Phase diagrams of binary mixtures of patchy colloids with distinct numbers of patches: The network fluid regime

Details Phase diagrams of binary mixtures of patchy colloids with distinct numbers of patches: The network fluid regime Phase diagrams of binary mixtures of patchy colloids with distinct numbers of patches: The network fluid regime

2010-12-16

arxiv.org/abs/1012.3605v2

Physics

Condensed Matter

Soft Condensed Matter

14 pages, 12 figures. Accepted for publication in Soft Matter

Scientific paper

10.1039/C0SM01493A

We calculate the network fluid regime and phase diagrams of binary mixtures of patchy colloids, using Wertheim's first order perturbation theory and a generalization of Flory-Stockmayer's theory of polymerization. The colloids are modelled as hard spheres with the same diameter and surface patches of the same type, $A$. The only difference between species is the number of their patches -or functionality-, $f_A^{(1)}$ and $f_A^{(2)}$ (with $f_A^{(2)}>f_A^{(1)}$). We have found that the difference in functionality is the key factor controlling the behaviour of the mixture in the network (percolated) fluid regime. In particular, when $f_A^{(2)}\ge2f_A^{(1)}$ the entropy of bonding drives the phase separation of two network fluids which is absent in other mixtures. This changes drastically the critical properties of the system and drives a change in the topology of the phase diagram (from type I to type V) when $f_A^{(1)}>2$. The difference in functionality also determines the miscibility at high (osmotic) pressures. If $f_A^{(2)}-f_A^{(1)}=1$ the mixture is completely miscible at high pressures, while closed miscibility gaps at pressures above the highest critical pressure of the pure fluids are present if $f_A^{(2)}-f_A^{(1)}>1$. We argue that this phase behaviour is driven by a competition between the entropy of mixing and the entropy of bonding, as the latter dominates in the network fluid regime.

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