Microcapsules allow for the controlled containment, transport, and release of cargoes ranging from pharmaceuticals to fragrances. Given the interest from a variety of industries in microcapsules and other core-shell structures, a multitude of fabrication strategies exist. Here, we report on a method relying on a mixture of temperature-responsive microgel particles, poly(N-isopropylacrylamide) (pNIPAM), and a polymer which undergo fluid-fluid phase separation. At room temperature this mixture separates into colloid-rich (liquid) and colloid-poor (gas) fluids. By heating the sample above a critical temperature where the microgel particles shrink dramatically and develop a more deeply attractive interparticle potential, the droplets of the colloid-rich phase become gel-like. As the temperature is lowered back to room temperature, these droplets of gelled colloidal particles reliquefy and phase separation within the droplet occurs. This phase separation leads to colloid-poor droplets within the colloid-rich droplets surrounded by a continuous colloid-poor phase. The gas/liquid/gas all-aqueous double emulsion lasts only a few minutes before a majority of the inner droplets escape. However, the colloid-rich shell of the core-shell droplets can solidify with the addition of salt. That this method creates a core-shell structures with a shell composed of stimuli-sensitive microgel colloidal particles using only aqueous components makes it attractive for encapsulating biological materials and making capsules that respond to changes in, for example, temperature, salt concentration, or pH.
A way forward for high throughput fabrication of microcapsules with uniform size and mechanical properties was reported irrespective of the kinetic process of shell assembly. Microcapsules were produced using lab-scale emulsification equipment with a micro-engineered membrane in the size range 10-100 $μ$m. The shell of the microcapsules was assembled at the water-oil interface by complexation of polyelectrolytes or cross-linking of proteins providing two different kinetic processes. Elasticity of microcapsules was characterized with an automated extensional flow chamber. Process parameters wer…
We investigate the deformation of elastic microcapsules adsorbed at liquid-liquid interfaces. An initially spherical elastic capsule at a liquid-liquid interface undergoes circumferential stretching due to the liquid-liquid surface tension and becomes lens- or discus-shaped, depending on its bending rigidity. The resulting elastic capsule deformation is qualitatively similar, but distinct from the deformation of a liquid droplet into a liquid lens at a liquid-liquid interface. We discuss the deformed shapes of droplets and capsules adsorbed at liquid-liquid interfaces for a whole range of diff…
An important goal of self-assembly is to achieve a preprogrammed structure with high fidelity. Here, we control the valence of DNA-functionalized emulsions to make linear and branched model polymers, or `colloidomers'. The distribution of cluster sizes is consistent with a polymerization process in which the droplets achieve their prescribed valence. Conformational dynamics reveals that the chains are freely-jointed, such that the end-to-end length scales with the number of bonds $N$ as $N^ν$, where $ν\approx3/4$, in agreement with the Flory theory in 2D. The chain diffusion coefficient $D$ ap…
In living cells, molecular motors create activity that enhances the diffusion of particles throughout the cytoplasm, and not just ones attached to the motors. We demonstrate initial steps toward creating artificial cells that mimic this phenomenon. Our system consists of active, Pt-coated Janus particles and passive tracers confined to emulsion droplets. We track the motion of both the active particles and passive tracers in a hydrogen peroxide solution, which serves as the fuel to drive the motion. We first show that correcting for bulk translational and rotational motion of the droplets indu…
Exploring the role of hydrodynamic interactions in spherically-confined drying colloidal suspensions
Auburn University（奥本大学）；Leibniz-Institut für Polymerforschung Dresden e.V.（德累斯顿莱布尼茨聚合物研究所）；Technische Universität Dresden（德累斯顿工业大学）；Johannes Gutenberg University Mainz（美因茨约翰内斯·古腾堡大学）
In this work, we unravel the role of surface properties of colloidal particles on the formation of supraparticles (clusters of colloidal particles) in a colloidal Ouzo droplet. Self-lubricating colloidal Ouzo droplets are an efficient and simple approach to form supraparticles, overcoming the challenge of the coffee stain effect in situ. Supraparticles are an efficient route to high-performance materials in various fields, from catalysis to carriers for therapeutics. Yet, the role of the surface of colloidal particles in the formation of supraparticles using Ouzo droplets remains unknown. Ther…
Active colloidal rafts perform swimming strokes that propel their host droplets
Université de Bordeaux（波尔多大学）；Collège de France（法兰西公学院）；Max Planck Institute for the Physics of Complex Systems（马克斯·普朗克复杂系统物理研究所）；Meiji University（明治大学）
Understanding flow patterns and coupled transport phenomena during evaporation of droplets loaded with colloidal particles is central to design technical applications such as organizing proteins/DNA on a solid surface. We review recent reports on evaporating sessile droplets of colloidal suspensions on a solid surface. Starting from the classical mechanism of formation of a ring-like deposit, we discuss the influence of several problem parameters. Notably, thermal or solutal Marangoni effect, particle size, particle concentration, particle shape, substrate wettability, pH of the suspension etc…
The pattern and profile of a dried colloidal deposit formed after evaporation of a sessile water droplet containing polystyrene particles on a non-uniformly heated glass are investigated experimentally. In particular, the effects of temperature gradient across the substrate and particles size are investigated. The temperature gradient was imposed using Peltier coolers, and side visualization, infrared thermography, optical microscopy, and optical profilometry were employed to collect the data. On a uniformly heated substrate, a ring with an inner deposit is obtained, which is attributed to axi…
Ring-shaped deposits can be often found after a droplet evaporates on a substrate. If the fluid in the droplet is a pure liquid and its contact line remains pinned during the process, the mechanism behind such ring-shaped deposition is the well-known coffee-stain effect. However, adding small amounts of salt to such a droplet can change the internal flow dramatically and consequently change the deposition mechanism. Due to an increase of surface tension in the contact line region, a Marangoni flow arises which is directed from the apex of the droplet towards the contact line. As a result, part…
Persistence of Coffee-Ring Deposits in Concentrated Suspensions of Anisotropic Colloids
Department of Physics, Brandeis University（布兰迪斯大学物理系）；Department of Physics and Astronomy, Northwestern University（西北大学物理与天文学系）；Applied Mathematics and Statistics, Colorado School of Mines（科罗拉多矿业大学应用数学与统计学系）
Living microorganisms in confined systems typically experience an affinity to populate boundaries. The reason for such affinity to interfaces can be a combination of their directed motion and hydrodynamic interactions at distances larger than their own size. Here we will show that self-propelled Janus particles (polystyrene particles partially coated with platinum) immersed in droplets of water and hydrogen peroxide tend to accumulate in the vicinity of the liquid/gas interface. Interestingly, the interfacial accumulation occurs despite the presence of an evaporation-driven flow caused by a so…
The present study experimentally and numerically investigates the evaporation and resultant patterns of dried deposits of aqueous colloidal sessile droplets, when the droplets are initially elevated to a high temperature before being placed on a substrate held at ambient temperature. The system is then released for natural evaporation without applying any external perturbation. Infrared thermography and optical profilometry were used as essential tools for interfacial temperature measurements and quantification of the coffee-ring dimensions, respectively. Initially, a significant temperature g…
We investigate deposit patterns and associated morphology formed after the evaporation of an aqueous droplet containing mono- and bi-dispersed colloidal particles. In particular, the combined effect of substrate heating and particle diameter is investigated. We employ high-speed visualization, optical microscopy and scanning electron microscopy to characterize the evaporating droplets, particle motion, and deposit morphology, respectively. In the context of mono-dispersed colloidal particles, an inner deposit and a typical ring form for smaller and larger particles, respectively, on a nonheate…
The deposition of particles on a substrate by drying a colloidal suspension droplet is at the core of applications ranging from traditional printing on paper to printable electronics or photovoltaic devices. The self-pinning induced by the accumulation of particles at the contact line plays an important role in the formation of the deposition. In this paper, we investigate both numerically and theoretically, the effect of friction between the particles and the substrate on the deposition pattern. Without friction, the contact line shows a stick-slip behaviour and a dot-like deposit is left aft…
A model is developed for describing the transport of charged colloidal particles in an evaporating sessile droplet on the electrified metal substrate in the presence of a solvent flow. The model takes into account the electric charge of colloidal particles and small ions produced by electrolytic dissociation of the active groups on the colloidal particles and solvent molecules. We employ a system of self-consistent Poisson and Nernst--Planck equations for electric potential and average concentrations of colloidal particles and ions with the appropriate boundary conditions. The fluid dynamics, …
Just like atoms combine into molecules, colloids can self-organize into predetermined structures according to a set of design principles. Controlling valence -- the number of inter-particle bonds -- is a prerequisite for the assembly of complex architectures. The assembly can be directed via solid `patchy' particles with prescribed geometries to make, for example, a colloidal diamond. We demonstrate here that the nanoscale ordering of individual molecular linkers can combine to program the structure of microscopic assemblies. Specifically, we experimentally show that covering initially isotrop…
In this work, we continue to study the formation of particle chains (clusters) inside the annular sediment during the drying of a colloidal droplet on a substrate. The average value of the cluster size was determined after processing experimental data from other authors. We performed a series of calculations and found the value of the model parameter allowed to get numerical results agreed with the experiment. Also, a modification of the previously proposed algorithm is analyzed here.
Effects of Substrate Heating and Wettability on Evaporation Dynamics and Deposition Patterns for a Sessile Water Droplet Containing Colloidal Particles
We experimentally investigate the profile and morphology of the ring-like deposits obtained after evaporation of a sessile water droplet containing polystyrene colloidal particles on a hydrophilic glass substrate. In particular, the coupled effect of particle size and concentration are studied. The deposits were qualitatively visualized under an optical microscope and profile of the ring was measured by an optical profilometer. The profile of the ring resembles a partial torus-like shape for all cases of particles size and concentration. The cracks on the surface of the ring were found to occu…
Recent experiments have shown how nematically-ordered tactoid shaped actin droplets can be reorganized and divided by the action of myosin molecular motors. In this paper, we consider how similar morphological changes can potentially be achieved under equilibrium conditions. Using simulations, both atomistic and continuum, and a phenomenological model, we explore how the nucleation dynamics, shape changes, and the final steady state of a nematic tactoid droplet can be modified by interactions with model adhesive colloids that mimic a myosin motor cluster. Our results provide a prescription for…
