Chemical inhibitors are widely used to protect metallic alloys from corrosion in aqueous environments. This Letter investigates the possible synergistic behavior of a quaternary ammonium carboxylate compound toward the development of a new system taking advantage of the surface activity of a known antimicrobial surfactant molecule, hexadecyl trimethylammonium cation, combined with a known organic corrosion inhibitor, the trans-4-hydroxy-cinnamate anion. Short-term potentiodynamic polarization (PP) studies combined with immersion in aqueous chloride solutions demonstrated the high inhibition efficiency of the combination of ions, and NMR pfg-diffusion measurements revealed micellar formation that was concentration- and pH-dependent. The NMR data suggest that speciation changes occur in the solution that correlate with enhanced corrosion inhibition efficiency at higher pH and at concentrations above the CMC of the compound. This new contribution may provide a rational molecular design toward delivering corrosion inhibitors to a metal surface through controlled speciation in solution.

No abstract

Carbon steel is one of the most used construction materials and makes up the bulk of steel production in the world. However, this alloy is vulnerable to corrosion, which reduces its safety and costs trillions of dollars worldwide in terms of corrosion protection and infrastructure maintenance. Corrosion inhibitors are among the cheapest and most effective methods to minimize corrosion and maximize the shelf life of this ubiquitous alloy; however, they are often harmful to the environment. Currently there are no reports in terms of engineering design methodology to develop highly effective, advanced corrosion inhibitors. The possible synergistic behavior of a surfaceactive quaternary ammonium with a tailored carboxylate compound provides a rational molecular design toward delivering corrosion inhibitors to a metal surface through controlled speciation in solution. Here we show how entrapment and delivery of the anion inhibitor through speciation and micellar formation can lead to high inhibition efficiency, as determined by potentiodynamic polarization and electrochemical impedance spectroscopy. In particular, we demonstrate how NMR spectroscopy, pfg NMR diffusion measurements, and Cryo-TEM, taken together with molecular dynamic simulations, can reveal the micellar formation and its concentration dependence, with wormlike micelles evident at higher concentrations correlating with a dramatic increase in viscosity. This new organic corrosion inhibitor, cetrimonium 4-ethoxy cinnamate, provides significantly higher corrosion inhibition efficiency compared with the 4-hydroxy cinnamate analogue and with reduced toxic impact in the zebrafish embryo compared to the surface active CTAB often used as an antimicrobial.

No abstract

Effective corrosion inhibition of mild steel 1030 at 0.01 M NaCl concentration was achieved by the use of the nontoxic surfactant salt cetrimonium trans-4-hydroxy-cinnamate (CTA-4OHcinn). Polarization analysis on the steel samples immersed for 24 h in the control and CTA-4OHcinn-containing solutions shows the development of a passivation potential that is more obvious at higher inhibitor concentrations along with a maximum inhibition efficiency of 97.8%. Electrochemical impedance spectroscopy (EIS) pinpoints the effect of the inhibitor on the corroding regions of the metal surface, showing an increase in the local electric resistance and conversely a decrease in the local capacitance, which indicates that the charge transfer in the corroding regions is being hindered by a deposition process. This is consistent with scanning electron microscopy (SEM) images, showing the presence of a porous oxide matrix that fills localized corrosion sites on the metal surface after 24 h of immersion in a 0.01 M NaCl + 10 mM inhibitor solution. Additionally, SEM analysis also shows the formation of an organic film surrounding the defects that is able to shield chloride attack. As a result of diffusion of chloride from the defects below the protective film, filiform corrosion can be seen. Time-resolved impedance analysis over the first 120 min of immersion in the control and inhibitor solution shows that significant inhibitor protection does not take place immediately and there is a lag phase in the first 50 min of immersion, suggesting that early localized corrosion drives further adsorption of inhibitor micelles on the metal surface. This is in agreement with X-ray photoelectron spectroscopy (XPS) analysis, which indicates a complete surface coverage over the first 2 h of immersion in a concentrated inhibitor solution. XPS also shows the heterogeneity of the film, where some parts are poorly covered, revealing the underlying surface containing iron.