Phase behavior of a suspension of hard spherocylinders plus ideal polymer chains

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We study isotropic-isotropic and isotropic-nematic phase transitions of fluid mixtures containing hard spherocylinders (HSC) and added non-adsorbing ideal polymer chains using scaled particle theory (SPT). First, we investigate isotropic-nematic (I -N phase coexistence using SPT in the absence of polymer. We compare the results obtained using a Gaussian form of the orientational distribution function (ODF) to minimize the free energy versus minimizing numerically. We find that formal numerical minimization gives results that are much closer to computer simulation results. In order to describe mixtures of HSC plus ideal chains we studied the depletion of ideal chains around a HSC. We analyze the density profiles of ideal chains near a hard cylinder and find the depletion thickness delta is a function of the ratio of the polymer's radius of gyration R(g) and the cylinder radius R(c). Our results are compared with a common approximation in which the depletion thickness is taken equal to the radius of gyration of the polymer chain. We incorporate the correct depletion thickness into SPT and find that for R (g)/R (c) < 1.56 using ideal chains gives phase transitions at smaller polymer concentrations, whereas for R (g)/R (c) > 1.56 , which is a common experimental situation, the phase transitions are found at larger polymer concentrations with respect to delta = R (g) . The differences are significant, especially for R (g) >> R (c) , so we can conclude it is essential to take into account the properties of ideal polymer chains and the resulting depletion near a cylinder. Finally, we present phase diagrams for rod-polymer mixtures which could be realized under experimental conditions.