Photoelectrochemical study of TiS3 in aqueous solution

TiS₃ single crystals have been grown by chemical vapor transport. They were characterized by X-ray diffraction and measurement of their electronic transport properties. A photoelectrochemical study shows both anodic and cathodic dark currents and anodic photocurrents. Flat band potentials and anodic corrosion p$\text{o}$te$\text{n}$tials in acidic and basic solutions and in the presence of an $\text{I}{}^{\mathrm{?}}{}_3\text{I}{}^{\mathrm{?}}$ redox couple have been determined from the onset of photocurrent and from the Schottky-Mott plot of capacitance. The flat band potential ex$\text{h}$ibits a pH dependence but is almost independent of the presenc$\text{e}$ o$\text{f}$ I^? in solution. The stability of this material in a 1N H₂SO₄+ 1N $\text{I}{}^{\mathrm{?}}{}_3\text{I}{}^{\mathrm{?}}$ solution has been observed for a period of fourteen days with a photocurrent of approximately $\text{1}\text{mA}\text{cm}{}^2$. A particular photocorrosion mechanism is reported. The reaction starts at the edges of the layer and proceeds toward the interior. These mechanisms are discussed in relation to the existence of two types of S atoms in the structure: sulfur dimers and S^2? ions.     

Structure cristalline et proprietes physiques de Cu0.65VS2

A second form of compounds Cu_xVS₂ is described here. As in Cu_0.75VS₂ (1) the structure of Cu_0.65VS₂ is related to the CdI₂-type. In Cu_0.75VS₂, Cu atoms are ordered in tetrahedral sites between the CdI₂-type subunits, whereas in the Cu_0.65VS₂, Cu atoms are partially disordered and occupy 4 different sites. Both structures differ from one another in vanadium atoms arrangements: In Cu_0.75VS₂, V-atoms form triangular clusters while in Cu_0.65VS₂ they form zigzag chains perpendicular to the hexagonal axis. The physical properties show a metallic type behaviour. Resistivity decreases with temperature with low 300 K/4.2 K ratio according to a disordered nature of the compound. Magnetic susceptibility shows a Pauli paramagnetism with an additionnal Curie-Weiss term due to a relatively large amount of paramagnetic impureties (0,9 % V³⁺ atoms). The observed low temperature localisation of the 3d electrons in Cu_0.75VS₂ disappears in the case of Cu_0.65VS₂.     

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 $\text{“α}{}_{\mathrm{<mtext>c</mtext>}}\text{” = 5.246 ×10}{}^{\mathrm{?6}}\text{+ 6.369 ×10}{}^{\mathrm{?9}}\text{T}\text{? 7.480 ×10}{}^{\mathrm{?14}}\text{T}{}^2\text{/°}\text{C}$.     

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.     

Structure and staging of intercalated AgxTaS2 and AgxTiS2

The crystal structure of the intercalation compounds Ag_xTaS₂ ($\text{0≤}\text{x}\text{≤}\text{2}\text{3}$) and Ag_xTiS₂ (0≤x≤0.42) are reported. For both intercalated dichalcogenides only stages n=2 and 1 are observed and there is no evidence for higher staging. In stage 1 $\text{Ag}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{TaS}{}_2$, the silver ions reside in tetrahedral sites and the 2H_b?TaS₂ structure changes to that of MoS₂. For stage 2 $\text{Ag}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{TaS}{}_2$, we observe a six layer unit cell with the silver ions again in tetrahedral sites. In stage 1 Ag_0.42TiS₂ and stage 2 Ag_0.2TiS₂, the silver ions are in octahedral sites and there is no change of the host lattice stacking. The samples were prepared both thermally and electrolytically and the same lattice parameters were obtained in both cases.     

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.     

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.     

The oxygen defect perovskite BaLa4Cu5O13.4, a metallic conductor

A new oxygen defect perovskite BaLa₄Cu₅O_13.4, characterized by a mixed valence of copper has been isolated; the parameters of the tetragonal cell are closely related to that of the cubic perovskite:a = 8.644(4)$\text{A}\text{?}\text{=}\text{a}{}_{\mathrm{p}}\text{5√}$ and c = 3.867(3) $\text{A}\text{?}\text{=}\text{a}{}_{\mathrm{p}}$. The X-ray diffraction study shows that the atoms are displaced from their ideal positions in the cubic cell, owing to the presence of ordered oxygen vacancies. The study of conductivity, magnetic susceptibility and thermoelectric power versus temperature shows that this oxide is a very good metallic conductor.     

Carburization and decarburization kinetics of iron in CH4 — H2 mixtures between 1000 – 1100 °C

In this study the rate constants of the methane decomposition reaction on iron surfaces were determined in the 1000–1100°C temperature range, by grav? metric methods. Earlier works showed that the reaction velocity was given by The results indicate that the constant values vary from 2.72 × 10^?6 to $\text{16.74 × 10}{}^{\mathrm{?6}}\text{mol C/cm}{}^2\text{/sec/atm}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ for k and 2.61 × 10^?8 to $\text{8.62 × 10}{}^{\mathrm{?8}}\text{mol C/cm}{}^2\text{/sec/atm}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ for k′ between 1000 and 1100°C.     

A new method of sulfur vapor pressure control and its application to the V-S system

A new apparatus for obtaining partial pressure of sulfur was devised by using liquid sulfur and carrier gas of nitrogen. This successfully works in the range of ～10^?4 to ～1 atm of Ps₂ at any temperature higher than about 400°C up to about 1000°C. As an application of it, the equilibrium study of V-S system was done at 800°C. Two phases V₃S₄ and V₅S₈, each having homogeneity range, were found while no existence of the V₂S₃ phase could be detected thermodynamically and X-ray crystallogrpahically at this temperature. The standard free energy of following reaction, $\text{VS}{}_{\mathrm{<mtext>4</mtext><mtext>3</mtext>}}\text{+}\text{2}\text{15}$$\text{S}{}_2\text{=}\text{VS}\text{8}\text{5}$, was calculated by considering the transition-Ps₂ and the activities and · ΔG° (1073K) = ?1150 cal·mole^?1was obtained with an estimated uncertainty of ± 100 cal to the above reaction.     

Conductivite electrique et spectres de diffusion raman des verres mixtes AgPO3 − MI2 AVEC M = Cd,Hg, Pb. Correlation entre conductivite et structure

The glass-forming regions in the AgPO₃ ? MI₂ systems with M = Cd,Pb,Hg were determined. Electrical conductivity measurements and Raman spectra were carried out. A maximum conductivity value of $\text{10}{}^{\mathrm{?2}}\text{(Ω}\text{cm}\text{)}{}^{\mathrm{?1}}$ at 25°C is obtained for a mole fraction of 0,19 in PbI₂ or in CdI₂, whereas a value of $\text{3×10}{}^{\mathrm{?5}}\text{(Ω}\text{cm}\text{)}{}^{\mathrm{?1}}$ at 25°C is found for a mole fraction of 0,5 in HgI₂. The conductivity results and Raman spectra are examined and compared with those of AgPO₃ ? AgI. An exchange between Ag⁺ and M²⁺ ions is proposed leading to AgI species in AgPO₃ ? CdI₂ and AgPO₃ ? PbI₂ glasses. It could explain the high conductivity values obtained and the similarities observed in Raman spectra.     

Crystal structure and magnetic properties of Cu4NiSi2S7

The structure of the compound Cu₄NiSi₂S₇ has been determined. It crystallizes in a new, monoclinic distorted sphalerite superlattice with the parameters: $\text{a}\text{= 11.551}\text{A}\text{?}$, $\text{b}\text{= 5.313}\text{A}\text{?}$, $\text{c}\text{= 8.165}\text{A}\text{?}$, β = 98.72°, $\text{V}\text{= 495.2}\text{A}\text{?}{}^3$, Z = 2, space group C2. The analogous compound Cu₄NiGe₂S₇ is isotypic. At a Neél temperature T_N = 20.2 K, Cu₄NiSi₂S₇ becomes antiferromagnetic. The magnetic moment of the paramagnetic phase is 2.6μ_B.     

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.     

Ordering of interstitial nitrogen and oxygen in vanadium near to V8N and V8O

The ordered structure of the V₈N subnitride was studied by X-rays, electron diffraction and electron microscopy. V₈N exists in two different modifications (α′ and α″). The vanadium sublattice of both phases is pseudo-tetragonal, in reality triclinic, with lattice parameters: $\text{α}{}_{\mathrm{<mtext>o</mtext>}}\text{=}\text{b}{}_{\mathrm{o}}\text{= 3.114}\text{A}\text{?}$, $\text{c}{}_{\mathrm{o}}\text{= 2.994}\text{A}\text{?}$, α_o = β_o = 90.5^o ± 0.1^o, γ_o = 90^o. The proposed unit cell of α′-V₈N has dimensions: a = 2√2 a_o, c = 2c_o and corresponds to V₃₂N₄. Doublets of nitrogen atoms occupy two sets of octahedral cavities whose shortest axes are aligned along the x and y directions of the sublattice in an ordered fashion. The α″-V₈N phase is a periodically twinned modification of the α′-V₈N, the twin plane being of the (001) type. The V₈O suboxide has the same structure as the α″-V₈N, the sublattice parameters being: $\text{a}{}_{\mathrm{o}}\text{=}\text{b}{}_{\mathrm{o}}\text{= 3.11}\text{A}\text{?}$, $\text{c}{}_{\mathrm{o}}\text{= 2.994}\text{A}\text{?}$, α_o = β_o = 90.3^o ± 0.1^o, γ_o = 90^o.     

Deviation from stoichiometry in α-HgI2

Measurements of lattice constants, density and transition temperature have been carried out on α-HgI₂ single crystals grown both from vapor phase and from solution under different stoichiometric conditions. Stoichiometry deviations on both Hg- and I-rich sides were found. Large supersaturations extending on the Hg-rich side up to about 4 × 10^?2$\text{I}{}_{\mathrm{Hg}}\text{HgI}{}_2$ mole ratio and on the I-rich side up to about 10^?2$\text{I}{}^{\mathrm{?}}{}_3\text{HgI}{}_2$ mole ratio were accomodated by the crystals. The interpretation of the results supports the assumption of the presence of mercury interstitials in the Hg-rich crystals and of I^?₃ anions in the I-rich crystals. The large deviations from stoichiometry are attributed to the non-stoichiometry of the mother phase and to the easiness of the crystal structure for accomodating interstitials rather than to characteristic thermodynamic equilibria of interstitials in the lattice.     

Un nouveau conducteur protonique [H(H2O)n]12Sb12O36 (n ⩽ 1)

Single crystals of K₁₄Sb₁₂O₃₆F₂ undergo rapid ion exchange in 9N sulfuric acid to produce “hydronium” compound (H(H₂O)_n)₁₂Sb₁₂O₃₆ (n ? 1). Between 30 and 140°C this phase undergoes a partial and reversible dehydratation in which approximately 85 % of its “H₃O⁺” content is converted to H⁺.The structures of hydrated and dehydrated phases have been refined by full-matrix least squares, respectively to factor R = 0.030 and 0.047. The conductivity of $\text{(H(H}{}_2\text{O)}{}_{\mathrm{<mtext>n</mtext>}}\text{)}{}_{12}\text{Sb}{}_{12}\text{O}{}_{36}\text{(σ}{}_{20}\text{? 1O}{}^7\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$) increases in an Arrhenius relationship with an activation energy of 8.8 kcal.mole^?1, the dehydrated compound (H(H₂O)_0.33)₁₂Sb₁₂O₃₆ has a much lower conductivity but the same activation energy.     

High pressure synthesis of Cu2GeO4 with hausmannite structure

Copper(II)metagermanate, CuGeO₃, decomposes at high pressure to rutile-type GeO₂ and Cu₂GeO₄. Very small single crystals of Cu₂GeO₄ can be obtained by direct high pressure synthesis from CuOGeO₂ mixtures. The compound has a distorted spinel structure (Hausmannite structure, space group $\text{I}\text{4}{}_1\text{amd}$) with $\text{a}\text{= 5.593}\text{A}\text{?}$, $\text{c}\text{= 9.396}\text{A}\text{?}$, Z = 4.     

Crystal chemistry of (Cd,Me)3(PO4)2 solid solutions

A number of solid solutions of $\text{Me}$₃(PO₄)₂ in Cd₃(PO₄)₂ have been prepared and equilibrated at 1070 K ($\text{Me}\text{=}\text{Mg, Mn, Fe, Co, Ni, Cu, Zn, or Ca}$). The respective ($\text{Cd}{}_{\mathrm{<mtext>1?</mtext><mtext>z</mtext>}}\text{Me}{}_{\mathrm{<mtext>z</mtext>}}\text{)}{}_3\text{(}\text{PO}{}_4\text{)}{}_2$ phases are either isotypic with β′-Cd₃(PO₄)₂ or with the mineral graftonite, both with five- and six- (or even seven)-coordinated cations. The monoclinic unit cell dimensions have been accurately determined from Guinier-Hägg photographs, and complete X-ray powder diffraction data are given for β′-Cd₃(PO₄)₂. The cell volumes are strongly correlated to the size and amount of incorporated $\text{Me}$²⁺ cation. The homogeneity regions and structures of the (Cd,$\text{Me}$)₃(PO₄)₂ phases, though, seem rather to be controlled by the $\text{Cd}{}^{\mathrm{2+}}\text{Me}{}^{\mathrm{2+}}$ cation ordering.     

The region of existence of CuInS2

It is shown from quenching experiments followed by X-ray analysis that the region of existence of CuInS₂ is very small and in fact is limited to 0<x<0.05 in $\text{Cu}{}_{\mathrm{<mtext>1?</mtext><mtext>x</mtext>}}\text{In}{}_{\mathrm{<mtext>1+</mtext><mtext>x</mtext>}}\text{3}{}^{\mathrm{<mtext>S</mtext>}}\text{2}$. Furthermore, an indication of solid state transition in this compound was obtained from DTA experiments.     

Concentration quenching of Tb3+ luminescence in LaOBr and Gd2O2S phosphors

The concentration quenching of trivalent terbium ${}^5\text{D}{}_{\mathrm{3,4}}\text{→}{}^7\text{F}{}_{\mathrm{J}}$ emissions from UV-excited (La, Tb) OBr and (Gd, Tb)₂O₂S phosphors was studied. The activation concentration x was varied from 5·10^?5 to 0.2 for (La_1?xTb_x) OBr and from 10^?3 to 0.1 for (Gd_1?xTb_x)₂O₂S. ${}^5\text{D}{}_3\text{→}{}^7\text{F}{}_{\mathrm{J}}$ emissions (blue) were observed to quench first and the Tb³⁺ concentration giving rise to maximum intensity was 0.003 in (La, Tb) OBr and between 0.005 and 0.01 in (Gd, Tb)₂O₂S. The optimum concentration for ${}^5\text{D}{}_4\text{→}{}^7\text{F}{}_{\mathrm{J}}$ (green) emissions was 0.05 in (La, Tb) OBr and 0.03 in (Gd, Tb)₂O₂S. Dipole-dipole and dipole-quadrupole interactions are possible mechanisms for the quenching of emissions from the ⁵D₃ and ⁵D₄ levels.A method for determining the Tb³⁺ concentration in these phosphors, based on the intensity ratios of the ${}^5\text{D}{}_3\text{→}{}^7\text{F}{}_{\mathrm{J}}$ and ${}^5\text{D}{}_4\text{→}{}^7\text{F}{}_{\mathrm{J}}$ transitions, is also presented.