Modulation of Central Depletion Zone in Evaporated Sessile Drops via Substrate Heating.

In this article, we report the influence of substrate temperature (Tsub) on the evaporation driven patterning of colloids on solid substrates. When the drops are dried in an environment maintained at temperature, Tenv, lower than Tsub, the temperature difference between the drop apex and the three-phase contact line leads to thermal Marangoni flow. We show that the interplay between the radial capillary flow, the thermal Marangoni flow, and the descending rate of the drop surface can be tuned to modulate the spatial distribution of colloids in the dried deposits. At ΔT (=Tsub - Tenv) ≥ 45 °C, the distribution of particles in the interior region of the pattern is nearly uniform with a significant decrease in concentration of particles in the ring-like deposit at the edge. The deposits formed at 15 °C ≤ ΔT ≤ 40 °C are accompanied by a particle depleted zone in the center, which has not been reported to date. The formation of the central depletion zone arises from the suppression of the thermal Marangoni flow at the penultimate stage of drying and the interplay between the radial capillary flow and the descending rate of the drop surface. At ΔT < 15 °C, the dried deposits are found to exhibit coffee-ring-like stains.

Tailoring crack morphology in coffee-ring deposits via substrate heating.

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 > 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 > 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.

Morphologies of electric-field-driven cracks in dried dispersions of ellipsoids.

We report an experimental and theoretical study of the morphology of desiccation cracks formed in deposits of hematite ellipsoids dried in an externally applied alternating current (ac) electric field. A series of transitions in the crack morphology is observed by modulating the frequency and the strength of the applied field. We also found a clear transition in the morphology of cracks as a function of the aspect ratio of the ellipsoid. We show that these transitions in the crack morphology can be explained by a linear stability analysis of the equation describing the effective dynamics of an ellipsoid placed in an externally applied ac electric field.

Synergy between the crack pattern and substrate elasticity in colloidal deposits.

Desiccation cracks in colloidal deposits occur to release the excess strain energy arising from the competition between the drying induced shrinkage of the deposit and its adhesion to the substrate. Here we report remarkably different morphology of desiccation cracks in the dried patterns formed by the evaporation of sessile drops containing colloids on elastomer (soft) or glass (stiff) substrates. The change in the crack pattern, i.e., from radial cracks on stiff substrates to circular cracks on soft substrates, is shown to arise solely due to the variation in elasticity of the underlying substrates. Our experiments and calculations reveal an intricate correlation between the desiccation crack patterns and the substrate's elasticity. The mismatch in modulus of elasticity between the substrate and that of the particulate deposit significantly alters the energy release rate during the nucleation and propagation of cracks. The stark variation in crack morphology is attributed to the tensile or compressive nature of the drying-induced in-plane stresses.

Cracks in dried deposits of hematite ellipsoids: Interplay between magnetic and hydrodynamic torques.

The orientation and morphology of cracks in coffee-ring like particulate deposit obtained by drying sessile drops containing anisotropic magnetic particles strongly depends on the magnitude of the applied magnetic field and its direction. This opens up the possibility of tuning the micro-structure of cracks via suitable manipulation of magnetic and hydrodynamic torques on the particles which has potential applications in nano-fabrication and field driven self-assembly. We report a systematic study of magnetic field driven self-assembly of hematite ellipsoids in sessile drops dried on solid substrates and resulting crack patterns. The experiments are carried out over a wide range of applied magnetic field strength (|B→|) varying from 0 to 400G and ellipsoids of two different aspect ratios. Dried coffee-ring deposits of ellipsoids in absence of the external applied magnetic field and at low field strength, |B→|≤20G exhibit circular cracks. However, at |B→|⩾30G, the cracks are observed to be linear and perpendicular to the direction of the applied magnetic field. Random cracks are observed in the intermediate field range of 20G<|B→|<30G. Thus our experiments reveal that there exists a critical magnetic field at which the orientation of cracks change from circular to linear. The knowledge of the critical field is exploited to measure the hydrodynamic torque experienced by nano-ellipsoids and fluid velocities during evaporation, which are challenging to measure experimentally.

Role of particle shape anisotropy on crack formation in drying of colloidal suspension.

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.

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

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.