Porous 3D Cu layers with the following average parameters: thickness ~35 µm, pore density ~4.0 × 106 cm−2, and pore sizes ~25 µm were electrodeposited from an acidic sulphate electrolyte, and the suitability of different electrochemically active surface area determination methods for characterising these electrodes was assessed. Structural characterisation of the samples was conducted using SEM and an optical profiler, while electrochemical measurements were performed using cyclic voltammetry and electrochemical impedance spectroscopy. The evaluation of electrochemically active surface area involved the underpotential deposition of Tl and Pb monolayers as well as double-layer capacitance measurements. The results obtained indicate that both methods yield similar results for non-porous Cu electrodes. However, for Cu 3D nanostructures, the evaluation mode significantly influences the results. Double-layer capacitance measurements show significantly higher values for the electrochemically active surface area compared to the underpotential deposition (UPD) technique. The complex spatial structure of the Cu 3D layer hinders the formation of a continuous monolayer during the UPD process, which is the principal reason for the observed differences.
Environmentally friendly alternatives to chromium—phosphate/molybdate and cerium-modified phosphate/molybdate conversion coatings—were deposited on a carbon steel surface. Different surface analytic techniques were applied to obtain complementary information on the composition, element distribution morphology and inner structure of the coatings in order to establish the relationship between coating properties and corrosion performance. The higher protective and stronger self-healing abilities were found for phosphate/molybdate/cerium conversion coating deposited in a sulphate-containing solution. The protective barrier strength was found to be related with certain aspects of the coating morphology such like homogeneous distribution of fine crystallites and, hence, lower number of structural defects. The self-healing ability depended on both, the composition (higher amount of Ce(IV)) and micro-structural characteristics, such as defectiveness, of the conversion layer.