Electrochemical, spectroscopic and theoretical studies for acid corrosion of zinc using glycogen

Abstract

The objective of the work is to introduce and establish anticorrosion capabilities of a novel biopolymer glycogen (GLY) against sulfamic acid (NH2SO3H) induced corrosion of zinc. The corrosion and inhibition studies were done by electrochemical techniques such as potentiodynamic polarization (PDP) measurements and electrochemical impedance spectroscopy technique (EIS). Conditions were optimized to get maximum inhibition efficiency by varying the concentration of the inhibitor in the temperature range of 303–323 K. Activation and thermodynamic parameters were evaluated and discussed in detail. Suitable adsorption isotherm was proposed to fit the experimental results. Scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and atomic force microscopy (AFM) studies were performed before and after the addition of inhibitor. Adsorption of inhibitor was further confirmed by UV–Visible spectroscopy. Quantum chemical calculations were done to establish the correlation between the structure of the inhibitor and its inhibition efficiency. Energy of HOMO, LUMO, energy gap ∆E, dipole moment (µ) Mullikan charges were calculated. Different theoretical factor descriptors like the hardness (η), and softness (σ) electronegativity (χ), global electrophilicity (ω), nucleophilicity (ε) and fraction of electron transferred (ΔN) were calculated. Inhibition efficiency of glycogen increased with increase in its concentration and with temperature. Maximum efficiency of 72% could be achieved for the addition of 0.05 g L−1 of GLY at 323 K. Results were fitted into Langmuir adsorption iostherm. The surface of the metal turned visibly smoother in the presence of GLY. In addition the EDX studies showed increase in carbon content which re-affirmed the adsorption of GLY on the metal surface. The density functional theory (DFT) based theoretical studies supported the experimental observations.