ABSTRACT
The principal possibility to grow layered double hydroxide (LDH) at ambient pressure on plasma electrolytic oxidation (PEO) treated magnesium alloy AZ91 in the presence of chelating agents is demonstrated for the first time. It avoids hydrothermal autoclave conditions, which strongly limit wide industrial application of such coating systems, and the presence of carbonate ions in the electrolyte, which lead to the formation of "passive" non-functionalizable LDH. A combination of chelating agents (sodium diethylenetriamine-pentaacetate (DTPA) and salicylate) were introduced to the treatment solution. The role of each additive and the influence of treatment bath composition on the LDH formation processes are discussed. A synergistic effect of DTPA and salicylate during LDH formation is discovered and its possible explanation is proposed.
ABSTRACT
In situ formation of layered double hydroxides (LDH) on metallic surfaces has recently been considered a promising approach for protective conversion surface treatments for Al and Mg alloys. In the case of Mg-based substrates, the formation of LDH on the metal surface is normally performed in autoclave at high temperature (between 130 and 170 °C) and elevated pressure conditions. This hampers the industrial application of MgAl LDH to magnesium substrates. In this paper, the growth of MgAl LDH conversion coating directly on magnesium alloy AZ91 at ambient conditions (25 °C) or elevated temperatures is reported in carbonate free electrolyte for the first time. The direct LDH synthesis on Mg alloys is enabled by the presence of organic chelating agents (NTA and EDTA), which control the amount of free and/or hydroxyl bound Mg2+ and Al3+ in the solution. The application of the chelating agents help overcoming the typical technological limitations of direct LDH synthesis on Mg alloys. The selection of chelators and the optimization of the LDH treatment process are supported by the analysis of the thermodynamic chemical equilibria.
ABSTRACT
This work contributes to the development of new feedback-active anticorrosion systems. Inhibitor-doped hydroxyapatite microparticles (HAP) are used as reservoirs, storing corrosion inhibitor to be released on demand. Release of the entrapped inhibitor is triggered by redox reactions associated with the corrosion process. HAP were used as reservoirs for several inhibiting species: cerium(III), lanthanum(III), salicylaldoxime, and 8-hydroxyquinoline. These species are effective corrosion inhibitors for a 2024 aluminum alloy (AA2024), used here as a model metallic substrate. Dissolution of the microparticles and release of the inhibitor are triggered by local acidification resulting from the anodic half-reaction during corrosion of AA2024. Calculated values and experimentally measured local acidification over the aluminum anode (down to pH = 3.65) are presented. The anticorrosion properties of inhibitor-doped HAP were assessed using electrochemical impedance spectroscopy. The microparticles impregnated with the corrosion inhibitors were introduced into a hybrid silica-zirconia sol-gel film, acting as a thin protective coating for AA2024, an alloy used for aeronautical applications. The protective properties of the sol-gel films were improved by the addition of HAP, proving their applicability as submicrometer-sized reservoirs of corrosion inhibitors for active anticorrosion coatings.
