Neutron powder diffraction investigations of hydrogenated Pd3P0.80 and Pd6P

The solid solutions Sr_3?xLa_xMn₂O₇ (0 ≤ x ≤ 1.50) and Sr_3?xLn_xMn₂O₇ (Ln = Nd, Sm, Gd; 0 ≤ x ≤ 1.40) with Sr₃Ti₂O₇-type structure have been prepared. Their cell parameters and $\text{c}\text{a}$ ratios are related to the size of the rare earths and to the Mn³⁺ ion concentration.     

The Family of Ln2Ti2S2O5 Compounds (Ln=Nd, Sm, Gd, Tb, Dy, Ho, Er, and Y): Optical Properties

The optical properties of Ln₂Ti₂S₂O₅ compounds (Ln=Nd, Sm, Gd, Tb, Dy, Ho, Er, and Y) have been measured. Diffuse reflectance spectra revealed a strong absorption band above 2 eV, which explains the color of the compounds. Moreover, other bands, with a lower intensity, have been attributed to 4f-4f rare earth transitions. In the case of neodymium the derived energy level scheme is rich enough to determinate a set of phenomenological crystal field parameters that correctly reproduce the spectrum. These parameters were also calculated from the crystallographic structure, in a good agreement with the experiment. Finally, the paramagnetic susceptibility, well reproduced by the calculation, confirms that the rare earth is in a trivalent state.     

Homogeneity regions of neodymium,samarium, and europium manganites in air

XRD phase analysis of homogeneous phases and heterogeneous compositions of general formula Ln_2?x Mn_xO_3±δ (Ln = Nd, Sm, Eu; 0.90 ≤ x ≤ 1.20; Δx = 0.22) prepared by ceramic synthesis from oxides in air at 900–1400°C was used to determine the solubility boundaries for Ln₂O₃ oxides and maganese oxides in LnMnO_3±δ. The results were represented as fragments of the phase diagrams for the Ln-Mn-O systems in air. It was assumed that the solubility of Ln₂O₃ oxides in LnMnO_3±δ is determined by lattice defects, while that of manganese oxides, in addition to above mechanism, by the disproportionation reaction 2Mn³⁺ = Mn²⁺ + Mn⁴⁺ followed by the partial substitution of divalent magnesium for Ln³⁺ at cuboctahedral positions of the perovskitelike crystal lattice.     

Synthesis, characterization and thermal analysis of 1:1 and 2:3 lanthanide(III) citrates

The synthesis and characterization of lanthanide(III) citrates with stoichiometries 1:1 and 2:3; [LnL·xH₂O] and [Ln₂(LH)₃·2H₂O], Ln=La, Ce, Pr, Nd, Sm and Eu are reported. L stands for (C₆O₇H₅)^3? and LH for (C₆O₇H₆)^2?. Infrared absorption spectra of both series evidence coordination of carboxylate groups through symmetric bridges or chelation. X-ray powder patterns show the amorphous character of [LnL·xH₂O]. The compounds [Ln₂LH₃·2H₂O] are crystalline and isomorphous. Emission spectra of Eu compounds suggest C _2v symmetry for the coordination polyhedron of [LnL·xH₂O] and C _4v for [Ln₂(LH)₃·2H₂O]. Thermal analyses (TG-DTG-DTA) were carried out for both series. The thermal analysis patterns of the two series are quite different and both fit in a 4-step model of thermal decomposition, with lanthanide oxides as final products.     

Lumineszenz und sensibilisierte Emission der dreiwertigen Seltenen Erden in Sr3La2W2O12

By activation of the new host lattice Sr₃La₂W₂O₁₂ with the trivalent rare earth ions Nd, Eu, Ho, Er, Tm, Yb an intense emission in the visible and/or infrared region is obtained. Energy transfer from Er³⁺ to Tm³⁺ and Nd³⁺ to Yb³⁺ has been found to occur. The excitation, emission, and diffuse reflectance spectra are analyzed for Sr₃La₂W₂O₁₂: Ln³⁺ (Ln = Nd, Sm, Eu, Dy, Ho, Er, Tm, Yb).     

Substitutional solid solutions of bismuth-containing lanthanide dititanates,Ln2−xBixTi2O7

The formation of solid solutions Ln_2?xBi_xTi₂O₇, where Ln = La to Lu and Y, except Ce, Pm, and Eu, has been studied by Raman spectroscopy and to a lesser extent by X-ray diffraction. It has been established that the solubility of bismuth increases with decreasing ionic radius of the lanthanide element. No evidence was experimentally found in this work for the existence of Bi₂Ti₂O₇.     

Phase equilibria and crystal structure of the complex oxides in the Ln-Ba-Co-O (Ln=Nd, Sm) systems

The phase equilibria in the Ln-Ba-Co-O (Ln=Nd, Sm) systems were systematically studied at 1100 °C in air. The homogeneity ranges and crystal structure of the solid solutions: Ln_2−xBa_xO_3−δ (0<x≤0.1 for Ln=Nd and 0<x≤0.3 for Ln=Sm), Nd_3−yBa_yCo₂O₇ (0.70≤y≤0.80), BaCo_1−zSm_zO_3−δ (0.1≤z≤0.2) were determined by X-ray diffraction of quenched samples. The values of oxygen content (5+δ) for slowly cooled LnBaCo₂O_5+δ (Ln=Nd, Sm) samples were estimated as 5.73 for Ln=Nd, and 5.60 for Ln=Sm. The unit cell parameters were refined using Rietveld full-profile analysis. It was shown that NdBaCo₂O_5.73 possesses tetragonal structure and SmBaCo₂O_5.60 - orthorhombic structure. The projections of isothermal-isobaric phase diagrams for the Ln-Ba-Co-O (Ln=Nd, Sm) systems to the compositional triangle of metallic components were presented.     

Synthesis and structural study of the new rare earth magnesium borates LnMgB5O10 (Ln = La, …, Er)

To obtain rare earth luminescent materials with weak concentration quenching, the B₂O₃-rich portion of the ternary diagram Ln₂O₃MgOB₂O₃ (Ln = rare earth) has been investigated. A ternary phase of composition LnMgB₅O₁₀ has been found for Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er. These compounds all crystallize in the monoclinic space group $\text{P2}{}_1\text{c}$. The structure has been determined on a LaMgB₅O₁₀ crystal. A full-matrix least-squares refinement leads to R = 0.039. The structure can be described as being made of (B₅O₁₀^5?)_n two-dimensional layers linked together by the lanthanum and magnesium ions. The rare earth atom coordination polyhedra form isolated chains. These borates are isostructural with some rare earth cobalt borates.     

Synthesis,characterization and tg-dsc study of lanthanide trifluoroacetate-2-azacyclononanone compounds

The synthesis, characterization and tg-dsc study of Ln(tfa)₃?·?3aza where Ln?=?La, Pr, Nd, Sm, Eu, Gd, Tb and Er, tfa?=?trifluoroacetate and aza?=?2-azacyclononanone are reported. The obtained X-ray powder diffraction patterns show that the compounds are divided in two isomorphous groups: La, Pr, Nd and Eu, Sm, Gd, Tb and Er. For all compounds, the thermodegradation under nitrogen gave the respective oxifluorides (LnOF) as the final product. The melting temperature intervals are 105–110°C, 100–112°C, 90–95°C, 79–101°C, 65–70°C, 75–90°C, 64–76°C and 50–65°C for the La, Pr, Nd, Sm, Eu, Gd, Tb and Er compounds, respectively, and it is verified that the lanthanide contraction induces a weaker intermolecular interaction between adjacent molecules in the solid state.     

Thermal decomposition of rare earth element suberates in air atmosphere

The condition of thermal decomposition of La, Ce(III), Pr(III), Nd, Sm, Eu(III), Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu suberates were studied. The suberates of Ce(III), Sm, Eu(III), Ho, Tm, Yb and Lu heated lose crystallization water. Anhydrous Sm and Eu(III) suberates decompose to oxides with intermediate formation Ln₂O₂CO₃, whereas suberates of other lanthanides decompose directly to oxides. Suberates of La, Pr(III), Nd, Gd, Tb, Dy and Er lose some water molecules and then decompose directly to oxides. Only La complex decomposes to La₂O₃ via the intermediate formation La₂O₂CO₃.

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Zusammenfassung Es wurden die UmstÄnde der thermischen Zersetzung von La-, Ce(III)-, Pr(III)-, Nd-, Sm-, Eu(III)-, Gd-, Tb-, Dy-, Ho-, Er-, Tm-, Yb- und Lu-suberat untersucht. Bei Erhitzen verlieren Ce(III)-, Sm-, Eu(III)-, Ho-, Tm-, Yb- und Lu-suberat Kristallwasser. Wasserfreies Sm-bzw. Eu(III)-suberat zersetzt sich über das Zwischenprodukt der Zusammensetzung Ln₂O₂CO₃ zum Oxid, wÄhrend sich die Suberate der anderen Lanthanoide direkt zu den Oxiden zersetzen. La-, Pr(III)-, Nd-, Gd-, Tb-, Dy- und Er-suberat geben einige Moleküle Kristallwasser ab und zersetzen sich dann direkt zu den Oxiden. Nur der Lanthankomplex zersetzt sich zu La₂O₃ über das Zwischenprodukt La₂O₂CO₃.

     

Thermal decompositions of lanthanum and lanthanide salts of sebacic acid

The conditions of thermal decomposition of La, Ce(III), Pr(III), Nd, Sm(III), Eu, Gd, Tb(III), Dy, Ho, Er, Tm, Yb and Lu sebacates have been studied. When heated in air atmosphere, the sebacates of La and lanthanides with general formula Ln₂(C₁₀H₁₆O₄)₃·nH₂O, wheren=6?24, lose some crystallization water molecules in one or two steps at 323–343 K and are then dehydrated and decomposed simultaneously to the oxides Ln₂O₃, CeO₂, Pr₆O₁₁ and Tb₄O₇. The oxides are formed over the range of temperature 783 K (CeO₂)?1073 K (Nd₂O₃).     

Verbindungen der Seltenerdelemente mit α-Benzoinoxim, 1. Mitt.

Zusammenfassung Substanzen der ZusammensetzungLnCl₃·3H₂ Box ^* (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Y) und LaBr₃·3 H₂ Box wurden isoliert und durch Thermoanalyse, IR-Absorptionsspektren und Röntgenstreuung charakterisiert.

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Compounds of the rare earth elements with -benzoin oxime

Compounds of compositionLnCl₃·3 H₂ Box ^* (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Y) and LaBr₃·3H₂ Box were isolated and characterized by thermoanalysis, IR spectroscopy and X-ray diffraction.

     

Les phases SrLnMnO4 (Ln = La,Nd, Sm,Gd), BaLnMnO4 (Ln = La,Nd) et M1+xLa1−xMnO4 (M = Sr,Ba)

The phases SrLnMnO₄ (Ln = La, Nd, Sm, Gd), BaLnMnO₄ (Ln = La, Nd) and the solid solutions M_1+xLa_1?xMnO₄ (M = Sr: 0 ? x ? 1; M = Ba: 0 ? x ? 0.50) have a K₂NiF₄-type structure. The $\text{c}\text{a}$ ratio of the unit cell is related to the electronic configuration of the Mn³⁺ ions.     

Multicolour Optical Coding from a Series of Luminescent Lanthanide Complexes with a Unique Antenna

The bis‐tetrazolate‐pyridine ligand H₂pytz sensitises efficiently the visible and/or near‐IR luminescence emission of ten lanthanide cations (Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb). The Ln^III complexes present sizeable quantum yields in both domains with a single excitation source. The wide range of possible colour combinations in water, organic solvents and the solid state makes the complexes very attractive for labelling and encoding.     

Stuffed rare earth pyrochlore solid solutions

Synthesis and crystal structures are described for the compounds Ln₂(Ti_2−xLn_x)O_7−x/2, where Ln=Tb, Dy, Ho, Er, Tm, Yb, Lu, and x ranges from 0 to 0.67. Rietveld refinements of X-ray powder diffraction data indicate that in the Tb and Dy titanate pyrochlores, the extra Ln³⁺ cations mix mainly on the Ti⁴⁺ site with little disorder on the original Ln³⁺ site. For the smaller rare earths (Ho-Lu), stuffing additional lanthanide ions results in a pyrochlore to defect fluorite transition, where the Ln³⁺ and Ti⁴⁺ ions become completely randomized at the maximum (x=0.67). Initial magnetic characterization for the fully stuffed x=0.67 samples for Ln=Tb-Yb shows no long range ordering down to 2 K, and only partial saturation of the full expected magnetic moment under applied fields up to 5 T. In all of these Ln-Ti-O pyrochlores, the addition of magnetic Ln³⁺ in place of non-magnetic Ti⁴⁺ adds edge sharing tetrahedral spin interactions to a normally corner sharing tetrahedral network of spins. The increase in spin connectivity in this family of solid solutions represents a new avenue for investigating geometrical magnetic frustration in the rare earth titanate pyrochlores.     

Sur une série de solutions solides de formule Ca2−xLnxMnO4 (Ln = Pr,Nd, Sm,Eu, Gd)

A new series of solid solutions Ca_2−xLn_xMnO₄ (Ln = Pr, Nd, Sm, Eu et Gd) in which manganese is found in both oxidation state of +III and +IV, have a structure derived from that of K₂NiF₄. The cationic distribution in sites of nine-fold coordination is random.     

Über die Auflösung der Seltenerdoxide in methanolischen Ammoniumacetatlösungen und die Darstellung von Verbindungen des TypsLn(OAc)3. 3NH4OAc. 1H2O bzw.Ln)OAc)3. 1 NH4OAc. 1H2O

Zusammenfassung Die Oxide der Lanthanide und des Yttriums lösen sich beim Erhitzen in methanol. Ammoniumacetatlösungen. Aus den Lösungen konnten Verbindungen vom TypLn(OAc)₃·3 NH₄ OAc· ·1 H₂O (Ln=La, Ce, Pr, Nd, Sm Eu, Gd, Tb, Dy, Ho) bzw. Ln(OAc)₃ 1 NH₄OAc 1 H₂O (Ln=Er, Yb, Y) isoliert werden.Die höheren Oxide PrO_1,83 und TbO_1,75 lösen sich nur unvollständig unter Valenzdisproportionierung. Der Löserückstand besteht aus PrO₂ bzw. TbO₂.

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The oxides of the lanthanides and yttrium are dissolved in the heat by methanolic ammonium acetate solutions. From the obtained solutions compounds of the typeLn(OAc)₃·3 NH₄ OAc· ·1 H₂O (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho) andLn(OAc)₃·1 NH₄OAc·1 H₂O (Ln=Er, Yb, Y), respectively, could be isolated.The higher oxides PrO_1,83 and TbO_1,75 react incompletely and disproportionation of valence is observed. The residues consist of PrO₂ and TbO₂, respectively. *** DIRECT SUPPORT *** A3615112 00028

     

A systematic study on crystal structure and magnetic properties of Ln3GaO6 (Ln=Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er)

The crystal structures of a series of compounds with the composition Ln₃GaO₆(Ln=Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er) synthesized by solid-state reaction at 1400°C are investigated. X-ray diffraction shows that Ln₃GaO₆ has a non-centrosymmetric orthorhombic structure (space group Cmc2₁). Lattice parameters a,b,c and cell volume and the average distances between Ln(1)-O, Ln(2)-O of these compounds decrease with the decreasing of the radii of trivalent Ln ions, which accord with the expected lanthanide contraction behavior. There are two sites of seven-fold coordination for Ln atoms with oxygens, and Ga atoms are in oxygen tetrahedra which are distorted and elongated along the a-axis. Magnetization measurements indicate that the susceptibility χ changes with temperature in Curie-type manner.     

Glycolate Ti1 − x Fe x (OCH2CH2O)2 − x/2 as a precursor for the preparation of quasi-one-dimensional (1D) solid solutions Ti1 − x Fe x O2 − 2x/2 (0 ≤ x ≤ 0.1)

Quasi-one-dimensional (1D) solid solutions Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} (0 < x ≤ 0.1) with the structure of anatase were prepared by heating the glycolate Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} in an atmosphere of air at a temperature of >450°C. The conditions of formation and the properties of the new glycolate Ti₃Fe₂(OCH₂CH₂O)₉ were described. It was found that the synthesized Ti_{1 ? x} Fe _x O_{2 ? 2x/2} solid solutions exhibit photocatalytic activity in the reaction of hydroquinone oxidation in an aqueous solution on irradiation with UV light. A correlation between the rate of oxidation of hydroquinone and the concentration of iron in the catalyst was established. A procedure for the preparation of titanium dioxide with the structure of anatase doped with iron and carbon (Ti_{1 ? x} Fe _x O_{(2 ? x/2) ? yCy)} and also composites on its basis, which contain an excess amount of carbon, was proposed.     

Thermal behaviour of hydrated lanthanide complexes with heptanedioic acid

The multi-step dehydration and decomposition of trivalent lanthanum and lanthanide heptanediate polyhydrates were investigated by means of thermal analysis completed with infrared study. Further more, X-ray diffraction data for investigated heptanediate complexes of general stoichiometry Ln₂(C₇H₁₀O₄)₃.nH₂O (wheren=16 in the case of La, Ce, Pr, Nd and Sm pimelates,n=8 for Eu, Gd, Tb, Dy, Er and Tm pimelates,n=12 for Ho, Yb and Lu pimelates) were also reported.

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Zusammenfassung Mittels TG, DTG, DTA wurde in Verbindung mit IR-Methoden der mehrstufige Dehydratations- und der Zersetzungsvorgang der Polyhydrate der PimelinsÄuresalze von dreiwertigem Lanthan und dreiwertigen Lanthanoiden untersucht. Röntgendiffraktionsdaten der untersuchten Heptandiat-Komplexe mit der allgemeinen Formel Ln₂(C₇H₁₀O₄)₃ nH₂O (mitn=16 für Ln=La, Ce, Pr, Nd und Sm,n=8 für Ln=Eu, Gd, Tb, Dy, Er und Tm sowien=12 für Ln=Ho, Yb und Lu) werden ebenfalls gegeben.