Magnetic properties of Zr(FeAl)2 pseudobinaries: A CPA study

An extension of the usual tight binding CPA to include local d-p hybridization induced by sp impurities (Al or Si) is proposed. Coupled self-consistency equations for the d and p effective medium self-energies are established. An application to Zr(Fe_1−xAl_x)₂ pseudobinary is presented.     

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.     

Spin fluctuations of Y(Mn1−xAlx)2 and Y1−xScxMn2

The thermal expansion and low temperature and low temperature specific heat were measured for Y_1−xScxMn2. The results are discussed in terms of spin fluctuations and compared with those of Y(Mn_1−xAl_x)₂, which show al local moment character. It is revealed that Y_1−xSc_xMn₂ is a typical nearly antiferromagnet in which giant spin fluctuations are thermally excited.     

Study of superconducting state parameters of alkali–alkali binary alloys by a pseudopotential

A detailed study of the superconducting state parameters (SSP) viz. electron–phonon coupling strength λ, Coulomb pseudopotential μ^*, transition temperature T_C, isotope effect exponent and effective interaction strength N_OV of ten alkali–alkali binary alloys i.e. Li_1−xNa_x, Li_1−xK_x, Li_1−xRb_x, Li_1−xCs_x, Na_1−xK_x, Na_1−xRb_x, Na_1−xCs_x, K_1−xRb_x, K_1−xCs_x and Rb_1−xCs_x are made within the framework of the model potential formalism and employing the pseudo-alloy-atom (PAA) model for the first time. We use the Ashcroft’s empty core (EMC) model potential for evaluating the superconducting properties of alkali alloys. Five different forms of local field correction functions viz. Hartree (H), Taylor (T), Ichimaru–Utsumi (IU), Farid et al. (F) and Sarkar et al. (S) are used to incorporate the exchange and correlation effects. A considerable influence of various exchange and correlation functions on λ and μ^* is found from the present study. Reasonable agreement with the theoretical values of the SSP of pure components is found (corresponding to the concentration x = 0 or 1). It is also concluded that nature of the SSP strongly depends on the value of the atomic volume Ω₀ of alkali–alkali binary alloys.     

Effects of cation- or oxide ion-defect on conductivities of apatite-type La–Ge–O system ceramics

A series of apatite-type La–Ge–O ceramics were prepared and their cation-defect at the 4f+6h sites and oxide ion-defect at 2a site were investigated. In La_xGe₆O_12+1.5x ceramics of x=6–12, the higher conductivities were obtained in the region of apatite composition, La_x(GeO₄)₆O_1.5x−12 (x=8–9.33), and the highest conductivity was achieved for La₉(GeO₄)₆O_1.5 (x=9), where the number of cation (La³⁺) occupying the 4f+6h sites is 9 and the number of oxide ion occupying the 2a site is 1.5. The ceramics with cation- and oxide ion-defects were La_9−0.66xSr_x(GeO₄)₆O_1.5 (x=0–1), La_9−1.33xZr_x(GeO₄)₆O_1.5 (x=0–1), La_9−xSr_x(GeO₄)₆O_1.5−0.5x (x=0–3), La_9−xZr_x(GeO₄)₆O_1.5+0.5x (x=0–1), La_x(GeO₄)_3x−21(AsO₄)_27−3xO_1.5 (x=0–3), La_x(GeO₄)_33−3x(AlO₄)_3x−27O_1.5 (x=0–3), La₉(GeO₄)_6−x (AlO₄)_xO_1.5−0.5x (x=0–3), La₉(GeO₄)_6−x(AsO₄)_xO_1.5+0.5x (x=0–1), La_9.33−xSr_x(GeO₄)₆O_2−0.5x (x=0–1.2) and La_x(GeO₄)_4.5(AlO₄)_1.5O_1.5x−12.75 (x=8.8–9.83), which were prepared by the partial substitution of La³⁺and GeO₄⁴⁻of the basic apatite La₉(GeO₄)₆O_1.5 with Sr²⁺ or Zr⁴⁺ and AlO₄⁵⁻ or AsO₄³⁻. Such substitutions lowered the conductivity of La₉(GeO₄)₆O_1.5. These results were discussed by the electrostatic interaction between Sr²⁺, Zr⁴⁺, AlO₄⁵⁻ or AsO₄³⁻ and oxide ion as a conductive species.     

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.     

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.     

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.     

Spectral editing in MAS NMR of aprotic solids P---Cd cross-polarization and heteronuclear double-quantum filtering studies in II-IV-V2 semiconductor alloys

Magic-angle-spinning NMR spectra of aprotic solids, ceramics and glasses frequently suffer from poor site resolution due to wide chemical shift distribution effects. In such cases, cross-polarization and heteronuclear double-quantum filtering experiments involving nuclei other than ¹H offer unique spectral editing capabilities. The utility of such assignment techniques for examining site populations in semiconductor alloys is demonstrated for the chalcopyrite systems CdGeAs_2−xP_x, CdSiAs_2−xP_x and Zn_xCd_1−xGeP₂. The results permit a distinction between local and non-local effects on experimental chemical shift trends and reveal that compositional dependences observed in these alloys are dominated by non-local chemical shift contributions.     

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.     

Erbium in silicon–germanium quantum wells

Strained Si_1−xGe_x/Si quantum wells have been doped with erbium by implantation. A comparison is made with strained Si_1−xGe_x/Si quantum wells and relaxed Si_1−xGe_x, with x between 10% and 25%, doped with erbium during MBE growth. The erbium concentration was between 1×10¹⁸ and 5×10¹⁸ cm⁻³ throughout the active regions. Transmission electron microscopy, X-ray diffraction, and photoluminescence studies indicate that good regrowth can been achieved after full amorphisation by implantation of the strained quantum wells. The erbium luminescence is more intense in the Si_1−xGe_x/Si layers, but erbium-implanted samples containing Si_1−xGe_x exhibit defect luminescence in the region of 0.9–1.0 eV. These defects are also present when Si_1−xGe_x/Si quantum wells are implanted with an amorphising dose of silicon, and then regrown. They are attributed to small germanium-rich platelets, rather than to erbium-related defects. Electroluminescence is presented from a forward biased erbium-implanted Si_0.87Ge_0.13/Si structure at a drive current density of only 1.8 mA/cm².     

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.     

Niobium based tetragonal tungsten bronzes as potential anodes for solid oxide fuel cells: synthesis and electrical characterisation

In this paper we report studies on a range of niobate based tungsten bronzes, with a view to analysing their potential as anode materials in SOFCs. Six systems were studied, (Sr_1−xBa_x)_0.6Ti_0.2Nb_0.8O₃, Sr_0.6−xLa_xTi_0.2+xNb_0.8−xO₃, (Sr_0.4−xBa_x)Na_0.2NbO₃, (Ba_1−xCa_x)_0.6Ti_0.2Nb_0.8O₃, Ba_0.5−xA_xNbO₃ (A=Ca, Sr), and Ba_0.3NbO_2.8, and the electrical conductivities were examined over a range of oxygen partial pressures (10⁻²⁰–1 bar). All the systems showed good conductivity in low oxygen partial pressures, with values as high as 8 S cm⁻¹ at 930°C (P(O₂)=10⁻²⁰ bar). As the oxygen partial pressure was raised the conductivity dropped showing in most cases an approximate [P(O₂)]^−1/4 dependence and good re-oxidation kinetics. Of all the samples studied the (Sr_1−xBa_x)_0.6Ti_0.2Nb_0.8O₃ and (Ba_1−xCa_x)_0.6Ti_0.2Nb_0.8O₃ systems appear most promising for potential use as anode materials in SOFCs.     

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.     

The solubility of phosphorus in GaN

IIIV_xN_1−x ternary alloys are promising materials for their applications in light-emitting devices in the range of wavelength from ultra violet to the infrared ray due to the large bowing of band gap energy. In this paper, molecular dynamical method was used to calculate the solubility of phosphorus in GaN by using the Gibbs free energy and the dielectric theory. The calculation results show that the content of P in GaN varies with the growth temperature, which may be larger than 25% in the N-rich GaP_xN_1−x or less than 90% in the P-rich GaP_xN_1−x, at the growth temperature of about 1500 K. We compared our theoretical results with those reported in references. By using light-radiation heating together with low-pressure metal-organic chemical vapor deposition, and ion implantation techniques, we have successfully synthesized N-rich (x < 0.17) and P-rich GaP_xN_1−x (x > 0.90) compounds.     

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.     

Cobalt substituted R---Fe(Co)---C alloys

The formation of tetragonal R₂(FeCo)₁₄C phase has been examined in as-cast and melt-spun R₁₄Fe_78−xCo_xC₈ alloys with cobalt substitutions (R = Y, Dy, Nd). The magnetic properties over a temperature range and the microstructure have been studied as a function of cobalt content. The Curie temperature is increased with Co content but the anisotropy K is decreased. High cobalt content leads to the formation of 1:5 phase. High corecivities have been developed in as-cast and melt-spun Dy₁₄Fe_78−xCo_xC₈ alloys with Co content at zero and 32 at %, respectively. As-cast Nd₁₆Fe_78−xCo_xC₈ alloys did not show any permanent magnetic properties although they had the 2:14:1 phase. However, melt-spun and powdered Nd---Fe---Co---C samples showed a coercivity with the highest value corresponding to a melt-spun Nd₁₄Fe₇₈C₈ sample. Microstructure studies showed that the high H_C in ribbons is due to the fine grain size which is in the range of 500–1000 Å.     

NMR study of coexistence of ferro- and antiferromagnetism in (Zr1−xNbx)Fe2

The magnetic phase diagram has been investigated in the C14 type (Zr_1−xNb_x)Fe₂ with x0.7 from ⁹³Nb NMR and magnetization measurements. In the compound with x = 0.825 a first order-like transition has been found to occur around 25 K from a canted state with the ferromagnetic moment in the basal plane to a ferromagnetic state with decreasing temperature.     

Structure, oxygen stoichiometry and electrical conductivity in the system Sr-Ce-Co-O

Mixed oxides in the system S-Ce-Co-O were prepared by solid state reaction and by freeze-drying of precursor compounds followed by thermal treatment. Two types of perovskite oxides exist in the system: Solid solutions of the type Sr_{1 − y}Ce_yCoO_{3 − x} and mixed oxides of the type (1 − y)SrCeO₃ − ySrCoO_{3 − x}. Microstructures and phase compositions were determined by electron microscopy and X-ray diffraction. SrCoO_{3 − x} forms a solid solution of ceria on the A-site in the strontium cobaltite lattice up to 0.15 mol Ce. This solid solution corresponds to the high-temperature structure of pure SrCoO_{3 − x} and is characterized by high oxygen exchange and electrical conductivity. The oxygen deficiency x was measured by solid electrolyte coulometry. The oxygen deficiency of solid solutions Sr_{1 − y}Ce_yCoO_{3 − x} increases with temperature and decreases with pO₂ in the ambient atmosphere and with increasing Ce dopant concentration. The pO₂-T-x diagram of the solid solution was determined. The T, pO₂ and dopant concentration dependencies of electrical conductivity were measured by a four-point d.c. technique. By Ce doping strontium cobaltite becomes a stabilized high-conductive material (maximum conductivity: 500 S cm⁻¹ at 400 °C, E_a = 0.025 eV, p-type). Above this temperature the T-coefficient of the conductivity changes from positive (semiconducting) to negative values.     

NMR study of Laves phase (Mg1−xRx)Co2 compounds

Nuclear magnetic resonances of ⁵⁹Co nuclei in (Mg_1−xR_x)Co₂ (R = Y, Gd) compounds at 4.2 K have been observed for 0x1. By replacing Mg with R, the ⁵⁹Co hyperfine field decreases or is nearly constant in the C14 range and increases in the C15 range. These results are explained by the difference of the contribution from R atoms.