Crystal growth and characterization of In23PSe3

Crystals of $\text{In}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{PSe}{}_3$ were grown by chemical vapor transport of the elements. The phase is structurally related to the hyposelenophosphates, M^IIPSe₃, but contains both indium atoms and vacancies on the metal ion sites. The compound shows a high electrical resistivity (>10⁸ ohm-cm) and has an optical absorption edge at 1.9 (1) e.V.     

Electrostriction in Pb (Zn13Nb23)O3

The electrostriction in $\text{Pb (Zn}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{Nb}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{)}\text{O}{}_3$ crystals has been investigated using a strain gauge method. In the ferroelectric phase below 140 C, the strain vs the electric field shows a hysteresis, which is ascribed to the effect of ferroelectric domains. A quadratic relation holds between the strain x and the electric polarization P as x = QP² above about 170 C in the paraelectric phase. Values of the electrostrictive Q coefficients are determined from the measurements near 190 C, as Q₁₁ = 1.6·10^?2m⁴/C², Q₁₂ = ?0.86·10^?2m⁴/C², and Q₄₄ = 0.85·10^?2m⁴/C².     

Photoelectrochemical study of the layered compound In23Pse3

The layered compound $\text{In}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{PSe}{}_3$ is studied by photoelectrochemical technique. Two modes of transition, indirect ～ 1.55 eV, and direct ～ 1.80 eV are evidenced. An estimation of the hole diffusion length is given through the use of Gärtner model ($\text{L}\text{? 4 μ}\text{m}$). The flat band positions of the junction $\text{In}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{PSe}{}_3\text{-}\text{electrolyte}$ at different pH values are determined in an electrochemical scale.     

X-ray study of the deficient perovskite La23TiO3

The A-site deficient perovskite $\text{La}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{TiO}{}_3$ was synthesized under the controlled atmosphere of CO₂H₂ mixed gas at 1350°C, and the structure was investigated by the powder X-ray diffraction method. The product is slightly oxygen deficient ($\text{La}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{TiO}{}_{\mathrm{3?\lambda }}$, where 0.007 ≦ λ ≦ 0.079), and the structure is dependent on λ: when λ is small, the perovskite cell is distorted to orthorhombic symmetry and the unit cell is doubled along the c′ (> b′, a′) axis, while a cubic perovskite structure is facilitated with the increase of λ. A structural model, which calls for an ordered arrangement of the A-site vacancies along the c′-axis, is proposed and its order parameter is calculated from the intensities of the superstructure lines.     

Une modelisation du comportement magnetique d'un compose de l'iridium pentavalent: LaLi12Ir12O3

A new interpretation is proposed for the magnetic properties of perovskite-type iridium (+V) oxide $\text{LaLi}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{Ir}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{O}{}_3$. In its unusual +5 oxidation state iridium has a t⁴_2ge⁰_g configuration. The magnetic susceptibility has been calculated assuming cubic symmetry of the crystal field and a Coulomb repulsion of the same order of magnitude than spin-orbit coupling. Fitting of the experimental data leads to a single spin-orbit constant $\text{ζ ? 3470}\text{cm}{}^{\mathrm{?1}}$ close to that of previously investigated Ir(+V) compounds.     

Synthesis of a new perovskite Pb(Li14Nb34)O3

A high-pressure technique was adopted to obtain perovskite-type $\text{Pb(Li}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{Nb}{}_{\mathrm{<mtext>3</mtext><mtext>4</mtext>}}\text{)}\text{O}{}_3$. A new perovskite $\text{Pb(Li}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{Nb}{}_{\mathrm{<mtext>3</mtext><mtext>4</mtext>}}\text{)}\text{O}{}_3$ was characterized to have a cubic symmetry with $\text{a}{}_{\mathrm{<mtext>o</mtext>}}\text{= 4.069}\text{A}\text{?}$; Li and Nb ions in the B-site of perovskite lattice may be in a random arrangement.     

Growth of Ca3Fe2Ge3O12 and Ca3Fe(Al,Cr) Ge3O12 garnets in molten bismuth germanate glasses

Additions of Fe₂O₃ to CaO·Bi₂O₃·2 GeO₂ cause Ca₃Fe₂Ge₃O₁₂ garnets to precipitate from the resultant melt at 1250°C. Garnets with the composition Ca₃Fe(Al, Cr) Ge₃O₁₂ are also precipitated by adding either $\text{Al}{}_2\text{O}{}_3\text{Fe}{}_2\text{O}{}_3$ or $\text{Cr}{}_2\text{O}{}_3\text{Fe}{}_2\text{O}{}_3$ mixtures. The well-formed crystals range from several to 100 μm in size and are obtained in 50 to 70% yields at $\text{Fe}\text{Bi}\text{= 0.4}$. Additions of Fe₂O₃ (up to $\text{Fe}\text{Bi}\text{= 1.0}$) to compositions containing ZnO, CdO, SrO, and BaO yield only dark glasses. The physical properties of these glasses suggest that Fe(III), in contrast to AL(III) & Ga(III), prefers octahedral coordination.     

The discharge of a I12TaSe4 cathode for lithium battery

The discharge process was investigated on a lithium battery using $\text{I}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{TaSe}{}_4$ as cathode. The battery works as primary battery. The potential gradually decreased from 2.1V to 1.8V upto a discharging of $\text{Li}\text{I}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{TaSe}{}_4\text{≈0.5}$. Then it was almost constant at 1.8V until the discharging of about 2.0. Iodine is partially removed out of $\text{I}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{TaSe}{}_4$, keeping the host TaSe₄ chain structure as it was in the first step of discharge. The new product has tetragonal crystal lattice having lattice parameters of $\text{a}\text{=9.532}\text{A}\text{?}$ and $\text{c}\text{=25.31}\text{A}\text{?}$, which is twice of c-parameter of $\text{I}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{TaSe}{}_4$.     

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.     

Solid solution phases from thermally crystallized Li2O-MgO-Al2O3-SiO2 glasses

Phase transformations have been studied in glasses related in composition to Li₂O-MgO-SiO₂ (930° C) eutectic glass modified by $\text{Al}{}_2\text{O}{}_3\text{Li}{}_2\text{O}$ replacement on a cation per cation basis. Crystallization processes and changes in the solid solutions of the mineral phases developed during the controlled heating of the glasses have been followed using X-ray and microscopic techniques.Solid solutions of lithia aluminosilicate phases (B-eucryptite and/or B-spodumene s.s.) are the essential minerals that crystallize in glasses through most of the heat treatment applied. Lithium metasilicate, disilicate, clinoenstatite and cordierite are also encountered.B-eucryptite s.s. is formed in early stage of crystallization of the glass which transforms into B-spodumene s.s. at higher temperature (800° C). However, in some cases, it persists at temperatures as high as 1000° C.Metastable B-eucryptite-B-quartz s.s. can accomodate considerable amounts of Mg²⁺ and Al³⁺ ions in its lattice especially at lower temperature. At higher temperature for long duration, a redistribution of the elements takes place, and the cordierite phase then developed.     

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.     

Electrical conductivity of solid solutions in the system CeO2La6WO12

The total electrical conductivities were studied for the solid solutions in the pseudo-binary system CeO₂La₆WO₁₂. Maximum conductivities were observed at about 90 mol.% CeO₂, 1.1 ohm^?1 cm^?1 at 1500°C and 4.4 × 10^?3 ohm^?1 at 600°C. A minimum point was observed in conductivity isotherms at about 10 mol.% CeO₂. A pyrochlore like stoichiometric compound La₂$\text{(}\text{LaCe}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{W}\text{1}\text{2}\text{)}\text{O}{}_7$ was assumed. The crystal structure of La₆WO₁₂ is discussed. Ionic conductions were observed at low temperatures.     

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.     

Thermoelectric power and annealing effects in NbAl2O3 cermet-type films

The effects of annealing on the structure and electrical conduction in $\text{Nb}\text{Al}{}_2\text{O}{}_3$ semiconducting films were investigated. Annealing increases the product of the density of states and the mobility near the Fermi level, and this suggests that the mobility increases because of structural changes in the alumina matrix.Thermopower measurements allowed us to evaluate the asymmetry about the Fermi level of the product Nμ.     

Système ternaire La2Se3-Ga2Se3-GeSe2 diagramme de phase — Etude des verres

Existence of a solid solution, hexagonal $\text{Ce}{}_6\text{Al}{}_{\mathrm{<mtext>10</mtext><mtext>3</mtext>}}\text{S}{}_{14}$-type, between $\text{La}{}_6\text{Ga}{}_{\mathrm{<mtext>10</mtext><mtext>3</mtext>}}\text{Se}{}_{14}$ and La₆Ge_2.5Se₁₄ compounds. Location of the eutectic valleys and ternary eutectic (650°C, for La₂Se₃, 3 Ga₂Se₃, 14 GeSe₂). Level curves of the liquidus.Obtention of glasses in a large domain of composition, along the eutectic valley. Measurements of Tg and crystallisation temperature.     

Stability of the perovskite phase LaBO3 (B = V,Cr, Mn,Fe, Co,Ni) in reducing atmosphere I. Experimental results

The chemical stability of perovskites LaBO₃ where B = V, Cr, Mn, Fe, Co, Ni was studied by thermogravimetry at 1000°C in gas mixtures of $\text{CO}{}_2\text{H}{}_2$, $\text{O}{}_2\text{CO}{}_2$ and $\text{O}{}_2\text{Ar}$ at 1 bar.The stability limits of the perovskite phases expressed in terms of -log Po₂★ (Po₂★ = critical oxygen partial pressure in bar) were for LaCrO₃ and LaVO₃ (greater than 21.1), LaFeO₃ (16.95), LaMnO₃ (15.05), LaCoO₃ (7.0) and for LaNiO₃ (～0.6). The changes in standard enthalpy ΔH° and entropy ΔS° of the following reactions were obtained.$\text{LaVO}{}_4\text{=}\text{LaVO}{}_3\text{+}\text{1}\text{20}{}_2\text{δ=328}\text{kJ}\text{mol}\text{°=135}\text{J}\text{mol·deg.}$,$\text{LaMnO}{}_3\text{=}\text{1}\text{2}\text{La}{}_2\text{O}{}_3\text{+}\text{MnO}$     

Thermal expansion of corundum structure Rh2O3

The directional thermal expansion coefficients of the corundum structure form of Rh₂O₃ were determined from room temperature to 850°C by x-ray diffraction methods. Rh₂O₃ has a lower thermal expansion and is less anisotropic in thermal expansion than alumina. The directional thermal expansion coefficients of Rh₂O₃ expressed in second degree polynominal form are: $\text{“α}{}_{\mathrm{<mtext>a</mtext>}}\text{” = 5.350 ×10}{}^{\mathrm{?6}}\text{+ 1.281 ×10}{}^{\mathrm{?9}}\text{T}\text{? 1.133 ×10}{}^{\mathrm{?14}}\text{T}{}^2\text{/°}\text{C}$ and $\text{“α}{}_{\mathrm{<mtext>c</mtext>}}\text{” = 5.246 ×10}{}^{\mathrm{?6}}\text{+ 6.369 ×10}{}^{\mathrm{?9}}\text{T}\text{? 7.480 ×10}{}^{\mathrm{?14}}\text{T}{}^2\text{/°}\text{C}$.     

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.     

Studies on crack growth rate under high temperature creep,fatigue and creep-fatigue interaction—II: On the role of fracture mechanics parameter aeffσg

For high temperature creep, fatigue and creep-fatigue interaction, several authors have recently attempted to express crack growth rate in terms of stress intensity factor $\text{K}{}_{\mathrm{I}}\text{= α}\text{aσ}{}_{\mathrm{g}}$, where a is the equivalent crack length as the sum of the initial notch length a₀ and the actual crack length $\text{a}{}^1$, that is, $\text{a = a}{}_0\text{+ a}{}^1$. On the other hand, it has been shown by Yokobori and Konosu that under the large scale yielding condition, the local stress distribution near the notch tip is given by the fracture mechanics parameter of $\text{aσ}{}_{\mathrm{g}}\text{?(σ}{}_{\mathrm{g}}$), where a is the cycloidal notch length, σ_g is the gross section stress and $\text{?(σ}{}_{\mathrm{g}}$) is a function of σ_g. Furthermore, when the crack growth from the initial notch is concerned, it is more reasonable to use the effective crack length a_eff taking into account of the effect of the initial notch instead of the equivalent crack length a. Thus we believe mathematical formula for the crack growth rate under high temperature creep, fatigue and creep-fatigue interaction conditions may be expressed at least in principle as function of $\text{a}{}_{\mathrm{eff}}\text{σ}{}_{\mathrm{g}}\text{, σ}{}_{\mathrm{g}}$ and temperature.In the present paper, the geometrical change of notch shape from the instant of load application was continuously observed during the tests without interruption under high temperature creep, fatigue and creep-fatigue interaction conditions. Also, the effective crack length a_eff was calculated by the finite element method for the accurate estimation of local stress distribution near the tip of the crack initiated from the initial notch root. Furthermore, experimental data on crack growth rates previously obtained are analysed in terms of the parameter of $\text{a}{}_{\mathrm{eff}}\text{σ}{}_{\mathrm{g}}$ with gross section stresses and temperatures as parameters, respectively.     

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.