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Mechanics of polymer brush based soft active materials -- theory and experiments

Brush-like structures emerge from stretching of long polymer chains, densely grafted on to the surface of an impermeable substrate. They arise due to the competition between conformational entropic elasticity of polymer chains and excluded volume interactions from the intra and interchain monomer repulsions. Recently, stimuli responsive polymer brush based soft materials have been developed to produce controllable and reversible large deformations of the host substrate. To understand these systems, and improve their functional properties, we study elastic stress distribution and surface stress-curvature relations of a neutral polymer brush grafted on to an elastic beam, made of a soft material. In the strongly stretched brush regime, we combine mean field theory from polymer physics with a continuum mechanics model and show that the residual stress variation is a quartic function of distance from the grafting surface, with maximum stress occurring at the grafted surface. Idealizing the brush as a continuum elastic surface layer with residual stress, we derive a closed form expression for surface stress and the surface elasticity of the layer as a function of brush parameters, such as graft density and molecular weight. The generalized continuum beam model accounts for the Young-Laplace and Ogden-Steigman curvature elasticity correction terms, and yields a surface stress-curvature relation, which contains existing relations in the literature as special cases. Further, we report experiments on a thermoresponsive random copolymer brush, Poly(N- isopropylacrylamide)-co-Poly(N,N-Dimethylacrylamide) (PNIPAm-co-PDMA) brush, grafted on one side of a plasticized pPVC thin film. Estimated surface stress from measured curvature is on the order of $-10~N/m$, and it decreases gradually, and reversibly, with increasing ambient temperature from $15~^\circ{}C$ to $55~^\circ{}C$.