Templated nanostructured PS‐b‐PEO nanotubes

With anodic aluminum oxide (AAO) membranes as wetting templates, nanotubes of the cylinder‐forming polystyrene‐block‐poly(ethylene oxide) (PS‐b‐PEO) copolymer were generated. The PS‐b‐PEO solution was introduced into the cylindrical nanopores of an AAO membrane by capillary force and polymeric nanotubes formed after solvent evaporation. Because of the water solubility of the cylindrical PEO microdomains and the orientation of the cylindrical PEO microdomains with respect to the nanotube walls, the nanotubes were permeable to aqueous media. PS‐b‐PEO nanotubes were also prepared on the interior walls of amorphous carbon nanotubes (a‐CNTs). Because of the unique water permeability of the PEO microdomains, an avenue for functionalizing the interior of the a‐CNTs is enabled. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2912–2917, 2007     

Wettability transition induced transformation and entrapment of polymer nanostructures in cylindrical nanopores

We apply the concept of wettability transition to manipulate the morphology and entrapment of polymer nanostructures inside cylindrical nanopores of anodic aluminum oxide (AAO) membranes. When AAO/polystyrene (PS) hybrids, i.e., AAO/PS nanorods or AAO/PS nanotubes, are immersed into a polyethylene glycol (PEG) reservoir above the glass transition temperature of PS, a wettability transition from wetting to nonwetting of PS can be triggered due to the invasion of the more wettable PEG melt. The wettability transition enables us to develop a nondestructive method to entrap hemispherically capped nanorods inside nanopores. Moreover, we can obtain single nanorods with the desired aspect ratio by further dissolving the AAO template, in contrast to the drawbacks of nonuniformity or destructiveness from the conventional ultrasonication method. In the case of AAO/PS nanotubes, the wettability transition induced dewetting of PS nanotube walls results in the disconnection and entrapment of nonwetting PS domains (i.e., nanospheres, nanocapsules, or capped nanorods). Moreover, PEG is then washed to recover the pristine wettability of PS on the alumina surface; further annealing of the PS nanospheres inside AAO nanopores under vacuum can generate some unique nanostructures, particularly semicylindrical nanorods.     

Nanoporous structured submicrometer carbon fibers prepared via solution electrospinning of polymer blends

A facile means for obtaining submicrometer carbon fibers with a nanoporous structure is presented. A mixture of polyacrylonitrile (PAN) and a copolymer of acrylonitrile and methyl methacrylate (poly(AN-co-MMA)) in dimethylformamide was electrospun into submicrometer fibers with a microphase-separated structure. During the followed oxidation process, the copolymer domains were pyrolyzed, resulting in a nanoporous structure that was preserved after carbonization. The microphase-separated structure of the PAN/poly(AN-co-MMA) electrospun fibers, the morphology, and porous structure of both the oxidized and the carbonized fibers were observed with scanning electron microscopy and transmission electron microscopy. The carbon fibers have diameters ranging from several hundred nanometers to about 1 microm. The nanopores or nanoslits throughout the fiber surface and interior with diameters of several tens of nanometers are interconnected and oriented along the longitudinal axis of the fibers. This unique nanoporous morphology similar to the microphase-separated structure in the PAN/poly(AN-co-MMA) fibers is attributed to the rapid phase separation, solidification, as well as the stretching of the fibers during electrospinning. The pore volume and pore size distribution of the carbonized fibers were investigated by nitrogen adsorption and desorption.     

New nanotube synthesis strategy--application of sodium nanotubes formed inside anodic aluminium oxide as a reactive template

Formation of Na nanotubes inside the channels of anodic aluminium oxide (AAO) membranes has been achieved by decomposing NaH thermally on AAO. The as-produced material, Na@AAO, is applied as a reactive template to prepare other tubular materials. Reacting Na@AAO with gaseous C6Cl6 generates carbon nanotubes (ca. 250 nm, wall thickness of 20 nm, tube length of 60 microm) inside the AAO channels. Highly aligned bundles of nearly amorphous carbon nanotubes are isolated after AAO is removed.     

Electrochemically active nitrogen-enriched nanocarbons with well-defined morphology synthesized by pyrolysis of self-assembled block copolymer

Novel nanoporous nitrogen-enriched carbon materials were prepared through a simple carbonization procedure of well-defined block copolymer precursors containing the source of carbon, i.e., polyacrylonitrile (PAN), and a sacrificial block, i.e., poly(n-butyl acrylate) (PBA). The preparation of nitrogen-enriched nanocarbons with hierarchical pore structure was enabled by the high fidelity preservation of the initial phase-separated nanostructure between two polymer blocks upon carbonization. Supercapacitors fabricated from the prepared carbons exhibited unusually high capacitance per unit surface area (>30 μF/cm(2)) which was attributed to the pseudocapacitance resulting from the high nitrogen content originating from the PAN precursor. Electrochemical availability of the nitrogen species was also evident from the results of oxygen reduction experiments. The hierarchical pore structure and the high nitrogen content in such materials make them particularly promising for use in supercapacitor and electrocatalyst applications.     

Carbohydrates as Additives for the Formation of Isoporous PS‐b‐P4VP Diblock Copolymer Membranes

Highly porous polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) diblock copolymer membranes are prepared using carbohydrates as additives. Therefore α‐cyclodextrine, α‐(D )‐glucose, and saccharose (cane sugar) are tested for the membrane formation of three different PS‐b‐P4VP polymers. The addition of the carbohydrates leads to an increasing viscosity of the membrane solutions due to hydrogen bonding between hydroxyl groups of the carbohydrates and pyridine units of the block copolymer. In all cases, the membranes made from solution with carbohydrates have higher porosity, an improved narrow pore distribution on the surface and a higher water flux as membranes made without carbohydrates with the same polymer, solvent ratio, and polymer concentration.     

Effect of Nonsolvent on the Formation of Polymer Nanomaterials in the Nanopores of Anodic Aluminum Oxide Templates

We study the effect of nonsolvent on the formation of polymer nanomaterials in the nanopores of porous templates. Water (nonsolvent) is added into a poly (methyl methacrylate) (PMMA) solution in dimethylformamide (DMF) confined in the nanopores of an anodic aluminum oxide (AAO) template. Water forms a wetting layer on the pore wall and causes the PMMA solution to be isolated in the center of the nanopore, resulting in the formation of PMMA nanospheres or nanorods after the solvent is evaporated. The formation of the polymer nanomaterials induced by nonsolvent is found to be driven by the Rayleigh‐instability‐type transformation. Without adding the nonsolvent, PMMA chains precipitate on the walls of the nanopores after the solvent is evaporated, and PMMA nanotubes are obtained.     

Selective swelling induced pore generation of amphiphilic block copolymers: The role of swelling agents

Swelling of block copolymers by selective solvents has emerged as an extremely simple and efficient process to produce nanoporous materials with well‐controlled porosities. However, the role of the swelling agents in this pore‐making process remains to be elucidated. Here we investigate the evolution of morphology, thickness, and surface chemistry of thin films of polystyrene‐block‐poly (2‐vinyl pyridine) (PS‐b‐P2VP) soaked in a series of alcohols with changing carbon atoms and hydroxyl groups in their molecules. It is found that, in addition to a strong affinity to the dispersed P2VP microdomains, the swelling agents should also have a moderate swelling effect to PS to allow appropriate plastic deformation of the PS matrix. Monohydric alcohols with longer aliphatic chains exhibit stronger ability to induce the pore formation and a remarkable increase in film thickness is associated with the pore formation. High‐carbon alcohols including n‐propanol, n‐butanol, and n‐hexanol produce cylindrical micelles upon prolonged exposure for their strong affinity toward the PS matrix. In contrast, methanol and polyhydric alcohols including glycol and glycerol show very limited effect to swell the copolymer films as their affinity to the PS matrix is low; however, they also evidently induce the surface segregation of P2VP blocks. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 926–933     

Polystyrene-based blend nanorods with gradient composition distribution

The polystyrene-based polymer blends, partially miscible poly(bisphenol A carbonate)/polystyrene (PC/PS) and completely miscible poly(2,6-dimethylphenylene oxide)/polystyrene (PPO/PS), in nanorods with gradient composition distribution were discussed. The polymer blend nanorods were prepared by infiltrating the polymer blends into nanopores of anodic aluminum oxide (AAO) templates via capillary action. Their morphology was investigated by micro-Fourier transform infrared spectroscopy (micro-FTIR) and nano-thermal analysis (nano-TA) with spatial resolution. The composition gradient of polymer blends in the nanopores is governed by the difference of viscosity and miscibility between the two polymers in the blends and the pore diameter. The capillary wetting of porous AAO templates by polymer blends offers a unique method to fabricate functional nanostructured materials with gradient composition distribution for the potential application to nanodevices.     

A facile synthesis of polypyrrole nanotubes using a template-mediated vapor deposition polymerization and the conversion to carbon nanotubes

Polypyrrole (PPy) nanotubes with highly uniform surface and tunable wall thickness were fabricated by one-step vapor deposition polymerization (VDP) using anodic aluminium oxide (AAO) template membranes, and transformed into carbon nanotubes through a carbonization process.     

Ultrathin and Large‐area Macroporous Polymeric Membranes Formed Through Self‐assembly of Sub‐10 nm Elastic Nanoparticles

A variety of sub‐10 nm nanoparticles are successfully prepared by crosslinking of polystyrene‐b‐poly(1,3‐butadiene) (PS‐b‐PB) and polystyrene‐b‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) block copolymer micelles and inverse micelles. Among them, the core‐crosslinked PS‐b‐PB micelles can self‐assemble into ultrathin (< 10 nm) macroporous (pore size <1 µm) membranes in a facile way, i.e., by simply drop‐coating the particle solution onto a mica surface. No continuous/porous membranes are produced from shell‐crosslinked PS‐b‐PB micelles and both forms of PS‐b‐P4VP micelles. This suggests that the unique structure of the block copolymer precursor, including the very flexible core‐forming block and the glassy corona‐forming block and the specific block length ratio, directly determines the formation of the macroporous membrane.

     

Polymer‐Coated PtCo Nanoparticles Deposited on Diblock Copolymer Templates: Chemical Selectivity versus Topographical Effects

Metal–polymer hybrid films are prepared by deposition of polymer‐coated PtCo nanoparticles onto block copolymer templates. For templating, a thin film of the lamella‐forming diblock copolymer poly(styrene‐b‐methyl methacrylate) P(S‐b‐MMA) is chemically etched and a topographical surface relief with 3 nm height difference is created. Two types of polymer‐grafted PtCo nanoparticles are compared to explore the impact of chemical selectivity versus the topographical effect of the nanotemplate. A preferable wetting of the polystyrene (PS) domains with poly(styrenesulfonate) (PSS)‐coated PtCo nanoparticles (instead of residing in the space between the domains) is observed. Our investigation reveals that the interaction between PSS‐coated nanoparticles and PS domains dominates over the topographical effects of the polymer surface. In contrast, a non‐selective deposition of poly(N‐vinyl‐2‐pyrrolidone) (PVP)‐coated PtCo nanoparticles and the formation of large metal‐particle aggregates on the film is observed.     

Fabrication of polyimide nanotubes and carbon nanotubes containing magnetic iron oxide in confinement

Polyimide nanotubes with tunable wall thickness were fabricated by a precursor impregnation method using an AAO template, and carbon nanotubes containing magnetic iron oxide were obtained using ferric chloride-embedded polyimide precursor by a carbonization process.     

Porous alumina membranes with branched nanopores as templates for fabrication of Y-shaped nanowire arrays

Porous anodic alumina membranes with Y-branched and double-branched nanopores were fabricated by the stepwise reduction of anodizing potential during the second step of anodization carried out in 0.3 M oxalic acid. The process of nanoporous layer formation and influence of anodizing parameters on structural features of as-obtained anodic aluminum oxide (AAO) membranes were discussed in detail. The pore rearrangement process occurring after the potential decrease was investigated on the basis of the current density vs. time curves, and results were correlated with the field-emission scanning electron microscope images of the pore bottoms taken after different anodizing durations. It was found that the reorganization of nanopores begins after 600 and 500 s from the time of the potential reduction to 42 and 30 V and the process seems to be completed after about 900 and 800 s, respectively. The through-hole AAO membranes were used as templates for the fabrication of gold and polystyrene nanowires via electrochemical deposition and simple immersing in the polymer solution, respectively. The arrays of hierarchically branched nanowires were synthesized, and the dimensions of nanowires were consistent with the shape and structure of used AAO templates.

     

Block copolymer assisted topochemical polymerization:A facile and efficient route to robust polymeric nanoporous membranes decorated with versatile amino acids

Based on block copolymer assisted topochemical polymerization,a new strategy for facilely producing robust nanoporous membranes with controlled incorporation of functional groups onto nanopores is developed.As exemplified by preparing nanoporous polypyrrole decorated with amino acids,this strategy exhibits a high degree of freedom for tailoring the surface functionality in the created pores.     

Fabrication of three dimensional interconnected porous carbons from branched anodic aluminum oxide template

In this communication, the morphology of double branched anodic aluminum oxide (AAO) templates from linear down or step down function of anodizing voltage is discussed. The interconnected AAO film is obtained when the thin pore wall at the final branched channels is dissolved by chemical etching. The three-dimensional interconnected porous carbons are fabricated by carbonization of polyimide film which is negative replicated from the layered interconnected AAO template.     

Nanochannel array plastics with tailored surface chemistry

The utilization of nanoporous substrates in applications such as selective ion transport, biomolecule separation, seeded templating, and catalysis necessitates the ability to efficiently control pore surface properties. We approached this task by preparing nanoporous polymer monoliths from ABC triblock copolymer precursors that assemble into a cylindrical morphology, where the A block constitutes matrix, C is the removable minor component, and B provides the functionality on the surface of the pores. Polystyrene-polydimethylacrylamide-polylactide (PS-PDMA-PLA) triblock copolymers were prepared by a combination of controlled ring-opening and free-radical polymerization techniques. After selective etching of the PLA cylinders from shear-aligned monoliths, a nanoporous polystyrene matrix containing a hexagonally packed array of hydrophilic, PDMA-coated channels was obtained. Extremely high degrees of alignment and order could be attained, and nanoporous substrates with second-order orientation factors of as high as 0.96 were prepared. PDMA brushes inside the pores were then hydrolyzed in a controlled fashion to introduce a desired number of carboxylic acid groups to the internal pore surface. Carbodiimide mediated couplings with amines were then used to confirm the accessibility of the interior acidic groups and to render materials with different functional content. This modular approach allows for the convenient preparation of functionalized nanoporous materials from a single block copolymer precursor.     

具有平整表面的定向纳米碳管膜的制备

为了获得表面平整的定向纳米碳管，通过化学及物理的方法将纳米碳管膜进行反转，使其原来的AAO模板底面成为新的表面，用溶液逐步去除表面的铝和氧化铝后，获得了平整的定向纳米碳管膜表面，从而可将其作为工作面使用. 还比较了5％NaOH和6%H₃PO₄＋1.8%H₂CrO₄溶液去除氧化铝的效果.     

利用AAO模板合成纳米材料

利用AAO模板合成纳米材料;氧化铝;纳米结构;综述     

Self‐assembled complexes of poly(acrylic acid) and poly(styrene)‐block‐poly(4‐vinyl pyridine)

Polymer complexes were prepared from high molecular weight poly(acrylic acid) (PAA) and poly(styrene)‐block‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) in dimethyl formamide (DMF). The hydrogen bonding interactions, phase behavior, and morphology of the complexes were investigated using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this A‐b‐B/C type block copolymer/homopolymer system, P4VP block of the block copolymer has strong intermolecular interaction with PAA which led to the formation of nanostructured micelles at various PAA concentrations. The pure PS‐b‐P4VP block copolymer showed a cylindrical rodlike morphology. Spherical micelles were observed in the complexes and the size of the micelles increased with increasing PAA concentration. The micelles are composed of hydrogen‐bonded PAA/P4VP core and non‐bonded PS corona. Finally, a model was proposed to explain the microphase morphology of complex based on the experimental results obtained. The selective swelling of the PS‐b‐P4VP block copolymer by PAA resulted in the formation of different micelles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1192–1202, 2009