Time-Dependent Film Formation from ZnDTPs and Nonphosphorus Antiwear Agents

Electrical contact resistance (ECR) studies, X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and X-ray absorption near-edge structure spectroscopy (XANES) were carried out on specimens run with oils containing 0.05% phosphorus as either primary zinc dialkyldithio-phosphate (ZnDTP) or secondary ZnDTP in Group II base oil. A series of progressively longer ECR experiments were run on each ZnDTP. At the end of each run in the series, the ball was removed and preserved for surface analysis. The surface analyses were designed to observe chemical species deposited on the surface and within the deposited films. The observation of surface phenomena at different intervening times during the ECR experiment, allowing for characterization of the maturing antiwear film, was the distinct feature of these experiments. In general, short ECR experiments gave poorer films than long ECR experiments. Atomic concentrations versus depth were determined from AES. Quite strikingly, the antiwear films formed after only 10 min of the ECR experiment showed that both primary and secondary ZnDTPs form a thin film (∼70 Å) very rapidly. Those films are rich in Zn, P, and S. Auger and XANES analyses of the same specimens were not as revealing, most likely due to the small wear scar on the balls and the unfortunately relatively large beam cross section. ECR, XPS, and AES were then performed on oils containing nonphosphorus antiwear agents in American Petroleum Institute Group II base oil. Several nonphosphorus supplemental antiwear inhibitors were evaluated. These experiments showed separation in apparent performance among the various components.

Keywords: Lubricants, Friction, Wear, Antiwear Agents, Bench Testing, Electrical Contact Resistance, Surface Analysis, XPS, XANES