Cathodic Polarization Behavior of Steel in Aqueous MgCl2 Solutions Containing Zn2+
Authors: Tada Eiji , Ooi Azusa 
Published: September 2023

So far, we have revealed that the dissolution rate of zinc is accelerated in relative high concentrations of MgCl2 in the corrosion process of galvanic couples consisting of zinc and steel. In this study, we investigated the cathodic polarization behavior of steel in MgCl2 solution containing Zn2+ and the effect of Zn2+ dissolved in the solution on the oxygen reduction reaction and hydrogen evolution reaction.
The specimens used in the experiments were carbon steel SS400 (Fe-0.12C-0.60Mn-0.011P-0.019S) machined into a 1.5×1.5×0.3 cm3. One side of the specimen was polished with SiC abrasive paper up to #2000 grit and degreased in acetone before being used for the experiment. The test solution was mixtures of 0.25 M MgCl2 + x mM ZnCl2 (x = 2.5, 5 mM, Mg/Zn molar ratio: 100, 50) at room temperature under a naturally aerated condition. As a comparison solution, 0.5 M NaCl + y mM ZnCl2 (x = 5, 10 mM, molar ratio of Na/Zn: 100, 50) with the same chloride ion concentrations were used. Cathodic polarization curves of steel were measured using a three-electrode method with a platinum wire as the counter electrode and an Ag/AgCl electrode (saturated KCl, SSE) as the reference electrode. The potential sweep rate was 0.5 mV/s. After the polarization test, the specimen surfaces were observed with a scanning electron microscope and analyzed for corrosion products formed during cathodic polarization with XRD and laser Raman spectroscopy.
The cathodic polarization behavior of steel in MgCl2 solution without Zn2+ was investigated and compared with that of NaCl solution without Zn2+. Diffusion-limited currents of dissolved oxygen reduction (ORR) were observed at -0.6 V to -0.8 V in MgCl2 and NaCl solutions. Furthermore, cathodic polarization in MgCl2 and NaCl solutions showed an increase in current due to hydrogen evolution reaction (HER), and the cathodic current due to HER on steel was larger in the MgCl2 solution than in the NaCl solution. To investigate the difference in HER in both solutions, the steel surface was observed after constant polarization at -1.0 V for 20 min. Mg(OH)2 deposition was observed on the steel surface in the MgCl2 solution, but not in the NaCl solution. This indicates that the increase in pH due to ORR and HER is mitigated by the formation of Mg(OH)2 during cathodic polarization. Therefore, due to the pH buffering action of Mg2+ associated with the formation of Mg(OH)2, it can be considered that a larger HER current flowed in the MgCl2 solution than in the NaCl solution when compared at the same potential.
On the other hand, cathodic polarization curves for steel in MgCl2 and NaCl solution containing Zn2+ were investigated. As a result, ORR and HER were observed at potentials down to -1 V in the MgCl2 and NaCl solutions containing Zn2+; the cathodic current due to ORR and HER in the MgCl2 and NaCl solutions containing Zn2+ was reduced compared to the solutions without Zn2+. The inhibition of ORR and HER can be attributed to the precipitation of Zn corrosion products.
These results suggest that in solution environments containing Mg2+ and Zn2+, the promotion of HER by the effect of Mg2+ and the inhibition of HER and ORR by Zn corrosion products occur simultaneously.