M5(PO4)3F (M=Ca, Sr, Ba)中Sm3+的电荷迁移态及Sm3+和Eu3+的电荷迁移能量关系

采用高温固相反应合成了M_5-2xSm_xNa_x(PO₄)₃F(M=Ca,Sr,Ba)荧光体,研究了其在真空紫外-可见光范围的发光特性。发现在Ca₅(PO₄)₃F中Sm³⁺的电荷迁移带约在191 nm,在Sr₅(PO₄)₃F中约在199 nm,而在Ba₅(PO₄)₃F中约在204 nm,随着被取代碱土离子半径的增大电荷迁移能量逐渐减小。比较了M₅(PO₄)₃F (M=Ca,Sr,Ba)中Sm³⁺和Eu³⁺电荷迁移能量的关系。     

Mechanism of thermal decomposition of hydrogenphosphities

Evolution of hydrogen during thermal decomposition of some M^IIHPO₃ (M= Mg, Ca, Zn, Sr, Cd, Ba) phosphities under nitrogen atmosphere was investigated. Step mechanism of thermal decomposition has been proposed.

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Zusammenfassung Es wurde die Wasserstoffentwicklung während der thermischen Zersetzung einiger Phosphite M^II)HPO₃ (mitM=Mg, Ca, Zn, Sr, Cd, Ba) in einer Stickstoffatmosphäre untersucht. Es wurde ein schematischer Mechanismus für die thermische Zersetzungsreaktion gegeben.

     

Structure and photoluminescence properties of Ce-doped novel silicon-oxynitride Ba4−zMzSi8O20−3xN2x (M=Mg, Ca, Sr)

Structural and photoluminescence properties of undoped and Ce³⁺-doped novel silicon-oxynitride phosphors of Ba_4−zM_zSi₈O_20−3xN_2x (M=Mg, Sr, Ca) are reported. Single-phase solid solutions of Ba_4−zM_zSi₈O_20−3xN_2x oxynitride were synthesized by partial substitutions of 3O²⁻→2N³⁻ and Ba→M (M=Mg, Ca, Sr) in orthorhombic Ba₂Si₄O₁₀. The influences of the type of alkaline earth ions of M, the Ce³⁺ concentration on the photoluminescence properties and thermal quenching behaviors of Ba₃MSi₈O_20−3xN_2x (M=Mg, Ca, Sr, x=0.5) were investigated. Under excitation at about 330 nm, Ba₃MSi₈O_20−3xN_2x:Ce³⁺ (x=0.5) exhibits efficient blue emission centered at 400-450 nm in the range of 350-650 nm owing to the 5d→4f transition of Ce³⁺. The emission band of Ce³⁺ shifts to long wavelength by increasing the ionic size of M due to the modification of the crystal field, as well as the Ce³⁺ concentrations due to the Stokes shift and energy transfer or reabsorption of Ce³⁺ ions. Among the silicon-oxynitride phosphors of Ba₃MSi₈O_18.5N:Ce³⁺, M=Sr_0.6Ca_0.4 possesses the best thermal stability probably related to its high onset of the absorption edge of Ce³⁺.     

Investigation of s, p, d-element Niobates and Their Solid Solution Formation Processes by Thermal Analysis

The binary and ternary systems M'O(M'CO₃)-Nb₂O₅ and M'O(M'CO₃)-MO-Nb₂O₅, where M'=Ca,Sr and Ba and M=Cu, Ni, Cd, Zn and Pb, were investigated by means of thermal analysis in the temperature range 20–1500°C. The boundaries of stability of the solid solutions Sr_2−xMe_xNb₂O₇,Sr_2−xM_xNb₂O₇, Sr_4−xM_xNb₂O₉ and Sr_6−xM_xNb₂O₁₁ were determined by means of X-ray diffraction, and IR and Raman spectroscopy. The possibility of prognostication of the phase fields of stable solid solutions by calculation from the diagrams of the ‘comparative electronegativity of atoms vs. tolerance factor’ was demonstrated. The kinetic parameters of the interactions in theSrCO₃+MO+Nb₂O₅ powder mixtures were established. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermogravimetrische Untersuchungen an zeolithischen Erdalkalithioferraten(III)

The degradation of the hydrates of the alkaline earth thioferratesM(FeS₂)₂·xH₂O,M=Ca, Sr, Ba, resulting from ion exchange on KFeS₂, is studied by TG and by X-ray diffraction analysis. The zeolitic character of the very loosely bound water in these compounds is proved. There exist several cristallographically distinct phases as a function of the water content.

Herrn Prof. Dr.O. Hoffmann-Ostenhof zum 65. Geburtstag gewidmet.     

Electronegativity force of cations and thermal decomposition of complex fluorides

The thermal decompositions of anhydrous fluorosilicates M₂SiF₆ (M=Li, Na, K, Rb, Cs) and MSiF₆ (M=Ca, Sr, Ba) were investigated. The decompositions proceeded according to a simple acid-base mechanism with evolution of SiF₄. The influence of the cationic counter-ion acidity (expressed by means of the electronegativity force) on the course of thermal decomposition was estimated quantitatively.     

Etude des systemes CaHPO4−MHPO4−H2O (M=Sr,Ba) A 50°C

The systems CaHPO₄−MHPO₄−H₂O (M=Sr, Ba) were studied at 50°C. ForM=Sr, the series of single phases, Ca_1−xSr_xHPO₄ for 0.95<X<0.75 and Ca_xSr_1−xHPO₄ for 0.4<X<1 have been prepared. These solid solution were caracterized by their infrared spectra and their crystallographic unit cell parameters. ForM=Ba a new phase Ca₂Ba(HPO₄)₃ has been determined. It was characterized by DRX, IR, ATD and chemical analyses.

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Zusammenfassung Bei 50°C wurde das System CaHPO₄−MHPO₄−H₂O (mitM=Sr, Ba) untersucht. FürM=Sr wurden Serien von Einzelphasen erhalten: Ca_1−xSr_xHPO₄ für 0.95<X< 0.75 und Ca_xSr_1−xHPO₄ für 0.4<X<1. Diese Mischkristalle wurden anhand ihrer Infrarotspektren und ihrer kristallographischen Elementarzellenparameter charakterisiert. FürM=Ba wurde die neue Phase Ca₂Ba(HPO₄)₃ ermittelt. Sie wurde mittels DRX, IR, ATD und chemischer Analyse charakterisiert.

     

Electronegativity force of cations and thermal decomposition of complex fluorides

The thermal decomposition of anhydrous fluoroborates MBF₄ (M=Li, Na, K, Rb, Cs) and M(BF₄)₂ (M=Ca, Sr, Ba) was investigated. The decomposition proceeds according to a simple acid-base mechanism with evolution of BF₃. The influence of the acidity of cationic counterions, expressed by the electronegativity force on the course of thermal decomposition was estimated quantitatively.     

A simple urea-based route to ternary metal oxynitride nanoparticles

Ternary metal oxynitrides are generally prepared by heating the corresponding metal oxides with ammonia for long durations at high temperatures. In order to find a simple route that avoids use of gaseous ammonia, we have employed urea as the nitriding agent. In this method, ternary metal oxynitrides are obtained by heating the corresponding metal carbonates and transition metal oxides with excess urea. By this route, ternary metal oxynitrides of the formulae MTaO₂N (M=Ca, Sr or Ba), MNbO₂N (M=Sr or Ba), LaTiO₂N and SrMoO_3−xN_x have been prepared successfully. The oxynitrides so obtained were generally in the form of nanoparticles, and were characterized by various physical techniques.     

PTX phase equilibrium study of new solid solution systems,Cd1−xMxS (M = Mg,Ca, Sr)

Pressure, temperature, and composition phase equilibrium diagrams of new solid solution systems of the Cd_1?xM_xS (M = Mg, Ca, Sr) type were investigated using the quenching method. The stable region for the rock-salt-type phase is widely extended toward the high-temperature/low-pressure region by substituting 10–20 mole% of Cd with Ca or Sr. Temperature and composition phase diagrams for each solid solution system were obtained at 2 GPa. The rock-salt-type phase stability is discussed in view of these phase relations.     

Phase Formation Study of The Substituted Lanthanum Manganites Solid Solutions

It is well known that the manganites-based solid solutions are interesting for their electric and magnetic properties. LaMnO₃ exhibits a distorted perovskite structure due to Mn³⁺ ion, which determines the presence of the Jahn–Teller effect. Replacing La³⁺ host ions by cations of lower valence leads to the disappearance of this effect and changes the characteristics of these materials. Although the formation of manganites-based solid solutions has been intensively studied, there are some unelucidated aspects concerning their formation mechanism, depending both on the precursors used and on the thermal treatment applied in order to obtain suitable properties. In this work the formation mechanism of La_0.7M_0.3MnO₃ (M=Ca, Sr, Ca+Sr in equimolecular mixture) solid solutions, in isothermal and non-isothermal conditions, was studied. For this purpose XRD, DTA/TG and spectral techniques were used. The solid solutions formation was found to be more dependent on the Mn-precursors type than the thermal treatment conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal Behaviour Studies on Some Heterotrinuclearpolyacids

An improved method for the synthesis of four heterotrinuclearpolyacids of the type: H_x[EM′_yM″_zO₄₀⋅nH₂O (E=P, Si; M′=Mo, W; M″=V, W) was elaborated. The studied compounds were characterized by elemental analysis, IR spectra and thermal behaviour over 20–800°C temperature range. This revised version was published online in August 2006 with corrections to the Cover Date.     

On the characterization of BiMO2NO3 (M=Pb, Ca, Sr, Ba) materials related with the Sillén X1 structure

The compounds BiMO₂NO₃, with M=Pb, Ca, Sr, and Ba, were obtained as single-phase products from solid-state reactions in an atmosphere of nitrous gases. The oxide nitrates with Pb and Ca crystallize in the tetragonal space group I4/mmm with two formula units per unit cell; the oxide nitrates with Sr and Ba crystallize in the orthorhombic space group Cmmm with four formula units per unit cell. Lattice parameters at room temperature are a=397.199(4), c=1482.57(2) pm for M=Pb; a=396.337(5), c=1412.83(3) pm for M=Ca; a=1448.76(3), b=567.62(1), c=582.40(1) pm for M=Sr and a=1536.50(8), b=571.67(3), c=597.55(3) pm for M=Ba. The structures, which were refined by powder X-ray diffraction, consist of alternating [BiMO₂]⁺ and [NO₃]⁻ layers stacked along the direction of the long axis. IR and thermogravimetric data are also given. The various M²⁺ cations in BiMO₂NO₃ are compatible with each other; therefore and because of their layer-type structure, these compounds are interesting precursors for oxide materials, e.g., the HTSC compounds (Bi,Pb)₂Sr₂Ca_n−1Cu_nO_x.     

Die IR-Spektren einiger Arsenat-Halogen-Apatite

The infrared spectra of orthoarsenates with apatite structure, of the formulaM ₅(AsO₄)₃ X (M=Ca, Sr, Ba, Pb andX=F, Cl,Br) are measured and interpreted on the basis of a site-symmetry analysis. The influence of the different cations on the internal vibrations of the AsO₃ ⁴-ions is discussed.

     

Studies of some perovskite oxidation catalysts using dta techniques

Differential thermal analysis was used to detect the onset and extent of the catalytic oxidation of 1% hexane and to a lesser extent 3% CO in air. Unsupported catalysts as ground single crystals and in polycrystaline form were selected principally from the system La_1?xM_xMnO₃ where M = Pb. Ca, Sr, and Ba; although other materials, also having the perovskite structure, were investigated. The catalytic activity of these previously reported materials was confirmed. In general, catalytic activity followed the order Ba～Sr～Ca>Pb. Work ov2r a wide range of x in the Pb system did not indicate a strong variation with x. CO proved easier to oxidize than hexane but generally exhibited similar trends. An acid etch was found to enhance the activity and the effect of subsequent reheating was studied. Catalysts prepared by a variety of techniques were compared.     

Spektralphotometrische Untersuchung der Systeme NiF2/Erdalkalifluoride sowie des Systems CaF2/CoF2

The light absorption of the phases occurring in the systemsMF₂/NiF₂ (M=Ba, Sr, Ca) has been investigated. The colour curves of Ba₂NiF₆ (I) and of BaNiF₄ (II) show characteristic differences. The colour curve of SrNiF₄ is similar to that of II. The colour curves of the system CaF₂/NiF₂ are compared with those of the system CaF₂/CoF₂. From the colour curve of the latter system one can unambiguously infer that mixed cristals Ca_1–x Co _x F₂ (x0,01) exist. No evidence could be found for the existence of mixed cristals Ca_1–x Ni _x F₂ by the spectrophtometric method.

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Mit 6 Abbildungen     

Thermoanalytical study of the formation of compounds in the PbO−MO (M=Ca,Sr, Ca+Sr) system

In order to clarify the effect of PbO addition on the formation steps of the superconducting phases in the system Bi₂O₃?SrO?CaO?CuO, a study of solid-state reactions under non-isothermal conditions, in the PbO?MO (M=Ca, Sr, Ca+Sr) system has been carried out. Results suggest that the reactivity of the components in the system containing PbO and CaO is much higher than in the system containing SrO. The Ca₂PbO₄ compound is formed first even in the system whereM=Ca+Sr. It is confirmed that Ca₂PbO₄ systems containing PbO.     

Synthesis and characterization thesulphides type ZnS(1-x)MSx

ZnS_(1-x)MS_x(x=0.01 and M=Mn²⁺, Cu²⁺ and Eu²⁺) compounds have been obtained by precipitation from homogeneous solutions of zinc, copper, manganese and europium salts, with S^2- as the precipitating anion, formed by the decomposition of thioacetamide. The thermal study of the milled zinc acetate, thioacetamide, copper acetate, manganese acetate and europium nitrate, respectively, was studied for thermal analyis TG/DSC. XRD respect exhibits a zinc blend crystal structure. This revised version was published online in August 2006 with corrections to the Cover Date.     

Contribution a l'etude des systemes Ca3(PO4)2-MSO4 (M=Sr,Ba)

In the systems Ca₃(PO₄)₂-MSO₄ (M = Sr, Ba), the series of single phase Ca_21?3xM_2xI(PO₄)_14?2x(SO₄)_2x with 0<x<0.15 forM=Sr and 0<x<0.1 forM = Ba have been prepared. These solid solutions, respectively strontium phosphosulfate and barium phosphosulfate, are isostructural with anhydrous tricalcium orthophosphate. They have been characterized by their infrared spectra and their crystallographic unit cell parameters.     

In situ synthesis of composite MTiO3–Al2O3 coatings via laser zone melting

Laser zone melting was employed in this work to prepare MTiO₃ based coatings over commercial, polycrystalline Al₂O₃ substrates, using the corresponding mixtures of powdered alkaline earth carbonates and TiO₂ as starting materials. In situ synthesis of the series M = Ca, Sr, Ba was studied using a CO₂ laser as the heating source, emitting at 10.6 μm, following substrate preheating to a temperature of 750 °C and sample displacement speed of 500 mm h⁻¹. Microstructure (SEM) and phase composition (XRD) demonstrated in situ formation of crystalline MTiO₃ perovskite (M = Ca, Sr), MAl₂O₄ (M = Ca), MAl₁₂O₁₉ magnetoplumbite type (M = Sr) and MAl₁₄O₂₂ β-alumina type (M = Ba) phases. Substantial interaction with the substrate resulted in stable, 50–150 μm thick, composite coatings.