Tribofilms with thickness ranging from 100-200 nm were developed in-situ during wear tests using a zinc dialkyl dithiophosphates (ZDDP) and fluorinated ZDDP (F-ZDDP). The influence of the antioxidant alkylated diphenyl amine on the formation and properties of these tribofilm is examined. Results indicate that the thickness of the tribofilms formed when F-ZDDP is used is always thicker than the tribofilm formed with ZDDP. In addition, in the presence of antioxidants the tribofilm thickness is increased. The hardness of these tribofilms in the absence of the antioxidants is significantly higher at the near surface region (0-30 nm) when compared to the films formed in the presence of antioxidant. Nanoscratch tests conducted to examine the abrasion resistance of the tribofilms also indicate that the tribofilms formed by F-ZDDP are more resistant to scratch compared to films formed by ZDDP. In the presence of antioxidant, tribofilms formed by F-ZDDP are significantly thicker while both films behave in a similar fashion in nanoscratch tests. Transmission electron microscopy of the wear debris formed during the tests were examined and results indicate the nucleation and growth of nanoparticles of Fe3O4 with an approximate size of 5-10 nm embedded within an otherwise amorphous tribofilm.
Environmental regulations have called for a reduction of phosphorus content in engine oils in recent years. The anti-wear additive zinc dialkyl dithiophosphate (ZDDP), which is also an antioxidant, is one of the most important components of engine oil additives. ZDDP is a major source of phosphorus. One way to reduce phosphorus levels is to replace ZDDP with new environmentally friendly antiwear agents that have similar or superior wear performance compared to ZDDP. Another way to address the environmental issue is to reduce the amount of ZDDP in engine oils. At the same time, it is necessary to increase the efficiency of ZDDP by finding optimum conditions that would result in improved antiwear performance. The antiwear mechanism of ZDDP involves its degradation thermally and tribologically, leading to the formation of an antiwear film that consists of polyphosphates and sulphides. The structure of the antiwear film is almost similar in both types of degradation. But the breakdown efficiency of ZDDP is diminished by the parallel reaction of ZDDP with other additives, as well as the antagonistic effects of these additives. The new fluorinated ZDDP complex developed has shown better wear performance compared to ZDDP. This would allow the possibility of further reduction of phosphorus in engine oils compared to current levels. In this paper we study the interaction of ZDDP and fluorinated ZDDP with alkylated diphenylamine. The impact of antioxidant on wear performance was examined using a ballon-cylinder tribometer. The interactions between ZDDP and the fluorinated ZDDP with the antioxidant were studied using NMR and the surface of the tribofilm was examined using SEM, TEM, and Auger spectroscopy.
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