Formation mechanisms and characterization of black and white cobalt electrodeposition onto stainless steel

Cobalt electrodeposition onto a stainless steel substrate from 1.17 M Co(II) aqueous solution containing 0.98 M H2SO4, 0.56 M KCl, and 0.2 M H3BO3 was evaluated in the absence ii) and presence iii) of 0.1 M KNO3. Cobalt electrodeposited from the electrolytic bath (i) was white-gray colored, whereas deposition from bath (ii) formed a black-colored surface. SEM-WDX, AFM, and XRD analysis of the steel surfaces covered with these two deposits revealed distinct characteristics for black and white cobalt films. Although both deposits were composed of metallic cobalt, the white cobalt deposit was a smooth, 2D film while the black deposit consisted of many dispersed, nano-sized clusters of 150 to 250 nm in diameter. Analysis of potentiostatic current transients (I-t curves) indicated that formation of white cobalt was carried our by multiple 3D nucleation limited by lattice incorporation of cobalt adatoms to the growth centers. Formation of black cobalt was shown to involve the simultaneous processes of 3D nucleus formation and growth, limited by mass transfer, and the reduction of nitrates in the medium onto the surfaces of these nuclei. It is shown that, beside this cobalt-nitrate interaction, NO3- ions in solution can block active sites for cobalt reduction and the effect of this phenomenon strongly depends on the nitrate concentration. These facts could explain the observed dispersion of the black cobalt coating. (C) 2000 The Electrochemical Society. S0013-4651(99)05-090-9. All rights reserved.