Materials surface heterogeneities obviously plays a crucial role in reactivity issues and generate various types of detrimental localized corrosion attacks. In corrosion science, a first question to be addressed is how these various materials microstructure affect oxidation / passivation and localized corrosion initiation mechanisms. A methodology for microscale characterization of initial stage of surface reactions has been developed based on the Atomic Force Microscopy (AFM) Scanning Kelvin Probe Force Microscopy (AFM-SKPFM). In very early work, potential mapping with micrometer lateral resolution (lateral detection limit of materials surface heterogeneities is better but the signal has to be deconvoluted) allowed to clearly identify "cathodic" and anodic sites on Al- alloys [1]. Careful potential calibration and surface conditioning with solution exposure generating the formation of an electrochemical double layer allow obtaining local thermodynamic information closely linked to "practical electrochemical potential series" measured in bulk solution conditions. This contribution will start by revisiting some "historical" examples of AFM-SKPFM characterization (a tribute to Jerry Frankel's activities) of aluminum and magnesium alloys [1,2]. These materials surfaces will further be used to show how reaction kinetic information on corrosion processes can be obtained with similar lateral resolution by means of the newly developed Scanning Electrochemical Nanocapillary (SEN) technique. After introducing the SEN technique and methodology, the presentation will focus on showing how the combination of these two approaches allows refining the local corrosion mechanism assessment of heterogeneous materials. The SEN technique is very versatile and allows various types of electrochemical measurements to be performed with constant tracking of the topography. The technique is based on a nanocapillary glass tip (< 100 nm) excited laterally by a piezoelectric element. A control of the capillary vibration damping when approaching the surface and a feedback loop (like the tapping mode in AFM) allows a very precise control of the approach and electrolyte contact on the surface. The glass capillary filled with the electrolyte of interest integrates a reference and Pt counter electrodes to perform electrochemical measurements exposing only the area of interest to aggressive electrolytes. Using its "hopping" mode (a scan with electrochemical characterization of successive individual nanoscale areas), corrosion initiation susceptibility can be addressed. This will be illustrated through the surface reactivity study of model Al-Cu-Mg microscale intermetallics and Mg-based alloys, using SEN OCP linescans. In addition information about extend of the attack can be subsequently retrieved from SEM observations. Using the precise positioning ability of the SEN setup with X, Y and Z direction piezos, potentiodynamic polarization measurements can furthermore be performed on selected area of interest. The example of an Mg-Fe composite material will be used to discuss its local electrochemical behavior.

After the presentation of the SEN characterization results, additional aspects of the measured potential by AFM-SKPFM will also be discussed as adsorbed species, especially strong dipolar molecules, can significantly contribute to the measured signal [3]. Modification of the AFM-SKPFM setup towards atmospheric corrosion investigation will finally be presented. This environmental AFM/SKPFM bridges the gap between the full electrochemical local characterizations that can be offered by the SEN technique and an "electrochemical reaction" diagnostic obtained by SKPFM in thin water layer. The example of a very reactive WC-Co composite will be presented to demonstrate the reactivity issue, galvanic coupling controlling local dissolution processes [4].

Acknowledgements

Gerald Frankel for the great time I spent at Ohio State University in the Fontana Corrosion Center developing the AFM-based SKPFM methodology. Empa for internal project financial support of the SEN instrument.

References

[1] P. Schmutz, G.S. Frankel, J. Electrochem. Soc., 145(7) (1998), 2285-2295

[2] P. Schmutz, V. Guillaumin, S. Lillard, J. Lillard, G.S Frankel, J. Electrochem. Soc., 150(4) (2003), B99-110 (2003)

[3] A. Vetushka, L. Bernard, O. Guseva,, Z. Bastl, J. Plocek, I. Tomandl, A. Fejfar, T. Baše, P. Schmutz, Physica Status Solidi (B) Basic Research, 253(3) (2016), 591-600

[4] S. Hochstrasser(-Kurz), C. Latkoczy, D. Günther, S. Virtanen, P.J. Uggowitzer, P. Schmutz, J. Electrochem. Soc., 155(8) (2008), C415-C426