Oxidative processes in power plant oils

This paper analyzes the chemical properties differences between thermal-oxidation and radioactive-oxidation in turbine oils in order to estimate the oils' Service Life. The oils were Turbine R type, provided by Repsol-YPF with only few additives such as: anti rust, antioxidant, anticorrosion and without viscosity index improvers. The oils were ISO 32 and ISO 68 grade -with viscosity index 95- and API (American Petroleum Institute) group I, due to its viscosity index (95), the percent of paraffinic component (<89%) and the sulphur content(>0.03%). Different samples from the heavy water main pumps were collected with different service times and radiation fields during an Embalse NPP's outage. For comparison purposes oils from feedwater pumps systems that convey light water to the steam generators in the Turbine building -without radiation- were obtained. The properties studied by ASTM standards were: colour (visual inspection), Viscosity Index VI (ASTM D227/93), viscosity at 40 C degrees (ASTM D445/96) and Total Acid Number, TAN (ASTM D974-97). Oxidative degradation of base oils could be described by two successive mechanisms that allow the definition of two stages: Primary and Secondary Oxidation. Primary oxidation begins with the thermal generation of alkylation's reactions and acid products formation. Radiation damage operates by two mechanisms: scission and cross-linking. The first one generates free radicals of low molecular weight while the other one can build-up complex molecular networks with high or low solubility in the base oil. Moreover, radiation damage destroys additives molecules and generates colour centres different from oxidative colour modification. Due to scission and cross-linking alkyl group substitution in the aromatic rings are formed. Then, radiation acts as a precursor of Primary Oxidation. Both, thermal and radioactive, damage mechanisms can act simultaneously making the isolated analysis for each one very difficult. To manage it, a Relative Damage Index (RDI) has been defined as a function of VI and TAN variation. The Viscosity, TAN and VI variations were represented in terms of RDI's increasing change that is more or less coincident with the colour change. The FTIR method was utilized to identify chemical reactions that can be attributed to different picks of the spectrum. In comparison with the FTIR spectra of new oil, the variation of characteristic peaks' height can be related between them as the production and disappearance of molecules and can give also account of: depletion of additives, generation of alkylbenzenes, organic acids, and high molecular weight products. Moreover, a relationship between FTIR results and Viscosity and TAN has been asset. (author)