The ordered structure, dislocation, and grain boundary character distribution (GBCD) in warm‐rolled Fe–6.9Si–0.01B alloy are characterized, and their effects on plastic deformation are investigated. The study reveals that some {110} recrystallized grains preferentially formed at {111} shear bands as the main nucleation sites at lower rolling temperature, whereas more {111} recrystallized grains occur at 680 °C rolling temperature. The content and size of B2 ordered phases increase with increasing deformation temperatures, meanwhile majority of superdislocations are changed into single dislocations, relieving the stress through cross‐slip. The plastic deformability of Fe–6.9Si–0.01B alloy improves by increasing deformation temperature is attributed to a contribution combining decrease in order degree and recrystallization softening with optimization of GBCD.
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