We present soft, layered nanocomposites that exhibit controlled swelling anisotropy and spatially specific shape reconfigurations in response to light irradiation. The use of gold nanoparticles grafted with a temperature-responsive polymer (poly(N-isopropylacrylamide), PNIPAM) with layer-by-layer (LbL) assembly allowed placement of plasmonic structures within specific regions in the film, while exposure to light caused localized material deswelling by a photothermal mechanism. By layering PNIPAM-grafted gold nanoparticles in between nonresponsive polymer stacks, we have achieved zero Poisson's ratio materials that exhibit reversible, light-induced unidirectional shape changes. In addition, we report rheological properties of these LbL assemblies in their equilibrium swollen states. Moreover, incorporation of dissimilar plasmonic nanostructures (solid gold nanoparticles and nanoshells) within different material strata enabled controlled shrinkage of specific regions of hydrogels at specific excitation wavelengths. The approach is applicable to a wide range of metal nanoparticles and temperature-responsive polymers and affords many advanced build-in options useful in optically manipulated functional devices, including precise control of plasmonic layer thickness, tunability of shape variations to the excitation wavelength, and programmable spatial control of optical response.
We compare the rheological behavior of three classes of polymer nanocomposites (PNCs) to understand the role of particle shape and interactions on mechanical reinforcement. The first two correspond to favorably interacting composites formed by mixing poly(2-vinylpyridine) with either fumed silica nanoparticles (NPs) or colloidal spherical silica NPs. We show that fumed silica NPs readily form a percolated network at low NP volume fractions. We deduce that the NPs act as network junctions with the effectively irreversibly bound polymer chains serving as the connecting bridges. By comparing with colloidal spherical silica, which has a significantly higher percolation threshold, we conclude that the fractal shape of the fumed silica is responsible for its unusually low percolation threshold. The third system corresponds to polystyrene grafted colloidal silica nanoparticles (PGNPs) in a polystyrene matrix. These PNCs have an even lower percolation threshold probably because the grafted chains increase the effective volume fraction of the NPs. When we take these different thickness of the polymer layers in the two cases into account (i.e., grafted layer vs adsorbed layer thickness), the percolation threshold for the fumed and the grafted system occurs at similar effective loadings, but the NP network with fumed silica has a higher low-frequency plateau modulus than that formed with the PGNPs. These findings can be reconciled by the fact that the fumed silica NPs are composed of fused entities, thus ensuring that they have a higher modulus than the PGNPs where the modulus is largely attributed to interactions between the grafts. Our results systematically stress the important role of the nanofiller shape and connectivity on the mechanical reinforcement of PNCs.
Dynamics of the interphase region between matrix and bound polymers on nanoparticles is important to understand the macroscopic rheological properties of nanocomposites. Here, we present neutron scattering investigations on nanocomposites with dynamically asymmetric interphases formed by a high-glass transition temperature polymer, poly(methyl methacrylate), adsorbed on nanoparticles and a low-glass transition temperature miscible matrix, poly(ethylene oxide). By taking advantage of selective isotope labeling of the chains, we studied the role of interfacial polymer on segmental and collective dynamics of the matrix chains from subnanoseconds to 100 nanoseconds. Our results show that the Rouse relaxation remains unchanged in a weakly attractive composite system while the dynamics significantly slows down in a strongly attractive composite. More importantly, the chains disentangle with a remarkable increase of the reptation tube size when the bound polymer is vitreous. The glassy and rubbery states of the bound polymer as temperature changes underpin the macroscopic stiffening of nanocomposites.
Dynamic mechanical response in responsive and adaptive composites can be achieved either through the responsive polymer; with the chemical regulators affecting the bonding between fillers or through reversible covalent bonding. Tuning the interfaces between fillers and polymer matrix potentially plays a critical role in all these systems to enhance their adaptive responses. Here, we present that the bonding–debonding of chains on nanoparticles can be modulated under extensive periodic strains. Mechanical response of an attractive model polymer composite, poly(methyl methacrylate) filled with silica nanoparticles, is monitored in a series of deformation–resting experiments allowing us to tune the interfacial strength of polymer. Chains that are desorbed from the surface with the oscillatory shear entangle with the free chains during the rest time. We show that periodic deformation process results in unusual stiffening of composites. Mechanical response during the recovery reveals this behavior arising from the enhancement in the entanglement of chains at interfaces. The interfacial hardening can be used in designing polymer composites with stress-sensitive interfaces to achieve new repair mechanisms for biomedical applications, and also in energy absorbing reinforced systems.
Using x-ray photon correlation spectroscopy, we examined the slow nanoscale motion of silica nanoparticles individually dispersed in an entangled poly (ethylene oxide) melt at particle volume fractions up to 42%. The nanoparticles, therefore, serve as both fillers for the resulting attractive polymer nanocomposites and probes for the network dynamics therein. The results show that the particle relaxation closely follows the mechanical reinforcement in the nanocomposites only at the intermediate concentrations below the critical value for the chain confinement. Quite unexpectedly, the relaxation time of the particles does not further slow down at higher volume fractions-when all chains are practically on the nanoparticle interface-and decouples from the elastic modulus of the nanocomposites that further increases orders of magnitude.
Nanoparticles functionalized with long polymer chains at low graft density are interesting systems to study structure−dynamic relationships in polymer nanocomposites since they are shown to aggregate into strings in both solution and melts and also into spheres and branched aggregates in the presence of free polymer chains. This work investigates structure and entanglement effects in composites of polystyrene-grafted iron oxide nanoparticles by measuring particle relaxations using X-ray photon correlation spectroscopy. Particles within highly ordered strings and aggregated systems experience a dynamically heterogeneous environment displaying hyperdiffusive relaxation commonly observed in jammed soft glassy systems. Furthermore, particle dynamics is diffusive for branched aggregated structures which could be caused by less penetration of long matrix chains into brushes. These results suggest that particle motion is dictated by the strong interactions of chains grafted at low density with the host matrix polymer.
Poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) have attracted much interest due to their high ionic conductivity resulting from inherently fast segmental dynamics and high salt solubility, yet they lack mechanical stability in their neat form. Blending PEO with another rigid, or high glass transition temperature, polymer is a versatile way to improve the mechanical stability; however, the ionic conductivity is strongly reduced due to slower segmental dynamics of highly interpenetrating linear polymer chains. In this work, we used model PEO/PMMA blend systems prepared with various well-defined PEO architectures (linear, stars, hyperbranched, and bottlebrushes) doped with lithium bis(trifluoromethane-sulfonyl)-imide (LiTFSI) and investigated, for the first time, the role of macromolecular architecture of PEO on crystallization, segmental dynamics, and ionic conductivity in the blends and electrolytes. The results suggest that room-temperature miscibility of these polymers can be dramatically extended by using nonlinear PEO in the blends instead of linear chains, which crystallize above 35 wt %. The broadband dielectric spectroscopy results revealed enhanced decoupling of PMMA and PEO segmental dynamics in compact branched architectures, which helps to achieve faster segmental motion of star PEO in glassy PMMA. This manifests as nearly three-fold higher ionic conductivity in these nonlinear blends compared to the conventional linear PEO/PMMA system. Regardless of the PEO architectures, the temperature dependence of ionic conductivity blends with PMMA and LiTFSI is well defined using the Vogel–Fulcher–Tammann mechanism, suggesting that ion transport is mainly affected by the segmental motion. The activation energy values decrease with the increasing ionic conductivity. Overall, our results show that macromolecular architecture can be a tool to decouple segmental dynamics and ion mobility to rationally design SPEs with improved performance.
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