Zirconium oxide deposits (ZrO₂) and titanium oxide (TiO₂) on 304l stainless steel

This research project aims to carry out the surface and electrochemical characterization to obtain the optimum conditions of the hydrothermal deposits of zirconium oxide ZrO₂ (baddeleyite) and titanium oxide TiO₂ (anatase and rutile phases) on 304l stainless steel, simulating an inhibiting protective layer. 304l steel specimens were cut, pre-oxidized in water at a temperature of 288 degrees Celsius and 8 MPa, similar to those of a typical BWR conditions. From the titanium oxide anatase crystalline phase, the rutile phase was obtained by a heat treatment at 1000 degrees Celsius. The Sigma-Aldrich pre-oxidized powders and steel 304l were characterized using techniques of X-ray diffraction, scanning electron microscopy, X-ray dispersive energy, chemical mapping and Raman spectrometry. The pre-oxidized steel has two oxide layers, an inner layer with nano metric crystals and another outer of larger crystals to 1μm, with the formation of hematite and magnetite, this predominating. The surface that contacted the sample holder has larger crystals. Hydrothermal deposits were carry out from suspensions of 10, 100 and 1000 ppm, of the crystal phases of anatase, rutile and baddeleyite, on the pre-oxidized steel at a temperature of 150 degrees Celsius for 2 and 7 days, samples were analyzed by X-ray diffraction, scanning electron microscopy, X-ray dispersive energy, Raman spectrometry and Tafel polarization. The suspension to 1000 ppm for 7 days coated surface most; the baddeleyite deposit is noticed more homogeneous than anatase and rutile. The deposit is favored when hematite and magnetite crystals are larger. The chemical mapping on deposits show that even after being immersed in water to 288 degrees Celsius during 30 days, the deposits are still present although a loss is observed. A reference electrode was assembled to conduct electrochemical tests of Tafel able to withstand a temperature of 288 degrees Celsius and pressure of 8 MPa. The baddeleyite deposit presented the electrochemical corrosion potential versus standard electrode of hydrogen (ECP_EEH) more negative, between -35 and -79 mV_EEH), is indicating that it has the greatest capacity to mitigate the stress corrosion, this at a temperature of 288 degrees Celsius. However at a lower temperature, between 250 and 150 degrees Celsius the rutile coating is having a negative ECP_EEH between -100 and -150 mV_EEH. The cathodic slopes of Tafel curves show that deposits are fulfilling their inhibitor functions. In some cases the anodic part of Tafel curve has a section where the potential remains constant while varying the current, suggesting the formation of oxides. (Author)