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We present experiments and theory relating to transpiration through unrestrained hydrogel beads in contact with a water reservoir below and air above. Experimentally, we find that saturated hydrogel beads shrink until a steady state is reached in which water flows continuously through the beads. The size of the bead in steady state is sensitive to the evaporation rate, which depends on the relative humidity and speed of the surrounding air, and to the pressure head imposed by the fluid reservoir. Specifically, the bead size decreases with increasing pressure head or evaporation rate. Our one-dimensional model proposes that transport in the hydrogel is driven by gradients in osmotic pressure, caused by gradients in polymer concentration in the hydrogel that correspond to gradients in swelling. If the evaporation rate or the pressure head changes, the adjustment of this gradient requires the bead to change shape and size. Smaller beads have larger gradients of osmotic pressure, which drive higher transpiration rates and can draw water against larger pressure heads.
We consider the solidification of idealised two-component mixtures comprising a solvent or suspending fluid and dissolved solute molecules or suspended colloidal particles, each considered as hard spheres. We review some fundamental thermodynamic ideas regarding relative motion between species and phase equilibria in such mixtures to show how the related solid–liquid phase diagrams depend on the size of the spheres. Using similarity solutions, we first describe freezing of the solvent to form a pure solid (here referred to as ‘ice’), with the solute rejected from the solid forming a boundary layer or dense particle layer ahead of the freezing front. We extend ideas of constitutional supercooling to the case of colloidal suspensions and show that, for a given temperature difference driving solidification, constitutional supercooling occurs only for an intermediate range of particle sizes. Constitutional supercooling promotes the formation of a mushy layer in which segregated ice separates regions of concentrated solute or particles on the microscale. We formulate a continuum model of the mushy layer that relies on a key observation that the regelative motion of concentrated clusters of particles is independent of the size and geometry of the cluster. Our modelling begins with a description of relative motion as a Fickian diffusive process. However, at high particle concentrations, we show that it is more convenient and more computationally tractable to use an equivalent formulation in terms of Darcy flow of the solvent. Within a mushy layer these diffusive fluxes correspond directly to the regelative flux of particle clusters at a rate determined by the local temperature and temperature gradient.
We present a mathematical model of the unidirectional solidification of a suspension of hard-sphere colloids. Similarity solutions are obtained for the volume fraction and temperature profiles ahead of a planar solidification front. The highly nonlinear functional dependence of the diffusion coefficient on the volume fraction gives rise to a range of behaviours. For small particles, Brownian diffusion dominates and the system behaviour is reminiscent of binary-alloy solidification. Constitutional supercooling occurs at the interface under certain conditions, leading potentially to an instability in the shape of the interface. For larger particles, Brownian diffusion is weak and the particles form a porous layer above the interface. In this case constitutional supercooling reaches a maximum near the surface of the layer, and the porous medium itself is potentially unstable. In stable systems there exists the possibility of secondary nucleation of ice.