This research found that when an acidic solution with a low surface tension spread on the surface of a glycerol solution mixed with milk, a star shaped pattern was spontaneously formed on the surface in the horizontal plane during the spreading process. We investigated the emergence of the star shaped pattern owing to an interfacial instability in experiments using glycerol solutions with several viscosities and 2-methoxyethanol aqueous solutions, which are acidic solutions, with several concentrations. This result demonstrated that the star shaped pattern emerged in the high concentration of 2-methoxyethanol. We proposed a phenomenological model, based on our experimental results, which explains three points as follows; the spreading of the 2-methoxyethanol aqueous solution on the surface of the glycerol solution, the colloidal aggregation of the milk protein colloids caused by the denaturation that occurs when mixed with 2-methoxyethanol, and the accumulation of the aggregates toward the dent regions of the moving interface by a sweeping effect. The model reproduces the formation of the star shaped pattern which was similar to the experimental one. Furthermore, the model provided a phase diagram against the concentration of the 2-methoxyethanol solution and the viscosity of the glycerol solution as control parameters in our experiments. The phase diagram was close to that obtained from our experiments. The results suggest that the above three points are important for the formation of the star shaped pattern.
We investigate the behavior of a mixture of asymmetric colloidal dumbbells and emulsion droplets by means of kinetic Monte Carlo simulations. The evaporation of the droplets and the competition between droplet-colloid attraction and colloid-colloid interactions leads to the formation of clusters built up of colloid aggregates with both closed and open structures. We find that stable packings and hence complex colloidal structures can be obtained by changing the relative size of the colloidal spheres and/or their interfacial tension with the droplets.
Drying a droplet of colloidal dispersion can result in complex pattern formation due to both development and deformation of a skin at the drop surface. The present study focus on the drying process of droplets of colloidal dispersions in a confined geometry where direct observations of the skin thickness are allowed. During the drying, a buckling process is followed by a single depression growth inside the drop. The deformation of the droplet is found to be generic and is studied for various colloidal dispersions. The final shape can be partly explained by simple energy analysis based on the c…
The nucleation and growth kinetics of highly ordered nanocrystal superlattices during the evaporation of nanocrystal colloidal droplets was elucidated by in situ time resolved small-angle x-ray scattering. We demonstrated for the first time that evaporation kinetics can affect the dimensionality of the superlattices. The formation of two-dimensional nanocrystal superlattices at the liquid-air interface of the droplet has an exponential growth kinetics that originates from interface "crushing".
We simulate the response of a particle-stabilized emulsion droplet in an external force field, such as gravity, acting equally on all $N$ particles. We show that the field strength required for breakup (at fixed initial area fraction) decreases markedly with droplet size, because the forces act cumulatively, not individually, to detach the interfacial particles. The breakup mode involves the collective destabilization of a solidified particle raft occupying the lower part of the droplet, leading to a critical force per particle that scales approximately as $N^{-1/2}$.
Understanding the influence of hydrodynamic stresses and colloidal interactions between droplets and membranes will inform better engineered membrane surfaces and process conditions. Using a long-wave hydrodynamic description that incorporates wettability and electrostatic repulsion, we numerically investigate the influence of droplet shapes and membrane characteristics on the overall repulsion-attraction towards the membrane surface. A stability phase diagram classifies stable-unstable drop shapes and investigate whether there is reversible deposition of droplets onto the membrane.
We report a novel surface-tension driven instability observed for droplets spreading on a compliant substrate. When a droplet is released on the surface of an agar gel, it forms arms/cracks when the ratio of surface tension gradient to gel strength is sufficiently large. We explore a range of gel strengths and droplet surface tensions and find that the onset of the instability and the number of arms depend on the ratio of surface tension to gel strength. However, the arm length grows with an apparently universal law L ~ t^{3/4}.
Evaporating suspensions of colloidal particles lead to the formation of a variety of patterns, ranging from a left-over ring of a dried coffee drop to uniformly distributed solid pigments left behind wet paint. To characterize the transition between single rings, multiple concentric rings, broad bands, and uniform deposits, we investigate the dynamics of a drying droplet via a multiphase model of colloidal particles in a solvent. Our theory couples the inhomogeneous evaporation at the evolving droplet interface to the dynamics inside the drop, i.e. the liquid flow, local variations of the part…
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…
We use a three-dimensional lattice Boltzmann model to investigate the spreading of mesoscale droplets on homogeneous and heterogeneous surfaces. On a homogeneous substrate the base radius of the droplet grows with time as $t^{0.28}$ for a range of viscosities and surface tensions. The time evolutions collapse onto a single curve as a function of a dimensionless time. On a surface comprising of alternate hydrophobic and hydrophilic stripes the wetting velocity is anisotropic and the equilibrium shape of the droplet reflects the wetting properties of the underlying substrate.
The spreading under surface tension and gravity of a droplet of yield-stress fluid over a thin film of the same material is studied. The droplet converges to a final equilibrium shape once the driving stresses inside the droplet fall below the yield stress. Scaling laws are presented for the final radius and complemented with an asymptotic analysis for shallow droplets. Moreover, numerical simulations using the volume-of-fluid method and a regularized constitutive law, and experiments with an aqueous solution of Carbopol are presented.
Understanding the relationship between colloidal building block shape and self-assembled material structure is important for the development of novel materials by self-assembly. In this regard, colloidal superballs are unique building blocks because their shape can smoothly transition between spherical and cubic. Assembly of colloidal superballs under spherical confinement results in macroscopic clusters with ordered internal structure. By utilizing Small Angle X-Ray Scattering (SAXS), we probe the internal structure of colloidal superball dispersion droplets during confinement. We observe and…
We present numerical results for the breakup of a pair of colloidal particles enveloped by a droplet under shear flow. The smoothed profile method is used to accurately account for the hydrodynamic interactions between particles due to the host fluid. We observe that the critical capillary number, $Ca_{\rm B}$, at which droplets breakup depends on a velocity ratio, $E$, defined as the ratio of the boundary shift velocity (that restores the droplet shape to a sphere) to the diffusive flux velocity in units of the particle radius $a$. For $E < 10$, $Ca_{B}$ is independent of $E$, as is consisten…
The influence of controlled vibrations on the granular rheology is investigated in a specifically designed experiment. We study experimentally a thin granular film spreading under the action of horizontal vibrations. A nonlinear diffusion equation is derived theoretically that describes the evolution of the deposit shape. A self-similar parabolic shape (the``granular droplet'') and a spreading dynamics are predicted that both agree quantitatively with the experimental results. The theoretical analysis is used to extract effective dynamic friction coefficients between the base and the granular …
When a droplet impacts a fabric mesh at a sufficiently high impact velocity, it not only spreads over the fabric but also penetrate its pores. To determine the influence of this liquid penetration of the fabric on droplet spreading on thin fabric meshes, we measured the droplet spreading ratio on fabric with and without an underlying substrate using a high-speed camera. For fabrics without a substrate, the droplet spreading ratio is reduced as the fabric penetration by the liquid reduces the droplet volume spreading on top of the fabric. Using entropic lattice Boltzmann simulations, we find th…
We demonstrate a variety of ordered patterns, including hexagonal structures and chains, formed by colloidal particles (droplets) at the free surface of a nematic liquid crystal (LC). The surface placement introduces a new type of particle interaction as compared to particles entirely in the LC bulk. Namely, director deformations caused by the particle lead to distortions of the interface and thus to capillary attraction. The elastic-capillary coupling is strong enough to remain relevant even at the micron scale when its buoyancy-capillary counterpart becomes irrelevant.
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…
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, …
The spreading of polymer droplets is studied using molecular dynamics simulations. To study the dynamics of both the precursor foot and the bulk droplet, large drops of ~200,000 monomers are simulated using a bead-spring model for polymers of chain length 10, 20, and 40 monomers per chain. We compare spreading on flat and atomistic surfaces, chain length effects, and different applications of the Langevin and dissipative particle dynamics thermostats. We find diffusive behavior for the precursor foot and good agreement with the molecular kinetic model of droplet spreading using both flat and a…
The quasistationary spreading of a circular liquid drop on a solid substrate typically obeys the so-called Tanner law, with the instantaneous base radius R(t) growing with time as R ~ t^{1/10} -- an effect of the dominant role of capillary forces for a small-sized droplet. However, for droplets of nematic liquid crystals, a faster spreading law sets in at long times, so that R ~ t^alpha with alpha significantly larger than the Tanner exponent 1/10. In the framework of the thin film model (or lubrication approximation), we describe this "acceleration" as a transition to a qualitatively differen…
Nanoscale topographic features of solid surfaces can induce complex metastable behavior in colloidal and multiphase systems. Recent studies on single microparticle adsorption at liquid interfaces have reported a crossover from fast capillary driven dynamics to extremely slow kinetic regimes that can require up to several hours or days to attain thermodynamic equilibrium. The observed kinetic regime resembling physical ageing in glassy materials has been attributed to unobserved surface features with dimensions on the order of a few nanometers. In this work, we study the spontaneous spreading o…
We consider a theoretical model for a binary mixture of colloidal particles and spherical emulsion droplets. The hard sphere colloids interact via additional short-ranged attraction and long-ranged repulsion. The droplet-colloid interaction is an attractive well at the droplet surface, which induces the Pickering effect. The droplet-droplet interaction is a hard-core interaction. The droplets shrink in time, which models the evaporation of the dispersed (oil) phase, and we use Monte Carlo simulations for the dynamics. In the experiments, polystyrene particles were assembled using toluene dropl…
The contact angle of a fluid droplet on an heterogeneous surface is analysed using the statistical dynamics of the spreading contact line. The statistical properties of the final droplet radius and contact angle are obtained through applications of depinning transitions of contact lines with non-local elasticity and features of pinning-depinning dynamics. Such properties not only depend on disorder strength and surface details, but also on the droplet volume and disorder correlation length. Deviations from Wenzel or Cassie/Baxter behaviour are particularly apparent in the case of small droplet…
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…
We describe a setup to perform systematic studies on the spreading of droplets of complex fluids under microgravity conditions. Tweaking the gravitational acceleration under which droplets are deposited provides access to different regimes of the spreading dynamics, quantified through the Bond number. In particular, microgravity allows to form large droplets while remaining in the regime where surface tension effects and internal driving stresses are predominant over hydrostatic forces. The VIP-DROP2 experimental module provides a versatile platform to study a wide range of complex fluids thro…
The spreading of one- and two-component polymer nanodroplets is studied using molecular dynamics simulation in a cylindrical geometry. The droplets consist of polymer chains of length 10, 40, and 100 monomers per chain described by the bead-spring model spreading on a flat surface with a surface-coupled Langevin thermostat. Each droplet contains ~350,000 monomers. The dynamics of the individual components of each droplet are analyzed and compared to the dynamics of single component droplets for the spreading rates of the precursor foot and bulk croplet, the time evolution of the contact angle,…
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…
We study the free energy landscapes of a pair of submicron spherical particles floating at the surface of a sessile droplet. The particles are subjected to radial external forces resulting in a deformation of the droplet shape relative to the reference shape of a spherical cap. This deformation leads to tangential forces on the particles. For small deformations and for the contact angle $θ_0$ at the substrate being equal to $π/2$, the corresponding linearized Young-Laplace equation is solved analytically. The solution is constructed by employing the method of images from electrostatics, where …
Evaporation-driven particle self-assembly can be used to generate three-dimensional microstructures. We present a new method to create these colloidal microstructures, in which we can control the amount of particles and their packing fraction. To this end, we evaporate colloidal dispersion droplets on a special type of superhydrophobic micro-structured surface, on which the droplet re- mains in Cassie-Baxter state during the entire evaporative process. The remainders of the droplet consist of a massive spherical cluster of the microspheres, with diameters ranging from a few tens up to several …
We report a study of reversible adsorption of DNA-coated colloids on complementary functionalized oil droplets. We show that it is possible to control the surface coverage of oil droplets by colloidal particles, by exploiting the fact that during slow adsorption, compositional arrest takes place well before structural arrest occurs. As a consequence, we can prepare colloid-coated oil droplets with a `frozen' degree of loading, but with fully ergodic colloidal dynamics on the droplets. We illustrate the equilibrium nature of the adsorbed colloidal phase by exploring the quasi two-dimensional (2…
The spreading of a cap-shaped spherical droplet of non-Newtonian power-law liquids on a completely wettable spherical substrate is theoretically studied. Both convex spherical substrates and concave spherical cavities with smooth or rough surfaces are considered. The droplet on a rough substrate is modeled by either the Wenzel or the Cassie-Baxter model. The two sources of driving force of spreading by the surface-tension and the line tension are considered. Also, the two channels of energy dissipation by the viscous dissipation within the bulk and the frictional dissipation at the contact lin…
We present results on the leveling of polymer microdroplets on thin films prepared from the same material. In particular, we explore the crossover from a droplet spreading on an infinitesimally thin film (Tanner's law regime) to that of a droplet leveling on a film thicker than the droplet itself. In both regimes, the droplet's excess surface area decreases towards the equilibrium configuration of a flat liquid film, but with a different power law in time. Additionally, the characteristic leveling time depends on molecular properties, the size of the droplet, and the thickness of the underlyin…
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…
We report an experimental investigation of spreading then shrinking of a surfactant droplet at the air-water interface with fingering instability appearing at the edge of the droplet stain. We find out that a droplet of a surfactant on the water shows three regimes of spreading, shrinking and resting at the appropriate parameters values. These regimes can be distinguished by measuring the mean square displacement of the droplet parts, fractal dimension of stain, or radius of fingerless part of the stain (to measure it, we define the angular box-counting dimension), versus time. The shrinking r…
The spreading of a cap-shaped spherical droplet on a completely wettable spherical substrate is studied. The non-equilibrium thermodynamic formulation is used to derive the thermodynamic driving force of spreading including the line-tension effect. Then the energy balance approach is adopted to derive the evolution equation of the spreading droplet. The time evolution of the contact angle $θ$ of a droplet obeys a power law $θ\sim t^{-α}$ with the exponent $α$, which is different from that derived from Tanner's law on a flat substrate. Furthermore, the line tension must be positive to promote c…
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）
Would a raindrop impacting on a coarse beach behave differently from that impacting on a desert of fine sand? We study this question by a series of model experiments, where the packing density of the granular target, the wettability of individual grains, the grain size, the impacting liquid, and the impact speed are varied. We find that by increasing the grain size and/or the wettability of individual grains the maximum droplet spreading undergoes a transition from a capillary regime towards a viscous regime, and splashing is suppressed. The liquid-grain mixing is discovered to be the underlyi…
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）
The spreading of a circular liquid drop on a solid substrate can be described by the time evolution of its base radius R(t). In complete wetting the quasistationary regime (far away from initial and final transients) typically obeys the so-called Tanner law, with R t^alpha_T, alpha_T=1/10. Late-time spreading may differ significantly from the Tanner law: in some cases the drop does not thin down to a molecular film and instead reaches an equilibrium pancake-like shape; in other situations, as revealed by recent experiments with spontaneously spreading nematic crystals, the growth of the base r…
When a droplet is brought in contact with an undercooled surface, it wets the substrate and solidifies at the same time. The interplay between the phase transition effects and the contact-line motion, leading to its arrest, remains poorly understood. Here we reveal the early solidification patterns and dynamics of spreading hexadecane droplets. Total internal reflection (TIR) imaging is employed to temporally and spatially resolve the early solidification behaviour. With this, we determine the conditions leading to the contact-line arrest. We quantify the overall nucleation behaviour, \textit{…
We study the spreading of droplets in a near-critical phase-separated liquid mixture, using a combination of experiments, lubrication theory and finite-element numerical simulations. The classical Tanner's law describing the spreading of viscous droplets is robustly verified when the critical temperature is neared. Furthermore, the microscopic cut-off length scale emerging in this law is obtained as a single free parameter for each given temperature. In total-wetting conditions, this length is interpreted as the thickness of the thin precursor film present ahead of the apparent contact line. T…
The surfactant-driven spreading of droplets is an essential process in many applications ranging from coating flow technology to enhanced oil recovery. Despite the significant advancement in describing spreading processes in surfactant-laden droplets, including the exciting phenomena of superspreading, many features of the underlying mechanisms require further understanding. Here, we have carried out molecular dynamics simulations of a coarse-grained model with a force-field obtained from the statistical associating fluid theory to study droplets laden with common and superspreading surfactant…
Particle-stabilized emulsions are commonly used in various industrial applications. These emulsions can present in different forms, such as Pickering emulsions or bijels, which can be distinguished by their different topologies and rheology. We numerically investigate the effect of the volume fraction and the uniform wettability of the stabilizing spherical particles in mixtures of two fluids. For this, we use the well-established three-dimensional lattice Boltzmann method, extended to allow for the added colloidal particles with non-neutral wetting properties. We obtain data on the domain siz…
Even a small fraction of nanoparticles in fluids affects the splashing behavior of a droplet upon impact on a smooth surface. Nanofluid drop impact onto a smooth sapphire substrate is experimentally investigated over wide ranges of Reynolds ($10^2<\mathrm{Re}<10^4$) and Weber ($50<\mathrm{We}<500$) numbers for three nanofluid mass concentrations (0.01%, 0.1%, 1%) using high-speed photography. Nanofluids are prepared by diluting a commercial Al$_2$O$_3$-water nanofluid in aqueous glycerol solutions without dispersants. In total, 30 samples are prepared and 1799 data points are acquired. Every s…
This short review is devoted to the simple process of drying a multi-component droplet consisting of a complex fluid containing a salt. These processes provide a fascinating subject for study. The explanation of the rich variety of patterns formed is not only an academic challenge, but a problem of practical importance, as applications are growing in medical diagnosis and improvement of coating/printing technology. The fundamental scientific problem is the study of the mechanism of micro- and nanoparticle self-organization in open systems. The specific fundamental problem to be solved, related…
The complicated dynamics of the contact line of a moving droplet on a solid substrate often hamper the efficient modeling of microfluidic systems. In particular, the selection of the effective boundary conditions, specifying the contact line motion, is a controversial issue since the microscopic physics that gives rise to this displacement is still unknown. Here, a sharp interface, continuum-level, novel modeling approach, accounting for liquid/solid micro-scale interactions assembled in a disjoining pressure term, is presented. By following a unified conception (the model applies both to the …
Drying of colloidal droplets on solid, rigid substrates is associated with a capillary pressure developing within the droplet. In due course of time, the capillary pressure builds up due to droplet evaporation resulting in the formation of a colloidal thin film that is prone to crack formation. In this study, we show that introducing a minimal amount of nematic liquid crystal (NLC) can completely suppress the crack formation. The mechanism behind the curbing of the crack formation may be attributed to the capillary stress-absorbing cushion provided by the elastic arrangements of the liquid cry…
We use molecular dynamics to study the ordering of a nematic liquid crystal around a spherical particle or droplet. Homeotropic boundary conditions and strong anchoring create a hedgehog director configuration on the particle surface and in its vicinity; this topological defect is cancelled by nearby defect structures in the surrounding liquid crystal, so as to give a uniform director field at large distances. We observe three defect structures for different particle sizes: a quadrupolar one with a ring defect surrounding the particle in the equatorial plane; a dipolar one with a satellite def…
