The Landau-de Gennes free energy expansion of a melt of V-shaped polymer molecules

J Chem Phys. 2016 Aug 28;145(8):084908. doi: 10.1063/1.4961662.

Abstract

The phase behavior of a monodisperse melt of polymer molecules consisting of two rod-like segments joined at an angle α has been inspected within the Landau theory of phase transitions. The interactions between monomer units were assumed to be of the Maier-Saupe form. The Landau-de Gennes expansion of the free energy of the melt has been obtained up to the sixth order in powers of the nematic order parameter, the coefficients of this expansion have been calculated from the microscopic model of polymer molecule. The phase diagram contains the regions of stability of isotropic, prolate uniaxial, oblate uniaxial, and biaxial nematic phases. The isotropic-uniaxial nematic and uniaxial-biaxial nematic transitions are of the first and second order, respectively. We found two Landau points in the phase diagram at which continuous transition from biaxial nematic state to isotropic phase occurs.