Autonomic composite hydrogels by reactive printing: materials and oscillatory response.

Autonomic materials are those that automatically respond to a change in environmental conditions, such as temperature or chemical composition. While such materials hold incredible potential for a wide range of uses, their implementation is limited by the small number of fully-developed material systems. To broaden the number of available systems, we have developed a post-functionalization technique where a reactive Ru catalyst ink is printed onto a non-responsive polymer substrate. Using a succinimide-amine coupling reaction, patterns are printed onto co-polymer or biomacromolecular films containing primary amine functionality, such as polyacrylamide (PAAm) or poly-N-isopropyl acrylamide (PNIPAAm) copolymerized with poly-N-(3-Aminopropyl)methacrylamide (PAPMAAm). When the films are placed in the Belousov-Zhabotinsky (BZ) solution medium, the reaction takes place only inside the printed nodes. In comparison to alternative BZ systems, where Ru-containing monomers are copolymerized with base monomers, reactive printing provides facile tuning of a range of hydrogel compositions, as well as enabling the formation of mechanically robust composite monoliths. The autonomic response of the printed nodes is similar for all matrices in the BZ solution concentrations examined, where the period of oscillation decreases in response to increasing sodium bromate or nitric acid concentration. A temperature increase reduces the period of oscillations and temperature gradients are shown to function as pace-makers, dictating the direction of the autonomic response (chemical waves).

Glass formation and shear elasticity in dense suspensions of repulsive anisotropic particles.

Kinetic vitrification, shear elasticity, and the approach to jamming are investigated for repulsive nonspherical colloids and contrasted with their spherical analog. Particle anisotropy dramatically increases the volume fraction for kinetic arrest. The shear modulus of all systems increases roughly exponentially with volume fraction, and a universal collapse is achieved based on either the dynamic crossover or random close packing volume fraction as the key nondimensionalizing quantity. Quantitative comparisons with recent microscopic theories are performed and good agreement demonstrated.