The atomic structure of as-prepared Fe_{61}Co_{(14-x)}Zr_{5}W_{x}B_{20} (x=1, 2 and 4) ribbon samples and their thermal stability were investigated by in-situ high-energy X-ray diffraction experiments. It was observed that higher W concentration causes the tiny shift of the main peak of the reduced atomic pair distribution function to higher values of interatomic distances and increases the coefficient of volume thermal expansion. The crystallization process occurs in two steps and is qualitatively the same for all studied specimens. Firstly the Fe_{23}B_{6} phase is created and later is transformed to other types of borides together with the creation of a Fe-based phase.
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