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Tanaka’s approach to swelling kinetics of a solid gel sphere is extended to a spherical microgel shell. The boundary condition at the inner surface is obtained from the minimization of shear elastic energy. Temporal evolution of a shell is represented in a form of expansion over eigenfunctions of the corresponding diffusion equation. The swelling of Tanaka’s solid spherical gel is recovered as a special case of our general solution if the inner radius approaches zero. In another limiting case of a thin (balloon-like) shell, the set of eigenfunctions is reduced to a single exponential term. In the general case, a solid sphere swells slightly faster than the same sphere with an internal cavity. To test our theoretical model, we prepared monodisperse poly-N-isopropylacrylamide (PNIPAM) hydrogel shells using a microfluidic device. The temporal dependence of the inner and outer radii of the shell were measured, and the data were fitted to our theoretical model. As a result, we obtained the collective diffusion...

We report on the use of hydrostatic pressure, P, to deswell thermosensitive poly(N-isopropylacrylamide) (pNIPAM) microgels and show that it can affect the polymer−solvent mixing as much as temperature, which is the traditional variable used to deswell pNIPAM particles. Interestingly, the microgel volume changes more gradually with pressure than it does with temperature. By comparing the pressure and temperature induced deswelling, we obtain the pressure dependence of the Flory solvency parameter, χ; it increases with P, indicating that pressure decreases the polymer−solvent miscibility. We interpret this increase in terms of the entropy change, △S, when a polymer−solvent contact is broken to form a solvent−solvent contact and find that |△S| also increases with P, consistent with previous experimental results with polymers and other gels. Hydrostatic pressure thus changes the entropic contribution of mixing, causing χ to increase and ultimately leading to particle deswelling.

The swelling of cationic microgel particles has been studied experimentally, in the weak screening regime. The solution pH was selected as the external variable triggering the swelling, which was followed by dynamic light scattering. The particle charge was determined by conductometric and potentiometric titrations, leading to a good correlation between the charge of the microgel network and its size. This leads to the conclusion that the swelling is mainly charge controlled. The Flory−Huggins thermodynamic theory for gels, including a term accounting for the counterion distribution within the microgel, has been used to interpret the experimental data. The osmotic term associated with the counterions explains fairly well the observed behavior, and additional contributions due to the internal microgel microscopic structure are not necessary, as Pincus et al. have suggested.