We propose a theory for the multi-ring pattern of the deposits that are formed when droplets of suspension are dried on a substrate. Assuming a standard model for the stick-slip motion of the contact line, we show that as droplets evaporate, many concentric rings of deposits are formed, but are taken over by a solid-circle pattern in the final stage of drying. An analytical expression is given to indicate when ring-pattern changes to solid-circle pattern during an evaporation process. The results are in qualitative agreement with existing experiments, and the other predictions on how the evaporation rate, droplet radius and receding contact angle affect the pattern are all subject to experimental test.
We isolate a nano-colloidal droplet of surrogate mucosalivary fluid to gain fundamental insights into the infectivity of air borne nuclei during the Covid-19 pandemic. Evaporation experiments are performed with salt-water solutions seeded with a viral load of inactive nanoparticles in an acoustic levitator. We seek to emulate the drying, flow and precipitation dynamics of such air borne mucosalivary droplets. Observations with the surrogate fluid are validated by similar experiments with actual samples from a healthy subject. A unique feature emerges with regards to the final crystallite dimen…
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 the optical and structural properties of starch films formed on drying droplets of starch solutions on a flat substrate. The starch films formed after drying are circular in shape and have an azimuthally symmetric "M-shaped" height profile along their diameter. These films are found to be semi-crystalline in nature and transparent in visible light. Our experimental results show that these films are optically uniaxial at their center but biaxial away from the center. The variation of birefringence along the radial direction is studied for the films formed after drying droplets with di…
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…
The size-dependent contact angle and the drying and wetting morphological transition are studied with respect to the volume change for a spherical cap-shaped droplet placed on a spherical substrate. The line-tension effect is included using the rigorous formula for the Helmholtz free energy in the droplet capillary model. A morphological drying transition from a cap-shaped to a spherical droplet occurs when the substrate is hydrophobic and the droplet volume is small, similar to the transition predicted on a flat substrate. In addition, a morphological wetting transition from a cap-shaped to a…
Self-assembled filament layers in drying sessile droplets: from morphology to electrical conductivity
Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IET-2), Forschungszentrum Jülich（于利希研究中心埃尔朗根-纽伦堡亥姆霍兹可再生能源研究所）；Friedrich-Alexander-Universität Erlangen-Nürnberg（埃尔朗根-纽伦堡弗里德里希·阿列克桑德大学）
Coalescence-induced alignment of anisotropic particles in drying sessile droplets
Forschungszentrum Jülich（于利希研究中心）；Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IET-2)（亥姆霍兹埃尔朗根-纽伦堡可再生能源研究所（IET-2））；Friedrich-Alexander-Universität Erlangen-Nürnberg（埃尔朗根-纽伦堡弗里德里希·亚历山大大学）
We present a study of patterns, formed in drying drops of aqueous gelatin solution containing sodium sulphate. The patterns are highly complex, consisting of a hierarchical sequence of rings which form concentric bands as well as dendritic crystalline aggregates. When the preparation of the complex fluid is done by mixing an aqueous solution of the salt with an aqueous solution of gelatin prepared separately, another feature is observed in the pattern on the dried out drop. This is a viscous fingering pattern, superposed on the series of rings. We try to explain the origin of these two feature…
We simulated an experiment in which a thin colloidal sessile droplet is allowed to dry out on a horizontal hydrophilic surface when a mask just above the droplet predominantly allows evaporation from the droplet free surface directly beneath the holes in the mask [Harris D J, Hu H, Conrad J C and Lewis J A 2007 \textit{Phys. Rev. Lett.} \textbf{98} 148301]. We considered one particular case when centre-to-centre spacing between the holes is much less than the drop diameter. In our model, advection, diffusion, and sedimentation were taken into account. FlexPDE was utilized to solve an advection…
We predict and analyze the drying time of respiratory droplets from a COVID-19 infected subject, which is a crucial time to infect another subject. The drying of the droplet is predicted by diffusion-limited evaporation model for a sessile droplet placed on a partially-wetted surface with a pinned contact line. The variation of droplet volume, contact angle, ambient temperature, and humidity are considered. We analyze the chances of the survival of the viruses present in the droplet, based on the lifetime of the droplets in several conditions, and find that the chances of survival of the virus…
The process of drying is a simple physical mechanism that drives a system to relax from one equilibrium point to another. The native states of the constituent particles in the droplets can be linked to the emergent morphological patterns via this drying process. This paper explores the interplay between different initial concentrations of a globular protein lysozyme ($ϕ_p$) and the salts ($ϕ_s$) in the phosphate buffer saline (PBS). The $ϕ_s$ = 0 wt% embodies the lysozyme solution prepared in de-ionized water. The samples at $ϕ_s$ = 0.9 wt% display a dark texture in the central region. We exam…
When a droplet containing a non-volatile component is dried on a substrate, it leaves a ringlike deposit on the substrate. We propose a theory which predicts the deposit distribution based on a model of fluid flow and contact line motion of the droplet. It is shown that the deposition pattern changes continuously from coffee-ring to volcano-like and to mountain-like depending on the mobility of the contact line and the evaporation rate. Analytical expression is given for the peak position of the distribution of deposit left on the substrate.
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）
We study the evaporation-induced stratification of a mixture of short and long polymer chains in a drying droplet using molecular simulations. We systematically investigate the effects of hydrodynamic interactions (HI) on this process by comparing hybrid simulations accounting for HI between polymers through the multiparticle collision dynamics technique with free-draining Langevin dynamics simulations neglecting the same. We find that the dried supraparticle morphologies are homogeneous when HI are included but are stratified in core--shell structures (with the short polymers forming the shel…
A bio-colloidal drying droplet can be used as a pre-diagnostic technique. However, a successful clinical setting requires a fundamental understanding of the final morphology and the way it is related to the initial state of the constituents present in the droplet. This chapter focuses on the physics associated with different pattern formations in the globular protein, bovine serum albumin (BSA) at different phosphate-buffered saline concentrations. The study reports that the first-order statistics (FOS) and the gray level co-occurrence matrix (GLCM) analysis are capable of capturing structural…
Drying colloidal droplets have a wide range of applications from medical diagnostics to coatings for industries. This paper explores the effects of the substrate temperature (ranging from $25$ to $55 ^{\circ}$C) and various initial concentrations ($ϕ$) of $1$ to $20$ wt% of lysozyme in an aqueous solution on its drying and final dried film state using bright-field optical microscopy. The $ϕ$ is divided into three regimes, ultra-concentrated ($20$ $<$ $ϕ$ $\leq$ $17$ wt%), concentrated ($17$ $<$ $ϕ$ $\leq$ $9$ wt%) and diluted ($9$ $<$ $ϕ$ $\leq$ $1$ wt%). Increasing $ϕ$ in these regimes finds …
A quantitative understanding of the evaporative drying kinetics and nucleation rates of aqueous based aerosol droplets is important for a wide range of applications, from atmospheric aerosols to industrial processes such as spray drying. Here, we introduce a numerical model for interpreting measurements of the evaporation rate and phase change of drying free droplets made using a single particle approach. We explore the evaporation of aqueous sodium chloride and sodium nitrate solution droplets. Although the chloride salt is observed to reproducibly crystallise at all drying rates, the nitrate…
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…
The deposition process at the edge of evaporating colloidal drops varies with the shape of suspended particles. Experiments with prolate ellipsoidal particles suggest that the spatiotemporal properties of the deposit depend strongly on particle aspect ratio. As the aspect ratio increases, the particles form less densely-packed deposits and the statistical behavior of the deposit interface crosses over from the Kardar-Parisi-Zhang (KPZ) universality class to another universality class which was suggested to be consistent with the KPZ plus quenched disorder. Here, we numerically study the effect…
The deposition of particles on a surface by an evaporating sessile droplet is important for phenomena as diverse as printing, thin-film deposition and self-assembly. The shape of the final deposit depends on the flows within the droplet during evaporation. These flows are typically determined at the onset of the process by the intrinsic physical, chemical and geometrical properties of the droplet and its environment. Here, we demonstrate deterministic emergence and real-time control of Marangoni flows within the evaporating droplet by an external point-source of vapor. By varying the source lo…
A method of simulating the drying process of a soft matter solution with an implicit solvent model by moving the liquid-vapor interface is applied to various solution films and droplets. For a solution of a polymer and nanoparticles, we observe "polymer-on-top" stratification, similar to that found previously with an explicit solvent model. Furthermore, "polymer-on-top" is found even when the nanoparticle size is smaller than the radius of gyration of the polymer chains. For a suspension droplet of a bidisperse mixture of nanoparticles, we show that core-shell clusters of nanoparticles can be …
Pattern formation in drying protein droplets continues to attract considerable research attention because it can be linked to specific protein-protein interactions. An extensive study of the drying evolution and the final crack patterns are presented, highlighting the concentration dependence (from 1 to 13 wt%) on two globular proteins, lysozyme (Lys) and bovine serum albumin (BSA), in de-ionized water. The drying evolution starts with a constant contact radius mode and shifts to a mixed mode where both fluid front and contact angle changes. The contact angle monotonically decreases, whereas, …
Evaporation-Driven Nanowire Self-Assembly in an Elongated Droplet
Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IET-2), Forschungszentrum Jülich（于利希研究中心埃尔朗根-纽伦堡亥姆霍兹可再生能源研究所）；Friedrich-Alexander-Universität Erlangen-Nürnberg（埃尔朗根-纽伦堡弗里德里希·亚历山大大学）
The present article highlights an approach to generate contrasting patterns from drying droplets in a liquid bridge configuration, different from well-known coffee rings. Reduction of the confinement distance (the gap between the solid surfaces) leads to systematized nano-particle agglomeration yielding to spokes-like patterns similar to those found on scallop shells instead of circumferential edge deposition. Alteration of the confinement length modulates the curvature that entails variations in the evaporation flux across the liquid-vapor interface. Consequently, flow inside different liquid…
Understanding the dynamics in the deposition of water droplets onto solid surfaces is of importance from both fundamental and practical viewpoints. While the deposition of a water droplet onto a heated surface is extensively studied, the characteristics of depositing a droplet onto a cold surface and the phenomena leading to such behavior remain elusive. Here we report the formation of a triple condensate halo observed during the deposition of a water droplet onto a cold surface, due to the interplay between droplet impact dynamics and vapor diffusion. Two subsequent condensation stages occur …
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…
Droplet impact on a surface is practically relevant to a variety of fields in nature and industry, while a complete control of its outcomes remains challenging due to various unmanageable factors. In this work, we propose the quantum simulation of droplet impact outcomes in the platform of ultracold atoms. Specifically, we study the quantum-fluctuation-driven dynamics (QFDD) of two-dimensional Bose-Bose mixtures from an initial Townes soliton towards the formation of a quantum droplet. By tuning the fluctuation energy of the initial Townes state through its size and number, the subsequent QFDD…
We report a study on the kinetics of drying of a droplet of aqueous gelatin containing sodium chloride. The process of drying recorded on video, clearly shows different regimes of growth leading to a variety of crystalline patterns. Large faceted crystals of $\sim$mm size form in the early stages of evaporation, followed by highly branched multi-fractal patterns with micron sized features. We simulate the growth using a simple algorithm incorporating aggregation and evaporation, which reproduces the cross-over between the two growth regimes. As evaporation proceeds, voids form in the gel film.…
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…
When a liquid droplet impacts a hot solid surface, enough vapor may be generated under it as to prevent its contact with the solid. The minimum solid temperature for this so-called Leidenfrost effect to occur is termed the Leidenfrost temperature, or the dynamic Leidenfrost temperature when the droplet velocity is non-negligible. We observe the wetting/drying and the levitation dynamics of the droplet impacting on an (isothermal) smooth sapphire surface using high speed total internal reflection imaging, which enables us to observe the droplet base up to about 100 nm above the substrate surfac…
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…
How particles are deposited at the edge of evaporating droplets, i.e. the {\em coffee ring} effect, plays a crucial role in phenomena as diverse as thin-film deposition, self-assembly, and biofilm formation. Recently, microorganisms have been shown to passively exploit and alter these deposition dynamics to increase their survival chances under harshening conditions. Here, we show that, as the droplet evaporation rate slows down, bacterial mobility starts playing a major role in determining the growth dynamics of the edge of drying droplets. Such motility-induced dynamics can influence several…
The effects of line tension on the morphology of a lens-shaped droplet and bubble placed on the inner wall of a spherical cavity are studied. The contact angle between the lens-shaped droplet and the concave spherical substrate is expressed by the generalized Young's formula. The equator of the spherical substrate is found to play a crucial role. Neither a droplet with its contact line on the upper hemisphere of the substrate nor one with its contact line on the lower hemisphere can transform into each other continuously. On a hydrophobic substrate, the contact angle jumps discontinuously to $…
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…
Drying suspensions often leave behind complex patterns of particulates, as might be seen in the coffee stains on a table. Here we consider the dynamics of periodic band or uniform solid film formation on a vertical plate suspended partially in a drying colloidal solution. Direct observations allow us to visualize the dynamics of the band and film deposition, and the transition in between when the colloidal concentration is varied. A minimal theory of the liquid meniscus motion along the plate reveals the dynamics of the banding and its transition to the filming as a function of the ratio of de…
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 …
