Effect of added free polymer on the swelling of neutral microgel particles: a thermodynamic approach

Microgel particles based on poly (N-isopropylacrylamide) have been shown to display an initial swelling behavior, followed by a collapse, with increasing concentration of added poly(ethylene oxide), PEO, chains. This paper considers the thermodynamic reasons for the observed expansion and subsequent shrinkage of the particles. At low concentrations of PEO, the free chains permeate into the microgel particles and cause an increase in osmotic pressure, expanding the particles. At higher concentrations of PEO, the particles are saturated and an increase in osmotic pressure in the external phase causes the particles to collapse again. The calculated magnitude of swelling and the effect of PEO molecular weight are, at least qualitatively, in agreement with the experimental observations reported elsewhere.