Surface stress and shape relaxation of gelling droplets.

Solidification is a heterogeneous transformation from liquid to solid, which usually combines transport, phase transition and mechanical strain. Predicting the shapes resulting from such a complex process is fascinating and has a wide range of implications from morphogenesis in biological tissues to industrial processes. For soft solids initially at equilibrium, elastic stresses, whether tensile or compressive, can be induced by heterogeneous volumetric deformations of the material. These stresses trigger surface instabilities leading to variations of curvature and shape of the solids. In this article, we study the shape evolution of elongated droplets of polymer and particle suspensions undergoing a solidification process caused by the inward diffusion of a gelling agent from the surface. We show experimentally and numerically that there appears a layer of gelled material growing at the surface. Due to volume contraction, this layer induces tensile stresses and drives a flow in the ungelled liquid core, resulting in the relaxation of the droplets toward spherical shapes. Over time, the thickness of this elastic membrane grows, hence the bending stiffness required to change its shape eventually balances the surface stresses, which arrests the relaxation process. These results provide general rules to understand the shape of solidifying materials combining both tension and bending driven deformations.

Sol/gel transition of thermoresponsive Hyaluronan: From liquids to elastic and sticky materials.

Thermoassociating copolymers were prepared by grafting temperature responsive poly(N-isopropylacrylamide-stat-N-tert-butylacrylamide) telomers onto hyaluronan. By varying the composition of LCST side chains, from 50 to 100 wt% of NIPAM units, it is shown that the sol/gel transition of entangled solutions can be accurately controlled in the range of 10 to 35 °C with an abrupt transition and reversible properties. Complementary experiments, performed by DSC and NMR, demonstrate the close relationship between thermoassociation of LCST grafts, forming microdomains of low mobility, and macroscopic properties. Moreover, by performing tack experiments during heating we demonstrate that hyaluronan formulations abruptly switch from a weak adhesive viscous behavior to an elastic adhesive profile in the gel regime. As LCST side-chains form concentrated micro-domains of low mobility, physical gels can resist to dissociation above their sol/gel transition for relatively long periods when immersed in excess physiological medium. The thermoassociative behavior of these copolymers, whose properties can be finely tuned in order to form sticky gels at body temperature, clearly demonstrates their potential in biomedical applications such as injectable gels for drug delivery or tissue engineering.

Environmental Nanoparticle-Induced Toughening and Pinning of a Growing Crack in a Biopolymer Hydrogel.

We study the interplay between a crack tip slowly propagating through a hydrogel and nanoparticles suspended in its liquid environment. Using a proteinic gel enables us to tune the electrostatic interaction between the network and silica colloids. Thereby, we unveil two distinct, local toughening mechanisms. The primary one is charge independent and involves the convective building of a thin particulate clog, hindering polymer hydration in the crack process zone. When particles and network bear opposite charges, transient adhesive bonding superimposes, permitting the remarkable pinning of a crack by a liquid drop.