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Mechanical activation was used to improve the extraction of chromium in molten NaOH. It is observed that the extraction ratio reaches 97% after leaching for 200 min when chromite ore is mechanically activated for 10 min, but only 34% if not activated. Mechanical activation can decrease the particle size, increase the surface area, and enhance the lattice distortion. Further, the mechanisms for mechanical activation were exposed. The results show that the mechanical activation mainly focuses on chromite ore particle size decrease and the lattice distortion. The formation of aggregation weakens the strengthening effect of mechanical activation for releasing high surface energy.