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The influence of the size of aggressive anions on the passivity breakdown of UNS K02700 carbon steel exposed to saturated Ca(OH)2 solutions with the addition of different halides was investigated by using the potentiodynamic polarization (PDP) experiments.
An important factor in determining the breakdown of the barrier layer of the passive film on carbon steel in halide-containing solutions is the anion size. In this study, the influence of the size of aggressive anions on the passivity breakdown of UNS K02700 grade carbon steel exposed to saturated Ca(OH)2 solutions with the addition of different halides was investigated by using the potentiodynamic polarization (PDP) experiments. The PDP results were interpreted by using a mechanistic description based on the Point Defect Model (PDM). The experimental results revealed a linear dependence of the critical breakdown potential (Ec) on the logarithm of the activity of the breakdown-inducing halide (F-, Cl-, Br-, and I-), as predicted by the PDM. Furthermore, the PDM successfully accounted for the order with which the halides induce passivity breakdown, F- < Cl- > Br- > I-, in terms of competitive Gibbs free energy of anion dehydration and expansion of surface oxygen vacancies, into which the halide must absorb as the initial event in the breakdown process.
Keyword: Passivity breakdown, Point Defect Model, Halide ion size
Autoclave tests were performed in CO₂, O₂, and H₂O at 8 MPa at 50°C and 245°C, (heat exchanger operating conditions). Results show significant corrosion in a pressure / temperature region where H₂O saturated with CO₂ condenses on the coupons.
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Special enhancements: (1) use the high temperature reference electrode - Ag/AgCl; (2) define the test temperature measurement procedure; (3) check the accuracy of the reference electrode; (4) develop an inexpensive anode isolation method.
This paper discusses the detailed inspection, testing, metallurgical analysis and supporting factors from which the most likely cause of pitting corrosion was revealed in the DSS flowline welds.