Binary Mixture Droplet Evaporation on Microstructured Decorated Surfaces and the Mixed Stick-Slip Modes.

The interactions between liquid droplets and solid surfaces during wetting and phase change are important to many applications and are related to the physicochemical properties of the substrate and the fluid. In this work, we investigate experimentally the evaporation of pure water, pure ethanol, and their binary mixture droplets, accessing a wide range of surface tensions, on hydrophobic micro-pillared surfaces varying the spacing between the pillars. Results show that on structured surfaces, droplets evaporate following three classical evaporative behaviors: constant contact radius/pinning, stick-slip, or mixed mode. In addition, we report two further droplet evaporation modes, which are a mixed stick-slip mode where the contact angle increases while the contact radius decreases in a stick-slip fashion and a mixed stick-slip mode where both the contact angle and the contact radius decrease in a stick-slip fashion. We name these evaporation modes not yet reported in the literature as the increasing and decreasing contact angle mixed stick-slip modes, respectively. The former ensues because the fluid surface tension increases as the most volatile fluid evaporates coupled to the presence of structures, whereas the latter is due to the presence of structures for either fluid. The duration of each evaporation mode is dissimilar and depends on the surface tension and on the spacing between structures. Pure water yields longer initial pinning times on all surfaces before stick-slip ensues, whereas for binary mixtures and pure ethanol, initial pinning ensues mainly on short spacing structures due to the different wetting regimes displayed. Meanwhile, mixed stick-slip modes ensue mainly for high ethanol concentrations and/or pure ethanol independent of the solid fraction and for low ethanol concentrations on large spacing. Contact line jumps, changes in contact angle and pinning forces are also presented and discussed. This investigation provides guidelines for tailoring the evaporation of a wide range of surface tension fluids on structured surfaces for inkjet printing, DNA patterning, or microfluidics applications.

Transition from Dendritic to Cell-like Crystalline Structures in Drying Droplets of Fetal Bovine Serum under the Influence of Temperature.

The desiccation of biofluid droplets leads to the formation of complex deposits which are morphologically affected by the environmental conditions, such as temperature. In this work, we examine the effect of substrate temperatures between 20 and 40 °C on the desiccation deposits of fetal bovine serum (FBS) droplets. The final dried deposits consist of different zones: a peripheral protein ring, a zone of protein structures, a protein gel, and a central crystalline zone. We focus on the crystalline zone showing that its morphological and topographical characteristics vary with substrate temperature. The area of the crystalline zone is found to shrink with increasing substrate temperature. Additionally, the morphology of the crystalline structures changes from dendritic at 20 °C to cell-like for substrate temperatures between 25 and 40 °C. Calculation of the thermal and solutal Bénard-Marangoni numbers shows that while thermal effects are negligible when drying takes place at 20 °C, for higher substrate temperatures (25-40 °C), both thermal and solutal convective effects manifest within the drying drops. Thermal effects dominate earlier in the evaporation process leading, we believe, to the development of instabilities and, in turn, to the formation of convective cells in the drying drops. Solutal effects, on the other hand, are dominant toward the end of drying, maintaining circulation within the cells and leading to crystallization of salts in the formed cells. The cell-like structures are considered to form because of the interplay between thermal and solutal convection during drying. Dendritic growth is associated with a thicker fluid layer in the crystalline zone compared to cell-like growth with thinner layers. For cell-like structures, we show that the number of cells increases and the area occupied by each cell decreases with temperature. The average distance between cells decreases linearly with substrate temperature.

Semicrystalline Polymer Micro/Nanostructures Formed by Droplet Evaporation of Aqueous Poly(ethylene oxide) Solutions: Effect of Solution Concentration.

Deposits formed after evaporation of sessile droplets, containing aqueous solutions of poly(ethylene oxide), on hydrophilic glass substrates were studied experimentally and mathematically as a function of the initial solution concentration. The macrostructure and micro/nanostructures of deposits were studied using stereo microscopy and atomic force microscopy. A model, based on thin-film lubrication theory, was developed to evaluate the deposit macrostructure by estimating the droplet final height. Moreover, the model was extended to evaluate the micro/nanostructure of deposits by estimating the rate of supersaturation development in connection with the driving force of crystallization. Previous studies had only described the macrostructure of poly(ethylene oxide) deposits formed after droplet evaporation, whereas the focus of our study was the deposit micro/nanostructures. Our atomic force microscopy study showed that regions close to the deposit periphery were composed of predominantly semicrystalline micro/nanostructures in the form of out-of-plane lamellae, which require a high driving force of crystallization. However, deposit central areas presented semicrystalline micro/nanostructures in the form of in-plane terraces and spirals, which require a lower driving force of crystallization. Increasing the initial concentration of solutions led to an increase in the lengths and thicknesses of the out-of-plane lamellae at the deposits' periphery and enhanced the tendency to form spirals in the central areas. Our numerical study suggested that the rate of supersaturation development and thus the driving force of crystallization increased from the center toward the periphery of droplets, and the supersaturation rate was lower for solutions with higher initial concentrations at each radius. Therefore, periphery areas of droplets with lower initial concentrations were suitable for the formation of micro/nanostructures which require higher driving forces, whereas central areas of droplets with higher initial concentration were desirable for the formation of micro/nanostructures which require lower driving forces. These numerical results were in good qualitative agreement with the experimental findings.

Acoustothermal Nucleation of Surface Nanobubbles.

Ultrasonic surface vibration at high frequencies (O(100 GHz)) can nucleate bubbles in a liquid within a few nanometres from a surface, but the underlying mechanism and the role of surface wettability remain poorly understood. Here, we employ molecular simulations to study and characterize this phenomenon, which we call acoustothermal nucleation. We observe that nanobubbles can nucleate on both hydrophilic and hydrophobic surfaces, and molecular energy balances are used to identify whether these are boiling or cavitation events. We rationalize the nucleation events by defining a physics-based energy balance, which matches our simulation results. To characterize the interplay between the acoustic parameters, surface wettability, and nucleation mechanism, we produce a regime map of nanoscopic nucleation events that connects observed nanoscale results to macroscopic experiments. This work provides insights to better design a range of industrial processes and clinical procedures such as surface treatments, mass spectroscopy, and selective cell destruction.

Crystallization-Driven Flows within Evaporating Aqueous Saline Droplets.

Using micro-PIV (particle image velocimetry), we observe for the first time, the direct correlation between crystallization and hydrodynamics in evaporating microliter saline (1 M NaCl) sessile drops. The relationship is demonstrated by a remarkable jet of liquid along the base of the drops, induced by, and directed at the point of nucleation and subsequent crystal growth. Prior to nucleation, the flow is more uniformly outward with the magnitude of the velocity decreasing with time. From calculations and the flow measurements in the two observed stages of evaporation (prior to nucleation and during crystallization), this jet can be explained on the basis of competition between solutal Marangoni convection and mass conservation flow. The jet of fluid leads to vortices on either side of the crystal in which the salt concentration is reduced, providing a potential explanation as to why NaCl deposits as a sequence of discrete crystals rather than as a continuous ring for such drops.

Complex Pattern Formation in Solutions of Protein and Mixed Salts Using Dehydrating Sessile Droplets.

A sessile droplet of a complex fluid exhibits several stages of drying leading to the formation of a final pattern on the substrate. We report such pattern formation in dehydrating droplets of protein (BSA) and salts (MgCl2 and KCl) at various concentrations of the two components (protein and salts) as part of a parametric study for the understanding of complex patterns of dehydrating biofluid droplets (blood and urine), which will eventually be used for diagnosis of bladder cancer. The exact analysis of the biofluid patterns will require a rigorous parametric study; however, the current work provides an initial understanding of the effect of the basic components present in a biofluid droplet. Arrangement of the protein and the salts, due to evaporation, leads to the formation of some very distinctive final structures at the end of the droplet lifetime. Furthermore, these structures can be manipulated by varying the initial ratio of the two components in the solution. MgCl2 forms chains of crystals beyond a threshold initial concentration of protein (>3 wt %). However, the formation of such a crystal is also limited by the maximum concentration of the salt initially present in the droplet (≤1 wt %). On the other hand, KCl forms dendritic and rectangular crystals in the presence of BSA. The formation of these crystals also depends on the relative concentration of salt and protein in the droplet. We also investigated the dried-out patterns in dehydrating droplets of mixed salts (MgCl2 + KCl) and protein. The patterns can be tuned from a continuous dendritic structure to a snow-flake type structure just by altering the initial ratio of the two salts in the mixture, keeping all other parameters constant.

On the Effect of Substrate Viscoelasticity on the Evaporation Kinetics and Deposition Patterns of Nanosuspension Drops.

This study investigates the evaporation of sessile pure water and nanosuspension drops on viscoelastic polydimethylsiloxane (PDMS) films. We varied the viscoelasticity of the PDMS films by controlling the curing ratio and categorized them into three types: stiff (10:1, 20:1, 40:1), soft (60:1, 80:1), and very soft (100:1, 120:1, 140:1, 160:1). On stiff surfaces, pure water drops initially evaporate in a constant contact radius (CCR) mode, followed by a constant contact angle mode, and finally in a mixed mode of evaporation. Nanosuspension drops follow the same trend as water drops but with a difference toward the end of their lifetimes, when a short second CCR mode is observed. Complete evaporation of nanosuspension drops on stiff substrates leads to particle deposition patterns similar to a coffee ring with cracks and deposition tails. On soft surfaces, the initial spreading is followed by a pseudo-CCR mode. Complete evaporation of nanosuspension drops on soft substrates leads to deposits in the form of a uniform ring with a sharp ox-horn profile. Unexpectedly, the initial spreading is followed by a mixed mode on very soft substrates, on which wetting ridges (WRs) pulled up by the vertical component of surface tension are clearly observed in the vicinity of the contact line (CL). As the evaporation proceeds, the decreasing contact angle breaks the force balance in the horizontal direction at the CL and gives rise to a net horizontal force, which causes the CL to recede, transferring the horizontal force to the WR. Because of the viscoelastic nature of the very soft substrate, this horizontal force acting on the WR cannot be completely countered by the bulk of the substrate underneath. As a result, the WR moves horizontally in a viscous-flow way, which also enables the CL to be continuously anchored to the ridge and to recede relative to the bulk of the substrate. Consequently, a mixed mode of evaporation occurs. Complete evaporation of nanosuspension drops on very soft substrates leads to finger-like deposits.

Water vapor uptake into hygroscopic lithium bromide desiccant droplets: mechanisms of droplet growth and spreading.

The study of vapor absorption into liquid desiccant droplets is of general relevance to a better understanding and description of vapor absorption phenomena occurring at the macroscale as well as for practical optimization of dehumidification and refrigeration processes. Hence, in the present work, we provide the first systematic experimental study on the fundamentals of vapor absorption into liquid desiccant at the droplet scale, which initiates a novel avenue for the research of hygroscopic droplet growth. More specifically we address the behavior of lithium bromide-water droplets on hydrophobic PTFE and hydrophilic glass substrates under controlled ambient conditions. Driven by the vapor pressure difference between the ambient air and the droplet interface, desiccant droplets absorb water vapor and increase in volume. To provide further insights on the vapor absorption process, the evolution of the droplet profile is recorded using optical imaging and relevant profile characteristics are extracted. Results show that, even though the final expansion ratio of droplet volume is only a function of relative humidity, the dynamics of contact line and the absorption rate are found to differ greatly when comparing data with varying substrate wettability. Droplets on hydrophilic substrates show higher absorption kinetics and reach equilibrium with the ambient much faster than those on hydrophobic substrates. This is attributed to the absorption process being controlled by solute diffusion on the droplet side and to the shorter characteristic length for the solute diffusion on hydrophilic substrates. Moreover, the apparent droplet spreading process on hydrophilic substrates when compared to hydrophobic ones is explained based on a force balance analysis near the triple contact line, by the change of liquid-vapor surface tension due to the increase in water concentration, and assuming a development of a precursor film.

Superstable Ultrathin Water Film Confined in a Hydrophilized Carbon Nanotube.

Fluids confined in a nanoscale space behave differently than in the bulk due to strong interactions between fluid molecules and solid atoms. Here, we observed water confined inside "open" hydrophilized carbon nanotubes (CNT), with diameter of tens of nanometers, using transmission electron microscopy (TEM). A 1-7 nm water film adhering to most of the inner wall surface was observed and remained stable in the high vacuum (order of 10-5 Pa) of the TEM. The superstability of this film was attributed to a combination of curvature, nanoroughness, and confinement resulting in a lower vapor pressure for water and hence inhibiting its vaporization. Occasional, suspended ultrathin water film with thickness of 3-20 nm were found and remained stable inside the CNT. This film thickness is 1 order of magnitude smaller than the critical film thickness (about 40 nm) reported by the Derjaguin-Landau-Verwey-Overbeek theory and previous experimental investigations. The stability of the suspended ultrathin water film is attributed to the additional molecular interactions due to the extended water meniscus, which balances the rest of the disjoining pressures.

Nonisothermal Spreading Dynamics of Self-Rewetting Droplets.

We experimentally studied the spreading dynamics of binary alcohol mixtures (and pure liquids for reference) deposited on a heated substrate in a partially wetting situation under nonisothermal conditions. We show that the spreading mechanism of an evaporating droplet exhibits a power-law growth with early-stage exponents that depend strongly and nonmonotonically on the substrate temperature. Moreover, we investigated the temporal and spatial thermal dynamics in the droplet using infrared thermography, revealing the existence of unique thermal patterns due to thermal and/or solutal instabilities, which lead to surface tension gradients, namely the Marangoni effect. Our key findings are that the temperature of the substrate drastically affects the early-stage inertial-capillary spreading regime owing to the nonmonotonic surface tension-temperature dependence of the self-rewetting liquids. At later stages of wetting, the spreading dynamics enters the viscous-capillary dominated regime, with the characteristic low kinetics mirroring the behavior of pure liquids.

Morphology of Poly(styrene- co-butadiene) Random Copolymer Thin Films and Nanostructures on a Graphite Surface.

We studied the morphology of poly(styrene- co-butadiene) random copolymers on a graphite surface. Polymer solutions were spin coated onto graphite, at various concentrations and molecular weights. The polymer films and nanostructures were imaged using atomic force microscopy. Above the overlap concentration, thin films formed. However, total wetting did not occur, despite the polymers being well above their Tg. Instead, dewetting was observed, suggesting the films were in a state of metastable equilibrium. At lower concentrations, the polymers formed networks, nanoislands, and nanoribbons. Ordered nanopatterns were observed on the surface; the polymers orientated themselves due to π-π stacking interactions reflecting the crystalline structure of the graphite. At the lowest concentration, this ordering was very pronounced. At higher concentrations, it was less defined but still statistically significant. Higher degrees of ordering were observed with poly(styrene- co-butadiene) than polystyrene and polybutadiene homopolymers as the copolymer's aromatic rings are distributed along a flexible chain, which maximizes π-π stacking. At the two lowest concentrations, the size of the nanoislands and nanoribbons remained similar with varying molecular weight. However, at higher concentrations, the polymer network features were largest at the lowest molecular weight, indicating that in this case, a large proportion of shorter chains stay on top of the adsorbed ones. The contact angles of the polymer nanostructures remained mostly constant with size, which is due to the strong polymer/graphite adhesion dominating over line tension and entropic effects.

Drop mobility on superhydrophobic microstructured surfaces with wettability contrasts.

Manipulation of drop motion has attracted considerable attention recently as it is pertinent to industrial/biological applications such as microfluidics. Wettability gradients/contrasts applied to microtextured, superhydrophobic surfaces are probable candidates for engineering drop motion by virtue of their wettability controllability and low contact angle hysteresis. In the present work, we present a systematic study of drop mobility induced via wettability contrasts. A millimetre-sized water drop, placed on the boundary between two surfaces with distinct, uniform arrays of pillars, immediately moved toward the surface more densely populated with asperities, which was relatively more hydrophilic. The velocity of the motion was found to increase proportionally with the difference in pillar densities on each surface, in circumstances where the rear side surface had sufficiently small contact angle hysteresis. To elucidate the underlying mechanism of drop motion, we implemented a surface energy analysis for each motion event. Motion was initiated by the excess surface free energy due to drop deformation and directed in favour of energy minimisation. Lastly, we propose a theory to predict the direction of the drop which at the same time acts as the criterion for the motion to ensue.

Quantifying vapor transfer into evaporating ethanol drops in a humid atmosphere.

The effect of ambient temperature and relative humidity on the dynamics of ethanol drop evaporation is investigated. Although drop evaporation of mixtures and pure fluids has been extensively studied, very little is known about the transition from a pure fluid to a binary mixture following transfer of a second component present in the atmosphere. This is of importance for industrial, biological and medical applications where the purity of the solvent is paramount. Adsorption-absorption and/or condensation of water into ethanol drops during evaporation is presented through direct quantification of the drop composition in time. In particular, we combine drop profile measurements with Gas Injection Chromatography (GIC) to directly quantify the amount of ethanol evaporated and that of water intake over time. As expected, drops evaporate faster at higher temperatures since both the ethanol saturation concentration and the vapor diffusion coefficient are directly proportional to temperature. On the other hand, increases in the ethanol evaporation rate and in the water intake are observed at higher relative humidity. The increase in ethanol evaporation at higher relative humidity is interpreted by the greater diffusion coefficient of ethanol into humid air when compared to dry air. Moreover, as ethanol evaporates in a high humidity environment, the drop interfacial temperature falls below the dew point due to evaporative cooling and water condenses compared to lower humidity conditions. As a consequence of the heat released by adsorption-absorption and/or condensation, a greater temperature is reported at the liquid-vapor interface as confirmed by IR thermography, inducing a greater ethanol saturation concentration at the surface and hence a greater driving force for evaporation. By coupling the drop profile and the composition of ethanol and water within the drop, we propose a combined evaporation-adsorption/absorption and/or condensation empirical correlation. The proposed correlation accounts for: the decreases in ethanol concentration due to water adsorption-absorption and/or condensation, the diffusion coefficient dependence on relative humidity, and the amount of water intake during evaporation. The proposed empirical correlation agrees remarkably well with experimental observations.

Influence of Local Heating on Marangoni Flows and Evaporation Kinetics of Pure Water Drops.

The effect of localized heating on the evaporation of pure sessile water drops was probed experimentally by a combination of infrared thermography and optical imaging. In particular, we studied the effect of three different heating powers and two different locations, directly below the center and edge of the drop. In all cases, four distinct stages were identified according to the emerging thermal patterns. In particular, depending on heating location, recirculating vortices emerge that either remain pinned or move azimuthally within the drop. Eventually, these vortices oscillate in different modes depending on heating location. Infrared data allowed extraction of temperature distribution on each drop surface. In turn, the flow velocity in each case was calculated and was found to be higher for edge heating, due to the one-directional nature of the heating. Additionally, calculation of the dimensionless Marangoni and Rayleigh numbers yielded the prevalence of Marangoni convection. Heating the water drops also affected the evaporation kinetics by promoting the "stick-slip" regime. Moreover, both the total number of depinning events and the pinning strength were found to be highly dependent on heating location. Lastly, we report a higher than predicted relationship between evaporation rate and heating temperature, due to the added influence of the recirculating flows on temperature distribution and hence evaporation flux.

Poly(styrene-co-butadiene) random copolymer thin films and nanostructures on a mica surface: morphology and contact angles of nanodroplets.

The self-assembly of poly(styrene-co-butadiene) random copolymers on mica surfaces was studied by varying solution concentrations and polymer molecular weights. Toluene solutions of the poly(styrene-co-butadiene) samples were spin coated onto a mica surface and the resulting polymer morphology was investigated by atomic force microscopy. At higher concentrations, thin films formed with varying thicknesses; some dewetting was observed which depended on the molecular weight. Total dewetting did not occur despite the polymer's low glass transition temperature. Instead, partial dewetting was observed suggesting that the polymer was in a metastable equilibrium state. At lower concentrations, spherical cap shaped nanodroplets formed with varying sizes from single polymer chains to aggregates containing millions of chains. As the molecular weight was increased, fewer aggregates were observed on the surface, albeit with larger sizes resulting from increased solution viscosities and more chain entanglements at higher molecular weights. The contact angles of the nanodroplets were shown to be size dependent. A minimum contact angle occurs for droplets with radii of 100-250 nm at each molecular weight. Droplets smaller than 100 nm showed a sharp increase in contact angle; attributed to an increase in the elastic modulus of the droplets, in addition, to a positive line tension value. Droplets larger than 250 nm also showed an increased contact angle due to surface heterogeneities which cannot be avoided for larger droplets. This increase in contact angle plateaus as the droplet size reaches the macroscopic scale.

Formation, Evolution, and Extinction of Standing Waves in Evaporation from Pores.

We report on the formation, evolution, and extinction of standing waves (SWs) detected by infrared measurements at the upper region of a curved meniscus interface pinned at the mouth of a horizontally positioned capillary pore. The SWs are clear and strong in acetone but absent in ethanol for both tube sizes investigated (1-2 mm diameter). Dependent upon the tube size and the initial liquid filling ratio, the SWs start sooner for a lower filling ratio. The intriguing experimental observation is that the SWs disappear at a specified liquid length between the receding meniscus and the one pinned at the tube mouth, which seems to depend strongly upon the tube size and independent of the initial liquid filling ratio. The origin of the SWs could be due to the strong interaction between surface tension and gravity, which also generates oscillatory periodic Marangoni flow in the meniscus liquid phase.

Wettability on Inner and Outer Surface of Single Carbon Nanotubes.

The surface wettability of a liquid on the inner and outer surface of single carbon nanotubes (CNTs) was experimentally investigated. Although these contact angles on both surfaces were previously studied separately, the available data are of limited help to elucidate the effect of curvature orientation (concave or convex) on wettability due to the difference in surface structure. Here, we report on the three-phase contact region and wettability on the outer surface of CNT during the dipping and withdrawing experiment of CNT into an ionic liquid. Furthermore, the wettability on the inner surface was measured using a liquid within the same CNT. Our results show that the contact angle on the outer surface of the CNT is larger than that on the flat surface and that on the inner surface is smaller than that on the flat one. These findings suggest that the surface curvature orientation has a noticeable effect on the contact angle at the nanoscale because both inner and outer surfaces expose the same graphite wall structure and the contact line tension will be negligible in this situation. The presented results are rationalized using the free energy balance of liquid on curved surfaces.

Kinetics of Evaporation of Pinned Nanofluid Volatile Droplets at Subatmospheric Pressures.

We examine the effects of nanoparticle addition at low concentration on the evaporation kinetics of droplets in the constant radius mode. The evaporative behavior of deionized water and Al2O3 nanoparticle laden water on an aluminum substrate was observed at atmospheric and at different subatmospheric pressures. The two fluids exhibit the same evaporative behavior, independent of the droplet volume or the subatmospheric pressure. Moreover, the linear relationship between evaporation rate and droplet radius, initially proposed by Picknett and Bexon nearly four decades ago for droplets evaporating in the constant radius mode, is satisfied for both liquids. In addition, we have established a unified correlation solely function of fluid properties that extends this relationship to any subatmospheric pressure and fluid tested. We conclude that the addition of a small quantity of nanoparticles to the base fluid does not modify the kinetics of evaporation for pinned volatile droplets.

"Biodrop" Evaporation and Ring-Stain Deposits: The Significance of DNA Length.

Small sessile drops of water containing either long or short strands of DNA ("biodrops") were deposited on silicon substrates and allowed to evaporate. Initially, the triple line (TL) of both types of droplet remained pinned but later receded. The TL recession mode continued at constant speed until almost the end of drop lifetime for the biodrops with short DNA strands, whereas those containing long DNA strands entered a regime of significantly lower TL recession. We propose a tentative explanation of our observations based on free energy barriers to unpinning and increases in the viscosity of the base liquid due to the presence of DNA molecules. In addition, the structure of DNA deposits after evaporation was investigated by AFM. DNA self-assembly in a series of perpendicular and parallel orientations was observed near the contact line for the long-strand DNA, while, with the short-stranded DNA, smoother ring-stains with some nanostructuring but no striations were evident. At the interior of the deposits, dendritic and faceted crystals were formed from short and long strands, respectively, due to diffusion and nucleation limited processes, respectively. We suggest that the above results related to the biodrop drying and nanostructuring are indicative of the importance of DNA length, i.e., longer DNA chains consisting of linearly bonded shorter, rod-like DNA strands.

Effect of substrate temperature on pattern formation of nanoparticles from volatile drops.

This study investigates pattern formation during evaporation of water-based nanofluid sessile droplets placed on a smooth silicon surface at various temperatures. An infrared thermography technique was employed to observe the temperature distribution along the air-liquid interface of evaporating droplets. In addition, an optical interferometry technique is used to quantify and characterize the deposited patterns. Depending on the substrate temperature, three distinctive deposition patterns are observed: a nearly uniform coverage pattern, a "dual-ring" pattern, and multiple rings corresponding to "stick-slip" pattern. At all substrate temperatures, the internal flow within the drop builds a ringlike cluster of the solute on the top region of drying droplets, which is found essential for the formation of the secondary ring deposition onto the substrate for the deposits with the "dual-ring" pattern. The size of the secondary ring is found to be dependent on the substrate temperature. For the deposits with the rather uniform coverage pattern, the ringlike cluster of the solute does not deposit as a distinct secondary ring; instead, it is deformed by the contact line depinning. In the case of the "stick-slip" pattern, the internal flow behavior is complex and found to be vigorous with rapid circulating flow which appears near the edge of the drop.