Cracks in a colloidal film formed by evaporation induced drying can be controlled by changing drying conditions. We show, for the first time that the crack morphologies in colloidal films are dependent on shape of constituting particles apart from the microstructure and particle assembly. In order to investigate the particle shape effect on crack patterns, monodispered spherical and ellipsoidal particles are used in sessile drop experiments. On observing the dried sessile drop we found cracks along the radial direction for spherical particle dispersions and circular crack patterns for ellipsoidal particle dispersions. The change in crack pattern is a result of self assembly of shape anisotropic particles and their ordering. The ordering of particles dictate the crack direction and the cracks follow the path of least resistance to release the excess stress stored in the particle film. Ellipsoids having different aspect ratio (∼3 to 7) are used and circular crack patterns are repeatedly observed in all experiments. © 2016 The Author(s).

Dillip Kumar Satapathy

Department Of Physics

Madivala Gurapa Basavaraja

Department Of Chemical Engineering

Venkateshwar Rao Dugyala

Hisay Lama

Anisotropy

particle size

Stress

Suspension

Fulltext

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Scientific Reports

Evaporation of colloidal dispersions leading to patterning of particles is a simple and elegant route for controlling the self-assembly of particles on a solid surface. In this article, we demonstrate that the configuration in which a colloidal dispersion is dried greatly influences the patterning of particles on a solid surface after complete evaporation of the solvent. Evaporation experiments are carried out using well-characterized stable aqueous dispersions of hematite ellipsoids and polystyrene spheres. The drying of particle laden sessile drops always give a "coffee-ring" deposit irrespective of the particle concentration. At a particle concentration ≥0.3 wt% circular cracks appear in the annular region of the coffee-ring deposit owing to the ordered arrangement of ellipsoids. In stark contrast, the deposits formed by drying the dispersion of ellipsoids in the sphere-on-plate configuration show a transition from "concentric rings" to "concentric cracks" in the micro-structure of the particulate film with an increase in the concentration of particles. Further, our experimental findings reveal that long-range circular cracks and long-range assemblies of particles can be achieved by drying of the dispersion in the sphere-on-plate configuration. While the nature of patterns-that is-coffee-rings and concentric rings-is independent of the shape of the particles, a strikingly different crack morphology is shown to be dictated by the shape of the particles in the dispersion. The results presented show that the drying of colloidal dispersions in the sphere-on-plate configuration enables the fabrication of a long range ordered assembly of particles over an area as large as few square millimeters. © 2019 the Owner Societies.

Physical Chemistry Chemical Physics

Influence of the drying configuration on the patterning of ellipsoids-concentric rings and concentric cracks

The drying of a sessile drop consisting of colloidal particles and the formation of particulate deposits with spatially periodic cracks were ubiquitous. The drying induced stress, which is generated during the evaporation of a colloidal drop, is released by the formation of cracks. We find that the morphology of cracks formed in particulate films dried at substrate temperature, Tsub = 25 °C is markedly different from that of cracks formed at Tsub &gt; 45 °C. The cracks are disordered in the former case, but ordered and periodic in the latter. The disorderedness of cracks observed at Tsub = 25 °C is mainly due to the formation of a coffee-ring like particle deposit that exhibits a larger height gradient. The ultimate deposit pattern after complete drying is observed to be different for colloidal dispersion drops evaporated at different substrate temperatures. This is attributed to temperature-dependent solvent flow mechanisms and capillary-driven flow, which occur inside the colloidal drop during the course of drying. In addition, for the coffee-ring-like particulate deposit obtained at Tsub ≤ 45 °C, the ratio between the width of the deposit w and the radius of the ring R scales with the volume fraction of the colloids φ, w/R ∼ φ0.5, in the range of volume fractions studied in this work. The deposited patterns obtained at temperature Tsub &gt; 45 °C are largely dominated by the capture of particles by the receding liquid-vapor interface. This is due to the faster rate of decrease of the liquid-vapor interface position with an increase in substrate temperature. © 2017 The Royal Society of Chemistry.

Soft Matter

Tailoring crack morphology in coffee-ring deposits: Via substrate heating

We report the effect of applied magnetic field on the morphology of cracks formed after evaporation of a colloidal suspension consisting of shape-anisotropic ellipsoidal particles on a glass substrate. The evaporation experiments are performed in sessile drop configuration, which usually leads to accumulation of particles at the drop boundaries, commonly known as the "coffee-ring effect." The coffee-ring-like deposits that accompany cracks are formed in the presence as well as in the absence of magnetic field. However, the crack patterns formed in both cases are found to differ markedly. The direction of cracks in the presence of the magnetic field is found to be governed by the orientation of particles and not solely by the magnetic field direction. Our experimental results show that at the vicinity of cracks the particles are ordered and oriented with their long-axis parallel to crack direction. In addition, we observe that the crack spacing in general increases with the height of the particulate film. ©2016 American Physical Society.

Physical Review E

Magnetic-field-driven crack formation in an evaporated anisotropic colloidal assembly

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 axisymmetric Marangoni recirculation and is consistent with previous reports. However, the dimensions of the ring formed on a non-uniformly heated substrate are significantly different on the hot and cold side of the substrate and are found to be a function of the temperature gradient and particles size. In the case of smaller particle size, the contact line on hot side depins and together with twin asymmetric Marangoni recirculations, it results in a larger ring width on the cold side as compared to the hot side. In contrast, the contact line remains pinned in case of larger particles, and the twin asymmetric Marangoni recirculations advect more particles on the hot side, resulting in a larger ring width at the hot side. A mechanistic model is employed to explain why the depinning is dependent on the particle size. A larger temperature gradient significantly increases or decreases the ring width depending on the particle size, due to a stronger intensity recirculation. A regime map is proposed for the deposit patterns on temperature gradient-particle size plane to classify the deposits. © 2019 Elsevier B.V.

Colloids and Surfaces A: Physicochemical and Engineering Aspects

Colloidal deposit of an evaporating sessile droplet on a non-uniformly heated substrate

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 occur only at smaller particle size and larger concentration. We plot a regime map to classify three deposit types - discontinuous monolayer ring, continuous monolayer ring, and multiple layers ring - on particles concentration - particle size plane. Our data shows a possible existence of a critical concentration (particle size) for a given particle size (concentration) at which the monolayer ring forms. For the larger particle sizes, the immersion capillary forces between the particles dominate, aiding the formation of a monolayer ring of the particles. We measure the width and height of the ring and show that they scale with particle concentration by a power law for the multiple layers ring. This scaling corroborates with an existing continuum based theoretical model. We briefly discuss the effect of the interaction of growing deposit with shrinking free surface on the ring dimensions and profile. The present results aid understanding of the ring formation process and will be useful in guiding the design of self-assemblies of the colloidal particles formed by the evaporating droplets. © 2019 Elsevier B.V.

Analysis of profile and morphology of colloidal deposits obtained from evaporating sessile droplets

The self-assembly of anisotropic particles into two or three dimensional ordered arrays has diverse applications in several areas of science and engineering. In this article, we report the formation of a multi-layer film of nano-sized ellipsoids with long-range orientation and positional order through an evaporation driven vertical deposition technique. Using nano-sized ellipsoids of tunable surface charge, we show that electrostatic interactions can be exploited to control the arrangement of ellipsoids in the film. The pH of the aqueous suspensions used for vertical deposition is adjusted such that the surface charge and hence the electro-static interactions can be controlled. We show that the interplay between various Derjaguin and Landau, Verwey and Overbeek (DLVO) interactions can be effectively controlled to fabricate films with a random arrangement of particles as well as to create particulate films with three-dimensional ordering of ellipsoids. When the particles are weakly charged, the nano-ellipsoids in the film are randomly oriented giving an amorphous particulate film. However, when the particles are highly charged, the nano-ellipsoids in the film are oriented with major axis parallel to each other and ordered in three dimensions. These particulate film are observed to have parallel cracks across the entire width of the film. The major axis of the particle is found to be parallel to the crack direction and therefore, the direction of crack formation can be exploited to indicate the nature of particle ordering. © The Royal Society of Chemistry 2015.

RSC Advances

Self-assembly of nano-ellipsoids into ordered structures via vertical deposition

Liquid drops containing insoluble solutes when dried on solid substrates leave distinct ring-like deposits at the periphery or along the three-phase contact line-a phenomena popularly known as the coffee-ring or the coffee stain effect. The formation of such rings as well as their suppression is shown to have applications in particle separation and disease diagnostics. We present an experimental study of the evaporation of sessile drops containing silica rods to elucidate the structural arrangement of particles in the ring, an effect of the addition of surfactant and salt. To this end, the evaporation of aqueous sessile drops containing model rod-like silica particles of aspect ratio ranging from ∼4 to 15 on a glass slide is studied. We first show that when the conditions such as (1) solvent evaporation, (2) nonzero contact angle, (3) contact line pinning, (4) no surface tension gradient driven flow, and (5) repulsive particle-particle/particle-substrate interactions, that are necessary for the formation of the coffee-ring are met, the suspension drops containing silica rods upon evaporation leave a ring-like deposit. A closer examination of the ring deposits reveals that several layers of silica rods close to the edge of the drop are ordered such that the major axis of the rods are oriented parallel to the contact line. After the first few layers of ordered arrangement of particles, a random arrangement of particles in the drop interior is observed indicating an order-disorder transition in the ring. We monitor the evolution of the ring width and particle velocity during evaporation to elucidate the mechanism of the order-disorder transition. Moreover, when the evaporation rate is lowered, the ordering of silica rods is observed to extend over large areas. We demonstrate that the nature of the deposit can be tuned by the addition of a small quantity of surfactant or salt. © 2014 American Chemical Society.

Journal of Physical Chemistry B

Evaporation of sessile drops containing colloidal rods: Coffee-ring and order-disorder transition

A control over the nature of deposit pattern obtained after the evaporation of solvent from a sessile drop containing dispersed materials has been demonstrated to have applications in materials engineering, separation technology, printing technology, manufacture of printed circuit boards, biology, and agriculture. In this article, we report an experimental investigation of the effect of particle shape and DLVO (Derjaguin-Landau-Verwey-Overbeek) interactions on evaporation-driven pattern formation in sessile drops. The use of a model system containing monodisperse particles where particle aspect ratio and surface charge can be adjusted reveals that a control over the nature of deposit pattern can be achieved by tuning the particle-particle and particle-substrate interactions. A clear coffee-ring formation is observed when the strength of particle-particle repulsion is higher than the particle-substrate attraction. However, complete suppression of ringlike deposits leading to a uniform film is achieved when particle-substrate and particle-particle interactions are attractive. Results illustrate that for the system of submicron ellipsoids that are hydrophilic, the nature of deposit patterns obtained after evaporation depends on the nature of interactions and not on particle shape. © 2014 American Chemical Society.

Langmuir

Control over coffee-ring formation in evaporating liquid drops containing ellipsoids

The recent surge to explore and exploit the effect of particle shape has led to several interesting and unique observations in various diverse fields, ranging from biology to material science. To this end, the development of novel synthesis methods has contributed immensely, and has directed this exciting research on the role of particle shape in colloidal systems and other diverse fields. Furthermore, such investigations have resulted in the development of advanced materials, which are novel and multi-functional. In this article, we review recent advances in the study of suspensions containing shape anisotropic particles. In particular, we investigate those pertaining to rod-like or ellipsoidal particles and highlight recent results in three areas-evaporation driven assembly, packing, interfacial behavior and the use of these particles in emulsion stabilization. © 2013 The Royal Society of Chemistry.

Journal	Scientific Reports
Publisher	Nature Publishing Group
ISSN	20452322
Open Access	No