Sulphur-phosphous components in gear oils: part 1, oxidation stability studies by 31P-NMR spectroscopic techniques

In the present investigations, the mechanism of oxidation stability of sulphur and phosphorus-based additives such as S-alkyl O,O-dialkyl phosphorodithioate, alkyl amine salt of dialkyl dithiophosphoric acid, dialkyl hydrogen phosphite and zinc dialkyl dithiophosphate used in lubricants has been studied by liquid and solid state 31P/lH-NMR spectroscopic techniques. These techniques have enabled to monitor the complex changes that occur during oxidation at different intervals during long duration oxidation tests and provide qualitative and quantitative information of products formed during degradation of S–P based additives. The nature of both soluble and insoluble products of decomposition has been /determined. The studies have revealed few important aspects regarding thermal stability of these additives. The ashless S-alkyl O,O-dialkyl phosphorodithioate have better thermal oxidative stability and retain their identity for longer period compared to other similar ashless additives and zinc dialkyl dithiophosphates. The loss of additives during oxidation is 12% in case of S-alkyl O,O-dialkyl phosphorodithioate compared to other mentioned additives (40–100%) during 64 h of heating at 165 °C in the presence of air and catalyst. The decomposed products are also solublised in case of S-alkyl O,O - dialkyl phosphorodithioate and dialkyl hydrogen phosphite, and small amount of solids are formed compared to other additives. During oxidation the main components are being converted into more complex insoluble polyphosphates. The nature of soluble and insoluble products of decomposition as a result of thermal degradation are similar irrespective of the types of additive used. The mechanism of degradation and subsequent composition and structure of products formed has been discussed in detail. These studies will facilitate correlation of the structure and performance of these additives in lubricants.