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).     

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.     

Some experimental observations on the Poisson's ratio of sea-ice

Measurements were made on the longitudinal and transverse strain of sea-ice beams loaded in flexure. The specimens were tested with stress rates varying from 10 to 600 kPa s^?1 and temperatures ranging from ?5°C to ?40°C. Under these conditions, the effective strain ratio μ increases with increasing temperature and decreasing stress rate. The strong influence of the stress rate, σ, suggests an empirical law of the form: μ = 0.24$\text{(}\text{σ}\text{?}\text{σ}\text{?}{}_1\text{)}{}^{\mathrm{?0.29}}\text{+ μ}{}_{\mathrm{D}}$ where σ is the stress rate (kPa s^?1), $\text{σ}\text{?}{}_1$ is a unit stress ratio (1 kPa s^?1) and μ_D is a dynamic value of Poisson's rate which depends on the temperature.     

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.     

Crack tip closure and environmental crack propagation

Crack propagation rate, da/dN, and crack tip closure stress, σ_cc, in part-through crack fatigue specimens of aluminum alloys are drastically affected by gaseous environments. The present studies indicate that the crack closure reflects the influence of the environment on the plastic deformation at the crack tip, and, therefore, on the crack propagation rates. Postulating that da/dN is mainly determined by $\text{ΔK}{}_{\mathrm{eff}}\text{∝ (σ}{}_{\max }\text{?σ}{}_{\mathrm{cc}}\text{)}$ (instead of $\text{ΔK ∝ (σ}{}_{\max }\text{?σ}{}_{\min }\text{)}$, as is done traditionally) leads to the relationship $\text{da/dN = A(ΔK}{}_{\mathrm{eff}}\text{)}{}^{\mathrm{n}}$ in which $\text{A}$ and $\text{n}$ are virtually independent of the gaseous environment. The exponents are $\text{n ≈ 3.3}$ for Al 7075 T651 and $\text{n ≈ 3.1}$ for Al 2024 T351, respectively.     

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.     

Some optical and electrical properties of the As2Se3−xTex system

Some optical and electrical properties of the As₂Se_3?xTe_x system (0 ≤ x ≤ 0.15) have been studied. The value of the optical gap decreases from 1.74 eV to 1.59 eV. The slope of the absorption edge changes, so that value of E_o from the relation α ～ exp ($\text{h}\text{?}\text{ω}\text{E}{}_{\mathrm{o}}$) exhibits a maximum value in neighbourhood of composition As₂Se_2.9Te_0.1. The d.c. and a.c. conductivities have been studied. The value of the activation energy E_el ～ 1.8 eV is almost unchanged up to x = 0.15. The a.c. conductivity fulfils the relation $\text{б(ω) ～ ω}{}^{\mathrm{<mtext>s</mtext>}}$ where s ? 1 and 1.1. at frequencies f < 1 kHz and f > 1 kHz respectively.     

A model for fatigue crack growth in a threshold region

The prediction of fatigue crack growth at very low ΔK values, and in particular for the threshold region, is important in design and in many engineering applications. A simple model for cyclic crack propagation in ductile materials is discussed and the expression

$\text{da}\text{dN}\text{=}\text{2}{}^{\mathrm{1+n}}\text{(1?2v)(ΔK}{}^2{}_{\mathrm{eff}}\text{?ΔK}{}^2{}_{\mathrm{c,eff}}\text{)}\text{4(1+n)π σ}{}^{\mathrm{1?n}}{}_{\mathrm{yc}}\text{E}{}^{\mathrm{1+n}}\text{?}{}^{\mathrm{1+n}}{}_{\mathrm{f}}$

developed. Here, n is the cyclic strain hardening exponent, σ_yc is cyclic yield, and ε_f is the true fracture strain. The model is successfully used in the analysis of fatigue data BS 4360-50D steel.     

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.     

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.     

Polycrystalline hydronium ββ″alumina: A ceramic fast proton conductor

Polycrystalline hydronium $\text{β}\text{β″}\text{-}\text{alumina}$ with f(β) of 0.16 to 0.25 has been fabricated with an electrical conductivity of $\text{～ 10}{}^{\mathrm{?2}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$ at 22°C and an activation energy of 0.24 eV (T < 100°C) and 0.09 eV (T > 100°C). This is comparable with single crystal behaviour. Proton magnetic resonance is correlated with conductivity and the effects of disorder on the conduction plane of the β″-alumina structure are shown to be important.     

Thermonuclear fusion neutrons under “Currentless plasmas” in Heliotron E

Thermonuclear fusion neutron emissions of up to 3 × 10⁹ neutrons/s have been observed in Heliotron E deuterium plasmas. “Currentless plasmas” were produced by electron cyclotron resonance (53 GHz, 150 kW) and further heated by hydrogen neutral beam injection (2.2 MW, H⁰→D⁺). It is found that all observed neutron emissions have thermonuclear origin due to the absence of hard X-ray background. Agreement between neutron and charge exchange ion temperature measurements (500 eV < T_i(0) × 900 eV) have been found at intermediate densities $\text{(1.5 ×}\text{n}{}_{\mathrm{<mtext>e</mtext>}}\text{× 3 × 10}{}^{13}\text{cm}{}^{\mathrm{?3}}\text{)}$. The neutrons reported in this paper are the first observations of pure thermonuclear fusion neutrons in a helical heliotron plasma confinement device.     

Chromium-doped CdF2 crystals by ESR spectroscopy

Single crystals of Cr-doped CdF₂ in which only Cr²⁺ ions were present were obtained by heating CdF₂:CrF₃ samples in Cd vapors. The crystals produced were studied by ESR spectroscopy at X band at 4.2 ^oK. The spectrum obtained is described by the effective spin Hamiltonian:

g⁽²⁾_eff = 4g_zcosΘ, g⁽¹⁾_eff = 2g_zcosΘ, where i = 1 for the doublet of the spin S = 1, and i = 2 for the doublet of the spin S = 2; net effective spin $\text{S}\text{=}\text{1}\text{2}$; g_z=1.85±0.03; |Δ₍₂₎|=3.08±0.07 GHz; |Δ₍₁₎|=5.85±0.07 GHz; $\text{1}\text{6}\text{(Δ}{}^{\mathrm{o}}{}_{\mathrm{(2)}}\text{? Δ}{}^{\mathrm{o}}{}_{\mathrm{(1)}}\text{)=?11.01±0.02}\text{GHz}$.     

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.     

Electrical and optical properties of MoSe2 films prepared by r.f. magnetron sputtering

The electrical resistivity of MoSe₂ films prepared by r.f. magnetron sputtering was measured between 300 and 10 K. The main sputtering parameter governing the physical properties of the films was found to be the substrate temperature T_sub. The room temperature resistivity of the as-sputtered films increased from $\text{1.7 × 10}{}^{-1}\text{Ω}\text{cm}$(T_sub = -70 °C) to $\text{1.4 × 10}{}^1\text{Ω}\text{cm}\text{(T}{}_{\mathrm{<mtext>sub</mtext>}}\text{= 150 °}\text{C}\text{)}$. A check of the thermo-electrical response showed that the majority charge carriers are holes except for films deposited at T_sub = 150 °C which are n type. Hall effect measurements indicated very low Hall mobilities (3–5 cm² V^-1 s^-1). Thermal annealing increased the room temperature resistivities by more than one order of magnitude for the specimens sputtered at a low substrate temperature. The optical properties were weakly influenced by the process conditions. The optical gap was determined to be 1.06 eV.     

Ellipsometry as a means of mass-thickness determination in the earliest film growth stages

Gold was evaporated onto a fused silica substrate, and the normalized Stokes parameters S₁, S₂ and S₃, which represent the state of polarization of the light reflected from the sample, were determined in situ for films of average thickness less than a few monolayers with an automatic ellipsometer; the film mass m per unit substrate area was measured simultaneously with a torsion microbalance. It was found that $\text{ΔS = {(ΔS}{}_1\text{)}{}^2\text{+ (ΔS}{}_2\text{)}{}^2\text{+ (ΔS}{}_3\text{)}{}^2\text{}}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ changes linearly with m for light of wavelength λ well outside the absorption band of the film. For λ = 440 nm the sensitivity is comparable with that of a good torsion microbalance. Thus an automatic ellipsometer can conveniently be employed in the microgravimetry of submonolayer films.     

Fracture of thin sections containing surface cracks

Surface-cracked specimens of several thicknesses of 7075-T651 and 7075-T6 aluminum were tested in uniaxial tension. For thicknesses t less than 0.25 in., the gross fracture stress σ_f of 7075-T651 Al was empirically related to flaw size by the following expression:

$\text{δ}{}_{\mathrm{f}}\text{σ}{}_{\mathrm{ult}}\text{= 1 + S(}\text{a}\text{φ}{}^2\text{.t}{}^{\mathrm{<mtext>?1</mtext><mtext>2</mtext>}}$

where σ_ult is the ultimate strength, a the crack depth, φ a function of crack shape, and S a proportionality constant equal to ?1.7 in.^{$\text{?1}\text{2}$}. For 0.25-in. thick 7075-T651 aluminum, σ_f was found to obey this relationship only when $\text{a}\text{φ}{}^2$ is less than 0.065 in.; for larger flaws, such that $\text{0.065 <}\text{a}\text{φ}{}^2\text{< 0.11, σ}{}_{\mathrm{f}}$ is better predicted by Irwin's surface-crack equation with an apparent K_IC value of $\text{32.2}\text{ksi-in.}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$.Fracture data for thin sections of 2014-T6 and 2014-T651 Al tested at ?423°F are analyzed in terms of the empirical relationship above and are found to be in good agreement. For these alloys, S has a value of ?2.6 in.^{$\text{?1}\text{2}$}.Applicability of the empirical relationship and Irwin's surface-crack analysis to the fracture of thin sections is discussed in terms of crack size, section thickness, and plastic zone size.     

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.     

Fast ionic lithium conduction in solid lithium nitride chloride

Lithium nitride chloride (Li_1.8N_0.4Cl_0.6) crystallizes in a defect anti-fluorite structure with 10% of the lithium sites being vacant. Its electrical conductivity and thermodynamic stability have been investigated in the temperature range from 25 to 400° C. Lithium ions are the predominant charge carriers, yielding a conductivity temperature product of σ T = 7.456 × 10⁴ exp(?0.49₅ eV/kT) $\text{Ω}{}^{\mathrm{?1}}$ cm^?K. The electronic contribution to the total conductivity is smaller by a factor of less than 10^?4. The material is thermodynamically stable against pure metallic lithium and has a decomposition voltage larger than 2.5 V.     

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.