Synergistic Use of Electrochemical Impedance Spectroscopy and Photoelectrochemical Measurements for Studying Solid State Properties of Anodic HfO2

Within the past years, intense research has been carried out on HfO2 as high k material, promising candidate to replace SiO2 as gate dielectric in CMOS based devices (1), and as metal oxide for resistive random access memory (ReRAM) (2). For both technological applications compact, uniform and flat oxides are necessary, and a detailed understanding of their physical properties as a function of the fabrication conditions is strongly. Hafnia performance can be significantly influenced by carrier trapping taking place at pre-existing precursors states (induced by oxygen vacancies, interstitial ions, impurities acting as dopants), or by self-trapping in a perfect lattice, where the potential we…

Electronic properties and corrosion resistance of passive films on austenitic and duplex stainless steels

Abstract Passive films were grown at constant potential in acidic (pH∼2) and alkaline (pH∼13) solutions on chromium, AISI 304L, AISI 316L and Duplex stainless steels. Passive films on chromium grow following a high field mechanism considering the presence of dissolution phenomena. According to the photoelectrochemical characterization, passive films on Cr have a bandgap of 3.4 eV when formed in acidic solution, and of 2.4 eV when formed in alkaline solution due to the formation of Cr(OH)3. These films result to be poorly stable against anodic dissolution due to a very anodic flat band potential. Conversely, impedance and photoelectrochemical measurements proved that passive films on stainle…

Effect of E. coli biofilm formation and removal on passive films on AISI 316L during fermentation processes

Abstract 316L coupons were sanitized in hot water vapour inducing iron enrichment in passive films. Coupons were then immersed in a pilot fed-batch fermenter in presence of E. coli. Sanitization causes iron enrichment in passive films. Fermentation causes the growth of biofilm on the SS, constituted by bacteria embedded in an extracellular polymeric substance. During fermentation SS open circuit potential is very negative due to low oxygen concentration on its surface, while the chelating action of siderophores induces chromium enrichment in the passive film. Disinfection in NaClO for 30 min allows removal of biofilm and formation of a protective passive film.

Role of Molybdenum on the Electronic Properties of Passive Films on Stainless Steels

Potentiostatic polarization of different stainless steel grades with a mirror surface finishing was performed in order to investigate the role of Mo on stainless steels corrosion behaviour. In the attempt to gain more insight into transpassive dissolution mechanism, passive films were grown in neutral aqueous solution (pH ∼ 7) at different polarizing potentials ranging from passive to transpassive conditions. According to the photoelectrochemical characterization, Cr dissolution occurs even at low polarizing potentials in the case of AISI 304L, while higher band gap values were obtained for passive films grown on austenitic 316L and duplex SSs. Capacitance measurements suggest that the flat…

Semiconducting properties of passive films and corrosion layers on weathering steel

Abstract Anodic films were grown on Weathering Steel by potentiostatic polarization in slightly alkaline solution. The photoelectrochemical results reveal that they are n-type iron oxide with Eg = 2.0 eV. Rust layer grown by atmospheric corrosion are n-type semiconductors with a band gap higher than that estimated for the anodic film attributed to the formation of γ-lepidocrocite. The electrochemical impedance spectra allow to evidence that rust layers have a higher conductivity with respect to anodic films due to the presence of highly doped iron oxide layers. The use of Mott-Schottky theory to model the dependence of oxide capacitance as function of potential is critically discussed.

First data on hydrobiological characterization of western Libyan sea area (August 2006)

Physico-Chemical Characterization of Anodic Oxides on Hf as a Function of the Anodizing Conditions

Anodic films were grown to 5 V (Ag/AgCl) on mechanically polished Hf in 0.1 M ammonium biborate and 0.1 M NaOH. Independent of the anodizing conditions, the photoelectrochemical characterization allowed the observation of optical transitions at 3.25 eV, i.e. at photon energy lower than the bandgap of HfO2. They are attributed to localized states inside the gap of the oxide induced by the presence of oxygen vacancies. From the cathodic photocurrent spectra, it was possible to estimate an energy threshold of ∼2.15 eV for internal electron photoemission phenomena. The impedance measurements proved the formation of insulating oxides with ϵ =19. The anodizing occurs under a high field regime wit…

YTTRIUM AND REE SIGNATURE RECOGNIZED IN CENTRAL MEDITERRANEAN SEA (ODP SITE 963) DURING THE MIS 6 – MIS 5 TRANSITION

The Mediterranean Sea acts as a miniature ocean with the development of its own conveyor belt. It constitutes an ideal location to study and forecast how the marine environment responds to rapid climatic change. Here we present a palaeoenvironmental study carried out on the sediments of ODP Site 963, recovered in the Sicily Channel, the sill which divides the western from the eastern Mediterranean basin. We focused on the transition between the penultimate glacial (MIS 6) and the last interglacial (MIS 5), between approximately 130 and 115 kyr BP. A novel approach is proposed, taking into account centennial-scale geochemical data on major elements, selected trace elements, and yttrium and R…

Effect of NaClO disinfection/cleaning on passive films on AISI 316L

Abstract 316 L stainless steel samples were passivated in NaClO containing solutions in order to simulate disinfection processes. Passive films were grown at the open circuit potential by immersion in NaClO aqueous solutions at different concentrations and temperature in order to understand how exposure to aggressive environments could affect subsequent corrosion resistance of SSs. In the attempt to study the passive film growth mechanism, in-situ Open Circuit Potential measurements were performed in the same growth solutions. Photoelectrochemical and impedance investigation of passive films was carried out in order to link their solid state properties with their corrosion behaviour.

Primary productivity variability on the Atlantic Iberian Margin over the last 70,000 years: evidence from coccolithophores and fossil organic compounds

This study analyzes coccolithophore abundance fluctuations (e.g., Emiliania huxleyi, Gephyrocapsa specimens, and Florisphaera profunda) in core MD01-2444 sediment strata retrieved at the Iberian Margin, northeastern Atlantic Ocean. Coccolithophores are calcareous nannofossils, a major component of the oceanic phytoplankton, which provide information about past ecological and climatological variability. Results are supported by data on fossil organic compounds (sea surface temperatures, alkenones, and n-hexacosan-1-ol index) and geochemical analyses (benthic δ13Ccc and planktonic δ18Occ isotopes). Three scenarios are taken into account for this location at centennial-scale resolution over th…

Corrosion resistance of passive films on different stainless steel grades in food and beverage industry

Abstract Passive films were grown on 304 L, 316 L and Duplex stainless steels by immersion at open circuit potential in solutions mimicking food and beverage industry environments. In acidic food stainless steel surfaces are covered by Cr rich passive films, and generalized dissolution occurs on their surface with consequent ions release into the electrolyte. In fatty food the concentration of released ions is significantly lower since generalized corrosion does not occur, but the loss on MnS inclusions strongly reduces the polarization resistance in this environment especially for 304 L due to its higher localized corrosion susceptibility with respect to the other grades.