XAFS has been used to investigate the local structure evolutions of ultrafi
ne amorphous NiB alloy during the annealed crystallization process. A nanoc
rystalline Ni phase with the local structure of crystalline Ni-like and a c
rystalline Ni3B, have been produced for ultrafine amorphous NiB alloy under
the annealed temperature of 573 K. The results rule out Rojo et al.'s devi
trification mechanism of Ni80B20 amorphous alloy in which they considered t
hat an amorphous pure Ni phase is formed in the first exothermic process. H
owever, our results are almost identical with Riveiro et al.'s conclusion i
n which the intermediate state is interpreted as two metastable crystalline
phases of Ni3B and Ni-rich NiB alloy. With the annealed temperature going
onto 773 K, the ultrafine NiB sample is further decomposed and crystallized
into crystalline Ni with long-range order.