morphology where unfavorable monomeric interactions are reduced by an antiparallel layering of the polymer chains (see Figure 2, discussed later). The symmetry of such a block copolymer is the same as for small-molecule, smectic-A liquid crystals, which also exhibit (parallel or antiparallel) layering. Because of their shared symmetry, their quasistatic mechanical properties are of the same form. To lowest order, the energy of distortion of the lamellar pattern can be expressed as a sum of a compressional/dilational and a bend energy (see, for example, Reference 2):

where n is a unit vector normal to the layers, and ε and ∇ n are the layer dilational and bending strain, respectively. B and K are the corresponding moduli. These have been measured only recently for block copolymers. The ratio of these moduli yields a characteristic microscopic length:

which is calculated to be a fraction of the layer spacing d0.

Similarities are also found in the dynamic properties of polymeric and smallmolecule smectics. These similarities are found at low strain rate and amplitude where the rheological response is controlled by their similar layered structures and associated defects. During either steady or dynamic shear, certain defect and domain motions are induced such that a steady-state alignment of the director has been observed. In this report, we discuss defect structure and how the much more viscous nature of these polymeric layered materials influences the distribution and relative population of each defect type. We also discuss how these defects can control material stress-relaxation behavior.

Type
Defects in Polymers
Information
MRS Bulletin , Volume 20 , Issue 9 , September 1995 , pp. 42 - 46
Copyright
Copyright © Materials Research Society 1995

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