During their service, engine oils suffer from various influencing parameters such as thermo-oxidative stress and nitration, hence, the accumulation of degradation products and the entry of contaminants. Accordingly, ICEs need to be able to operate satisfactorily, especially with a degraded lubricant, making it highly recommendable to use such oils for component testing in ICE development. Thus, a new nitrative thermo-oxidative ageing method is presented for closer-to-reality simulation of engine oil alteration with the intention to provide reproducibly aged oils for subsequent bench testing. With this method, a target used oil from field application was replicated and the comparability of oil condition in the lab vs. field regarding oxidation, nitration, additive depletion, and acidification amongst others was verified by conventional and advanced analyses. Special focus was laid on the identification of nitration products, proving them to be predominantly oxidized aromatic species or organophosphates. The presented method gives valuable benefit for the closer-to-reality ageing of engine oils in reasonable time frames with moderate costs and, hence, for the provision of test oils for ICE bench testing enabling rapid engine component assessment.

Engine oil degradation and tribological properties are strongly interrelated. Hence, understanding the chemical processes resulting in additive depletion and degradation products is necessary. In this study, in-service engine oils from petrol and diesel vehicles were analyzed with conventional and advanced methods (mass spectrometry). Additionally, the effect of the utilization profile (short- vs. long-range) was studied. Petrol engine oils generally showed accelerated antioxidant and antiwear degradation and higher oxidation, especially in the case of a short-range utilization profile, which can be attributed to the higher air-to-fuel ratio (more rich combustion) compared to diesel engines. A detailed overview of oxidation and nitration products, as well as degradation products resulting from zinc dialkyl dithiophosphate and boron ester antiwear additives, diphenylamine antioxidants and salicylate detergents is given. A side reaction between oxidation products (aromatic carboxylic acids) and the boron ester antiwear is highlighted. This reaction was only detected in the petrol engine oils, where the oxidation products were measured in a high abundance. However, no side reaction was found in the samples from the diesel vehicles, since there the aromatic carboxylic acids were largely absent due to lower oxidation.

In the study at hand, a systemic investigation regarding the tribochemical effects of crankcase soot is presented. Sooted oils were generated via an engine dynamometer test. Both conventional as well as advanced oil condition monitoring methods indicated a mild degradation of additives. The wear volume was greatly increased with the sooted oils in model tribometer tests, despite the high residual zinc dialkyl dithiophosphate (ZDDP) antiwear (AW) levels. Once the soot was removed via ultracentrifugation, the wear volume returned to levels comparable to the fresh oil. Surface investigations revealed that ZDDP tribofilms could not form in the sooted oils, as only a thin sulfide layer was present on the metal surfaces. Meanwhile, typical tribofilms were observable with centrifuged oils. The results indicated that a tribocorrosive mechanism is most likely responsible for the elevated wear in the sooted oils, where only the iron sulfide base layer of ZDDP films is formed, which is then rapidly removed by the soot particles in an abrasive manner.

In the study at hand a systemic investigation regarding the tribochemical effects of crankcase soot is presented. Sooted oils were generated via an engine dynamometer test. Both conventional as well as advanced oil condition monitoring methods indicated a mild degradation of additives. The wear volume was greatly increased with the sooted oils in model tribometer tests, despite the high residual zinc dialkyl dithiophosphate (ZDDP) antiwear (AW) levels. Once the soot was removed via ultracentrifugation, the wear volume returned to levels comparable to the fresh oil. Surface investigations revealed that ZDDP tribofilms could not form in the sooted oils, as only a thin sulfide layer was present on the metal surfaces. Meanwhile, typical tribofilms were observable with centrifuged oils. The results indicated that a tribocorrosive mechanism is most likely responsible for the elevated wear in the sooted oils, where only the iron sulfide base layer of ZDDP films is formed, which then is rapidly removed by the soot particles in an abrasive manner.

Engine oil degradation and tribological properties are strongly interrelated. Hence, understanding the chemical processes resulting in additive depletion and degradation products is necessary. In this study, in-service engine oils from petrol and diesel vehicles were analyzed with conventional and advanced methods (mass spectrometry). Additionally, the effect of the utilization profile (short- vs. long-range) was studied. Petrol engine oils generally showed accelerated antioxidant and antiwear degradation and higher oxidation, especially in case of a short-range utilization profile, which can be attributed to the higher air-to-fuel ratio (more rich combustion) compared to diesel engines. A detailed overview of oxidation and nitration products, as well as degradation products resulting from zinc dialkyl dithiophosphate and boron ester antiwear additives, diphenylamine antioxidants and salicylate detergents is given. A side-reaction between oxidation products (aromatic carboxylic acids) and the boron ester antiwear is highlighted. This reaction was only detected in the petrol engine oils, where the oxidation products were measured in a high abundance. However, no side reaction was found in the samples from the diesel vehicle, since there the aromatic carboxylic acids were largely absent due to lower oxidation.