Luminescence of unusual bismuth in barium berates BaB8O13 : Bi)

The luminescence of unusual divalent bismuth (Bi2+) in BaB8O13 is reported. The emission band with maximum peak at 592 nm corresponds to the P-2(3/2)-->P-2(1/2) transition of Bi2+ in the matrix and the excitation spectrum with two bands peaked at 470 and 580 nm respectively corresponds to two split crystal-field levels of P-2(3/2) state. The small Stokes shift (similar to 350 cm(-1)) reflects the rigid structure of the host for the Bi2+ ions.

Studies on liquid crystalline bis[4-(p-phenoxy)-phenylbenzoate] alkyldicarboxylate

A new series of liquid crystals of bis[4-(p-phenoxy)-phenylbenozoate] alkyldicarboxylate which contain two rigid groups connected by a flexible spacer was synthesized. These liquid crystals show nematic phase and were found to show odd-even effect in isotropization temperature and entropy change.

Blue-light emitting diodes and flat display based on poly(p-phenylenevinylene) copolymers

Copolymers containing alternating flexible aliphatic blocks and rigid poly(p-phenylenevinylene) (PPV) blocks were synthesized and characterized. It was found that the fluorescent intensity increases with increasing length of the flexible blocks. Bright blue-light emitting diodes were fabricated using PPV copolymers as electroluminescent layers. The devices show 190 cd/m(2) light-emitting brightness at 460 nm and 15 V rum-on voltage. The effects of oxadiazole derivative PBD and tris(8-hydroxyquinoline) aluminum Alq(3) electron-transporting layers on the luminance and stability of the devices are discussed.

Permeation of nitrogen and water vapor through sulfonated polyetherethersulfone membrane

The novel polyetherethersulfone (PES-C) prepared from phenol-phthalein in our institute is an amorphous, rigid, tough material with good mechanical properties over a wide temperature range. To improve its water vapor permeability for the application of gas drying, the PES-C was sulfonated with concentrated sulfuric acid and transferred in sodium, cupric, and ferric salt forms. The sulfonation degree can be regulated by controlling the temperature and reaction time. Characterization of sulfonated PES-C in sodium form was made by IR. Some properties of the sulfonated PES-C, such as solubility, glass transition temperature, thermal stability, mechanical properties, and transport properties to nitrogen and water vapor have also been discussed. (C) 1997 John Wiley & Sons, Inc.

Isolation, spectra, structure, and ring-opening polymerization of strained macrocyclic aryl(ether ketone) dimer

Macrocyclic arylene ether ketone dimer was isolated from a mixture of cyclic oligomers obtained by the nucleophilic substitution reaction of bisphenol A and 4,4'-difluorobenzophenone and easily polymerized to high molecular weight linear poly(ether ketone). The cyclic compound was characterized by FTIR, H-1- and C-13-NMR, and single-crystal x-ray diffraction. Analysis of the spectral and crystal structure reveals extreme distortions of he phenyl rings attached to the isopropylidene center and of the turning points of the molecular polygons. The release of the ring strain on ring-opening combined with entropical difference between the linear polymer chain and the more rigid macrocycle at temperatures of polymerization may be the proposed motivating factors in the polymerization of this precursor to high molecular weight poly(ether ketone). (C) 1997 John Wiley & Sons, Inc.

Sulfonation of polyetheretherketone and its effects on permeation behavior to nitrogen and water vapor

The novel polyetheretherketone (PEK-C) prepared from phenolphthalein in our institute is an amorphous, rigid, tough material with good mechanical properties over a wide temperature range. To improve its water vapor permeability for the application of gas drying, PEK-C was sulfonated with concentrated sulfuric acid and transferred in sodium, cupric, and ferric salt forms. Sulfonation degree can be regulated by controlling the temperature and reaction time. Characterization of sulfonated PEK-C in sodium form was made by infrared spectroscopy. Some properties of the sulfonated PEK-C, such as solubility, glass transition temperature, thermal stability, mechanical properties, and transport properties to nitrogen and water vapor, are also discussed. (C) 1996 John Wiley & Sons, Inc.

Influence of crystal structure on the luminescence properties of bismuth(III), europium(III) and dysprosium(III) in Y2SiO5

The luminescence properties of Bi3+, EU(3+), Dy3+ and energy transfer from Bi3+ to Dy3+ and EU(3+) have been studied in two modifications of Y2SiO5 (low-temperature X(1) type and high-temperature X(2) type) and discussed in relation to their crystal structures. The Bi3+ ion luminesces in the blue region of the spectrum in X(1)-Y2SiO5 but in the UV region in X(2)-Y2SiO5. Two obviously different luminescent centres have been observed for Bi3+ and Eu3+ ill X(1)-Y2SiO5, but only one has been seen in X(2)-Y2SiO5. The Stokes shift (9200 cm(-1)) for Bi3+ in X(1)-Y2SiO5 is much larger than that (5000 cm(-1)) in X(2)-Y2SiO5. This suggests that the host lattice is more rigid in X(2)-Y2SiO5 than in X(1)-Y2SiO5. As a result, the Bi3+, EU(3+) and Dy3+ ions show higher emission intensity in the former than in the latter type. X(1)-Y2SiO5 is more suitable for Bi3+ --> EU(3+) energy transfer and X(2)-Y2SiO5 is more suitable for Bi3+ --> Dy3+ energy transfer.

NMR-STUDY OF MISCIBILITY AND MORPHOLOGY OF POLYIMIDE POLYIMIDE BLENDS

The miscibility and morphology of polyimide/polyimide blends, PEI-E/PTI-E(a)) and PBPI-E/IPTI-E(a)), have been studied by means of C-13 CPMAS NMR technique. The results indicate that PEI-E/PTI-E blends are miscible on a molecular level, but molecular aggregation exists in pure PBPI-E specimen as well as PBPI-E/PTI-E blends with high content of PBPI-E, which vanishes in the blends with high content of PTI-E. When the content of PBPI-E is higher than that of PTI-E, the addition of PTI-E to PBPI-E has almost no effect on the size of the PBPI-E rigid domains, but has a large effect on the populations of the PBPI-E rigid domains. It is the intermolecular charge-transfer interaction that plays a critical role in the miscibility of PEI-E/PTI-E and PBPI-E/PTI-E blends.

SOLID-STATE VOLTAMMETRY OF ELECTROACTIVE SOLUTES IN POLYMER SOLVENTS (PEO) AT ULTRAMICROELECTRODES

This paper describes the electrochemical oxidation and reduction of electroactive solutes which are dissolved in and diffusing through the polymer electrolyte solvent, poly(ethylene oxide) (PEO). The characteristics of electrochemical reactions in polymeric solutions are discussed, including how rigid solvent environments affect mass transport rates, and the transport phenomenon of electroactive species in PEO with bathing gases is explained by using the voltammetric theory of ultramicroelectrodes. The possibility that the microelectrode coated with PEO film can be used as a gas sensor has been discussed.

SYNTHESIS AND PROPELLER PROPELLER TRANSITION OF OPTICALLY-ACTIVE POLY(DIPHENYL-O-METHOXYPHENYLMETHYL METHACRYLATE)

Diphenyl-o-methoxyphenylmethyl methacrylate was polymerized with several organolithium complexes of chiral ligand such as (-)-sparteine (Sp) and (S,S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane (DDB). (+)-DDB was effective in preparing a polymer of high optical rotation, whereas (-)-Sp only gave oligomers with low optical rotation for the repulsive hindrance between the bulky ester group and the rigid ligand. The optical rotation of the polymer decreased rapidly to a constant value due to the propeller-propeller transition, which has been demonstrated by H-1 n.m.r. and circular dichroic spectra.

MICROSTRUCTURE ANALYSIS OF 3 SEGMENTED COPOLYMERS CONTAINING POLYDIMETHYLSILOXANE BY SOLID-STATE HIGH-RESOLUTION NMR

The microstructure of two bicomponent and one tricomponent segmented copolymers, based on polydimethylsiloxane, poly(p-hydroxystyrene) or/and polysulfone, were investigated using an extended Goldman-Shen pulse sequence, proton spin-spin relaxation measurements, and C-13 and Si-29 NMR spectra. The results indicate that there exist four phases with different sizes, components and morphological structure in the segmented copolymers studied in this work, i. e., a rigid-chain phase of very slow motion, a rigid-chain-rich phase of slow motion, a flexible-chain-rich phase of fast motion and a flexible-chain phase of faster motion. The sizes of different domains, calculated from the spin diffusion rates, are about 50-100 angstrom for the flexible-chain-rich phase of fast motion and 200-300 angstrom for the flexible-chain phase of faster motion. The relative quantities of polydimethylsiloxane in the flexible-chain phase of fast motion are slightly different in different kinds of segmented copolymers.

BETA-RELAXATION IN POLYIMIDES

A series of polyimides with different structures have been synthesized and studied by dynamic mechanical analysis. The results obtained indicate that the beta relaxation in polyimides is related to the rotation of rigid segment(s) of p-phenylene and imide groups around 'hinges' such as -O-, -CH2- and so on in diamines. It is noticed that two kinds of polyimides both with [GRAPHICS] imide groups have verv weak beta relaxation below the glass transition temperature. This phenomenon is due to the fact that the configuration of chains with the above imide groups hinders the rotation of the rigid segments in the chains.

HREM IMAGING OF POLY(ARYL-ETHER-KETONE) CRYSTAL

High resolution transmission electron microscope (HREM) was used to observe the rigid chain polymer poly(aryl-ether-ketone) (PEK), so as to study the morphology of the crystals and molecular arrangement within a crystal.Many kinds of material crystal structures have been studied with HREM in recent years. So far as polymeric materials are concerned, the application of HREM

Higher-order Boussinesq-type equations for interfacial waves in a two-fluid system

Interfacial waves propagating along the interface between a three-dimensional two-fluid system with a rigid upper boundary and an uneven bottom are considered. There is a light fluid layer overlying a heavier one in the system, and a small density difference exists between the two layers. A set of higher-order Boussinesq-type equations in terms of the depth-averaged velocities accounting for stronger nonlinearity are derived. When the small parameter measuring frequency dispersion keeping up to lower-order and full nonlinearity are considered, the equations include the Choi and Camassa's results (1999). The enhanced equations in terms of the depth-averaged velocities are obtained by applying the enhancement technique introduced by Madsen et al. (1991) and Schaffer and Madsen (1995a). It is noted that the equations derived from the present study include, as special cases, those obtained by Madsen and Schaffer (1998). By comparison with the dispersion relation of the linear Stokes waves, we found that the dispersion relation is more improved than Choi and Camassa's (1999) results, and the applicable scope of water depth is deeper.

A kind of extended Korteweg-de Vries equation and solitary wave solutions for interfacial waves in a two-fluid system

This paper considers interfacial waves propagating along the interface between a two-dimensional two-fluid with a flat bottom and a rigid upper boundary. There is a light fluid layer overlying a heavier one in the system, and a small density difference exists between the two layers. It just focuses on the weakly non-linear small amplitude waves by introducing two small independent parameters: the nonlinearity ratio epsilon, represented by the ratio of amplitude to depth, and the dispersion ratio mu, represented by the square of the ratio of depth to wave length, which quantify the relative importance of nonlinearity and dispersion. It derives an extended KdV equation of the interfacial waves using the method adopted by Dullin et al in the study of the surface waves when considering the order up to O(mu(2)). As expected, the equation derived from the present work includes, as special cases, those obtained by Dullin et al for surface waves when the surface tension is neglected. The equation derived using an alternative method here is the same as the equation presented by Choi and Camassa. Also it solves the equation by borrowing the method presented by Marchant used for surface waves, and obtains its asymptotic solitary wave solutions when the weakly nonlinear and weakly dispersive terms are balanced in the extended KdV equation.