Luminescence properties of the ternary rare earth complexes with beta-diketones and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method

Ternary complexes of rare earth Eu(dbm)(3).phen and Tb(acac)(3).phen (dbm = dibenzoylmethanide, acac = acetylacetone and phen = 1,10-phenanthroline) were introduced into silica gel by the sol-gel method. The result indicated that the rare earth ions (EU3+ and Tb3+) showed fewer emission lines and slightly lower emission intensities in the silica gel than in the pure rare earth complexes. The lifetimes of rare earth ions in silica gel (Eu3+ and Tb3+) doped with Eu(dbm)(3).phen and Tb(acac)(3).phen were longer than those in purl Eu(dbm)(3).phen and Tb(acac)(3).phen. A very small amount of rare earth complexes doped in a silica gel matrix can retain excellent luminescence properties. (C) 1997 Elsevier Science S.A.

Application of the Sanchez-Lacombe lattice fluid theory to the system pvme/ps and model calculations

Cloud point curves reported in the literature for five representatives of the system poly(vinyl methyl ether)/polystyrene were evaluated theoretically by means of the Sanchez-Lacombe lattice fluid theory. The measured phase separation behavior can be described within experimental error using only one adjustable parameter (quantifying the interaction between the unlike mers). The Flory-Huggins interaction parameters calculated from this theoretical description depend in good approximation linearly on composition (volume fractions) and on the inverse temperature. An evaluation of these data yields a maximum heat effect which is almost one order of magnitude less (ca. -0.25 J/cm(3)) than obtained via Hess's cycle (dissolution of the components and of the blend) from calorimetric measurements. Model calculations on the basis of the present theory demonstrate that the critical points shift to a different extent upon a certain relative change in the molar mass of the blend components. The sensitivity of the calculated phase diagrams against changes in the scaling parameter decreases in the following order: interaction energies between unlike mers, differences in the scaling temperatures, pressures and densities.

Structure and luminescence properties of some new AgLnW(2)O(8) compounds

Three new compounds, AgLnW(2)O(8) (Ln(3+)=Eu, Gd or Tb), have been prepared by a solid-state reaction and crystallize with a scheelite-related monoclinic symmetry. Their IR spectra show absorption transitions in the region 1000-400 cm(-1) similar to KLnW(2)O(8). Broad excitation and emission bands of the tungstate group with a large Stokes shift (12573 cm(-1)) are observed in AgGdW2O8. Excitation and emission spectra of AgLnW(2)O(8) (Ln=Eu or Tb) show that energy transfer from tungstate to Eu and Tb occurs and that Eu3+ ions occupy a unique crystallographic site with C-2 site symmetry.

Study on the microstructure and properties of nanosized stannic oxide powders

Stannic oxide xerogel was prepared by a forced hydrolysis method using SnCl4 as the precursor. The average grain sizes of the nanosized stannic oxide powders varied with the sintering temperatures. The powders were characterized by several different physico-chemical techniques. TEM was employed for the direct observation on grain sizes, shape and state of aggregation of the particles. XRD technique was used for the determination of the crystalline structure. Microstructural parameters of average crystallite size () and mean-square root microstrain (epsilon(2)>(1/2)) for the samples were calculated from the broadened values of the half-peak intensity of XRD. The atomic ratio between oxygen and tin in the surface region of the particles was estimated through the analysis of XPS. Attributing to lots of oxygen vacancies in the surface region of the nanoparticulates and the 'trapped electrons' in the vacancies, an ESR signal was observed in the sample sintered at 300 degrees C for 2 h. FTIR of the powders showed that intensity of the transverse optical mode of Sn-O stretching vibration increased with the sintering temperature while the bending vibration of O-Sn-O showed a blue shift. For Raman spectra, very important spectral characteristics such as variations of intensity and width of the bands were observed. A new Raman vibrational band located at 572 cm(-1) was identified in the samples of nanosized stannic oxide powders. Variation of these spectroscopic properties were strongly affected by grain size, shape and state of aggregation of the nanosized particulates.

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.

Structure/permeability and permselectivity relationship of polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride .3.

Gas permeability coefficients of a series of aromatic polyetherimides prepared from 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) and four (methylene dianiline)s with a methyl side group to H-2, CO2, O-2, N-2, and CH4 were measured under 7 atm and within a temperature range from 30 to 150 degrees C. The gas permeabilities and permselectivities of these polymers were compared with those of the HQDPA-based polyetherimides from methylene dianiline (MDA) and isopropylidene dianiline (IPDA). The number and position of the methyl side groups on the benzene rings of the diamine residues strongly affect the gas permeabilities and permselectivities of the HQDPA-based polyetherimides. The gas permeability of the polyetherimide progressively increases with an increase in the number of the methyl side groups. Both the gas permeability and permselectivity of the polyetherimides with methyl side groups are higher than those of HQDPA-MDA. The polyetherimide prepared from 3,3'-dimethyl 4,4'-methylene dianiline (DMMDA1) possesses both higher permeability and permselectivity than the polyetherimides prepared from 2,2'-dimethyl 4,4'-methylene dianiline (DMMDA2). However, two of the polyetherimides prepared 2,2',3,3'-tetramethyl 4,4'-methylene dianiline (TMMDA1) or 2,2', 5,5'-tetramethyl 4,4'-methylene dianiline (TMMDA2) possess almost the same gas permeability and permselectivity.

LUMINESCENCE AND ENERGY-TRANSFER OF RARE-EARTH-METAL IONS IN MG2Y8(SIO4)(6)O-2

The photoluminescence of Ce3+, Tb3+ and Sm3+, and energy transfer from Ce3+ to Tb3+, Dy3+ and Sm3+ in Mg2Y8(SiOd(4))(6)O-2 are reported and discussed. The Ce3+ ion shows blue luminescence under UV excitation, and occupies simultaneously the 4f site and 6h site in the host lattice. The optimum concentrations for the D-5(3) and D-5(4) emissions of Tb3+ and the (4)G(5/2) emission of Sm3+ are determined to be 0.04, 0.20 and 0.10 mol in every mol of Mg2Y8(SiO4)(6)O-2, respectively. The critical distances responsible for the cross-relaxation between the D-5(3)-D-5(4) and F-7(6)-F-7(0) transitions of Tb3+ and between the (4)G(5/2)-F-4(9/2) and H-6(5/2)-F-4(9/2) transitions of Sm3+ are estimated to be 1.43 and 1.06 nm, respectively. Both Tb3+ and Dy3+ can be sensitized by Ce3+, but Ce3+ and Sm3+ quench each other.

COMPARATIVE-STUDY OF CA4Y6(SIO4)(6)O-A PHOSPHORS PREPARED BY SOL-GEL AND DRY METHODS (A=PB2+,EU3+, TB3+,DY3+)

Ca4Y6(SiO4)(6)O:A (A = Pb2+, Eu3+, Tb3+, Dy3+) phosphors have been prepared by two methods: the sol-gel method and the conventional dry method. The crystallization processes and the luminescence characteristics of the phosphors were studied, The sol-gel method features low-temperature formation of the phosphor, leading to successful preparation of Pb2+-activated phosphors which could not be prepared by the dry method at high temperature. The (4f)(8-)(4f)(7)(5d)(1) absorption band of Tb3+ and the charge-transfer (CT) band of Eu3+ have higher energies and narrower half-widths in the sol-gel-derived phosphors than in the phosphors prepared by the dry method, respectively. The Tb3+ and Dy3+ ions show stronger emission in the former than in the latter. Both the yellow-to-blue intensity ratio (Y:B) of Dy3+ and the red-to-orange intensity ratio (R:O) of Eu3+ in the sol-gel-derived phosphors are smaller than those for the phosphors derived by the dry method.

MODIFIED POLYSULFONES .1. SYNTHESIS AND CHARACTERIZATION OF POLYSULFONES WITH UNSATURATED END-GROUPS

Chloro-terminated polysulfones with various molecular weights were modified with poly(ethylene oxide) and poly[(ethylene oxide)(propylene oxide)] macromers carrying alpha-hydroxyl and omega-allyl end groups via classical polycondensation reactions. The pr

PENDANT FUNCTIONAL-GROUP COPOLYETHER SULFONES .1. SYNTHESIS AND CHARACTERIZATION OF NEW COPOLYETHER SULFONES WITH PENDANT ALDEHYDE GROUPS MODIFIED INTO PHENOLIC AZOMETHINE GROUPS

New functional copolyether sulfones with pendant aldehyde groups were synthesized by the classical polycondensation reaction between 4,4' -dichlorodiphenyl sulfone (I) and various bisphenols such as 5,5'-methylene bis-salicylaldehyde (II-2), 2,2-bis( 4-hydroxyphenyl)propane (III), and 2,6-bis(4-hydroxybenzylidene)cyclohexanone (IV). Condensation reaction with 4-aminophenol led to pendant phenolic azomethine groups containing copolyether sulfones. The structures of the resulting polymers were confirmed by IR, H-1-NMR spectra, and elemental analyses. The polymers were characterized by reduced viscosity, solubility, thermal stability, DSC, and x-ray diffraction measurements.

ARYLIDENE COPOLYETHER SULFONES .1. SYNTHESIS AND CHARACTERIZATION OF SOME NEW COPOLYETHER SULFONES CONTAINING DIBENZYLIDENE CYCLOPENTANONE MOIETIES

New copolyether sulfones containing 2,5-bis(4-oxo-benzylidene)-cyclopentanone moieties were prepared in the conventional literature manner by condensing the dipotassium salts of 2,5-bis(4-hydroxybenzylidene)cyclopentanone (I) and 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A, III) with 4,4'-dichlorodiphenyl sulfone (II), or by condensing the dipotassium salts of I with chlorine-terminated Bisphenol A-4,4'-dichlorodiphenylsulfone copolymers (V). The resulting copolyether sulfones were confirmed by IR, viscometry, DSC measurements, thermooptical analysis (TOA), and thermogravimetric analysis (TGA).

THE OPTICAL AND ELECTRICAL-PROPERTIES OF DYSPROSIUM AND YTTERBIUM MONOPHOSPHIDES

Dysprosium and ytterbium monophosphides have been prepared by the solid state reaction. The optical and electrical properties have been studied. Evidence that DyP and YbP are semiconductors has been obtained from the study of the absorption spectrum, the negative temperature coefficient of resistance and the rectifying effect. Their energy gaps are determined as 1.15 eV for DyP and 1.30 eV for YbP, electric conduction type is n-type, resistivities are about 10(-2) ohm cm and Hall mobility is 8.5-80 cm2/Vs. The p-n junction is formed on the LnP/Si.

两种超微细矿物粉体材料的制备及应用研究

Superfine mineral materials are mainly resulted from the pulverization of natural mineral resources, and are a type of new materials that can replace traditional materials and enjoy the most extensive application and the highest degree of consumption in the present day market. As a result, superfine mineral materials have a very broad and promising prospect in terms of market potential. Superfine pulverization technology is the only way for the in-depth processing of most of the traditional materials, and is also one of the major means for which mineral materials can realize their application. China is rich in natural resources such as heavy calcite, kaolin, wollastonite, etc., which enjoy a very wide market of application in paper making, rubber, plastics, painting, coating, medicine, environment-friendly recycle paper and fine chemical industries, for example. However, because the processing of these resources is generally at the low level, economic benefit and scale for the processing of these resources have not been realized to their full potential even up to now. Big difference in product indices and superfine processing equipment and technologies between China and advanced western countries still exists. Based on resource assessment and market potential analysis, an in-depth study was carried out in this paper about the superfine pulverization technology and superfine pulverized mineral materials from the point of mineralogical features, determination of processing technologies, analytical methods and applications, by utilizing a variety of modern analytical methods in mineralogy, superfine pulverization technology, macromolecular chemistry, material science and physical chemistry together with computer technology and so on. The focus was placed on the innovative study about the in-depth processing technology and the processing apparatus for kaolin and heavy calcite as well as the application of superfine products. The main contents and the major achievements of this study are listed as follows: 1. Superfine pulverization processing of mineral materials shall be integrated with the study of their crystal structures and chemical composition. And special attention shall be put on the post-processing technologies, rather than on the indices for particle size, of these materials, based on their fields of application. Both technical feasibility and economic feasibility shall be taken into account for the study about superfine pulverization technologies, since these two kinds of feasibilities serve as the premise for the industrialized application of superfine pulverized mineral materials. Based on this principle, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in this study, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in this study. Heavy calcite and kaolin are two kinds of superfine mineral materials that enjoy the highest consumption in the industry. Heavy calcite is mainly applied in paper making, coating and plastics industries, the hard kaolin in northern China is mainly used in macromolecular materials and chemical industries, while the soft kaolin in southern China is mainly used for paper making. On the other hand, superfine pulverized heavy calcite and kaolin can both be used as the functional additives to cement, a kind of material that enjoys the biggest consumption in the world. A variety of analytical methods and instruments such as transmission and scanning electron microscopy, X-ray diffraction analysis, infrared analysis, laser particle size analysis and so on were applied for the elucidation of the properties and the mechanisms for the functions of superfine mineral materials as used in plastics and high-performance cement. Detection of superfine mineral materials is closely related to the post-processing and application of these materials. Traditional detection and analytical methods for superfine mineral materials include optical microscopy, infrared spectral analysis and a series of microbeam techniques such as transmission and scanning electron microscopy, X-ray diffraction analysis, and so on. In addition to these traditional methods, super-weak luminescent photon detection technology of high precision, high sensitivity and high signal to noise ratio was also utilized by the author for the first time in the study of superfine mineral materials, in an attempt to explore a completely new method and means for the study of the characterization of superfine materials. The experimental results are really exciting! The innovation of this study is represented in the following aspects: 1. In this study, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in an innovative way, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in the industrialized production process*. Moreover, a new modification technology and related directions for producing the chemicals were invented, and the modification technology was even awarded a patent. 2. The detection technology of super-weak luminescent photon of high precision, high sensitivity and high signal to noise ratio was utilized for the first time in this study to explore the superfine mineral materials, and the experimental results can be compared with those acquired with scanning electron microscopy and has demonstrated its unique advantages. It can be expected that further study may possibly help to result in a completely new method and means for the characterization of superfine materials. 3. During the heating of kaolinite and its decomposition into pianlinite, the diffraction peaks disappear gradually. First comes the disappearance of the reflection of the basal plane (001), and then comes the slow disappearance of the (hkl) diffraction peaks. And this was first discovered during the experiments by the author, and it has never before reported by other scholars. 4. The first discovery of the functions that superfine mineral materials can be used as dispersants in plastics, and the first discovery of the comprehensive functions that superfine mineral materials can also be used as activators, water-reducing agents and aggregates in high-performance cement were made in this study, together with a detailed discussion. This study was jointly supported by two key grants from Guangdong Province for Scientific and Technological Research in the 10th Five-year Plan Period (1,200,000 yuan for Preparation technology, apparatus and post-processing research by using sub-micron superfine pulverization machinery method, and 300,000 yuan for Method and instruments for biological photon technology in the characterization of nanometer materials), and two grants from Guangdong Province for 100 projects for scientific and technological innovation (700,000 yuan for Pilot experimentation of superfine and modified heavy calcite used in paper-making, rubber and plastics industry, and 400,000 yuan for Study of superfine, modified wollastonite of large length-to-diameter ratio).

Synthesis and characterization of manganese-modified MCM-41

Manganese-modified mesoporous MCM-41 molecular sieves were synthesized at the absence of alkaline metal ions under mild alkaline condition using cetylpyridinium bromide surfactant as a template, and characterized with X-ray diffraction, N-2 adsorption, transmission electron microscopy, electron spin resonance (ESR), and nuclear magnetic resonance (NMR) spectroscopies. The synthesized MnMCM-41 has a high pore volume of 1.30 cm(3) g(-1) with a corresponding surface area of 1510 m(2) g(-1). The ESR and Si-29 MAS NMR spectra revealed the presence of framework manganese ions in either the as-synthesized or calcined forms. (C) 2002 Elsevier Science B.V. All rights reserved.