Lithium carbonate and lithium oxalate were incorporated as leachable corrosion inhibitors in model organic coatings for the protection of AA2024-T3. The coated samples were artificially damaged with a scribe. It was found that the lithium-salts are able to leach from the organic coating and form a protective layer in the scribe on AA2024-T3 under neutral salt spray conditions. The present paper shows the first observation and analysis of these corrosion protective layers, generated from lithium-salt loaded organic coatings. The scribed areas were examined by scanning and transmission electron microscopy before and after neutral salt spray exposure (ASTM-B117). The protective layers typically consist of three different layered regions, including a relatively dense layer near the alloy substrate, a porous middle layer and a flake-shaped outer layer, with lithium uniformly distributed throughout all three layers. Scanning electron microscopy and white light interferometry surface roughness measurements demonstrate that the formation of the layer occurs rapidly and, therefore provides an effective inhibition mechanism. Based on the observation of this work, a mechanism is proposed for the formation of these protective layers.

Lithium salts are being investigated as leachable corrosion inhibitor and potential replacement for hexavalent chromium in organic coatings. Model coatings loaded with lithium carbonate or lithium oxalate demonstrated active corrosion inhibition and the formation of a protective layer in a damaged area during neutral salt spray exposure. The present paper provides an abridged overview of the initial studies into this novel inhibitor technology for the active corrosion protection of aluminum alloys. Coating defects were investigated by microscopic techniques before and after exposure to corrosive conditions. Scanning electron microscopy analysis of cross-sections of the coating defect area demonstrated that the protective layer comprises a typical three-layered structure, which included a dense layer near the alloy surface, a porous middle layer, and a flake-shaped out layer. Potentiodynamic polarization measurements obtained with a microcapillary cell positioned in the coating defect area and electrochemical impedance spectroscopy confirmed the corrosion protective properties of these protective layers. The long-term corrosion inhibition of the lithium-based coating technology was tested in industrial coating systems.

An investigation into corrosion inhibition properties of a primer coating containing lithium carbonate as corrosion inhibitive pigment for AA2024 aluminum alloy was conducted. It was found that, during neutral salt spray exposure, a protective film of about 0.2 to 1.5 μm thickness formed within the area where an artificial defect was introduced by scribing through the coating to the base alloy. This film showed a multilayered structure consisting of a relatively compact layer near the alloy substrate, a porous middle layer and a columnar outer layer. The thicknesses of the layers varied, as a consequence of the difference in the local concentration of lithium species leaching from the primer coating. The presence of the film in the scribed area significantly reduced corrosion of the alloy, with little consumption of the metal substrate within the scribed area during neutral salt spray exposure. Furthermore, the presence of the protective film resulted in a significant increase of impedance modulus, measured after the salt spray exposure.

This work presents the electrochemical evaluation of protective layers generated in a coating defect from lithium-leaching organic coatings on AA2024-T3 aluminum alloys as a function of neutral salt spray exposure time. Electrochemical impedance spectroscopy was used to study the electrochemical properties on a macroscopic scale. An electrochemical model allowed to quantitatively link the electrochemical behavior with the physical model of the layer in the damaged area as studied by scanning electron microscopy. Local potentiodynamic polarization curves obtained from micro-cell measurements showed an increase of the passive range in the defect area due to the formation of a robust protective layer. Scanning vibrating electrode technique measurements confirmed the non-reversible long-term corrosion protection of these generated layers in the coating defect.

This study focuses on the elucidation of the formation mechanism of passive layers on AA2024-T3 during the exposure to alkaline lithium carbonate solutions in the presence of sodium chloride. Under controlled conditions, in an electrochemical cell, a protective layer was generated comprising an amorphous inner layer and a crystalline outer-layer. In order to resolve the formation mechanism, the layers were characterized using surface analytical techniques to characterize the surface morphology, thickness and elemental composition of the layers at different stages of the formation process. In addition, electrochemical techniques were applied to link the electrochemical properties of the layers with the different stages of formation. The results demonstrate that the formation mechanism of these layers comprises three different stages: (I) oxide thinning, (II) anodic dissolution and film formation, followed by (III) film growth through a competitive growth-dissolution process. The passive properties of the layers are generated in the third stage through the densification of the amorphous layer. The combined results provide an enhanced insight in the formation mechanism and the development of the passive properties of these layers when lithium salts are used as leaching corrosion inhibitor for coated AA2024-T3.