Structural Changes in Tribo-Stressed Zinc Polyphosphates

The influences of pressure, shear stress and temperature on the structure of zinc orthophosphate and zinc metaphosphate was investigated. Tribological tests were performed to study the combined effect of pressure and shear stress at two temperatures. Friction tests were carried out in the boundary lubrication regime from dispersions of zinc polyphosphates in base oil. The effects of pressure alone were investigated using a diamond anvil cell in order to separate it from those of shearing. Raman spectroscopy was used to follow in situ or ex situ the structural changes of the zinc polyphosphate powders and the tribo-stressed areas. Tribofilms obtained with both polyphosphates display a partial and full depolymerization of the zinc metaphosphate at ambient and high (120 °C) temperature, respectively. The large stress and strain conditions of the tribological tests are necessary to induce a tribochemical reaction between zinc metaphosphate and iron oxide leading to a depolymerization of the phosphate in the tribofilm. The tribochemical reaction and antiwear tribofilm formation are significantly enhanced by the modest temperature increase from ambient to 120 °C. Pressure alone induces only disordering in the structure of zinc polyphosphates, with only minor changes of the chain length in phosphates and does not contribute significantly to the observed structural changes in tribofilms.