Improvement of the corrosion and oxidation resistance of Ni-based alloys by optimizing the chromium content

Abstract : This fundamental study is focused on the understanding of the influence of the chemical composition of Ni-based alloys on their corrosion and oxidation mechanisms. This work is not dedicated for a particular application. It is well known for instance that Ni-based alloys are susceptible to intergranular stress corrosion cracking (IGSCC) in primary water. Thus, Alloy600 (Ni-16Cr-9Fe), used in steam generator (SG) tubing, was replaced by higher chromium content material Alloy690 (Ni-30Cr-9Fe). This later shows a better resistance to IGSCC which may be linked to the growth of more protective oxide layer as chromium content is increased to 30 wt.%. The main goal of this study is to investigate: i) the influence of chromium content, ii) impact of iron addition on the corrosion and oxidation resistance of Ni-based alloys in primary water and superheated steam at 700°C. Furthermore, analytical approach in acidic solution is conducted at room temperature. This allowed to establish a relationship between alloying elements and physical properties of the oxide layers. For this purpose, Ni-xCr (14 ≤ x≤ 30 wt.%), Ni-xCr-8Fe (x=14,22 and 30 wt.%) model alloys and industrial material Alloy600 have been studied. To characterize the oxide scales, conventional technics were used: SEM, STEM, EDX, Potentiodynamic, EIS, Chronoamperometry, Mott-Schottky. Furthermore, steam oxidation kinetics was evaluated by means of weight gain measurements. To uncouple the effect of surface cold-work and the chemical composition of the base metal, mirror and electro polishing were carried out. In primary water, critical chromium content (20 wt.%), which corresponds to the minimum amount of chromium required to the transition from non-protective to protective and compact Cr-oxide layer, is determined. However, the analytical approach, using electrochemical technics, at room temperature elucidated the existence of optimum chromium content (26 wt.%) in terms of corrosion resistance. In superheat steam, oxidation kinetics and oxide scale characteristics showed the existence of optimum chromium content (24 wt.%) in terms of oxidation resistance. The corrosion and oxidation resistance is degraded as chromium content was increased more than optimal amount. Iron addition (8 wt.%) had a detrimental effect on the protectivess of the resulting oxide scales. Finally, this study showed that optimizing of chromium content is more appropriate method for enhancing corrosion and oxidation resistance, that increasing chromium content to high level is not necessary beneficial to those parameters. This work provides a useful knowledge to design new alternative materials. For this purpose, more investigations should be conducted to test other parameters such as: weldability, fabricability, thermal conductivity,etc.
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Fethi Hamdani. Improvement of the corrosion and oxidation resistance of Ni-based alloys by optimizing the chromium content. Materials. INSA de Lyon; Tohoku gakuin university (Sendai, Japon), 2015. English. ⟨NNT : 2015ISAL0012⟩. ⟨tel-01247500⟩

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