LOCAL PARAMETERS OF THE SURFACE ROUGHNESS OF ELECTROCHEMICALLY DEALLOYED Ag-Pd ALLOYS
Abstract
Local characteristics of surface roughness of the polycrystalline Ag-Pd solid solutions (4 and 8 at. % Pd) which underwent potentiostatic electrochemical dealloying in an acidic nitrate aqueous solution were determined by scanning electron and atomic force microscopy. A qualitative analysis of the SEM and AFM micrographs demonstrated substantial morphological roughening of the surface of Ag-Pd alloys. This results from the formation of hollows and cracks caused by selective leaching of electronegative silver and recrystallization of electropositive palladium into its highly-developed phase. A quantitative analysis of the AFM-data allowed us to determine the numerical values of the main local roughness characteristics of anodically modified alloys. The negative value of the coefficient of surface asymmetry indicates the formation of deep cavities during the dealloying process. The recorded mean roughness generally depends on the AFM-scanning zone, but it stabilizes if the scan zone exceeds several tens of micrometers. The roughness of dealloyed Ag-Pd systems is of micro- and nano-size and increases with anodic potential and electric charge of the electrochemical modification of both studied Ag4Pd and Ag8Pd alloys. This effect can be accounted for by a significant rise in the anodic dissolution rate of silver from the alloys in the overcritical region of polarization, resulting in the formation of deeper surface defects. An increase in the average height of surface irregularities with modification time conforms to the square root law, confirming the non-stationary mass transfer kinetics of the selective dissolution process. Variation of the anodic potential and electric charge makes it possible to find the optimal conditions for the electrochemical synthesis of electrode Ag-Pd materials with given values of arithmetic mean and root-mean-square roughness. The assumption that harmonic sinusoidal function represents the Ag-Pd surface microprofile proved the linear dependence of the roughness factor on dealloying time.
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