title: Characteristics of colored passive layers on zirconium: morphology, optical properties, and corrosion resistance.
abstract: Brightly colored and uniform passive layers on Zr can be formed by applying alternating current (ac) voltage (V(ac)) for 10 s in 10 wt % aqueous Na(2)SO(4) solution at T = 298 K. The coloration originating from iridescence can be fine-tuned by adjusting V(ac) in the 10-80 V range. Visible light microscopy analysis shows that different grains reveal two or three different colors due to the polycrystalline nature of Zr, and the resultant coloration is the sum of these contributions. Reflectance spectroscopy spectra show maxima that can be related to the coloration displayed by various grains. Surface morphology and roughness in the micrometer and nanometer ranges are examined using stylus surface profilometry and atomic force microscopy. The formation of colored passive layers on polished Zr makes them smoother but their formation on etched Zr decreases the roughness in the case of low V(ac) and increases in the case of high V(ac). Focused ion beam and scanning electron microscopy are used to determine the thickness (d) of the colored passive layer on etched Zr. It is found that d is in the 51-264 nm range and increases linearly with V(ac). Scanning transmission electron microscopy and electron back scattered diffraction measurements demonstrate that the colored passive layers are uniform and crystalline in nature. Corrosion behavior of the colored passive layers in 1 wt % aqueous NaCl solution is examined using inductively coupled plasma-mass spectrometry. The results indicate that the polished samples hardly undergo any corrosion and the amount of dissolved Zr does not exceed 12 ppb even after exposure for 56 days. On the other hand, the corrosion of the etched samples is ~3 orders of magnitude greater than that of the polished ones, and the amount of dissolved Zr approaches 970 ppb after exposure for 56 days. Corrosion behavior of etched and colored passive layers on Zr in 1 wt % aqueous NaCl solution is also analyzed by recording potentiodynamic polarization curves in the -1.0 to 3.0 V vs RHE range at a scan rate of s = 1 mV s(-1) and at T = 298 K. They have similar shapes but the formation of colored passive layers decreases the current density (j) at any given potential (E), and the thicker the passive layer the greater the reduction in j. The development of colored passive layers on etched Zr increases the corrosion potential (E(corr)) and decreases the corrosion current density (j(corr)).
authors.affiliation: Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, ON, Canada K7L 3N6.
authors.forename: Rebecca J
authors.initials: RJ
authors.lastname: Holmberg
authors.forename: Sylvain
authors.initials: S
authors.lastname: Bolduc
authors.forename: Diane
authors.initials: D
authors.lastname: Beauchemin
authors.forename: Gregory
authors.initials: G
authors.lastname: Jerkiewicz
authors.forename: Hubert
authors.initials: H
authors.lastname: Schulz
authors.forename: Ulrich
authors.initials: U
authors.lastname: Kohlhaas
authors.forename: Henryk
authors.initials: H
authors.lastname: Strzelecki