In situ study of the interactions between metal surfaces and cationic surfactant corrosion inhibitors by surface-enhanced Raman spectroscopy coupled with visible spectroscopy.

Cationic surfactants are widely used as corrosion inhibitors for industrial tubings and pipelines. They protect the surface of steel pipes through a film-forming mechanism, providing both anodic and cathodic inhibition. To improve the efficiency of the corrosion protection, it is essential to understand the interactions between the surfactants and metal surfaces. To achieve this, surface enhanced Raman spectroscopy (SERS) can serve as a powerful tool due to its surface sensitivity and potential to detect trace amounts of analytes in complex media. In this contribution, we have investigated the behaviour of in situ prepared AgNPs in the presence of benzalkonium chloride as a model corrosion inhibitor using SERS coupled to visible spectroscopy and combined with light scattering methods. By combining these experimental methods, we were able to correlate the aggregation of silver particles with the concentration of added surfactant in the resulting mixture. Using this insight, we also established a SERS method for the detection of benzalkonium chloride traces in water. For this, we utilised the quenching of the SERS response of methylene blue by competitive adsorption of methylene blue and the surfactant on SERS active AgNPs. We believe that our approach can serve a variety of applications to improve the industrial water treatment. For example, the modelling of the interaction of different surfactants with SERS can be used for process intensification, and ultimately, to move towards the digital twinning of corrosion processes for more efficient corrosion inhibition. Furthermore, the ability to adapt our sensing protocol for on-line corrosion inhibitor monitoring allows a fast response to process changes, hence, enabling resource-efficient, continuous process control.