Depleted Depletion Drives Polymer Swelling in Poor Solvent Mixtures

Abstract

Macromolecular solubility in solvent mixtures often exhibit striking and paradoxical nature. For example, when two well miscible poor solvents for a given polymer are mixed together, the same polymer may swell within intermediate mixing ratios. We combine computer simulations and theoretical arguments to unveil the first microscopic, generic origin of this collapse-swelling-collapse scenario. We show that this phenomenon naturally emerges at constant pressure in mixtures of purely repulsive components, especially when a delicate balance of the entropically driven depletion interactions is achieved.

References in corpus (2)

• Co-non-solvency: Mean-field polymer theory does not describe polymer collapse transition in a mixture of two competing good solvents
• Dramatic effect of fluid chemistry on cornstarch suspensions: linking particle interactions to macroscopic rheology

Cited by in corpus (11)

• Numerical modelling of non-ionic microgels: an overview
• Why Do Elastin-Like Polypeptides Possibly Have Different Solvation Behaviors in Water-Ethanol and Water-Urea Mixtures?
• Comparing simulated specific heat of liquid polymers and oligomers to experiments
• Tuning morphology and thermal transport of asymmetric smart polymer blends by macromolecular engineering
• Elasticity and thermal transport of commodity plastics
• Comparison of all atom and united atom models for thermal transport calculations of amorphous polyethylene
• The conformational phase diagram of neutral polymers in the presence of attractive crowders
• Computing the thermal transport coefficient of neutral amorphous polymers using exact vibrational density of states: Comparison with experiments
• Correlating thermodynamics, morphology, mechanics and thermal transport in PMMA-PLA blends
• Simple generic picture of toughness in solid polymer blends
• Thermal conductivity of commodity polymers under high pressures