Structure and Mössbauer spectra for the Fe–Cr system: From bulk alloy to nanoparticles

Abstract

The structure and hyperfine fields of ${\mathrm{Fe}}_{\text{1−x}}{\mathrm{Cr}}_x$ $\text{(x=0.0236–0.803)}$ nanoparticles (average size of 27±2 nm) are studied at room temperature by combined x-ray diffraction and Mössbauer spectroscopy techniques. They are produced by fast evaporation of bulk alloys at 3 Torr Ar pressure. The bulk alloys of any composition are shown to exhibit a bcc structure, whereas the nanoparticles demonstrate a mixture of bcc and tetragonal σ phases in the Cr range from 24.4 to 83.03 at. %. At the Cr content of 2.36 at. % the lattice constant for nanoparticles is larger than that of the bulk alloy, though the values of hyperfine fields on Fe nuclei do not differ. The Mössbauer spectrum of nanoparticles contains an oxide doublet in addition to the sextet specific to that of the bulk alloy. In both cases the width of the sextet lines is rather narrow. However, even at ∼8 at. % Cr the lines of the sextet are broadened so much that it can be decomposed by two-three components. This is explained by freezing the high-temperature ferromagnetic fcc phase regions in the bcc lattice. As the Cr content increases, the Mössbauer spectra become more complex, transforming finally into a paramagnetic singlet. A complete ferromagnetic→paramagnetic transition is observed for the bulk alloy at 68 at. % Cr and for nanoparticles at 35 at. % Cr. The results are discussed under the assumption that at high temperatures the alloys are not homogeneous and exhibit fluctuations of the composition. With decrease of temperature these fluctuations result in decomposition of the alloy into two phases for nanoparticles whereas they are frozen at the cluster level in the bulk alloys holding a macroscopic homogeneity.