Influence of composition of heteropolyphosphatotungstate catalyst on epoxidation of propylene

A series of heteropolyphosphatotungstate catalysts with different W/P ratio were prepared by different means. P-31 MAS NMR spectra show every heteropolyphosphatotungstate contains several species with different W/P ratio. Combined with propylene epoxidation results, it is shown that the band at chemical shift ca. delta = 5 ppm maybe corresponds to a catalyst precursor which can be the most efficiently converted to the structure {PO4 [WO(O-2)(2)](4)}(3-). Characterization results of ICP show, the catalysts with low W/P ratio show a good reactivity for propylene epoxidation. (C) 2004 Elsevier B.V. All rights reserved.

Composition effect on dewetting of ultrathin films of miscible polymer blend

Two kinds of dewetting and their transition induced by composition fluctuation due to different composition in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on SiOx substrate at 145 degrees C have been studied by in-situ atomic force microscopy (AFM). The results showed that morphology and pathway of dewetting depended crucially on the composition. Possible reason is the variation in intensity of composition fluctuation resulted from the change of components in polymer blend. Based on the discussion of this fluctuation due to the composition gradient, parameter of U-q0/E, which describes the initial amplitude of the surface undulation and original thickness of film respectively, has been employed to distinguish the morphologies of spontaneous dewetting including bicontinuous structures and holes.

Complex Transition of Double-Diffusive Convection in a Rectangular Enclosure with Height-to-Length Ratio Equal to 4: Part I

This is the first part of direct numerical simulation (DNS) of double-diffusive convection in a slim rectangular enclosure with horizontal temperature and concentration gradients. We consider the case with the thermal Rayleigh number of 10^5, the Pradtle number of 1, the Lewis number of 2, the buoyancy ratio of composition to temperature being in the range of [0,1], and height-to-width aspect ration of 4. A new 7th order upwind compact scheme was developed for approximation of convective terms, and a three-stage third-order Runge-Kutta method was employed for time advancement. Our DNS suggests that with the buoyancy ratio increasing form 0 to 1, the flow of transition is a complex series changing fromthe steady to periodic, chaotic, periodic, quasi-periodic, and finally back to periodic. There are two types of periodic flow, one is simple periodic flow with single fundamental frequency (FF), and another is complex periodic flow with multiple FFs. This process is illustrated by using time-velocity histories, Fourier frequency spectrum analysis and the phase-space rajectories.

Structural role of fluoride in aluminophosphate sol-gel glasses: High-resolution double-resonance NMR studies

The local structure of Na-Al-P-O-F glasses, prepared by a novel sol-gel route, was extensively investigated by advanced solid-state NMR techniques. Al-21{F-19} rotational echo double resonance (REDOR) results indicate that the F incorporated into aluminophosphate glass is preferentially bonded to octahedral Al units and results in a significant increase in the concentration of six-coordinated aluminum. The extent of Al-F and Al-O-P connectivities are quantified consistently by analyzing Al-27{P-31} and Al-21{F-19} REDOR NMR data. Two distinct types of fluorine species were identified and characterized by various F-19{Al-27}, F-19{Na-23}, and F-19{P-31} double resonance experiments, which were able to support peak assignments to bridging (Al-F-Al, -140 ppm) and terminal (Al-F, -170 ppm) units. On the basis of the detailed quantitative dipole-dipole coupling information obtained, a comprehensive structural model for these glasses is presented, detailing the structural speciation as a function of composition.

Spectroscopic properties of Er3+-doped tellurite glass for 1.55 mu m optical amplifier

Er3+-doped TeO2-BaO (Li2O, Na2O)-La2O3 tellurite glass system was prepared and their density, characteristic temperatures and optical properties were determined and investigated. For the TeO2-BaO-La2O3-Er2O3 system, composition with 10 mol% BaO presented the highest thermal stability and good infrared transmittance. Intense and broad 1.53 mu m infrared fluorescence were observed under 977 nm diode laser excitation and the most full width at half-maximum (FWHM) is similar to 60nm. According to absorption spectrum, we calculated the optical parameters by means of Judd-Ofelt and McCumber theory such as the fluorescence lifetimes which are about 2.72-3.25 ms and the maximum emission cross-sections which are similar to 1.0pm(2) at 1.531 mu m. The sigma(e) x FWHM value of composition with 10 mol% BaO for gain bandwidth is similar to 600 exceeding those in silicon and phosphate glasses. Our results indicated this kind of tellurite glasses could be used as an ideal host glass for optical amplifier. (c) 2005 Elsevier B.V. All rights reserved.

Effect of OH- content on emission properties in Er3+-doped tellurite glasses

A series of tellurite glasses of composition, 75TeO(2)-20ZnO-(5 - x)La2O3-xEr(2)O(3) (x = 0.05, 0.1, 0.3, 0.6, 1.0, 2.0, and 3.0 mol%) with different hydroxl content were prepared. The effect of Er3+ and OH- groups concentration on the emission properties of Er3+: I-4(13/2) -> I-4(15/2) transition in tellurite glasses was investigated. The constant KOH-Er for Er3+ in tellurite glasses, which represents the strength of interaction between Er3+ and OH- groups in the case of energy migration, was about 14 x 10(-19) cm(4) s(-1). The interaction parameter C-Er,C-Er for the migration rate of Er3+ : 4I(13/2) -> I-4(13/2) transition in tellurite glass was 46 x 10(-40) cm(2), which indicates that concentration quenching in Er3+-doped modified tellurite glass for a given Er3+ concentration is much stronger than in silicate and phosphate glasses. (c) 2007 Elsevier B.V. All rights reserved.

Effect of layer thickness of immiscible alloy In0.52Al0.48As on the morphology of InAs nanostructure grown on In0.52Al0.48As/InP(001)

Thickness effect of immiscible alloy InAlAs as matrix layer on the morphology of InAs nanostructure grown on InAlAs/InP (0 0 1) by solid-source molecular-beam epitaxy has been studied. Experiments demonstrate that InAs nanostructure grown on thin InAlAs matrix layer forms randomly distributed quantum dot, whereas, grown on thick InAlAs matrix layer forms one-dimension ordered mixture of quantum wire and quantum dot. This drastic modification in the nanostructure morphology is attributed to the generation of composition modulation in the immiscible InAlAs alloy with the increase of the layer thickness. (C) 2004 Elsevier B.V. All rights reserved.

Synthesis and Aqueous Solution Properties of Hydrophobically Modified Anionic Acrylamide Copolymers

In this investigation, hydrophobically modified polyacrylamide with low amounts of anionic long-chain alkyl was synthesized by the free radical polymerization in deionized water. This water-soluble copolymerization method is more convenient compared with the traditional micellar copolymerization methods. The copolymers were characterized using Fourier transform infrared, H-1 NMR, and the molecular weight and polydispersity were determined using gel permeation chromatography. The solution behavior of the copolymers was studied as a function of composition, pH, and added electrolytes. As NaCl was added to solutions of AM/C(11)AM copolymers or pH was lowered, the shielding or elimination of electrostatic repulsions between carboxylate groups of the C(11)AM unit lead to coil shrinkage.

Control of self-organized low-dimensional morphology in Poly(styrene-b-4vinylpyridine)/polystyrene blend thin films

The surface morphologies of poly(styrene-b-4vinylpyridine) (PS-b-P4VP) diblock copolymer and homopolystyrene (hPS) binary blend thin films were investigated by atomic force microscopy as a function of total volume fraction of PS (phi(PS)) in the mixture. It was found that when hPS was added into symmetric PS-b-P4VP diblock copolymers, the surface morphology of this diblock copolymer was changed to a certain degree. With phi(PS) increasing at first, hPS was solubilized into the corresponding domains of block copolymer and formed cylinders. Moreover, the more solubilized the hPS, the more cylinders exist. However, when the limit was reached, excessive hPS tended to separate from the domains independently instead of solubilizing into the corresponding domains any longer, that is, a macrophase separation occurred. A model describing transitions of these morphologies with an increase in phi(PS) is proposed. The effect of composition on the phase morphology of blend films when graphite is used as a substrate is also investigated.

What has brought on the effects of number-average molecular weight on the spinodals in polymer mixtures?

On the basis of the thermodynamics of Gibbs, the spinodal for the quasibinary system was derived in the framework of the Sanchez-Lacombe lattice fluid theory. All of the spinodals were calculated based on a model polydisperse polymer mixture, where each polymer contains three different molecular weight subcomponents. According to our calculations, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights, whereas that of the z-average molecular weight is invisible. Moreover, the extreme of the spinodal decreases when the polydispersity index (eta = (M) over bar (w)/(M) over bar (n)) of the polymer increases. The effect of polydispersity on the spinodal decreases when the molecular weight gets larger and can be negligible at a certain large molecular weight. It is well-known that the influence of polydispersity on the phase equilibrium (coexisting curve, cloud point curves) is much more pronounced than on the spinodal. The effect of M, on the spinodal is discussed as it results from the infuluence of composition temperatures, molecular weight, and the latter's distribution on free volume. An approximate expression, which is in the assumptions of v* v(1)* = v(2)* and 1/r --> 0 for both of the polymers, was also derived for simplification. It can be used in high molecular weight, although it failed to make visible the effect of number-average molecular weight on the spinodal.

Miscibility and hydrogen-bonding interactions in blends of carbon dioxide/epoxy propane copolymer with poly (p-vinylphenol)

The miscibility and hydrogen-bonding interactions of carbon dioxide and epoxy propane copolymer to poly(propylene carbonate) (PPC)/poly(p-vinylphenol) (PVPh) blends were investigated with differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The single glass-transition temperature for each composition showed miscibility over the entire composition range. FTIR indicates the presence of strong hydrogen-bonding interassociation between the hydroxyl groups of PVPh and the oxygen functional groups of PPC as a function of composition and temperature. XPS results testify to intermolecular hydrogen-bonding interactions between the oxygen atoms of carbon-oxygen single bonds and carbon-oxygen double bonds in carbonate groups of PPC and the hydroxyl groups of PVPh by the shift of C-1s peaks and the evolution of three novel O-1s peaks in the blends, which supports the suggestion from FTIR analyses.

Luminescence of Eu2+ in sodium polyaluminates

The sodium polyaluminates were synthesized by a high temperature solid state method and the luminescence of Eu2+ in the sodium polyaluminates was studied. The results show that the structure of the system Na1+xMgxAl11-xO17 from x=0.1 to x=1.0 belongs to Na-beta-alumina and the structure of the system Na1.67-2xBaxMg0.67Al10.33O17 changes at about x equal to 0.30, when x is smaller than 0.30 the system forms the solid solution structure of Na-beta-alumina, when x is larger than 0.30 the system becomes the ordered structure of Ba-beta-alumina, correspondingly the emission peak position and the relative emission intensity of Eu2+ change with the changes of composition and structure of the system. There exist two kinds of the luminescent centers of high and low energies of Eu2+ in the matrix of Na-beta-alumina structure. New phosphor with Ba-beta-alumina structure, Na0.67Ba0.50Mg0.67Al10.33O17:Eu2+, was obtained.

Effects of molecular weight and interaction parameter on the glass transition temperature of polystyrene mixtures and its blends with polystyrene/poly(2,6-dimethyl-p-phenylene oxide)

The glass transition temperature (T-g) of mixtures of polystyrene (PS) with different molecular weight and of blends of poly(2,6-dimethyl-p-phenylene oxide) (PPO) and polystyrene with different molecular weight (DMWPS) was studied by a DSC method. For the whole range of composition, the curves of T-g vs composition obtained by experiment were compared with predictions from the Fox, Gordon-Taylor, Couchman and Lu-Weiss, equations. It was found that the experimental results were not in agreement with those from the Fox, Gordon-TayIor and Couchman equations for the binary mixtures of DMWPS, where the interaction parameter chi was approximately zero. However, for the blends PPO/DMWPS (chi < 0), with an increase of molecular weight of PS, it was shown that the experimental results fitted well with those obtained from the Couchman, Gordon-Taylor and Fox equations, respectively. Furthermore, the Gordon-Taylor equation was nearly identical to the Lu-Weiss equation when \chi\ was not very large. Further, the dependence of the change of heat capacity associated with the glass transition (Delta C-p) on the molecular weight of PS was investigated and an empirical equation was presented. (C) 1997 Elsevier Science Ltd.

The multiple melting behaviour of immiscible poly(ether ether ketone) poly(ether diphenyl ether ketone) blend

Poly(ether ether ketone)/poly(ether diphenyl ether ketone) blend containing 30 wt% PEDEK was used to investigate the melting behaviour of immiscible PEEK/PEDEK blends. The results measured from differential scanning calorimetry (d.s.c.) and wide-angle X-ray diffraction (WAXD) showed that immiscible PEEK/PEDEK blends isothermally crystallized at a temperature between Tg and Tm-2 (PEEK's normal melting point) from the glassy state also exhibited the multi-melting behaviour like poly(aryl ether ketones) homopolymers. In addition, the low-temperature melting peak was independent of composition of poly(aryl ether ketones) blends and only associated with the thermal history. (C) 1997 Elsevier Science Ltd.

Mechanical properties and miscibility of polyethersulfone phenoxy blends

The blends of polyethersulfone and phenoxy were prepared by melt mixing in a Brabender-like apparatus. The specimens for measurements were made by compression molding and then were water-quenched at room temperature under pressure. The tensile strength, tensile modulus, elongation at break and yield, density, thermal analysis, and dynamic mechanical properties were each measured. The dependence of tensile strength, tensile modulus, elongation at break and yield, and density on composition was obtained. The relationship between tensile modulus and elongation at break and yield and speed of the crosshead at different weight ratios of the blends is shown. The effects of composition and miscibility on the mechanical properties are discussed. (C) 1996 John Wiley & Sons, Inc.