A series of rare earth silicates RE3+2M3+[SiO4]2 (OH)

A series of isotypic silicates of composition RE₂M[SiO₄]₂ (OH) with RE = La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, and M = Al³⁺, Fe³⁺ has been synthesized under hydrothermal conditions. Lattice constants of two members as determined from single crystal X-ray diffraction data are: La₂Al[SiO₄]₂ (OH) (La₂Fe[SiO₄]₂ (OH)) $\text{a}{}_{\mathrm{o}}\text{= 7.401 (7.346)}\text{A}\text{?}$, $\text{b}{}_{\mathrm{o}}\text{= 5.702 (5.862)}\text{A}\text{?}$, $\text{c}{}_{\mathrm{o}}\text{= 17.072 (97.196)}\text{A}\text{?}$, gb = 112.4 (112.5°), $\text{P}\text{2}{}_1\text{c}$, Z=4.     

The crystal structures of Ba2LaRuO6 and Ca2LaRuO6

Neutron diffraction experiments have been performed to determine the structures of Ba₂LaRuO₆ and Ca₂LaRuO₆. Both are ordered, distorted perovskites. Ba₂LaRuO₆ is monoclinic, space group $\text{P}\text{2}{}_{\mathrm{<mtext>1</mtext>}}\text{n}$ with $\text{a}{}_0\text{=6.0285(7)}\text{A}\text{?}$, $\text{b}{}_0\text{=6.0430(7)}\text{A}\text{?}$, $\text{c}{}_0\text{=8.5409(6)}\text{A}\text{?}$, β=90.44(1)^o. The A sites are occupied by barium and the B sites by an ordered arrangement of lanthanum and ruthenium. Ca₂LaRuO₆ is triclinic, space group P1 with a₀=5.6179(5), b₀=5.8350(5), c⁰=8.0667(4), α=90.0^o, β=89.76(1)^o, γ=90.0^o. The A sites are occupied by calcium and lanthanum in a disordered manner, and the B sites are occupied by an ordered arrangement of calcium and ruthenium. The results reported in this paper thus contradict those of previous workers. The low-temperature magnetic structures are discussed briefly.     

Syntheses and magnetic properties of Eu3B2O6 and Sr3B2O6

Europium orthoborate and strontium orthoborate crystallize in the rhombohedral system with two formula units in a cell of dimensions $\text{a}{}_{\mathrm{R}}\text{=6.697}\text{A}\text{?}$, α_R=85.17° for Eu₃B₂O₆, and $\text{a}{}_{\mathrm{R}}\text{=6.695}\text{A}\text{?}$, α_R=85.00° for Sr₃B₂O₆. The equivalent hexagonal lattice parameters are $\text{a}{}_{\mathrm{H}}\text{=9.069}\text{A}\text{?}$, $\text{c}{}_{\mathrm{H}}\text{=12.542}\text{A}\text{?}$, and $\text{a}{}_{\mathrm{H}}\text{=9.046}\text{A}\text{?}$, $\text{c}{}_{\mathrm{H}}\text{=12.566}\text{A}\text{?}$ respectively. Eu₃B₂O₆ appears to be ferromagnetic below 7.5K.     

Structure determination of (3D) P2NbS8

Tridimensional P₂NbS₈ crystallizes in P4?n2 tetragonal space group, with $\text{a}\text{= 12.0483(4)}\text{A}\text{?}$, $\text{c}\text{= 7.2070(5)}\text{A}\text{?}$, $\text{V}\text{= 1046.2(1)}\text{A}\text{?}{}^3$ and Z = 4. The structure was anisotropically refined down to R = 2.3% from 468 reflexions and 53 variables. It is built from [Nb₂S₁₂] biprismatic bicapped units (average $\text{d}{}_{\mathrm{Nb?S}}\text{= 2.571}\text{A}\text{?}$) made of S^?II and S^?II₂ anions (dianionic distance of 2.014(3) Å). The niobium atoms are found as isolated Nb^IV ? Nb^IV pairs ($\text{d}{}_{\mathrm{Nb?Nb}}\text{= 2.859(1)}\text{A}\text{?}$) in these niobium group otherwise linked to each other through (PS₄) tetrahedral units (average $\text{d}{}_{\mathrm{P?S}}\text{= 2.051}\text{A}\text{?}$) themselves constituting interbonded [P₄S₁₂] rings. The P₂NbS₈ three-dimensional network thus obtained is compared to the (2D) P₂NbS₈, layered phase already described.     

Refinement of the structure of K2Cr2O7

The parameters for the structure of K₂Cr₂O₇ have been refined from 7511 observed reflections; $\text{a}{}_{\mathrm{o}}\text{= 7.4200(6)}\text{A}\text{?}$, $\text{b}{}_{\mathrm{o}}\text{= 13.399(3)}\text{A}\text{?}$, $\text{c}{}_{\mathrm{o}}\text{= 7.3845(9)}\text{A}\text{?}$, cosα = ?0.1396(2) (α = 98°2'), cosβ = ?0.0154(2) (β = 90°53'), cosγ = ?0.1078(2) (γ = 96°11'). The discrepancy factor R(F_o²) = 0.0702 with a type 2 extinction correction. The average CrO distances are 1.609Å (unshared) and 1.783Å (shared).     

New phase with K2NiF4 structure in the LaLiFeO system

The existence has been proved, for the first time, in the LaLiFeO system of the phase (La_1.75Li_.25) (Fe_.5Li_.5)O_4?x with tetragonal symmetry ($\text{a}{}_{\mathrm{o}}\text{=3.765±0.001}\text{A}\text{?}$; $\text{c}{}_{\mathrm{o}}\text{=12.918±0.01}\text{A}\text{?}$; $\text{c}{}_{\mathrm{o}}\text{a}{}_{\mathrm{o}}\text{=3.43}$) and K₂NiF₄-type structure.This phase gives probably the first example of lithium distribution in both A and B sites of A₂BO₄-type mixed oxides. The high $\text{c}{}_{\mathrm{o}}\text{a}{}_{\mathrm{o}}$ ratio suggests a strong elongation of FeO₆ octahedra induced by a high spin Fe(IV) d⁴ configuration. The results of structural studies and of Mössbauer analysis, confirming the above conclusions, are reported.     

Crystal data and thermal expansion of tricalciumborate

Single crystals of tricalciumborate were grown by the flux method. Ca₃B₂O₆ crystallizes in the rhombohedral system with the unit cell parameters $\text{a}{}_{\mathrm{R}}\text{= 6.3577(7)}\text{A}\text{?}$, α_R = 85.68(8)°, Z = 2. The equivalent hexagonal lattice parameters are a_H = 8.640(1), $\text{C}{}_{\mathrm{H}}\text{= 11.854(1)}\text{A}\text{?}$. The anisotropic thermal expansion parameters α_a = (1.00 ± 0.14) × 10^?5, α_c = (3.60 ± 0.47) × 10^?5 were determined by X-ray methods in the temperature interval 25 – 1000°C.     

Macle et structure cristalline de Mn0,75Ga2,17S4

Twins of $\text{Mn}{}_{\mathrm{<mtext>1?</mtext><mtext>x</mtext>}}\text{Ga}{}_{\mathrm{<mtext>2+</mtext><mtext>2</mtext><mtext>3</mtext><mtext>x</mtext>}}\text{S}{}_4$ were used for crystal structure determination. Twinning is explained by a reticular pseudomerihedry. Axis, plane and obliquity of the twin have been determined. Cell dimensions are: $\text{a = b}\text{= 5.456(2)}\text{A}\text{?}$; $\text{c}\text{= 10.220(4)}\text{A}\text{?}$; α = β = γ = 90°; space group 14; Z = 2. The final R value is 0.059. The material is isostructural with CdGa₂S₄.     

Single crystals of In2Te5

Single crystals of semiconducting compound In₂Te₅ were grown by chemical transport employing iodine as a transport agent. The crystals had a plate-like habit with the [100] direction perpendicular to the flat surface of the platelets. Nominal dimensions are 10 × 1 × 0.05 mm. In₂Te₅ has a monoclinic structure with dimensions of the base centered cell: $\text{a}\text{= 13.47}\text{A}\text{?}$, $\text{b}\text{= 16.51}\text{A}\text{?}$, $\text{c}\text{= 4.365}\text{A}\text{?}$, β = 92°5′. The space group is $\text{C}{}_{\mathrm{<mtext>2</mtext><mtext>c</mtext>}}$. Pycnometric density is 5.96 g/cm³. The single crystals were all p-type. The conductivity, thermoelectric power and hardness were about 10^?5Ω^?1cm^?1, 650 mkV/°C, and 30 kg/mm², respectively. The minimum energy gap is 1.26 eV.     

Strontium metaniobate: Its crystallography,polymorphism, and isomerism

Three polymorphic forms of SrNb₂O₆ are recognized. The monoclinic form has been prepared and studied by x-ray powder diffraction techniques and differential thermal analysis. The results of this study show that SrNb₂O₆ crystallizes in a pseudo-orthorhombic unit cell with $\text{a}{}_{\mathrm{o}}\text{= 10.99}\text{A}\text{?}$, $\text{b}{}_{\mathrm{o}}\text{= 7.70}\text{A}\text{?}$ and $\text{c}{}_{\mathrm{o}}\text{= 5.66}\text{A}\text{?}$. Its crystal chemical relations to the other meta-niobates and its thermodynamic stability are discussed.     

TlxTi6Se8 and TlxNb6Se8, two phases with filled up Nb3Te4 type of structure showing pronounced cation disorder

The new ternary chalcogenides Tl_xTi₆Se₈ (x= 0.76) and Tl_xNb₆Se₈ (x= 0.70) crystallize with a partially filled up Nb₃Te₄-structure: space group $\text{P}\text{6}{}_3\text{m}$, z= 1 with

$\text{a= 9.882(1) c= 3.590(1)}\text{A}\text{?}\text{(Tl}{}_{0.76}\text{Ti}{}_6\text{Se}{}_8\text{)}$

$\text{a= 10.033(2) c= 3.475(1)}\text{A}\text{?}\text{(Tl}{}_{0.70}\text{TNb}{}_6\text{Se}{}_8\text{)}$

The crystal structures were determined from single crystal diffractometer data and refined to a conventional R-value of 0.077 and 0.055 respectively. The T1 atoms in the octahedral channels cannot be localized. In Tl_xTi₆Se₈ diffuse scattering indicates one-dimensional short range order. A model of the cation distribution in Tl_0.76Ti₆Se₈ is discussed.     

Copper doped zinc oxide Y2BaZnO5: ERS and optical investigation

In copper doped Y₂BaZnO₅ oxides, copper exhibits a distorted square pyramidal coordination which is consistant with the values of g and A tensors obtained from O band ERS spectrum for a sample containing about 1 % Cu. Three values for g and A are observed, g₁ = 2.049₅, g₂ = 2.051₅, g₃ = 2.275, $\text{¦}\text{A}{}_1\text{¦ = 13 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$, $\text{¦}\text{A}{}_2\text{¦ = 10 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$ and $\text{¦}\text{A}{}_3\text{¦ = 147.5 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$. Since $\text{g}{}_1\text{?}\text{g}{}_2$ an approximate C_4v point symmetry can be assumed for copper. The electronic spectrum shows three bands at 11700, 14500 and 20500 cm^?1 which can be assigned to the transitions A₁ → B₁, B₂ → B₁ and E → B₁ respectively. The orbital reduction parameters are calculated and the bonding covalency is discussed.     

Determination de la structure cristalline de la variete a des hydroxycarbonates de terres rares LnOHCO3 (Ln = Na)

A probable model for the structure of the orthorhombic A - type neodymium hydroxycarbonate is presented. It relies on an optical determination of the site symmetry of OH^?, CO^2?₃, and Nd³⁺ atoms from infrared and visible absorption spectra, together with a computation of 50 X-ray diffraction lines intensities of a high resolution Guinier orthorhombic powder pattern ($\text{a}\text{= 4,953}\text{A}\text{?}$, $\text{b}\text{= 8,477}\text{A}\text{?}$, $\text{c}\text{= 7,210}\text{A}\text{?}$; space group Pmcn (n^o62)). The CO^2?₃ groups lies flat between mettalic planes as in the aragonite type of structure and are linked to OH^? by hydrogen bond ($\text{d(CO}{}^{\mathrm{2?}}{}_3\text{?}\text{OH}{}^{\mathrm{?}}\text{) = 2,52}\text{A}\text{?}$). The rare earth coordination is nine fold: two OH^? groups being closer (2,58 Å) than the seven oxygen from the CO^2?₃ groups (2,58 to 2,70 Å).     

On the pyrochlore type Ln2V2O7 (Ln: Rare-earth elements)

Pyrochlore type rare-earth vanadites (Ln₂V₂O₇) were prepared and some physical properties were investigated. Ln₂V₂O₇ (Ln:Tm, Yb or Lu) crystallized in the cubic space group $\text{O}{}_{\mathrm{<mtext>h</mtext>}}\text{=}\text{Fd}{}_3\text{m}\text{,}\text{a}{}_0\text{= 9.9575}\text{A}\text{?}\text{, 9.9346}\text{A}\text{?}\text{and}\text{9.9231}\text{A}\text{?}$ for Tm₂V₂O₇, Yb₂V₂O₇ and Lu₂V₂O₇, respectively. These compounds were all n-type semiconductors and paramagnets in the temperature range 90–300K.     

New tetrahedrally coordinated A2CdBr4 compounds (A = Cs,CH3NH3)

(CH₃NH₃)₂CdBr₄ and Cs₂CdBr₄ are two compounds with a tetrahedral CdBr₄-coordination. Their room temperature structures are determined. (CH₃NH₃)₂CdBr₄: monoclinic, $\text{P}\text{2}{}_1\text{c}$, $\text{a}\text{= 8.1227(13)}\text{A}\text{?}$, $\text{b}\text{= 13.4355(16)}\text{A}\text{?}$, $\text{c}\text{= 11.4194(13)}\text{A}\text{?}$, β = 96.194(11) °, z = 4. Cs₂CdBr₄: orthorhombic, Pnma, $\text{a}\text{= 10.235(5)}\text{A}\text{?}$, $\text{b}\text{= 7.946(3)}\text{A}\text{?}$, $\text{c}\text{= 13.977(5)}\text{A}\text{?}$, z = 4.     

Deformation and fracture processes during creep of 12Cr12Mo14V ferritic steel

The creep and fracture properties of $\text{1}\text{2}\text{Cr}\text{1}\text{2}\text{Mo}\text{1}\text{4}\text{V}$ ferritic steel have been determined over the stress range 125 to 362 MNm^?2 at 838 K using high precision, constant stress equipment. When the variation of the rupture life, t_f, and the secondary creep rate, $\text{?}\text{dot}{}_{\mathrm{<mtext>s</mtext>}}$, with stress, σ, was described as ${}_{\mathrm{<mtext>f</mtext>}}\text{α}\text{?}\text{dot}{}_{\mathrm{<mtext>s</mtext>}}\text{ασ}{}^{\mathrm{n}}$ a stress exponent of was recorded. Comparison with long term data then established that, at stresses below ～ 100 MNn^?2, n decreased gradually until values close to unity were obtained at stresses approaching those encountered in electricity generating plant. This decrease in stress exponent is shown to be attributable to a progressive loss of creep resistance associated with changes in carbide dispersion rather than to any change in the mechanisms by which deformation and failure occur.     

Structure cristalline et proprietes physiques de Cu0.75 VS2

A new compound with composition Cu_0.75 VS₂ has been prepared. Its preparation, X-Ray structure, electrical and magnetic properties are reported. The structure is related to the CdI₂-type, as in the case of the previously described Cu_xTiS₂ (1); in Cu_0.75 VS₂, Cu atoms are ordered in tetrahedral sites between the CdI₂-type subunits, whereas in Cu_xTiS₂ Cu atoms are disordered in two independent sites. The vanadium atoms are shifted with respect to the titanium sites which leads a monoclinic distortion of the hexagonal cell. The relation between the CdI₂ unit cell and the true monoclinic cell of Cu_0.75 VS₂ is:

$\text{a}{}_{\mathrm{<mtext>mono</mtext>}}\text{= 2}\text{a}{}_{\mathrm{<mtext>hex</mtext>}}\text{3}\text{;}\text{b}{}_{\mathrm{<mtext>mono</mtext>}}\text{=}\text{4}\text{3}\text{a}{}^2{}_{\mathrm{<mtext>hex</mtext>}}\text{+}\text{c}{}^2{}_{\mathrm{<mtext>hex</mtext>}}\text{9}\text{;}\text{c}{}_{\mathrm{<mtext>mono</mtext>}}\text{= 2}\text{a}{}_{\mathrm{<mtext>hex</mtext>}}$

In Cu_0.75 VS₂, vanadium atoms occupy two independent sites, three vanadium atoms forming a triangular cluster (V₂—V₃ distances are 2.91 Å and V₃—V₃ are 2.92 Å) while one vanadium atom is isolated ($\text{V}{}_1\text{?}\text{V}{}_2\text{= 3.36}\text{A}\text{?}$ and $\text{V}{}_1\text{?}\text{V}{}_3\text{= 3.37}\text{A}\text{?}$. The physical properties exhibit a transition at 50°K approximately, the magnetic susceptibility being temperature-independent above and temperature dependent below the transition (Curie-Weiss behavior). Resistivity and Hall measurements confirm the metallic nature of the compound and show the existence of the low temperature transition. The observed properties could be interpreted as a result of the low temperature localisation of the 3d electron of V₁.     

High pressure synthesis of Gd3InO6, Tb3InO6 and Lu3InO6

Three new compounds, X₃InO₆ (X = Gd, Tb, Lu) were prepared at 1–4 GPa, ～1050°C. They are monoclinic, space group $\text{P}\text{2}{}_1\text{n}$ with $\text{a}\text{? 8.9}\text{A}\text{?}$, $\text{b}\text{? 9.8}\text{A}\text{?}$, $\text{c}\text{? 5.9}\text{A}\text{?}$, β ～ 95° and Z = 4.     

n-PbTep+−Pb1−xSnxTe heterojunctions prepared by a modified hot wall technique

$\text{n-PbTe}\text{p}{}^{\mathrm{+}}\text{?}\text{Pb}{}_{\mathrm{1?x}}\text{Sn}{}_{\mathrm{x}}\text{Te}$ heterojunctions with a long wavelength spectral cutoff (λ_c ≈ 6 μm) were prepared using the double-channel hot wall technique. The electrical and photoelectrical properties of the heterojunctions at 77, 197 and 300 K were investigated. Detectors with R_oA equal to 170 Ω cm² and a quantum efficiency of 25–40% were obtained. Reasons for the shift of the long wavelength spectral cutoff of the heterojunctions towards shorter wavelengths are given.     

A mixed valence compound in the two dimensional MPS3 family: V0.78PS3 structure and physical properties

The non stoichiometric compound V_0.78PS₃ has been obtained as single crystals from a preparation corresponding to the atomic ratio V/P/S = 1/1/3. It cristallizes with monoclinic symmetry, space group C2/m, with the unit cell parameters $\text{a}\text{= 5.867(1)}\text{A}\text{?}\text{,}\text{b}\text{= 10.160(2)}\text{A}\text{?}\text{,}\text{c}\text{= 6.657(1)}\text{A}\text{?}\text{, β = 107.08(2)°,}\text{V}\text{= 379.3(1)}\text{A}\text{?}{}^3$ and Z =4. The structure refinement was made down to a reliability factor value R = 3.3% from 445 reflexions (I > 3 σ (I)) and 31 variables. The material has same layer structure as FePS₃ with the occurrence of the thiophosphate anion (P₂S₆)^4?-including a P₂ pair. In V_0.78PS₃, the charge equilibrium implies the following developped formula : V_0.34^II V_0.44^III □_0.22 P^IV S₃^?II. The phase is a semi-conductor with a small activation energy of 0.24 eV, in accord with a vanadium mixed valence, and it presents, at low temperature, an antiferromagnetic order (T_N = 62 K).