Ammonia is a prospective zero-carbon-emission fuel for use in large marine diesel engines. Current research focuses on several technical aspects, such as injection strategies or exhaust gas aftertreatment options, but investigations regarding the impact of ammonia on engine oil degradation are largely absent from the literature. This study provides a methodology with which to evaluate this phenomenon via artificial oil alteration. By using an admixture of various contaminations to air, such as ammonia and its partial combustion product nitrogen dioxide, their respective impacts on chemical oil degradation were assessed. Subsequently, the lubricating performance of altered oils was investigated, with a focus on corrosion properties, deposit formation, and load-bearing capability. Although the application of a stoichiometric ammonia–air mixture resulted in less pronounced thermo-oxidative degradation compared to alteration with neat air, static and dynamic deposit formation as well as corrosion properties and load-bearing capability were severely impacted by the presence of ammonia. On the contrary, nitrogen dioxide contamination resulted in higher oxidation and acidification of the oil, but altered samples performed considerably better than ammonia-altered aliquots in terms of coking tendencies, corrosivity, and load bearing.

An innovative and informed methodology for the rational design and testing of anti-knock additives is reported. Interaction of the additives with OH● and HO2● is identified as the key reaction pathway by which non-metallic anti-knock additives are proposed to operate. Based on this mechanism, a set of generic design criteria for anti-knock additives is outlined. It is suggested that these additives should contain a weak X-H bond and form stable radical species after hydrogen atom abstraction. A set of molecular structural, thermodynamic, and kinetic quantities that pertain to the propensity of the additive to inhibit knock by this mechanism are identified and determined for a set of 12 phenolic model compounds. The series of structural analogues was carefully selected such that the physical thermodynamic and kinetic quantities could be systematically varied. The efficacy of these molecules as anti-knock additives was demonstrated through the determination of the research octane number (RON) and the derived cetane number(DCN), measured using an ignition quality tester (IQT), of a RON 95 gasoline treated with 1 mole % of the additive. The use of the IQT allows the anti-knock properties of potential additives to be studied on one tenth of the scale, compared to the analogous RON measurement. Using multiple linear regression, the relationship between DCN/RON and the theoretically determined quantities is studied. The overall methodology reported is proposed as an informed alternative to the non-directed experimental screening approach typically adopted in the development of fuel additives.