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 $g(r) \sim r^{-a}$. Applying the field-theoretical renormalization group approach we show in a double expansion in $ε=4-d$ and $δ=4-a$ that there is a range of correlation strengths $δ$ 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 $γ_f$ that govern entropic effects. We find that $γ_f-1$, the deviation of $γ_f$ from its mean field value is amplified by the disorder once we increase $δ$ beyond a threshold. The consequences for a solution of diluted chain and star polymers of equal molecular weight inside a porous medium are: 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.