The influence of finite system size on the free energy of a spherical particle floating at the surface of a sessile droplet is studied both analytically and numerically. In the special case that the contact angle at the substrate equals $π/2$ a capillary analogue of the method of images is applied in order to calculate small deformations of the droplet shape if an external force is applied to the particle. The type of boundary conditions for the droplet shape at the substrate determines the sign of the capillary monopole associated with the image particle. Therefore, the free energy of the particle, which is proportional to the interaction energy of the original particle with its image, can be of either sign, too. The analytic solutions, given by the Green's function of the capillary equation, are constructed such that the condition of the forces acting on the droplet being balanced and of the volume constraint are fulfilled. Besides the known phenomena of attraction of a particle to a free contact line and repulsion from a pinned one, we observe a local free energy minimum for the particle being located at the drop apex or at an intermediate angle, respectively. This peculiarity can be traced back to a non-monotonic behavior of the Green's function, which reflects the interplay between the deformations of the droplet shape and the volume constraint.
We propose simple model of colloidal sessile drop desiccation. The model describes correctly both evolution of the phase boundary between sol and gel inside such a drop and the final shape of the dried film (deposit). The model is based on mass conservation and natural assumption that deposit (gel phase) prevents flows and evaporation.
We have proposed and investigated a model of drying colloidal suspension drop placed onto a horizontal substrate in which the sol to gel phase transition occurs. The temporal evolution of volume fraction of the solute and the gel phase dynamics were obtained from numerical simulations. Our model takes into account the fact that some physical quantities are dependent on volume fraction of the colloidal particles.
Using lubrication theory, drying processes of sessile colloidal droplets on a solid substrate are studied. A simple model is proposed to describe temporal dynamics both the shape of the drop and the volume fraction of the colloidal particles inside the drop. The concentration dependence of the viscosity is taken into account. It is shown that the final shapes of the drops depend on both the initial volume fraction of the colloidal particles and the capillary number. The results of our simulations are in a reasonable agreement with the published experimental data. The computations for the drops…
It is shown here that concurrence between advection and diffusion in a drying sessile drop of a biological fluid can produce spatial redistribution of albumen and salt. The result gives an explanation for the patterns observed in the dried drops of the biological fluids.
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 …
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 stability of nonvolatile thin liquid films and of sessile droplets is strongly affected by finite size effects. We analyze their stability within the framework of density functional theory using the sharp kink approximation, i.e., on the basis of an effective interface Hamiltonian. We show that finite size effects suppress spinodal dewetting of films because it is driven by a long-wavelength instability. Therefore nonvolatile films are stable if the substrate area is too small. Similarly, nonvolatile droplets connected to a wetting film become unstable if the substrate area is too large. T…
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…
Phase separated macromolecules play essential roles in many biological and synthetic systems. Physical characterization of these systems can be challenging because of limited sample volumes, particularly for phase-separated proteins. Here, we demonstrate that a classic method for measuring the surface tension of liquid droplets, based on the analysis of the shape of a sessile droplet, can be effectively scaled down for this application. The connection between droplet shape and surface tension relies on the density difference between the droplet and its surroundings. This can be determined with…
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, …
We compare the lateral retention forces on sessile drops (which are drops that are placed on top of a solid surface), pendant drops (which are drops that are placed on the underside of the surface), and inverted sessile drops (which are drops that are first placed on top and then on the underside of the surface by flipping the surface). We have found experimentally that the retention force on a truly pendant drop is always smaller than that on a sessile drop. However, the retention force on an inverted sessile drop is comparable to, and usually larger than, that on a sessile drop. Thus, the re…
We address the issues raised in [R. Tadmor et al., Langmuir 2020, 36, 475-476]. In particular, we explain why we did not use Tadmor's theory to explain our results.
Coupled self-charging and self-propulsion of evaporating sessile droplets
Okinawa Institute of Science and Technology Graduate University（冲绳科学技术大学院大学）；Max Planck Institute for Polymer Research（马克斯·普朗克高分子研究所）；King Abdullah University of Science and Technology (KAUST)（阿卜杜拉国王科技大学）
Sessile drops of soft hydrogels were vibrated vertically by subjecting them to a mechanically induced Gaussian white noise. Power spectra of the surface fluctuation of the gel allowed identification of its resonant frequency that decreases with their mass, but increases with its shear modulus. The principal resonant frequencies of the spheroidal modes of the gel of shear moduli ranging from 55 Pa to 290 Pa were closest to the lowest Rayleigh mode of vibration of a drop of pure water. These observations coupled with the fact that the resonance frequency varies inversely as the square root of th…
We present a simple experiment that demonstrates how a water drop hanging from a Plexiglas surface (pendant drop) experiences a lateral retention force that is comparable to, and in some cases larger than, the lateral retention force on a drop resting on top of the surface (sessile drop). The experiment also affords a simple demonstration of the Coriolis effect in two dimensions.
A new set of mathematical identities is presented for axi-symmetric sessile drops on flat and curved substrates. The geometrical parameters, including the apex curvature and height, and the contact radius, are related by the identities. The validity of the identities are checked by various numerical solutions both for flat and curved substrates.
We studied the dependence of solid deposit shape obtained by free drying of sessile drops on the particles concentration and Derjaguin-Landau-Verwey-Overbeek (DLVO) particle/substrate interaction. In contrast to previous contributions using pH as a control parameter of interactions, we investigated an unprecedentedly wide range of concentrations and particle/substrate DLVO forces by modifying the nature of the substrate and particles as well as their size and surface chemistry whereas long-distance repulsive interactions between particles were maintained for most of the drying time. Our main r…
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…
Using an identity, directly derived from the Young-Laplace equation, the problem of the equilibrium shape of an axisymmetric sessile drop is reduced to a one-parameter shooting method problem. Based on the method the numerical solutions for drops with Bond number up to 15 are plotted. The agreement between the method and the ADSA-D method as well as the experimental data is tested. A Mathematica code based on the method is presented.
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…
The effects of line tension on the morphology of a sessile droplet placed on top of a convex spherical substrate are studied. The morphology of the droplet is determined from the global minimum of the Helmholtz free energy. The contact angle between the droplet and the spherical substrate is expressed by the generalized Young's formula. When the line tension is positive and large, the contact angle jumps discontinuously to $180^{\circ}$, the circular contact line shrinks towards the top of the substrate, and the droplet detaches from the substrate, forming a spherical droplet if the substrate …
We present a theoretical study related to a recent experiment on the coalescence of sessile drops. The study deals with the kinetics of relaxation towards equilibrium, under the action of surface tension, of a spheroidal drop on a flat surface. For such a nonspherical drop under partial wetting conditions, the dynamic contact angle varies along the contact line. We propose a new nonlocal approach to the wetting dynamics, where the contact line velocity depends on the geometry of the whole drop. We compare our results to those of the conventional approach in which the contact line velocity depe…
Effects of substrate temperature, substrate wettability and particles concentration are experimentally investigated for evaporation of a sessile water droplet containing colloidal particles. Time-varying droplet shapes and temperature of the liquid-gas interface are measured using high-speed visualization and infrared thermography, respectively. The motion of the particles inside the evaporating droplet is qualitatively visualized by an optical microscope and profile of final particle deposit is measured by an optical profilometer. On a non-heated hydrophilic substrate, a ring-like deposit for…
A finite element model was developed to compute the fluid flow inside a sessile evaporating droplet on hydrophilic substrate in ambient conditions. The evaporation is assumed as quasi-steady and the flow is considered as axisymmetric with a pinned contact line. The Navier-Stokes equations in cylindrical coordinates were solved inside the droplet. Galerkin weight residual approach and velocity pressure formulation was used to discretise the governing equations. Six node triangular mesh and quadratic shape functions were used to obtain higher accuracy solutions. Radial velocity profiles in axial…
The evaporation of a sessile droplet spontaneously induces an internal capillary liquid flow. The surface-tension driven minimisation of surface area and/or surface-tension differences at the liquid-gas interface caused by evaporation-induced temperature or chemical gradients set the liquid into motion. This flow drags along suspended material and is one of the keys to control the material deposition in the stain that is left behind by a drying droplet. Applications of this principle range from the control of stain formation in the printing and coating industry, to the analysis of DNA, to fore…
Motile Bacteria Modify Salt Precipitation Patterns in Dried Sessile Droplet
Georgia Institute of Technology（佐治亚理工学院）；University of Nebraska - Lincoln（内布拉斯加大学林肯分校）；Illinois Institute of Technology（伊利诺伊理工学院）；Blue Valley North High School（蓝谷北高中）
On a sufficiently-soft substrate, a resting fluid droplet will cause significant deformation of the substrate. This deformation is driven by a combination of capillary forces at the contact line and the fluid pressure at the solid surface. These forces are balanced at the surface by the solid traction stress induced by the substrate deformation. Young's Law, which predicts the equilibrium contact angle of the droplet, also indicates an a priori radial force balance for rigid substrates, but not necessarily for soft substrates which deform under loading. It remains an open question whether the …
The evaporation of sessile droplets on a flat surface involves a complex interplay between phase change, diffusion, advection and surface forces. In an attempt to significantly reduce the complexity of the problem and to make it manageable, we propose a simple model hinged on a surface free energy-based relaxation dynamics of the droplet shape, a diffusive evaporation model and a contact line pinning mechanism governed by a yield stress. Our model reproduces the known dynamics of droplet shape relaxation and of droplet evaporation, both in the absence and in the presence of contact line pinnin…
The investigation of evaporating liquid drop deposited onto a flat surface is of great importance for physical, engineering and medical applications. Novel analytical expressions are proposed to calculate the evaporation rate of sessile drop (mass loss per unit surface area per unit time) and total evaporation rate (mass loss per unit time). To obtain these results, the H.M. Macdonald's solution for a flat wedge was transformed by method of inversion in a sphere originally developed by J.C. Maxwell in the Treatise on Electricity and Magnetism with further derivation the solution for a lens bas…
Coalescence of sessile polymeric fluid drops on a partially wettable substrate exhibits a transition from inertial to viscoelastic regime at concentration ratio $c/c^* \sim 1$. Our findings unveil that the temporal evolution of the growing bridge height follows a power-law behaviour $t^b$, such that the coefficient $b$ continuously decreases from 2/3 in the inertial regime ($c/c^*<1$) to an asymptotic value of 1/2 in the visco-elastic regime ($c/c^*>1$). To account for fluid elasticity and characteristic time-scale in the viscoelastic regime, a modified thin film equation under lubrication app…
Spreading of respiratory diseases, such as COVID-19, from contaminated surfaces is dependent on the drying time of the deposited droplets containing the virus. The evaporation rate depends on environmental conditions, such as ambient temperature and relative humidity and physical properties (e.g., droplet volume, contact angle and composition). The respiratory droplets contain salt (NaCl), protein (mucin), and surfactant (dipalmitoylphosphatidylcholine) in addition to water, which are expected to influence the evaporation in a big way. A diffusion-based theoretical model for estimating the dry…
We investigate evaporation of a sessile droplet on a non-wetted surface in the framework of diffusion-limited and quasi-steady evaporation. We extend previous models and numerically solve Laplace equation for the diffusion of liquid vapor in ambient. We propose a unified, simple and accurate expression of the evaporation mass flux valid for 90^o < theta < 180^o, where theta is the equilibrium contact angle. In addition, using the derived expression of the evaporation mass flux, we propose a simple and accurate expression of the evaporation mass rate for a non-wetted surface, which does not exh…
We study here the microscopic deformations of elastic lamellae constituting a superhydrophobic substrate under different wetting conditions of a sessile droplet using electrowetting. The deformation profiles of the lamellae are experimentally evaluated using confocal microscopy. These experimental results are then explained using a variational principle formalism within the framework of linear elasticity. We show that the local deformation profile of a lamella is mainly controlled by the net horizontal component of the capillary forces acting on its top due to the pinned droplet contact line. …
This article explores the governing role of the internal hydrodynamics and advective transport within sessile colloidal droplets on the self assembly of nanostructures to form floral patterns. Water acetone binary fluid and Bi2O3 nanoflakes based complex fluids are experimented with. Microliter sessile droplets are allowed to vaporize and the dry out patterns are examined using scanning electron microscopy. The presence of distributed self assembled rose like structures is observed. The population density, structure and shape of the floral structures are noted to be dependent on the binary flu…
We study numerically the deformation of sessile dielectric drops immersed in a second fluid when submitted to the optical radiation pressure of a continuous Gaussian laser wave. Both drop stretching and drop squeezing are investigated at steady state where capillary effects balance the optical radiation pressure. A boundary integral method is implemented to solve the axisymmetric Stokes flow in the two fluids. In the stretching case, we find that the drop shape goes from prolate to near-conical for increasing optical radiation pressure whatever the drop to beam radius ratio and the refractive …
Evaporating droplets of polymer or colloid solution may produce a glassy crust at the liquid-vapour interface, which subsequently deforms as an elastic shell. For sessile droplets, the known radial outward flow of solvent is expected to generate crusts that are thicker near the pinned contact line than the apex. Here we investigate, by non-linear quasi-static simulation and scaling analysis, the deformation mode and stability properties of elastic caps with a non-uniform thickness profile. By suitably scaling the mean thickness and the contact angle between crust and substrate, we find data co…
We study the effects of vertical sinusoidal vibrations on a liquid droplet with a low surface tension (ethanol) deposited on a solid substrate. In a precise range of amplitudes and frequencies, the drop exhibits a dramatic worm-like shape instability with a strong symmetry breaking, comparable to the one observed by Pucci et al. (Phys. Rev. Lett., 106 (2011) 024503) on a vibrated floating lens. However, the geometry of our system is much simpler since it does not involve the oscillation and deformation of a liquid-liquid-air contact line. We show that the Faraday waves appearing on the surface…
The article reports droplet evaporation kinetics on inclined substrates. Comprehensive experimental and theoretical analyses of the droplet evaporation behaviour for different substrate declination, wettability and temperatures have been presented. Sessile droplets with substrate declination exhibit distorted shape and evaporate at different rates compared to droplets on the same horizontal substrate and is characterized by more often changes in regimes of evaporation. The slip stick and jump stick modes are prominent during evaporation. For droplets on inclined substrates, the evaporative flu…
The evaporation of a binary sessile ethanol-water droplet on an inclined substrate is studied experimentally just below the critical sliding angles for different substrate temperatures. A customized goniometer equipped with a CMOS camera and an infrared (IR) camera is used. The droplet is observed to remain pinned in the advancing side during the evaporation process, while the receding side contracts. The asymmetry in the advancing and receding contact angles of the droplet on inclined substrate results in complex thermo-solutal Marangoni convection that is captured through IR images. The drop…
The directional motion of sessile drops can be induced by slanted mechanical vibrations of the substrate. As previously evidenced \cite{Brunet07,Brunet09,Noblin09}, the mechanical vibrations induce drop deformations which combine axisymmetric and antisymmetric modes. In this paper, we establish quantitative trends from experiments conducted within a large range of parameters, namely the amplitude $A$ and frequency $f$ of the forcing, the liquid viscosity $η$ and the angle between the substrate and the forcing axis $α$. These experiments are carried out on weak-pinning substrates. For most para…
Molecular dynamics simulation is used for studying the contact angle of nanoscale sessile drops on a planar solid wall in a system interacting via the truncated and shifted Lennard-Jones potential. The entire range between total wetting and dewetting is investigated by varying the solid--fluid dispersive interaction energy. The temperature is varied between the triple point and the critical temperature. A correlation is obtained for the contact angle in dependence of the temperature and the dispersive interaction energy. Size effects are studied by varying the number of fluid particles at othe…
We study a spontaneous relaxation dynamics of arbitrarily shaped liquid drops on solid surfaces in the partial wetting regime. It is assumed that the energy dissipated near the contact line is much larger than that in the bulk of the fluid. We have shown rigorously in the case of quasi-static relaxation using the standard mechanical description of dissipative system dynamics that the introduction of a dissipation term proportional to the contact line length leads to the well known local relation between the contact line velocity and the dynamic contact angle at every point of an arbitrary cont…
We study the equilibrium solutions of a sessile drop on top of a horizontal substrate when it is partially covered by another inmiscible liquid, so that part of the drop is in contact with a third fluid (typically, air). The shapes of the interfaces are obtained by numerical integration of the differential equations resulting from the application of the Neumann's and Young's laws at the three fluids junction (triple point) and the two fluids--solid contact line (at the substrate), as well as no--flow boundary conditions at the wall of the container under axial symmetry. The formulation shows t…
