Entropy driven phase transitions in colloid-polymer suspensions: Tests of depletion theories

By S. Ramakrishnan, M. Fuchs, K. Schweizer, C. Zukoski. 2002

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The phase behavior of model athermal silica (radius R=50 nm)–polystyrene–toluene suspensions has been determined over nearly two orders of magnitude in polymer or colloid size asymmetry. Fluid–gel, fluid–crystal, and fluid–fluid transitions are observed as Rg, the polymer radius of gyration, increases. Based on the polymer concentration relative to the dilute–semidilute crossover density, cp/cp*, as the relevant measure of depletion attraction, we find that suspension miscibility monotonically improves as Rg increases for all colloid volume fractions. This trend is in contradiction to all classic depletion theories of which we are aware. However, the predictions of fluid–fluid spinodal phase separation by the microscopic polymer reference interaction site model integral equation theory of athermal polymer–colloid suspensions are in agreement with the experimental observations. Polymer–polymer interactions, chain fractal structure, and structural reorganizations are implicated as critical physical factors....

Subfields: Condensed Matter Physics, Materials Chemistry, Organic Chemistry

View Paper: https://www.semanticscholar.org/paper/fe56121ef998d8ff48f1636fb66f28d4acd4d2ea