The magnetic properties of a series of Nd2Fe17−xAlx solid solutions, with x equal to 2.04, 4.01, 5.97, 7.94, and 9.06, have been studied by magnetic measurements, neutron diffraction, and Mössbauer spectroscopy. Magnetization studies indicate that the Curie temperature increases from 330 K in Nd2Fe17 to a maximum of ∼470 K at an x of 3.5. The compounds crystallize in the Th2Zn17 structure with lattice parameters and unit cell volumes which increase linearly with increasing aluminum content. The neutron diffraction results indicate that aluminum atoms are excluded from the 9d site, prefer the 18h site at low aluminum content, and prefer the 6c and 18f sites at high aluminum content. At 10 K the magnetic moments of the iron and neodymium atoms are collinear and take up a basal orientation at all aluminum contents. The moments decrease with increasing aluminum content and the magnetic moments per unit cell at 10 K are in excellent agreement with the 4.2 K saturation magnetization values. At 295 K the Nd2Fe17−xAlx solid solutions for x equal to 7.94 and 9.06 are paramagnetic. The magnetic Mössbauer spectra have been fit with a binomial distribution of the near-neighbor environments. The weighted average isomer shift increases, as expected, with increasing aluminum content as a result of interatomic charge transfer and intraatomic iron 4s–3d charge redistribution. The weighted average maximum hyperfine field at 295 K shows a maximum of 221 kOe at x equal to 2.04 but at 85 K it decreases uniformly with increasing aluminum content. The weighted average decremental field, ΔH, the change in the hyperfine field per aluminum near-neighbor, decreases with increasing aluminum content. It is proposed that, as a consequence of the increase in the average distance between an iron atom and its next near-neighbor shell with increasing aluminum content, the wavelength of the Friedel oscillation increases and the ratio of this wavelength and the shell distance becomes more favorable for ferromagnetic exchange.

The magnetic properties of a series of Ce2Fe17−xSix solid solutions with x equal to 0.0, 0.23, 0.4, 0.6, 0.8, 1.02, 1.98, and 3.20 have been studied by magnetic measurements, neutron diffraction, and Mössbauer spectroscopy. An x-ray-diffraction study indicates that the compounds adopt the rhombohedral Th2Zn17-type structure. The substitution of silicon for iron in Ce2Fe17 leads to a contraction of the a axis by 0.2%, an expansion of the c axis by 0.2%, and a consequent reduction of the unit-cell volume by about 0.2% per substituted silicon. Magnetization studies indicate that the Curie temperature increases uniformly from 238 K for Ce2Fe17 to 455 K for Ce2Fe14Si2. Powder neutron-diffraction results, obtained at 295 K, indicate both that the silicon atoms preferentially occupy the 18h sites and that the iron moments increase with increasing silicon content, an increase which is related to the increase in Curie temperature. The Mössbauer spectra have been fit with a binomial distribution of the near-neighbor environments in terms of a maximum hyperfine field Hmax for an iron with zero silicon near neighbors, and a decremental field ΔH per silicon near neighbor. The compositional independence of both the weighted average maximum hyperfine field and of the decremental field indicates that the silicon acts as a magnetic hole, a hole which does not perturb the magnetic moments at the iron sites. The compositional dependence of the weighted average isomer shift is explained in terms of an interband mixing of the iron 4s and silicon 2p bands, due to the reduction of the iron 18h bond lengths. This interband mixing affects the charge but not the spin distribution at the iron sites.

An x-ray diffraction study of the substitution of gallium in Tb2Fe17 to form the Tb2Fe17−xGax solid solutions indicates that the compounds adopt the rhombohedral Th2Zn17 structure. The unit cell volume and the a-axis lattice parameter increase linearly with increasing gallium content. The c-axis lattice parameter increases linearly from x=0 to 6 and then decreases between x=7 and 8. Magnetic studies show the Curie temperature increases by ∼150° above that of Tb2Fe17 to reach a maximum between x=3 and 4, and then decreases with further increases in x. Neutron diffraction studies of Nd2Fe15Ga2 and Tb2Fe17−xGax, with x equal to 5, 6, and 8, indicate that the gallium completely avoids the 9d site, occupies the 6c ‘‘dumbell’’ site only at high values of x and strongly prefers the 18f site at high values of x. The magnetic neutron scattering indicates both that the terbium sublattice magnetization couples antiferromagnetically with the iron sublattice and that there is a change in easy magnetization direction from planar to axial with increasing gallium concentration. This change in easy magnetization direction is explained in terms of a sign reversal of the second-order crystal field parameter, A02, the most important parameter responsible for determining the terbium sublattice anisotropy. The Mössbauer effect spectra indicate a larger room-temperature average hyperfine field at the iron site in the Tb2Fe17−xGax solid solutions than in several related R2Fe17 compounds. The large observed increase in the isomer shift with increasing gallium content results from interatomic charge transfer and intraatomic s-d charge redistribution in the presence of gallium.