Understanding the effects of dipolar interactions on the thermodynamics of diblock copolymer melts

R Kumar and W Li and BG Sumpter and M Muthukumar, JOURNAL OF CHEMICAL PHYSICS, 151, 054902 (2019).

DOI: 10.1063/1.5114799

We present results highlighting the roles of dipolar interactions in affecting thermodynamics of diblock copolymer melts. Field theoretic methods and coarse-grained molecular dynamics (MD) simulations are used to understand the effects of dipolar interactions among copolymer segments. In particular, the effects of dipolar interactions on disorder-lamellar transition and domain spacing of the lamellar morphology are studied. It is shown that dipolar interactions stabilize the lamellar morphology over the disordered phase. Furthermore, the domain spacing for the lamellar morphology is predicted to increase with an increase in disparity between dipole moments of two kinds of monomers in the diblock or equivalently a mismatch in the dielectric constant of homopolymers forming the diblock. MD simulations reveal that additional orientational effects resulting from the anisotropic nature of the dipolar interaction potential are significant for highly polar monomers. In contrast, the field theoretic models based on orientationally averaged dipolar interaction potentials, such as those used in this work, fail to capture the effects of orientational correlations.

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