Nonsolvent-induced dewetting of thin polymer films

The process of nonsolvent-induced dewetting of thin polystyrene (PS) films on hydrophilic surfaces at room temperature has been studied by using water as a nonsolvent. It is observed that the process of nonsolvent-induced dewetting is greatly different from other previous dewetting processes. The PS film is found in nonviscous state in our study. A mechanism of nonsolvent-induced dewetting is deduced in an order of penetration, replacement, and coalescent, and it is different from other previous dewetting mechanisms. The results of experiments are analyzed from thermodynamics and dynamics to support the hypothetical mechanism.

Synthesis of a (sic)-shaped amphiphilic block copolymer by the combination of atom transfer radical polymerization and living anionic polymerization

The functionalization of monomer units in the form of macroinitiators in an orthogonal fashion yields more predictable macromolecular architectures and complex polymers. Therefore, a new there exists E-shaped amphiphilic block copolymer, (PMMA)(2)-PEO-(PS)(2)-PEO-(PMMA)(2) [where PMMA is poly(methyl methacrylate), PEO is poly (ethylene oxide), and PS is polystyrene], has been designed and successfully synthesized by the combination of atom transfer radical polymerization (ATRP) and living anionic polymerization. The synthesis of meso-2,3-dibromosuccinic acid acetate/diethylene glycol was used to initiate the polymerization of styrene via ATRP to yield linear (HO)(2)-PS2 with two active hydroxyl groups by living anionic polymerization via diphenylmethylpotassium to initiate the polymerization of ethylene oxide. Afterwards, the synthesized miktoarm-4 amphiphilic block copolymer, (HO-PEO)(2)-PS2, was esterified with 2,2-dichloroacetyl chloride to form a macroinitiator that initiated the polymerization of methyl methacrylate via ATRP to prepare the there exists E-shaped amphiphilic block copolymer.

Improvement of amplified spontaneous emission performance by doping tris(8-hydroxyquinoline) aluminum (Alq3) in dye-doped polymer thin films

A well-known red fluorescent dye 4-(dicy-anomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)4H-pyran (DCJTB) was codoped with an electron transport organic molecule tris(8-hydroxyquinohne) aluminum (Alq3) in a host matrix of polystyrene (PS), and the amplified spontaneous emission (ASE) was studied by optically pumping. It was found that the ASE performance was significantly improved by the introduction of Alq3. The Alq3:DCJTB:PS blending thin films showed a low threshold (2.4 mu J/pulse) and a high net gain coefficient (109.95 cm(-1)) compared with the pure DCJTB:PS system (threshold of 15.2 mu J/pulse and gain of 35.94 cm(-1)). The improvement of the ASE performance was considered to be attributable to the effective Foster energy transfer from Alq(3) to DCJTB. Our results demonstrate that the Alq(3):DCJTB could be a promising candidate as gain medium for red organic diode lasers.

Improved amplified spontaneous emission by doping of green fluorescent dye C545T in red fluorescent dye DCJTB : PS polymer films

Amplified spontaneous emission (ASE) characteristics of a red fluorescent dye, 4-(dicy-anomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB), and a green fluorescent dye, (10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-[1] benzopyrano [6,7,8-ij]quinohzin-11-one) (C545T) codoped polystyrene (PS) as the active medium were studied. It was found that the performance of ASE is greatly improved due to the introduction of C545T. By optimizing the concentrations of C545T and DCJTB in PS, an ASE threshold of 0.016 mJ pulse(-1), net gain of 52.71 cm(-1), and loss of 11.7 cm(-1) were obtained. The efficient Forster energy transfer from C545T to DCJTB was used to explain the improvement of the ASE performance in the coguest system.

Fabrication of conductive metallized nanostructures from self-assembled amphiphilic triblock copolymer templates: Nanospheres, nanowires, nanorings

Various metallized nanostructures (such as rings, wires with controllable lengths, spheres) have been successfully fabricated by coating metallic nanolayers onto soft nanotemplates through simple electroless methods. In particular, bimetallic nanostructures have been obtained by using simple methods. The multiple functional polymeric nanostructures, were obtained through the self-assembly of polystyrene/poly(4-vinyl pyridine) triblock copolymer (P4VP-b-PS-b-P4VP) in selective media by changing the common solvent properties. By combining field emission scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) characterization, it was confirmed that polymer/metal and bimetallic (Au@Ag) core-shell nanostructures could be achieved by chemical metal deposition method.

Monte Carlo simulation of the compatibility of graft copolymer compatibilized two incompatible homopolymer blends: Effect of graft structure

Compatibility of graft copolymer compatibilized two incompatible homopolymer A and B blends was simulated by using Monte Carlo method in a two-dimensional lattice model. The copolymers with various graft structures were introduced in order to study the effect of graft structure on the compatibility. Simulation results showed that incorporation of both A-g-B (A was backbone) and B-g-A (B was backbone) copolymers could much improve the compatibility of the blends. However, A-g-B copolymer was more effective to compatibilize the blend if homopolymer A formed dispersed phase. Furthermore, simulation results indicated that A-g-B copolymers tended to locate at the interface and anchor two immiscible components when the side chain is relatively long. However, most of A-g-B copolymers were likely to be dispersed into the dispersed homopolymer A phase domains if the side chains were relatively short. On the other hand, B-g-A copolymers tended to be dispersed into the matrix formed by homopolymer B. Moreover, it was found that more and more B-g-A copolymers were likely to form thin layers at the phase interface with decreasing the length of side chain.

Templated synthesis of composite rings using core-shell toroids

In difference to compact objects of a similar size, toroidal structures have some distinguishing properties that originate from their open inner cavity and closed circuit. Here, a general facile methodology is developed to prepare composite rings with varied compositions on a large scale by using core-shell toroids assembled from tri-block copolymers of poly(4-vinyl pyridine) (PVP)/polystyrene (PS)/PVP. Taking advantage of the complexation ability of the PVP shell, varied components that range from polymers, inorganic materials, metals and their compounds, as well as pre-formed nanoparticles are introduced to the toroidal structures to form composite nanostructures. Metal ions can be adsorbed by PVP through complexation. After in situ reduction, a large number of metal-based functional materials can be prepared. PVP is alkaline, and thus capable of catalyzing the sol-gel process to generate an inorganic shell. Furthermore, pre-formed nanoparticles can also be absorbed by the shell through specific interactions. The PS core is not infiltrative during synthesis, and hollow rings can be derived after the polymer templates are removed.

Tethered diblock copolymer chains on platelets prepared by semicrystalline ABC triblock copolymers in toluene with trace amounts of water

Lamellar platelets of triblock copolymers grown in dilute toluene solution with trace amounts of water can be used as templates for tethered diblock copolymer chain preparation and analysis. Polystyrene-bpoly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) with two different block fractions were used as model templates to generate tethered P2VP-b-PS chains on the platelet basal surfaces. In toluene solution the aggregation states of PS-b-P2VP-b-PEO were sensitive to the water content in the solution. For toluene with trace amount of water, spherical micelles were formed in the early stage and large square platelets would gradually grow from these spherical micelles. The hydrogen bonding between water and EO units was responsible for the formation of micelles and subsequent square platelets in the solution. Tethered P2VP-b-PS chains on basal surface of PEO platelets could be regarded as diblock copolymer brushes and the density (or: 0.086-0.36) and height (d: 3.5-14.3 nm) of these tethered chains could be easily modulated by changing the crystallization condition and/ or the molecular weight of each block. The tethered P2VP-b-PS chains were responsive to different solvent vapor.

Transformation from ordered islands to holes in phase-separating P2VP/PS blend films by adding triton X-100

Our previous investigation showed that the ordered hexagonal island pattern in the phase-separating polymeric blend films of polystyrene and poly(2-vinylpyridine) (PS/P2VP) formed due to the convection effect by proper control of PS molecular weight, solvent evaporation rate, and the weight ratio of PS to P2VP. In this paper, we further illustrate that, by adding a proper amount of the surfactant Triton X-100 to the PS/P2VP toluene solution, the ordered hexagonal island pattern can be transformed to the ordered honeycomb pattern. The effects of the amount of Triton X-100 on the surface morphology evolution and the pattern transformation are discussed in terms of the collapse of Triton X-100, phase separation between Triton X-100/P2VP and PS, the interfacial interaction between Triton X-100/P2VP and the mica substrate, and the Benard-Marangoni convection.

Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer

In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared.

Self-assembly morphology effects on the crystallization of semicrystalline block copolymer thin film

Self-assembly morphology effects on the crystalline behavior of asymmetric semicrystalline block copolymer polystyrene-block-poly(L-lactic acid) thin film were investigated. Firstly, a series of distinctive self-assembly aggregates, from spherical to ellipsoid and rhombic lamellar micelles (two different kinds of rhombic micelles, defined as rhomb 1 and rhomb 2) was prepared by means of promoting the solvent selectivity. Then, the effects of these self-assembly aggregates on crystallization at the early stage of film evolution were investigated by in situ hot stage atomic force microscopy. Heterogeneous nucleation initiated from the spherical micelles and dendrites with flat on crystals appeared with increasing temperature. At high temperature, protruding structures were observed due to the thickening of the flat-on crystals and finally more thermodynamically stable crystallization formed. Annealing the rhombic lamellar micelles resulted in different phenomena. Turtle-shell-like crystalline structure initiated from the periphery of the rhombic micelle 1 and spread over the whole film surface in the presence of mostly noncrystalline domain interior. Erosion and small hole appeared at the surface of the rhombic lamellar micelle 2; no crystallization like that in rhomb 1 occurred. It indicated that the chain-folding degree was different in these two micelles, which resulted in different annealing behaviors.

Highly oriented tunable wrinkling in polymer bilayer films confined with a soft mold induced by water vapor

The authors report the formation of highly oriented wrinkling on the surface of the bilayer [polystyrene (PS)/poly(vinyl pyrrolidone) (PVP)] confined by a polydimethylsiloxane (PDMS) mold in a water vapor environment. When PVP is subjected to water vapor, the polymer loses its mechanical rigidity and changes to a viscous state, which leads to a dramatic change in Young's modulus. This change generates the amount of strain in the bilayer to induce the wrinkling. With a shape-controlled mold, they can get the ordered wrinkles perfectly perpendicular or leaned 45 S to the channel orientation of the mold because the orientation of the resultant force changes with the process of water diffusion which drives the surface to form the wrinkling. Additionally, they can get much smaller wrinkles than the stripe spacing of PDMS mold about one order. The wrinkle period changes with the power index of about 0.5 for various values of the multiplication product of the film thicknesses of the two layers, namely, lambda similar to (h(PS)h(PVP))(1/2).

Motion of integrated CdS nanoparticles by phase separation of block copolymer brushes

A new method of reversibly moving US nanoparticles in the perpendicular direction was developed on the basis of the phase separation of block copolymer brushes. Polystyrene-b-(poly(methyl methaerylate)-co-poly(cadmium dimethacrylate)) (PS-b-(PMMA-co-PCdMA)) brushes were grafted from the silicon wafer by surface-initiated atom transfer radical polymerization (ATRP). By exposing the polymer brushes to H2S gas, PS-b-(PMNlA-co-PCdNlA) brushes were converted to polystyrene-b-(poly(methyl methacrylate) -co-poly(methacrylic acid)(CdS)) (PS-b-(PMMA-co-PMAA(CdS))) brushes, in which US nanoparticles were chemically bonded by the carboxylic groups of PMAA segment. Alternating treatment of the PS-b-(PMMA-co-PMAA(CdS)) brushes by selective solvents for the outer block (a mixed solvent of acetone and ethanol) and the inner PS block (toluene) induced perpendicular phase separation of polymer brushes, which resulted in the reversible lifting and lowering of US nanoparticles in the perpendicular direction. The extent of movement can be adjusted by the relative thickness of two blocks of the polymer brushes.

Development of nanodomain and fractal morphologies in solvent annealed block copolymer thin films

We have systematically studied the thin film morphologies of asymmetric polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer subjected to solvent vapors of varying selectivity for the constituent blocks. Upon a short treatment in neutral or PS-selective vapor, the film exhibited a highly ordered array of hexagonally packed, cylindrical microdomains. In the case of PEO selective vapor annealing, such ordered cylindrical microdomains were not obtained. instead, fractal patterns on the microscale were observed and their growth processes investigated. Furthermore, hierarchical structures could be obtained if the fractal pattern was exposed to neutral or PS selective vapor.

Colloidal photonic crystals with a graded lattice-constant distribution

In this work, a gradient polystyrene colloidal photonic crystal was fabricated by annealing in a graded temperature field. The lattice constant of the gradient crystal gradually varied along the temperature-gradient direction. The positional bandgap wavelength as well as the attenuation of the bandgap wavelength could be tuned dependent on the position of the gradient colloidal crystal along the gradient direction because of the lattice-constant variation.