Thermal annealing study of swift heavy-ion irradiated zirconia

Sintered samples of monoclinic zirconia (alpha-ZrO2) have been irradiated at room temperature with 6.0-GeV Pb ions in the electronic slowing down regime. X-ray diffraction (XRD) and micro-Raman spectroscopy measurements showed unambiguously that a transition to the 'metastable' tetragonal phase (beta-ZrO2) occurred at a fluence of 6.5x10^12 cm-2 for a large electronic stopping power value (approx 32.5 MeV $\mu$m-1). At a lower fluence of 1.0x10^12 cm-2, no such phase transformation was detected. The back-transformation from beta- to alpha-ZrO2 induced by isothermal or isochronal thermal annealing was followed by XRD analysis. The back-transformation started at an onset temperature around 500 K and was completed by 973 K. Plots of the residual tetragonal phase fraction deduced from XRD measurements versus annealing temperature or time are analyzed with first- or second-order kinetic models. An activation energy close to 1 eV for the back-transformation process is derived either from isothermal annealing curves, using the so-called "cross-cut" method, or from the isochronal annealing curve, using a second-order kinetic law. Correlation with the thermal recovery of ion-induced paramagnetic centers monitored by EPR spectroscopy is discussed. Effects of crystallite size evolution and oxygen migration upon annealing are also addressed

Thermal recovery of colour centres induced in cubic yttria-stabilized zirconia by charged particle irradiations

We have used electron paramagnetic resonance to study the thermal annealing of colour centres induced in cubic yttria-stabilized zirconia by swift electron and heavy ion-irradiations. Single crystals were irradiated with 1 or 2-MeV electrons, and 200-MeV 127I, or 200-MeV 197Au ions. Electron and ion beams produce the same colour centres: namely i) an F+-like centre, ii) the so-called T-centre (Zr3+ in a trigonal oxygen local environment), and iii) a hole center. Isochronal annealing was performed up to 973 K. Isothermal annealing was performed at various temperatures on samples irradiated with 2-MeV electrons. The stability of paramagnetic centres increases with fluence and with a TCR treatment at 1373 K under vacuum prior to the irradiations. Two distinct recovery processes are observed depending on fluence and/or thermal treatment. The single-stage type I process occurs for F+-like centres at low fluences in as-received samples, and is probably linked to electron-hole recombination. T-centres are also annealed according to a single-stage process regardless of fluence. The annealing curves allow one to obtain activation energies for recovery. The two-stage type II process is observed only for the F+-like centres in as-received samples, at higher fluences, or in reduced samples. These centres are first annealed in a first stage below 550 K, like in type I, then transform into new paramagnetic centres in a second stage above 550 K. A simple kinetics model is proposed for this process. Complete colour centre bleaching is achieved at about 1000 K

Sodium Selenide Toxicity Is Mediated by O2-Dependent DNA Breaks

Hydrogen selenide is a recurrent metabolite of selenium compounds. However, few experiments studied the direct link between this toxic agent and cell death. To address this question, we first screened a systematic collection of Saccharomyces cerevisiae haploid knockout strains for sensitivity to sodium selenide, a donor for hydrogen selenide (H2Se/HSe−/Se2−). Among the genes whose deletion caused hypresensitivity, homologous recombination and DNA damage checkpoint genes were over-represented, suggesting that DNA double-strand breaks are a dominant cause of hydrogen selenide toxicity. Consistent with this hypothesis, treatment of S. cerevisiae cells with sodium selenide triggered G2/M checkpoint activation and induced in vivo chromosome fragmentation. In vitro, sodium selenide directly induced DNA phosphodiester-bond breaks via an O2-dependent reaction. The reaction was inhibited by mannitol, a hydroxyl radical quencher, but not by superoxide dismutase or catalase, strongly suggesting the involvement of hydroxyl radicals and ruling out participations of superoxide anions or hydrogen peroxide. The •OH signature could indeed be detected by electron spin resonance upon exposure of a solution of sodium selenide to O2. Finally we showed that, in vivo, toxicity strictly depended on the presence of O2. Therefore, by combining genome-wide and biochemical approaches, we demonstrated that, in yeast cells, hydrogen selenide induces toxic DNA breaks through an O2-dependent radical-based mechanism

New stabilized VK-type center in electron-irradiated sodium fluoride observed by electron paramagnetic resonance

Sodium fluoride crystals were bombarded with MeV electrons near room-temperature or at 21 K and their EPR spectra measured. While after RT-irradiation one observes the spectrum of the classical cubic F-center, the low-T irradiation introduces a new low-symmetry defect which transforms reversibly into the F-center above 200K. We suggest for the new center a triplet VK-type defect stabilized during irradiation by the nearby created F-center. While the ordinary VK-center as observed after low-T X-ray and c-irradiation vanishes at 200 K the present electron-induced defect is stable and reappears upon cooling; it is still discernible after anneals up to 200 C

Colour centre production in yttria-stabilized zirconia by X-ray and electron irradiations: effect of yttria content

International audienceYttria-stabilized zirconia (YSZ) single crystals (for 9.5 and 18 mol% yttria)were irradiated at room temperature (RT) by X-rays (W white spectrum) and2.5-MeV electrons. The growth curves of the so-called T-centre (for trigonalcentre, i.e. Zr3+ sitting in a trigonal symmetry site) were studied as a functionof absorbed dose, or irradiation time, by UV–visible optical absorption (OA)spectroscopy and X-band electron paramagnetic resonance spectroscopy. Thedefect concentration at saturation and the production rate are increased by afactor around two for 18 mol% yttria with respect to 9.5 mol%. Defect decaywas then followed after irradiation by OA spectroscopy as a function ofageing time at RT. Growth and decay curves of the T-centre are modelled onthe basis of rate equations of charge-exchange reactions with the zirconiumlattice ions. Increase in yttrium content is thought to decrease hole trappingon Zr3+ ions, thereby enhancing T-centre formation

Swift heavy ion-beam induced amorphization and recrystallization of yttrium iron garnet

International audiencePure and (Ca and Si)-substituted yttrium iron garnet (Y3Fe5O12 or YIG) epitaxial layers and amorphous films on gadolinium gallium garnet (Gd3Ga5O12, or GGG) single crystal substrates were irradiated by 50 MeV (32)Si and 50 MeV (or 60 MeV) (63)Cu ions for electronic stopping powers larger than the threshold value (~4 MeV μm(-1)) for amorphous track formation in YIG crystals. Conductivity data of crystalline samples in a broad ion fluence range (10(11)-10(16) cm(-2)) are modeled with a set of rate equations corresponding to the amorphization and recrystallization induced in ion tracks by electronic excitations. The data for amorphous layers confirm that a recrystallization process takes place above ~10(14) cm(-2). Cross sections for both processes deduced from this analysis are discussed in comparison to previous determinations with reference to the inelastic thermal-spike model of track formation. Micro-Raman spectroscopy was also used to follow the related structural modifications. Raman spectra show the progressive vanishing and randomization of crystal phonon modes in relation to the ion-induced damage. For crystalline samples irradiated at high fluences (⩾10(14) cm(-2)), only two prominent broad bands remain like for amorphous films, thereby reflecting the phonon density of states of the disordered solid, regardless of samples and irradiation conditions. The main band peaked at ~660 cm(-1) is assigned to vibration modes of randomized bonds in tetrahedral (FeO4) units

X-RAY DIFFRACTION STUDY OF THE DAMAGE INDUCED IN YTTRIA-STABILIZED ZIRCONIA BY SWIFT HEAVY ION IRRADIATIONS

International audienceThe lattice damage was investigated by x-ray diffraction techniques in yttria-stabilized zirconia single crystals with the (100) or (110) orientation upon irradiation with swift heavy ions (from 100-MeV C to 2.6-GeV U) in a broad electronic stopping power range (from about 0.3 to 48 keV nm−1). The -2 scans show that no amorphization or change to a new crystalline phase occurs regardless of the ion and crystal features. However, the rocking curves ( scans) and reciprocal space mappings show evidence of the mosaicity of the crystals, which is produced above a threshold electronic stopping power between 18 and 27 keV nm−1. This threshold is in agreement with our previous Rutherford backscattering spectroscopy/channeling spectroscopy data. Two kinds of damage phenomena are found: (i) nuclear-collision induced clusters of point defects which generate Bragg peak shifts and broadening in the 2- and -2 scans, and (ii) electronic-excitation induced lattice damage yielding broad peaks in the scans above the stopping power threshold at high fluence

Anomalous electron spin resonance behavior of single-walled carbon nanotubes

International audienceWe have studied the electron spin resonance (ESR) of single-walled carbon nanotubes (SWNTs) both in their pristine state and after irradiation with fast electrons in order to detect the signal of conduction electrons. No metallic Pauli contribution was observed in the global spin susceptibility, the ESR signal of the conduction electrons is undetectable because it is broadened by magnetic impurities. We measured a paramagnetic contribution from localized states, with an effective Curie constant decreasing when the temperature increases, following a deactivation law of the type A-B exp(-E-a/k(B)T). This behavior is supposed to be characteristic of semiconducting SWNTs interacting with metallic impurities from the catalys

Generation of colour centres in yttria-stabilized zirconia by heavy ion irradiations in the GeV range

International audienceWe have studied the colour centre production in yttria-stabilized zirconia by heavy ion irradiation in the GeV range using on-line UV-visible optical absorption spectroscopy. Experiments were performed with 11.4 MeV amu−1 Xe, Au, Pb and U ion irradiations at 8 K or room temperature. A broad and asymmetrical absorption band peaked at a wavelength about 500 nm is recorded regardless of the irradiation parameters, in agreement with previous RT irradiations with heavy ions in the 100 MeV range. This band is de-convoluted into two broad Gaussian-shaped bands centred at photon energies about 2.4 and 3.1 eV that are respectively associated with the F+-type centres and T centres observed by EPR spectroscopy. In the case of 8 K Au ion irradiation at low fluences, six bands are used. The three bands near 2.0-2.5 eV can be assigned to oxygen divacancies. No significant effect of the irradiation temperature is found on the widths of all absorption bands for the same ion and fluence. This is attributed to the inhomogeneous broadening arising from the static disorder due to the native charge-compensating oxygen vacancies. However, the colour centre production yield is strongly enhanced at 8 K with respect to RT. When heating irradiated samples from 8 K to RT, the extra colour centres produced at low temperature do not recover completely to the level of RT irradiation