Effect of Chain-Length and Countersurface on the Tribochemistry of Bulk Zinc Polyphosphate Glasses

Zinc polyphosphate glasses are considered to be chiefly responsible for the anti-wear efficiency of ZnDTP tribofilms. In this work, the tribochemical properties of amorphous bulk zinc polyphosphates of different chain lengths (ranging from zinc metaphosphate to zinc pyrophosphate) have been investigated. Tribological tests on bulk polyphosphate discs have been carried out using steel and quartz balls as counter-surfaces in a poly-α-olefin (PAO) bath at room temperature. The composition in the wear track and on the contact region of the balls has been monitored by small-area and imaging X-ray photoelectron spectroscopy (i-XPS). The XPS analysis revealed that the composition of short-chain-length polyphosphates remained unchanged following tribological stress. Long-chain-length polyphosphates are depolymerized in the wear track as a consequence of a tribochemical reaction. By comparing the results obtained using quartz and steel balls, it could be observed that while the reaction of iron oxide with the polyphosphates certainly plays a role in the depolymerization of the samples under sliding conditions, pressure and shear stress alone and also in the presence of water or oil-oxidized species are able to depolymerize the glass when an inert material is used as counterpart; the composition of the wear track, in this case, is dependent on the applied load. All samples were able to form an adhesive, glassy transfer film on both steel and quartz balls, but the short-chain-length polyphosphates showed a lower friction coefficient and wear coefficient. The results suggest a third-body mechanism with the polyphosphates acting as a solid lubricant. Differences in tribological behavior of the different-chain-length polyphosphates are attributable to their mechanical and rheological properties.