Improved surface charge and corrosion resistance at the near-nanocrystalline chromium/nano-bilayer oxide interface in advanced thin dense chromium coatings
Ehsan Rahimi, T.J. Nijdam, Adwait Jahagirdar, Esteban Broitman, J.M.C. Mol
Abstract
• Dense near-nanocrystalline TDC coating and bilayer oxide ensure exceptional corrosion resistance in NaCl solution. • XPS reveals vertical differential charging from nonconductive Cr(OH) 3 and especially multiplet splitting of Cr 3+ in the oxide layer. • EIS shows increased charge transfer resistance at the metal/complex oxide interface, reaching 1 MΩ cm 2 . • SKPFM confirms high surface potential and work function on TDC surface, with moderate reductions after NaCl exposure. Chromium coatings, famed for their superior wear and corrosion resistance, are a critical component in countless industrial processes. However, the longevity of these coatings in aggressive corrosive environments continues to be a significant hurdle, even with recent advances in deposition technology and microstructural improvements. An advanced thin dense chromium (TDC) coating, with a near-nanocrystalline structure and unique morphology, naturally forms a non-conductive nano-bilayer oxide. This passive and protective layer effectively moderates electrical charge transfer, offering superior corrosion resistance. X-ray photoelectron spectroscopy (XPS) shows significant Cr 3+ oxide layer formation, distinguished by multiplet splitting, after 7 days in a 0.6 M NaCl solution. The unique characteristics of this non-conductive bilayer oxide structure promote its growth and densification, leading to vertical differential charging in the O1s electron energy region. This effect arises from the enhanced resistivity of the oxide layer. Electrochemical impedance spectroscopy (EIS) confirmed these findings, showing a substantial increase in charge transfer resistance at the chromium metal/bilayer oxide interface, reaching 1.01 MΩ. Scanning Kelvin probe force microscopy (SKPFM) analysis shows that both TDC nodules and their boundaries exhibit high surface potential and work function. However, after exposure to NaCl media, these values are moderately reduced, likely due to diminished electrical surface charge distribution.