The incommensurate solid solution phase Na5−4x Zr1+x(PO4)3:0.04 <x <0.15

The orthophosphate solid solution phase, Na_5?4x Zr_1+x(PO₄)₃:0.04 ? x ? 0.15 has trigonal symmetry with an apparent one dimensional incommensurate superstructure parallel to c_HEX. Using selected area electron diffraction patterns as a guide, an indexing scheme for the powder X-ray data has been devised. The parameter $\text{k = c}{}_{\mathrm{<mtext>supercell</mtext>}}\text{c}{}_{\mathrm{<mtext>subcell</mtext>}}$ varies smoothly with composition from ～ 10.4 at x = 0.04 to ～4.4 at x = 0.11 and is believed to originate in ordering of the extra interstitial Zr⁴⁺ ions. The Na⁺ ion conductivity increases gradually with x and for x = 0.108 varies from ～5×10^?8 ohm^?1 cm^?1 at 25°C to ～1×10^?3 ohm^?1 cm^?1 at 300°C.     

Ionic conductivity of Li4GeO4, Li2GeO3 and Li2Ge7O15

The ionic conductivity of polycrystalline samples of three lithium germanates: Li₄GeO₄, Li₂GeO₃, and Li₂Ge₇O₁₅, has been determined using a c techniques and complex plane analysis. Conductivities at 400°C are 8.7 × 10^?5, 1.5 × 10^?5, and $\text{1.4 × 10}{}^{\mathrm{?7}}\text{(Ω·}\text{cm}\text{)}{}^{\mathrm{?1}}$ respectively. The conductivity of Li₄GeO₄ rises appreciably in the range 700–750°C.     

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.     

Ionic conductivity in low carnegieite compositions based on NaAlSiO4

Carnegieite compositions of the type Na_1+xAl_1+xSi_1?xO₄ with x = 0 to ～0.7 were prepared. Na ion conductivities, measured with Na and Au electrodes at ～10³ Hz, range from $\text{4×10}{}_{\mathrm{?5}}\text{(Ω-}\text{cm}\text{)}{}^{\mathrm{?1}}$ for NaAlSiO₄ to $\text{5×10}{}^{\mathrm{?3}}\text{(Ω-}\text{cm}\text{)}{}^{\mathrm{?1}}$ at 300 C for Na_1.7Al_1.7Si_0.3O₄. Substitutions of Li, K, Ca, or Sr for Na lowered σ whereas substitution of Ti for Si raised σ. Na aluminum silicates with the nepheline structure had lower σ than carnegieite compositions.     

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.     

Ionic conductivity of substituted Li2SO4 phases

Lithium ion conductivity of Li₂SO₄-Y₂(SO₄)₃, Li₂SO₄-La₂(SO₄)₃ and Li₂SO₄-Li₃PO₄ systems has been measured as a function of composition and temperature using AC complex impedance methods. Substitution of the trivalent cations results in a small enhancement of the ionic conductivity within the limit of solid solution formation. Considerable increase of the conductivity results by substitution of PO₄^3? for SO₄^2?. The maximum conductivity observed is $\text{1.1×10}{}^{\mathrm{?3}}\text{(Ω}\text{cm}\text{)}{}^{\mathrm{?1}}$ at 300°C for the composition Li_2.2S_0.8P_0.2O₄ with E_a = 0.8 eV. These results are discussed in terms of the structural properties.     

Conductivity of Zr-doped Na3PO4: A new Na+ ion conductor

Na₃PO₄ forms an extensive range of solid solutions with the replacement mechanism, 4Na⁺ ? Zr⁴⁺ and formula Na_3–4xZr_xPO₄:0 < x < 0.20. With increasing x, the conductivity increases markedly and passes through a maximum at $\text{x ? 0.13}$ with a value of 2.5 × 10^?2 ohm^?1cm^?1 at 300°C. The solid solutions are thermodynamically stable, easily prepared and sinter into dense ceramics at ～1000°C.     

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.     

Preferential oxygen sputtering from Nb2O5

The bombardment of Nb₂O₅ with Kr⁺ or O⁺₂ ions leads to the development of a surface layer NbO. The layer begins to form at (2–4) × 10¹⁵ ions cm^-2 as random nuclei which can be resolved by transmission electron microscopy. It is half complete at (4–8) × 10¹⁶ ions cm^?2, a much higher dose than that required for sputter equilibrium to be half complete. The final thickness is roughly 31 nm. These features, together with the further result that the layer forms independently of the bombarding current provided beam heating is avoided, can be understood from a model which combines preferential oxygen sputtering at the surface, diffusion of the relevant point defects, and random nucleation of a phase with lower stoichiometry. The governing equation is an extended form of the diffusion equation

$\text{?C}\text{?t}\text{=}\text{D?}{}^2\text{C}\text{?x}{}^2\text{+}\text{υ?C}\text{?x}\text{?}\text{DC}\text{L}{}^2$

where υ is the velocity of the surface recession due to sputtering and L is the diffusion length for trapping. Appropriate solution of the equation suggests that the altered layer will have a mean thickness similar to L, will be formed with a half-dose given by $\text{0.693LN}\text{S}$ where S is the sputtering coefficient, and will involve a total amount given by $\text{DC}{}_0\text{υ}$ atoms cm^?2, where C₀ is the stoichiometry at the outer surface. Current independence follows if the diffusion is bombardment enhanced, so that D is approximately proportional to υ. The main difficulty with the model is that it is strictly valid only for low concentrations.     

Studies on the formation of a solid solution compound in Li2O impregnated CuAl2O4 catalyst

Li₂O impregnated CuAl₂O₄ samples were calcined at two temperatures (673 K and 1173 K). X-ray analysis showed that the lattice parameter of the spinel phase decreased with increasing calcining temperature. X-ray studies on the solid solution series Cu_1?x$\text{Li}{}_{\mathrm{<mtext>x</mtext><mtext>2</mtext>}}$$\text{Al}{}_{\mathrm{<mtext>2+</mtext><mtext>x</mtext><mtext>2</mtext>}}$ O₄ (x = 0, 0.1, 0.2, 0.3, 0.4 and 0.5) showed that the lattice parameter decreased with increasing concentration of lithium and from the comparison of lattice parameters it appears that Cu_0.84 Li_0.08 Al_2.08 O₄ is formed in the impregnated sample calcined at 673 K. Electrical resistivity measurements are consistent with the formation of a solid solution compound.     

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.     

LixCoO2 (0<x<-1): A new cathode material for batteries of high energy density

A new system Li_xCoO₂ (0<x〈-1) has been prepared by electrochemical extraction of lithium from the parent LiCoO₂ ordered rock-salt structure. Measured open-circuit voltages with respect to lithium metal are approximately twice those of Li_xTiS₂ (0〈-x〈-1), and a theoretical energy density of 1.11 kWh kg^?1 is calculated for $\text{Li}{}_{\mathrm{x}}\text{CoO}{}_2\text{Li}$. Preliminary voltage-composition curves show low overvoltages and good reversibility for current densities up to 4 mA cm^?2 over a large range of x.     

Contribution a l'etude de la conductivite ionique de l'orthophosphate Na3PO4

The present work is concerned with the ionic conductivity of pure trisodium orthophosphate Na₃PO₄, devoid of any trace of hydroxide NaOH. At the allotropic transition (330°C), we observe a jump of the ionic conductivity and a slight decrease in the activation energy (ΔE = 0,70 ± 0,02 eV for the quadratic variety and ΔE = 0,60 ± 0,04 eV for cubic γ-Na₃PO₄). Na₃PO₄ can be considered to be an electrolytic solid with medium conductivity ($\text{σ = 1.10}{}^{\mathrm{?4}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$ at 370°C).     

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.     

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.     

Preparation and structure of EuIINb4O11

The occurrence of compound in the system has been studied by means of X-ray powder diffraction. A compound, Eu^IINb₄O₁₁, was found. The X-ray powder diffraction data for Eu^IINb₄O₁₁ could be indexed on a tetragonal cell with $\text{a}\text{=52.52}\text{A}\text{?}$, $\text{C}\text{=7.69}\text{A}\text{?}$. The temperature dependence of the magnetic susceptibility for this compound is expressed by the equation, $\text{X}{}_{\mathrm{M}}\text{=}\text{7.10}\text{(}\text{T}\text{+0.20)}$. This compound is oxidized at about 290°C or above in air.     

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.     

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.     

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.