Magnetism of the Tb2Fe14−xCoxB system

The Tb₂Fe_14−xCo_xB materials were synthesized for the entire composition range (x = 0–14) and studied by X-ray and magnetometry methods. All materials have a tetragonal crystal structure with decreasing lattice parameters upon Co substitution. The Curie temperature markedly rises for alloys with low Co content. Saturation magnetization at 77 K reaches a slight maximum around x ≈ 1 and gradually decreases for higher Co concentrations. An antiparallel coupling of 3d and Tb magnetic moments is inferred from saturation magnetization data. Anisotropy fields exhibit a maximum at low Co contents, but they decrease rapidly for x > 5. A spin reorientation (axis-to-plane) occurs at high temperature in materials with x ⩾ 12.5 due to competing effects of the terbium sublattice anisotropy and the 3d sublattice anisotropy. The spin-reorientation temperature becomes lower for alloys with higher Co content. The observed magnetic behavior is discussed in terms of preferential Co substitution into 16 k₂ sites and changes in the 3d sublattice due to Co introduction. A magnetic phase diagram is constructed for the Tb₂Fe_14-xCo_xB system and compared with that of Pr₂Fe_14-xCo_xB and Nd₂Fe_{14 -x}Co_xB systems.     

Diffusion of Fe,Co, Nd,and Dy in R2(Fe1−xCox)14B where R=Nd or Dy

Transition metal and rare earth diffusion coefficients at 1323 K in Dy_2−yNd_y(Fe_1−xCo_x)₁₄B were determined by field emission energy dispersive spectroscopy compositional analysis of diffusion couple specimens. Various arrangements of component materials and temperatures were examined in order to understand the mechanisms affecting diffusion of the components and to predict the stability of functionally graded microstructures consisting of a dysprosium-rich (Dy_2−yNd_y(Fe_1−xCo_x)₁₄B) outer layer and a neodymium-rich (Nd₂(Fe_1−xCo_x)₁₄B) interior. Estimates of the mutual interdiffusion coefficients of Dy, Nd, Fe, and Co in this system were obtained from the preparation of arc melted and annealed polycrystalline specimens, assuming that the diffusion coefficients were independent of concentration (Grube solution). Fifteen diffusion couples were prepared and heat treated at 1323 K for various times in order to provide data for calculation of the diffusion coefficients. The results indicate that the diffusion coefficients of Fe and Co (D_Fe=3.28×10⁻¹⁰ cm²/s and D_Co=7.63×10⁻¹⁰ cm²/s) were significantly higher at 1323 K in this system than those for Dy and Nd (D_Nd=2.3×10⁻¹² cm²/s and D_Dy=2.9×10⁻¹² cm²/s).     

Observations of multi-phase microstructures in R2(Fe1−xCox)14B where R=Nd or Dy

Multi-phase microstructures were observed in the psuedo-quaternary phase field of the 2–14–1 magnet materials Nd₂Fe₁₄B, Nd₂Co₁₄B, Dy₂Fe₁₄B, and Dy₂Co₁₄B. At equilibrium, (Nd_1−yDy_y)₂(Fe_1−xCo_x)₁₄B had heretofore been widely assumed to be single phase where 1>x>0 and 1>y>0. In this study, three-phase microstructures were observed in (Nd_1−yDy_y)₂(Fe_1−xCo_x)₁₄B when x>0.3 and y>0.5. The Curie temperatures and peritectic decomposition temperatures for Nd₂(Fe_1−xCo_x)₁₄B are reported for several values of x in the range 1>x>0.     

Effects of Co substitution on structural and magnetic properties of R3(Fe1−xCox)29−yVy (R=Tb,Dy)

Synthesis of two novel series of intermetallic compounds Tb₃(Fe_1−xCo_x)_27.4V_1.6 (x=0,0.1, 0.2, 0.3, 0.4) and Dy₃(Fe_1−xCo_x)_27.8V_1.2 (x=0, 0.1, 0.2, 0.3) with the monoclinic Nd₃(Fe,Ti)₂₉-type structure (3:29) is presented. In the Dy series for x=0.4 a disordered variant of the hexagonal Th₂Ni₁₇-type structure is formed. The cell parameters decrease and the Curie temperature increases with increasing of the Co content. In the case of the Tb₃(Fe_1−xCo_x)_27.4V_1.6 series in the M(T) curve a magnetic transition is observed which is attributed to spin reorientation phenomena. This critical temperature decreases with increasing Co from 473 K for x=0.1 to 393 K for x=0.3, and was not observed in the case of 0.4. XRD patterns of magnetically aligned powder samples reveal the presence of a tilted magnetic structure.     

Phase relations of the (Pr1−xSmx)2Fe14B system

The phase relations in the (Pr_1?xSm_x)₂Fe₁₄B system in a whole concentration range have been studied by means of X-ray powder diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM) equipped with energy-dispersive X-ray spectroscopy (EDS). The XRD patterns of the (Pr_1?xSm_x)₂Fe₁₄B samples have been refined by Rietveld method. These results reveal that all the alloys (Pr_1?xSm_x)₂Fe₁₄B are similar to the end member of the investigated system Pr₂Fe₁₄B with tetragonal structure (space group P4₂/mnm). The continuous solid solutions were formed in this system. The normalized lattice parameters and unit cell volumes of (Pr_1?xSm_x)₂Fe₁₄B solid solutions decrease linearly with x ranging from 0 to 1.0. The DTA measurements show that the peritectic temperature of (Pr_1?xSm_x)₂Fe₁₄B increases with increasing Sm content and no metastable phases are detected. Based on the DTA data, SEM–EDS and XRD results, the vertical section of Pr₂Fe₁₄B–Sm₂Fe₁₄B in the Pr–Sm–Fe–B system has been constructed.     

A Mössbauer spectroscopic study of 3d magnetism of R2Fe14B

Guided by the occupancies and iron magnetic moments μ³, ⁵⁷Fe Mössbauer parameters of Y₂Fe₁₄B at 250K, and in turn for other temperatures, of the sublattices of iron were deduced. Plots of μ(T) in reduced coordinates, through the established correlation between hyperfine field Hn and μ, show that the corresponding state of different iron sites is different and all experimental points fall below Brillouin function. The relation between exchange integral deviation parameter Δ and standard deviation of Fe-Fe interatomic distances S is linear, indicating electrostatic nature of exchange interactions between spins in neighboring atoms. It is inclined to the view that fluctuations of exchange integral is responsible for low T_c of R₂Fe₁₄B.     

Magnetic structures of non-stoichiometric hexagonal RNi1−xIn1+x (R=Dy,Ho, Er) compounds

Results of neutron diffraction studies of DyNi_0.9In_1.1, HoNi_0.8In_1.2 and ErNi_0.9In_1.1 compounds crystallizing in the hexagonal ZrNiAl-type structure are reported. Previously published data for stoichiometric 1–1–1 compounds indicate that HoNiIn and ErNiIn compounds are ferromagnets (ordering along the c-axis) with T_C of 22 and 9 K, respectively, while DyNiIn was found to be an antiferromagnet with T_N of 32 K (J. Magn. Magn. Mater. 262 (2003) L177; J. Magn. Magn. Mater., in press). DC bulk magnetic measurements show that with the rise of the x parameter the ordering temperature is lowered; moreover changes in the magnetic ordering occur. At 1.5 K the HoNi_0.8In_1.2 compound has a non-collinear magnetic structure, for the ErNi_0.9In_1.1 compound an additional sine-modulated component lying in the basal plane was found. For the DyNi_0.9In_1.1 compound the antiferromagnetic character of magnetic coupling is conserved, but some changes in comparison to 1–1–1 stoichiometry were noticed.     

Ordering of atoms in 3d sublattice of the intermetallic quasibinary system Dy(Fe1−xMnx)2

Methods of x-ray analysis and nuclear -resonance (Mössbauer effect) have been used to study the distribution of iron and manganese atoms in the intermetallic quasibinary system Dy(Fe_1–xMn_x)₂, which is isostructural to the Laves phase C15. Ordering of atoms of transition metals has been found in 3d sublattice of intermetallic compounds Dy(Fe_1–xMn_x)₂ with the formation of a triple superstructure having the stoichiometric composition Dy(Fe_0·.25Mn_0·.75)₂.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 55–60, June, 1986.     

155Gd and 161Dy Mössbauer study of R1+εFe4B4 alloys (R = Gd,Dy)

Tetragonal R_1+εFe₄B₄ alloys with R = Gd and Dy have been investigated by Mössbauer spectroscopy, using the ¹⁵⁵Gd and ¹⁶¹Dy resonances, respectively. The Gd quadrupolar interaction e²qQ = 12.65(5)mm/s is the largest observed to date in metallic compounds of Gd. For Dy this interaction is e²qQ = 74(2) mm/s, a value rather small for a Dy compound. Both results imply a strong lattice contribution to the electric field gradient. A crystal-field term A⁰₂ = -2450(50) K/a²_o is inferred. Our data are consistent with a point-charge calculation, provided charges of opposite signs are assumed for Fe and B atoms. Hyperfine parameters show some dispersion, reflecting the quasi incommensurate nature of the R and Fe+B sublattices in the R_1+εFe₄B₄ structure.     

Local model for magnetism in Y(Fe1−cAlc)2 alloys

The magnetic behavior of Y(Fe_1−cAl_c)₂ alloys (T = 4 K, 0 ⩽c < 1) is described in a local model. This model accounts for the variation with c of the spontaneous magnetization related to magnetic Fe atoms (with at least 15 Fe neighbours) and the high-field susceptibility which arises from the non-magnetic Fe atoms.     

Magnetic and crystallographic properties of substituted Pr2Fe14−xMxB compounds (M = Si,Ga, CrandCu)

Structural and magnetic properties of Pr₂Fe_14−xM_xB systems (M = Si, Ga, CrandCu) are investigated. These compounds crystallize in a tetragonal system of P4₂/mnm-type for a Si content up to x = 2, Cr content up to x = 3 and for Ga and Cu concentration up to x = 1. The Curie temperature increases when Fe is substituted by Si, Ga and Cu, decreases when Fe is replaced by Cr. The saturation magnetization decreases with increasing content of an M element. The rate of the decrease is larger than that expected by a simple dilution model. The influence of M atoms on the anisotropy field is discussed.     

Temperature variation of the spin reorientation in Er2−xDyxFe14B alloys

The competition between the uniaxial magnetic anisotropy of the iron sublattice and the basal anisotropy of the rare earth sublattice in the R₂Fe₁₄B alloys, occuring for the rare earths with a positive Steven's factor (a_j> 0), leads to spin reorientation at 316 K for the Er₂Fe₁₄B compound. We have succeeded, by making a series of pseudoternaries of the type Er_2−xDy_xFe₁₄b, to establish a correlation between the spin reorientation temperature and the quantity x. Mossbauer spectra of aligned powders show a smooth decrease of the spin reorientation temperature for values of x up to 1, while for larger values spin reorientation is absent.     

Spin reorientation and magnetocrystalline anisotropy of (Nd1−xDyx) Fe14B

Spin reorientation and magnetocrytalline anisotropy of (Nd_1−xDy_x)₂Fe₁₄B (x=0.25, 0.5, 0.75) have been studied from mangetization curves of magnetically aligned powders. In (Nd_1−xDy_x)₂Fe₁₄B, the spin reorientation temperature (T_SR) decreases linearly on increasing Dy-substitution from 135 to 56 K with the ratio of ΔT_SR=−1.11 K/Dy at% in the composition range of 0⩽x⩽0.75. The spin reorientation angle at 4.2 K decreases on Dy-substitution from 30.4° at x=0 to 14.7° at x=0.75. From the investigation of the magnetocrystalline anisotropy at 4.2 K, the disappearance of the spin reorientation for compositions x≳0.85 is expected.     

Magnetic properties of U (Fe x Al1−x )2 and U(Fe y Ni1−y )2 compounds

The results of magnetic measurements and ferromagnetic resonance studies performed on U(Fe _x Al_1–x )₂ and U(Fe _y Ni_1–y )₂ compounds over a large temperature range are reported. The saturation magnetization decreases nearly linearly when substituting Fe by Al or Ni. In the composition range x<0.84 and y<0.81, the compounds are Pauli paramagnets, except in the region with y0.10. For UNi₂ two types of magnetic behaviours are shown. This compound can be both a ferromagnet withT _c =23.5 K and a Pauli paramagnet, depending on the crystal structure. Above the Curie temperatures, the reciprocal susceptibility for the compounds with x>0.84 and y>0.81 obeys a temperature dependence of the formX=X _o+C(T-) ^–1. The effective iron moments decrease when substituting iron by nickel or aluminium. The ferromagnetic resonance measurements show that theg values are not composition-dependent. A linear variation of the mean iron magnetization with the exchange field is observed. Finally, the magnetic behaviour of iron in these compounds is analysed.     

Magnetic properties of RNi1−xIn1+x (R=Gd–Er) compounds

AC and DC bulk magnetic measurements were performed for RNi_1−xIn_1+x (R=Gd–Er and x=0,0.1, 0.25) compounds. These compounds crystallize in the hexagonal ZrNiAl-type structure. The lattice parameters a and c for the RNiIn series decrease linearly with increasing number of 4f electrons. For nonstoichiometric RNi_1−xIn_1+x additional indium atoms occupy the 2(c) crystallographic site and the a parameter increases while the c parameter decreases with increasing indium content. The stoichiometric samples show ferromagnetic behavior with the critical temperature changing from 96 K for R=Gd to 9 K for R=Er. In the nonstoichiometric RNi_1−xIn_1+x compounds increase in the indium content leads to decrease in the ferromagnetic critical temperatures and to a change of the antiferromagnetic ordering for x=0.25 in the case of R=Dy, Ho and Er.     

Magnetic properties of RPdIn (R=Gd–Er) compounds

AC susceptibility and DC magnetization measurements were performed for the RPdIn (R=Gd–Er) compounds both in the paramagnetic and in the ordered state. In opposite to GdPdIn, which is a ferromagnet (T_c=102 K), the other samples show a complex ferrimagnetic behavior with the additional transition at T_t<T_c. In the high-temperature phase (for T_t<T<T_c), a ferromagnetic interaction dominates, while in the low-temperature phase (for T⩽T_t) antiferromagnetic interactions with the magnetocrystalline anisotropy, especially strong for TbPdIn, come into play. The ordering temperatures are T_c=70, 34, 25 and 12.3 K for Tb-, Dy-, Ho- and ErPdIn respectively, while transition temperatures are T_t=6, 14 and 6 K for Tb-, Dy- and HoPdIn respectively. TbPdIn reveals an additional transition at 27 K connected with the intermediate ferrimagnetic phase. The critical fields for the magnetization process of the low-temperature phase are high (52 and 150 kOe for TbPdIn and 32 kOe for DyPdIn at T=4.2 K) yet these values decrease remarkably with increasing temperature. Results of the study are compared with magnetic and neutron diffraction data hitherto available. We state that irreversibility of the zero-field cooled–field cooled magnetization is not connected with the spin-glass phase claimed elsewhere.     

Correlation between the magnetic and electrical properties of the (VS)x(Fe2O3)2−x oxysulfide system

The correlation between the magnetic and electrical properties of the (VS)_x(Fe₂O₃)_2?x (0.9<x<1.25) oxysulfide solid solutions has been studied. The crossover of conductivity from the semimetallic to semiconducting type is accompanied by changes in the magnetic susceptibility, which are characteristic of the transition from delocalized to localized electrons. For x=1.25, a region of the ferromagnetic ordering has been established in the temperature range 90–120 K.     

Structure and properties of the anions MF4−, MCl4− and MBr4− (M = C,Si, Ge)

Density functional theory (DFT), Møller–Plesset (MP2) and coupled cluster with single and double substitutions including non-iterative triple excitations (CCSD(T)) calculations on the anions MX₄^?, with M = C, Si, Ge and X = F, Cl, Br, show that GeF₄^?, SiCl₄^?, GeCl₄^? and SiBr₄^? prefer a C_2v conformation, but CCl₄^? is an elongated C_3v structure. CBr₄^? has T_d symmetry in MP2, but is slightly more stable in elongated C_3v form with DFT and CCSD(T). GeBr₄^? has T_d symmetry. CF₄^? and SiF₄^? are unstable with respect to loss of an electron. Vertical electron affinities (EAs) are negative also for CCl₄ and SiCl₄, and close to zero for GeF₄ and SiBr₄. Adiabatic EAs range from 0.47 eV for SiCl₄ to 1.78 eV for GeBr₄. The lowest excited states at T_d symmetry are ²T₂ resonances with energies of 2.1–3.5 eV, resulting from excitation of the a₁ singly occupied molecular orbital to vacant t₂ orbitals. Vertical excitation energies (VEEs) and vibrational frequencies are given for the most stable anionic geometries. Comparison with experimental VEEs for CCl₄^? is made. From dissociation energies of MX₄, MX₄^?, MX₃ and MX₃^?, appearance energies of X^?, MX₃^?, X₂^? and MX₂^? were calculated. Most were found to be in reasonable agreement with experimental values. Theoretical spin densities and g-factors have been compared with experimental results available for CCl₄^?, SiCl₄^? and GeCl₄^?.     

Structure and magnetic properties of RFe13−xSix (R = Pr,Nd or Gd,x = 2.5–5)

RFe_13−xSi_x (R = Pr, Nd and Gd) alloys with x = 2.5–5 have been synthesized and characterized in a magnetic field up to 17 kOe and in a temperature range 10–1173 K to ascertain whether they might be useful as high temperature, high-energy permanent magnet materials. It was found that a body-centered tetragonal (BCT) Ce₂Ni₁₇Si₉-type structure forms in PrFe_13−xSi_x alloys when x ⩾ 4. The Curie temperatures T_c of this BCT phase are in a range 50–90 K, higher than that of the corresponding PrCo_13−xSi_x BCT phase (∼ 20 K). The PrFe_13−xSi_x alloys with x⩾ 4 show spin reorientation at cryogenic temperatures (15–47 K) and exhibit significant coercivity in loose powder samples below their spin-reorientation temperature. Using the information about the magnetization of LaFe_13−xSi_x BCT alloys, one can estimate the moment of Pr ion in PrFe_13∼-xSi_x alloys. It is found to be very close to that in PrCo_13−xSi_x BCT alloys, around 2 μ_2/atom. For RNd or Gd, the RFe_13−xSi_x alloys occur only as mixtures of RFe₂Si₂, R(Fe, Si)₁₁ and FeSi. The Ce₂Ni₁₇Si₉-type structure cannot be formed in these alloys even when x = 5. The low T_c for the PrFe_13−xSix alloys precludes their use as a permanent magnet material, except perhaps at low temperature.