Characterisation of anodic oxide films on zirconium formed in sulphuric acid: XPS and corrosion resistance investigations

Present work describes investigations of a two-step process consisting of galvanostatic anodising in a 1 M H₂SO₄ solution at 100 mA cm⁻² up to the limiting voltages of 20, 60, 80, 100 and 120 V, directly after which potentiostatic regime was employed and the current was allowed to drop. The total treatment time (5 min) was held constant for all samples. The treatment was carried out to improve the corrosion resistance of zirconium in physiological conditions, which was determined by electrochemical evaluation in Ringer’s solution. XPS studies revealed that after anodising sulphur was incorporated into the oxide film in the form of sulphated zirconia. The maximum content of sulphate in the oxide layer was observed after anodising at 80 V. Anodising at higher voltages resulted in formation of coatings with decreasing amount of sulphur. It was found that there is a strong correlation between the sulphur content in the oxide layers and the measured corrosion current density. On the other hand, the pitting corrosion resistance seemed to be unaffected by the presence of S and it was improving with the increasing limiting voltage of the treatment.

     

Nonradiative relaxation of photoexcited O<Stack><Subscript>1</Subscript><Superscript>0</Superscript></Stack> centers in glassy SiO<Subscript>2</Subscript>

The processes involved in the excited-state relaxation of hole O ₁ ⁰ centers at nonbridging oxygen atoms in glassy SiO₂ were studied using luminescence, optical absorption, and photoelectron emission spectroscopy. An additional nonradiative relaxation channel, in addition to the intracenter quenching of the 1.9-eV luminescence band, was established to become operative at temperatures above 370 K. This effect manifests itself in experiments as a negative deviation of the temperature-dependent luminescence intensity from the well-known Mott law and is identified as thermally activated external quenching with an energy barrier of 0.46 eV. Nonradiative transitions initiate, within the external quenching temperature interval, the migration of excitation energy, followed by the creation of free electrons. In the final stages, this relaxation process becomes manifest in the form of spectral sensitization of electron photoemission, which is excited in the hole O ₁ ⁰ -center absorption band.     

Electronic excitations and defects in nanostructural Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A time-resolved cathodo-and photoluminescence study of nanostructural modifications of Al₂O₃ (powders and ceramics) excited by heavy-current electron beams, as well as by pulsed synchrotron radiation, is reported. It was found that Al₂O₃ nanopowders probed before and after Fe⁺ ion irradiation have the same phase composition (the γ-phase/δ-phase ratio is equal to 1), an average grain size equal to ～17 nm, and practically the same set of broad cathodoluminescence (CL) bands peaking at 2.4, 3.2, and 3.8 eV. It was established that Al₂O₃ nanopowders exhibit fast photoluminescence (PL) (a band at 3.2 eV), whose decay kinetics is described by two exponential stages (τ₁ = 0.5 ns, τ₂ = 5.5 ns). Three bands, at 5.24, 6.13, and 7.44 eV, were isolated in the excitation spectrum of the fast PL. Two alternate models of PL centers were considered, according to which the 3.2-eV luminescence either originates from radiative relaxation of the P^? centers (anion-cation vacancy pairs) or is due to the formation of surface analogs of the F⁺ center (F _S ⁺ -type centers). In addition to the fast luminescence, nano-Al₂O₃ was found to produce slow luminescence in the form of a broad band peaking at 3.5 eV. The excitation spectrum of the 3.5-eV luminescence obtained at T = 13 K exhibits two doublet bands with maxima at 7.8 and 8.3 eV. An analysis of the luminescent properties of nanostructural and single-crystal Al₂O₃ suggests that the slow luminescence of nanopowders at 3.5 eV is due to radiative annihilation of excitons localized near structural defects.     

Ion-Assisted α-Al2O3 Coating Deposition by Anodic Arc Evaporation at 500–550°С

Russian Physics Journal - The paper studies the α-phase formation and structure of Al2O3 coatings deposited by the anodic arc evaporation in the low temperature range of...     

Cu-Site Disorder in CuAl2O4 as Studied by XPS Spectroscopy

JETP Letters - The results of full study of X-ray photoelectron spectra (XPS) of spin-liquid candidate CuAl2O4 including the measurements of high-energy resolved core level (Cu $$2p$$ , Al $$3p$$ ,...     

Magnetic resonance of metallic nanoparticles in vitreous silicon dioxide implanted with iron ions

Silica glasses exposed to steady-state and pulsed irradiation with Fe⁺ ions are studied using magnetic resonance. The irradiation doses used in experiments are equal to 1 × 10¹⁵, 1 × 10¹⁶, and 1 × 10¹⁷ cm^?2. It is found that, under both steady-state and pulsed irradiation conditions, glass samples exposed at a dose of 1 × 10¹⁷ cm^?2 exhibit a broadband orientation-dependent signal. The shape of inclusions is evaluated under the assumption that the observed spectrum is caused by the ferromagnetic resonance induced in a new phase of metallic iron.     

Determining the phase composition of yttrium oxide nanopowders by means of luminescence

The possibility of developing a luminescence technique for phase composition analysis is demonstrated via the example of bi-phase yttria nanopowders doped with neodymium ions. The deviation from X-ray diffraction reference values is ±2%. It is found that the results depend on the inhomogeneity of the crystalline phase distribution within a sample’s bulk, rather than on the luminescence scattering by powder nanoparticles. A luminescence coefficient that determines the phase inhomogeneity in nanopowders is introduced.     

Localized electronic excitations in crystalline phenacite Be2SiO4

The results of coordinated spectroscopic studies of the nature and properties of electronic excitations localized at regular and defect sites of the Be₂SiO₄ lattice are presented. The methods employed are electron-beam-excited pulsed absorption spectroscopy, pulsed cathodoluminescence, and low-temperature VUV spectroscopy with selective excitation by synchrotron radiation. The bands in luminescence spectra of Be₂SiO₄ at 2.70 and 3.15 eV are assigned to [AlO₄]^5? and [SiO₄]^4? centers formed both in direct relaxation of electronic excitations at defect levels and through the formation of exciton-defect complexes. Disruptions of beryllium-oxygen bonds (short-lived defects in the form of beryllium vacancies V _Be ^? ) are considered as initiating the formation of optically active centers with characteristic absorption bands in the range 1.5–4.0 eV. The intrinsic luminescence of the Be₂SiO₄ crystal at 3.6 and 4.1 eV is attributed to radiative decay of self-trapped excitons of two types. A mechanism of exciton self-trapping at the [SiO₄] and [BeO₄] tetrahedral groups is proposed, which involves excitation transfer from a threefold-coordinated oxygen atom to neighboring silicon or beryllium atoms.