Toward a flow-dependent phase-stability criterion: Osmotic pressure in sticky flowing suspensions

  • Derek E. Huang
    Department of Chemical Engineering, Stanford University , Stanford, California 94302, USA
  • Roseanna N. Zia
    Department of Chemical Engineering, Stanford University , Stanford, California 94302, USA

抄録

<jats:p>Equilibrium phase instability of colloids is robustly predicted by the Vliegenthart–Lekkerkerker (VL) critical value of the second virial efficient, but no such general criterion has been established for suspensions undergoing flow. A transition from positive to negative osmotic pressure is one mechanical hallmark of a change in phase stability in suspensions and provides a natural extension of the equilibrium osmotic pressure encoded in the second virial coefficient. Here, we propose to study the non-Newtonian rheology of an attractive colloidal suspension using the active microrheology framework as a model for focusing on the pair trajectories that underlie flow stability. We formulate and solve a Smoluchowski relation to understand the interplay between attractions, hydrodynamics, Brownian motion, and flow on particle microstructure in a semi-dilute suspension and utilize the results to study the viscosity and particle-phase osmotic pressure. We find that an interplay between attractions and hydrodynamics leads to dramatic changes in the nonequilibrium microstructure, which produces a two-stage flow-thinning of viscosity and leads to pronounced flow-induced negative osmotic pressure. We summarize these findings with an osmotic pressure heat map that predicts where hydrodynamic enhancement of attractive bonds encourages flow-induced aggregation or phase separation. We identify a critical isobar—a flow-induced critical pressure consistent with phase instability and a nonequilibrium extension of the VL criterion.</jats:p>

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