Novel Pyridine Oxime-Based Complexing Agents for Enhanced Corrosion Resistance in Zinc–Nickel Alloy Electroplating: Mechanisms and Applications

The novel pyridine oxime-based complexing agents 2-pyridinecarboxaldehyde oxime, 2-acetylpyridine ketoxime and 2-pyridine amidoxime were synthesized for alkaline Zn-Ni alloy electrodeposition, outperforming conventional citrate/TEPA systems in corrosion resistance and microstructural control. The N,O-bidentate chelation mechanism governs metal ion reduction kinetics via diffusion-limited pathways, enabling γ-phase Ni5Zn21 intermetallic formation and nanocrystalline refinement. Electrochemical and microstructural analyses demonstrate suppressed random nucleation and hydrogen evolution side reactions, leading to enhanced charge transfer resistance and reduced corrosion current density. Notably, 2-pyridine amidoxime achieves ultrasmooth surfaces through defect-free nanocluster growth, while 2-pyridinecarboxaldehyde oxime maximizes γ-phase crystallinity. The synergy between grain boundary density and surface integrity establishes a dual protection mechanism combining barrier layer formation and active dissolution suppression. This work advances microstructure engineering via coordination chemistry, offering a breakthrough over traditional zincate electroplating for high-performance anti-corrosion coatings.