Corrosion propagation monitoring using electrochemical noise measurements on carbon steel in hydrogenocarbonated solution containing chloride ions

doi:10.1016/j.corsci.2021.109885

Corrosion Science

Volume 193, December 2021, 109885

https://doi.org/10.1016/j.corsci.2021.109885 Get rights and content

Highlights

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Study of localized corrosion of API 5L X65 carbon in NaHCO₃ solution with Cl^- ions.
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Corrosion propagation studied with EN during long immersion times (100 h) in ZRA mode.
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Corrosion mechanism identification by noise transients only at short immersion times.
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Corrosion propagation may be monitored from the increase in noise amplitude.
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Noise impedance follows same time evolution as the coupled potential of the WEs.

Abstract

The propagation of localized corrosion on API 5L X65 carbon steel in hydrogenocarbonated solution containing chloride ions was monitored during long immersion times by electrochemical noise (EN) measurements in ZRA mode. Monitoring corrosion propagation from the EN amplitude is possible but interpreting the potential and current transients after long immersion times is made difficult by the different corrosion processes (metastable or stable pits, crevices, corrosion products detachment…) occurring simultaneously. The noise impedance at 0.1 Hz, directly derived from the EN measurements, is shown to decrease and stabilize in the same time scale as the coupled potential of the electrodes.

Introduction

Localized corrosion sometimes occurs freely on passive surfaces in the presence of aggressive anionic species like chloride ions. It proceeds according to several stages: passive film breakdown and metastable pitting, then stable pit growth. When localized corrosion occurs, an electrochemical coupling is established between the free surfaces and the confined zones in which the chemical composition of the medium is strongly modified [1], [2]. Many authors studied localized corrosion of carbon steel at Open Circuit Potential (OCP) or under polarization in different passivating media containing chloride ions such as simulated concrete pore solution [3], [4], saturated Ca(OH)₂ [3], [5], [6], [7], NaNO₂ [8], [9], or NaHCO₃ [8], [10], [11] using deterministic electrochemical techniques (polarization curves, electrochemical impedance spectroscopy (EIS)…).

Localized corrosion of carbon steel induced by chloride ions in these environments was also studied by Electrochemical Noise Measurements (ENM) to detect the onset of corrosion, identify its mechanism and quantify the damage caused by a given corrosion mode [6], [12], [13], [14]. It is well known that ENM presents potentialities for such application [15], [16]. This non-intrusive technique consists in measuring the random fluctuations of electrical parameters such as the potential of the electrode and/or the current flowing through it when an electrochemical process takes place at the material-environment interface. Measurements can be carried out in galvanostatic, potentiostatic or zero resistance ammeter (ZRA) modes. The latter mode involves two electrodes, most commonly identical, coupled to each other to measure both current and voltage fluctuations. The current generated by the electrochemical processes is measured between the two electrodes while their coupling potential is monitored using a reference electrode [17], [18]. A metastable corrosion process (breakdown and repassivation of passive film) can often be identified from the signature of the current or potential transients that can have different shapes according to the metal undergoing corrosion: for stainless steel, the current transient due to a pit is characterized by a slow rise followed by a sharp drop while a sudden rise followed by a slow decay can be observed for carbon steel [15]. Potential transients can present such characteristics too but they are also influenced by the charge and discharge of the capacitance of the passive film [12].

The objective of the present paper is to investigate propagation of localized corrosion on API 5L X65 carbon steel during long immersion times (up to 100 h) in NaHCO₃ aqueous solution containing chloride ions at OCP using ENM and to evaluate the capacities and limitations of the EN technique for such study. Indeed, the EN technique is generally used to detect the onset of localized corrosion, not its propagation on long times. Great care was taken for validating the ENM and identify the influence of the instrumentation noise sometimes present.

Section snippets

Experimental

The tested material was an API 5L X65 grade carbon steel whose chemical composition is given in Table 1. The samples were rectangular plates of 30 × 100 mm dimensions and thickness of 3 mm (Fig. 1). After grinding up to 1200 grit SiC paper, one side and the cut edges of the samples were covered with a thin layer of cataphoretic paint (black color in Fig. 1) commonly used in the automotive industry for its anticorrosion properties, leaving one side of 7.5 or 1.5 cm² surface area exposed to

Procedure and validation

ENM were performed using the Gamry® ESA 410® software in ZRA mode. The electrochemical cell was placed in a Faraday cage connected to the floating ground of the potentiostat in order to reduce the mains interference (50 Hz and harmonics) [19]. In this work, the noise measurements were performed in three successive steps by using sampling frequencies f_s of 10 Hz during 28 min, 1 Hz during 70 min and 10 Hz during 28 min with an I-E range of 6 or 60 µA corresponding to a current-measuring

Preliminary study

Fig. 3a. presents the time evolution of the OCP of single API 5 L X65 carbon steel electrodes of surface area of 27.3 cm² immersed in 0.5 M NaHCO₃ without, for test 1, or with 0.2 M NaCl for the three other tests. In 0.5 M NaHCO₃, the free corrosion potential of the electrode shifted to positive values resulting from the formation of a protective barrier layer on the metal [10], [23]. Indeed, NaHCO₃ reacts with ferric ions when the concentration of HCO₃^- is high enough to saturate the solution

Conclusion

This paper is aimed at studying the propagation of localized corrosion on API 5 L X65 carbon steel electrodes in a 0.5 M NaHCO₃ solution containing chloride ions using electrochemical noise measurements. While the EN technique is generally used to detect the early stage of localized corrosion, long-term experiments (about 100 h) were performed to investigate the corrosion propagation and assess the suitability of the EN technique for such study.

The main conclusions drawn from the analysis of

CRediT authorship contribution statement

C. Comas: Conceptualization, Methodology, Investigation, Validation, Formal analysis, Writing – Original draft, Data curation. F. Huet: Conceptualization, Methodology, Supervision, Validation, Formal analysis, Data curation, Writing – Original draft, Visualization, Software, Writing – review & editing. K. Ngo: Conceptualization, Methodology, Writing – Review & Editing, M. Fregonese: Project administration, Funding acquisition, Conceptualization, Supervision, Resources. H. Idrissi: Supervision,

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This operation was conducted with the assistance of the " Investissements d′avenir " (FIA) program of the French government, the management of which has been entrusted to Andra (French national radioactive waste management agency).

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View full text

Corrosion propagation monitoring using electrochemical noise measurements on carbon steel in hydrogenocarbonated solution containing chloride ions

Highlights

Abstract

Introduction

Section snippets

Experimental

Procedure and validation

Preliminary study

Conclusion

CRediT authorship contribution statement

Declaration of Competing Interest

Acknowledgments

Cem. Concr.

Electrochim. Acta

Constr. Build. Mater.

Corros. Sci.

Constr. Build. Mater.

Corros. Sci.

Appl. Surf. Sci.

Corros. Sci.

Appl. Surf. Sci.

Thin Solid Films

Corros. Sci.

Corros. Sci.

Pitting corrosion of metals. A review of critical factors

J. Electrochem. Soc.