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.

Novel acidic porous clay heterostructure with highly ordered organic-inorganic hybrid structure: one-pot synthesis of mesoporous organosilica in the galleries of clay

A new class of organic-inorganic hybrid porous clay heterostructures (HPCHs) have been prepared through the surfactant-directed assembly of organosilica in the galleries of montmorillonite. The reaction involved hydrolysis and condensation of phenyltriethoxysilane and tetraethoxysilane in the presence of intragallery surfactant templates (dodecylame and cetyltrimethylammonium ion). The surfactant templates were removed from the pores by solvent-extraction. The products were characterized by X-ray diffraction (XRD), N-2 adsorption, solid-state Si-29 and C-13 NMR, and FTIR. XRD patterns indicated a regular interstratification of the clay layers for HPCHs. Depending on loading of phenyl groups, HPCHs had BET surface areas of 390-771 m(2) g(-1), pore volumes of 0.3-0.59 cm(3) g(-1), and the framework pore sizes in the supermicropore to small mesopore range (1.2-2.6 nm). HPCHs were hydrophobic and acidic.

The formation of ordered nanoholes in binary, chemically similar, symmetric diblock copolymer blend films

Binary symmetric diblock copolymer blends, that is, low-molecular-weight poly(styrene-block-methyl methacrylate) (PS-b-PMMA) and high-molecular-weight poly(styrene-block-methacrylate) (PS-b-PMA), self-assemble on silicon substrates to form structures with highly ordered nanoholes in thin films. As a result of the chemically similar structure of the PMA and the PMMA block, the PMMA chain penetrates through the large PMA block that absorbs preferentially on the polar silicon substrate. This results in the formation of nanoholes in the PS continuous matrix.

Ordered macroporous films from self-assembly of two-armed polymer with a crown ether core

Highly ordered honeycomb-like macroporous films were obtained via self-assembly of a two-armed polymer with a crown ether core under controlled conditions. A possible mechanism is speculated, primarily based on the strong affinity between the crown ether cores. The pore size and arrangement are sensitive to the solvent evaporation rate and the solution concentration. Upon spontaneous drying, the pore diameter (D) depends on the concentration (c) by a relation of D=518c(-0.610).

Tunable ordered droplets induced by convection in phase-separating P2VP/PS blend film

Ordered hexagonal droplets patterns in phase-separating polymeric blend films of polystyrene and poly(2-vinylpyridine) (PS/PVP) formed due to the convection effect by solvent evaporation. The influences of PS molecular weight, solvent evaporation rate, and the weight ratio of PS to PVP on the PVP-rich domains pattern formation and distributions were investigated by atomic force microscope (AFM). Only in an appropriate range of molecular weight of PS, can the ordered pattern form. Too low or too high molecular weight of PS led no ordered pattern due to the viscosity effects. The increase of solvent evaporation rate decreased the mean radius of the PVP-rich domains and the intervals between the centers of the domains due to the enhancement of the viscosity on the top layer of the fluid film. The increase of the weight ratio of PS to PVP decreased mean radius of the PVP-rich domains whereas the intervals between the centers of droplets remained constant. Therefore, the size and the distributions of ordered patterns can be tuned by the polymer molecular weight, the weight ratio of the two components and the solvent evaporation rate.

Ordered pattern formation from dewetting of polymer thin film with surface disturbance by capillary force lithography

The dewetting process of thin polystyrene (PS) film with built-in ordered disturbance by capillary force lithography (CFL) has. been investigated in situ by AFM. Two different phenomena are observed depending on the excess surface energy (DeltaF(gamma)) of the system. When DeltaF(gamma) is less than a certain critical value (i.e., the disturbance amplitude is under a critical value), the PS film would be flattened and become stable finally by heating above T-g. While, if the size of the disturbance amplitude is larger than the critical value, ordered PS liquid droplets form by further dewetting. The pattern formation mechanisms and influencing factors have been discussed in detail.

Ordered droplet formation by thin polymer film dewetting on a stripe-patterned substrate

The dewetting process of thin polystyrene (PS) film on flat and stripe-patterned substrates is presented. Different dewetting processes were observed when the thin PS films annealed at above the glass transition temperature on these different kinds of substrates. The final dewetting on the flat substrate led to formation of polygonal liquid droplets, while on the stripe-patterned substrate, the droplets were observed to align at the centers of the stripes. A possible explanation for the dewetting process on the stripe-patterned substrate is proposed.

Stable ordered mesoporous silica materials templated by high-temperature stable surfactant micelle in alkaline media

Ordered hexagonal mesoporous silica material (JLU-30) has been successfully synthesized in alkaline media at high temperature (> 160 degreesC, using cationic (1,3-dimethyl-2-imidazolidin-2-ylidene)hexadecylmethyl-ammonium bromide (DIHAB) as a template, and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption isotherms, differential thermal analysis (DTA), and thermogravimetric analysis (TG), as well as Al-27 and Si-29 nuclear magnetic resonance (NMR) spectroscopy. Mesoporous JLU-30 shows much higher hydrothermal stability than MCM-41. Si-29 NMR spectra indicate that the pore walls of JLU-30 samples synthesized at high temperature (160 degreesC) are fully condensed, giving a Q(4)/Q(3) ratio as high as 6.2. In contrast, MCM-41 synthesized at relatively low temperature (100 degreesC) shows the Q(4)/Q(3) + Q(2) ratio at 1.1. Such unique structural feature might be responsible for the observed highly hydrothermal stability of the mesoporous silica materials (JLU-30).

Structure and properties of the ordered double perovskites Sr2MWO6 (M = Co, Ni) by sol-gel route

The single-phase double perovskites Sr2MWO6 (M=Co, Ni) were prepared by sol-gel method. Crystal Structure, magnetic properties and the morphology of Sr2CoWO6 and Sr2NiWO6 were investigated. X-ray powder diffraction (XRD) analysis shows single phase structure for Sr2MWO6 (M=Co, Ni) without any traces of impurities and the crystal structure of all the samples belongs to the tetragonal I4/m space group. SEM image for Sr2MWO6 (M=Co, Ni) indicate that the grains are homogeneous and connect each other very well. The Neel temperature for Sr2CoWO6 and Sr2NiWO6 are 23 K and 59 K, respectively. Magnetic measurements showed that the magnetic moment in these double perovskites originates mainly from the interactions between Ni ions and Co ions.

Competition between band filling and steric effect in ordered double perovskites Sr2-xLaxMnMoO6

The ordered double perovskites, Sr2-xLaxMnMoO6, were prepared by sol-gel reaction. Structural, magnetic, and electrical properties were investigated for a series of ordered double perovskites Sr2-xLaxMnMoO6(0 <= x <= 1). The compounds have a monoclinic structure (space group P2(1)/n) and the cell volume expands monotonically with La doping. The T-C and the magnetic moment rise and the cusp-like transition temperature below which the magnetic frustration occurs shifts to high temperature as x increases. With La doping, electrical resistivity of Sr2-xLaxMnMoO6 decreases only at low doping levels (x <= 0.2); while at high doping levels (0.8 <= x <= 1), electrical resistivity tends to increase greatly. The results suggest that the competition between band filling effect and steric effect coexists in the whole doping range, and the formation of ferrimagnetic interactions is not simply at the expense of antiferromagnetic interactions.

Study on highly ordered luminescent Langmuir-Blodgett films of heteropolytung state complexes containing lanthanide

Luminescent thin films of heteropolytungstate complexes containing lanthanide (europium or samarium) were successfully fabricated by the Langmuir-Blodgett (LB) technique. The pressure-area isotherm of the monolayer of dimethyldioctadecylammonium. bromide (DODA) is modified rather markedly when the subphase contains the complex of Na9EuW10O36 or Na9SmW10O36. The above results indicate that the monolayer of DODA has a strong interaction with the polyanions of EuW10O369-. (or SmW10O369-). X-ray photoelectron spectra and fluorescent spectra verify that europium and tungsten atoms are 36 36 incorporated into the LB films. Ultraviolet (UV), fluorescent spectra and low-angle X-ray diffraction experiments demonstrate that these LB films have a well-defined lamellar structure. The LB film containing EuW10O369- can give off strong fluorescence 16 on UV irradiation. The characteristic emission behaviors of europium ions in LB films and in the powder of Na9EuW10O369- are discussed. It is found that the intensity ratio of the D-5(0)-F-7(2) transition to the D-5(0)-->F-7(1) transition in LB film is quite different from that in the powder of Na9EuW10O36. The difference of the ratio indicates that the site symmetry of europiurn is distorted in LB film, which is probably due to the strong electrostatic interactions between DODA and polyanions.

Preparation and characterization of ordered yttrium arachidate multilayer

The behavior of arachidic acid on the surface of YCI3 aqueous subphase was studied by LB and Brewster angle microscopy techniques. The results showed that the pre-compressing time and the pH of the subphase played an important role in the forming of the monolayer. The monolayer on the subphase surface was irreversible. If the monolayer was compressed into wrinkles, the monolayer could not become uniform again. The optimum transferring conditions were selected and the ordered yttrium arachidate multilayer with a long spacing of 4.96 nm and a tilt angle of 28.5degrees of the three alkyl chains from the surface normal was fabricated and characterized.

Fabrication and characterization of ordered oligoaniline film

highly organized phenyl-capped teraniline (PC-teraniline) film at the molecular level was fabricated on carbon surfaces by electrochemical reduction of diazonium salts. Cyclic voltammetry (CV). scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) were employed for the characterization of the film.

Preparation, structure, and properties of three-dimensional ordered alpha-Fe2O3 nanoparticulate film

alpha-Fe2O3 nanoparticulate films could be formed on the surface of alpha-Fe2O3 hydrosol after aging of the hydrosol or by compressing of the nanoparticles on the sol surface, in. which a three-dimensional ordered structure was constructed by the Langmuir-Blodgett; technique and colloid chemical methods. The structure of the LB film was characterized by AFM, TEM, XPS, and UV-vis spectra and small-angle X-ray diffraction. Gas-sensing measurement shows that the LB film has good sensitivity to alcohols at room temperature,