Interfacial tension between immiscible phases is a well-known phenomenon, which manifests itself in everyday life, from the shape of droplets and foam bubbles to the capillary rise of sap in plants or the locomotion of insects on a water surface. More than a century ago, Korteweg generalized this notion by arguing that stresses at the interface between two miscible fluids act transiently as an effective, nonequilibrium interfacial tension, before homogenization is eventually reached. In spite of its relevance in fields as diverse as geosciences, polymer physics, multiphase flows, and fluid removal, experiments and theoretical works on the interfacial tension of miscible systems are still scarce, and mostly restricted to molecular fluids. This leaves crucial questions unanswered, concerning the very existence of the effective interfacial tension, its stabilizing or destabilizing character, and its dependence on the fluid's composition and concentration gradients. We present an extensive set of measurements on miscible complex fluids that demonstrate the existence and the stabilizing character of the effective interfacial tension, unveil new regimes beyond Korteweg's predictions, and quantify its dependence on the nature of the fluids and the composition gradient at the interface. We introduce a simple yet general model that rationalizes nonequilibrium interfacial stresses to arbitrary mixtures, beyond Korteweg's small gradient regime, and show that the model captures remarkably well both our new measurements and literature data on molecular and polymer fluids. Finally, we briefly discuss the relevance of our model to a variety of interface-driven problems, from phase separation to fracture, which are not adequately captured by current approaches based on the assumption of small gradients.

We form films of carboxylated polystyrene particles (C-PS) at the air water interface and investigate the effect of subphase pH on their structure and rheology by using a suite of complementary experimental techniques. Our results suggest that electrostatic interactions drive the stability and the structural order of the films. In particular, we show that by increasing the pH of the subphase from 9 up to 13, the films exhibit a gradual transition from solid to liquidlike, which is accompanied by a loss of the long-range order (that characterizes them at lower values of pH). Direct optical visualization of the layers, scanning electron microscopy, and surface pressure isotherms indicate that the particles deposited at the interface form three-dimensional structures involving clusters, with the latter being suppressed and a quasi-2D particle configuration eventually reached at the highest pH values. Evidently, the properties of colloidal films can be tailored significantly by altering the pH of the subphase.

The phenomenon of complexation between oppositely charged colloids or macromolecules in aqueous solution is a fundamental process, widely exploited by nature, as for example in DNA packaging within biological cells [2], but also by technology, as in industrial colloidal stabilization, water treatment and paper making [3].Being the result of a delicate balance of forces of different nature, small variations in the physico-chemical parameters may induce large changes in the resulting complexes [4]. Electrostatics is clearly the relevant interaction in driving the aggregation, although non-electrostatic interactions can be important in modulating the process and can deeply affect the characteristics of the resulting self-assembled structures. However, despite the intense experimental, theoretical and computational research aimed to understand the mechanisms driving the formation and the stabilization of the complexes [5], [6] and [7] in the physical context of macroion-multivalent counterion interactions [8], due to the great complexity of these systems, also the details of purely electrostatic interactions remain to be completely clarified.The possibility to get a fine control of the stability of the complexes by tuning the competition between attractive and repulsive electrostatic interactions justifies the actual enduring attention on polyion–colloid complexation, being key to the technological development of nano-structured materials or nano-devices to be used for example in drug delivery or gene-therapy [9] and [10].In particular, a rich literature exists on the variety of structures formed by charged liposomes interacting via electrostatic forces with oppositely charged linear polyions, whether they are synthetic polymers, polypeptides or DNA [11], [12] and [13]. A feature characterizing the phase behavior of these systems is the presence of a “reentrant condensation” accompanied by a marked “overcharging”, or charge inversion [14] and [15]. Indeed, when a given volume of a liposome suspension is mixed with the same volume of a solution containing oppositely charged polyelectrolytes, the complexation is systematically observed due to a rapid adsorption of polyelectrolytes chains at the liposome surface, forming what we have defined as “polyelectrolyte-decorated particles” (hereafter pd-particles), followed by their aggregation in pd–liposome clusters, as it is schematically represented in panel A of Fig. 1. For low enough polyelectrolyte concentration the clusters are small (they are formed by a few liposomes), after their rapid formation they are very stable, their measured ζ-potential being only slightly lower, in absolute value, than that measured for the liposomes in the absence of adsorbed polyelectrolytes. As the polyion concentration (and hence the ratio, ξ, between the number of stoichiometric charges on the polymer and on the particles) is increased, larger but still stable clusters are formed, with a ζ-potential which is further reduced in absolute value. At a sufficiently high polyelectrolyte concentration, the liposome suspension is completely destabilized, the large clusters that form are not stable, their ζ-potential is close to zero and they rapidly coalesce in macroscopic “flocs”. Going beyond the isoelectric point, hence further increasing the polyelectrolyte concentration, stable clusters form again, but now their size decreases upon increasing the polyelectrolyte concentration in the mixture: the polyelectrolyte-induced condensation of the liposomes is hence “reentrant”. At the same time, the ζ-potential after having passed through the zero, increases again in absolute value, and the sign of the excess charge of the clusters is that of the polyelectrolyte, i.e. opposite to that of the original liposomes (charge inversion).

Surface tension between immiscible fluids is a well-understood and well-characterized phenomenon. By contrast, much less is known about the effective, off-equilibrium surface tension that arises when a (transient) interface is created between miscible fluids.This effective surface tension plays a key role in many driven phenomena, from jetting and drop formation and coalescence to precipitation and deposition, as it was already recognized more than 100 years ago by Korteweg [1]. However, experimental investigations in this field remain scarce and the theoretical predictions by Korteweg have not quantitatively tested so far, to the best of our knowledge. We present a thorough experimental investigation of the Saffman-Taylor instability arising when a simple fluid (the solvent of a colloidal or polymer suspension) is pushed through a miscible, more viscous one (the colloidal or polymer suspension itself). We show [2] that the resulting interface pattern can be accounted for by the non-linear rheological properties of the suspension and an effective surface tension. By measuring the effective surface tension for suspensions at a variety of polymer volume fractions, we successfully test Korteweg's theory for free and cross-linked polymer suspensions. We moreover find that the effective surface tension increases with the size of polymers, a surprising result at odd with the typical behavior in atomic or colloidal systems at equilibrium, where the surface tension usually decreases as the squared particle size. Finally we present new data on the effective surface tension between suspensions of hard, compact particles and their own solvent showing that polymers and hard particles exhibit vastly different effective surface tension properties. We discuss this surprising result in view of available models for interfacial stresses.[1] D. Korteweg, Arch. Neerlandaises Sci. Exactes Naturelles, 6, 1 (1901).[2] D.Truzzolillo, S. Mora, C. Dupas, L. Cipelletti, Phys. Rev. Lett., 112, 208303 (2014).

We present extensive experimental and theoretical investigations on the structure, phase behavior, dynamics and rheology of model soft–hard colloidal mixtures realized with large, multiarm star polymers as the soft component and smaller, compact stars as the hard one. The number and length of the arms in star polymers control their softness, whereas the size ratio, the overall density and the composition are additional parameters varied for the mixtures. A coarse-grained theoretical strategy is employed to predict the structure of the systems as well as their ergodicity properties on the basis of mode coupling theory, for comparison with rheological measurements on the samples. We discovered that dynamically arrested star–polymer solutions recover their ergodicity upon addition of colloidal additives. At the same time the system displays demixing instability, and the binodal of the latter meets the glass line in a way that leads, upon addition of a sufficient amount of colloidal particles, to an arrested phase separation and reentrant solidification. We present evidence for a subsequent solid-to-solid transition well within the region of arrested phase separation, attributed to a hard-sphere-mixture type of glass, due to osmotic shrinkage of the stars at high colloidal particle concentrations. We systematically investigated the interplay of star functionality and size ratio with glass melting and demixing, and rationalized our findings by the depletion of the big stars due to the smaller colloids. This new depletion potential in which, contrary to the classic colloid–polymer case, the hard component depletes the soft one, has unique and novel characteristics and allows the calculation of phase diagrams for such mixtures. This work covers a broad range of soft–hard colloidal mixture compositions in which the soft component exceeds the hard one in size and provides general guidelines for controlling the properties of such complex mixtures.

We explore the influence of particle softness and internal structure on both the bulk andinterfacial rheological properties of colloidal suspensions. We probe bulk stresses byconventional rheology, by measuring the flow curves, shear stress versus strain rate, forsuspensions of soft, deformable microgel particles and suspensions of near hard-sphere-likesilica particles. A similar behaviour is seen for both kinds of particles in suspensions atconcentrations up to the random close packing volume fraction, in agreement with recenttheoretical predictions for sub-micron colloids. Transient interfacial stresses are measured byanalyzing the patterns formed by the interface between the suspensions and their solvent, dueto a generalized Saffman–Taylor hydrodynamic instability. At odds with the bulk behaviour,we find that microgels and hard particle suspensions exhibit vastly different interfacial stressproperties. We propose that this surprising behaviour results mainly from the difference inparticle internal structure (polymeric network for microgels versus compact solid for the silicaparticles), rather than softness alone.