Magnetic characteristics of R2(Fe, Co)14B systems (R = Y, Nd and Gd)

R₂(Fe, Co)₁₄B compounds (R = Y, Nd and Gd) were prepared in high purity. The magnetic behavior of R₂(Fe, Co)₁₄B compounds is reported over the temperature range 4 to 300 K. The effects of Fe substitution by Co on the saturation magnetization, Curie temperature and anisotropy are presented. The spin-reorientation temperature is lowered as Co replaces Fe. This also results in a reduced cone angle.

The R₂Fe_14−xCo_xB alloys crystallize in the tetragonal structure over the entire concentration range of 0 x 14. When Fe is substituted by Co, the Curie temperature increases significantly, the saturation magnetization increases to a maximum value around x = 2, and the anisotropy becomes planar for R = Y and Gd. The Nd₂(Fe, Co)₁₄B systems all exhibit uniaxial anisotropy at room temperature and Nd₂Co₁₄B is strongly uniaxial at 77 K. The Nd₂(Fe, Co)₁₄B systems are conical at 77 K.     

Phase formation and magnetic properties of Nd2Fe14B-type Nd16Co76B8−xCx alloys and their hydrides

An attempt is made to synthesize Nd₂Co₁₄C compound by mechanical alloying Nd₁₆Co₇₆B_8−xC_x (0x8) alloys and subsequent annealing. Phase formation and magnetic properties of Nd₂Fe₁₄B-type Nd₁₆Co₇₆B_8−xC_x alloys and their hydrides are investigated. The Nd₂Co₁₄(B,C) phase with Nd₂Fe₁₄B-type structure is formed for Nd₁₆Co₇₆B_8−xC_x (0x7) alloys, while NdCo₇C_δ phase with TbCu₇-type structure is observed in Nd₁₆Co₇₆C₈ alloy. The lattice parameter c of the Nd₂Co₁₄(B,C) phase decreases with increasing the carbon content. A limit volume of the unit cell to form the Nd₂Fe₁₄B-type structure is estimated to be 0.870 nm³. The spin-reorientation temperature T_SR increases with increasing the carbon content, due to an enhancement of magnetocrystalline anisotropy caused by carbon substitution for boron. After hydrogenation, the lattice expansion is observed for Nd₁₆Co₇₆B_8−xC_x (0x7) alloys. The spin-reorientation temperature of Nd₁₆Co₇₆B_8−xC_xH_y (0x7) is much lower than that of the host alloys. Some structural and magnetic properties of hypothetic Nd₂Co₁₄C and Nd₂Co₁₄CH_y compounds are estimated by extrapolation.     

Magnetic properties and spin reorientation of iron rare earth based intermetallics

The Curie temperature and saturation magnetization M_s(μ_B/f.u.) of R₂Fe₁₄B have been discussed. The spin reorientations of Nd₂Fe₁₄B compounds have been studied by many authors with various methods, but have not been checked with the neutron diffraction method. We investigated the spin reorientation of Nd₁₅Fe₇₈B₇ by neutron diffraction and obtained θ = 26°34' at 77 K which is in good agreement with other authors' results. The small amount substitution of Si for Fe in Nd₂(Fe_1−xSi_x)₁₄B increases T_c and _cH_c of the compound. These will be able to make an advantage for Nd-Fe -B magnets.     

Coercivity mechanism in nanophase (Nd–Pr)–Fe–B melt spun alloys

The nucleation mechanism to predict coercivity values in melt-spun exchange-coupled (Nd_1−xPr_x)_yFe_94−yB₆ alloys for various Nd:Pr ratios x, and Fe:RE ratios y, was tested using the dependence of the anisotropy constant K₁ on Pr content x for the minimum nucleation field H_N^min in the modified Brown's equation. Very good agreement was found between experimental data and theoretical values, confirming the predominance of the nucleation of reverse domains over the wall pinning process in the coercivity mechanism of melt spun REFeB alloys.     

Mixed electronic and ionic conductivity of LaCo(M)O3 (M=Ga, Cr, Fe or Ni).: V. Oxygen permeability of Mg-doped La(Ga, Co)O3−δ perovskites

The LaGa_1−x−yCo_xMg_yO_3−δ solid solutions with rhombohedrally-distorted perovskite structure were ascertained to form in the concentration range of 0≤y≤0.10 at x=0.60 and 0≤y≤0.20 at x=0.35–0.40. Increasing cobalt content results in increasing electrical conductivity and thermal expansion of the perovskites. Thermal expansion coefficients of the LaGa_1−x−yCo_xMg_yO_3−δ ceramics were calculated from the dilatometric data to vary in the range of 12.4–19.8×10⁻⁶ K⁻¹ at 300–1100 K. Doping La(Ga,Co)O_3−δ solid solutions with magnesium leads to increasing oxygen nonstoichiometry, electronic and oxygen ionic conductivity. Oxygen permeation fluxes through LaGa_1−x−yCo_xMg_yO_3−δ membranes were found to be limited by the bulk ionic conduction and to increase with magnesium concentration, being essentially independent of cobalt content.     

Magnetic properties of Gd2Fe14−xCoxB compounds

The magnetization of magnetically-aligned Gd₂Fe_14−xCo_xB samples with x = 0, 2, 4, 6, 8.4, 11.2 and 14 has been measured at 4.2 K in fields up to 14 T and the anisotropy fields have been derived. The effect of substitution of Co for Fe on the magnetic properties of Gd₂Fe₁₄B has been investigated.     

Itinerant metamagnetic transition in Y(Co1−xFex)2

High field magnetization measurements have been performed to examine the existence of itinerant metamagnetism in exchange-enhanced systems related to YCo₂ together with Fe_1−x Co_xSi. In the Y(Co_−xFe_x)₂ system, the meta magnetism inherent in YCo₂ has been observed in 0.04 x0.07. The transition is not as sharp as in the Y(Co_1−xAl_x)₂ system. Other exchange-enhanced paramagnets Y(Co_−xCu_x)₂ and Y_1−xLa_xCo_x2 and weakly itinerant ferromagnet Fe_1−xCo_xSi exhibit no metamagnetic transition up to 430 kOe.     

Oxygen permeability of La2Cu(Co)O4+δ solid solutions

Formation of the La₂Cu_1−xCo_xO_4+δ solid solutions with orthorhombic K₂NiF₄-type structure was found to be in the range of 0≤x≤0.30 at temperatures above 1270 K. Incorporating cobalt into the copper sublattice of lanthanum cuprate leads to increasing oxygen hyperstoichiometry and decreasing electrical conductivity. Thermal expansion coefficients of the La₂Cu_1−xCo_xO_4+δ (x=0.02–0.30) ceramics at 470–1100 K were calculated from the dilatometric data to vary in the range (12.2–13.2)×10⁻⁶ K⁻¹. Studying the dependence of oxygen permeation fluxes through La₂Cu(Co)O_4+δ on the membrane thickness demonstrated that the oxygen transport at the thickness values below 1 mm is limited by both surface exchange rate and bulk ionic conductivity. Oxygen permeability of the La₂Cu_1−xCo_xO_4+δ solid solutions was ascertained to increase with cobalt concentration at x=0.02–0.10 and to decrease with further dopant additions, indicating a participation of interstitial oxygen in the ionic transport.     

Dy,Co共掺杂对BiFeO3陶瓷磁特性和磁相变温度Tc的影响

采用快速液相烧结法制备BiFeO₃和Bi_0.95Dy_0.05Fe_1-xCo_xO₃ (x=0, 0.05, 0.1, 0.15)陶瓷样品. 实验结果表明: 所有样品的主衍射峰与纯相BiFeO₃相符合且具有良好的晶体结构, 随着Co³⁺掺杂量的增大, Bi_0.95Dy_0.05Fe_1-xCo_xO₃样品的主 衍射峰由双峰(104)与(110)逐渐重叠为单峰(110), 当掺杂量x>0.05时, 样品呈现正方晶系结构; SEM形貌分析可知: Dy³⁺, Co³⁺共掺杂使BiFeO₃晶粒尺度由原来的3—5 μ减小到约1 μ. 室温下, BiFeO₃样品表现出较弱的铁磁性, 随着Dy³⁺和Co³⁺掺杂, BiFeO₃样品的铁磁性显著提高. 在外加磁场为30 kOe的作用下, Bi_0.95Dy_0.05Fe_1-xCo_xO₃ (x=0.05, 0.1, 0.15)的M_r分别为0.43, 0.489, 0.973 emu/g; M_S分别为0.77, 1.65, 3.08 emu/g. BiFeO₃和Bi_0.95Dy_0.05Fe_1-xCo_xO₃样品磁矩M随着温度T的升高而逐渐减小, Dy掺杂使BiFeO₃样品的T_N由644 K升高到648 K, 而T_C基本没有变化. Dy和Co共掺杂导致BiFeO₃样品磁相变温度T_C由870 K降低到780 K, 其T_C变化主要取决于Fe-O-Fe反铁磁超交换作用的强弱和磁结构的相对稳定性. 关键词： 铁磁电材料 磁滞回线 磁相变温度     

Intercalation thermodynamics and chemical diffusion of oxygen in the solid solution YBa2Cu3−xCoxO6+δ

The equilibrium oxygen content as a function of the temperature and oxygen pressure was measured for the solid solution YBa₂Cu_3−xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6, 0.8, by using coulometric titration in the temperature range 600–850°C and oxygen pressures between 10⁻⁵ and 1.0 atm. The change in the partial molar enthalpy and entropy of the intercalated oxygen was determined at different oxygen and cobalt contents. The oxygen chemical diffusion was studied by thermogravimetric relaxation in the oxygen-controlled atmosphere. The thermodynamic data were employed to determine how the chemical diffusion coefficient, the thermodynamic factor and the random-diffusion coefficient depend on oxygen content in specimens with different cobalt concentration. The oxygen intercalation thermodynamics and diffusivity results provide evidence of ordering phenomena on a microscopic scale in the basal plane of the tetragonal solid solution YBa₂Cu_3−xCo_xO_6+δ. A model for the oxygen diffusion is suggested to explain the large difference between the random and tracer diffusion coefficients in YBa₂Cu₃O_6+δ     

Iodometric titration for determining the oxygen content of samples doped with Fe and Co

Double iodometric titration is a method developed for high-T_c superconductivity. It has been widely used to determine the effective oxidation of copper and to figure out the oxygen content in a sample in the past years. If a sample is doped with some metals like iron and cobalt, these metal ions can interfere in experiment results. This is a major defect for iodometric titration. To solve this problem, we introduce ammonium hydrogen fluoride as a complex agent into the method. The agent can prevent the interference of ions of iron and cobalt. For samples LaBa₂Cu_3−xFe_xO_y and YBa₂Cu_3−xCo_xO_y, we determine the oxygen content by an improved double iodometric titration in which the ammonium hydrogen fluoride is used as an interference-free agent. For samples doped with a small amount of Fe or Co, experiment results agree well with those of other researchers. As to samples doped with a large amount of Fe or Co, we determine their values of oxygen content and the results are reasonable.     

Temperature dependence of induced magnetic anisotropy in metallic glasses (Fe1 − xCox)78Si10B12

The variations of induced magnetic anisotropy with annealing and measuring temperatures in metallic glasses (Fe_{1 − x}Co_x)₇₈Si₁₀B₁₂ have been measured. It was found that K_u (T) was proportional to Mⁿ_s (T) for T below 200°C, and the index n varied with the cobalt content x and annealing conditions, not being smaller than 3. To the predictions of the existing pair-ordering and single-ion theories, the above results are anomalous. By considering the distributions of exchange integrals and activation energies in metallic glasses, this anomalous behaviour could be explained properly.     

The order of magnetic phase transition in La(Fe1−xCox)11.4Si1.6 compounds

Magnetic transitions in La(Fe_1−xCo_x)_11.4Si_1.6 compounds with x=0–0.08, have been studied by DC magnetic measurements and Mössbauer spectroscopy. The temperature dependence of the Landau coefficients has been derived by fitting the magnetization, M(μ₀H), using the Landau expansion of the magnetic free energy. For x0.02 there is a strongly first-order magnetic phase transition between ferromagnetic and paramagnetic (F–P) states in zero external field and a metamagnetic transition from paramagnetic to ferromagnetic (P–F) above T_c. Increasing the cobalt content drives the F–P transition towards second order and eliminates the metamagnetic transition.     

Improvement of the magnetic properties of low-neodymium magnets by minor addition of titanium

Rapidly solidified nanocomposite Nd₉Fe_77−xB₁₄Ti_x alloys, consisting of magnetic Nd₂Fe₁₄B phase and soft magnetic phases, were investigated. The effect of titanium addition on the structure and magnetic properties was studied. It was found that 2–4 at% Ti addition leads to substantial increase of the coercivity and maximum energy product, maintaining the remanence unchanged. The highest properties: J_r=0.81 T, _JH_c=907 kA/m, (BH)_max=99 kJ/m³, were achieved for the Nd₉Fe₇₃B₁₄Ti₄ alloy. This effect we attribute to the formation of fine and homogeneous grain structure and a change of the phase morphology in the Ti-containing alloys. The initial magnetization curve indicates a change of the coercivity mechanisms giving rise to pinning of domain walls, which is caused by reduction of the crystallite size.     

NMR study of hyperfine interactions in R1−xLuxFe2 (R = Gd, Tb)

Spin-echo NMR measurements on ¹⁵⁵Gd, ¹⁵⁹Tb and ¹⁷⁵Lu have been done for the cubic Laves phase compounds Gd_1−xLu_xFe₂ and Tb_1−xLu_xFe_x. The observed hyperfine fields of Gd and Lu in those compounds increase with increasing Lu concentration. The concentration dependence of the Lu hyperfine field is qualitatively discussed.     

Oxygen nonstoichiometry and phase transitions of the neodymium-rich Nd1+xBa2−xCu3Oz solid solution

On the basis of chemical, thermal analysis and Cu K-edge X-ray absorption measurements, oxygen content in the Nd_1+xBa_2−xCu₃O_z solid solution was determined between 1000°C in air and 400°C in oxygen for x=0.05–0.9 compositions. It has been observed that the oxygen nonstoichiometry Δz of the Nd_1+xBa_2−xCu₃O_7+x/2−Δz solid solution decreases 2–2.5 times for a large substitution (Δz≈0.3–0.33 for x=0.9), despite of the acclaimed higher total oxygen content. The difference in nonstoichiometry is explained by a higher average value of the copper oxidation state (ACV), which is vital for the solid solution with large x even at elevated temperatures (ACV≈2–2.05 for x>0.3 at 1000°C, PO₂=0.21 atm). On the contrary, the ACV after complete oxygenation is almost constant (about 2.25–2.3) for the whole series. The x-dependence of the oxygen content is not monotonous and structural phase transitions can be observed at x=0.3 and x=0.6, as confirmed by the X-ray diffraction and the Raman scattering spectroscopy. The first well-known transition is connected with the oxygen disorder due to the Nd substitution for Ba at random Ba-sites. In the present work, it is proved by the apical oxygen mode broadening in Raman spectra. Ordering of the Nd and Ba atoms with a subsequent orthorhombic distortion of the lattice may occur even at 1000°C in air due to the second transformation at x≈0.6. The invariable orthorhombicity of the Nd-rich solid solution with x>0.6 is not caused by the oxygen absorption as in the x=0.05 case. Existence of high- and low-temperature orthorhombic modifications of this solid solution has been observed for the first time. Finally, a tentative 3D (z–x–T) diagram is suggested for the Nd_1+xBa_2−xCu₃O_z solid solution up to 1000°C in air, including the new x=0.6–0.9 region.     

Perovskite-like system (Sr,La)(Fe,Ga)O3−δ: structure and ionic transport under oxidizing conditions

The maximum solid solubility of gallium in the perovskite-type La_1−xSr_xFe_1−yGa_yO_3−δ (x=0.40–0.80; y=0–0.60) was found to vary in the approximate range y=0.25–0.45, decreasing when x increases. Crystal lattice of the perovskite phases, formed in atmospheric air, was studied by X-ray diffraction (XRD) and neutron diffraction and identified as cubic. Doping with Ga results in increasing unit cell volume, while the thermal expansion and total conductivity of (La,Sr)(Fe,Ga)O_3−δ in air decrease with gallium additions. The average thermal expansion coefficients (TECs) are in the range (11.7–16.0)×10⁻⁶ K⁻¹ at 300–800 K and (19.3–26.7)×10⁻⁶ K⁻¹ at 800–1100 K. At oxygen partial pressures close to atmospheric air, the oxygen permeation fluxes through La_1−xSr_xFe_1−yGa_yO_3−δ (x=0.7–0.8; y=0.2–0.4) membranes are determined by the bulk ambipolar conductivity; the limiting effect of the oxygen surface exchange was found negligible. Decreasing strontium and gallium concentrations leads to a greater role of the exchange processes. As for many other perovskite systems, the oxygen ionic conductivity of La_1−xSr_xFe_1−yGa_yO_3−δ increases with strontium content up to x=0.70 and decreases on further doping, probably due to association of oxygen vacancies. Incorporation of moderate amounts of gallium into the B sublattice results in increasing structural disorder, higher ionic conductivity at temperatures below 1170 K, and lower activation energy for the ionic transport.     

Magnetic behavior of Pr1 − xMxCo5 compounds (M = Ti, Zr and Hf)

Magnetic characteristics of Ti-, Zr- and Hf-substituted PrCo₅ alloys have been studied over the temperature range from 77 to 300 K and for applied fields up to 20 kOe. It is established that Ti, Zr and Hf substitute for Pr. Single-phase materials are formed for all values of x up to 0.2 in the system Pr_1−xZr_xCo₅ but for x only up to 0.1 for Pr_1−xTi_x Co₅ and Pr_1−xHfxCo₅ alloys. Larger amounts of Zr can be substituted if the material is made hyperstoichiometric in Co, e.g., Pr_0.7Zr_0.3Co_5.5. All the alloys show a decrease in magnetic moment and an increase in Curie temperature as x increases. Anisotropy fields decrease as x increases at 295 K. Anomalous behavior is observed at 77 K, suggested that these ternary alloys may have a cone structure at this temperature.     

The effect of rare earth substitution on the magnetic properties of Ni0.5Zn0.5MxFe2−xO4 (M: rare earth)

Variation of the complex permeability with frequency of Ni_1−xZn_xFe₂O₄ (x=0.5, 0.6 and 0.7) prepared by a combustion method has been measured over a wide range of frequency, up to 1.8 GHz. Zn content improves permeability but moves the onset of resonance to lower frequencies.

The influence on some properties of samples prepared by the insertion of small amounts of Ruthenium, Yttrium and rare-earth cations into the Ni_0.5Zn_0.5M_xFe_2−xO₄ ferrite has been also investigated. Relative losses and Curie temperature of all the samples have been measured. Ferrites substituted with Ru and Gd improve microwave behavior compared to non-substituted samples.     

Magnetic properties of Sm–Co–B-based nanocomposite magnets

The magnetic properties of nanocomposite melt-spun magnets with composition Sm_16−xCo_68+xB₁₆ (x=0–10, 2 at% interval) and Sm₈Co_92−yB_y (y=10–18, 2 at% interval) have been studied systematically. Several ribbons were fabricated with a wheel speed of 50 m/s, followed by annealing in the temperature range of 700–800°C for 2.5–40 min. XRD results and magnetization versus temperature curves showed that almost all of the samples were composed of the tetragonal Sm₂Co₁₄B and rhombohedral SmCo₁₂B₆ phases which are not magnetically hard at room temperature. However, a relatively high coercivity in the range of 3.5–5.5 kOe has been obtained in these samples. The highest coercivity of 5.5 kOe and a very promising β value of −0.28%/°C were obtained in Sm₈Co₇₄B₁₈ ribbons annealed at 750°C for 5 min. The high coercivities are attributed to the small grain size of the 2 : 14 : 1 phase, in which the large surface areas enhance its effective anisotropy, and make it uniaxial type.