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With the current use of bio-renewable fuel, the application of Ethanol in Flex-Fuel vehicles presents a very low CO2 emission alternative when the complete cycle, from plantation, fuel production, till vehicle use, is considered. In Brazil more than 80% of the car production is composed of Flex-Fuel vehicles. Due to the lower heating content of the Ethanol, more aggressive combustion calibrations are used to obtain the same engine power than when burning gasoline. Such Ethanol demands, associated with the continuous increase of engine specific power has lead to thermo-mechanical loads which challenges the tribology of piston rings. The ethanol use brings also some specific tribological differences not very well understood like fuel dilution in the lube oil, especially on cold start, corrosive environment etc. Under specific driving conditions, incipient failures like spalling on nitrided steel top rings have been observed.