Alberto Fernandez-Nieves

Designer emulsions using microfluidics

We describe new developments for the controlled fabrication of monodisperse emulsions using microfluidics. We use glass capillary devices to generate single, double, and higher order emulsions with exceptional precision. These emulsions can serve as ideal templates for generating well-defined particles and functional vesicles. Polydimethylsiloxane microfluidic devices are also used to generate picoliter-scale water-in-oil emulsions at rates as high as 10 000 drops per second. These emulsions have great potential as individual microvessels in high-throughput screening applications, where each drop serves to encapsulate single cells, genes, or reactants.

Soft colloids make strong glasses

Glass formation in colloidal suspensions has many of the hallmarks of glass formation in molecular materials. For hard-sphere colloids, which interact only as a result of excluded volume, phase behaviour is controlled by volume fraction, φ; an increase in φ drives the system towards its glassy state, analogously to a decrease in temperature, T, in molecular systems. When φ increases above φ* ≈ 0.53, the viscosity starts to increase significantly, and the system eventually moves out of equilibrium at the glass transition, φg ≈ 0.58, where particle crowding greatly restricts structural relaxation. The large particle size makes it possible to study both structure and dynamics with light scattering and imaging; colloidal suspensions have therefore provided considerable insight into the glass transition. However, hard-sphere colloidal suspensions do not exhibit the same diversity of behaviour as molecular glasses. This is highlighted by the wide variation in behaviour observed for the viscosity or structural relaxation time, τα, when the glassy state is approached in supercooled molecular liquids. This variation is characterized by the unifying concept of fragility, which has spurred the search for a ‘universal’ description of dynamic arrest in glass-forming liquids. For ‘fragile’ liquids, τα is highly sensitive to changes in T, whereas non-fragile, or ‘strong’, liquids show a much lower T sensitivity. In contrast, hard-sphere colloidal suspensions are restricted to fragile behaviour, as determined by their φ dependence, ultimately limiting their utility in the study of the glass transition. Here we show that deformable colloidal particles, when studied through their concentration dependence at fixed temperature, do exhibit the same variation in fragility as that observed in the T dependence of molecular liquids at fixed volume. Their fragility is dictated by elastic properties on the scale of individual colloidal particles. Furthermore, we find an equivalent effect in molecular systems, where elasticity directly reflects fragility. Colloidal suspensions may thus provide new insight into glass formation in molecular systems.

The Polymer/Colloid Duality of Microgel Suspensions

Colloidal dispersions have been studied for decades as a result of their utility in numerous applications and as models for molecular and atomic condensed phases. More recently, a number of groups have exploited in such studies submicrometer-sized hydrogel particles (microgels) that have environmentally tunable sizes. The experimental convenience of tuning the dispersions colloidal volume fraction while maintaining a constant number density of particles provides a clear advantage over more tedious studies that employ traditional hard-sphere particles. However, as studies delved deeper into the fundamental physics of colloidal dispersions comprising microgel particles, it became abundantly clear that a microgels utility as a tunable hard sphere was limited and that the impact of softness was more profound than previously appreciated. Herein we review the brief history of microgel-based colloidal dispersions and discuss their transition from tunable hard spheres to a class of soft matter that has revealed a landscape of physics and chemistry notable for its extraordinary richness and diversity.

Microgel suspensions : fundamentals and applications

Providing a vital link between chemistry and physics on the nanoscale, this book offers concise coverage of the entire topic in five major sections, beginning with synthesis of microgel particles and continuing with their physical properties. The phase behavior and dynamics of resulting microgel suspensions feature in the third section, followed by their mechanical properties. It concludes with detailed accounts of numerous industrial, commercial and medical applications. Edited by David Weitz, Professor at Harvard and one of the worlds pre-eminent experts in the field.

Salt effects over the swelling of ionized mesoscopic gels

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 adequatel...

Scaling the drop size in coflow experiments

We perform extensive experiments with coflowing liquids in microfluidic devices and provide a closed expression for the drop size as a function of measurable parameters in the jetting regime that accounts for the experimental observations; this expression works irrespective of how the jets are produced, providing a powerful design tool for this type of experiments.

Temperature‐Controlled Transitions Between Glass, Liquid, and Gel States in Dense p‐NIPA Suspensions

In this article we demonstrate that concentrated p-NIPA suspensions in a low temperature glassy state can liquefy and then solidify again as the temperature is raised across the LCST. Our system exhibits all the typical behavior of disordered colloidal suspensions, but the behavior is controlled by temperature. Below the LCST it shows the behavior typical of a colloidal glass, near the LCST it behaves like a liquid, while above the LCST it exhibits the properties typical of a colloidal gel. Moreover, we show that the elasticity of these suspensions exhibits critical-like behavior as a function of temperature both above and below the LCST, with a critical temperature that corresponds to the LCST. Our results thereby suggest interesting analogies between the glass and gel phases of these thermosensitive microgel particles.

Osmotic de-swelling of ionic microgel particles

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.

Phase switching of ordered arrays of liquid crystal emulsions

We report a fabrication method for producing interference-based electro-optic phase gratings that switch between diffracting and transparent states. The phase grating consists of a hexagonal-close-packed array of monodisperse emulsion drops of nematic liquid crystal, embedded in a polymer matrix. Monodisperse droplet size allows for fast switching at low electric fields.

The role of ζ potential in the colloidal stability of different TiO2/electrolyte solution interfaces

Abstract The present paper deals with the electrokinetic characterization and colloidal stability of different TiO2/water interfaces under the presence of several electrolytes. The electrophoretic mobility of the TiO2 particles was measured versus NaCl, NaNO3, Na2SO4 and CaCl2 concentrations, at pHs 4, 5.5 and 10.5. ζ Potential calculations have been carried out with the aid of O’Brien and Whites’ conversion theory. The medium pH and the valence of the ions have proven to be of great influence in our suspension electrokinetic behaviour. The colloidal stability has been studied by means of the Eilers and Korff index. The different flocculant character of the ionic species has been established, which is of great importance in the solar photocatalytic proccess where our titanium dioxide is employed.