EFFECTS OF SO42- ON THE CORROSION BEHAVIOR OF NiCu LOW ALLOY STEEL IN DEAERATED BICARBONATE SOLUTIONS

doi:10.11900/0412.1961.2015.00133

Acta Metall Sin

2015, Vol. 51

Issue (9): 1067-1076 DOI: 10.11900/0412.1961.2015.00133

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EFFECTS OF SO₄²^- ON THE CORROSION BEHAVIOR OF NiCu LOW ALLOY STEEL IN DEAERATED BICARBONATE SOLUTIONS

Yunfei LU^1,²,Junhua DONG¹(

),Wei KE¹

1 Environmental Corrosion Center, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016
2 Wuhan the Second Ship Design and Research Institute, Wuhan 430064

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Yunfei LU,Junhua DONG,Wei KE. EFFECTS OF SO₄²^- ON THE CORROSION BEHAVIOR OF NiCu LOW ALLOY STEEL IN DEAERATED BICARBONATE SOLUTIONS. Acta Metall Sin, 2015, 51(9): 1067-1076.

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Abstract

High level radioactive waste (HLW) is an extremely dangerous by-product of the global nuclear industry. Due to its intensely radioactive nature and ultra long half-life, HLW has to be safely managed and disposed for thousands of years, isolated from the biosphere. Deep geological repository (DGR) is considered to be the most feasible option worldwide because of its operability, stability, durability, environmental protection and so on. Basically, DGR relies on a multibarrier system and it consists of metallic canisters, backfill materials and a stable geologic formation. Since radionuclides could be moved into the biosphere by action of groundwater, both the geologic formation and backfill materials have to be of very low hydraulic permeability and metal canisters have to be corrosion resistant and prevent contact between the groundwater and the radioactive waste for as long as possible. Low carbon steel has been selected and studied as a candidate canister material in many countries because its long industrial experience, high-strength, low cost and it is less prone to localized corrosion than materials that passivity, but its larger corrosion rate may also set an insuperable barrier for the practical application. Recently, our studies revealed that NiCu low alloy steel is a more promising candidate for the canister material compared with the popular one, low carbon steel, since the former performs a more acceptable corrosion rate without increasing much cost and has better resistance to localized corrosion in environments with high concentration of Cl^-. In this work, effects of SO₄²^-, another ubiquitous species in deep groundwater, on the corrosion behavior of NiCu low alloy steel during immersion in simulated deep groundwater environments were investigated by in situ electrochemical measurements and surface analysis techniques. Results show that the addition of SO₄²^- can promote the substrate dissolution during the initial stage of immersion. In the later stage, SO₄²^- weakens the protectiveness of formed films and consequently, active dissolution prevails on the electrode surface rather than the prepassivation. Concentrated SO₄²^- and HCO₃^- can both promote the formation of Fe₆(OH)₁₂CO₃. The main components of corrosion products are a-FeOOH, Fe₃O₄ and Fe₆(OH)₁₂CO₃, and uniform corrosion is observed.

Key words: low alloy steel rust HCO₃^- SO₄²^-

Fund: Supported by National Natural Science Foundation of China (No.51471175)

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	Yunfei LU
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https://www.ams.org.cn/EN/10.11900/0412.1961.2015.00133 OR https://www.ams.org.cn/EN/Y2015/V51/I9/1067

Fig.1 Polarization curves of NiCu low alloy steel in the deaerated 0.05 mol/L (a) and 0.10 mol/L (b) bicarbonate solutions containing different concentrations of SO₄²^- and without SO₄²^-[15,16](E_corr—corrosion potential, P1—the first oxidation peak, P2—the second oxidation peak, P3—the third oxidation peak)

Fig.2 Evolution curves of open circuit potential of NiCu low alloy steel in the deaerated 0.05 mol/L (a) and 0.10 mol/L (b) bicarbonate solutions with or without^[15,16] 0.10 mol/L SO₄²^-

Fig.3 Bode phase plots (a, c) and Bode impedance plots (b, d) of NiCu low alloy steel for the first (a, b) and third (c, d) stages in the deaerated 0.05 mol/L bicarbonate solution containing 0.10 mol/L SO₄²^-

Fig.4 Bode phase plots (a, c) and Bode impedance plots (b, d) of NiCu low alloy steel for the first (a, b) and third (c, d) stages in the deaerated 0.10 mol/L bicarbonate solution containing 0.10 mol/L SO₄²^-

Fig.5 Equivalent circuits for fitting the EIS data measured in the 0.05 mol/L NaHCO₃+0.10 mol/L Na₂SO₄ (a)and 0.10 mol/L NaHCO₃+0.10 mol/L Na₂SO₄ (b) solutions (Q_HF—capacitance caused by high frequency phase shift, R_e—electrolyte resistance, Q_dl—double layer capacitance, R_ct—charge transfer resistance, W—Warburg impedance, Q_cp—capacitance of precipitated corrosion products layer, R_cp—resistance of precipitated corrosion products layer)

Table 1 Fitted results for EIS data measured in the deaerated 0.05 mol/L NaHCO₃+0.10 mol/L Na₂SO₄ solution

Fig.6 Evolution of the R_ct obtained from EIS data as a function of immersion time in the deaerated 0.05 mol/L (a) and 0.10 mol/L (b) bicarbonate solutions with or without^[15,16] 0.10 mol/L SO₄²^-

Table 2 Fitted results for EIS data measured in the deaerated 0.10 mol/L NaHCO₃+0.10 mol/L Na₂SO₄ solution

Fig.7 XRD spectra of the surface layer of NiCu low alloy steel after immersion tests

Fig.8 Low (a, c) and high (b, d) magnified surface morphologies of low alloy steel after immersion tests in 0.05 mol/L NaHCO₃+0.10 mol/L Na₂SO₄ solution for 56 d (a, b) and 0.10 mol/L NaHCO₃+0.10 mol/L Na₂SO₄ solution for 43 d (c, d)

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