Diffusion of 55Fe in Fe2O3 single crystals

The diffusion of ⁵⁵Fe has been measured parallel to the c axis of Fe₂O₃ single crystals at temperatures in the range 708–1303°C and at an oxygen activity of unity. The tracer penetration profiles were determined using sectioning techniques. For temperatures above 900°C the tracer diffusion coefficient is given byD¹(Fe) = 1.6 × 10⁹ exp[?6.0 (eV)/kT] cm² s^?1 and below 900°C by 2.8 × 10^?9 exp[?1.8 (eV)kT]. The high-temperature behaviour is probably characteristic of pure Fe₂O₃, whereas diffusion at lower temperatures may be influenced by impurities. The most likely defects responsible for diffusion of Fe are iron interstitials and, for oxygen, oxygen vacancies, and the observed activation energies are discussed in terms of the properties of these defects. The diffusion data and defect models have been used to predict the rate of growth of Fe₂O₃ and indicate that outward Fe diffusion is the dominant transport process. Previously published data for Fe₂O₃ growth in a variety of experimental situations have been corrected to a single rate constant using a model for multilayer growth. The corrected data are all in good agreement but are approximately two orders of magnitude greater than predicted from diffusion data, which suggests that grain boundary diffusion controls the growth of Fe₂O₃ in practice.     

Pressure dependent optical absorption edge shift and compressibility of CdCr2Se4 single crystals

The pressure shift of the optical absorption edge (dE_g/dp = (1.1 ± 0.1) × 10^?6 eV bar^?1) and the compressibility (κ = (1.3 ± 0.) × 10^?6 bar^?1) of single crystalline CdCr₂Se₄ have been measured at ambient temperature. These data suggest an interpretation of the fundamental absorption in terms of either p → p interband or p → localized d charge transfer transitions, but exclude excitations involving s-band states.     

Dipolar dielectric relaxation in CeO2-YO1,5 solid solutions

The dielectric properties of yttrium oxide-doped cerium oxide solid solutions have been studied by using a.c. techniques. Frequency and temperature respectively range from 10 to 10⁵ Hz and from 70 to 200°C. Both a complex impedance plot (Z″ vs Z′) and a conductance plot (G at fixed frequency vs inverse of temperature T^?1) are shown to be complementary for an accurate determination of the bulk resistance and of the dielectric loss. For the three investigated concentrations of yttrium oxide (m/% YO_1,5:0.001, 0.01 and 0.1), the activation energies for conduction are equal to 0.86, 0.75 and 0.75 eV, while the activation energy for dipole reorientation is found to be concentration independent (0.75 eV; angular frequency preexponential factor: 6.0 × 10¹², 1.43 × 10¹³ and 3.05 × 10¹³ s^?1). Moreover, the dipolar relaxation rates are found to be of the same order of magnitude as that of the migration rate. Interpretation is given on the basis of Wachtman's model and of previous results obtained by Nowick et al. from ITC (ionic thermo-current) investigations. The observed dielectric peak appears to be due to the redistribution of oxyygen vacancies between charged (Y_Ce-V₀) pairs and fixed charged Y_Ce defects.     

Field dependence of the NMR frequency in BaFe12O19

The field dependence of the NMR frequencies for the “a” and “c” sites of BaFe₁₂O₁₉ has been re-examined. In a polycrystalline grain-oriented sample at 4.2 K no indication for a deviation from the antiparallel orientation of the sublattice magnetization is found. For Fe⁵⁷, a gyromagnetic ratio of γ/2π = (138.0 ± 0.3) × 10⁴ Hz/T is found in fair agreement with the generally accepted value of (137.7 ± 1.0) × 10⁴ Hz/T.     

Magnetic annealing and crystallization kinetics of the metallic glass Fe5Co70Si15B10

Magnetic annealing and crystallization kinetics of amorphous ribbons of Fe₅Co₇₀Si₁₅B₁₀ were studied. For a toroid stress-relieved at 365°C for 2 h, the anistropy energy K_u obtained by cooling in a magnetic field from 300°C was ≈1.1 × 10³erg/cm³ at room temperature. The reorientation of induced anisotropy of this toroid followed the equation for first-order kinetics closely, yielding an activation energy ΔE = 1.9 eV and a pre-exponential frequency factor v₀ = 3.2 × 10¹³s^-1. Anisotropy reorientation in a toroid partially stress-relieved at 220°C, although was clearly reversible during 8 cycles of isothermal annealing in tranverse and in longitudinal field, exhibited significant deviations from the equation for first order kinetics. Treating the data in terms of the equation for first order kinetics, a narrow spectrum of activation energy from 1.2 to 1.8 eV, with corresponding frequency factors from 1.8 × 10⁸ s^-1 to 5.6 × 10¹² s^-1, was obtained. The difference in behavior between the two samples is discussed in the light of concepts in structural relaxation recently proposed by T. Egami. Crystallization kinetics was studied on a DSC apparatus, using Kissinger's method. At 10 K/min heating rate, the temperature of incipient crystallization was found to be 770 K. The activation energies found were in the range 4.8–4.2 eV.     

Conductivity enhancement in fluorite-structured Ba1−xLaxF2+x solid solutions

The ionic conductivity of single crystals of the fluorite-structured solid solutions Ba_1?xLa_xF_2+x(10^?3 <×<0.45) has been studied as a function of temperature and composition in the range 300–900 K. Three regions can be discerned in the concentration dependence of the ionic conductivity: a dilute concentration region (x<10^?3), where classic relations between solute content and ionic conductivity hold; an intermediate concentration region (10^?3<x?5×10^?2), where large changes occur in the conductivity activation enthalpy and the magnitude of the conductivity; and a concentrated solid solution region (x?5×10^?2) characterized by enhanced ionic motion. In the dilute region the migration enthalpy for interstitial fluoride ions is determined to be 0.714 eV, while a value of 0.39 eV is found for the (La_BaF_i)^X association enthalpy. The defect chemistry in the intermediate concentration region is shown to be controlled by a superlinear increase of the concentration of mobile defects, while in the concentrated solid solution region a composition-independent amount of ≈1 mole% of interstitial fluoride ions with enhanced mobility, carry the current.     

Magnetic anisotropy and saturation of LaFe12O19 and some related compounds

The saturation magnetization σ_s and uniaxial anisotropy constants K₁ and K₂ are measured on a polycrystalline, crystal-oriented sample of LaFe₁₂O₁₉ contaminated with known amounts of Fe₃O₄ and LaFeO₃. K₁ and K₂ increase strongly with decreasing temperature and the value of K₁ = (19–24) × 10⁵ erg/g at T = 0 shows that the substance is considerably more anisotropic than BaFe₁₂O₁₉ (K₁ ? 8·5 × 10⁵ erg/g) at low temperatures. The σ_s-T curve is more convex than that of BaFe₁₂O₁₉, so that σ_s is 11 per cent higher at room temperature but lower at T = 0. The value σ_s(T = 0) = 96·2 G cm³/g (19·2 μ_B/molecule) and the anisotropic behaviour are attributed to the presence of 1 Fe²⁺/molecule occupying the octahedral 2a sites in the magnetoplumbite lattice and having a uniaxial anisotropy of 10–15 cm^?1/ion.From measurements on polycrystalline, crystal-oriented samples of BaFe_10·8Fe²⁺_0·6Ti⁴⁺_0·6O₁₉ and BaFe_10·5Fe²⁺_1·0Sb⁵⁺_0·5O₁₉ it was found that, in comparison with LaFe₁₁Fe²⁺O₁₉, σ_s (T = 0) is smaller and K₁ is much smaller and much less temperature-dependent. The difference in anisotropic behaviour is attributed to a different distribution of the Fe²⁺ ions among the lattice sites due to the effective positive charge of the Ti⁴⁺ and Sb⁵⁺ ions.     

Absolute intensity measurements of the CO2 bands 401III←000 and 411III←010

The absolute intensities of the transitions 401_III←000 and 411_III←010 of CO₂ have been measured from spectra obtained under high resolution. Both the vibration-rotation line intensities and the integrated band intensities are reported. The rotationless transition moment of 401_III←000 is deduced and a vibration-rotation interaction factor F(m) = 1+(4.92×10^?4)m+(4.4×10^?7)m² is determined. The values obtained are: S_Band(401_III←000) = (25.54±0.22)×10^?5 cm^?2atm_{(293 K)}^?1, |R₀₀₀^401_III| = (1.87±0.02)×10^?4D, and S_Band(411_III←010) = (1.83±0.13)×10^?5 cm^?2atm_{(293 K)}^?1.     

Shubnikov-de haas effect in n-CdSnAs2

Shubnikov-de Haas oscillations in the transverse magnetoresistance of single-crystalline n-type CdSnAs₂ have been recorded at temperatures between 2 and 25 K in magnetic fields up to 5T. The electron concentration of the samples ranged from 2 × 10¹⁷ to 2 × 10¹⁸ cm^?3. The angular dependences of the oscillation periods and cyclotron effective masses showed that the conduction band exhibits an energy dependent anisotropy, obeying the Kildal band structure model. For the low-temperature values of the band parameters we found: a band gap E_g = 0.30 eV, a spin-orbit splitting Δ = 0.50 eV, a crystal field splitting parameter δ = ?0.09 eV, and an interband matrix element P = 8.5 × 10^?8eV cm. This simple four-level model was found to be not adequate to describe quantitatively the observed electronic effective g-factor for a sample with low electron concentration.     

Magnetostriction of Fe81Ga19 oriented crystals

The effect of the orientation on the magnetostriction in Fe 81 Ga 19 alloy has been investigated experimentally and theoretically.The Fe 81 Ga 19 [001] and [110] oriented crystals were prepared and the magnetostriction was measured under different pre-stress.The saturation magnetostriction of the [001] oriented crystal increases from 170×10-6 to 330×10-6 under the pre-stress from 0 to 50 MPa.The [110] oriented crystal has a saturation magnetostriction from 20×10-6 to 140×10-6 with the compressive pre-stress from 0 to 40 MPa.The magnetostriction of [001] and [110] oriented crystals has been simulated based on the phenomenological theory.The domain rotation path has been determined and the resultant magnetostriction calculated under different pre-stress.The experimental and simulated results both show that the [001] oriented crystal exhibits better magnetostriction than [110] oriented crystal.The enhancement of the saturation magnetostriction by the compressive pre-stress in the [110] oriented crystal is higher than that in the [001] oriented crystal.     

Knight shifts and magnetic susceptibilities of the intermetallic compounds CeCu4 and CeCu5

The magnetic susceptibility and Knight shift of the compounds CeCu₄ and CeCu₅ have been measured over the temperature ranges 80–800 and 140–400 K, respectively. The most important contributions to the magnetic susceptibility are the Curie-Weiss term, expressing the paramagnetism of the localized ?-electrons, and a temperature independent term, which have both been determined. The phenomenological exchange integral F_s? between the 4?-electron spins and conduction electron spins was found to be ?10.43× 10^?3 eV for CeCu₄ and 3.9 × 10^?3 eV for CeCu₅. A reversal in the sign of the s?? coupling for CeCu₅ is noted.     

Optical,magneto-optical and mössbauer spectroscopy on Co3+ substituted cobalt ferrite Co2+Fe2−xCo3+xO4(0 ⩽ x ⩽ 2)

The magneto-optical spectra of Co_1+xFe_2?xO₄ show with increasing Co³⁺ content an increasing intensity of the 4A₂ ? 4T₁(F) and 4A₂ ? 4T₁(P) transition of Co²⁺ at 0.8 and 2.0 eV. A decrease in the Co²⁺-Fe³⁺ charge transfer transitions on octahedral sites is found. In the optical spectra a strong increase in optical absorption is found with dominant transitions at 0.8, 1.6 and 2.6 eV due to Co³⁺ crystal field transitions on octahedral sites and a Co²⁺-Co³⁺ charge transfer. Conversion Electron Mössbauer Spectroscopy has been used to determine the cation distribution in the surface layer of the samples. The results indicate a shift of Co²⁺ from octahedral to tetrahedral sites when Co³⁺ is substituted in CoFe₂O₄. This results in enhanced optical absorption, enhanced magneto-optical effects and a lower Curie temperature.     

Conductivity of β″ and ion rich β alumina.I.H.+(H2O)n compounds

The conductivity and thermal stability of H⁺(H₂O)_n β″ and ion rich β alumina single crystals have been measured by the complex impedance method in the 25–700°C temperature range. Two mechanisms of conductivity were assumed: proton transfer at lower temperatures and H₃O⁺ diffusion in the high-temperature range. Both structures have similar properties, but ion rich β alumina possesses the best stability and the lowest activation energy (β: 0.15 eV, β″: 0.20 eV below 400 and 300°C respectively). The room-temperature conductivity is ≈5×10^?6 Ω^?1 cm^?1. The conducting properties and mechanisms are discussed and compared to other protonic or ionic conductors.     

Switching phenomenon and optical properties of Se85Te10Bi5 films

Se₈₅Te₁₀Bi₅ films of different thicknesses ranging from 126 to 512 nm have been prepared. Energy-dispersive X-ray (EDX) spectroscopy technique showed that films are nearly stoichiometric. X-ray diffraction (XRD) measurements have showed that the Se₈₅Te₁₀Bi₅ films were amorphous. Electrical conduction activation energy (ΔE_σ) for the obtained films is found to be 0.662 eV independent of thickness in the investigated range. Investigation of the current voltage (I-V) characteristics in amorphous Se₈₅Te₁₀Bi₅ films reveals that it is typical for a memory switch. The switching voltage V_th increases with the increase of the thickness and decreases exponentially with temperature in the range from 298 to 383 K. The switching voltage activation energy (ε) calculated from the temperature dependence of V_th is found to be 0.325 eV. The switching phenomenon in amorphous Se₈₅Te₁₀Bi₅ films is explained according to an electrothermal model for the switching process. The optical constants, the refractive index (n) and the absorption index (k) have been determined from transmittance (T) and reflectance (R) of Se₈₅Te₁₀Bi₅ films. Allowed non-direct transitions with an optical energy gap (E_g^opt) of 1.33 eV have been obtained. ΔE_σ is almost half the obtained value of E_g^opt, which suggested band to band conduction as indicated by Davis and Mott.     

Cation self-diffusion and impurity diffusion in Fe2O3+

Cation self-diffusion D¹_Fe, parallel to the c axis has been measured as a function of temperature (1100–1300°C) and oxygen partial pressure p_o2 (2 × 10^?3-1 atm) in the same single crystals of Fe₂O₃ as those used by Chang and Wagner. Whereas the p_o2 dependence of D1_Fe, observed by Chang and Wagner has been confirmed, the absolute value of D¹_Fe and the activation enthalpy for self-diffusion are much higher than those reported by them. The various diffusion studies indicate that cation self-diffusion occurs by an interstitial-type mechanism. However, the sample-to-sample variations in D¹_Fe, suggest that all diffusion measurements may have been performed on samples where the defect concentrations are impurity controlled. Impurity diffusion of ⁶⁰Co, ⁵¹Cr, and ⁸⁸Y has also been measured as a function of p_o2 at 1200°C. The results indicate that these impurities diffuse by an interstitialcy mechanism in Fe₂O₃.     

Intraband and interband optical transitions in Zn3AS2

Absorption measurements were made on single crystals and thin films of Zn₃As₂; within the photon energy range of 0.12–1.16 eV at temperatures of 300, 80 and 5 K and reflectivity was measured in the range of 1.0–5.5 eV at 300 K. Absorption below the fundamental edge has been interpreted as a process involving three mechanisms: (i) free-carrier absorption, (ii) intraband transitions between levels in the valence band, and (iii) direct transitions from valence levels to the acceptor level/band. The fundamental absorption edge has been ascribed to direct interband transitions from three valence levels to one conduction level. An isotropic three-level Kane band model has been used to interpret the experimental data, modified by introducing the light-hole level split from the heavy-hole level due to the tetragonal crystal field. A reasonable fit of the model to the experimental results has been obtained in the region of both intraband and interband absorption for the following set of parameters: E_g = 0.985 eV, Δ_SO = 0.30 eV, Δ_CF = 0.05 eV, m^*_hh = 0.36 m₀ and P = 4 × 10^?10eVm (at 300 K). A proposed Zn₃As₂ energy-band model near the Γ point is described to interpret the observed absorption.     

Optical band-gap of Zn3As2

Absorption measurements of single Zn₃As₂ crystals were made at temperatures 5, 80 and 300 K. Free-carrier absorption is interpreted in the simple classical model. Interband absorption shows contributions from Urbach-like excitations. The direct optical gap has been estimated as 0.99 eV at 300 K, 1.09 eV at 80 K and 1.11 eV at 5 K. The linear dependence of band-gap on temperature was found in the range 80–300 K with dE_g/dT = ? 4.55 × 10^?4eVK^?1.     

12C16O18O: Analysis of rovibrational transitions Ov′2v3 → Ov′2(v3 − 1) (v2 = 0 and 1) observed in high-resolution emission spectra in the 4.5-μm region

Emission spectra of six isotopic species of CO₂ excited by dc discharge were recorded under Doppler limited resolution using the Fourier transform spectrometer of the Laboratoire d'Infrarouge in the 4.5-μm region. In this paper, the results concerning ¹²C¹⁶O¹⁸O are given. The band centers and the spectroscopic constants for 19 levels involved in vibrational transitions Δv₃ = 1 are reported. They reproduce 853 experimental wavenumbers with a RMS of the order of 2 × 10^?5 cm^?1 for the best vibrational transition, less than 1 × 10^?4 cm^?1 for most of the others. From experimental wavenumbers, to determine molecular parameters, it is shown that it is impossible to include in the same fit all the transitions Σ-Σ until v₃ = 10 using a polynomial representation of the rovibrational energy, the responsible phenomenon being the small Fermi resonance which occurs on Σ levels. Nevertheless, the 321 wavenumbers belonging to the first four vibrational transitions are satisfactorily reproduced by the model.     

Cross sections for slow ion production and charge transfer in H+3(D+3)−H2(D2) collisions

Slow ion production cross sections for collisions of H⁺₃ and D⁺₃ ions with H₂ and D₂ have been measured at collision energies between 100 eV and 500 eV. The values vary from 2 × 10^-17 cm² to 6 × 10^-17 cm². The smaller cross sections for D₃ projectiles may be explained as an internal energy effect.     

Ne(I) spectral lines from a Ne-O2 d.c. glow discharge

Measurements have been made of intensities of the spectral lines emitted from an Ne-O₂ d.c. discharge with small discharge current (1–4 mA) under the following conditions: gas pressures of 2 and 3 torr and oxygen partial pressures (P₀₂) up to 0.1 torr. All of the Ne(I) line intensities observed decrease when O₂ is added. The Ne(I) λ5852 line (1s₂-2p₁) has been studied in detail as a representative example. The population density of the 2p₁ level of neon has been obtained from the intensity measurements as a function of P₀₂. The energy-distribution function of electrons has been determined using Druyvesteyn's method in order to calculate the population density for a corona model. The high-energy tail of the measured distribution function is markedly reduced when O₂ is added. It is shown that inelastic collisions of electrons with O₂ produce large energy losses for the electrons. These cause a decrease in population density of the 2p₁ level when O₂ is added. The population density of the 2p₁ level at a gas pressure of 2 torr is 1.2×10⁴ cm^-3 in pure neon and 5.2×10² cm^-3 in an Ne-O₂ mixture (P₀₂ = 0.01 torr). The electron densities and average electron energies are 3.5×10⁸ cm^-3 and 8.7 eV and 1.7×10⁸ cm^-3 and 5.3 eV, respectively, for the specified two cases.