Search for: All records

Soft machines will require soft materials that exhibit a rich diversity of functionality, including shape morphing and photoresponsivity. The combination of these functionalities enables useful behaviors in soft machines that can be further developed by synthesizing materials that exhibit localized responsivity. Localized responsivity of liquid crystal elastomers (LCEs), which are soft materials that exhibit shape morphing, can be enabled by formulating composite inks for direct ink writing (DIW). Gold nanorods (AuNRs) can be added to LCEs to enable photothermal shape change upon absorption of light through a localized surface plasmon resonance. We compared LCE formulations, focusing on their amenability for printing by DIW and the photoresponsivity of AuNRs. The local responsivity of different three-dimensional architectures enabled soft machines that could oscillate, crawl, roll, transport mass, and display other unique modes of actuation and motion in response to light, making these promising functional materials for advanced applications. 

Arrested soft materials such as gels and glasses exhibit a slow stress relaxation with a broad distribution of relaxation times in response to linear mechanical perturbations. Although this macroscopic stress relaxation is an essential feature in the application of arrested systems as structural materials, consumer products, foods, and biological materials, the microscopic origins of this relaxation remain poorly understood. Here, we elucidate the microscopic dynamics underlying the stress relaxation of such arrested soft materials under both quiescent and mechanically perturbed conditions through X-ray photon correlation spectroscopy. By studying the dynamics of a model associative gel system that undergoes dynamical arrest in the absence of aging effects, we show that the mean stress relaxation time measured from linear rheometry is directly correlated to the quiescent superdiffusive dynamics of the microscopic clusters, which are governed by a buildup of internal stresses during arrest. We also show that perturbing the system via small mechanical deformations can result in large intermittent fluctuations in the form of avalanches, which give rise to a broad non-Gaussian spectrum of relaxation modes at short times that is observed in stress relaxation measurements. These findings suggest that the linear viscoelastic stress relaxation in arrested soft materials may be governed by nonlinear phenomena involving an interplay of internal stress relaxations and perturbation-induced intermittent avalanches. 

The organization of plasmonic nanoparticles (NPs) determines the strength and polarization dependence of coupling of their surface plasmons. In this study, plasmon coupling of spherical Au NPs with an average diameter of 15 nm was investigated in shape-memory polymer films before and after mechanical stretching and then after thermally driving shape recovery. Clusters of Au NPs form when preparing the films that exhibit strong plasmon coupling. During stretching, a significant polarization-dependent response develops, where the optical extinction maximum corresponding to the surface plasmon resonance is redshifted by 19 nm and blueshifted by 7 nm for polarization parallel and perpendicular to the stretching direction, respectively. This result can be explained by non-uniform stretching on the nanoscale, where plasmon coupling increases parallel to the shear direction as Au NPs are pulled into each other during stretching. The polarization dependence vanishes after shape recovery, and structural characterization confirms the return of isotropy consistent with complete nanoscale recovery of the initial arrangement of Au NPs. Simulations of the polarized optical responses of Au NP dimers at different interparticle spacings establish a plasmon ruler for estimating the average interparticle spacings within the experimental samples. An investigation of the temperature-dependent recovery behavior demonstrates an application of these materials as optical thermal history sensors. 

New materials are advancing the field of soft robotics. Composite films of magnetic iron microparticles dispersed in a shape memory polymer matrix are demonstrated for reconfigurable, remotely actuated soft robots. The composite films simultaneously respond to magnetic fields and light. Temporary shapes obtained through combined magnetic actuation and photothermal heating can be locked by switching off the light and magnetic field. Subsequent illumination in the absence of the magnetic field drives recovery of the permanent shape. In cantilevers and flowers, multiple cycles of locking and unlocking are demonstrated. Scrolls show that the permanent shape of the film can be programmed, and they can be frozen in intermediate configurations. Bistable snappers can be magnetically and optically actuated, as well as biased, by controlling the permanent shape. Grabbers can pick up and release objects repeatedly. Simulations of combined photothermal heating and magnetic actuation are useful for guiding the design of new devices. 

Plasmonic nanoparticles that can be manipulated with magnetic fields are of interest for advanced optical applications, diagnostics, imaging, and therapy. Alignment of gold nanorods yields strong polarization‐dependent extinction, and use of magnetic fields is appealing because they act through space and can be quickly switched. In this work, cationic polyethyleneimine‐functionalized superparamagnetic Fe₃O₄nanoparticles (NPs) are deposited on the surface of anionic gold nanorods coated with bovine serum albumin. The magnetic gold nanorods (MagGNRs) obtained through mixing maintain the distinct optical properties of plasmonic gold nanorods that are minimally perturbed by the magnetic overcoating. Magnetic alignment of the MagGNRs arising from magnetic dipolar interactions on the anisotropic gold nanorod core is comprehensively characterized, including structural characterization and enhancement (suppression) of the longitudinal surface plasmon resonance and suppression (enhancement) of the transverse surface plasmon resonance for light polarized parallel (orthogonal) to the magnetic field. The MagGNRs can also be driven in rotating magnetic fields to rotate at frequencies of at least 17 Hz. For suitably large gold nanorods (148 nm long) and Fe₃O₄NPs (13.4 nm diameter), significant alignment is possible even in modest (<500 Oe) magnetic fields. An analytical model provides a unified understanding of the magnetic alignment of MagGNRs.

 

Stimulus‐responsive polymers are attractive for microactuators because they can be easily miniaturized and remotely actuated, enabling untethered operation. In this work, magnetic Fe microparticles are dispersed in a thermoplastic polyurethane shape memory polymer matrix and formed into artificial, magnetic cilia by solvent casting within the vertical magnetic field in the gap between two permanent magnets. Interactions of the magnetic moments of the microparticles, aligned by the applied magnetic field, drive self‐assembly of magnetic cilia along the field direction. The resulting magnetic cilia are reconfigurable using light and magnetic fields as remote stimuli. Temporary shapes obtained through combined magnetic actuation and photothermal heating can be locked by switching off the light and magnetic field. Subsequently turning on the light without the magnetic field drives recovery of the permanent shape. The permanent shape can also be reprogrammed after preparing the cilia by applying mechanical constraints and annealing at high temperature. Spatially controlled actuation is demonstrated by applying a mask for optical pattern transfer into the array of magnetic cilia. A theoretical model is developed for predicting the response of shape memory magnetic cilia and elucidates physical mechanisms behind observed phenomena, enabling the design and optimization of ciliary systems for specific applications.