Interactions between interfaces dictate stimuli-responsive emulsion behaviour.

Stimuli-responsive emulsions offer a dual advantage, combining long-term storage with controlled release triggered by external cues such as pH or temperature changes. This study establishes that thermo-responsive emulsion behaviour is primarily determined by interactions between, rather than within, interfaces. Consequently, the stability of these emulsions is intricately tied to the nature of the stabilizing microgel particles - whether they are more polymeric or colloidal, and the morphology they assume at the liquid interface.

Light, Matter, Action: Shining Light on Active Matter.

Light carries energy and momentum. It can therefore alter the motion of objects on the atomic to astronomical scales. Being widely available, readily controllable, and broadly biocompatible, light is also an ideal tool to propel microscopic particles, drive them out of thermodynamic equilibrium, and make them active.

Versatile strategy for homogeneous drying patterns of dispersed particles.

After spilling coffee, a tell-tale stain is left by the drying droplet. This universal phenomenon, known as the coffee ring effect, is observed independent of the dispersed material. However, for many technological processes such as coating techniques and ink-jet printing a uniform particle deposition is required and the coffee ring effect is a major drawback.

Boxes fabricated from plate-stabilized liquid marbles.

Polyhedral liquid marbles were fabricated using hydrophobic polymer plates in the shape of a circle, a heart and a star as a stabilizer and water as an inner liquid phase. Boxes could be fabricated by the evaporation of the inner water from the liquid marbles. The fabrication efficiency and stability of these boxes as a function of the plate shape were investigated.

Anisotropic silicon nanowire arrays fabricated by colloidal lithography.

The combination of metal-assisted chemical etching (MACE) and colloidal lithography allows for the affordable, large-scale and high-throughput synthesis of silicon nanowire (SiNW) arrays. However, many geometric parameters of these arrays are coupled and cannot be addressed individually using colloidal lithography. Despite recent advancements towards higher flexibility, SiNWs fabricated colloidal lithography and MACE usually have circular, isotropic cross-sections inherited from the spherical templates.

Interface-induced hysteretic volume phase transition of microgels: simulation and experiment.

Thermo-responsive microgel particles can exhibit a drastic volume shrinkage upon increasing the solvent temperature. Recently we found that the spreading of poly(N-isopropylacrylamide) (PNiPAm) microgels at a liquid interface under the influence of surface tension hinders the temperature-induced volume phase transition. In addition, we observed a hysteresis behavior upon temperature cycling, i.

Collapse-induced phase transitions in binary interfacial microgel monolayers.

Microgels, consisting of a swollen polymer network, exhibit a more complex self-assembly behavior compared to incompressible colloidal particles, because of their ability to deform at a liquid interface or collapse upon compression. Here, we investigate the collective phase behavior of two-dimensional binary mixtures of microgels confined at the air/water interface. We use stimuli-responsive poly(N-isopropylacrylamide) microgels with different crosslinking densities, and therefore different morphologies at the interface.

Soft Particles at Liquid Interfaces: From Molecular Particle Architecture to Collective Phase Behavior.

Soft particles such as microgels can undergo significant and anisotropic deformations when adsorbed to a liquid interface. This, in turn, leads to a complex phase behavior upon compression. To date, experimental efforts have predominantly provided phenomenological links between microgel structure and resulting interfacial behavior, while simulations have not been entirely successful in reproducing experiments or predicting the minimal requirements for the desired phase behavior.

Large-Scale Synthesis of Highly Uniform Silicon Nanowire Arrays Using Metal-Assisted Chemical Etching.

The combination of metal-assisted chemical etching (MACE) with colloidal lithography has emerged as a simple and cost-effective approach to nanostructure silicon. It is especially efficient at synthesizing Si micro- and nanowire arrays using a catalytic metal mesh, which sinks into the silicon substrate during the etching process. The approach provides a precise control over the array geometry, without requiring expensive nanopatterning techniques.

Spatioselective Deposition of Passivating and Electrocatalytic Layers on Silicon Nanowire Arrays.

Metal-silicon nanowire array photoelectrodes provide a promising architecture for water-splitting because they can afford high catalyst loading and decouple charge separation from the light absorption process. To further improve and understand these hybrid nanowire photoelectrodes, control of the catalyst amount and location within the wire array is required. Such a level of control is currently synthetically challenging to achieve.

Effect of Stabilizing Particle Size on the Structure and Properties of Liquid Marbles.

A liquid marble (LM) describes a liquid droplet that is wrapped by nonwetting micro- or nanoparticles and therefore obtains characteristics of a solid powder particle. Here, we investigate the effect of the stabilizing particle size on the resulting structure and properties of the LM. We synthesize a series of polystyrene particles with ultrathin coatings of heptadecafluorooctanesulfonic acid-doped polypyrrole with diameters ranging between 1 and 1000 μm by an aqueous chemical oxidative seeded polymerization of pyrrole.

Chiral Surface Lattice Resonances.

Collective excitation of periodic arrays of metallic nanoparticles by coupling localized surface plasmon resonances to grazing diffraction orders leads to surface lattice resonances with narrow line width. These resonances may find numerous applications in optical sensing and information processing. Here, a new degree of freedom of surface lattice resonances is experimentally investigated by demonstrating handedness-dependent excitation of surface lattice resonances in arrays of chiral plasmonic crescents.

Pattern formation in two-dimensional hard-core/soft-shell systems with variable soft shell profiles.

Hard-core/soft shell (HCSS) particles have been shown to self-assemble into a remarkably rich variety of structures under compression due to the simple interplay between the hard-core and soft-shoulder length scales in their interactions. Most studies in this area model the soft shell interaction as a square shoulder potential. Although appealing from a theoretical point of view, the potential is physically unrealistic because there is no repulsive force in the soft shell regime, unlike in experimental HCSS systems.

Probing particle heteroaggregation using analytical centrifugation.

The controlled aggregation of colloidal particles is not only a widespread natural phenomenon but also serves as a tool to design complex building blocks with tailored shape and functionalities. However, the quantitative characterization of such heteroaggregation processes remains challenging. Here, we demonstrate the use of analytical centrifugation to characterize the heteroaggregation of silica particles and soft microgels bearing similar surface charges.

Morphology-Graded Silicon Nanowire Arrays via Chemical Etching: Engineering Optical Properties at the Nanoscale and Macroscale.

We report on a quick, simple, and cost-effective solution-phase approach to prepare centimeter-sized morphology-graded vertically aligned Si nanowire arrays. Gradients in the nanowire diameter and shape are encoded through the macroscale substrate via a "dip-etching" approach, where the substrate is removed from a KOH etching solution at a constant rate, while morphological control at the nanowire level is achieved via sequential metal-assisted chemical etching and KOH etching steps. This combined approach provides control over light absorption and reflection within the nanowire arrays at both the macroscale and nanoscale, as shown by UV-vis spectroscopy and numerical three-dimensional finite-difference time-domain simulations.

Particle Monolayer-Stabilized Light-Sensitive Liquid Marbles from Polypyrrole-Coated Microparticles.

Liquid marbles are water droplets coated with solid particles that prevent coalescence and allow storage, transport, and handling of liquids in the form of a powder. Here, we report on the formation of liquid marbles that are stabilized entirely by a single monolayer of solid particles and thus minimize the amount of required solid material. As stabilizing particles, we synthesize relatively monodisperse, 80 μm-sized polystyrene (PS) particles coated with heptadecafluorooctanesulfonic acid-doped polypyrrole (PPy-CF) shell (PS/PPy-CF particles) by aqueous chemical oxidative seeded polymerization of pyrrole using FeCl as an oxidant and heptadecafluorooctanesulfonic acid as a hydrophobic dopant.

Poly--isopropylacrylamide Nanogels and Microgels at Fluid Interfaces.

The confinement of colloidal particles at liquid interfaces offers many opportunities for materials design. Adsorption is driven by a reduction of the total free energy as the contact area between the two liquids is partially replaced by the particle. From an application point of view, particle-stabilized interfaces form emulsions and foams with superior stability.

Stimuli-Responsive Behavior of PNiPAm Microgels under Interfacial Confinement.

The volume phase transition of microgels is one of the most paradigmatic examples of stimuli-responsiveness, enabling a collapse from a highly swollen microgel state into a densely coiled state by an external stimulus. Although well characterized in bulk, it remains unclear how the phase transition is affected by the presence of a confining interface. Here, we demonstrate that the temperature-induced volume phase transition of poly(-isopropylacrylamide) microgels, conventionally considered an intrinsic molecular property of the polymer, is in fact largely suppressed when the microgel is adsorbed to an air/liquid interface.

A Dirty Story: Improving Colloidal Monolayer Formation by Understanding the Effect of Impurities at the Air/Water Interface.

Colloidal monolayers are important tools to fabricate surface structures at the nanoscale. A typical monolayer fabrication strategy involves the self-assembly of colloidal building blocks at liquid interfaces, which are subsequently deposited on a solid substrate. Even though this process is well established, the resulting order of the particles within the colloidal monolayer differs between batches of colloidal particles and can even change with the age of the dispersion.

Three-Dimensional Electrochemical Axial Lithography on Si Micro- and Nanowire Arrays.

A templated electrochemical technique for patterning macroscopic arrays of single-crystalline Si micro- and nanowires with feature dimensions down to 5 nm is reported. This technique, termed three-dimensional electrochemical axial lithography (3DEAL), allows the design and parallel fabrication of hybrid silicon nanowire arrays decorated with complex metal nano-ring architectures in a flexible and modular approach. While conventional templated approaches are based on the direct replication of a template, our method can be used to perform high-resolution lithography on pre-existing nanostructures.

Surface Patterning with SiO@PNiPAm Core-Shell Particles.

Colloidal lithography is a cost-efficient method to produce large-scale nanostructured arrays on surfaces. Typically, colloidal particles are assembled into hexagonal close-packed monolayers at liquid interfaces and deposited onto a solid substrate. Many applications, however, require non close-packed monolayers, which are more difficult to fabricate.

Amphiphile-Induced Anisotropic Colloidal Self-Assembly.

Spherical colloidal particles typically self-assemble into hexagonal lattices when adsorbed at liquid interfaces. More complex assembly structures, including particle chains and phases with square symmetry, were theoretically predicted almost two decades ago for spherical particles interacting via a soft repulsive shoulder. Here, we demonstrate that such complex assembly phases can be experimentally realized with spherical colloidal particles assembled at the air/water interface in the presence of molecular amphiphiles.

Anisotropic Self-Assembly from Isotropic Colloidal Building Blocks.

Spherical colloidal particles generally self-assemble into hexagonal lattices in two dimensions. However, more complex, non-hexagonal phases have been predicted theoretically for isotropic particles with a soft repulsive shoulder but have not been experimentally realized. We study the phase behavior of microspheres in the presence of poly(N-isopropylacrylamide) (PNiPAm) microgels at the air/water interface.

Interfacial arrangement and phase transitions of PNiPAm microgels with different crosslinking densities.

Microgels are colloidal hydrogel particles that exhibit a pronounced softness, which arises from the swollen nature of the constituent polymer network. This softness leads to a substantial deformability of such particles at liquid interfaces, which, in turn translates into a complex phase behaviour that can exhibit a phase transition between a non-close packed and a close packed arrangement. Here, we explore how the degree of swellability and deformability - and therefore the softness of the particles - affects the phase behaviour of microgels at the air/water interface upon compression.