The optical spectroscopic properties of rare earth-activated barium orthophosphate in VUV-Vis range

The optical properties of rare earth ions-activated barium orthophosphate phosphors, Ba-3(PO4)(2):RE (RE = Ce3+, Sm3+, Eu3+, Eu2+, and Tb3+), were investigated in vacuum ultraviolet (VLTV)-Vis range. A band-band transition Of PO43- in Ba-3(PO4)(2) is observed in the region of 150-170 nm. The partial reduction of Eu3+ to Eu2+ was observed and confirmed by luminescent spectra under the VUV-UV excitation. It is proposed that the electronegative defects that formed by aliovalent substitution of Eu3+ on the Ba2+ site in the host are responsible for the reduction process.

Study on the cyclization of cis-1,4 polybutadiene in various solvents and its mechanism

The cyclization of cis-1,4 polybutadiene in various solvents (mesitylene,xylene, toluene,benzene and cyclohexane) with the catalyst composed of CH2=CHCH2Cl-AlEt2Cl was studied. The infrared spectra of the cyclized products were investigated. It was shown that the products produced in cyclohexane and mesitylene have infrared spectra identical with those of the original cis-1,4-polybutadiene and the products obtained in other aromatics have infrared spectra different from each other and distinguishing with those of the parent cis-1,4 polybutadiene. The analyses of infrared spectra came to the conclusion that the molecules of aromatic solvent participate in cyclization of cis-1,4 polybutadiene at the given condition. A possible reaction scheme involving an electrophilic substitution of carbonium ions for Ar-H of aromatic solvents was proposed. Some experimental facts were explained with great satisfaction on the basis of the above mechanism.

Shear induced mixing/demixing: Blends of homopolymers, of homopolymers plus copolymers, and blends in solution

Shear may shift the phase boundary towards the homogeneous state (shear induced mixing, SIM), or in the opposite direction (shear induced demixing, SID). SIM is the typical behavior of mixtures of components of low molar mass and polymer solutions, SID can be observed with solutions of high molar mass polymers and polymer blends at higher shear rates. The typical sequence with increasing shear rate is SIM, then occurrence of an isolated additional immiscible area (SLD), melting of this island into the main miscibility gap, and finally SIM again. A three phase line originates and ends in two critical end points. Raising pressure increases the shear effects. For copolymer containing systems SID is sometimes observed at very low shear rates, preceding the just mentioned sequence of shear influences.

Circular dichroism spectro electrochemical and voltammetric studies of vitamin B-2

Electroreduction of vitamin B-2 (VB2) was studied by in situ circular dichroism (CD) spectroelectrochemistry (SEC) with a long optical path length thin layer cell (LOPLTLC). The results showed that the electroreduction of VB2 in phosphate buffer solution (PBS) (PH 6.8) was a two-electron electrochemical process with weak adsorption of the reactant at the glassy carbon (GC) electrode surface. The CD spectra change of VB2 in the reduction process was explained with the theory of electronic states. We also treated the CD spectra with a singular value decomposition least square (SVDLS) method, and have found not only the number of components and their spectra, but also the fraction distribution of each component in the electroreduction process of VB2.

Luminescent centers of EU2+ in BaMgAl10O17 phosphor

Two kinds of luminescent centers an observed in BaMgAl10O17:Eu2+ phosphor. Influence of flux on luminescence of Eu2+ in the phosphor is discussed in detail. There exists Eu2+ (F-) center (a luminescent center with 277 nm excitation band and 386 nm emission band) due to the substitution of F- ions for O2- ions, Effective energy transfer from Eu2+ (F-) to Eu2+ (O2-) (a luminescent center with 334 nm excitation band and 450 nm emission band) is observed. The quenching concentration of Eu2+ in BaMgAl10O17 is raised by 0.20 mole per mole host due to forming of new luminescent center Eu2+ (F-). (C) 2001 Elsevier Science Ltd. All rights reserved.

A study on the mechanism of the abnormal reduction of Eu3+ -> Eu2+ in Sr2B5O9Cl prepared in air at high temperature

This paper reports a new observation of the abnormal reduction of Eu3+ --> Eu2+ in Sr2B5O9Cl when prepared in air at high temperature. A model based on the nature of substitution defects is proposed to explain this abnormal reduction. Electrons, which reduced the Eu3+ ions, are created by the substitution of cations first and then transferred to the target Eu3+ ions via tetrahedral berate anion groups. Codoping experiments are designed and performed. The results of these experiments support the model proposed. (C) 1999 Academic Press.

Valence stability and change of Eu(II)in oxides

Valence stability and change of Eu(II) in oxides have been studied by luminescence spect a. The results show that the valence stability and change of Eu(II)in oxides is closely related to the radius and electric charge of positive ions substituted by Eu(II) and crystal structure of the host such as Al2O3 which can form alpha-Al2O3 single phase and alpha-Al2O3 and gamma-Al2O3 mixed phases under different reaction temperatures. A, fairly good explanation is made by the proposed relation between energy coefficient and crystal structure for the first time to the observed experiment results. if the energy coefficients of substitution ions is more than that of Eu(II), the lattice substitution of Eu(II)for these ions is not occured generally and valence stare of Eu(II)is not stable and be easily changed into Eu(III). The lattice of gamma-Al2O3 can stablize the valence state of Eu(II)within certain coped concentration and in alpha-Al2O3 crystal lattice Eu(II)can be easily changed into Eu(III).

Structural and magnetic properties of (PrxSm1-x)Mn2Si2

Crystallographic and magnetic properties of intermetallic compounds (PrxSm1-x) Mn2Si2 (x = 0 similar to 0.80) have been investigated by X-ray powder diffraction, XPS and magnetic measurements. All the compounds crystallize in ThCr2Si2-type structure. Substitution of Pr for Sm leads to the increase of the lattice constants and the transition from antiferromagnetism (AFM) to ferromagnetism (FM). The valence-fluctuation in the compounds was observed and the relation between the change of electron binding energy and magnetic properties was also discussed preliminarily.

Studies of methane reforming with carbon dioxide on hexaaluminates

In this paper, a series of Sr1-xLaxNiAl11O19 catalysts were synthesized and their chemical and physical properties were investigated by XRD, UV-DRS, H-2-O-2 titration, TPR and Py-IR techniques. The experimental results show that the Sr1-xLaxNiAl11O19 catalysts have a magnetoplumbite structure and Ni ion is shared between tetrahedral and octahedral sites of the spinel blocks, and the amount of nickel ions in the tetrahedral environment increases with the increase of x value in Sr1-xLaxNiAl11O19. The TPR study revealed that the reducibility of the series of the catalysts depends strongly on the substitution value x, that is, a low temperature peak appears for samples without substitution, in case of samples with x = 1 high temperature peak appears, and for samples with 0substitution of Sr2+ by La3+ shows no significant effect on the catalytic activity for reforming reaction due to the similar dispersion of Ni particle. Whereas, the substitution has a great effect on the acidity of catalyst, the number of acidic sites and amount of the carbon deposition on the catalyst surface. So it is evident that carbon deposition in carbon dioxide reforming of methane can be suppressed by decreasing the acidity of the complex oxides catalysts.

Physico-chemical properties and catalytic behavior of LnSrNiO(4) mixed oxides for NO decomposition

A series of LnSrNiO(4)(A(2)BO(4), Ln = La, Pr, Nd, Sm, Gd) mixed oxides with K2NiF4 structure, in which A-site(Sr) was partly substituted by individual light rare earth element, was prepared. The solid state physico-chemical properties including crystal structure, defect structure, IR spectrum, valence state of H-site ion, nonstoichiometric oxygen, oxygenous species, the properties of oxidation and reduction etc. as well as the catalytic behavior for NO decomposition on these mixed oxides were investigated. The results show that all of these mixed oxide catalysts have high activity for the direct decomposition of NO(at 900 degrees C the conversion of NO is more than 90%). The effect of the substitution of light rare earth elements at A-site on catalytic behavior for NO decomposition was elucidated.

Electrochemical properties of LaAl2 laves phase alloy

The electrochemical performance of Laves phase alloys LaAl2 and LaAl1.5Ni0.5 were investigated. The results showed that LaAl2 alloy milled for 2 hours has the larger discharge capacity than that of as-cast alloy. In addition, partial substitution of Ni for Al will clearly increases the discharge capacity of milled LaAl2 alloy.

Synthesis and properties of optically active aromatic polyimides derived from optically pure 1,1'-bi-2-naphthol

A series of new optically active aromatic polyimides containing axially dissymmetric 1,1'-binaphthalene-2,2-diyl units were prepared from optically pure (R)-(+)-or (S)-(-)-2,2'-bis(3,4-dicarboxyphenoxy)-1,1'-binaphthalene dianhydrides and various aromatic diamines via a conventional two-step procedure that included ring-opening polycondensation and chemical cyclodehydration. The optically pure isomer of dianhydride was prepared by a nucleophilic substitution of optically pure (R)-(+)or (S)-(-)1,1'-bi-2-naphthol with 4-nitrophthalonitrile in aprotic polar solvent and subsequent hydrolysis of the resultant tetranitrile derivatives, followed by the dehydration of the corresponding tetracarboxylic acids to obtain the dianhydrides. These polymers were readily soluble in common organic solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and m-cresol, etc., and have glass transition temperatures of 251-296 degrees C, and 5% weight loss occurs not lower than 480 degrees C. The specific rotations of the optically active polyimides ranged from +196 degrees to +263 degrees, and the optical stability and chiroptical properties of them were also studied. (C) 1997 John Wiley & Sons, Inc.

Single crystal growth and spectroscopic properties of KZnF3:Eu3+

Single crystal of KZnF3 : Eu3+ has been grown by means of Bridgman-Stockbarger technique in Ar atmosphere, The emission and excitation spectra of europium ion were measured, The results show that a small amount of Eu2+ exists in the crystal, The existence of Eu2+ ions was also confirmed by ESR data, The valence change of Eu ions during the crystal growth is due to unequivalent substitution of Eu3+ ions for the lattice ions. The sites possibly occupied by Eu ions in this crystal were also discussed.

Catalysis of the rare earth containing mixed oxides Ln(2)CuO(4) in phenol hydroxylation

Mixed oxides Ln(2)CuO(4+/-lambda)(Ln = La, Pr, Nd, Sm, Gd) with K2NiF4 structure were prepared. Their crystal structures were studied with XRD and IR spectra. Meanwhile, the average valence of Cu ions and nonstoichiometric oxygen (lambda) were determined through chemical analyses. Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated. Results show that the catalysis of these mixed oxides has close relation with their structures and composition. Substitution of A site atom in Ln(2)CuO(4+/-lambda) has a great influence on their catalysis in the phenol hydroxylation.

The synthesis of a 1,1'-bi-2-naphthol-based bis(ether anhydride) and aromatic polyimides derived therefrom

2,2'-Bis(3,4-dicarboxyphenoxy)-1,1'-binaphthyl dianhydride was used as a new monomer with various aromatic diamines to obtain polyimides by the usual two-step method. The bis(ether anhydride) was prepared by a nucleophilic substitution of I,1'-bi-2-naphthol with N-phenyl-4-chlorophthalimide, N-methyl-4-nitrophthalimide or 4-nitrophthalonitrile in aprotic polar solvent, and subsequent hydrolysis of the resulting bis(ether imide)s or bis(ether dinitrile), and then dehydration of the corresponding tetracarboxylic acid to afford the dianhydride. Most of the obtained polyimides were soluble in chloroform, pyridine, DMF, etc. The polyimide prepared from p-phenylene diamine was partial crystalline, whereas the others showed amorphous patterns in a WAXD study. These polymers have glass transition temperatures between 255-294 degrees C and 5% weight loss temperatures in the range of 502-541 degrees C in nitrogen and 473-537 degrees C in air. (C) 1997 Elsevier Science Ltd.