A. R. López García

Hyperfine interaction of ZrO2 — Tetragonal phase

The quadrupole hyperfine interaction of the tetragonal phase of the zirconium oxide has been measured at 1523 K using the time-differential perturbed angular correlation technique. The electric field gradient at zirconium sites was determined to beVzz=(17.5±0.4)·1017 Vcm−2 and axially symmetric.

Time‐differential perturbed angular correlations investigation of the (NH4)2ZrF6 thermal decomposition

Via the TDPAC technique and complementary x‐ray diffraction analysis, the thermal decomposition of (NH4)2ZrF6 has been observed to occur in the range 400–800 K according to the thermolysis scheme (NH4)2ZrF6→485 KNH4ZrF5→560 KNH4Zr2F9 →620 KZrF4→760 KZrO2. Assuming that the first transformation takes place through the simple chemical reaction (NH4)2ZrF6→NH4ZrF5+NH4F, the corresponding activation energy has been determined to be Ea=(82±6) kJ/mol. The hyperfine parameters of the NH4Zr2F9 decomposition product have been determined between 14 and 560 K. A complete analogy with the isomorphous compound NH4Hf2F9 was observed.

TDPAC investigation on thermally related HfF4.3H2O and HfO2

The hyperfine quadrupole interaction of HfF4.3H2O at Hf sites is investigated from 14 to 820 K. No transitions have been found. After the complete dehydration of this compound at 393 K, chemical reactions take place which give rise to hafnium oxifluorides and metastable forms of hafnium oxide. Heating treatments at increasing temperatures make HfO2 turn into its monoclinic phase.

On the kinetics of chemical reactions in hafnium tetrafluorides using time differential-perturbed angular correlations

Abstract Quadrupole hyperfine interactions in HfF 4 and HfF 4 ·3H 2 O determined by time differential-perturbed angular correlations technique are reported. Changes in the hyperfine interactions of HfF 4 ·3H 2 O with temperature are interpreted in terms of a dehydration process. The reversal process is studied at room temperature as a function of time. Assuming that the hydration obeys a first-order rate law, a rate constant k = 0.49 ± 0.10 d −1 is obtained.

High-resolution TDPAC measurement in K2ZrF6

A time resolution of 2τ=0.75 ns, achieved with a conventional TDPAC setup with FCs detectors, allowed a determination of the very high electric field gradient at Hf impurity sites in K2ZrF6.Simple theoretical calculations seem to indicate that nearest neighbours are responsible for the interaction observed.

Positron trapping in BaTiO3 perovskite

Positron lifetime spectra in BaTiO3 single crystals were measured at temperatures up to 873 K, also at room temperature after quenching from temperatures up to 473 K. The explored temperature range includes the ferroelectric to paraelectric phase transition. The material displays an irreversible behaviour when heated, with anomalies around TC. The temperature dependence of the positron lifetime becomes reversible only after annealing above 550 K. The results suggest modifications of the charge state of non-equilibrium vacancies occurring at moderate temperature and microstructural changes taking place at high temperature. The reversible behaviour of the annealed crystal is consistent with thermally activated positron trap formation.

TDPAC study on the thermal stability of zirconium tetrafluoride

The thermal evolution of the hyperfine interaction in α-ZrF4 is investigated between 293 K and 788 K. The first change, observed ay 534 K, is attributed to the appearance of the non-stoichiometric compound ZrO1.3F1.4. During the transformation, the relative fraction of the latter shows an Arrhenius behaviour with an activation energyEa=(22.6±5.5) kJ/mol. At approximately 700 K, ZrO1.3F1.4 gives rise to the monoclinic phase of ZrO2 and to β-ZrF4.

TDPAC investigation on NH4Hf2F9

Time-differential perturbed angular correlation (TDPAC) measurements in NH4Hf2F9 were performed between 15 and 580 K. The compound was found to be stable in the whole temperature range and no phase transitions were observed. Experimental results could be explained assuming two equally populated quadrupole interactions which suggest a neat inequivalence between the two sites occupied by the hafnium atoms in the molecule.

Temperature dependence of the nuclear quadrupole interaction at Zr-Ti sites in in the Zr-rich rhombohedral and cubic phases

In this paper, the hyperfine quadrupole interaction at the Zr-Ti site of (PZT) polycrystalline samples is studied for the first time. Powders for x = 0, 0.1, 0.2, 0.4, 0.6, 0.8, 0.9 and 1 were prepared and characterized by XRD. The lattice constants and space groups were obtained as functions of Ti concentration. PAC analyses were done for ferroelectric PZT for x = 0.9 and 0.8 as a function of temperature, and for x = 0.6 at RT. Also antiferroelectric was analysed. Low-concentration nuclei were used as probes. In the ferroelectric and paraelectric phases of PZT compounds two sites were occupied by probes. For each site the quadrupole frequency, asymmetry and relative distribution width parameters were obtained as functions of temperature above and below the Curie temperature. For only one site was detected with a static quadrupole interaction below and a nuclear spin-relaxation process above it. Furthermore, the temperature dependence of the hyperfine parameters, the possible origin of both quadrupole interactions in PZT and the perturbation that characterizes the cubic phases of and compounds are discussed.

The thermal behaviour of the quadrupole hyperfine interaction in (NH4)2HfF6

A TDPAC investigation has been accomplished on (NH4)2 HfF6 between 14 and 620 K. A phase transition was observed below 390 K. The low temperature phase is characterized by two non-equivalent sites for hafnium atoms in a 1∶1 ratio. The high temperature phase, on the other hand, is depicted by a unique quadrupole interaction. Above 400 K, the compound decomposes successively to NH4 HfF5, NH4 Hf2F9 and HfF4. An enthalpy of 76±4 kJ/mol could be determined for the (NH4)2 HfF6→NH4 HfF5+NH4F chemical reaction. The hyperfine interaction and thermal evolution of (NH4)2 HfF6 was found to be quite similar to that of (NH4)2 ZrF6.