Thermal and spectroscopic analysis of worn polyoxymethylene surfaces and wear debris explaining degradation and polymerisation mechanisms

Degradation and polymerization of polyoxymethylene homopolymer (POM-H) surfaces after sliding at 8 to 150 MPa and 0.005 m/s over a total sliding distance of 3000 m is investigated by using thermal analysis (DSC, TGA, DTA) and Raman spectroscopy of worn surfaces or wear debris. There is mainly mechanical interaction and slight softening at 8 MPa (relatively high friction, low wear), softening at 16 to 55 MPa (decreasing friction and high wear) and finally melting at 150 MPa (very low friction, overload wear). At low contact pressures, wear debris remains amorphous and degradation of noncrystallised material during sliding manifests in broadening of the melting peak below the melting temperature. Degradation of C–O–C due to chain scission and radical reactions into CH₃ end groups are illustrated by Raman spectra. It is confirmed that the debris has long resident times and the maximum polymer surface temperature (T* = 93°C) is below the crystallisation temperature. At intermediate contact pressures, crystallisation results in a polymer fraction with higher thermal resistance. From the calculated temperatures T* = 120 to 150°C, crystallisation is beneficial for coherent transfer with larger particle sizes. At high contact pressures, the wear debris is immediately removed from the contact interface due to melting (T* = 200°C) and has thermal properties similar to the bulk material. There is no reaction between the debris in the interface, resulting in a thick polymer transfer film.