New Li+ ion conductors in the system,Li4GeO4-Li3VO4

New Li⁺ ion conducting solid electrolytes have been found in the system Li₄GeO₄-Li₃VO₄. Of the compositions studied, Li_3.6Ge_0.6V_0.4O₄ has the highest conductivity with σ ～ 4 × 10^?5 ohm^?1cm^?1 at 18°C rising to ～ 10^?2 ohm^?1 cm^?1 at 190°C. The activation energy is ～0.44 eV. These conductivity values are among the highest yet found for Li⁺ ion conductors; the room temperature value is much higher than in LISICON, Li_3.5Zn_0.25GeO₄, or in Li_3.4Si_0.4P_0.6O₄ and is comparable to that in $\text{LiI/A}\text{l}{}_2\text{O}{}_3$ mixtures. These solid electrolytes are easy to synthesize, thermodynamically stable and insensitive to atmospheric attack. Structurally, they are solid solutions based on γ_II Li₃VO₄, a γ tetrahedral structure; high conductivity is due to the interstitial Li⁺ ions which are created during solid solution formation.     

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.     

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.     

CuTa2O6 - crystal growth and characterization

The compound CuTa₂O₆ has been prepared as crystals from a Cu/O melt and found to be tetragonal ($\text{a}\text{= 7.510}\text{A}\text{?}$, $\text{c}\text{= 7.526}\text{A}\text{?}$) rather than cubic as reported in the literature. The coefficient of thermal expansion between room temperature and 1000°C was found to be 8.0 × 10^?6°C^?1. Electrical resistivity measurements on a crystal showed semiconductor behavior between room temperature ($\text{? = 2 × 10}{}^3\text{Ω}\text{cm}$) and 140°K ($\text{? = 7 × 10}{}^6\text{Ω}\text{cm}$) with an activation energy of E_A = 0.2 eV. Magnetic measurements between 4.2°K and room temperature showed Curie-Weiss behavior with a change in μeff at 120°K. For T>120°K, μeff = 1.76μ_B and θ_p = 0°K while for T<120°K μeff = 1.91 μB and θ_p = ?15°K.     

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

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.     

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.     

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.     

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.     

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).     

Growth,electrical and photoelectrical properties of Tl3SbS3single crystal

The growth of Tl₃SbS₃ single crystal is reported for the first time. 5×1×1 cm³ ingots are obtained by using vertical Bridgmann method with a 2°C/mm gradient and a 0.7 mm/h growth rate. Intrinsic conductivity and photoconductivity are investigated. The weak dark conductivity, $\text{～ 10}{}^{\mathrm{?10}}\text{(Ω}\text{cm}\text{)}{}^{\mathrm{?1}}$ at 300° K, contrasts with a strong photosensitivity. The value of the fundamental band gap deduced from spectral dependence of the photocurrent is in rather good agreement with the value 1.61 eV obtained from temperature dependence of the dark conductivity. The Lux-Ampere characteristics can be described by I ∝ L ^α but changes in α with illumination intensity and temperature show that at least two different local centers are involved in the carrier recombination mechanism.     

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.     

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 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.     

Etude des proprietes structurales et electrioues d'un nouveau conducteur anionique: PbSnF4

Three allotropic varieties of PbSnF₄ - α, β and γ - have been detected by DTA and X-ray diffraction. The α ai β and β ai γ transitions are reversible and occur at 80 and 355°C respectively. The high temperature form γ - PbSnF₄ is cubic and of fluorite type. The structures of the tetragonal β - PbSnF₄ and the orthorhombic α - PbSnF₄ forms are derived from the same structural type. PbSnF₄ has a high anionic conductivity ($\text{σ200°C ? 10}{}^{\mathrm{?1}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$). The temperature dependence of the conductivity indicates the existence of a break in the activation energy at 90°C.     

Crystal structure and cation transport properties of the ortho - diphosphates Na7(MP2O7)4PO4 (M = Al,Cr, Fe)

The isotypic ortho-diphosphates Na₇(MP₂O₇)₄PO₄ (M = Al, Cr, Fe) have been synthesized. They are tetragonal, space group P4&#x0304;2₁c. The structure of the iron member has been solved and refined to a final R = 0.037 for 577 independent reflections. It consists of (FeP₂O₇)₄PO₄ units interconnected so as to form a 3D framework into which the sodium ions are inserted. The units are made of a PO₄ tetrahedron linked to four FeO₆ octahedra; each octahedron is connected to a P₂O₇ group by two oxygens. Ion exchange experiments and conductivity measurements give evidence of some mobility of the sodium ions at high temperature. However, the σ-values ($\text{～ 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$ at 300°C) are relatively low. The narrowness of the windows between the sodium sites as well as the presence of an oxygen atom linked to only one polyhedron of the framework are unfavourable features to fast cation transport.     

Phase diagram of the LISICON,solid electrolyte system,Li4GeO4Zn2GeO4

The phase diagram of the system Li₄GeO₄Zn₂GeO₄ is fairly similar to the corresponding silicate system and contains a wide range of solid solutions that extend to either side of the composition Li₂ZnGeO₄. These solid solutions are polymorphic. The high temperature ^γII solid solutions have a crystal structure derived from that of ^γII Li₃PO₄ and a formula, Li_{2 + 2x}Zn_1?xGeO₄ : ?0.36 < x < +0.87. LISICON, x = 0.75, is one member of the ^γII solid solution series. The compositional extent of the ^γII solid solutions is temperature dependent and eg. the LISICON composition is stable as a single phase γII structure only ? 630°C. On annealing LISICON and other lithiumrich, ^γII solid solutions in the range ～100 to 600°C, various reactions occur, including 1) precipitation of Li₄GeO₄, 2) phase transition(s) to metastable low temperature, γ-derivative structure(s) and 3) atmospheric attack to give Li₂GeO₃, Li₂CO₃ and other phases. The low temperature ^βII, ^βII′ solid solutions occur over a much smaller range of compositions to either side of Li₂ZnGeO₄ and have a crystal structure derived from that of ^βII Li₃PO₄. Li₄GeO₄ forms a short range of solid solutions.     

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.     

Pressure induced phase transformation in BaWO4

A new dense form of BaWO₄(BaWO₄-II) was prepared under high pressure. The phase boundary between the normal pressure form (BaWO₄-I, scheelite structure) and BaWO₄-II was determined as P(kb) = 26.₇+0.26₅T(°C), (T=600–1000 °(C). Crystallographic data were obtained from the single crystal and powder X-ray analyses. BaWO₄-II is monoclinic with 8 formula units in the unit cell. The possible space group is $\text{P}\text{2}{}_{\mathrm{<mtext>1</mtext><mtext>n</mtext>}}$ and the cell parameters are; $\text{a}\text{= 13.159}\text{A}\text{?}\text{,}\text{b}\text{= 7.161}\text{A}\text{?}\text{,}\text{c}\text{= 7.499}\text{A}\text{?}\text{, β = 93.76°}$ and the cell $\text{volume}\text{= 705}\text{A}\text{?}{}^3$. The volume decrease upon transformation is estimated to be 12.1%.     

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.