A Study Of The Antiwear Behavior And Oxidation Stability Of Fluorinated Zinc Dialkyl Dithio Phosphate In The Presence Of Antioxidants

The antiwear additive Zinc dialkyl dithio phosphate (ZDDP) is one of the most important components of engine-oil additives and a major source of phosphorus. Phosphorus plays a crucial part in mitigating engine wear, yet has been proven harmful to modern catalytic converters. Progressive regulatory caps on phosphorus content in automotive lubricants have led to widespread efforts to reduce its levels. A new fluorinated ZDDP (F-ZDDP) complex developed at the University of Texas at Arlington has found to breakdown at lower temperatures compared to ZDDP and has showed better wear performance than ZDDP alone. This would allow the possibility of further reduction of phosphorus in engine oils than current levels. This work begins with a study of the interaction of ZDDP and fluorinated ZDDP with the antioxidant alkylated diphenyl amine. The impact of antioxidant on wear performance was examined using a custom-built ball-on-cylinder tribometer. Interactions between ZDDP and fluorinated ZDDP with antioxidant were studied using Fourier transform infrared spectroscopy and nuclear magnetic resonance, and the surface of the tribofilm was examined using scanning electron microscopy, transmission electron microscopy and Auger electron spectroscopy. Nanoscale mechanical properties of in-situ tribofilms generated from ZDDP and F-ZDDP in the presence of alkylated diphenyl amine are compared to films obtained from ZDDP and F-ZDDP without antioxidant. Tribofilms in the thickness regime of 100nm to 200nm are developed in-situ during wear tests using ZDDP and F-ZDDP. The influence of alkylated diphenyl amine on the creation and characteristics of these tribofilms is studied. Nanomechanical properties such as hardness, modulus, scratch resistance and nano-wear resistance of the films thus formed are explored to understand the effect of various variables on the nature of these tribofilms. A focused ion beam is used to image the substrate-tribofilm interface and measure tribofilm thickness. Oxidative stability of oil formulations containing ZDDP and F-ZDDP with various antioxidants is examined through measurements of viscosity and total acid number. Oxidation products formed are identified through Fourier transform infrared spectroscopy. Several of these formulations are subjected to tribological conditions and the nature of the chemical composition of these films is studied using X-Ray near-edge absorption spectroscopy.