Microstructure and Rheology of Stimuli-Responsive Nanocolloidal Systems&sbd;Effect of Ionic Strength

The effect of ionic strength on the rheological behavior of model pH-responsive nanocolloidal systems consisting of methacrylic acid−ethyl acrylate (MAA−EA) cross-linked with diallyl phthalate (DAP) was examined. Neutralization of acid groups increases the osmotic pressure exerted by counterions trapped in the polymeric network against ions in bulk solution, which is responsible for the swelling and increase in viscosity. Swelling decreases with increasing salt concentration as a result of reduced osmotic pressure inside the microgels, which is attributed to the charge shielding effect of counterions (salt) on the negatively charged carboxylate groups. Electromotive measurements using ion-selective electrodes confirmed that not all the counterions, that is, K⁺, remain mobile, but a fraction of these ions can penetrate the porous microgel particles to shield the negatively charged carboxylate groups. A consequence of this is that some of the Na⁺ counterions inside the particles are expelled, thus regaining their translational entropy, and become mobile sodium ions in the bulk solution. We successfully developed a new scaling law that relates the swelling ratio, Q, of microgels as a function of neutralization degree, α, cross-linked density, N<INF>x</INF><INF></INF>, molar fraction of acidic units, y, and concentration of mobile counterions, C<INF>K</INF>^{+</SUPINF> and C<INF>Na</INF>+</SUPINF>, represented as (N<INF>x</INF><INF></INF>/c<INF>0</INF>)(C<INF>K</INF>+</SUPINF> + C<INF>Na</INF>+</SUPINF>)Q + Q2/3 ∝ yN<INF>x</INF><INF></INF>α. The new scaling law no longer assumes that all the counterions are trapped inside the microgels. The proportionality reduces to the form Q ∝ (yαN<INF>x</INF><INF></INF>)3/2 in the absence of salt, that is, C<INF>K</INF>+</SUPINF> + C<INF>Na</INF>+</SUPINF> ≈ 0. By combining the results from light scattering and rheological measurements, we are able to correlate the microstructural evolution of the colloidal systems with their bulk rheological behavior.}