ZDDP Tribofilm Formation and Removal

While ZDDP tribofilm formation has been widely studied, the mechanism of ZDDP tribofilm removal during rubbing is still unclear. The study employs a ball on disc tribometer to monitor ZDDP tribofilm development in rolling-sliding, mixed lubrication conditions. It is found that when ZDDP tribofilms are formed very rapidly, as is the case with short alkyl chain, secondary ZDDPs, a large proportion of the initially-formed tribofilm is suddenly lost during rubbing. By contrast, the tribofilms that form more slowly from primary ZDDPs and longer chain secondaries are not partially lost during rubbing. XPS analysis showed that a rapidly-formed tribofilm before its partial removal has a very small Zn/O ratio, and a high BO/NBO. This suggests that such tribofilm contains a significant proportion of ultraphosphate, which is likely to have a relatively weak structure due to lack of stabilising cations. This may result in the tribofilm being partially removed when it reaches a certain thickness. By comparison, the remaining tribofilm, and also tribofilms that form slowly, have high Zn/O and low BO/NBO. This suggests that they consist of short chain polyphosphates and are thus stronger and more durable.