Form factor of pNIPAM microgels in overpacked states.

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.

Transient formation of bcc crystals in suspensions of poly(N-isopropylacrylamide)-based microgels.

We present a small-angle x-ray scattering study of crystals formed by temperature-sensitive, swollen microgel particles consisting of poly(N-isopropylacrylamide) copolymerized with acrylic acid and 5 mol % of a cross-linker. As for hard spheres, the random hexagonal close-packed structure is predominant during crystal growth and slowly transforms toward the face-centered-cubic structure. However, a transient phase of body-centered-cubic crystal is observed in an intermediate range of effective volume fractions. We estimate that the studied suspensions are close to a transition from face-centered-cubic to body-centered-cubic structure that can be understood by the tendency of the system to maximize the excluded volume and minimize the contact area between the particles.

Structural changes of poly(N-isopropylacrylamide)-based microgels induced by hydrostatic pressure and temperature studied by small angle neutron scattering.

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.

The role of polymer polydispersity in phase separation and gelation in colloid-polymer mixtures.

Mixtures of nonadsorbing polymer and colloidal particles exhibit a range of different morphologies depending on the particle and polymer concentrations and their relative size ratios. These can be very important for technological applications, where gelation can produce a weak solidlike structure that can help reduce phase separation, extending product shelf life. However, industrial products are typically formulated with polydisperse polymers, and the consequences of this on the phase behavior of the mixture are not known. We investigate the role of polymer polydispersity and show that a small amount of larger polymer in a distribution of nominally much smaller polymer can drastically modify the behavior. It can induce formation of a solidlike gel structure, abetted by the small polymer, but still allow further evolution of the phase separation process, as is seen with a monodisperse distribution of larger polymer. This coarsening ultimately leads to gravitational collapse. We describe the full phase behavior for polydisperse polymer mixtures and account for the origin of the behavior through measurements of the structure and dynamics and by comparing to the behavior with monodisperse polymers.

Motion of microgels in electric fields.

We review existing experimental results on the motion of microgels in the presence of electric fields and find that there can be striking differences depending on whether the polymer network comprising the microgel is neutral or charged: While for neutral microgels, the electrophoretic mobility, micro, typically decreases as the particle swells, in the case of ionic microgels, micro typically increases with particle swelling. We explain this difference in behavior by recurring to electro-osmotic fluid flows inside the particles, which are relevant in the presence of electric fields when the polymer network is ionized; these flows render the particles permeable to the solvent qualitatively changing the way to think about their electrophoretic behavior. We show that this interpretation is consistent with calculations of the drag force experienced by a permeable object as it moves inside a liquid and with recent theoretical models for the electrophoresis of soft particles. The analysis emphasizes that the electrophoresis of neutral microgels can be qualitatively treated as that of charged hard spheres, irrespective on whether the particles are swollen or de-swollen. By contrast, ionic microgels behave like free-draining polyelectrolytes in the presence of electric fields.

Gravitational compression of colloidal gels.

We study the compression of depletion gels under the influence of a gravitational stress by monitoring the time evolution of the gel interface and the local volume fraction, φ, inside the gel. We find φ is not constant throughout the gel. Instead, there is a volume fraction gradient that develops and grows along the gel height as the compression process proceeds. Our results are correctly described by a non-linear poroelastic model that explicitly incorporates the φ-dependence of the gravitational, elastic and viscous stresses acting on the gel.

State diagram for the electrostatic adsorption of charged colloids on confining walls: simulation and theory.

We study the structure of charged colloidal suspensions under confinement and determine a state diagram for the occurrence of electrostatic adsorption onto the confining walls, an effect that results in the accumulation of particles on the bounding surfaces and that could be relevant in experiments. We use Monte Carlo simulations to quantify this structural transition and perform theoretical calculations based on integral equations. Overall, our results provide a guide for experimentalists dealing with charged colloidal systems to determine the relevance of this purely electrostatic effect.

Particle migration induced by confinement of colloidal suspensions along the gravitational direction.

We confine charged spheres in cells with the smallest dimension along the direction of gravity g. The particles are density mismatched with the surrounding medium and sediment along g with typical Péclet numbers of Pe approximately 10(-3). After a certain time, we find that the number of particles N increases near both upper and lower plates until a characteristic time tau is reached; above this time N plateaus. We attribute the observed phenomenology to collective particle motions driven by gravity and mediated by hydrodynamic interactions; these could yield formation of swirls made of particles with correlated velocities that could eventually drive the particles towards the upper plate. The characteristic time for these migrations scales with plate-to-plate separation Lz as tau approximately Lz1.2, exactly as the characteristic decay time of velocity fluctuations in sedimentation processes [S. Y. Tee, Phys. Rev. Lett. 89, 054501 (2002)], despite that in these experiments the smallest cell dimension is perpendicular to g and 7

Electrophoresis of large polyelectrolyte-coated colloidal particles.

We perform electrophoretic mobility mu measurements of spherical colloidal particles coated with a charged polyelectrolyte shell versus 1:1 electrolyte concentration c. Instead of the expected Smoluchowski scaling law mu approximately c(- 1 / 2) for large kappaa, with kappa the inverse of the Debye length, we find that mu scales as mu approximately c(- 1 / 3). We account for this result using a general theory for the electrophoresis of soft particles [H. Ohshima, Adv. Colloid Interface Sci. 62, 189 (1995)] combined with the salt concentration dependence of the shell thickness, as described by Pincus [P. Pincus, Macromolecules 24, 2912 (1991)].