Corrosion of passive metals Jacek Banaś University of Science and Technology (AGH-UST) Faculty of Foundry Engineering Department of General and Analytical.

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Presentation transcript:

Corrosion of passive metals Jacek Banaś University of Science and Technology (AGH-UST) Faculty of Foundry Engineering Department of General and Analytical Chemistry

Effect of chemical composition on passive behaviour of the alloy Stationary polarization curves of austenitic Fe-Cr-Ni alloys in 1M H 2 SO 4 Model of passive film on pure chromium Stationary polarization curves of Fe-Si alloys in 1M H 2 SO 4 Effect of chromium on the structure of passive film on Fe- Cr alloys in neutral aqueous solutions J.Kruger in Passivity of Metals, ed.by Electroche. Soc. Inc. Princetown,N. Jersey 1978

Effect of chemical composition on passive behaviour of the alloy

Corrosion of passive alloys Pitting corrosion Crevice corrosion Inergranular corrosion Stress corrosion Corrosion-erosion degradation

Pitting corrosion Mechanism of pitting corrosion in chloride containing media Pitting corrosion of iron in atmosphere polluted with SO 2

Autocatalytic process occurring in a corrosion pit. The metal, M, is being pitted by an aerated NaCl solution. Rapid dissolution occurs in the pit, while oxygen reduction takes place on the adjacent metal surfaces. Schematic of a polarization curve showing critical potentials and metastable pitting region. EP, pitting potential; ER, repassivation potential; Ecorr, corrosion potential. Pitting corrosion

Pitting corrosion of Ti in CH 3 OH-LiCl solutionsPitting corrosion of Fe-18%Cr alloy in CH3OH-H 2 SO 4 solutions Corrosion of heat exchanger (carbon steel) in water

Effect of molybdenum on stability of passive film on stainless steels N. Sato: Corrosion 45, 5, 354 (1989) Adsorption of ions on hydrous metal oxide surface which provides the fixed charge whose determines the ion selectivity of the membranes. (a) anion- selective, (b) cation- selective membrane[53].

Inergranular corrosion Inergranular corrosion of NIROSTA 2202 steel (22%Cr,6%Ni,3%Mo) in 93.5 wt.% H 2 SO 4 (100 0 C)

Stress corrosion cracking Surface mobility model of Stress corrosion cracking (SCC) according to Galvele J.R. Galvele, Corrosion Science 27,1 (1987) Crack velocity: D s. – surface self diffusion coeficient L – diffusion length  – elastic surface stress at the crack tip a 3 – volumen of vacancy

The effect of H 2 S on hydrogen embrittlement HIC – hydrogen induced cracking, occurs in low- and high-strength steels even without external stress. Crack propagation proceeds paralell to surface. SSCC – sulphide stress corrosion cracking, occurs in high-strength steels. Crack propagation proceeds perpendicular to surface.

HIC and HISCC of pipelines after 10 years exploitation in natural gas containing 4.5% H 2 S. HIC, mikrocracs parallel to pipe surface   HISCC, mikrocracs perpendicular to pipe surface  Nucleation of cracks The effect of H 2 S on hydrogen embrittlement

Mechanism of hydrogen embrittlement by stress iduced hydride formation. Hydrogen embrittlement

Corrosion (H + +e  H ad ) Hydrogen embrittlement Crack initiation  Crack propagation  Hydrogen absorption H ad  H Lattice Inclusions (elongated MnS)  Anomalous structure Segregation of Mn and P  Alloy components Coatings Inhibitors  Low content of S and P Spheroidization of inclusions  Heat treatment Rolling conditions  