Self-diffusion in α-Fe2O3 natural single crystals

Measurements of¹⁸O self-diffusion in hematite (Fe₂O₃) natural single crystals have been carried out as a function of temperature at constant partial pressure a_{O 2}=6.5·10^?2 in the temperature range 890 to 1227 °C. The a_{O 2} dependence of the oxygen self-diffusion coefficient at fixed temperature T=1150 °C has also been deduced in the a_{O 2} range 4.5·10^?4 - 6.5·10^?1. The concentration profiles were established by secondary-ion mass spectrometry; several profiles exhibit curvatures or long tails; volume diffusion coefficients were computed from the first part of the profiles using a solution taking into account the evaporation and the exchange at the surface. The results are well described by $$D_O \left( {{{cm^2 } \mathord{\left/ {\vphantom {{cm^2 } s}} \right. \kern-\nulldelimiterspace} s}} \right) = 2.7 \cdot 10^8 a_{O_2 }^{ - 0.26} \exp \left( { - \frac{{542\left( {{{kJ} \mathord{\left/ {\vphantom {{kJ} {mol}}} \right. \kern-\nulldelimiterspace} {mol}}} \right)}}{{RT}}} \right)$$ From fitting a grain boundary diffusion solution to the profile tails, the oxygen self-diffusion coefficient in sub-boundaries has been deduced. They are well described by $$D''_O \left( {{{cm^2 } \mathord{\left/ {\vphantom {{cm^2 } s}} \right. \kern-\nulldelimiterspace} s}} \right) = 3.2 \cdot 10^{25} a_{O_2 }^{ - 0.4} \exp \left( { - \frac{{911\left( {{{kJ} \mathord{\left/ {\vphantom {{kJ} {mol}}} \right. \kern-\nulldelimiterspace} {mol}}} \right)}}{{RT}}} \right)$$ Experiments performed introducing simultaneously¹⁸O and⁵⁷Fe provided comparative values of the self-diffusion coefficients in volume: iron is slower than oxygen in this system showing that the concentrations of atomic point defects in the iron sublattice are lower than the concentrations of atomic point defects in the oxygen sublattice. The iron self-diffusion values obtained at T>940 °C can be described by $$D_{Fe} \left( {{{cm^2 } \mathord{\left/ {\vphantom {{cm^2 } s}} \right. \kern-\nulldelimiterspace} s}} \right) = 9.2 \cdot 10^{10} a_{O_2 }^{ - 0.56} \exp \left( { - \frac{{578\left( {{{kJ} \mathord{\left/ {\vphantom {{kJ} {mol}}} \right. \kern-\nulldelimiterspace} {mol}}} \right)}}{{RT}}} \right)$$ The exponent - 1/4 observed for the oxygen activity dependence of the oxygen self-diffusion in the bulk has been interpreted considering that singly charged oxygen vacancies V _O ^? are involved in the oxygen diffusion mechanism. Oxygen activity dependence of iron self-diffusion is not known accurately but the best agreement with the point defect population model is obtained considering that iron self-diffusion occurs both via neutral interstitals Fe _x ⁱ and charged ones.     

Hydrogen-deuterium exchange induced by an electric field in α-Al2O3 single crystals

Abstract

Hydrogen and deuterium are observed in α-Al₂O₃ crystals in the form of OH^? and OD^? radicals, respectively, which absorb in the infrared region. Infrared-absorption measurements were used to monitor diffusion of deuterons and protons in α-Al₂O₃ single crystals under the application of a moderate electric field parallel to the crystallographic c-axis, in the temperature range of 973—1333K. A linear dependence of the percent of exchange with both annealing time and applied voltage is observed, indicating that ionic conduction was taking place. The activation energy for the H⁺  D⁺ exchange was determined to be 2.4 eV, less than half the value obtained by pure thermal means, suggesting that under the application of an electric field the deuteron (proton) diffusion mechanism is different.     

Dislocation centers in α-martensite formation and dual couplings of thinly-laminated martensite crystals

The spectrum of observable dual couplings of crystals of thinly-laminated martensite with habiti {3 15 10} is discussed within the framework of the concept of the dislocation formation of -martensite crystals. A spectrum of dislocation centers of formation arising together with the developing martensite crystal is proposed. Here it is essential to divide the arising dislocation centers of formation into two groups associated with different displacement mechanisms. This difference permits understanding of the difference in the frequency of observation of couplings and the introduction of the concept of a comb structure — a set of secondary parallel crystals of martensite, associated with the same initial crystal.Urals Forestry Institute. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 64–67, June, 1994.     

Tunable laser radiation,nonlinear absorption,and “anti-stokes” luminescence of color centers in α-Al2O3

This work investigates the generation of laser radiation by color centers of leucosapphire, nonlinear absorption, and the excitation mechanism of UV-luminescence. It is shown that UV-luminescence from color centers, excited in the 0.68 m absorption band, is caused by a two-staged excitation mechanism. The optical characteristics of the color centers are measured and calculation is made of the variation of the absorption coefficient with laser pulse's duration.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 41–46, October, 1987.     

Thermoluminescence of α-Al 2O 3 by neutron irradiation at low temperature

Thermoluminescence (TL) mechanisms of neutron-irradiated α-Al₂O₃ at 20 K is reported. The TL glow curves of neutron-irradiated and γ-ray-irradiated α-Al₂O₃ were observed. The TL emission bands near 340, 430, 530 and 694 nm were observed in the neutron-irradiated α-Al₂O₃. The γ-ray-irradiated α-Al₂O₃ only showed the TL emission line nearly at 694 nm, corresponding to the R lines of α-Al₂O₃:Cr³⁺. Therefore, the first three emission bands are related to the atomic displacement defects as F-type centers caused by neutron irradiation.     

Formation of optical color and fluorescence centers in polytetrafluoroethylene under γ-irradiation

Fluorescent properties and colors of polytetrafluoroethylene (PTFE) samples were studied as functions of absorbed dose of γ-radiation at a temperature above the melting temperature of the crystallites (327°C) in the dose range 0.2–0.8 MGy. The samples were irradiated at low pressure (10^–6 Torr) in glass ampuls and at atmospheric pressure in a chamber purged with argon. Samples in ampuls acquired an off-white tint and fluoresced weakly. The fluorescence intensity increased slowly as the radiation dose increased from 0.2 to 0.6 MGy and decreased at 0.8 MGy. Samples irradiated in the chamber fluoresced more strongly and acquired colors that changed from gray (0.2 MGy) to dark-brown (0.8 MGy). Color centers were formed only in the sample surface layer. Their appearance was associated with the adsorption of particles of an unknown nature from the environment. The argon-purged samples turned white upon removing their surface layer (50 μm). The intensity and shape of fluorescence bands emitted by these samples remained essentially unaltered, i.e., depended weakly on the absorbed dose in the range 0.2–0.8 MGy.     

Ablation efficiency of α-Al2O3 in liquid phase and ambient air by nanosecond laser irradiation

Ablation efficiency and influences of laser parameters on a material removal rate by a nanosecond laser irradiation of α-Al₂O₃ are studied in gas and liquid phases. The laser ablation in the air yields maximum material removal rate of 12 ng/pulse using a 4.6-mJ pulse energy at 4-kHz repetition rate, compared to 88 ng/pulse in the water flow. Using a specific interpulse distance and a laser repetition rate further increase material removal rate by factor of 3 and 65, respectively, owing to an optimized lattice temperature and laser pulse interactions with the generated cavitation bubble. For the ablation in the air, these parameters do not significantly affect the ablation efficiency.     

The effect of annealing on the proton conductivity of Mg-doped α-Al2O3

In order to evaluate the effect of annealing treatment on the proton conductivity of ??-alumina, the electrical conductivity of Mg-doped polycrystalline ??-alumina kept at 1,873?K under various conditions of the surrounding atmosphere and then cooled in the furnace was measured in the temperature range 1,173?C1,473?K. The H⁺/D⁺ isotope effect on the electrical conductivity was also examined under a hydrogen atmosphere at 1,273?K. The protonic conductivity measured at 1,273?K increased with the increase in the activity of oxygen and water vapor in the annealing atmosphere at 1,873?K. It is considered that the solubility limit of magnesium ions in ??-alumina in equilibrium with the small amount of the spinel phase increased with the increase in the activity of oxygen and water vapor at 1,873?K. This enhanced amount of magnesium ions is frozen in a non-equilibrium state to 1,273?K and works as the enriched acceptor dopant for the incorporation of protons.     

Lowering of magnetic field intensity at the surfaces of α-Fe2O3 and FeBO3 single crystals

Depth-selective conversion electron Mössbauer spectroscopy was used to study magnetic properties of the thin surface layers of the α-Fe₂O₃ and FeBO₃ single crystals. An analysis of the experimental spectra indicates that the magnetic properties of the layers at a depth of more than ～100 nm from the surface are similar to the properties of crystal bulk, and the corresponding spectra consist of narrow lines. The lines gradually broaden as the crystal surface is approached. The spectra of the ～10-nm-thick surface layers consist of broad lines, indicating a wide distribution δ=2.1 T of the effective magnetic field about its mean value of 32.2(4) T. The experimental spectra were used to determine the effective magnetic fields (H _eff) for the iron ions situated in the surface layers of thickness ～100 nm. The effective fields in these layers were found to gradually decrease at room temperature (291 K) as the crystal surface was approached. The H _eff values in the 2.4(9)-nm-thick surface layer of the α-Fe₂O₃ crystal and 4.9(9)-nm layer of FeBO₃ are 0.7(2) and 1.2(3)%, respectively, smaller than for the nuclei of the ions in the bulk of these crystals.     

Nature of the anomalies of the thermolumenescence properties of dosimetric α-Al2O3 crystals

The results of investigations into the anomalies of the thermoluminescence properties of dosimetric corundum crystals are presented. The decisive role of deep-lying traps in the quenching of luminescence in anion-defect Al₂O₃ monocrystals is shown. The existence of deep-lying traps is demonstrated by the method of direct observations of thermoluminescence (TL) peaks associated with them. Experimental evidence for the influence of the degree of occupation of deep-lying traps on the main features of the TL dosimetric peak at 450 K is given. The results obtained are interpreted for a model of the interactive system of traps, which differs radically from the models described in the literature by a consideration of the temperature dependence of the probability of trapping of charge carriers on deep-lying traps. We believe that the heat quenching of luminescence is due to the thermal ionization of excited F-center states. Ural State Technical University. Translated from Izvestiya Vysshikh Uchebhykh Zavedenii, Fizika, No. 3, pp. 55–65, March, 2000.     

Effect of recoil atoms on radiation-defect formation in semiconductors under 1–10-MeV proton irradiation

The formation of radiation defects in Si under 1–10-MeV proton bombardment is analyzed. Numerical simulation is carried out, and histograms of the distribution of the energy transferred to recoil atoms are obtained. Two energy ranges are considered when analyzing the histograms. Single Frenkel pairs with closely located components are produced in the first range (small energies). Recoil atoms of the second range have an energy sufficient for the production of a displacement cascade. As a result, nanoscale regions with high densities of vacancies and different types of their complexes appear. In addition, as the energy of the primary knocked-out atoms increases, the average distance between genetically related Frenkel pairs increases, and, as a consequence, the fraction of pairs that are not recombined under bombardment increases.     

Electron spin resonance of aluminum-related color centers in α-TeO2:Al

ESR observations of aluminum-doped paratellurite (α-TeO₂:Al) single crystals after electron irradiation near room temperature indicate four radiation-induced electron-like defects with similarities to the intrinsic V_o^. center, which is also present. From measurements of angular variations and tellurium hyperfine interactions it is evident that the four centers represent a family of V_o^. centers perturbed by Al³⁺; that is, V_oAl_Te^x centers. The new centers are detected only in Al-doped crystals; however, the aluminum impurity ions appear to be too far from the V_o^. to yield ²⁷Al hyperfine interaction measurable by ESR.     

Low-temperature optical spectra and zero-phonon transition of color centers in γ-rayed lithium fluoride crystals

The zero-phonon lines on R_2, R~ , N_1 and R′_2 centers and some new narrow lines have been observed in bivalent-metal-doped and air-grown LiF crystals irradiated by γ-ray in the temperature range of 9.5—130K. The spectral properties and thermostabilities of the lines are investigated systematically at different temperatures.     

Structure determination of MnO2 films grown on single crystal α-Al2O3 substrates

Manganese oxide films have been grown by atomic layer deposition and investigated using electron diffraction and high-resolution electron microscopy (HREM). The films were deposited on the (001) surface of monocrystalline α-Al₂O₃. The films were found to consist of an ordered version of the hexagonal ε-MnO₂ (Akhtenskite) type. Using X-ray diffraction, the cell parameters were determined to be a?=?2.75(2)?Å and c?=?4.302(5)?Å. The films are epitaxial with a specific orientation relative to the Al₂O₃ substrate. The [210] and [001] axes of ε-MnO₂ are parallel to the [110] and [001] axes of α-Al₂O₃, respectively. Evidence of cation ordering was found by parallel beam electron diffraction. The ordered domains are needle shaped with widths of 2–10?nm. The unit cell of the ordered structure was found to be orthorhombic with cell dimensions a?=?2.75, b?=?4.76, c?=?4.302?Å and space group Pmnn (No. 58).     

NO 3 2− and CO 2 − centers in synthetic hydroxyapatite: Features of the formation under γ- and UV-irradiations

The EPR studies of synthetic hydroxyapatite containing carbonate and nitrate ions exposed to γ-ray and UV irradiations have been performed. It has been found that γ irradiation leads to the formation of both NO₃²⁻ and CO₂⁻ paramagnetic centers, while the UV irradiation induces only NO₃²⁻ centers. To explain this fact, the hypothesis has been proposed, according to which in the hydroxyapatites studied, there coexist complexes consisting of nitrate ions and shallow electron traps that serve as sources of secondary electrons during UV irradiation. The EPR spectroscopy parameters (g and A) of the detected centers have been determined and compared with similar centers in hydroxyapatite with a different impurity composition. The study of the thermal stability of the centers has demonstrated that, in the temperature range 20–300°C, the NO₃²⁻ centers formed by UV irradiation are more stable than the same centers created by γ-ray irradiation.     

Crystallographic aspects of structure formation under the β → α transformation in oriented cobalt single crystals

The crystallographic parameters of the β → α transformation in oriented cobalt single crystals quenched from 1000°C have been studied by X-ray structure analysis and light microscopy. It is shown that the orientation of martensite crystals of the α phase correspond to the Wasserman orientation relationship.     

Raman spectra of single crystals of α-P4S3

Polarization data for the Raman-active k = 0 phonons of single crystals of α-P₄S₃ have been measured at 10 K and at high resolution. Of the 24 external and 60 internal phonons expected for the D_2h factor group of α-P₄S₃ we have observed 16 external and 38 internal phonons. The effect of the layer lattice has been proposed to explain the absence of some expected phonon structure. The present work together with an earlier study of the pressure and temperature dependence of the Raman-active phonons have enabled the 4A₁, A₂ and 5E internal molecular modes to be assigned. The resulting normal coordinates give good fits for the Raman-active bands of the heavy isotope P₄ ³²S₂ ³⁴S and for the mixed chalcogen species P₄S_{3 − x}Se_x.