Physical chemistry of reactive ball milling

Reactive ball milling has been proposed as a new route for producing carbides from oxides through carbothermic reduction. It is claimed that through milling oxide and graphite powders to the nanoscale, amorphous materials with very high reactivity are formed, that allows for easy transformation of the starting material to another in a subsequent thermal process. Thermodynamic analysis of this proposed process suggests that unless particle sizes are reduced to below 10nm, then reduction in size alone cannot explain a change in the stability of oxides. Even with nanometer scale powders, the products formed need to have a lower total surface energy than the reactants before a chemical change will occur. A model developed by Bhattacharya and Arzt for predicting localized temperature changes based on milling conditions suggest that temperature rises less than 400 K will be achieved in laboratory conditions. The present calculations suggest that nanometer scale powders formed through high speed ball milling (>10 m/s) may have undergone a process analogous to melting and quenching. Further work is required to fully distinguish these features.