Using Torsion for Controllable Reconfiguration of Binary Nanoparticle Networks.

Mechanical deformation can potentially provide an effective means of controlling the nanoscale morphology in hybrid materials. The challenge, however, is establishing optimal couplings of the deformation and mechano-responsive components in the material to achieve nanoscopic structural reorganization without causing catastrophic damage. Through computational modeling, we investigate how torsion can be utilized to induce controllable structural changes in networks formed from binary mixtures (A and B) of polymer-grafted nanoparticles (PGNs). The nanoparticles' rigid cores are decorated with a corona of grafted polymers, which contain reactive functional groups at the chain ends. With the overlap of the neighboring coronas, these reactive groups form labile bonds, which can reform after breakage. The labile bond energy between similar PGNs (UAA, UBB) is different than the energy between dissimilar species (UAB). By tailoring the relative values of these bond energies and the boundary conditions acting on the system, the application of a torsional deformation can result in a controllable reconfiguration of the network, leading to intertwining helical structures, or homogeneously mixed nanocomposites. In effect, our mechano-mutable system resembles a "Rubik's cube" material, whose nanostructure, and hence global properties, can be tailored by mechanically twisting the sample.

The role of curvature anisotropy in the ordering of spheres on an ellipsoid.

Non-spherical emulsion droplets can be stabilized by densely packed colloidal particles adsorbed at their surface. In order to understand the microstructure of these surface packings, the ordering of hard spheres on ellipsoidal surfaces is determined through large scale computer simulations. Defects in the packing are shown generically to occur most often in regions of strong curvature; however, the relationship between defects and curvature is nontrivial, and the distribution of defects shows secondary maxima for ellipsoids of sufficiently high aspect ratio. As with packings on spherical surfaces, additional defects beyond those required by topology are observed as chains or "scars". The transition point, however, is found to be softened by the anisotropic curvature which also partially orients the scars. A rich library of symmetric commensurate packings are identified for low particle number. We verify experimentally that ellipsoidal droplets of varying aspect ratio can be arrested by surface-adsorbed colloids.

Simulating defect textures on relaxing nematic shells.

Two nematic shells brought in contact coalesce in order to reduce their combined interfacial tension, and, following this topological transition, relax to an equilibrium state. In this work, we study the defect textures as the combined shell shape evolves. By varying the sizes of the shells, we perform a quasistatic investigation of the director field and the defect valence on the doublet. Regimes are found where positive and negative defects exist due to the large negative Gaussian curvature at the neck. Using large-scale computer simulations, we determine how annihilating defect pairs on coalescing shells are selected and the stage of coalescence at which annihilation occurs.

Shape and chirality transitions in off-axis twist nematic elastomer ribbons.

Using both experiments and finite element simulations, we explore the shape evolution of off-axis twist nematic elastomer ribbons as a function of temperature. The elastomers are prepared by cross-linking the mesogens with planar anchoring of the director at top and bottom surfaces with a 90° left-handed twist. Shape evolution depends sensitively on the off-axis director orientation at the sample midplane. Both experiments and theoretical studies show that when the director at midplane is parallel to either the ribbon's long or short axes, ribbons form either helicoids or spirals depending on aspect ratio and temperature. Simulation studies show that if the director at midplane is off-axis, ribbons never form helicoids, instead evolving to distorted spiral shapes. Experimental studies for two samples with off-axis geometry show agreement with this prediction. Samples in all these geometries show a remarkable transition from right- to left-handed chiral shapes on change of temperature. Simulations predict off-axis samples also change their macroscopic chirality at fixed temperature, depending on the angular offset. These results provide insight into the mechanisms driving shape evolution and macroscopic chirality, enabling engineering design of these materials for future applications.

Frustrated order on extrinsic geometries.

We study, numerically and theoretically, defects in an anisotropic liquid that couple to the extrinsic geometry of a surface. Though the intrinsic geometry tends to confine topological defects to regions of large Gaussian curvature, extrinsic couplings tend to orient the order along the local direction of maximum or minimum bending. This additional frustration is generically unavoidable, and leads to complex ground-state thermodynamics. Using the catenoid as a prototype, we show, in contradistinction to the well-known effects of intrinsic geometry, that extrinsic curvature expels disclinations from the region of maximum curvature above a critical coupling threshold. On catenoids lacking an "inside-outside" symmetry, defects are expelled altogether above a critical neck size.

Modeling elastic instabilities in nematic elastomers.

Liquid crystal elastomers are cross-linked polymer networks covalently bonded with liquid crystal mesogens. In the nematic phase, due to strong coupling between mechanical strain and orientational order, these materials display strain-induced instabilities associated with formation and evolution of orientational domains. Using a three-dimensional finite element elastodynamics simulation, we investigate one such instability, the onset of stripe formation in a monodomain film stretched along an axis perpendicular to the nematic director. In our simulation, we observe the formation of striped domains with alternating director rotation. This model allows us to explore the fundamental physics governing dynamic mechanical response of nematic elastomers and also provides a potentially useful computational tool for engineering device applications.