Bidirectional Actuation of Silk Fibroin Films: Role of Water and Alcohol Vapors.

Three-dimensional (3D) shape morphism observed in nature inspires the development of stimuli-responsive soft actuators. Vapor-responsive actuators are promising among the different stimuli-responsive materials due to their capability to produce macroscale movements in response to a minuscule amount of specific chemical vapor. Here, we report unusual multiple vapor-responsive bidirectional macroscale actuation behaviors of single-layer regenerated silk fibroin films. The vapor-responsive silk fibroin actuator exhibits antagonistic actuation characteristics in a reversible manner to both water and ethanol vapors. For instance, it produces an upward bending in the presence of water vapor and downward bending in ethanol vapor, which demonstrates the chemical vapor-specific actuation. However, the actuation characteristics remain largely invariant upon changing the polarity of alcohol molecules. The silk fibroin actuators effectively utilize the vapor-induced minuscule expansion and contraction of the film surface to produce large-scale actuation, which is fully reversible. The intrinsic water content of the films and the vapor pressure of the stimulants are exploited to control the actuation performance. Further, we demonstrated the 3D shape morphing ability of the actuator by generating an undulating wavelike motion via preprogrammed water and ethanol vapor exposure conditions. The change in the actuation direction is instantaneous, which ensures the sensitivity and rapid response of the fabricated actuators.

Penetrant-Induced Glass-like Transition in Thin Chitosan Films.

We present the water vapor-induced swelling and the emergence of a penetrant-induced glass-like transition in the substrate-supported glassy chitosan thin films. The time evolution of the film thickness under different levels of relative humidity conditions is measured in real-time using a spectroscopic ellipsometer equipped with a humidity cell. In a dry film, the network of chitosan chains is in a glassy state, and upon exposure to water vapor, initially, the film swells by Fickian diffusion of water molecules, which triggers the structural relaxations of the chains. Under higher humidity conditions, a relatively slower evolution of thickness succeeds the initial rapid swelling due to the non-Fickian sorption of water molecules. The swelling characteristics of the polymer films are accounted for by considering the diffusion-relaxation mechanism of chains in the presence of smaller penetrant molecules. The penetrant-induced glass-like transition (Pg), where the polymer film isothermally transits from a glassy to a rubbery state, is determined for pristine and cross-linked chitosan films. Pg is determined from the abrupt change in the rate of swelling observed upon increasing the relative humidity. Chemical crosslinking has an evident influence on the penetrant-induced glass-like transition of the chitosan films. Pg was found to rise sharply for stiffer films with higher cross-linking density.