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Recently, with the increasing interest on some potential alternative substitutes of petroleum fuels such as biodiesel and butanol, more and more researches are focused on the field of bio-fuels because they are renewable and friendly to the environment and can possibly reduce domestic demand on foreign petroleum. Bio-fuels are generally used in the commercial market by mixing with petroleum-based diesel or gasoline. Since the volatilities and boiling points of ethanol/butanol and diesel/biodiesel fuels are significantly different, micro-explosion can be expected in the blend mixture. In this study, a numerical model of micro-explosion including bubble generation, bubble expansion, and final breakup for multi-component bio-fuel droplets is proposed. From the simulated results of droplet characteristics at the onset of micro-explosion, it is concluded that micro-explosion is possible under engine operation condition for ethanol/butanol-diesel/biodiesel fuel blends.