When thin films of colloidal fluids are dried, a range of transitions are observed and the final film profile is found to depend on the processes that occur during the drying step. This article describes the drying process, initially concentrating on the various transitions. Particles are seen to initially consolidate at the edge of a drying droplet, the so-called coffee-ring effect. Flow is seen to be from the centre of the drop towards the edge and a front of close-packed particles passes horizontally across the film. Just behind the particle front the now solid film often displays cracks and finally the film is observed to de-wet. These various transitions are explained, with particular reference to the capillary pressure which forms in the solidified region of the film. The reasons for cracking in thin films is explored as well as various methods to minimize its effect. Methods to obtain stratified coatings through a single application are considered for a one-dimensional drying problem and this is then extended to two-dimensional films. Different evaporative models are described, including the physical reason for enhanced evaporation at the edge of droplets. The various scenarios when evaporation is found to be uniform across a drying film are then explained. Finally different experimental techniques for examining the drying step are mentioned and the article ends with suggested areas that warrant further study.

https://iopscience.iop.org/article/10.1088/0034-4885/76/4/046603/pdf

Drying of thin colloidal films.

We consider natural and artificial hygromorphs, objects that respond to environmental humidity by changing their shape. Using the pine cone as an example that opens when dried and closes when wet, we quantify the geometry, mechanics and dynamics of closure and opening at the cell, tissue and organ levels, building on our prior structural knowledge. A simple scaling theory allows us to quantify the hysteretic dynamics of opening and closing. We also show how simple bilayer hygromorphs of paper and polymer show similar behaviour that can be quantified via a theory which couples fluid transport in a porous medium and evaporative flux to mechanics and geometry. Our work unifies varied observations of natural hygromorphs and suggests interesting biomimetic analogues, which we illustrate using an artificial flower with a controllable blooming and closing response.

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Hygromorphs: from pine cones to biomimetic bilayers

Capillary forces arising during the evaporation of liquids from dense carbon nanotube arrays are used to reassemble the nanotubes into two-dimensional contiguous cellular foams. The stable nanotube foams can be elastically deformed, transferred to other substrates, or floated out to produce free-standing macroscopic fabrics. The lightweight cellular foams made of condensed nanotubes could have applications as shock-absorbent structural reinforcements and elastic membranes. The ability to control the length scale, orientation, and shape of the cellular structures and the simplicity of the assembly process make this a particularly attractive system for studying pattern formation in ordered media.

https://www.pnas.org/content/pnas/101/12/4009.full.pdf

Capillarity-driven assembly of two-dimensional cellular carbon nanotube foams

Thin films of latex dispersions containing particles of high glass transition temperature generally crack while drying under ambient conditions. Experiments with particles of varying radii focused on conditions for which capillary stresses normal to the film deform the particles elastically and generate tensile stresses in the plane of the film. Irrespective of the particle size, the drying film contained, simultaneously, domains consisting of a fluid dispersion, a fully dried packing of deformed spheres, and a close packed array saturated with water. Interestingly, films cast from dispersions containing 95-nm sized particles developed tensile stresses and ultimately became transparent even in the absence of water, indicating that van der Waals forces can deform the particles. Employing the stress-strain relation for a drying latex film along with the well-known Griffith's energy balance concept, we calculate the critical stress at cracking and the accompanying crack spacing, in general agreement with the observed values.

Cracking in Drying Latex Films

It is shown that an elastic film on a viscoelastic substrate under biaxial compressive stress forms a hierarchical network of folds generated by repetitive wrinkle-to-fold transitions. The morphology of the hierarchical patterns can be controlled by modifying the geometry and boundary conditions of the membrane.

Hierarchical folding of elastic membranes under biaxial compressive stress

We have studied shrinkage-crack patterns which form when a thin layer of an alumina/water slurry dries. Both isotropic and directional drying were studied. The dynamics of the pattern formation process and the geometric properties of the isotropic crack patterns are similar to what is expected from recent models, assuming weak disorder. There is some evidence of a gradual increase in disorder as the drying layer become thinner, but no sudden transition, in contrast to what has been seen in previous experiments. The morphology of the crack patterns is influenced by drying gradients and front propagation effects, with sharp gradients having a strong orienting and ordering effect.

Kelly A. Shorlin

Papers

Development and geometry of isotropic and directional shrinkage-crack patterns.