Manipulating Semicrystalline Polymers in Confinement

Because final properties of nanoscale polymeric structures are largely determined by the solid-state microstructure of the confined polymer, it is imperative not only to understand how the microstructure of polymers develops under nanoscale confinement but also to establish means to manipulate it. Here we present a series of processing strategies, adapted from methods used in bulk polymer processing, that allow to control the solidification of polymer nanostructures. Firstly, we show that supramolecular nucleating agents can be readily used to modify the crystallization kinetics of confined poly(vinylidene fluoride) (PVDF). In addition, we demonstrate that microstructural features that are not traditionally affected by nucleating agents, such as the orientation of crystals, can be tuned with the crystallization temperature applied. Interestingly, we also show that high crystallization temperatures and long annealing periods induce the formation of the modification of PVDF, hence enabling the simple production of ferro/piezoelectric nanostructures. We anticipate that the approaches presented here can open up a plethora of new possibilities for the processing of polymer-based nanostructures with tailored properties and functionalities

Evidence for hand-size constancy:the dominant hand as a natural perceptual metric

The hand is a reliable and ecologically useful perceptual ruler that can be used to scale the sizes of close, manipulatable objects in the world in a manner similar to the way in which eye height is used to scale the heights of objects on the ground plane. Certain objects are perceived proportionally to the size of the hand, and as a result, changes in the relationship between the sizes of objects in the world and the size of the hand are attributed to changes in object size rather than hand size. To illustrate this notion, we provide evidence from several experiments showing that people perceive their dominant hand as less magnified than other body parts or objects when these items are subjected to the same degree of magnification. These findings suggest that the hand is perceived as having a more constant size and, consequently, can serve as a reliable metric with which to measure objects of commensurate size

Honeycombs in Honeycombs: Complex Liquid Crystal Alumina Composite Mesostructures

Small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM) were used to study orientation patterns of two polyphilic liquid crystals (LC) confined to cylindrical pores of anodic aluminum oxide (AAO). The hierarchical hybrid systems had the LC honeycomb (lattice parameter 3.5–4 nm) inside the pores of the AAO honeycomb (diameters 60 and 400 nm). By conducting complete reciprocal space mapping using SAXS, we conclude that the columns of both compounds align in planes normal to the AAO pore axis, with a specific crystallographic direction of the LC lattice aligning strictly parallel to the pore axis. AFM of LC-containing AAO fracture surfaces further revealed that the columns of the planar anchoring LC (compound <b>1</b>) formed concentric circles in the plane normal to the pore axis near the AAO wall. Toward the pore center, the circles become anisometric “racetrack” loops consisting of two straight segments and two semicircles. This mode compensates for slight ellipticity of the pore cross section. Indications are, however, that for perfectly circular pores, circular shape is maintained right to the center of the pore, the radius coming down to the size of a molecule. For the homeotropically anchoring compound <b>2</b>, the columns are to the most part straight and parallel to each other, arranged in layers normal to the AAO pore axis, like logs in an ordered pile. Only near the pore wall the columns splay somewhat. In both cases, columns are confined to layers strictly perpendicular to the AAO pore axis, and there is no sign of escape to the third dimension or of axial orientation, the latter having been reported previously for some discotic LCs. The main cause of the two new LC configurations, the “racetrack” and the “logpile”, and of their difference from those of confined nematic LC, is the very high splay energy and low bend energy of columnar phases