UV patternable thin film chemistry for shape and functionally versatile self-oscillating gels

Abstract

We describe a new planar processing chemistry that allows the synthesis and patterning of dynamically self-actuating gels of diverse form. The chemical reaction covalently incorporates a methacrylate-modified ruthenium trisbipyridine monomer within a poly acrylamide (PAAm) gel, modified to provide a flexible chemistry for UV-curable, self-oscillating Belousov–Zhabotinsky (BZ) gels. The photoinitiated polymerization offers significant advantages over previously reported BZ gel chemistries – fast polymerization rates, broad flexibility in the structural and functional attributes that impact the BZ reaction driven mechanics, and a facility for net shape fabrication via projection mode photo lithographic exposure. The facility of the synthetic method enabled an opportunity to broadly explore the structure/property and structure/rate correlations characterizing the dynamics of these gels and develop means to both control and predict the detailed features of the self-oscillating chemical waves they embed. The PAAm systems initiate under the control of transport-dominated influences weighted heavily by the diffusion/depletion of reagents present in the ambient contacting fluid medium. These initiating modes of oscillation are generally unstable temporally, showing shape- and property-sensitive conversions to oscillating modes controlled by the attributes of the gel-phase environment. The present work establishes the nature of these sensitivities, developing insights related to such features in patterned gel objects or films as composition, size, thickness, shape, degree of crosslinking, and gradient forms of structure within the gel. We observed in this work that, across a broad design-rule and compositional space, the PAAm based BZ gel systems exhibit contractions in dimension for regions in which the Ru catalyst is present in the +3 oxidation state (PNIPAAm BZ gels expand in this state). The chemomechanics of the PAAm system are further differentiated from those of PNIPAAm in the generally (and relatively) fast oscillatory rates it can sustain. This work suggests the dynamics in the PAAm gels do not reflect a simple osmotic force driven by differences in the solvation of Ru(II/III) centers. Computational modeling supports a mechanism in which the charge state of Ru centers mediate a differential degree of intra/inter-chain segmental interactions – dynamics that mediate a temporally varying degree of reversibly formed association crosslinks within the gel.