Journal of the Electrochemical Society, Vol.146, No.7, 2598-2605, 1999
Electrochemical studies of the automotive lubricant additive zinc n-dibutyldithiophosphate
Zinc dialkyldithiophosphates (ZDTPs) are widely incorporated in lubricant formulations as antioxidant and antiwear additives. Using the model compound zinc n-dibutyldithiophosphate (Bu-ZDTP) in dimethylformamide (DMF) solution, cyclic voltammetry is applied to a detailed study of Bu-ZDTP electro-oxidation. Bu-ZDTP is shown to be oxidized in a chemically irreversible electron transfer process under diffusion-limited conditions. A similar study of Bu-ZDTP reduction revealed nucleation of zinc at the electrode surface. A chronoamperometric investigation of zinc deposition classified the nucleation according to a progressive mechanism with the diffusion coefficient for Bu-ZDTP in DMF solution as 6.5 x 10(-6) cm(2) s(-1). By comparison with diffusion coefficients obtained via Levich analysis of Bu-ZDTP oxidation, the oxidation process is assigned as a two-electron transfer. The use of atomic force microscopy as a means of directly visualizing zinc nuclei formed as a result of Bu-ZDTP reduction is described.