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We study the assembly and morphology transformation of gold nanorods tethered with polystyrene ligands (AuNRs@PS). The AuNRs@PS nanotubes are first fabricated in the nanopores of anodic aluminum oxide (AAO) templates by the solution wetting method. When the samples are thermally annealed, the Rayleigh-instability-driven transformations of the nanostructures are triggered by the decrease of the interfacial energies between the nanotubes and the inner air cylinders. Four different morphologies are identified: nanotubes (I), undulated structures (II), Rayleigh-instability-induced structures (III), and nanorods (IV). The morphology diagrams of the AuNRs@PS structures using different thermal annealing temperatures and times are also made, showing that the morphology transformation rates are higher at higher annealing temperatures. This work has implications to be applied in different fields such as biomedical applications.

In this work, we study the structure transformations of cylinder-forming polystyrene-block-polydimethylsiloxane (PS31k-b-PDMS14.5k) confined in cylindrical nanopores. PS-b-PDMS nanotubes, nanospheres, and curved nanodiscs are ingeniously prepared by a facile template wetting strategy using anodic aluminum oxide (AAO) templates. Quantitative analyses of the structure transformations from nanospheres to curved nanodiscs are also conducted, showing that the lengths of the curved nanodiscs can be controlled by adjusting the annealing temperature and time. Furthermore, the PDMS domains of the nanostructures can be selectively etched using HF solutions, generating porous PS nanostructures. This work not only offers versatile routes to prepare block copolymer nanostructures with controlled shapes but also provides a deeper understanding of the structure transformation of block copolymers in confined geometries.

Poly(3-hexylthiophene) (P3HT) films have been usually prepared by spin-coating for the applications of electronic devices such as organic photovoltaic devices (OPV) and organic field-effect transistors (OFETs). The wetting and dewetting behaviors of the swollen P3HT films during the spin-coating processes, however, are still poorly understood. In this work, we investigate the dewetting behaviors of P3HT thin films and the formation of ring structures during the spin-coating process by controlling the spin rates and the solution temperatures. Quantitative studies of the dewetting phenomena are conducted by measuring the sizes of the ring structures of the dewetting patterns. It is observed that the sizes of the ring structures are larger at lower spin rates because of the longer dewetting times allowed during the spin-coating processes. More importantly, the dewetting behaviors of the P3HT films are discovered to be affected by the formation of the P3HT nanowhiskers (nanowires). This work offers a deeper u...

We report on a versatile strategy to fabricate shape-controlled polymeric nano-objects with an internal compartmentalized structure by replication from pore-diameter-modulated and interconnected nanoporous anodized aluminum oxide (AAO). The AAO with modulated pore diameters is synthesized in a refined temperature-modulated hard anodization (TMHA) approach, by alternating the flow rate of an air stream cooling the electrolyte. Through pore-widening of the templates with modulated pore diameters, a stable interconnected 3D network with transversal ellipsoidal holes is fabricated as a second template structure. From these unprecedented template structures exhibiting modulated pores and an intricate 3D network structure, shape-controlled polymeric nano-objects are replicated using the melt wetting method with polystyrene homopolymer (PS) and cylinder-forming block copolymer polystyrene-block-polydimethylsiloxane (PS298-b-PDMS195). The replicated nanostructures are separated into individual anisotropically sha...

Over the past few decades, anisotropic polymer particles are of significant interest because of their unique properties which can be applied in various areas, such as drug delivery, biotechnology, and electronics. Most approaches to synthesize anisotropic polymer particles, however, are complicated, and the three-dimensional shapes of the anisotropic particles are usually difficult to be controlled. In this work, we develop a solvent on-film annealing (SOFA) method to fabricate anisotropic polymer particles by studying the morphological evolution of polystyrene (PS) microspheres on poly(methyl methacrylate) (PMMA) films annealed in toluene vapor. At different annealing stages, the isotropic PS microspheres gradually transform to anisotropic PS particles with different morphologies, such as UFO-, cymbal-, peanut-, and bowl-shaped particles. The morphology evolution is driven by the surface and interfacial tensions during the annealing processes and can be confirmed by a selective removal technique. Acetic ...

A feasible processing of zwitterionic polymer-grafted anodic aluminum oxide (AAO) membranes by surface-initiated atom transfer radical polymerization (SI-ATRP) and the geometric effect on the polymer chain growth in the confined nanopores were investigated. A zwitterionic poly(3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate) (PMAPS) brush was produced on an AAO membrane via introduction of an initiator with a phosphonate group and subsequent SI-ATRP. The PMAPS-grafted AAO membranes were characterized by water droplet contact angle measurement, size exclusion chromatography (SEC), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and laser Raman micro-spectroscopy. The linear relationship between the grafting yield (Y) of the PMAPS brush and number-average molecular weight (Mn) of the unbound PMAPS indicates that there is no significant geometric effect on the chain growth under the spatial confinement inside the nanopores with diameters of ∼200 nm. The PMAPS brushes were diminished near the center section along the nanopores because the monomer supply was retarded. The capability of the PMAPS-grafted AAO membranes for inorganic nanoparticle immobilization was also demonstrated using gold nanoparticles (AuNPs) through ion-exchange and reduction processes.

Electrochromic devices (ECDs) play an important role in smart window applications for blocking heat from sunlight. Tungsten trioxide (WO3) is one of the best candidates for making electrochromic films. Current manufacturing processes are, however, costly, have long processing time, and often use non-eco-friendly precursors. Here an alternative facile method integrating electro-exploding wire and spray coating techniques is demonstrated for applications in large size ECDs. The electro-exploding wire technique is used to synthesize WO3 nanomaterials (NMs) in deionized water. The varied size distribution of WO3 NMs is achieved by changing the exploding voltage. The NMs are characterized by X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The exploding voltage of 36 V is selected to generate WO3 NMs in a wide size distribution for making porous WO3 films. Subsequently, spray coating is used to disperse WO3 NM suspension on the ITO/glass substrate to form an electrochromic film. The films are characterized by scanning electron microscopy (SEM) and by cycle voltammetry, chronoamperometry, and chronocoulometry measurements in dilute sulfuric acid. The WO3 NM films prepared at a high exploding voltage and a high substrate temperature present a higher electrochemical stability. Considering porosity and electrochemical stability, WO3 NMs exploded at 36 V are used to prepare WO3 films on substrates heated at 300 °C. The electrochromic WO3 film can be operated for over 1000 cycles. We demonstrate an ECD with an area of 15 × 15 cm2 and propose a way to make large size ECDs with low cost and eco-friendly processes.

To manipulate the functions of nanomaterials more precisely for diverse applications, the controllability and critical influencing factors of their properties must be thoroughly investigated. In this work, the macroscopic and microscopic effects are studied on the photophysical properties of various pyrene-ended poly(styrene-block-methyl methacrylate) nanostructures. Fluorescent polymer nanospheres, nanorods, and nanotubes are prepared by different template-based methods using anodic aluminum oxide membranes. Chain arrangements and conformations are determined as the key factors affecting the photophysical properties of the fluorescent polymer nanostructures. This work not only gives a deeper understanding of the effects on the photophysical properties of polymer nanomaterials influenced by morphologies, chain arrangements, and chain conformations, but also provides a reference for designing proper fluorescent nanostructures for specific applications.

We develop a simple and feasible method to fabricate polymer nanoparticles by annealing polymer films in a uniform environment. Different from the conventional methods, no extra additive or emulsifier is needed in the preparation processes. Poly(methyl methacrylate) (PMMA) films are used as a model system and annealed at elevated temperatures in ethylene glycol, which provides a uniform three-dimensional annealing environment and acts as stabilizers once the nanoparticles are formed. After the annealing process, PMMA nanoparticles with monodisperse diameters are formed. By examining the remaining films after the annealing process, the formation mechanism, which involves surface undulation and detachment of polymer nanoparticles, is proposed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2471–2475

In this work, the authors study the fabrication of three-dimensional block copolymer nanostructures in which the morphologies can be reversibly controlled. Polystyrene-block-polydimethylsiloxane (PS-b-PDMS), a promising candidate for nanolithography, is introduced into cylindrical nanopores of anodic aluminum oxide (AAO) templates using a solvent annealing–induced nanowetting in templates (SAINT) method. Not only the morphologies of the infiltrated PS-b-PDMS nanostructures can be tuned by the annealing solvents, but also the solvent-vapor-controlled morphologies can be altered reversibly by annealing the samples repeatedly between different solvent vapors.

The microphase separation behavior of block copolymers confined in cylindrical nanopores has been extensively investigated. Recently, the solvent-annealing-induced nanowetting in templates (SAINT) method has been demonstrated to be a versatile approach for the infiltration of block copolymers into the nanopores of porous templates. The function of the annealing solvents, however, is still not well understood, especially in the morphology control of the fabricated block copolymer nanostructures. In this work, we elucidate the function of the annealing solvents in the SAINT method using a lamella-forming block copolymer, polystyrene-block-polydimethylsiloxane (PS-b-PDMS), and anodic aluminum oxide (AAO) templates. By changing the composition of the annealing solvents, different morphologies such as the concentric lamellar morphology, the winding cylinder morphology, and the irregular hybrid morphology are observed, mainly caused by the annealing-solvent-induced volume change. The morphology of the block copolymer nanostructures can be further confirmed using an HF solution to remove the PDMS domain selectively.

We develop a novel route based on the solution wetting method using anodic aluminum oxide (AAO) templates to fabricate hierarchical hybrid nanostructures assembled from polystyrene-encapsulated gold nanoparticles (Au@PS NPs). Hybrid nanostructures including nanotubes and nanospheres can be reliably prepared, in which the spatial arrangement of the Au@PS NPs is determined by the pore diameters of the templates and the molecular weights of the thiol-ended polystyrene (PS-SH) ligands. In particular, the Rayleigh-instability-driven transformation plays a key role in the formation of the hybrid nanospheres.

Amphiphilic block copolymer micelles have been intensively investigated and applied into various research fields for decades. One of the most promising characteristics for block copolymer micelles is the selective incorporation of metal precursors in the cores or coronas of the micelles. By combining with nanoporous membranes, aligned polymer nanostructures can be generated, facilitating the applications such as nanolithography and catalysis. The morphology transitions and controllability of block copolymer micelles in confined geometries, however, have seldom been studied. In addition, for hybrid micelles in which polymer segments are selectively incorporated with inorganic metal precursors, the relationship between hybridization and morphologies of polymer nanostructures in the confined states is still under discussion. In this work, we investigate the effects of annealing solvents and hybridization with metal precursors (gold(III) chloride trihydrate (HAuCl4 · 3H2O)) on the morphologies of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer micelles confined in the nanopores of anodic aluminum oxide (AAO) templates. Tuned by the annealing solvent vapors and the selective ion complexation between HAuCl4 and P4VP cores, various morphologies can be effectively controlled, such as the spherical-micelles-in-rod morphology, the parallel-cylinders-in-rod morphology, and the hemispherical-micelles-in-rod morphology. This study not only investigates the effects of annealing solvent vapors and hybridization on the morphologies of block copolymer micelles confined in cylindrical nano-geometries but also offers a viable route for preparing metal nanoparticles embedded in porous templates.

Block copolymers have attracted great attention because of their abilities to self-assemble into well-ordered microphase-separated structures. To generate nanopatterns of block copolymers with long-range ordering and low-defect densities in shorter time scales, microwave annealing has recently been applied. Microwave annealing, however, has so far only been used for block copolymer bulks and thin films. In this work, we discover that microwave annealing can be successfully applied to three-dimensional block copolymer nanostructures by studying the infiltration and microphase separation of block copolymers in cylindrical nanopores upon microwave irradiation. Cylinder-forming and lamella-forming poly(styrene-block-dimethylsiloxane) (PS-b-PDMS) are introduced into the nanopores of anodic aluminum oxide (AAO) templates. In addition, AAO templates with different pore sizes are used to study the effect of the commensurabilities between the pore diameters and the repeating periods of the block copolymers on the morphologies of the block copolymer nanostructures.

Block copolymers have been widely studied over the last few decades because of their ability to self-assemble into well-ordered nanoscale structures. Here, we present a novel approach to fabricate nanostructures using block copolymer thin films as three-dimensional nanomasks. Polystyrene-block-polydimethylsiloxane (PS- b -PDMS) are coated in the nanopores of anodic aluminum oxide (AAO) templates via solvent-vapor induced wetting. The morphologies of the block copolymer thin films coated on the nanopores are controlled by the annealing solvents. The PDMS domains of the coated PS- b -PDMS thin films can then be etched selectively using HF solutions, and the patterns of the block copolymers can be transferred to the nanopore walls.

Block copolymer micelles have been extensively discussed for many decades because of their applications, such as lithography and drug delivery. However, controlling the morphologies of nanostructure assembly using block copolymer micelles as building elements remains a great challenge. In this work, we developed a novel route to induce micelle assembly in confined geometries. Polystyrene-block-polydimethylsiloxane (PS-b-PDMS) micelle solutions were used to prepare micelle nanostructures, and the critical parameters affecting the morphologies were determined. Micelle nanorods, micelle nanospheres, and multi-component nanopeapods were prepared by wetting anodic aluminum oxide (AAO) templates with micelle solutions. Rayleigh-instability-driven transformation was discovered to play an important role in controlling the morphologies of the micelle nanostructures. This study not only proposes a versatile approach to preparing block copolymer micelle nanostructures, but it also provides deeper insight into the controlling factors of block copolymer micelle morphologies in cylindrical confinement.

The microphase separation of block copolymers in confined geometries has been widely investigated over the last few decades. The controllability and versatility of the confinement-induced morphologies, however, are still difficult to be achieved because of the limited experimental parameters in the process of fabricating the confined nanostructures. In this work, we study the morphology transitions of lamellae-forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS) nanorods confined in the nanopores of anodic aluminum oxide (AAO) templates. The nanorods are formed by solvent-assisted template wetting, and the morphologies are compared to those in the bulk state. By blending PS-b-PDMS with homopolystyrene (hPS), the morphologies of the nanorods can be controlled because of the changes of the effective volume fractions. Special morphology transitions from concentric lamellar morphology, to multihelical morphology, and finally to spherical-like morphology are observed by increasing the weight ratios of hPS. hPS with different molecular weights is also applied to investigate the effect of hPS on the morphologies of the PS-b-PDMS/hPS blend nanostructures. The unusual morphologies are further confirmed by a selective removal process, which also generates nanochannels for possible refilling with functional materials.

Anisotropic polymer particles such as Janus particles have attracted significant attention in recent years because of their unique properties and unusual self-assembly behavior. Most anisotropic polymer particles synthesized so far, however, only have different chemical regions compartmentalized on the particles. It remains a great challenge to fabricate anisotropic polymer particles with different shapes within a single particle. A novel approach is developed to prepare anisotropic polymer particles that contain two hemispheres with different curvatures by annealing polystyrene microspheres on poly(vinyl alcohol) films. During the annealing process, the polymer microspheres gradually sink into the polymer films and transform to asymmetric polymer particles, driven by the surface and interfacial tensions of the polymers. Selective removal techniques are also used to confirm the morphologies of the asymmetric particles.

Summary Objectives The structural stability and adhesive strength of a large-cavity premolar with a CEREC restoration is a frequent problem in long-term use. This study sought to determine whether an additional reinforced slot could increase tooth/ceramic retention using finite element (FE) analysis and fracture testing. Methods The cavity was designed in a typical MODL restoration failure shape when the lingual cusp has been lost. Two FE restored-tooth models with different cavity designs were created using image processing, contour stacking, and mesh generation. Interfacial (normal and shear) stresses were then calculated with and without the slot design for restored teeth under lateral and axial forces and different interfacial conditions (bonded and de-bonding). For validation, a fracture experiment was performed with and without reinforced slot designs for large ceramic CEREC restorations. Results The maximum stresses at the buccal wall increased when a lateral occlusal force acted on the restored tooth with a slot design. Conversely, the interfacial stresses decreased when the restored tooth received a uniform axial occlusal force. After de-bonding on the buccal tooth/ceramic interface, the stresses increased by an average factor of three over those obtained with a bonded interface. The fracture forces were consistent with the tendencies predicted in FE analyses. Conclusions An additional reinforced slot for the CEREC restoration of a large cavity could increase retention when a restored tooth receives an axial occlusal load. However, the benefits of a slot seem to be doubtful for a premolar often subjected to a lateral load.