Engine Oils in the Field: A Comprehensive Chemical Assessment of Engine Oil Degradation in a Passenger Car

For the understanding of oil degradation in a combustion engine, in particular zinc dialkyl dithiophosphate (ZDDP) deterioration and its impact on wear expressed as iron content, a field test with a passenger car was carried out, which covered a distance of 19,800 km and represented an entire oil change interval. Condition monitoring of the SAE 5W-30 engine oil used in the turbocharged petrol engine combined the use of conventional and advanced analytical methods. The conventional data collected from the used oils revealed the progress of additives (antioxidants, base reserve, ZDDP), oil degradation products (oxidation, nitration, sulfation, acids), and contaminations (water, soot, wear, fuel dilution). High-resolution mass spectrometry was included to identify ZDDP additive compounds and their fate during the field test as well as their correlation with wear formation. Dialkyl dithiophosphates as the main ZDDP compounds were rapidly degraded and no longer detected after 6000 km. Dialkyl thiophosphate as intermediate ZDDP degradation product was formed and largely depleted within the first 6000 km. Dialkyl phosphates, phosphoric acid, and sulfuric acid as organic and inorganic ZDDP degradation products were generated early and reached high levels at the end of the field test. The presence of intact ZDDP and its degradation products, notably phosphoric and sulfuric acid, correlated with the oil’s iron content. Wear largely remained at low level as long as intact ZDDP was available for tribofilm formation. The lack of ZDDP along with the formation of inorganic acids from ZDDP resulted in an increase in the wear rate by a factor of four.