Thermally induced Fe atom transition from substitutional to interstitial sites in InP and its influence on material property

As-grown Fe-doped semi-insulating InP single crystal has been converted into n-type low-resistance material after high temperature annealing. Defects in the InP materials have been studied by conventional Hall effect measurement, thermally stimulated current spectroscopy, deep level transient spectroscopy and X-ray diffraction respectively. The results indicate that Fe atoms in the InP material change from the substitutional to the interstitial sites under thermal activation. Consequently, the InP material loses its deep compensation centers which results in the change in types of conduction. The mechanism and cause of the phenomena have been analyzed through comparison of the sites of Fe atom occupation and activation in doping, diffusion and ion implantation processes of InP.

Distribution of 45S and 5S rDNA sites in 23 species of Eleocharis (Cyperaceae)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Interstitial Ti for intermediate band formation in Ti-supersaturated silicon

We have analyzed by means of Rutherford backscattering spectrometry (RBS) the Ti lattice location and the degree of crystalline lattice recovery in heavily Ti implanted silicon layers subsequently pulsed laser melted (PLM). Theoretical studies have predicted that Ti should occupy interstitial sites in silicon for a metallic-intermediate band (IB) formation. The analysis of Ti lattice location after PLM processes is a crucial point to evaluate the IB formation that can be clarifyied by means of RBS measurements. After PLM, time-of-flight secondary ion mass spectrometry measurements show that the Ti concentration in the layers is well above the theoretical limit for IB formation. RBS measurements have shown a significant improvement of the lattice quality at the highest PLM energy density studied. The RBS channeling spectra reveals clearly that after PLM processes Ti impurities are mostly occupying interstitial lattice sites.

Nanostructured metal hydrides for hydrogen storage studied by in situ synchrotron and neutron diffraction

This work was focused on studies of the metal hydride materials having a potential in building hydrogen storage systems with high gravimetric and volumetric efficiencies of H storage and formed / decomposed with high rates of hydrogen exchange. In situ diffraction studies of the metal-hydrogen systems were explored as a valuable tool in probing both the mechanism of the phase-structural transformations and their kinetics. Two complementary techniques, namely Neutron Powder Diffraction (NPD) and Synchrotron X-ray diffraction (SR XRD) were utilised. High pressure in situ NPD studies were performed at D2 pressures reaching 1000 bar at the D1B diffractometer accommodated at Institute Laue Langevin, Grenoble. The data of the time resolved in situ SR XRD were collected at the Swiss Norwegian Beam Lines, ESRF, Grenoble in the pressure range up to 50 bar H2 at temperatures 20-400°C. The systems studied by NPD at high pressures included deuterated Al-modified Laves-type C15 ZrFe2-xAlx intermetallics with x = 0.02; 0.04 and 0.20 and the CeNi5-D2 system. D content, hysteresis of H uptake and release, unit cell expansion and stability of the hydrides systematically change with Al content. Deuteration exhibited a very fast kinetics; it resulted in increase of the unit cells volumes reaching 23.5 % for ZrFe1.98Al0.02D2.9(1) and associated with exclusive occupancy of the Zr2(Fe,Al)2 tetrahedra. For CeNi5 deuteration yielded a hexahydride CeNi5D6.2 (20°C, 776 bar D2) and was accompanied by a nearly isotropic volume expansion reaching 30.1% (∆a/a=10.0%; ∆c/c=7.5%). Deuterium atoms fill three different interstitial sites including Ce2Ni2, Ce2Ni3 and Ni4. Significant hysteresis was observed on the first absorption-desorption cycle. This hysteresis decreased on the absorption-desorption cycling. A different approach to the development of H storage systems is based on the hydrides of light elements, first of all the Mg-based ones. These systems were studied by SR XRD. Reactive ball milling in hydrogen (HRBM) allowed synthesis of the nanostructured Mg-based hydrides. The experimental parameters (PH2, T, energy of milling, ball / sample ratio and balls size), significantly influence rate of hydrogenation. The studies confirmed (a) a completeness of hydrogenation of Mg into MgH2; (b) indicated a partial transformation of the originally formed -MgH2 into a metastable -MgH2 (a ratio / was 3/1); (c) yielded the crystallite size for the main hydrogenation product, -MgH2, as close to 10 nm. Influence of the additives to Mg on the structure and hydrogen absorption/desorption properties and cycle behaviour of the composites was established and will be discussed in the paper.

Disorder-driven electronic localization and phase separation in superconducting Fe1+yTe0.5Se0.5 single crystals

We have investigated the influence of Fe excess on the electrical transport and magnetism of Fe1+yTe0.5Se0.5 (y=0.04 and 0.09) single crystals. Both compositions exhibit resistively determined superconducting transitions (T-c) with an onset temperature of about 15 K. From the width of the superconducting transition and the magnitude of the lower critical field H-c1, it is inferred that excess of Fe suppresses superconductivity. The linear and nonlinear responses of the ac susceptibility show that the superconducting state for these compositions is inhomogeneous. A possible origin of this phase separation is a magnetic coupling between Fe excess occupying interstitial sites in the chalcogen planes and those in the Fe-square lattice. The temperature derivative of the resistivity d(rho)/d(T) in the temperature range T-c < T < T-a with T-a being the temperature of a magnetic anomaly, changes from positive to negative with increasing Fe. A log 1/T divergence of the resistivity above T-c in the sample with higher amount of Fe suggests a disorder-driven electronic localization.

Rietveld refinements of SnO(2) ceramic powders doped with ZnO, WO(3), CoO, Nb(2)O(5) and MoO(3)

Polycrystalline materials of SnO(2) doped with ZnO, WO(3), CoO, Nb(2)O(5), and MoO(3). were synthesized by solid state reaction. X-ray powder diffraction data were collected with Cu K(alpha) radiation from a Rigaku-Rint 2000 rotating anode source. The structural and profile parameters were refined by the Rietveld method using GSAS [2]. The obtained residual parameters are R(wp) = 11,93% and R(Bragg) = 4,19%. The refined profile parameters indicate no anisotropic crystallite microstrain. The refinement results and Fourier differences calculations indicate that the dopants do not occupy interstitial sites in the crystal structure of SnO(2).

Intrachromosomal distribution of telomeric repeats in Eumops glaucinus and eumops perotis (Molossidae, Chiroptera)

The location of chromosomal telomeric repeats (TTAGGG)(n) was investigated in two species of the Molossidae family, Eumops glaucinus and Eumops perotis. The diploid chromosome number (2n) is 40 in E. glaucinus and 48 in E. perotis and the fundamental numbers (FN) are 64 and 58, respectively. It has been suggested that the E. glaucinus karyotype has evolved from the E. perotis karyotype through Robertsonian fusion events. In the present study, the telomeric sequences were detected at the termini of chromosomes in both species. In addition, E. glaucinus also displayed telomeric repeats in centromeric and pericentromeric regions in almost all biarmed chromosomes. Conversely, in E. perotis pericentromeric signals were only observed in two biarmed chromosomes. In both E. glaucinus and E. perotis, such telomeric sequences were observed as part of the heterochromatin. The interstitial sites of telomeric sequences suggest that they are remnants of telomeres of ancestral chromosomes that participated in the fusion event.

Magnetic resonance study of the crystallization behavior of InF3-based glasses doped with Cu2+, Mn2+ and Gd3+

The crystallization of fluoroindate glasses doped with Gd3+, Mn2+ and Cu2+ heat treated at different temperatures, ranging from the glass transition temperature (Tg) to the crystallization temperature (Tc), are investigated by electron paramagnetic resonance (EPR) and 19F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu2+ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba2ZnF6, which correspond to Cu2+ in a tetragonal compressed F- octahedron and to Cu2+ on interstitial sites with a square-planar F- co-ordination. The EPR spectra of the Mn2+ doped glasses exhibit a sextet structure due to the Mn2+ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn2+ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn2+ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn2+ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd3+ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g ≈ 2.0, suggesting Gd3+ ions in environment close to cubic symmetry. The 19F NMR spin-lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above Tc. For the glass samples (doped or undoped) the 19F magnetization recoveries were found to be adjusted by an exponential function and the spin-lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above Tc, the 19F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu2+, Mn2+, Gd3+ EPR spectra and NMR relaxation, are always observed for the samples annealed above Tc. © 2006 Elsevier B.V. All rights reserved.

Diffusion phenomena of the oxygen and nitrogen in niobium by mechanical spectroscopy

The short-range diffusion phenomenon (Snoek Effect) was investigated by mechanical spectroscopy measurements between 300 K and 650 K, in a polycrystalline niobium sample, containing oxygen and nitrogen, using a torsion pendulum. Experimental spectra of anelastic relaxation were obtained under three conditions: as-received sample; annealed sample and subsequently annealed in an oxygen atmosphere for three hours at 1170 K in partial pressure of 5°10 -5mbar. The experimental spectra obtained were decomposed in elementary Debye peaks and the anelastic relaxation processes were identified. With anelastic relaxation parameters and the lattice parameters, the interstitial diffusion coefficients of the oxygen and nitrogen in niobium were calculated for each kind of preferential occupation (octahedral and tetrahedral). The results were compared with the literature data, and confirmed that the best adjustment is for the preferential occupation octahedral model for low concentrations of interstitial solutes, but at higher concentration of oxygen were observed deviations of experimental data for the interstitial diffusion coefficients of oxygen in niobium when compared with the literature data, this could be related to the possible occurrence of a double occupation of interstitial sites in the niobium lattice by oxygen interstitials. © (2010) Trans Tech Publications.

Expansão térmica de nanotubos de carbono de duas camadas

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Determination of the magnetostrictive atomic enviroments in FeCoB alloys

The atomic environments of Fe and Co involved in the magnetostriction effect in FeCoB alloys have been identified by differential extended x-ray fine structure (DiffEXAFS) spectroscopy. The study, done in amorphous and polycrystalline FeCoB films, demonstrates that the alloys are heterogeneous and that boron plays a crucial role in the origin of their magnetostrictive properties. The analysis of DiffEXAFS in the polycrystalline and amorphous alloys indicates that boron activates magnetostriction when entering as an impurity into octahedral interstitial sites of the Fe bcc lattice, causing its tetragonal distortion. Magnetostriction would be explained then by the relative change in volume when the tetragonal axis of the site is reoriented under an externally applied magnetic field. The experiment demonstrates the extreme sensitivity of DiffEXAFS to characterize magnetostrictive environments that are undetectable in their related EXAFS spectra.

Boron solubility in Fe-Cr-B cast irons

Boron solubility in the as-cast and solution treated martensite of Fe-Cr-B cast irons, containing approximately 1.35 wt.% of boron, 12 wt.% of chromium, as well as other alloying elements, has been investigated using conventional microanalysis. The significant microstructural variations after tempering at 750 degreesC for 0.5-4 h, compared with the original as-cast and solution treated microstructures, indicated that the matrix consisted of boron and carbon supersaturated solid solutions. The boron solubility detected by electron microprobe was between 0.185-0.515 wt.% for the as-cast martensite and 0.015-0.0589 wt.% for the solution treated martensite, much higher than the accepted value of 0.005 wt.% in pure iron. These remarkable increases are thought to be associated with some metallic alloying element addition, such as chromium, vanadium and molybdenum, which have atomic diameters larger than iron, and expand the iron lattice to sufficiently allow boron atoms to occupy the interstitial sites in iron lattice. (C) 2002 Elsevier Science B.V. All rights reserved.

Valence-tautomeric RbMnFe Prussian blue analogues:composition and time stability investigation

Three different stoichiometric forms of RbMn[Fe(CN) ]y·zHO [x = 0.96, y = 0.98, z = 0.75 (1); x = 0.94, y = 0.88, z = 2.17 (2); x = 0.61, y = 0.86, z = 2.71 (3)] Prussian blue analogues were synthesized and investigated by magnetic, calorimetric, Raman spectroscopic, X-ray diffraction, and Fe Mössbauer spectroscopic methods. Compounds 1 and 2 show a hysteresis loop between the high-temperature (HT) Fe(S = 1/2)-CN-Mn(S = 5/2) and the low-temperature (LT) Fe(S = 0)-CN-Mn(S = 2) forms of 61 and 135 K width centered at 273 and 215 K, respectively, whereas the third compound remains in the HT phase down to 5 K. The splitting of the quadrupolar doublets in the Fe Mössbauer spectra reveal the electron-transfer-active centers. Refinement of the X-ray powder diffraction profiles shows that electron-transfer-active materials have the majority of the Rb ions on only one of the two possible interstitial sites, whereas nonelectron-transfer-active materials have the Rb ions equally distributed. Moreover, the stability of the compounds with time and following heat treatment is also discussed. © Wiley-VCH Verlag GmbH & Co. KGaA, 2009.

Extensive spreading of interstitial telomeric sites on the chromosomes of Characidium (Teleostei, Characiformes)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Chemical and isotope compositions of interstitial water in sediments from Mediterranean basin at DSDP Sites 42-372 and 42-374

The Br/Cl, Li/Cl and B/Cl ratios and boron isotope compositions of hypersaline pore fluids from DSDP Sites 372 and 374 were measured in an attempt to evaluate the origin of the brines. In Site 374 the relationships between the Cl concentrations (up to 5000 mM) and Br/Cl (~0.012), Na/Cl (as low as 0.1), B/Cl (0.0025), and d11B values (43-55?) of the deep pore water between 380 and 405 mbsf, located within the Messinian sediments, reflect remnants of ~65-fold evaporated sea water. The original evaporated sea water was modified by: (1) dilution with overlying or less saline water by about 30%; and (2) slight dissolution of NaCl evaporites. The variations in d11B show a continuous increase in d11B values with depth in Site 374, up to 66.7? at a depth of 300 mbsf (Upper Pliocene marl sediments). The conspicuous 11B enrichment trend is consistent with elemental boron depletion, which was calculated from the expected boron concentrations of evaporated sea water with corresponding Br/Cl and Na/Cl ratios. Li/Cl variations also show a depletion of Li relative to evaporated sea water. The apparent depletions of B and Li, as well as the 11B enrichment, reflect uptake of these elements by clay minerals at low water/sediment ratios.