In rapidly solidified eutectic Nb-Al alloys a change in morphology fro
m a lamellar microstructure to a globular anomalous eutectic one has b
een observed. This behavior results from the decomposition of an inter
mediate metastable tetragonal sigma-Nb2Al phase. By means of TEM, ele
ctron diffraction and EDXS this metastable phase was characterized and
the solidification behavior via different transition steps of the met
astable sigma-Nb2Al was elucidated.