In this work we present the pulsed current (PC) electrodeposition of Sn-Cu-Ni alloy as lead-free solder candidate, from choline chloride – ethylene glycol eutectic mixtures (1:2 molar ratio) onto copper metallic substrates. Electrolytes containing Sn²⁺, Cu²⁺ and Ni²⁺ salts in the selected deep eutectic solvent have been considered. The effect of the applied frequency of PC on the morphology, composition and melting point of the alloy is discussed and compared to the ones obtained using direct current (DC) plating mode. A refinement of the grain size and lower melting temperature of the alloy were noticed when pulsed current was applied. A comparative analysis of the electrochemical corrosion behaviour at macro- and micro- scale has been performed in 0.5 M and 0.1 M NaCl solutions involving potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode (SVET) techniques. Furthermore, an analysis after 96 h of exposure to salt mist test simulating a corrosive attack in harsh environment is presented, too. The obtained results showed enhanced corrosion resistance of the ternary alloys electrodeposited under PC conditions (the best for 1.67 Hz frequency) as compared to those using DC. Additionally, Raman spectroscopy evidenced the presence of tin oxi/hydroxy chloride and tin oxides as surface corrosion products. A corrosion mechanism has been proposed.

A detailed microstructural and electrochemical analysis of electroless nickel phosphorous (NiP) coatings with P contents of 13.2 ± 1.2 wt%, 12.9 ± 0.7 wt%, and 8.3 ± 0.8 wt% on a copper substrate was performed to study the corrosion behaviour of electroless NiP/Cu systems. The P content of the electroless NiP coatings plays an essential role in the microstructure of the coatings in terms of crystallinity. The crystallinity variations, representing the extent of crystalline and amorphous phases within the material, with P content, affect the local electrochemical characteristics and, hence, the corrosion protection behaviour of electroless NiP coatings. The coatings with the highest P content showed the best corrosion performance in a 3.5 wt-% NaCl solution. In contrast, the surface of the electroless NiP coatings with low P content is more susceptible to corrosion due to the presence of locations with heterogeneous electronic properties that initiate localised corrosion. Microgalvanic interactions with a high cathode-to-anode surface ratio govern the localised corrosion kinetics of the low P-content samples. A high concentration of nodule boundaries and/or other existing structural defects on the surface serve as anodic sites, whereas the remainder of the surface serves as cathodic sites.

Electroless nickel (Ni) immersion gold (Au), commonly referred to by the acronym ENIG, is the most common protective coating applied on the exposed copper (Cu) traces of printed circuit boards (PCBs). In this work, we elucidate the local corrosion mechanism of the ENIG-Cu system by applying microscopic, surface analysis and electrochemical techniques with high spatial resolution to provide a comprehensive understanding of the complex local corrosion mechanism of the ENIG-Cu system. The corrosion initiation is highly localised and associated with pores or micro-defects in the Au layer. The corrosion initiates by the dissolution of the underlying Ni layer, being less noble than Au. The dissolution propagates in lateral and perpendicular directions relative to the surface in an elliptical fashion. With time, the direction of corrosion propagation changes to a predominantly lateral attack of the Ni layer. The corrosion process is governed by the cathode/anode ratio of the Au/Ni galvanic couple.