Membranes with uniform, straight nanopores have important applications in diverse fields, but their application is limited by the lack of efficient producing methods with high controllability. In this work, we reported on an extremely simple and efficient strategy to produce such well-defined membranes. We demonstrated that neutral solvents were capable of annealing amphiphilic block copolymer (BCP) films of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) with thicknesses up to 600 nm to the perpendicular orientation within 1 min. Annealing in neutral solvents was also effective to the perpendicular alignment of block copolymers with very high molecular weights, e.g., 362 000 Da. Remarkably, simply by immersing the annealed BCP films in hot ethanol followed by drying in air, the originally dense BCP films were nondestructively converted into porous membranes containing highly ordered, straight nanopores traversing the entire thickness of the membrane (up to 1.1 μm). Grazing incident small-angle X-ray spectroscopy confirmed the hexagonal ordering of the nanopores over large areas. We found that the overflow of P2VP chains from their reservoir P2VP cylinders and the deformation of the PS matrix in the swelling process contributed to the transformation of the solid P2VP cylinders to empty straight pores. The pore diameters can be tuned by either changing the swelling temperatures or depositing thin layers of metal oxides on the preformed membranes via atomic layer deposition with a subnanometer accuracy. To demonstrate the application of the obtained porous membranes, we used them as templates and produced centimeter-scale arrays of aligned nanotubes of metal oxides with finely tunable wall thicknesses.
Stimuli-responsive color-changing
hydrogels, commonly colored using
embedded photonic crystals (PCs), have potential applications ranging
from chemical sensing to camouflage and anti-counterfeiting. A major
limitation in these PC hydrogels is that they require significant
deformation (>20%) in order to change the PC lattice constant and
generate an observable chromatic shift (∼100 nm). By analyzing
the mechanism of how chameleon skin changes color, we developed a
strain-accommodating smart skin (SASS), which maintains near-constant
size during chromatic shifting. SASS is composed of two types of hydrogels:
a stimuli-responsive, PC-containing hydrogel that is patterned within
a second hydrogel with robust mechanical properties, which permits
strain accommodation. In contrast to conventional “accordion”-type
PC responsive hydrogels, SASS maintains near-constant volume during
chromatic shifting. Importantly, SASS materials are stretchable (strain
∼150%), amenable to patterning, spectrally tunable, and responsive
to both heat and natural sunlight. We demonstrate examples of using
SASS for biomimicry. Our strategy, to embed responsive materials within
a mechanically matched scaffolding polymer, provides a general framework
to guide the future design of artificial smart skins.
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