Nanostructures in calcia stabilized hafnia thin films observed by PAC as a function of temperature

The hyperfine quadrupole interaction at Hf sites in films and powders of 14 mol% CaO–HfO₂ and 20 mol% CaO–HfO₂ has been determined as a function of temperature. Results indicate the formation of a cubic solid solution and other microstructures assigned to the ?₁ (CaHf₄O₉) and ?₂ (Ca₆Hf₁₉O₄₄) phases. Dynamical effects on the electric field gradient reveal the existence of oxygen vacancies movements in the solid solution. The thermal behavior of the relaxation constant observed in films allowed the determination of activation energies of 0.54 eV and 0.70 eV for the 14 mol% and 20 mol% CaO doped hafnias, respectively. The influence of the microdomains and the stability of the cubic solid solution are discussed.     

Advances in constant-velocity Mössbauer instrumentation

A prototype of a programmable constant-velocity scaler is presented. This instrument allows the acquisition of partial Mössbauer spectra in selected energy regions using standard drivers and transducers. It can be fully operated by a remote application, thus data acquisition can be automated. The instrument consists of a programmable counter and a constant-velocity reference. The reference waveform generator is amplitude modulated with 13-bit resolution, and is programmable in a wide range of frequencies and waveforms in order to optimize the performance of the transducer. The counter is compatible with most standard SCA, and is configured as a rate-meter that provides counts per selectable time slice at the programmed velocity. As a demonstration of the instrument applications, a partial Mössbauer spectrum of a natural iron foil was taken. Only positive energies were studied in 512 channels, accumulating 20 s per channel. A line width of 0.20 mm/s was achieved, performing with an efficiency of 80%.     

Temperature dependence of the electric field gradient at Ta nuclei in hafnium pyrovanadate

The electric field gradient EFG in hafnium pyrovanadate has been measured at Hf sites at different temperatures with the time-differential perturbed angular correlation method. The results obtained show the existence of a phase transition around 110°C.     

Hyperfine interactions in intermetallic rare earth-gallium compounds studied by 111 Cd PAC

Magnetic and electric hyperfine interaction of the nuclear probe ¹¹¹In/¹¹¹Cd in intermetallic compounds of the rare earth-gallium system have been investigated by perturbed angular correlation (PAC) spectroscopy. The PAC measurements, supported by X-ray diffraction, provide evidence for a marked phase preference of ¹¹¹In for hexagonal RGa₂ over orthorhombic RGa and of RGa₃ with the L12 structure over RGa₂. In the case of SmGa₂, the magnetic hyperfine field B_hf, the electric quadrupole interaction and the angle β between B_hf and the symmetry axis of the electric field gradient have been determined as a function of temperature. The angle β?=?0 is consistent with the results of previous magnetization studies. Up to T?≤?17 K the magnetic hyperfine field has a constant value of B_hf?=?3.0(2) T. The rapid decrease at higher T gives the impression of a first-order transition with an order temperature of T_N?=?19.5 K. In the RKKY model of indirect 4f interaction the ratio T_C/B_hf(0) is a measure of the coupling constant. For ¹¹¹Cd:SmGa₂ (T_C/B_hf(0)~6.5 K/T) this ratio is significantly smaller than for the same probe in other R intermetallics (SmAl₂ ~9.5 K/T, Sm₂In ~13.5 K/T).     

Characterization of Two New Copper(II) Complexes with Saccharinate and Benzimidazole as Ligands

The crystal structure of the complexes [Cu(sac)₂(bzim)₂(H₂O)] ( 1 ) and [Cu(sac)₂(bzim)(H₂O)(EtOH)] · 2 EtOH ( 2 ) (sac = saccharinate anion; bzim = benzimidazole; EtOH = ethanol) was determined by single crystal X‐ray diffractometry. Complex 1 crystallizes in the monoclinic C2/c space group with Z = 8 whereas complex 2 belongs to the triclinic P1 space group with Z = 2. Room temperature magnetic susceptibilities as well as electronic and IR spectra of both complexes were discussed. Their thermal behaviour was investigated by means of TG and DTA methods.     

Glutathione complexed Fe-S centers

Glutathione (γ-glutamyl-cysteinyl-glycine, GSH) is a major thiol-containing peptide with cellular levels of up to 10 mM. (1) Several recent reports have demonstrated glutaredoxins (Grx) to form [Fe(2)S(2)] cluster-bridged dimers, where glutathione provides two exogenous thiol ligands, and have implicated such species in cellular iron sulfur cluster biosynthesis. We report the finding that glutathione alone can coordinate and stabilize an [Fe(2)S(2)] cluster under physiological conditions, with optical, redox, M?ssbauer, and NMR characteristics that are consistent with a [Fe(2)S(2)](GS)(4) composition. The Fe-S assembly protein ISU catalyzes formation of [Fe(2)S(2)](GS)(4) from iron and sulfide ions in the presence of glutathione, and the [Fe(2)S(2)] core undergoes reversible exchange between apo ISU and free glutathione.     

Thermal Behavior of Galena Ore in Chlorine Atmospheres

The thermal behavior of a purified galena in a chlorine surrounding was determined. The kinetic of the chlorination of galena and the stoichiometry of this reaction between 723 to 973 K (450 to 700°C) were measured by thermogravimetry. The microstructural characterization of the solid residues were determined by SEM, EDXS and XRD. The ΔH _vap of the produced lead chloride volatilization was obtained by the application of Clausius-Clapeyron equation considering the process in an equilibrium state. This revised version was published online in July 2006 with corrections to the Cover Date.