Dewetting of polymer thin films on modified curved surfaces: preparation of polymer nanoparticles with asymmetric shapes by anodic aluminum oxide templates.

We study the dewetting behaviors of poly(methyl methacrylate) (PMMA) thin films coated in the cylindrical nanopores of anodic aluminum oxide (AAO) templates by thermal annealing. Self-assembled monolayers (SAMs) of n-octadecyltrichlorosilane (ODTS) are introduced to modify the pore surfaces of the AAO templates to induce the dewetting process. By using scanning electron microscopy (SEM), the dewetting-induced morphology transformation from the PMMA thin films to PMMA nanoparticles with asymmetric shapes can be observed. The sizes of the PMMA nanoparticles can be controlled by the original PMMA solution concentrations. The dewetting phenomena on the modified nanopores are explained by taking into account the excess intermolecular interaction free energy (ΔG). This work opens a new possibility for creating polymer nanoparticles with asymmetric shapes in confined geometries.

Fabrication of multicomponent polymer nanostructures containing PMMA shells and encapsulated PS nanospheres in the nanopores of anodic aluminum oxide templates.

Multi-component polymer nanomaterials have attracted great attention because of their applications in areas such as biomedicine, tissue engineering, and organic solar cells. The precise control over the morphologies of multi-component polymer nanomaterials, however, is still a great challenge. In this work, the fabrication of poly(methyl methacrylate)(PMMA)/poly-styrene (PS) nanostructures that contain PMMA shells and encapsulated PS nanospheres is studied. The nanostructures are prepared using a triple solution wetting method with anodic aluminum oxide (AAO) templates. The nanopores of the templates are wetted sequentially by PS solutions in dimethylformamide (DMF), PMMA solutions in acetic acid, and water. The compositions and morphologies of the nanostructures are controlled by the interactions between the polymers, solvents, and AAO walls. This work not only presents a feasible method to prepare multi-component polymer nanomaterials, but also leads to a better understanding of polymer-solvent interactions in confined geometries.

Fabrication of Core-Shell Polymer Nanospheres in the Nanopores of Anodic Aluminum Oxide Templates Using Polymer Blend Solutions.

Spherical core-shell structures have been widely investigated in recent years, and they can be used for various applications, such as drug delivery, biological labeling, and batteries. Although many methods have been developed to prepare core-shell structures, it is still a great challenge to fabricate core-shell structures in the nanoscale with well-controlled morphologies and sizes. In this work, we present a simple method to fabricate core-shell polymer nanospheres consisting of polystyrene (PS) cores and poly(methyl methacrylate) (PMMA) shells. The nanostructures are prepared by a solution-based template wetting method. After the nanopores of anodic aluminum oxide (AAO) templates are wetted sequentially by PS/PMMA blend solutions and water, the core-shell nanostructures can be formed. The formation process is related to the Rayleigh-instability-type transformation. Selective removal techniques are also used to confirm the morphologies of the core-shell nanostructures.

Three-dimensional block copolymer nanostructures by the solvent-annealing-induced wetting in anodic aluminum oxide templates.

Block copolymers have been extensively studied over the last few decades because they can self-assemble into well-ordered nanoscale structures. The morphologies of block copolymers in confined geometries, however, are still not fully understood. In this work, the fabrication and morphologies of three-dimensional polystyrene-block-polydimethylsiloxane (PS-b-PDMS) nanostructures confined in the nanopores of anodic aluminum oxide (AAO) templates are studied. It is discovered that the block copolymers can wet the nanopores using a novel solvent-annealing-induced nanowetting in templates (SAINT) method. The unique advantage of this method is that the problem of thermal degradation can be avoided. In addition, the morphologies of PS-b-PDMS nanostructures can be controlled by changing the wetting conditions. Different solvents are used as the annealing solvent, including toluene, hexane, and a co-solvent of toluene and hexane. When the block copolymer wets the nanopores in toluene vapors, a perpendicular morphology is observed. When the block copolymer wets the nanopores in co-solvent vapors (toluene/hexane = 3:2), unusual circular and helical morphologies are obtained. These three-dimensional nanostructures can serve as naontemplates for refilling with other functional materials, such as Au, Ag, ZnO, and TiO2 .

Curved polymer nanodiscs by wetting nanopores of anodic aluminum oxide templates with polymer nanospheres.

Although nanostructures with diverse morphologies have been fabricated, it is still a great challenge to prepare anisotropic two-dimensional (2-D) nanostructures, especially non-planar disc-like nanostructures. In this work, we develop a simple method to prepare curved polymer nanodiscs with regular sizes by wetting polymer nanospheres in the nanopores of anodic aluminum oxide (AAO) templates. Polystyrene (PS) nanospheres are first fabricated by using a non-solvent-assisted template wetting method. By annealing the PS nanospheres in the nanopores of AAO templates, curved PS nanodiscs can be produced. The length and morphology of the curved PS nanodiscs can be controlled by the wetting conditions such as the annealing temperatures and times. For some stacked nanospheres, the annealing process can result in the formation of helix-like nanostructures. To demonstrate the universality of this work, this approach is also applied to poly(methyl methacrylate) (PMMA), another common polymer, and similar results are obtained.

Porous polymer nanostructures fabricated by the surface-induced phase separation of polymer solutions in anodic aluminum oxide templates.

We study the formation of porous polymer nanostructures fabricated by the surface-induced phase separation of polymer solutions in anodic aluminum oxide (AAO) templates. Poly(methyl methacrylate) (PMMA) and tetrahydrofuran (THF) are used to investigate the evolution process of the surface-induced phase separation. With the longer immersion time of the AAO template in the polymer solution, the size of the solvent-rich droplet is increased by the coarsening process, resulting in the formation of porous polymer nanostructures. The coarsening mechanism is further evaluated by changing the experimental parameters including the immersion time, the polymer concentration, the polymer molecular weight, and the solvent quality. Under conditions in which polymer solutions have higher viscosities, the coarsening process is slowed down and the formation of the porous nanostructures is prohibited. The prevention of the porous nanostructures can also be realized by adding water to the PMMA/THF solution before the immersion process.