Entropy-induced separation of star polymers in porous media

Abstract

We present a quantitative picture of the separation of star polymers in a solution where part of the volume is influenced by a porous medium. To this end, we study the impact of long-range-correlated quenched disorder on the entropy and scaling properties of f-arm star polymers in a good solvent. We assume that the disorder is correlated on the polymer length scale with a power-law decay of the pair correlation function g(r) approximately r-a. Applying the field-theoretical renormalization group approach we show in a double expansion in epsilon=4-d and delta=4-a that there is a range of correlation strengths delta for which the disorder changes the scaling behavior of star polymers. In a second approach we calculate for fixed space dimension d=3 and different values of the correlation parameter a the corresponding scaling exponents gammaf that govern entropic effects. We find that gammaf-1, the deviation of gammaf from its mean field value is amplified by the disorder once we increase delta beyond a threshold. The consequences for a solution of diluted chain and star polymers of equal molecular weight inside a porous medium are that star polymers exert a higher osmotic pressure than chain polymers and in general higher branched star polymers are expelled more strongly from the correlated porous medium. Surprisingly, polymer chains will prefer a stronger correlated medium to a less or uncorrelated medium of the same density while the opposite is the case for star polymers.