The effect of substitution of La for Tb on some physical properties of Tb1−xLaxNi2 solid solutions

The standard Gibbs energy of formation, , of MgLa in the temperature range from near absolute 0 to 525 K were determined by calorimetry. The heat capacities, C_p, from 2 K to 525 K were measured by the relaxation method and DSC. Also, a thermal anomaly at 5.9 K, which appeared to be a superconductive phase transition, was found in the obtained C_p values. The values were determined by combining the C_p data with the standard enthalpy of formation at 298 K which was measured by the Calvet-type calorimeter using hydrochloric acid solution. From 2 to 300 K, the increases gradually, and it can be evaluated as a linear function of temperature above 300 K as follows:

This result is expected to be useful as basic thermodynamic data of Mg-based alloys.     

Modification to the composition of nanocrystalline RuO2 through reactive milling under O2

Crystalline ruthenium dioxide (RuO₂) has been ball-milled in an O₂ atmosphere and the changes in the physico-chemical properties induced by different milling atmospheres (Ar and O₂) or milling sequences have been established. Cyclic voltammetry and BET measurements were used to evaluate the electrochemically active surface charge (, expressed in C g⁻¹) and the specific surface area (expressed in m² g⁻¹), respectively. The extent of oxygen uptake in the processed samples was determined by X-ray photoelectron spectroscopy (XPS). The value of RuO₂ milled under O₂ for 30 h (sample S4) is 120.7 C g⁻¹, a factor of two higher than the value of RuO₂ milled under Ar for the same period of time (sample S1, 60.3 C g⁻¹). A still higher value is obtained when the O₂ atmosphere of the crucible is frequently replenished (sample S5, 138.7 C g⁻¹) or when the milling operation is prolonged up to 81 h (sample S6, 160.5 C g⁻¹). These changes are paralleled by a variation of the BET surface area, which increases from 24 m² g⁻¹ for sample S1 to 51.5 m² g⁻¹ for sample S5. The concentration ratio [O_{bound to Ru}]/[Ru] determined by XPS increases steadily from sample S1 to sample S6, indicating that the amount [O_{bound to Ru}] increases with the exposure of RuO₂ to oxygen during the milling process. All these changes are explained by the fact that freshly exposed RuO₂ surfaces created during the milling process react with O₂ molecules, thereby lowering the surface energies and the tendency of the milled material to cluster into larger aggregates.     

The dielectric function of Mgy NiHx thin films ()

Mg_y Ni (2≤y≤10) thin films covered with a Pd cap layer are hydrogenated in 10⁵  Pa H₂ between room temperature and 80 ° C and their dielectric function is determined from reflection and transmission measurements. The hydrogenated Mg_y NiH_x thin films show a continuous shift of the optical absorption towards higher photon energies with increasing y. Comparison of the obtained dielectric functions with predictions from an effective medium theory show that a considerable doping of the Mg₂ NiH₄ host takes place at least for y≤3.5 while no signature of MgH₂ is observed in that composition range in the optical spectra. This is in contrast to the predictions from the bulk phase diagram where a mixture of semiconducting Mg₂ NiH₄ (energy gap E_g=1.6  eV) and MgH₂ (E_g=5.6  eV) is expected.     

Two polymorphs of Ba3Sn2P4: Single crystal and electronic structures

Two polymorphs (I and II) of Ba₃Sn₂P₄ have been found in the same preparative batch. Both compounds crystallize in the centrosymmetric monoclinic space group P2₁/c (#14, a = 7.8669(2) Å, b = 19.2378(5) Å, c = 7.8472(2) Å, β = 112.77(1)°, V = 1095.06(5) Å³, Z = 4, and R/wR = 0.0303/0.0710 for I; a = 7.8771(3) Å, b = 19.4099(7) Å, c = 7.7040(3) Å, β = 112.44(1)°, V = 1088.67(7) Å³, Z = 4, and R/wR = 0.0224/0.0415 for II). Both structures consist of one-dimensional chains separated by Ba²⁺ cations. The isolated chain consists of condensed ethane-like [Sn₂P₆] units. In polymorphs I and II, the condensation and connectivity of the [Sn₂P₆] units are quite different. While [Sn₂P₆] units form four- and six-membered rings in I, they form the five-membered rings in II. The electronic structure calculations indicate that semiconducting behavior is expected for both compounds.     

Fragility and thermal stability of Pt- and Pd-based bulk glass forming liquids and their correlation with deformability

The fragility parameter m of (Pt or Pd)–(Ni, Cu)–P bulk metallic glasses (BMGs) was characterized and compared to other systems. The results indicate that the Pt₆₅Ni₁₅P₂₅ alloy is the most fragile and thermally stable at the supercooled liquid state, thus is the most workable among the presently developed BMGs. To express the degree of workability, a deformability is introduced then correlated with m and the reduced thermal stability . A master curve in term of and has been established for various BMGs, d^* thus can be uniquely related to .     

Growing ledge structures of AlN crystals in a Fe–Mn–Al–C alloy

The Fe–30.4Mn–8.7Al–1.0C (wt.%) alloy was nitridized at 1000 °C. The AlN formed into a Widmanstätten side-plate shape. The side-plate of the AlN is parallel to the basal plane of the HCP crystal. There are three possible growing riser planes; namely ()_AlN, ()_AlN, and ()_AlN planes. The angle for growing riser planes met on the (0 0 0 1) terraces is 120°.     

Synthesis characterization of magnetic properties in La0.7−x Lnx Pb0.3 MnO3 (, Nd, Gd, Dy, Sm and Y) perovskite compounds

The influence of La substitution by rare-earth elements on the magnetization behaviors of perovskite oxides, La_0.7−x Ln_x Pb_0.3 MnO₃ (Ln=Pr, Nd, Gd, Dy, Sm and Y), is investigated. The replacement of La ion by Pr, Nd, Gd, Dy, Sm or Y results in a considerable decrease in the ferromagnetic ordering temperature T_C and clearly irreversible behavior in the FC–ZFC curves showing a short-range spin order phase. The fact is in agreement with the smaller ionic radii of Pr, Nd, Gd, Dy, Sm and Y ions in contrast to La ion and the corresponding larger distortion of perovskite structures. The saturation magnetization M_S increases as Pr or Nd content increases while M_S decreases as Sm or Y content increases. Moreover, the saturation magnetization M_S increases and then decreases as Gd or Dy content increases. These results can be explained in terms of the competition between the increase of ferromagnetically interacting spins due to the introduction of magnetic ions with f-shell electrons and suppression of ferromagnetism due to structure tuning induced by the small ionic radius of the interpolated cation into the La-site.     

Optical absorption and spectroscopic characteristics of Tm ions doped NaY(MoO4)2 crystal

The polarized absorption and emission spectra have been measured for the Tm³⁺ doped NaY(MoO₄)₂ crystal and spectral parameters have been estimated from the absorption data based on the Judd–Ofelt theory. The effective intensity parameters (t = 2, 4, 6) are 11.67 ×10⁻²⁰, 2.21 × 10⁻²⁰, 1.74 × 10⁻²⁰ cm², respectively. From the intensity parameters, the radiative transition probabilities, radiative lifetimes, branching ratios and the emission cross-section have been calculated. In comparison with other Tm³⁺ doped laser crystals, Tm³⁺:NaY(MoO₄)₂ crystal has potential as a promising laser crystal.     

Investigation of cation-deficient quaternary thiospinels: single crystal study of Ag1.4Cr1.47Sn2.53S8

Single crystals of the quaternary thiospinel Ag_1.41(1)Cr_1.47(5)Sn_2.52(5)S₈ have been obtained by heating stoichiometric mixtures of elemental metals and sulfur at 750 °C. Structural analysis by single crystal X-ray diffraction shows that the above phase crystallizes in the space group with a = 10.4142(3) Å (R₁ = 0.0156 and wR₂ = 0.0416). The Ag-deficiency has been confirmed by solving the structures of crystals prepared in different batches and was observed to vary slightly between crystals. Magnetic studies on a monophasic powder sample with a nominal composition of Ag_1.63CrSn₃S₈ indicates anti-ferromagnetic ordering at low temperature. The high temperature susceptibility leads to a magnetic moment of 3.45 B.M. suggesting that chromium exists predominantly in a trivalent state.     

Crystal and magnetic structures of Laves phase compound NdCo2 in the temperature range between 9 and 300 K

The crystal and magnetic structures of the Laves phase compound NdCo₂ in the temperature range from 9 to 300 K are determined by Rietveld refinement technique, using high-resolution neutron powder diffraction data. The compound crystallizes in space group above the magnetic ordering temperature T_C (≈100 K), in space group I4₁/amd below T_C and in space group Imma below the tetragonal–orthorhombic structural/magnetic transitions at T_M ≈ 42 K. The assignment of the space groups to the crystal structures of NdCo₂ in different temperature ranges complies with the reported Mössbauer studies. Detailed information of the crystal and magnetic structures of NdCo₂ at different temperatures are reported.     

Synthesis, structural, magnetic and electrical properties of La1−xCdxMnO3 manganites (0.1 ≤ x ≤ 0.5)

Cd-substituted LaMnO₃ compounds have been prepared using sol–gel method at a relatively low temperature of 900 °C. The crystal structure examined by X-ray powder diffraction indicates that the samples were single phase and crystallize in a rhombohedral () structure with increase the Cd content. The Rietveld refinement of the structure shows that the substitution of La by Cd in the La site changes the structure parameters, such as MnO bond length and MnOMn angles. Magnetic measurements reveal that the magnetization of these compounds exhibit a ferromagnetic to paramagnetic transition with an increasing in the Curie temperature T_C when x increases from 0.1 to 0.5. The resistivity measurements reveal that the samples exhibit a metallic to semiconductor transition and the electrical temperature transition T_P present a similar trend of T_C, with increasing the Cd content.     

Extrinsic and intrinsic magnetic properties of Co1−x Fex Sb3

We report magnetic properties of iron in Co_1−x Fe_x Sb₃ for x in the range 0<x<0.2, since x=0.2 is found to be the limit of solubility of iron in the skutterudite lattice. The magnetic ions diluted in the matrix carry a small magnetic moment reduced to that of the spin-only S=1/2 value of the Fe³⁺ in the low spin d⁵ configuration in presence of a strong crystal field that screens the orbital momentum. The magnetic properties give evidence that a small fraction of iron is spin-frozen in magnetite ferrimagnetic clusters, and antiferromagnetic FeO clusters. Because both types of clusters represent only very minor phases, their detection by the usual analytical means such as X-rays is not possible. The remaining part is diluted in the matrix to form a semimagnetic semiconductor characterized by a Fe–Fe nearest-neighbor exchange interaction J that is antiferromagnetic, with |J|/k_B19.6  K.     

Temperature dependent neutron powder diffraction study of the Laves phase compound TbCo2

The structure, magnetization and magnetostriction of Laves phase compound TbCo₂ are investigated by temperature dependent high resolution neutron powder diffraction. The compound crystallizes in the cubic Laves phase C15 structure above its Curie temperature T_C and exhibits a rhombohedral distortion (space group ) below T_C. By an appropriate extrapolation of the temperature factor of Co atom above T_C, the Rietveld refinement of the neutron powder diffraction data of the rhombohedral structure converges satisfactorily and reveals that the moments of Co1(3b) and Co2(9e) are almost equal. Tb moment follows well the Brillouin function. The total magnetic moment of TbCo₂ is about 5.8μ_B/f.u., the anisotropic magnetostriction constant λ₁₁₁ is about 4.6 × 10⁻³ and the volume magnetostriction ω_s is about 8.7 × 10⁻³ at 14 K.     

Structure at abrupt copper–alumina interfaces: An ab initio study

The atomistic structure and the energetics of Cu(1 1 1)/-Al₂O₃(0 0 0 1) interfaces for two experimentally observed interface orientation relationships were investigated from first-principles by means of the mixed-basis pseudopotential method. In the first orientation relationship, the direction of Cu is parallel to the direction of -Al₂O₃, and in the second the Cu is rotated with respect to the -Al₂O₃ by 90° around the interface normal [0 0 0 1]. Numerous candidate systems were considered for each case, covering all high-symmetry interface configurations, and with either Al or O termination of the -Al₂O₃(0 0 0 1) surfaces. For each of the most stable interfaces, full relaxations of the positions of all atoms were performed. It is found that despite the different atomistic structures of the two interface types, their interface stabilities, in terms of the work of separation, and their local atomistic structures are similar.     

First-principles investigations of the MMgH3 (, Na, K, Rb, Cs) series

The structural stability of the MMgH₃ (M=Li, Na, K, Rb, Cs) series has been investigated using the density-functional projector-augmented-wave method within the generalized-gradient approximation. Among the 24 structural arrangements used as inputs for the structural optimization calculations, the experimentally known frameworks are successfully reproduced, and positional and unit-cell parameters are found to be in good agreement with the experimental findings. The crystal structure of LiMgH₃ has been predicted, the most stable arrangement being the trigonal LiTaO₃-type (R3c) structure, which contains highly distorted octahedra. The formation energy for all members of the MMgH₃ series is investigated along different reaction pathways. The electronic density of states reveals that the MMgH₃ compounds are wide-band-gap insulators. Analyses of chemical bonding in terms of charge density, charge transfer, electron-localization function, Born effective charge, and Mulliken population show that these hydrides are basically saline hydrides similar to the parent alkali-/alkaline-earth mono-/di-hydrides.     

Kinetic study on Li2.8(V0.9Ge0.1)2(PO4)3 by EIS measurement

Kinetics for lithium ion transfers in the fast ionic conductor Li_2.8(V_0.9Ge_0.1)₂(PO₄)₃ prepared by solid-state reaction method has been studied by electrochemical impedance spectroscopy (EIS) at various temperatures and the results were correlated with observed cathodic behavior. The specific conductivities of Li_x(V_0.9Ge_0.1)₂(PO₄)₃ (x = 0.9–2.8) versus temperatures were analyzed from blocking-electrodes by Wagner's polarization method and the activation energy was calculated. It was observed that electronic conductivities of Li_x(V_0.9Ge_0.1)₂(PO₄)₃ increased with lithium contents in the materials. The compounds show a reversible capacity of 131 mAh g⁻¹ at low current density (13 mA g⁻¹). Modeling the EIS data with equivalent circuit approach enabled the determination of charge transfer and surface film resistances. The Li ion diffusion coefficient (D_Li⁺) versus voltage plot shows three valleys during the first charge cycle coinciding with the irreversible plateau of the voltage versus lithium content profiles reflecting the irreversible phase change in the compound. The obtained D_Li⁺ from EIS varies within 10⁻⁸ to 10⁻⁷ cm² s⁻¹, so Li_2.8(V_0.9Ge_0.1)₂(PO₄)₃ shows excellent chemical diffusion performance.     

An atomistic analysis of the interface mobility in a massive transformation

A new multi-lattice kinetic Monte Carlo method has been used for an atomistic study on the interpretation of the interface mobility parameter for a massive face-centred cubic (fcc) to body-centred cubic (bcc) transformation in a single element system. For lateral growth of bcc in a system with an fcc(1 1 1)//bcc(1 1 0) and fcc[1 1 ]//bcc[0 0 ] interface orientation the overall activation energy for the interface mobility parameter is governed by energetically unfavourable atomic jumps. The atoms on the fcc lattice often cannot jump directly to bcc lattice sites because neighbouring atoms block the empty bcc sites. By single unfavourable jumps and by groups of unfavourable jumps a path from fcc to bcc is created. The necessity of these unfavourable jumps leads to an overall activation energy considerably larger than the activation energy barrier for a single atomic jump.     

Magnetic structures of Zr6CoAs2-type Ho6−xErxMnBi2 solid solutions

Investigations were made by neutron diffraction on Zr₆CoAs₂-type (space group no. 189) Ho_6−xEr_xMnBi₂ solid solutions. The ferromagnetic ordering temperature decreases from Ho₆MnBi₂ (T_C = 200(6) K) to Er₆MnBi₂ (T_C = 100(4) K), whereas temperatures of ferrimagnetic (or antiferrimagnetic) ordering (T_Ferri and T_AFerri) are found to have non-monotonic dependences on the content of Er: T_Ferri = 58(4) K for Ho₆MnBi₂, T_Ferri = 162(4) K for Ho_4.5Er_1.5MnBi₂, T_Ferri = 150(4) K for Ho₃Er₃MnBi₂, T_AFerri = 78(4) K for Ho_1.5Er_4.5MnBi₂ and T_AFerri = 52(4) K for Er₆MnBi₂.

In these compounds, no local moment was detected on the manganese ion site, except for Ho_1.5Er_4.5MnBi₂ and Er₆MnBi₂ compounds. The manganese magnetic moments (μ_Mn) is 1.5μ_B and these are antiferromagnetically coupled with that of rare earth moments.     

The ternary system Na2O–ZnO–WO3: Compounds and phase relationships

The subsolidus phase relationships of ternary system Na₂O–ZnO–WO₃ have been investigated by X-ray diffraction (XRD) and differential thermal analyzer (DTA). All the samples were synthesized in the temperature range from 530 to 850 °C in air. There are one ternary compound and five binary compounds in the Na₂O–ZnO–WO₃ system, which can be divided into eight three-phase regions. The crystal structure of the ternary compound Na_3.6Zn_1.2(WO₄)₃ is determined by single-crystal structure analysis method. It belongs to triclinic system with space group and lattice constants a = 7.237 (5) Å, b = 9.172 (6) Å, c = 9.339 (6) Å and  = 94.920 (4)°, β = 105.772 (9)°, γ = 103.531 (8)°, Z = 2. DTA analyses indicate that the compound Na₂WO₄ is not suitable to be the flux for ZnO crystal growth below 1250 °C, since no liquidus was observed in the system before 1250 °C.     

Synthesis and magnetic structure of the YbMn2Sb2 compound

A neutron diffraction investigation has been carried out on the trigonal La₂O₃-type (hP5, space group , No. 164; also CaAl₂Si₂-type) YbMn₂Sb₂ intermetallic. A two-step synthesis route has been tried in this work, and successfully utilised to prepare single phase samples of this compound. This study shows that YbMn₂Sb₂ presents antiferromagnetic ordering below 120 K. The magnetic structure of this intermetallic consists of antiferromagnetically coupled magnetic moments of the manganese atoms, in the Mn1 (1/3, 2/3, Z_Mn) and Mn2 (2/3, 1/3, 1 − Z_Mn) sites; the direction of magnetic moments of manganese atoms forming a φ and a θ angle, respectively with the X- and the Z-axis. At 4 K the magnetic moment of the Mn1 atom is μ_Mn = 3.6(1) μ_B, with φ = 0° and θ = 62(4)°, whilst the Mn2 atom has a magnetic moment μ_Mn = 3.6(1) μ_B, with φ = 0° and θ = 242(4)°. On the other hand, in this compound no local moment was detected on the Yb site.