In this study, corrosion weight loss experiments were conducted to explore the corrosion-inhibiting properties of a composite inhibitor consisting of carboxymethyl chitosan (CMCS) and sodium humate (SH) at varying concentrations on EH40 steel in seawater. An investigation was conducted into the electrochemical behavior of EH40 steel in seawater and the mechanism of composite inhibitor consisting of carboxymethyl chitosan (CMCS) and sodium humate (SH) at varying concentrations on EH40 steel in seawater through an electrochemical test. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy and energy-dispersion spectroscopy (SEM-EDS), Fourier transform infrared absorption spectroscopy (FTIR), and contact angle measurements were performed to confirm the mechanism of CMCS and SH as well as their composite corrosion inhibitors at the interface between seawater and EH40 steel. Furthermore, density functional theory (DFT) calculation supports the experimental findings. The results show that CMCS, SH, and their composite inhibitor are a mixed type of corrosion inhibitor that mainly inhibits cathodic reactions and corrosion through the active site blocking mechanisms. Their corrosion inhibition effect increases with the increase of mass concentration, and the composite inhibitor performs better in corrosion inhibition and scale inhibition than the individual inhibitor. When the CMCS mass concentration reaches 100 mg/L and the SH mass concentration reaches 50 mg/L, the corrosion inhibition rate is 74.65%, the corrosion potential shifts by about 47.39 mV, the R p value increases from 358.6 to 1102.4 Ω•cm 2 , and the Y dl value decreases from 177.31 S n Ω −1 cm −2 × 10 −6 to 92.672 S n Ω −1 cm −2 × 10 −6 . CMCS and SH are adsorbed onto the surface of EH40 steel, forming a protective film through the complexation of carboxyl, amino, and other functional groups to inhibit corrosion and prevent the further formation of scale. In addition, synergistic coadsorption occurs between CMCS and SH, and the composite corrosion inhibitor exerts a better effect than the individual corrosion inhibitor.
