Inkjet Printing of Structurally Colored Self-Assembled Colloidal Aggregates.

Structurally colored materials offer increased stability, high biocompatibility, and a large variety of colors, which can hardly be reached simultaneously using conventional chemical pigments. However, for practical applications, such as inkjet printing, it is vital to compartmentalize these materials in small building blocks (with sizes ideally below 5 µm) and create "ready-to-use" inks. The latter can be achieved by using photonic balls (PB): spherical aggregates of nanoparticles. Here, we demonstrate, for the first time, how photonic ball dispersions can be used as inkjet printing inks. We use solvent drying techniques to manufacture structurally colored colloidal aggregates. The as-fabricated photonic balls are dispersed in pentanol to form ink. A custom-made inkjet printing platform equipped with an industrial printhead and recirculation fluidic system is used to print complex structurally colored patterns. We increase color purity and suppress multiple scattering by introducing carbon black as a broadband light absorber.

Macroporous Silica Foams Fabricated via Soft Colloid Templating.

Macroporous materials with controlled pore sizes are of high scientific and technological interest, due to their low specific weight, as well as unique acoustic, thermal, or optical properties. Solid foams made of titania, silica, or silicon, as representative materials, have been previously obtained with several hundred nanometer pore sizes, by using sacrificial templates such as spherical emulsion droplets or colloidal particles. Macroporous structures in particular are excellent candidates as photonic materials with applications in structural coloration and photonic bandgap devices. However, whereas using spherical building blocks as templates may provide tight control over pore shape and size, it results in materials with an often unfavorable local topology. Templating dry-foam or compressed-emulsion structures appear as attractive alternatives, but have not been demonstrated so far for submicron pore sizes. Herein, the use of soft, flexible microgel colloids decorated with silica nanoparticles as templates of macroporous foams is reported. These purposely synthesized core-shell colloids are assembled at ultra-high effective volume fractions by centrifuging and thermal swelling, thereby resulting in uniform disordered materials with facetted pores, mimicking dry foams. After removal of the polymer component via calcination, lightweight pure silica structures are obtained with a well-defined cellular or network topology.

Manufacturing Large-scale Materials with Structural Color.

Living organisms frequently use structural color for coloration as an alternative mechanism to chemical pigmentation. Recently there has been a growing interest to translate structural color into synthetic materials as a more durable and less hazardous alternative to conventional pigments. Efforts to fabricate structurally colored materials take place in different fronts, from 3D printing to spray-coating and roll-to-roll casting. Stability, performance, and quality of the color, the environmental impact of the materials or their manufacturing methods are some of the heavily researched topics we discuss. First, we highlight recent examples of large-scale manufacturing technologies to fabricate structurally colored objects. Second, we discuss the current challenges to be tackled to create perfect appearances which aim at the full color gamut while caring for environmental concerns. Finally, we discuss possible scenarios that could be followed in order to involve other manufacturing methods for creating structurally colored objects.

Light scattering from colloidal aggregates on a hierarchy of length scales.

Disordered dielectrics with structural correlations on length scales comparable to visible light wavelengths exhibit interesting optical properties. Such materials exist in nature, leading to beautiful structural non-iridescent color, and they are also increasingly used as building blocks for optical materials and coatings. In this article, we explore the angular resolved single-scattering properties of micron-sized, disordered colloidal assemblies. The aggregates act as structurally colored supraparticles or as building blocks for macroscopic photonic glasses. We obtain first experimental data for the differential scattering and transport cross-section. Based on existing macroscopic models, we develop a theoretical framework to describe the scattering from densely packed colloidal assemblies on a hierarchy of length scales.

Foam as a self-assembling amorphous photonic band gap material.

We show that slightly polydisperse disordered 2D foams can be used as a self-assembled template for isotropic photonic band gap (PBG) materials for transverse electric (TE) polarization. Calculations based on in-house experimental and simulated foam structures demonstrate that, at sufficient refractive index contrast, a dry foam organization with threefold nodes and long slender Plateau borders is especially advantageous to open a large PBG. A transition from dry to wet foam structure rapidly closes the PBG mainly by formation of bigger fourfold nodes, filling the PBG with defect modes. By tuning the foam area fraction, we find an optimal quantity of dielectric material, which maximizes the PBG in experimental systems. The obtained results have a potential to be extended to 3D foams to produce a next generation of self-assembled disordered PBG materials, enabling fabrication of cheap and scalable photonic devices.

Surfactant Interactions and Organization at the Gas-Water Interface (CTAB with Added Salt).

We have studied adsorbed layers of cetyltrimethylammonium bromide (CTAB) at air-water interfaces in the presence of added electrolyte. Fast bubble compression/expansion measurements were used to obtain the surface equation of state, i.e., the surface tension vs CTAB surface concentration dependence. We show that while a simple model where the surfactant molecules are assumed to be noninteracting is insufficient to describe the measured response of the surfactant layer, a modified Frumkin equation where the local interactions between the molecular components depend on their surface concentration captures the response. The variation of the effective interactions in the surfactant layer in the model shows that the interactions in the surfactant layer change from effectively repulsive to attractive with increasing surface concentration. Molecular dynamics simulations are performed to probe the origins of the change in the interactions. The simulations indicate that already at low surface concentrations the surfactants aggregate as highly dynamic rafts with surfactant orientation parallel to the interface. Increasing the concentration leads to a change in the assembly morphology at the interface: the surfactant layer thickens and the surfactants sample a range of tilted orientations with respect to the interfacial plane. The change from transient raftlike assemblies to dynamical aggregates at the interface involves a clear increase in the degree of counterion binding: we speculate that the flip of the effective interaction parameter in the model used to interpret the experimental results could result from this. The work here presents basic steps toward a proper understanding of the molecular organization and interactions of surfactants at an air-water interface. This is crucially important in understanding macroscopic properties of surfactant-stabilized systems such as foams, emulsions, and colloidal dispersions.

Optimizing Hyperuniformity in Self-Assembled Bidisperse Emulsions.

We study long range density fluctuations (hyperuniformity) in two-dimensional jammed packings of bidisperse droplets. Taking advantage of microfluidics, we systematically span a large range of size and concentration ratios of the two droplet populations. We identify various defects increasing long range density fluctuations mainly due to organization of local particle environment. By choosing an appropriate bidispersity, we fabricate materials with a high level of hyperuniformity. Interesting transparency properties of these optimized materials are established based on numerical simulations.

Probing foam with neutrons.

Foams are multiscale materials that have an enormous number of uses. As the relevant structural length-scales span from a few nanometres up to millimetres a number of characterisation methods need to be combined to obtain the full material structure. In this review we explain how foams can be explored using Small Angle Neutron Scattering (SANS). We remind the reader of the basics of SANS and contrast variation before we describe the different types of experiments that have been carried out on foams emphasising the specific role of neutrons in learning about the systems. To date SANS has been used to measure different foam structural parameters, such as the film thickness and the bubble size. Several studies have also been carried out to elucidate the organisation of the stabilising objects in the bulk solution. Finally we show how SANS measurements can be used to measure foam composition. Some of the accessible information is unique to SANS experiments, but as the method is still not very widely used on foams the review is also aimed to act as an introduction on how to carry out such measurements on foams.

Drainage in a rising foam.

Rising foams created by continuously blowing gas into a surfactant solution are widely used in many technical processes, such as flotation. The prediction of the liquid fraction profile in such flowing foams is of particular importance since this parameter controls the stability and the rheology of the final product. Using drift flux analysis and recently developed semi-empirical expressions for foam permeability and osmotic pressure, we build a model predicting the liquid fraction profile as a function of height. The theoretical profiles are very different if the interfaces are considered as mobile or rigid, but all of our experimental profiles are described by the model with mobile interfaces. Even the systems with dodecanol are well known to behave as rigid in forced drainage experiments. This is because in rising foams the liquid fraction profile is fixed by the flux at the bottom of the foam. Here the foam is wet with higher permeability and the interfaces are not in equilibrium. These results demonstrate once again that it is not only the surfactant system that controls the mobility of the interface, but also the hydrodynamic problem under consideration. For example liquid flow through the foam during generation or in forced drainage is intrinsically different.

Precipitating Sodium Dodecyl Sulfate to Create Ultrastable and Stimulable Foams.

Ultrastable foams are made very simply by adding salt (NaCl or KCl) to sodium dodecyl sulfate. The addition of high concentrations of salt leads to the precipitation of the surfactant on the bubble surfaces and as crystals in the interstices between the bubbles. As a consequence, the ageing of the foams is stopped to make them stable indefinitely, or until they are heated above the melting temperature of the crystals. The use of KCl is shown to be much more effective than that of NaCl because potassium dodecyl sulfate has a higher melting temperature and faster rates of crystallization. The crystalline structures have been investigated inside the foam using small angle neutron scattering. The larger lattice spacing of the crystals formed with NaCl in comparison with KCl has been evidenced. These simple temperature stimulable foams could have many potential applications.

Electrical conductivity of quasi-two-dimensional foams.

Quasi-two-dimensional (quasi-2D) foams consist of monolayers of bubbles squeezed between two narrowly spaced plates. These simplified foams have served successfully in the past to shed light on numerous issues in foam physics. Here we consider the electrical conductivity of such model foams. We compare experiments to a model which we propose, and which successfully relates the structural and the conductive properties of the foam over the full range of the investigated liquid content. We show in particular that in the case of quasi-2D foams the liquid in the nodes needs to be taken into account even at low liquid content. We think that these results may provide different approaches for the characterization of foam properties and for the in situ characterization of the liquid content of foams in confining geometries, such as microfluidics.

How antifoams act: a microgravity study.

Antifoams are widely used to control or to avoid foam production. In order to work, antifoam particles need to break foam films efficiently, which many antifoams do very well. However, once they have broken a film, to continue to be effective they need to be transported to the next film. We show, for the first time, that buoyancy has an important part in the transport of the antifoam particles. In microgravity, where buoyancy and gravitational drainage are strongly slowed down, diffusion leads to poor antifoam performance. The foam is stable for the duration of the experiment, whereas on Earth the foam starts to disappear immediately. Indeed, microgravity renders highly efficient antifoam practically useless.

Adsorption-desorption kinetics of surfactants at liquid surfaces.

The paper discusses adsorption and desorption energy barriers for macroscopic interfaces of surfactant solutions. Literature data suggest that adsorption and desorption are not always fully diffusion controlled. Apart from electrostatic barriers that lead to strong deviations, other types of barriers are less easy to identify, because smaller deviations from diffusion controlled mechanisms are evidenced. Complete models involving both diffusion and sorption barriers are very complex and involve many adjustable parameters, making the data analysis frequently unreliable. Empirical equations of state are used in most cases, although they are inaccurate, especially close to the cmc. The variation of sorption energies with surface concentration is not accurately described in the models. Finally, convection can mask the effect of sorption energy barriers. Experiments are presented to illustrate the main difficulties encountered.