Magnetic anisotropy induced in Nd16Fe76B8 by Hf additions

Remanence, coercivity and maximum energy product (BH)_max of Nd₁₆Fe_76−xHf_xB₈ (x=0, 0.1, 0.2) magnets processed under different hydrogenation-disproportionation-desorption-recombination (HDDR) conditions, were studied. Vibrating sample magnetometry results showed that Hf-doped materials develop an important degree of anisotropy, especially for the case of solid-HDDR treatments at 800°C and 850°C, with the largest effect at 850°C. Maximum values of remanence and coercivity were observed for Hf-added samples S-HD at 850°C, and 900°C, respectively. The highest (BH)_max value was also observed in S-HD 900°C Hf-added samples. These results are discussed in terms of the expected microstructure of the intermediate HD and final HDDR processed powders.     

The relationship between crystal structure and electrical conductivity in the LaY1−xInxO3 (x=0.0–0.7) system

The electrical conductivity of the LaY_1−xIn_xO₃ (x=0.0–0.7) system has been studied from the viewpoint of crystal chemistry. The high temperature form of LaYO₃ (x=0.0) was ascertained to be the Sm₂O₃-type (B-type rare earth) structure, not perovskite-type one. The X-ray diffraction (XRD) experiments revealed that the samples with x=0.05 and 0.10 were the mixed phase of Sm₂O₃-type and perovskite-type structure, and changed to perovskite phase in the range of x0.20. From oxygen partial pressure dependence of the electrical conductivity, it was found that both the Sm₂O₃-type and the perovskite-type single phases showed hole conduction, but the mixed phase did oxide-ion one. The electrical conductivity of the LaY_1−xIn_xO₃ (x=0.0–0.7) system increased with increasing x, and showed the maximum value in the range of x=0.05–0.10, and then decreased with increasing x. The occurrence of oxide-ion conduction was discussed from the viewpoint of lattice distortion in the mixed phase.     

On the appearance of ferromagnetism in Y(Co1−xAlx)2 alloys

The appearance of ferromagnetism in Y(Co_1−xAl_x)₂ is discussed in terms of a d band model. The approximate d bands for YCo₂ and Y(Co_1−x)₂ are calculated and the decrease in the electronic energy due to magnetization of the spin of estimated. The energy decrease is the largest in YCo₂, and it gradually decreases as the Al content increases, if the lattice constant is fixed, while this energy decrease increases if the lattice constant increases with increasing Al content. These results of calculations give a good account of the appearance of ferromagnetism in Y(Co_1−xAl_x)₂ around x = 0.15. The ferromagnetism in Sc(CO_1−xAl_x)₂ is also discussed, leading to the appearance of ferromagnetism between x = 0.15 and 0.30.     

Disruption of antiferromagnetic order in Zn-doped La2CuO4

The magnetic phase diagram of La₂(Cu_1−xZn_x)O₄ has been determined from zero-field muon-spin-rotation (ZF-μSR) data taken at LAMPF for 0 ≤ x ≤ 0.10. Antiferromagnetic onset temperatures follow T_N(x) from susceptibility measurements on the same samples. However, the order becomes long range, as evidenced by a well-defined internal magnetic field, only at temperatures well below T_N. Extrapolation of our results yields T_N → 0 K at x = 0.11 for a single (Cu_1−xZn_x)O₂ plane, and comparison with YBa₂(Cu_1−xZn_x)₃O₆ implies identical disruption of magnetism by Zn doping in the single- and double-plane systems.     

A Raman study of the structural properties of YBa2(Cu1 − xFex)3Oy

The effects of Fe-substitution of YBa₂Cu₃O_y have been investigated by means of Raman scattering, X-ray diffraction, resistivity and susceptibility measurements. A series of samples of YBa₂(Cu_{1 − x}Fe_x)₃O_y with different dopant concentration (0 x 0.15) has been prepared in two batches, the second set having undergone twice the heat and mechanical treatment used to produce the first batch. Considerable improvement in the superconducting transition temperature, T_c, is obtained upon reprocessing. A phase transformation from orthorhombic to tetragonal symmetry is observed for x=0.05 from the X-ray measurements in agreement with previous work. Using a micro-Raman technique, all five A_g vibrational modes have been measured and their dependence on Fe-concentration is analyzed. There are indications that iron substitutes for copper at both sites and that the structure is a mixture of orthorhombic and tetragonal microdomains for all x.     

Oxide-ion conductivity of (Ba1−xLax)2In2O5+x system based on brownmillerite structure

(Ba_1−xLa_x)₂In₂O_5+x, whose end member is Ba₂In₂O₅, is an oxygen-deficient perovskite oxide showing high oxide-ion conductivity. In order to clarify the reason why the high oxide ion conductivity appeared in this system, the electrical conductivity was measured as a function of temperature and La content. With an increasing La content, the discontinuous jump of ion conductivity in the Arrhenius plot, which is related to the disordering of the oxygen vacancies, disappeared for the sample with x0.2. Above x=0.12, the ion conductivity linearly increased with La content, while the activation energy remained constant with respect to the La content. Moreover, the conductivity for x=0.6 was 0.042 (S/cm) at 1073 K, which exceeded that of 8 mol% yttria-stabilized zirconia. The higher oxide-ion conductivity of this system could be dominated by the amount of mobile oxygen ions.     

Tuning the multiferroic properties of Pb(Fe1/2Nb1/2)O3 by cationic substitution

A series of substituted lead iron niobate compounds with the general formula Pb²⁺_(1−x)A^Z_x(Fe_{{(1−(2−Z)x)/2}}Nb_{{(1+(2−Z)x)/2}})O₃ (0<x<0.6 and A=La³⁺, K⁺ or Sr²⁺) were prepared by a modified solid-state synthesis. The relative concentrations of Fe³⁺ and Nb⁵⁺ were adjusted to compensate the charge imbalance due to the aliovalent substitution. The dielectric constant and magnetic susceptibilities were studied as a function of temperature. The temperature of the dielectric maximum, T_M, of the substituted compounds decreased linearly with increasing concentration of the substituent ions. The magnetic measurements showed an antiferromagnetic transition at temperatures T_N1 due to the superexchange interactions mediated by Fe–O–Fe and an additional antiferromagnetic-type transition at T_N2. T_N1 linearly increased with the increasing concentration of Fe³⁺ ion at the B-site of ABO₃-type substituted compounds. T_M is shown to be directly dependent on the concentration of the ferroactive Nb⁵⁺ ions at the B-site and Pb²⁺ ions at the A-site.     

Oxygen diffusion and surface exchange in La1−xSrxFe0.8Cr0.2O3−δ (x=0.2, 0.4 and 0.6)

Oxygen tracer diffusion (D*) and surface exchange rate constant (k*) have been measured, using isotopic exchange and depth profiling by secondary ion mass spectrometry (SIMS), in La_1−xSr_xFe_0.8Cr_0.2O_3−δ (x=0.2, 0.4 and 0.6). Measurements were made as a function of temperature (700–1000 °C) and oxygen partial pressure (0.21–10⁻²¹ atm) in dry oxygen, water vapour and water vapour/hydrogen/nitrogen mixtures. At high oxygen activity, D* was found to increase with increasing temperature and Sr content. The activation energies for D* in air are 2.13 eV (x=0.2), 1.53 eV (x=0.4) and 1.21 eV (x=0.6). As the oxygen activity decreases, D* increases as expected qualitatively from the increase in oxygen vacancy concentration. Under strongly reducing conditions, the measured values of D* at 1000 °C range from 10⁻⁸ cm² s⁻¹ for x=0.2 to 10⁻⁷ cm² s⁻¹ for x=0.4 and 0.6. The activation energies determined at constant H₂O/H₂ ratio are 1.21 eV (x=0.2), 1.59 eV (x=0.4) and 0.82 eV (x=0.6).

The surface exchange rate constant of oxygen for the H₂O molecule is similar in magnitude to that for the O₂ molecule and both increase with increasing Sr concentration.     

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.     

Superconductivity at 27 K in Nb-1222 cuprate: NbSr2(GdCe)2Cu2Oy

Samples of NbSr₂Gd_2−xCe_xCu₂O_y have been prepared by solid state reaction. The X-ray powder diffraction patterns show that a single phase can be formed in the composition range of 0.49<x<0.51 that has TaSr₂ (NdCe)₂Cu₂O_y structure [1], the cell parameters being a=3.8669±0.0046 Å and c=28.742±0.0048 Å. Superconductivity was found by resistance measurements in the sample of NbSr₂Gd_1.5Ce_0.5Cu₂O_y: the onset transition temperature is 27.4 K, and zero resistance appears at approximately 13 K.     

Giant pressure effect in oxygen deficient YBa2Cu3Ox

The pressure effect on T_c of polycrystalline and single crystalline YBa₂Cu₃O_x investigated as a function of oxygen content x by ac-susceptibility measurements under helium pressure. In the overdoped region x> 6.93 the single crystals show a negative dT_c/d p, as expected from the charge transfer model. For optimally doped samples with x = 6.93 we find dT_c/d P = 0.4 K/GPa which points to pressure effects on T_c aside from charge transfer. In the underdoped region x < 6.93 the dT_c/d p values obtained from the experiment depend strongly on the storage temperature of the sample during the experiment. When the samples are stored at temperatures well below 240 K throughout the entire experiment including pressure application and pressure release, dT_c/d p increases to approx. 7 K/GPa at x = 6.7 but with a further decrease of the oxygen content the dT_c/d p drops to approx. 2 K/GPa at x = 6.4. These effects are intrinsic to the YBa₂Cu₃O_x structure and can be explained by considering the anisotropic structure of YBa₂Cu₃O_x. The decrease of the c-axis lattice parameter results in a charge transfer to the CuO₂-planes mainly [1], whereas the compression of the a- and b-axis lattice parameter is known to produce different pressure effects which are responsible for the peak in dT_c/d p at x = 6.7 [2]. When pressure is changed at room temperature oxygen ordering effects occur which cause a relaxation of T_c to the equilibrium value T_c(p) at this pressure with a time constant depending on the oxygen content x. A decrease x results in a peak effect in dT_c/d p at x = 6.7 again, which is enhanced to approx. 12 K/GPa. If the oxygen content is decreased further, dT_c/d p first drops to 5 K/GPa at x = 6.6, but the increases to values of more than 20 K/GPa for x < 6.42. These giant pressure effects at low oxygen contents are mainly caused by a reversible T_c increase (dT_c/d p)_O due to pressure induced oxygen ordering via oxygen motion between unit cells.     

Magnetic moments and Fe hyperfine field interactions in Y(Fe1−xRux)2 ternaries

Measurements of magnetization and ⁵⁷Fe Mössbauer spectra have been made for Y(Fe_1−xRu_x)₂. The C15 type cubic structure is stabilized for xx 0.7. The C15 compounds is ferromagnetic with T_c200 K and its saturation moment decreases monotonically with increasing x, while the ⁵⁷Fe hyperfine field decreases only slightly with x. From these results, it is deduced that the Ru atoms have an induced moment of ≈1μ_B in the range x 0.2. In the C14 type phase, no magnetic ordering develops even at 4.2 K.     

Superconductivity in Ba2−xSrxYCu3Oz prepared at GPa

The compounds Ba_1.4Sr_0.6YCu₃O_z (7.0≤z<7.4) were synthesized at 2 GPa to clarify the effect of high temperature and pressure on the superconducting properties. The structure as observed by powder X-ray diffraction was tetragonal for z≥7.2, and orthorhombic or tetragonal for z<7.1. It has been revealed that high-pressure syntheses suppress the superconductivity in the compounds with z<7.1. Recovery of the superconducting properties occurs above z≥7.2. The effect of Sr substitution on the superconducting properties was also studied. The magnitude of diamagnetism at 5–30 K decreases monotonically from −0.003 to −0.0002 emu/g Oe with increasing x in Ba_2−xSr_xYCu₃O_z (x≥1.2).     

Magnetic anisotropy of the Y(Co1-xFex)3 pseudobinary compounds

The anisotropy energy of the Y(Co_{1 - x}Fe_x)₃ compounds has been determined between 4.2 and 250 K. The concentration dependence of the anisotropy energy behaves anomalously in this pseudo-binary series. Upon increasing the iron content, the anisotropy energy increases up to x = 0.25, then decreases, changes sign around x = 0.45 and reaches a flat minimum at the iron-rich side. This anomaly can satisfactorily be explained in terms of the individual site anisotropy model by considering the different occupancy factors of iron and cobalt for the 3d sites.     

Superconductivity and crystallographic properties of La2 − xMxCuO4 − δ (M = Na, K)

Superconductivity and crystallographic properties of La_{2 − x}M_xCuO_{4 − δ} (M = Na, K) are studied. In the La_{2 − x}M_xCuO_{4 − δ} system, superconductivity is detected for x 0.2. Oxygen content analysis shows that the system has more oxygen vacancies than the La_{2 − x}Sr_xCuO_{4 − δ} system. These oxygen vacancies may reduce the hole concentration, and high Na-doping is needed to produce superconductivity. In the La_{2 − x}K_xCuO_{4 − δ} system, superconductivity is observed for the first time. Resistivity and magnetic susceptibility measurements show that T_c(onset) is 40 K and the Meissner volume fraction is about 4% for x = 0.7. The system changes from orthorhombic to a tetragonal K₂NiF₄ structure at x ≈ 0.3 and only tetragonal samples show superconductivity.     

Material design of new lithium ionic conductor, thio-LISICON, in the Li2S–P2S5 system

A new lithium ionic conductor of the thio-LISICON (LIthium SuperIonic CONductor) family was found in the binary Li₂S–P₂S₅ system; the new solid solution with the composition range 0.0≤x≤0.27 in Li_3+5xP_1−xS₄ was synthesized at 700 °C and characterized by X-ray diffraction measurements. Its electrical and electrochemical properties were studied by ac impedance and cyclic voltammetry measurements, respectively. The solid solution member at x=0.065 in Li_3+5xP_1−xS₄ showed the highest conductivity value of 1.5×10⁻⁴ S cm⁻¹ at 27 °C with negligible electronic conductivity and the activation energy of 22 kJ mol⁻¹ which is characteristic of high ionic conduction state. The extra lithium ions in Li₃PS₄ created by partial substitution of P⁵⁺ for Li⁺ led to the large increase in ionic conductivity. In the solid solution range examined, the minimum conductivity was obtained for the compositions, Li₃PS₄ (x=0.0 in Li_3+5xP_1−xS₄) and Li₄P_0.8S₄ (x=0.2 in Li_3+5xP_1−xS₄); this conductivity behavior is similar to other thio-LISICON family with the general formula, Li_xM_1−yM_y′S₄ (M=Si, Ge, and M′=P, Al, Zn, Ga, Sb). Conduction mechanism and the material design concepts are discussed based on the conduction behavior and the structure considerations.     

Nax/2Bi1−x/2MoxV1−xO4 and Bi1−x/3MoxV1−xO4 New Scheelite-related phases

New Scheelite-related solid solutions of the compositions Na_x/2Bi_1−x/2Mo_xV_1−xO₄ (0≤x≤1) and Bi_1−x/3 Mo_xV_1−xO₄(0≤x≤0.2) have been synthesised by the substitution of Na and Mo at the A and B sites respectively of the ABO₄ type ferroelastic BiVO₄. The phases were characterised using chemical analysis, powder X-ray diffraction, scanning electron microscopy, EDAX, and Raman spectroscopy. While almost a continuous solid solution is obtained for the series Na_x/2Bi_1−x/2Mo_xV_1−xO₄, the absence of Na at the A-site results only in a narrow stability region for the other series, Bi_1−x/3 Mo_xV_1−xO₄ where 0≤x≤0.2. Raman spectra of selected samples at room temperature also suggest that vanadium and molybdenum atoms are disordered at the tetrahedral sites.     

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.     

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.     

Study on the superconducting composite material formation in the system Bi2Sr2CaCu2O8+x/Al-containing phases

Phase evolution in the Bi---Sr---Ca---Cu---Al---O system was studied. Two Al-containing phases BiSr_1.5Ca_0.5Al₂O_z and (Sr_1−xCa_x)₃Al₂O₆ (x = 0.4 − 0.45) were determined to be chemically compatible with Bi_2.18Sr₂CaCu₂O_8+x (Bi-2212) at temperatures of the samples processing. The phase equilibria in the title system were investigated above the solidus temperature. The BiSr_1.5Ca_0.5Al₂O_z was found to be in equilibrium only with the melt and the (Sr_1−xCa_x)₃Al₂O₆ phase. This latter aluminate equilibrated with Ca,Sr cuprates, CaO, the Cu-free phase, and the liquid. The melting and solidification in Bi-2212, doped with the aluminate, corresponded to the reversible reaction Bi-2212 + BiSr_1.5Ca_0.5Al₂O_z ↔ (Sr_1−xCa_x)₃Al₂O₆ + liquid. Two sets of superconducting composite materials with initial compositions Bi-2212 + nBiSr_1.5Ca_0.5Al₂O_z and Bi-2212 + m(Sr_1−xCa_x)₃Al₂O₆ were prepared by solidification from the partial melt. The former material was composed mostly of large Bi-2212 lamellas separated by the BiSr_1.5Ca_0.5Al₂O_z phase, which destroyed superconducting links between Bi-2212 grains. The latter material consisted of a Bi-2212 polycrystalline matrix with high concentration of small (ca. 3 μm) grains of (Sr_1−xCa_x)₃Al₂O₆ imbedded in Bi-2212 lamellas. The Bi-2212 + m(Sr_1−xCa_x)₃Al₂O₆ materials displayed a trend to enhance flux pinning at T = 60 K with the increase of aluminate phase content.