First-Principles Investigation of the Effect of Interstitial Carbon on Corrosion Resistance of Martensitic Medium-Carbon Steel

Abstract

Martensitic carbon steels with fine grains are used for many industrial applications. Interstitial carbon provides high strength to martensitic structure. Although it has been reported that the interstitial carbon has the beneficial effect on the pitting corrosion resistance of steels,1,2 the role of interstitial carbon is still unclear. In this research, first-principles calculations were applied to the clarification of the effect of interstitial carbon on the anodic dissolution of martensite. The base specimen was AISI 1045 carbon steel, and the chemical composition of this steel (mass%) was 0.44%C, 0.20%Si, 0.85%Mn, 0.008%P, 0.002%S, <0.01%Ni, <0.01%Cr, <0.01%Mo, <0.01%Cu, <0.001%Ti, <0.002%Nb, 0.035%Al, 0.003%N, and 0.002%O. The specimens were heat-treated at 1123 K for 10 h in air and then, quenched in water. Since the surface of the specimens was decarburized during this heat-treatment, the low carbon martensitic structure was formed in the surface region of the specimens, and high carbon martensitic structure remained in the core area. Potentiodynamic polarization of the low and high carbon martensitic specimens was conducted using boric-borate buffer solution with 1 mM NaCl at pH 8.0. In addition to the electrochemical measurement, the first-principles calculations based on density functional theory (DFT) were carried out. For the calculation, the carbon concentration was varied from 0.40 at.% to 5.88 at.%. In the potentiodynamic polarization curves of the low and high carbon martensitic specimens in 1mM NaCl containing boric-borate buffer at pH 8.0, the region of active dissolution appeared on both specimens at about -0.5 V. The dissolution current density for high carbon martensitic specimen was lower than that of the low carbon martensitic one, suggesting that the interstitial carbon suppressed the active dissolution. Next, the effect of interstitial carbon atoms on the electronic structure of the martensitic structure was analyzed. It was clarified that the electronic density of states (DOS) of iron atoms at and near the Fermi level decreased by increasing carbon concentration. This result indicates that the interstitial carbon atom makes weak atomic bonding with the nearest iron atom, and stabilizes the electronic structure of martensite. This change in the energy state of iron atom was, therefore, attributed to the high corrosion resistance of martensitic carbon steels. References; M. Kadowaki, I. Muto, Y. Sugawara, T. Doi, K. Kawano, and N. Hara, J. Electrochem. Soc., 164, C962 (2017).M. Kadowaki, I. Muto, Y. Sugawara, T. Doi, K. Kawano, and N. Hara, J. Electrochem. Soc., 165, C711 (2018).