Nanoscale Mechanical Properties of In-Situ Tribofilms Generated from ZDDP and F-ZDDP with and without Antioxidants

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.