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A set of Fe-based amorphous alloys, Fe93−x−yZr7BxCuy, with x=4, 6, 8, or 12, and 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 x=12 but less of a role for 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 y=2 compared to y=0 for fixed 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.

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The properties of the TbBa(Co2−xFex−)O5+δ (0<x⩽1) system, exhibiting the giant magnetoresistance effect, were studied by magnetization, thermogravimetric analysis (TGA), and resistivity measurements as well as by Mössbauer spectroscopy. It was found that the properties of this system dramatically change at x>0.1, at which a concentration-dependent orthorhombic–tetragonal transition takes place. The orthorhombic composition with x=0.1 exhibits a transition from an antiferromagnetic to weak ferromagnetic state at a temperature Ti=200 K on warming and at 160 K on cooling, and a transition from a weak ferromagnetic to paramagnetic state at TN=304 K. A metal–insulator transition occurs at TM=348 K on warming. Transformation into a tetragonal phase (x⩾0.12) leads to the disappearance of both the weak ferromagnetic state and the metal–insulator phase transition. Also, the Néel point drops. The orthorhombic and tetragonal phases coexist in the concentrational range (0.1<x<0.12). Mössbauer spectroscopy has shown that Fe3+ ions preferentially occupy two low-symmetry positions that are interpreted to be pyramidal sites with fivefold coordination. Both Mössbauer spectroscopy and TGA data revealed that the increase of Fe content leads to the decrease of oxygen content according to the formula TbBa(Co2−xFex)O5.5−x/2. It is supposed that at x⩾0.12 a change of the type of oxygen vacancy ordering occurs.