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In this work, we study experimentally the effect of an external osmotic pressure πext on the swelling of ionic mesoscopic gels in the weak screening limit, where the Debye screening length is larger than the mesh size of the gel. Variations in the osmotic pressure were induced by adding dextran to the solution. The results show that ionic microgels do not respond to πext below a given value of the normal stress; above this value the system de-swells with increasing osmotic pressure. The start of de-swelling is set by the gel charge density. The Flory thermodynamic theory for ionic gels captures the essential characteristics of the de-swelling behavior; in particular, it predicts with fairly good accuracy the value of πext at which de-swelling begins. Finally, due to the colloidal character of the gels, we observe that the system flocculates by a depletion interaction mechanism at high dextran concentrations.

We study the form factor of thermoresponsive microgels based on poly(N-isopropylacrylamide) at high generalized volume fractions, ζ, where the particles must shrink or interpenetrate to fit into the available space. Small-angle neutron scattering with contrast matching techniques is used to determine the particle form factor. We find that the particle size is constant up to a volume fraction roughly between random close packing and space filling. Beyond this point, the particle size decreases with increasing particle concentration; this decrease is found to occur with little interpenetration. Noteworthily, the suspensions remain liquid-like for ζ larger than 1, emphasizing the importance of particle softness in determining suspension behavior.

In this work, the effects of salt concentration over the swelling of ionic mesoscopic gels will be studied theoretically and verified with experiments. We will restrict ourselves to the weak screening limit where the Debye screening length is larger than the mesh size of the gel. Under this condition, direct electrostatic interactions are negligible and the swelling is driven by the osmotic pressure of the ions. The swelling response of a mesoscopic gel is strongly dependent on the ionization degree of the gel. In particular, a maximum in the size–salt concentration curve appears for a partially ionized gel, when the salt concentration equals the network charge concentration. This maximum is removed for a totally ionized polymer network. Despite these facts, a charge independent asymptotic behavior between size and salt concentration becomes apparent, at sufficiently high values of the latter. The Flory–Huggins mean-field approach together with the Donnan relations describe the observed swelling adequately, thus accounting for the essential physics of the problem. As a final remark, an experimental method for determining gel charge will be inferred from the results.

We review a powerful regularization method, known as CONTIN, for obtaining the size distribution of colloidal suspensions from dynamic light scattering data. We show that together with the so-called L-curve criterion for selecting the optimal regularization parameter, the method correctly describes the average size and size distribution of microgel suspensions independently characterized using small-angle neutron scattering. In contrast, we find that when using the default regularization process, where the regularizer is selected via the "probability to reject" method, the results are not as satisfactory.

We use electrophoretic mobility (mu) measurements of charged colloidal particles under the presence of multivalent counterions as a probe of the electrostatic correlations between them; they become important for sufficiently high surface charge densities of the colloid (sigma) and result in a decreasing mu upon increasing sigma. The physics of this decrease is the same as that giving rise to charge inversion. We account qualitatively for the observations by considering recent theoretical arguments that assume the counterions next to the colloid surface as a strongly correlated liquid of properties similar to that of a Wigner crystal.

We perform electrophoretic mobility measurements of ionic microgel particles in the deswollen and swollen phases. The results show that microgels behave as charged hard spheres in the first case and as free-draining spherical polyelectrolytes in the latter. A unified theory for the electrophoresis of polyelectrolyte-coated particles [H. Ohshima, Adv. Colloid Interface Sci. 62, 189 (1995)] is shown to contain the essential physics for describing the experiments, upon adequate consideration of the particles swelling behavior and network-solvent friction variations.

We perform static light scattering experiments on a dilute suspension of microgel particles and model the resultant form factors P(q) by assuming an exponentially decaying dielectric permittivity. The result is that P(q) is a Lorentzian function of the scattering wavevector q for length scales greater than the particle size; the width approximately corresponding to twice the particle radius. This simple model reasonably accounts for scattered light from both swollen and shrunken microgel phases.

We present investigations of the structural properties of thermoresponsive poly(N-isopropylacrylamide) (PNiPAM) microgels dispersed in an aqueous solvent. In this particular work poly(ethyleneglycol) (PEG) units flanked with acrylate groups are employed as cross-linkers, providing an architecture designed to resist protein fouling. Dynamic light scattering (DLS), static light scattering (SLS), and small angle neutron scattering (SANS) are employed to study the microgels as a function of temperature over the range 10 °C ≤ T ≤ 40 °C. DLS and SLS measurements are simultaneously performed and, respectively, allow determination of the particle hydrodynamic radius, R(h), and radius of gyration, R(g), at each temperature. The thermal variation of these magnitudes reveals the microgel deswelling at the PNiPAM lower critical solution temperature (LCST). However, the hydrodynamic radius displays a second transition to larger radii at temperatures T ≤ 20 °C. This feature is atypical in standard PNiPAM microgels and suggests a structural reconfiguration within the polymer network at those temperatures. To better understand this behavior we perform neutron scattering measurements at different temperatures. In striking contrast to the scattering profile of soft sphere microgels, the SANS profiles for T ≤ LCST of our PNiPAM-PEG suspensions indicate that the particles exhibit structural properties characteristic of star polymer configurations. The star polymer radius of gyration and correlation length gradually decrease with increasing temperature despite maintenance of the star polymer configuration. At temperatures above the LCST, the scattered SANS intensity is typical of soft sphere systems.

A direct consequence of the finite compressibility of a swollen microgel is that it can shrink and deform in response to an external perturbation. As a result, concentrated suspensions of these particles exhibit relaxation dynamics and rheological properties which can be very different with respect to those of a hard sphere suspension or an emulsion. We study the reduction in size of ionic microgels in response to increasing number of particles to show that particle shrinkage originates primarily from steric compression, and that the effect of ion-induced de-swelling of the polymer network is negligible. With increasing particle concentration, the single particle dynamics switch from those typical of a liquid to those of a super-cooled liquid and finally to those of a glass. However, the transitions occur at volume fractions much higher than those characterizing a hard sphere system. In the super-cooled state, the distribution of displacements is non-gaussian and the dependence of the structural relaxation time on volume fraction is describable by a Volger-Fulcher-Tammann function.

We study the structural properties of microgels made of poly(N-isopropylacrylamide) and acrylic acid as a function of hydrostatic pressure and temperature using small angle neutron scattering. Hydrostatic pressure induces particle deswelling by changing the mixing of the microgel with the solvent, similar to temperature. We extend this analogy to the structural properties of the particles and show that the form factor at a certain temperature is equal to the form factor at a certain hydrostatic pressure. We fit the results with an existent model for the microgel structure and carefully analyze the fitting procedure in order to obtain physically meaningful values of the free parameters in the model.