Delinkage of Metal Surface Saturation Concentration and Micellization in Corrosion Inhibition

Long-distance transmission of oil is usually performed in large-diameter steel pipelines, where water present therein may cause severe internal corrosion. An effective method of mitigating such corrosion is to inject organic corrosion inhibitors (CIs). Their surface adsorption, via heteroatom functionalities, can markedly enhance the corrosion resistance of metals. In this study, three CI model compounds with different head groups but the same alkyl tail length (-C₁₄H₂₉), specifically tetradecyltetrahydropyrimidinium (THP-C14), tetradecylphosphate ester (PE-C14), and tetradecylimidazolinium (IMID-C14), were synthesized, their purities being determined using nuclear magnetic resonance spectroscopy. The critical micelle concentrations (CMCs) of each compound were measured using surface tensiometry (Du Noüy ring) and fluorescence spectroscopy techniques, with differences being found between these indirect and direct methods. In addition, linear polarization resistance was used to determine inhibition efficiencies (IEs) for carbon steel immersed in a 5 wt% NaCl electrolyte saturated with CO₂. CI surface saturation concentrations, with maximum IEs, were compared with the determined CMCs. Excellent IEs were observed at concentrations of THP-C14, PE-C14, and IMID-C14 which do not correspond with their CMCs, the differences involved being significantly greater than what was previously reported for tetradecylbenzyldimethylammonium (BDA-C14). These results demonstrate that there is no direct link between CMC and metal surface saturation/corrosion IE that can be made on a generalized basis for the different head groups but with the same tail length CI, indicating that the selection of the appropriate CI concentration for an industrial application should not be based on CMC alone.