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Oxidation Behavior of Zr–1Nb Corroded in Air at 400 °C after Plasma Immersion Titanium Implantation
(2018)
In this paper, the influence of plasma immersion titanium implantation into the zirconium alloy Zr-1Nb on the oxidation behavior at 400 °C for 5, 24, 72, and 240 h in air under normal atmospheric pressure (101.3 kPa) was shown. The influence of implantation on the protective properties of the modified layer was shown. The valence of the oxides before and after implantation was analyzed by means of X-ray photoelectron spectroscopy (XPS). Grazing incidence X-ray diffraction (GIXRD) was carried out to examine the phase composition after titanium ion implantation and oxidation. Differential scanning calorimetry (DSC) revealed that titanium implantation exhibited effects of stabilizing the β phase. The formation of the t-ZrO2 and m-ZrO2 was observed during the oxidation of the as-received and modified Zr-1Nb. The measurement of weight gain showed an improvement in oxidation resistance of Ti implanted Zr-1Nb at the oxidation up to 24 h when compared with that of the as-received Zr-1Nb. However, at longer oxidation cycle the oxidation rate of Ti-implanted zirconium alloy is the same with the as-received alloy, which attributed to the layer thickness. Nevertheless, the corrosion of the Ti-implanted alloy is more uniform, while a local corrosion and cracks was detected on the surface of the as-received alloy.
Oxidation behavior of Zr–1Nb in air at 400°C after Titanium Plasma Immersion Ion Implantation
(2018)
Zirconium alloys have been widely used in nuclear reactors due to low thermal neutron capture cross-section, excellent corrosion resistance and acceptable mechanical properties [1, 2]. Nowadays several methods apply for improving hydrogen and corrosion resistance such as addition of stabilizing additives (yttrium) [3, 4], deposition of thin solid films [5, 6], micro-arc oxidation [7] and modification of the surface by electron beam [8, 9]. Despite the multiplicity of the methods hydrogen embrittlement is still a pressing issue. Previous results [10, 11] have shown the positive influence of plasma immersion titanium implantation on the hydrogenation behavior of Zr–1Nb and Zr–2.5 Nb. After Ti implantation hydrogen preferably accumulates in the modified surface layer comprising the implanted Ti. Furthermore, the hydrogen concentration is considerably less inside the zirconium modified sample than in the as-received samples.
The integration of elements into the zirconium lattice can influence the valence of the surface and change corrosion and oxidation rates of the alloys. So it is very important not to decrease the zirconium oxidation resistance due to Ti implantation. Therefore, the purpose of this research is to study of the influence of Ti implantation on surface morphology, oxidation rate and phase structure of the Zr–1Nb alloy after oxidation on air at 400 0C for 5, 24, 72 and 240 h. The surface structure of the samples and their elemental composition were investigated with the scanning electron microscope Mira II XMH (Tescan) with energy dispersive x-ray spectroscopy system (EDS). X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC) as well as X-ray diffraction (XRD) was used to characterise the influence of titanium implantation on the oxidation behaviour. The results show that the oxidation kinetics after Ti modification of the zirconium alloy changed. Although the weight gain of the implanted sample remains approximately the same, it can be considered that Ti implantation stabilizes the oxide layer and has beneficial influence on the oxidation protection of Zr-1Nb.