Adsorption Characteristics between Ti Atoms of TiO(2)(100) and Corrosive Species of CO(2)-H(2)S-Cl(−) System in Oil and Gas Fields

The service environment of OCTG (Oil Country Tubular Goods) in oil and gas fields is becoming more and more severe due to the strong affinity between ions or atoms of corrosive species coming from solutions and metal ions or atoms on metals. While it is difficult for traditional technologies to accurately analyze the corrosion characteristics of OCTG in CO(2)-H(2)S-Cl(−) systems, it is necessary to study the corrosion-resistant behavior of TC4 (Ti-6Al-4V) alloys based on an atomic or molecular scale. In this paper, the thermodynamic characteristics of the TiO(2)(100) surface of TC4 alloys in the CO(2)-H(2)S-Cl(−) system were simulated and analyzed by first principles, and the corrosion electrochemical technologies were used to verify the simulation results. The results indicated that all of the best adsorption positions of corrosive ions (Cl(−), HS(−), S(2−), HCO(3)(−), and CO(3)(2−)) on TiO(2)(100) surfaces were bridge sites. A forceful charge interaction existed between Cl, S, and O atoms in Cl(−), HS(−), S(2−), HCO(3)(−), CO(3)(2−), and Ti atoms in TiO(2)(100) surfaces after adsorption in a stable state. The charge was transferred from near Ti atoms in TiO(2) to near Cl, S, and O atoms in Cl(−), HS(−), S(2−), HCO(3)(−), and CO(3)(2−). Electronic orbital hybridization occurred between 3p(5) of Cl, 3p(4) of S, 2p(4) of O, and 3d(2) of Ti, which was chemical adsorption. The effect strength of five corrosive ions on the stability of TiO(2) passivation film was S(2−) > CO(3)(2−) > Cl(−) > HS(−) > HCO(3)(−). In addition, the corrosion current density of TC4 alloy in different solutions containing saturated CO(2) was as follows: NaCl + Na(2)S + Na(2)CO(3) > NaCl + Na(2)S > NaCl + Na(2)CO(3) > NaCl. At the same time, the trends of R(s) (solution transfer resistance), R(ct) (charge transfer resistance), and R(c) (ion adsorption double layer resistance) were opposite to the corrosion current density. The corrosion resistance of TiO(2) passivation film to corrosive species was weakened owing to the synergistic effect of corrosive species. Severe corrosion resulted, especially pitting corrosion, which further proved the simulation results mentioned above. Thus, this outcome provides the theoretical support to reveal the corrosion resistance mechanism of OCTG and to develop novel corrosion inhibitors in CO(2)-H(2)S-Cl(−) environments.