Recent developments in paper-based microfluidic devices.

Nanoparticles at fluid interfaces are becoming a central topic in colloid science studies. Unlike in the case of colloids in suspensions, the description of the forces determining the physical behavior of colloids at interfaces still represents an outstanding problem in the modern theory of colloidal interactions. These forces regulate the formation of complex two-dimensional structures, which can be exploited in a number of applications of technological interest; optical devices, catalysis, molecular electronics or emulsions stabilization. From a fundamental viewpoint and typical for colloidal systems, nanoparticles and microparticles at interfaces are ideal experimental and theoretical models for investigating questions of relevance in condensed matter physics, such as the phase behavior of two-dimensional fluids. This review is a topical survey of the stability, self-assembly behavior and mutual interactions of nanoparticles at fluid interfaces. Thermodynamic models offer an intuitive approach to explaining the interfacial stability of nanoparticles in terms of a few material properties, such as the surface and line tensions. A critical discussion of the theoretical basis, accuracy, limitations, and recent predictions of the thermodynamic models is provided. We also review recent work concerned with nanoparticle self-assembly at fluid interfaces. Complex two-dimensional structures varying considerably with the particle nature have been observed in a number of experiments. We discuss the self-assembly behavior in terms of nanoparticle composition, focusing on sterically stabilized, charged and magnetic nanoparticles. The structure of the two-dimensional assemblies is a reflection of complex intercolloidal forces. Unlike the case for bulk colloidal suspensions, which often can be described reasonably well using DLVO (Derjaguin-Landau-Verwey-Overbeek) theory, the description of particles at interfaces requires the consideration of interfacial deformations as well as interfacial thermal fluctuations. We analyze the importance of both deformation and fluctuations, as well as the modification of electrostatic and van der Waals interactions. Finally, we discuss possible future directions in the field of nanoparticles at interfaces.

http://iopscience.iop.org/article/10.1088/0953-8984/19/41/413101/pdf

Nanoparticles at fluid interfaces

Pickering–Ramsden emulsions and other forms of particle stabilized soft materials have received quite some attention recently because of the relative ease of formulation and the possibility to create novel materials. There is, however, a clear need for approaches that are versatile and efficient. In the present work the effect of aspect ratio of particles on the stability of both water-in-oil and oil-in-water emulsions is investigated experimentally. Two types of non-spherical particles are used. Hydrophobic prolate ellipsoids with aspect ratios ranging from 1 to 9 are obtained by stretching polystyrene latex particles. Hydrophilic spindle type hematite particles have been synthesized with aspect ratios ranging from 1 to 6. A strong dependence of emulsion stability on the aspect ratio of the particles is observed. Optical as well as cryogenic scanning electron microscopy are used to visualize the droplet morphology and particulate structure and reveal fairly densely packed monolayers of ellipsoids, consistent with the mechanism of limited coalescence. Yet stable emulsions are only obtained for particles with a sufficient aspect ratio. Surface rheology on planar monolayers demonstrates the pronounced effect of aspect ratio on the surface moduli. The magnitude of the interfacial viscoelastic properties is shown to strongly depend on the aspect ratio at a given surface coverage. This is most probably due to an increased effective coverage and the occurrence of strong attractive shape induced capillary interactions. The dependence of the surface rheological properties on the aspect ratio of the particles rationalizes the observed emulsion stability as the surface rheological properties play a role in the coalescence process. The results demonstrate that interfaces with controlled surface rheology, as obtained by using shape induced capillary forces and packing effects, can be used for the rational design of Pickering emulsions and other types of high interface materials.

Exploiting particle shape in solid stabilized emulsions

Colloidal particles confined at liquid interfaces have important applications, for example in the stabilization of emulsions and foams. Also the self-assembly of particles at interfaces offers potential for novel applications and structured particle films. As the colloidal interactions of colloidal particles at interfaces differ from those in bulk, colloidal microstructures can be achieved at an interface which cannot be produced in bulk. In the present work the particle shape, surface charge, and wetting properties are varied, and the resulting self-assembly of particles at a fluid interface is studied. Model monodisperse micrometer-sized ellipsoidal particles were prepared by a mechanical stretching method. These particles were chosen to be well-suited for investigation by optical microscopy. When deposited at an interface between two fluids, shape-induced capillary interactions compete with the electrostatic repulsion. Changing the surface charge and the position at the interface can be used to manipulate the experimentally observed self-assembly process. The initial microstructure of charged ellipsoids at a decane-water interface consists of individual ellipsoids coexisting with linear chains of ellipsoids, connected at their tips. The aggregation behavior in these monolayers was investigated by optical microscopy combined with quantitative image analysis and a dominant tip-tip aggregation was observed. Microstructural information was quantified by calculating the pair-distribution and orientation-distribution functions, as a function of time. Compared to particles at an oil-water interface, particles of the same surface chemistry and charge at an air-water interface seem to have weaker electrostatic interactions, and they also have a different equilibrium position at the interface. The latter leads to differences in the capillary forces. The subsequent change in the balance between electrostatic and capillary forces gave rise to very dense networks having as a typical building block ellipsoids connected at their tips in triangular or flower-like configuration. These networks were very stable and did not evolve in time. The resulting monolayers responded elastically and buckled under compression. Furthermore, the mechanical properties of these monolayers, as measured by surface shear rheology, showed that the monolayer of ellipsoids exhibit a substantial surface modulus even at low surface coverage and can be used to create more elastic monolayers compared to aggregate networks of spheres of the same size and surface properties.

Self-assembly and rheology of ellipsoidal particles at interfaces.

Capillarity can be used to direct anisotropic colloidal particles to precise locations and to orient them by using interface curvature as an applied field. We show this in experiments in which the shape of the interface is molded by pinning to vertical pillars of different cross-sections. These interfaces present well-defined curvature fields that orient and steer particles along complex trajectories. Trajectories and orientations are predicted by a theoretical model in which capillary forces and torques are related to Gaussian curvature gradients and angular deviations from principal directions of curvature. Interface curvature diverges near sharp boundaries, similar to an electric field near a pointed conductor. We exploit this feature to induce migration and assembly at preferred locations, and to create complex structures. We also report a repulsive interaction, in which microparticles move away from planar bounding walls along curvature gradient contours. These phenomena should be widely useful in the directed assembly of micro- and nanoparticles with potential application in the fabrication of materials with tunable mechanical or electronic properties, in emulsion production, and in encapsulation.

https://www.pnas.org/content/pnas/108/52/20923.full.pdf

Curvature-driven capillary migration and assembly of rod-like particles

The role of surface rheology in fundamental fluid dynamical systems, such as liquid coating flows and soap film formation, is poorly understood. We investigate the role of surface viscosity in the classical film-coating problem. We propose a theoretical model that predicts film thickening based on a purely surface-viscous theory. The theory is supported by a set of new experimental data that demonstrates slight thickening even at very high surfactant concentrations for which Marangoni effects are irrelevant. The model and experiments represent a new regime that has not been identified before.

/pdf/the-role-of-surface-rheology-in-liquid-film-formation-4ovd5pgs4w.pdf

The role of surface rheology in liquid film formation

We show that near-spherical micrometer-sized colloidal particles at an interface of two fluids experience inter-particle forces merely as a consequence of their shape-induced capillary interaction. The interaction is strong even if the deviations from sphericity are on the nm-scale, and can hardly be avoided in experiment. For particles of 2 μm radius, a deformation of 20 nm can result in an attractive potential of 2kBT at a distance of 4 particle radii. Dynamical simulations of many particles confirm that the forces lead to aggregates of dendritic or hexagonal-lattice type. The latter pattern exhibits strong herringbone-phase orientational order.

https://iopscience.iop.org/article/10.1209/epl/i2005-10279-7/pdf

Shape-induced capillary interactions of colloidal particles

We study imbibition of a wetting fluid into layers of packed beads and examine how variations of permeability in the flow direction affect the dynamics of imbibition. In the case of systems made of two distinct layers, we show that the imbibition dynamics exhibit three regimes including diffusive-like imbibition as well as an unusual constant speed imbibition, which can be fine-tuned by adjusting the bead diameters and the length of the initial layer. We also perform experiments with gradients of permeability by ordering layers of beads of increasing (or decreasing) sizes in a tube. A continuum description is used to explain the results from the discrete experimental systems. In all cases, analytical models based on Darcy's equation show excellent agreement with the experiments.

https://iopscience.iop.org/article/10.1209/0295-5075/86/56002/pdf

Imbibition in layered systems of packed beads

We report on the formation of films supported by a wire frame using aqueous solutions of PEO with and without SDS. We find that it is possible to make films in the absence of the surfactant SDS, and that films can be made that are thicker than the diameter of the wires that support them. Upon addition of SDS, for capillary numbers (Ca) above 10-3 we find that initial film thickness decreases as a function of Ca when using high molecular weight PEO (106 g/mol) at concentrations above 0.5%wt. Comparisons with data in the literature are provided, as well as a discussion of the general rheology of PEO-SDS complexes to gain an understanding of the experimental observations. Finally, we observe abrupt changes in the rate of film thinning corresponding to the moment when film formation stops. We discuss this change in thinning rate and how it may relate to mechanisms of film formation.

E. A. Van Nierop

Papers

The role of surface rheology in liquid film formation

Shape-induced capillary interactions of colloidal particles

Imbibition in layered systems of packed beads

Formation of free films of aqueous solutions of poly(ethylene oxide): The influence of surfactant

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