The crystallization behaviour of amorphous Fe93-xZr7Bx ( x = 3, 6, 12 at.%) alloys, the microstructures of the primary crystallization products of stable and metastable phases and the subsequent transformations, have been studied using a combination of differential scanning calorimetry, differential thermal analysis, X-ray diffraction and transmission electron microscopy, including microdiffraction. It has been found that, for x = 3 and 6 at.%, the sole product of primary crystallization is the bcc alpha-Fe phase and the average grain sizes of the crystalline phase were 14 nm and 12 nm for the two alloys, respectively. However, when x = 12 at.%, primary crystallization results in more than one crystalline phase, and a metastable phase with the cubic "Fe12Si2ZrB" structure is the major crystallization product after the primary crystallization reaction, accompanied by the alpha-Fe phase. The average grain size of this metastable phase was 35 nm for the alloy heated to 883 K at 20 K/min. Isothermal heat treatments at 873 K and 973 K confirm that after being heated for 240 h, this metastable phase transforms into equilibrium phases: bcc alpha-Fe, hcp ZrB2 and probably hcp Fe2Zr. The apparent activation energies for the primary crystallization reaction during continuous heating for these three alloys are 4.4 +/- 0.2 eV, 3.5 +/- 0.2 eV and 6.9 +/- 0.3 eV, respectively. (C) 2003 Kluwer Academic Publishers.