Image processing and pattern recognition offer a useful and versatile method for optically characterizing drops of a colloidal solution during the drying process and in its final state. This paper exploits image processing techniques applied to cross-polarizing microscopy to probe birefringence and the bright-field microscopy to examine the morphological patterns. The bio-colloidal solution of interest is a mixture of water, liquid crystal (LC) and three different proteins [lysozyme (Lys), myoglobin (Myo), and bovine serum albumin (BSA)], all at a fixed relative concentration. During the drying process, the LC phase separates and becomes optically active detectable through its birefringence. Further, as the protein concentrates, it forms cracks under strain due to the evaporation of water. The mean intensity profile of the drying process is examined using an automated image processing technique that reveals three unique regimes: a steady upsurge, a speedy rise, and an eventual saturation. The high values of standard deviation show the complexity, the roughness, and inhomogeneity of the image surface. A semi-automated image processing technique is proposed to quantify the distance between the consecutive cracks by converting those into high contrast images. The outcome of the image analysis correlates with the initial state of the mixture, the nature of the proteins, and the mechanical response of the final patterns. The paper reveals new insights on the self-assembly of the macromolecules during the drying mechanism of any aqueous solution.
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…
A drop of aqueous potato starch gel with a certain mole fraction of NaCl, when dried on a glass slide, exhibits strong segregation and intricate pattern formation phenomena. The salt forms radial dendritic crystalline aggregates near the centre, with the starch separating out in the form of a transparent band at the periphery. Photographs and micrographs show a series of concentric rings with different texture.
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 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.…
We performed a thorough investigation of the drying dynamics of a charged colloidal dispersion drop in a confined geometry. We developed an original methodology based on Raman micro-spectroscopy to measure spatially-resolved colloids concentration profiles during the drying of the drop. These measurements lead, for the first time, to estimates of the collective diffusion coefficient of the dispersion over a wide range of concentration. The collective diffusion coefficient is one order of magnitude higher than the Stokes-Einstein estimate showing the importance of the electrostatic interactions…
We studied the morphology of linear particle deposits obtained by inkjet-printing of silica nanoparticle suspension in drying condition where contact line depinning occurs. We show that this evaporation mode can be obtained by adjusting the particle concentration in different solvents. For isolated drops, deposited manually or by inkjet printing, drying induces the formation of two concentric rings in which particles self-assemble into a monolayer. For fused drops, our main result is that stable rivulets could be formed by drop overlap leading, after drying, to the formation of three parallel …
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…
We study the stress developed during the drying of a colloidal drop of silica nanoparticles. In particular, we use the wrinkling instability of a thin floating sheet to measure the net stress applied by the deposit on the substrate and we focus on the effect of the particle polydispersity. In the case of a bidisperse suspension, we show that a small number of large particles substantially decreases the expected stress, which we interpret as the formation of lower hydrodynamic resistance paths in the porous material. As colloidal suspensions are usually polydisperse, we show for different avera…
In the present work, we use Mach-Zehnder interferometry to thoroughly investigate the drying dynamics of a 2D confined drop of a charged colloidal dispersion. This technique makes it possible to measure the colloid concentration field during the drying of the drop at a high accuracy (about 0.5%) and with a high temporal and spatial resolution (about 1 frame/s and 5 $μ$m/pixel). These features allow us to probe mass transport of the charged dispersion in this out-of-equilibrium situation. In particular, our experiments provide the evidence that mass transport within the drop can be described by…
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 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…
Using a phase field crystal model we study the structure and dynamics of a drop of colloidal suspension during evaporation of the solvent. We model an experimental system where contact line pinning of the drop on the substrate is non-existent. Under such carefully controlled conditions, evaporation of the drop produces an ordered or disordered arrangement of the colloidal residue depending on the initial average density of solute and the drying rate. We obtain a non-equilibrium phase boundary showing amorphous and crystalline phases of single component and binary mixtures of colloidal particle…
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.
We investigate experimentally the drying of a small volume of perfectly wetting liquid on two crossed fibers. We characterize the drying dynamics for the three liquid morphologies that are encountered in this geometry: drop, column and a mixed morphology, in which a drop and a column coexist. For each morphology, we rationalize our findings with theoretical models that capture the drying kinetics. We find that the evaporation rate depends significantly on the liquid morphology and that the drying of liquid column is faster than the evaporation of the drop and the mixed morphology for a given l…
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…
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…
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 evapo…
We develop a theory for drying-induced stresses in sessile, poroelastic drops undergoing evaporation on rigid surfaces. Using a lubrication-like approximation, the governing equations of three-dimensional nonlinear poroelasticity are reduced to a single thin-film equation for the drop thickness. We find that thin drops experience compressive elastic stresses but the total in-plane stresses are tensile. The mechanical response of the drop is dictated by the initial profile of the solid skeleton, which controls the in-plane deformation, the dominant components of elastic stress, and sets a limit…
When colloidal suspensions dry, stresses build up and cracks often occur - a phenomenon undesirable for important industries such as paint and ceramics. We demonstrate an effective method which can completely eliminate cracking during drying: by adding emulsion droplets into colloidal suspensions, we can systematically decrease the amount of cracking, and eliminate it completely above a critical droplet concentration. Since the emulsion droplets eventually also evaporate, our technique achieves an effective function while making little changes to the component of final product, and may therefo…
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…
Sessile droplets of aqueous poly(ethylene oxide) solution, with average molecular weight of 100 kDa, are monitored during evaporative drying at ambient conditions over a range of initial concentrations $c_0$. For all droplets with $c_0 \geq 3%$, central conical structures, which can be hollow and nearly 50% taller than the initial droplet, are formed during a growth stage. Although the formation of superficially similar structures has been explained for glass-forming polymers using a skin-buckling model which predicts the droplet to have constant surface area during the growth stage (L. Paucha…
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.
A deposited drop of bovine serum albumin salt solution experiences both gelation and fracturation during evaporation. The cracks appearing at the edge of the gelling drop are regularly spaced, due to the competition between the evaporation-induced and relaxation-induced stress evolution. Subsequently, the mean crack spacing evolves in an unexpected way, being inversely proportional instead of proportional to the deposit thickness. This evolution has been ascribed to the change with time of the average shrinkage stress, the crack patterning being purely elastic instead of evaporation-controlled…
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, …
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…
The drying of a colloidal dispersion can result in a gel phase defined as a porous matrix saturated in solvent. During the drying process, high mechanical stresses are generated. When these stresses exceed the strength of the material, they can be released in the formation of cracks. This process strongly depends on both the mechanical properties of the material and the way the gel consolidates. In this report, we give experimental evidences that the number of cracks formed in the consolidating film depend on the drying rate, the nature of the solvent and the mechanical properties of the collo…
Drying of colloidal dispersion and their consolidation into a particulate deposit is a common phenomenon. This process involves various physical processes such as diffusion of liquid molecules into the ambient atmosphere and advection of dispersed particles via evaporation driven flow. The colloidal particles forming a dried deposit exhibits distinct patterns and frequently possess structural defects such as desiccation cracks. This chapter gives an introductory review of the drying of colloidal dispersion and various associated phenomena. In principle, the drying of colloid dispersion, the pr…
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…
The work is devoted to particles dynamics simulation in a colloidal drop, when it dries on a substrate and the triple-phase boundary is fixed. Experimental observations [Deegan R. D. et. al., 2000] show a ring deposition on a solid substrate after full droplet desiccation. This phenomenon of macrolevel is known as coffee ring effect. There are other experiments that show a co-effect at the microlevel. We are talking about the formation of a quasicrystalline structure on the outer part of the ring and occurrence amorphous inner zone of ring [Mar\'ın Á. G. et. al., 2011]. The goal of this work i…
The theory of solute transfer and deposit growth in evaporating sessile drops on a plane substrate is presented. The main ideas and the principal equations are formulated. The problem is solved analytically for two important geometries: round drops (drops with circular boundary) and pointed drops (drops with angular boundary). The surface shape, the evaporation rate, the flow field, and the mass of the solute deposited at the drop perimeter are obtained as functions of the drying time and the drop geometry. In addition, a model accounting for the spatial extent of the deposit arising from the …
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…
We report a study of the structure of droplets of colloidal gels containing dissolved sodium chloride. The components segregate and form intricate patterns. The salt crystalizes in fractal and multi-fractal dendritic forms which are determined by the material which forms the colloidal gel. Here potato starch, gelatine and carboxymethyl cellulose have been used. The substrate also plays a role in some cases. Photographs and micrographs at different level of magnification are shown.
The drying of a drop containing particles often results in the accumulation of the particles at the contact line. In this work, we investigate the drying of an aqueous colloidal drop surrounded by a hydrogel that is also evaporating. We combine theoretical and experimental studies to understand how the surrounding vapor concentration affects the particle deposit during the constant radius evaporation mode. In addition to the common case of evaporation on an otherwise dry surface, we show that in a configuration where liquid is evaporating from a flat surface around the drop, the singularity of…
Aiming at fabrication of hybrid plasmonic-photonic crystals, gel-immobilized colloidal crystals made of a polystyrene colloidal suspension and an N-(Hydroxy methyl)acrylamid-based gel were immersed into an aqueous dispersion of gold nanoparticles. Atomic force microscope (AFM) observations have been performed for the gel-immobilized colloidal crystals with gold nanoparticles deposited on their surfaces. In the present study, the diameter of a colloidal sphere was c.a. 190 nm. The diameter of a gold nanoparticle was the same as in a preliminary study, c.a. 40 nm. Various immersion times up to t…
We report an experimental study of the crack pattern formed during the drying of a colloidal suspension. A horizontal fiber, which provides a one dimensional, boundary-free substrate, is coated by a film of micronic thickness. The geometry imposes a remarkable annular crack pattern and allowing precise measurements of the crack spacing over a short range of film thickness (between 2 and 10 $μ$m) which varies linearly with the film height. We compare our experimental data with a model proposed by Kitsunezaki which suggests that the variation of the crack spacing with the film thickness depends …
We present a Monte Carlo (MC) grid-based model for the drying of drops of a nanoparticle suspension upon a heterogeneous surface. The model consists of a generalised lattice-gas in which the interaction parameters in the Hamiltonian can be varied to model different properties of the materials involved. We show how to choose correctly the interactions, to minimise the effects of the underlying grid so that hemispherical droplets form. We also include the effects of surface roughness to examine the effects of contact-line pinning on the dynamics. When there is a `lid' above the system, which pre…
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…
The performance of solution-processed solar cells strongly depends on the geometrical structure and roughness of the photovoltaic layers formed during film drying. During the drying process, the interplay of crystallization and liquid-liquid demixing leads to the structure formation on the nano- and microscale and to the final rough film. In order to better understand how the film structure can be improved by process engineering, we aim at theoretically investigating these systems by means of phase-field simulations. We introduce an evaporation model based on the Cahn-Hilliard equation for the…
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…
We investigate freely expanding liquid sheets made of either simple Newtonian fluids or solutions of high molecular water-soluble polymer chains. A sheet is produced by the impact of a drop on a quartz plate covered with a thin layer of liquid nitrogen that suppresses shear viscous dissipation thanks to an inverse Leidenfrost effect. The sheet expands radially until reaching a maximum diameter and subsequently recedes. Experiments indicate the presence of two expansion regimes: the capillary regime, where the maximum expansion is controlled by surface tension forces and does not depend on the …
