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.     

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.     

Magnetic hardening in Cu-Mn-Al alloys

The magnetic and structural properties of Cu₄₂Mn₂₅Al₃₃ and Cu₄₄Mn₂₅Al₃₁ alloys have been examined in as-cast and heat-treated samples. Magnetic hardening was achieved by heat treating the as-cast samples at 300°C, where they developed two finely dispersed phases identified as the ferromagnetic Heusler phase and the nonmagnetic γCu-Al phase. A maximum coercive field of 8 kOe was obtained in a heat-treated Cu₄₄Mn₂₅Al₃₁ sample. Single domain particle behavior is suggested to explained the observed magnetic hysteresis.     

Non-stoichiometric barium ferrite particles for high-density magnetic recording

The organometallic precursor method was employed for the synthesis of β” ferrites, from which non-stoichiometric Ba ferrite particles have been prepared by ionic exchange. The magnetic grains are hexagonal platelets with diameters as low as 50 nm and aspect ratio of 1.5. After annealing, the sample diameter increases to 200 nm while the grains remain single-domain. The Curie temperature is 455°C. Annealed samples show specific magnetization up to 62 emu/g, coercive fields _jH_c close to 2 kOe, and an SFD factor 1−S* of 0.55     

Ln1−xSrxCoO3(Ln = Sm, Dy) for the electrode of solid oxide fuel cells

The perovskite-type oxides were synthesized in the series of Ln_1−xSr_xCoO₃(Ln = Sm, Dy). The formation of solid solutions in Dy_{1 − x}Sr_xCoO₃ was limited, compared with that in Sm_{1 − x}Sr_xCoO₃. The electrical conductivities of the sintered samples were measured as a function of x in the temperature range 30 to 1000 °C. The highest conductivity of around 500 S/cm at 1000 °C was found in Sm_0.7Sr_0.3CoO₃. The reactivity of all the samples with YSZ was examined at 800–1000 °C for 96 h. The Sr-doped perovskite oxides were more reactive with YSZ and produced SrZrO₃ at 900 °C after 96 h. However, no reaction product between SmCoO₃ and YSZ was observed at 1000 °C for 96 h. The cathodic polarization of the oxide electrodes, sputtered on yttria stabilized zirconia (YSZ), was studied at 800–1000 °C in air. SmCoO₃ shows no degradation of the electrode performance at higher temperatures. The thermal expansion measurements on the sintered samples were carried out from room temperature to 1000 °C. Large thermal expansion coefficients were found in these samples.     

Enhanced magnetic properties of Nd–Fe–B thin films crystallized by heat treatment

Nd₂Fe₁₄B Φ phase crystallites were formed in Nd_16.7Fe_65.5B_17.8 thin films prepared by RF sputtering with subsequent heat treatment. The 2 μm-thick films were deposited onto 0.1 mm Mo sheets at an average substrate temperature (T_s) of 365°C. The enhanced magnetic properties of the magnetically anisotropic thin films were investigated using different heating rates (h_r) of 10°C, 20°C, 50°C and 100°C/min in an annealing experiment. Transformation from the amorphous phase to the crystalline phase is clearly manifested by the formation of fine crystallites embedded as a columnar matrix of Nd₂Fe₁₄B phase. High-resolution scanning electron microscope data of the cross-section of the annealed films show columnar stacking of Nd₂Fe₁₄B crystallites with sizes <500 nm. Transmission electron microscope observations revealed that the microstructure of these films having out-of-plane magnetization consists of uniformly distributed Φ phase with grain size around 400 nm together with small Nd rich particles. This grain size of Φ phase is comparable to the single domain particle diameter of Nd₂Fe₁₄B. Significant change in _iH_c, 4πM_r and 4πM_s with h_r was confirmed. Annealing conditions with a heating rate of 50°C/min to an annealing temperature (T_a) of 650°C for 30 min was consequently found to give optimum properties for the NdFeB thin films. The resulting magnetic properties, considered to be the effect of varying h_r were _iH_c= 1307–1357 kA/m, 4πM_r=0.78–1.06 T and 4πM_s=0.81–1.07 T.     

Nanocrystalline Pr0.5Sm0.5Co5 alloy obtained by mechanical milling

Starting from arc-melted alloys, nanostructured Pr_0.5Sm_0.5Co₅ powders were synthesized by mechanical milling and subsequent vacuum annealing during short times to develop an optimal microstructure with high hard magnetic properties. The best magnetic properties were obtained for the stoichiometric Pr_0.5Sm_0.5Co₅ powders milled for 4 h and annealed at 800 °C for 1 min with a high coercitivity of 13.5 kOe, a high M_r/M_max ratio of 0.72 and a maximum energy product of 11 MGOe. From X-ray diffraction and transmission electron microscopy, CaCu₅-type phase and an average grain size of about 12 nm were determined in the annealed powders, and we calculated that 59% of the volume of the grains/crystallites are exchange-coupled. The observed magnetic hardening is associated to the high magnetic anisotropy field of the PrCo₅ and SmCo₅ phases and also to the microstructure developed by the processing used.     

Effect of a magnetic field on MnAs0.88P0.12 below 80 K

MnAs_0.88P_0.12 has been studied by powder neutron diffraction in external magnetic fields up to 15.2 kOe and temperatures down to 4.2 K. MnAs_0.88P_0.12 takes the MnP type atomic arrangement and exists in para-, ferro- and different (essentially) helimagnetic states. The observation of a double 000^± satellite at 4.2 K < T 70 K adds further evidence to the chain of arguments for distinction between the helimagnetic states H'_a (4.2 K < T < T_S,1 ≈ 70 K) and H_a (T_S,2 ≈ 180 K < T < T_N = (243 ± 5) K). External magnetic fields at 4.2 K < T < 70 K evoke a new magnetic state, which is also characterized by a satellite doublet, and is tentatively designated H'_a,fan.     

Effect of Ti and C additions on structural and magnetic properties of (Pr,Nd)–Fe–B nanocrystalline magnetic materials

Effects of titanium carbide (TiC) addition on structural and magnetic properties of isotropic (Pr,Nd)–Fe-B nanocrystalline magnetic materials have been investigated. In this work, we investigate the effect of TiC addition on a (Pr,Nd)-poor and B-rich composition, as well as on a B-poor and (Nd,Pr)-rich composition. Rapidly solidified (Pr,Nd)–Fe–B alloys were prepared by melt-spinning. The compositions studied were (Pr_1−xNd_x)₄Fe₇₈B₁₈ (x=0, 0.5, and 1) with addition of 3 at% TiC. Unlike the (Pr_xNd_1−x)_9.5Fe_84.5B₆ materials that present excellent values for coercive field and energy product, the (Pr,Nd)-poor and B-rich composition alloys with TiC addition present lower values. Rietveld analysis of X-ray data and Mössbauer spectroscopy revealed that samples are predominantly composed of Fe₃B and -Fe. For the RE-rich compositions (Pr_xNd_1−x)_9.5Fe_84.5B₆ (x=0.1, 0.25, 0.5, 0.75, and 1) with the addition of 3 at% TiC, the highest coercive field and energy product (8.4 kOe and 14.4 MGOe, respectively) were obtained for the composition Pr_9.5Fe_84.5B₆.     

Properties of nonstoichiometric Pr0.6−xSr0.4MnO3 as the cathodes of SOFCs

A series of samples Pr_0.6−xSr_0.4MnO₃ (x=0, 0.01, 0.05, 0.1, 0.15, 0.2) were synthesized by a solid state reaction method. Pr deficiency at the A site has a great effect on the properties of Pr_0.6−xSr_0.4MnO₃ as the cathode of SOFCs (solid oxide fuel cells). Compared to the commonly used La_0.6Sr_0.4MnO₃ and La_0.55Sr_0.4MnO₃ cathode, Pr_0.6−xSr_0.4MnO₃ is better in the properties of conductivity, overpotential and impedance. In all the samples, the one with x=0.05, Pr_0.55Sr_0.4MnO₃, revealed the best performance in the measured temperature range.     

Effect of Cu doping in MgB2 superconductor at various processing temperatures

The effects of Cu doping in MgB₂ superconductor has been studied at different processing temperatures. The polycrystalline samples of Mg_1−xCu_xB₂ with x = 0.05 were synthesized through the in-situ solid sate reaction method in argon atmosphere at different temperature range between 800–900 °C. The samples were characterized through X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and low temperature R–T measurement techniques for the phase verification, microstructure and superconducting transition temperature, respectively. The XRD patterns of Mg_1−xCu_xB₂ (x = 0.05) do not exhibit any impurity traces of MgB₄ or MgB₆ and they show the sharp transition in the samples prepared at 850 °C. The onset transition temperature of the prepared samples is around 39 K, which is almost the same as that for the pure MgB₂. This indicates that Cu doping in MgB₂ does not affect the transition temperature. The SEM micrograph of Mg_0.95Cu_0.05B₂ has shown that the sample is dense with grain size smaller than 1 μm.     

Effect of Sn doping on the magnetic and transport properties of LaMnO3+δ

We report the influence of the Sn doping on the magnetotransport properties of the LaMnO_3+δ perovskite. Two series of samples with nominal LaSn_xMn_1−xO_3+δ (I series) and La_{(1−x)/(1+x)}Sn_xMn_1−xO_3+δ (II series) compositions (x=0, 0.025, 0.05 and 0.10) were prepared at T_s=750°C. The M(T) data under 0.01 and 0.5 T for the I series reveal a depressed magnetization as the Sn content increases suggesting the presence of magnetic clusters with a superparamagnetic behavior. Resistivity measurements indicate an insulator material for all Sn content independently of the applied magnetic field. On the contrary, for the II series the M(T) and M(H) data reveal FM behavior and an improvement of the magnetization as Sn increases. These samples show magnetoresistance. The magnetotransport properties are discussed in terms of the presence of A-site cation vacancies.     

Coercivity enhancement of sintered Nd-Fe-B magnets by grain boundary diffusion with Pr80-xAlxCu20 alloys

A grain boundary diffusion (GBD) process with Pr_80-xAl_xCu₂₀ (x = 0, 10, 15, 20) low melting point alloys was applied to commercial 42M sintered Nd-Fe-B magnets. The best coercivity enhancement of a diffused magnet was for the Pr₆₅Al₁₅Cu₂₀ GBD magnet, from 16.38 kOe to 22.38 kOe. Microstructural investigations indicated that increase in the Al content in the diffusion source can form a continuous grain boundary (GB) phase, optimizing the microstructure to enhance the coercivity. The coercivity enhancement is mainly due to the formation of a continuous GB phase to separate the main phase grains. Exchange decoupling between the adjacent main phase grains is enhanced after the GBD process. Meanwhile, the introduction of Al can effectively promote the infiltration of Pr into the magnet, which increases the diffusion rate of rare-earth elements within a certain range. This work provides a feasible method to enhance coercivity and reduce the use of rare-earth resources by partial replacement of rare-earth elements with non-rare-earth elements in the diffusion source.     

Oxygen nonstoichiometry and electrical conductivity of the solid solutions La2−xSrxNiOy (0≤x≤0.5)

Oxygen nonstoichiometry and electrical resistance of a series La_2−xSr_xNiO_y solid solutions, where x=0.0, 0.2 and 0.5 in argon flows at oxygen partial pressures 1.5, 10.2, 49.2, 100 and 286 Pa within the temperature range of 20–1050°C were studied. Nickelate oxygen desorption/sorption spectra when heating–cooling at constant rate demonstrated strong dependence of cation composition of the samples. Unlike La_1.5Sr_0.5NiO_y compounds those of La₂NiO_y and La_1.8Sr_0.2NiO_y have weakly bonded oxygen, capable to exchange reversibly with the gas phase at the temperatures higher than 250°C. The equilibrium values of oxygen nonstoichiometry and specific resistance for the these nickelates were determined at 300–1050°C and p_O2=1.5–286 Pa as a functions of temperature versus oxygen partial pressure. All nickelate studied appear to be p-type conductors with metal electric conductivity at equilibrium states.     

Amorphous Si/insulator multilayers grown by vacuum deposition and electron cyclotron resonance plasma treatment

a-Si/insulator multilayers have been deposited on (0 0 1) Si by electron gun Si evaporation and periodic electron cyclotron resonance plasma oxidation or nitridation. Exposure to an O or N plasma resulted in the formation of a thin SiO₂ and SiN_x layer whose thickness was self-limited and controlled by process parameters. For thin-layer (2 nm) Si/SiO₂ and Si/SiN_x multilayers no visible photoluminescence (PL) was observed in most samples, although all exhibited weak “blue” PL. For the nitride multilayers, annealing at 750°C or 850°C induced visible PL that varied in peak energy with Si layer thickness. Depth profiling of a-Si caps on thin insulating layers revealed no detectable contamination for the SiN_x layers, but substantial O contamination for the SiO₂ films.     

Magnetic properties of rapidly quenched amorphous Fe-Sm alloys

The structural analysis and investigation of magnetic properties were carried out on rapidly quenched Fe_100−xSm_x (10.5 x 80) alloys. Amorphous alloys are fabricated in a wide composition range from x = 17 to 72.5. After heating the amorphous alloys up to 900 K, they transform into metastable phase I (T_c = 465 K)+ -Fe (x < 20), metastable phase II (T_c = 555 K)+-Fe (20 x 33.3) and Fe₂Sm+Sm (x40). The composition dependence of Curie temperature and magnetization is found to be similar to that of amorphous Fe-(Nd, Pr) alloys. A maximum coercive force of about 1.1 kOe at 300 K and 12 kOe at 77 K is obtained in the x = 40 alloy. The rapid decrease in coercive force with raising temperature can be explained by the wall pinning model proposed by Gaunt. The pronounced composition dependence of these magnetic properties for the amorphous Fe-Sm alloys can be considered to be caused by the change in the short-range atomic order with Sm concentration on the basis of the results of X-ray structural analysis.     

Use of the ac inductive method to assess the quality of bulk melt textured superconductors

Through a measurement of flux profiles, the inductive method of Campbell has not only been used for determining the bulk critical current density of large sized samples but has also been extended to study the coupling strength of the domains in melt textured NdBa₂Cu₃O_7−δ superconductors. An analysis of the profiles measured for the slow (1°C/h) and fast cooled (40°C/h) samples through peritectic temperature, T_p clearly showed that the domain boundaries in the fast cooled samples are decoupled in the presence of external dc fields. The observed features of flux profiles are correlated to the microstructural features of the samples. It is proposed that this technique can be used routinely to assess the quality of large size melt textured samples for high current applications like magnetic bearings or quasi permanent magnets.     

Magnetic behaviour of some Mn.III2.VI4 compounds and their alloys

Measurement of the magnetic susceptibility χ as a function of temperature were made on polycrystalline samples from the alloy systems Cd_1−zMn_zGa₂Se₄, Zn_1−zMn_zGa₂Se₄ and Cd_1−zMn_zIn₂Te₄ which had been subjected to various heat treatments. The 1/χ versus T curves indicated that for the Zn---Se alloys, for all values of z, samples slowly cooled to room temperature were antiferromagnetic showing ideal Curie-Weiss behaviour, but for samples quenched from 700°C the behaviour was a mixture of antiferromagnetic and spin-glass. For the Cd---Se alloys, samples from the range (0.6 < z < 1.0) showed very similar behaviour, but in the range (0 < z < 0.6) even the very slowly cooled samples showed a mixture of antiferromagnetic and spin-glass behaviour. For the Cd---Te alloys, all samples, however heat-treated, showed spin-glass form. Values of the Curie-Weiss constant Ф were determined from all of the 1/χ versus T curves, and by comparison with the T(z) phase diagrams for the different alloy systems, the values of Ф were correlated with the ordering of the Mn atoms on the cation lattice. It is shown that the experimental values of Ф can give a very convenient way of determining the type of ordering and the degree of order in such alloys.     

Reversible H2 passivation of Si ≡ Si3 interface defects in (1 1 1)Si/SiO2

K-band electron spin resonance (ESR) at 4.3 K has revealed the dipole-dipole (DD) interaction effects between [1 1 1]P_b centers (^*Si ≡ Si₃ defects with unpaired sp³ hybrid [1 1 1]) at the 2 dimensional (1 1 1)Si/SiO₂ interface. This has been enabled by the perfectly reversible H₂ passivation of P_b, which affects the defect's spin state. Sequential hydrogenation at 253–353°C and degassing treatments in high vacuum at 743–835°C allowed to vary the P_b density in the range 5 × 10¹⁰ < [P_b] (1.14 ± 0.06) × 10¹³ cm^-2. With increasing [P_b] fine structure doublets are clearly resolved. It is found that (1 1 1)Si/SiO₂ interfaces, dry thermally grown at ≈920°C, naturally comprise a ^*Si ≡ Si₃ defect density — passivated or not — of 1.14 × 10¹³ cm^-2.     

Synthesis and characterization of the Aurivillius phases Bi2 − xPbxSr1 − xNdxNb2O9

The n = 2 Aurivillius phase Bi_{2 − x}Pb_xSr_{1 − x}Nd₂O₉ was successfully synthesized as a ceramic material over the whole range of simultaneous, charge compensated substitution x = 0–1.0. Structural investigations were performed by Rietveld refinement applying different space groups Fmmm and A2₁am, and additionally by X-ray absorption spectroscopy (EXAFS) on the Nd L_III-edge, confirming the accommodation of Nd on the atomic sites of Sr, which implies the substitution of Bi³⁺ by the isoelectronic Pb²⁺. The ferroelectric transition temperature T_c = 270 °C of the substituted powders with x = 0.4 and 1.0 is distinctly reduced compared to the unsubstituted sample with T_c = 450 °C. In temperature resolved powder X-ray diffraction patterns no structural phase transition could be detected.