Volatile corrosion inhibitor (VCI) films have become essential tools in safeguarding metal surfaces from corrosion. To maximize the effectiveness of VCI films, it is crucial to understand the relationship between their thermal properties and vapor phase inhibition ability. In this study, the optimal and modified standard test was performed for the evaluation of the VCI films’ ability and also investigated how their thermal characteristics influence their protective efficiency via the weight-loss method and differential scanning calorimetry (DSC) analysis. The results showed that under the simulated and standard test conditions, the steel surface exposed to VCI films shows a model of a “preservative memory for VCI material,” at higher temperature/humidity. This memory is affected by different adsorption power due to the roughness of the surface, humidity, and temperature as well as the rate of release of inhibitors. The results of the computational method confirmed that the orientation of the inhibitor molecule when interacting with the polymer chain is the determining factor in the inhibition efficiency, consistent with the FTIR results. This behavior caused by chemical or electrochemical reactions with the temperature-dependent release rate of inhibitors has a greater effect on inhibition.

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