Engine oil is mainly comprised of
base oils and various additives,
which are low molecular weight polymers mixed into the oil resulting
in a polymer blend. Dispersants and detergents, the two most abundant
additives, are intended to keep the engine free of particulate but
are not always successful. At high temperatures, species not combusted
may undergo oxidation and degradation or create other byproducts,
generating particulate deposition. Knowledge of the molecular makeup
of these byproducts is essential, as particulate accumulation can
cause serious issues to the engine and ultimately to the operator.
In this study, unknown deposits from the air-intake valve of a vehicular
engine have been analyzed via a palette of mass spectrometry (MS)
methods, including matrix-assisted laser desorption/ionization MS
with postacquisition data processing, atmospheric solids analysis
probe MS, and electrospray ionization MS interfaced with 2D separation
via reversed-phase liquid chromatography and ion mobility spectrometry.
Low molecular weight, aminated poly(propylene glycol) and polyisobutylene
detergents and a poly(methyl methacrylate) viscosity modifier were
conclusively identified in the deposit, along with oxidized polyethylene
chains leaked into the oil/additives blend from vehicular tubing and
tanks. The use of different methods was essential for the confident
elucidation of the low molecular weight macromolecules giving rise
to the vehicular engine particulates.