A set of Fe-based amorphous alloys, ${\mathrm{Fe}}_{\text{93−x−y}}{\mathrm{Zr}}_{\mathrm{7}}{\mathrm{B}}_x{\mathrm{Cu}}_y,$ with $\text{x=4,}$ 6, 8, or 12, and $\text{y=0}$ or 2 has been systematically characterized in their ability to form nanocrystalline, magnetically soft material via annealing in the range of 430–600 °C. Conventional Mössbauer spectroscopy is used to follow the degree of bcc-Fe formation as well as changes in the hyperfine field distribution of the amorphous phase as a function of anneal temperature. Copper plays a strong role in the bcc-Fe formation for $\text{x=12}$ but less of a role for $\text{x=8}$ and 6. Unconventional Mössbauer studies utilizing radio frequency (rf) fields provide information on the soft magnetic nature of the alloys by observing the degree of rf-induced collapse of the hyperfine fields. The Mössbauer experiment in which the rf collapse and rf sideband effects are used allows the soft nanocrystalline bcc phase to be distinguished from magnetically harder microcrystalline α-Fe. The rf Mössbauer technique, being particularly sensitive to the magnetic anisotropy, provides information on the anisotropy fields and hence on the grain size distribution. X-ray diffraction (XRD) is used to estimate the bcc-Fe grain size based on the diffraction peak linewidths. Average grain sizes of 5–14 nm are found for 500–550 °C annealed specimens where smaller grain sizes are always observed for $\text{y=2}$ compared to $\text{y=0}$ for fixed $\mathrm{x.}$ Small-angle x-ray scattering is also used to study the grain size and this method yields sizes in the range from 3 to 7 nm, consistently almost a factor of 2 smaller than those from the XRD line broadening. This discrepancy is attributed to the difference in the regions of the 20-μm-thick ribbons probed by the two methods.

The specialized technique of radio‐frequency‐induced collapse of Mössbauer spectra combined with conventional Mössbauer spectroscopy, x‐ray diffraction (XRD), small‐angle x‐ray scattering (SAXS), and differential scanning calorimetry (DSC) are used to investigate in detail the magnetic and structural properties of the two magnetic materials Fe₈₁Zr₇B₁₂ and Fe₇₉Zr₇B₁₂Cu₂. Thermal treatments to convert the as‐quenched, fully amorphous state into mixtures of nanocrystalline and amorphous states and the effect of the small Cu addition were of primary interest due to the improved magnetic behavior in the mixed state. DSC shows that the Cu leads to a lowering of the onset temperature for formation of the nanocrystalline phase and also to an increase in the range of temperatures over which this phase forms. XRD and Mössbauer data show the nanoscale phase to be bcc Fe and the Mössbauer spectral parameters demonstrate it to be essentially pure Fe (i.e., with little or no Zr, B, or Cu substitutional impurities). The electron density contrast between the amorphous matrix and the bcc Fe permits the detection of the Fe grains by SAXS and significant volume fractions with sizes of only 2.8–8 nm are shown to exist. Larger sizes are also present as demonstrated by the XRD and Mössbauer data and a bimodal size distribution is suggested. The Mössbauer experiments in which the radio‐frequency‐induced effects (rf collapse and rf sidebands) are used, allows the nanocrystalline bcc phase to be distinguished from magnetically harder microcrystalline α‐Fe. The complete rf collapse of the magnetic hyperfine structure occurs only in the amorphous and nanocrystalline phases and is suppressed by the formation of larger grains. The rf sidebands disappear when the nanocrystalline phase is formed, revealing that magnetostriction vanishes. The rf‐Mössbauer studies are shown to be particularly sensitive to magnetic softness of the material in that large changes in the spectra are observed for applied field changes as small as 2 Oe.

The role of alloying elements, such as Cr, Al, Ti, and Mn, in the formation and stability of the nitride phases formed due to nitrogen ion implantation into metallic α‐iron was studied by conversion electron Mössbauer spectroscopy. The thermal stability of the nitride phases of α‐Fe implanted with N was greatly increased by coimplanting with N the alloying elements. For instance, the stability of α’‐martensite at low N‐dose implantation is strongly enhanced and also that of γ’‐Fe₄N at high N dose. Titanium stabilizes the ε‐Fe_3−xN‐type nitride preventing the formation of the γ’ phase. The presence of alloying elements influences the thermal stability of nitrides by increasing their binding energy and thus preventing the dissociation of nitrogen and also by forming traps that lead to the formation of TiN, AlN, or CrN nitrides. The thermal stability of nitrides, especially of ε‐Fe_3−xN and γ’‐Fe₄N ones, is improved in decreasing order by the presence of Ti, Al, Cr, and Mn.