AbstractIn 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.