Characterization of hydrothermally prepared BaTi1−xZrxO3

BaTiO₃ (BTO) and BaTi_0.8Zr_0.2O₃ (BZT) powders were prepared using the hydrothermal method, starting from BaO, TiO₂ and Zr(NO₃)₂, 7H₂O. X-ray diffraction analysis showed that the cubic phase is stable at room-temperature and the pure perovskite phase is obtained after heating the powders for 2 h at 1280 °C. The temperature dependence of the dielectric constant points to ferroelectric behavior. This ferroelectric behavior can likely be due to the presence of a possible quadraticity gradient in the grains since the cubic phase may not be ferroelectric. The diffuse character of the transition is attributed to this quadraticity gradient, to grain size distribution and (for BZT) to spatial fluctuations in the concentrations of the substituted ion (Zr) leading to the coexistence of regions of different Curie temperatures.     

Synthesis and properties of lithium ion conductors Li3−2x(Sc1−xZrx)2(PO4)3

Lithium ion conductors, Li_3−2x(Sc_1−xZr_x)₂(PO₄)₃ (0 x 0.3), were prepared by a solid-state reaction. TG–DTA analysis indicated no phase transition in the samples with x superior to 0.05. X-ray powder diffraction analysis of these samples clearly showed the stabilization of a superionic conduction phase at room temperature with an orthorhombic system Pbcn. The highest conductivity was observed for the sample with x=0.05, and ascribed to the stabilization of the superionic conduction phase and the introduction of vacancies on the Li⁺ sites by substituting Zr⁴⁺ for Sc³.     

Electronic structure and magnetism of PrNixPt1−x compounds

We have studied influence of the Pt–Ni substitution on the crystal structure and magnetic behavior of the PrNi_xPt_1−x compounds. Polycrystalline samples with x = 1, 0.9, 0.75, 0 were prepared and characterized by X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM). The analysis of XRPD data confirmed that the orthorhombic CrB-type structure owned by the parent binary compounds remains conserved through the entire series. The samples were subsequently investigated by specific heat (C_p), magnetization (M) and ac susceptibility measurements in the temperature range 2–350 K and in magnetic fields up to 9 T. All compounds were found to order ferromagnetically. The T_C values monotonously increase with increasing Ni content. To inspect the crystal-field (CEF) effects and magnetocaloric properties specific-heat data were analyzed in detail and the magnetic contribution to the specific heat together with the magnetic entropy have been determined. The results of first principles electronic structure calculations of the PrNi and PrPt confirmed that besides the stable Pr magnetic moments due to localized 4f-electrons only a very small magnetic moments of at most 0.2μ_B is induced at the Ni (Pt) site due to the polarized 3d-electron states (5d-electron states) hybridizing with the Pr 5d-electron states, i.e. the Ni (Pt) moment plays only minor role in the total balance of the magnetic moments in these compounds.     

Microstructure and tribological properties of LaxCeyO1 − x − y composite nanofilms

A series of La_xCe_yO_{1 − x − y} films (x = 0–0.54, y = 0–0.58) with thickness of 35–45 nm was deposited by unbalanced magnetron sputtering. High-resolution transmission electron microscope observation shows that La_0.24Ce_0.34O_0.42 film has polycrystalline structure. La₂O₃ and CeO₂ are formed within the La_xCe_yO_{1 − x − y} films confirmed by the X-ray diffraction and X-ray photoelectron microscopy. The friction coefficient and residual compressive stress of five kinds of three-element compound films exhibit symmetric distribution with the relative equilibrium of La and Ce atomic concentration within the films. The critical load of all deposited films is between 28 and 33 mN. The friction coefficient of two kinds of rare earth complex oxide films is in the range of 0.08–0.09, which is lower than that of only one kind of rare earth oxide films, and the friction mechanism is discussed.     

Preparation and structures of the La1−xKxCo1−xNbxO3 (x = 0–l) system

The La_1−xK_xCo_1−xNb_xO₃ system was performed by conventional solid state reaction technique using metal oxides. By DSC analysis, the activation energy of crystallization of the powders with x = 0.3 is 388.4 kJ/mol. The crystal structure of the compound reveals a transition from rhombohedral to cubic, and then to orthorhombic structure as the amount of the potassium niobate (KNbO₃) increases. It is found that the structure of the samples with x < 0.3 is similar to that of lanthanum cobaltate (LaCoO₃), while at the compositions with 0.7 ≥ x ≥ 0.3, the structure transforms to cubic. Finally, with x ≥ 0.7, the structures were similar to that of KNbO₃. According to the results of selected-area-diffraction (SAD) patterns and X-ray diffraction (XRD) identifications, the lattice parameters were calculated. The direction of superlattice structure along [2 1 0] was found for x = 0.5 as identified from SAD patterns. The dielectric constants were measured with cubic structure. Dielectric constant (K) decreases with increasing x.     

Magnetic properties of CeMn2−xCoxGe2

The structure and magnetic properties of CeMn_2−xCo_xGe₂ (0.0≤x≤1.0) were studied by X-ray powder diffraction and magnetization measurements. All compounds crystallize in the ThCr₂Si₂-type structure with space group I4/mmm. Substitution of Co for Mn leads to a linear decrease in the lattice constants and the unit cell volume. Increasing substitution of Co for Mn shows a depression of ferromagnetic ordering.     

Lattice parameter values and phase transitions for the Cu2Cd1−zMnzSnSe4 and Cu2Cd1−zFezSnSe4 alloys

X-ray powder diffraction measurements and differential thermal analysis (DTA) were made on polycrystalline samples of the Cu₂Cd_1−zMn_zSnSe₄ and Cu₂Cd_1−zFe_zSnSe₄ alloy systems. The diffraction patterns were used to show the equilibrium conditions and to derive lattice parameter values. For Cu₂Cd_0.8Fe_0.2SnSe₄ as well as for Cu₂Cd_0.2Fe_0.8SnSe₄ the crystal structures were refined using the Rietveld method. It was found that the internal distortion parameter σ decreases as Cd is replaced by either Mn and/or Fe. For the Cu₂Cd_1−zMn_zSnSe₄ and Cu₂Cd_1−zFe_zSnSe₄ alloy systems, only two single solid phase fields, the tetragonal stannite α and the wurtz–stannite δ (Pmn2₁) structures were found to occur in the diagram. In addition to the tetragonal stannite α phase extra X-ray diffraction lines due to MnSe and/or FeSe₂ were observed for as grown samples in the range 0.7 < z < 1.0. However, it was found that the amount of the extra phase decreased for the compressed samples.     

Synthesis and characterization of proton conducting Sr(Ce1−xZrx)0.95Yb0.05O3−δ by the citrate method

The citrate method was used to synthesize Sr(Ce_1−xZr_x)_0.95Yb_0.05O_3−δ (x = 0.1, 0.2, 0.3, 0.4) and to avoid the drawbacks of the conventional solid state reaction method. The products were characterized by thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron probe X-ray microanalyzer (EPMA). The results indicate that the citrate method is an advantageous route in producing Sr(Ce_1−xZr_x)_0.95Yb_0.05O_3−δ materials. Sr(Ce_0.9Zr_0.1)_0.95Yb_0.05O_3−δ powders are composed of nanoscaled crystallites with the average grain size in the range of 60–70 nm. Single phase is confirmed over the whole x range. In addition, chemical stability against CO₂ and electrical conduction behavior of the sintered Sr(Ce_1−xZr_x)_0.95Yb_0.05O_3−δ ceramics were investigated. The chemical stability of the ceramics against CO₂ is certified to increase with the increase in zirconium content. Impedance spectroscopy was used to study the electrical conduction behavior of Sr(Ce_0.9Zr_0.1)_0.95Yb_0.05O_3−δ ceramic.     

Crystallographic site of Mn in the icosahedral cluster of LaCo13−xMnx compounds

Studies on the structure and the crystallographic site of Mn in LaCo_13−xMn_x compounds were carried out by using X-ray diffraction and X-ray absorption fine structure (XAFS) of the Mn K-edge. These compounds with x≤3.0 adopt a NaZn₁₃-type structure consisting of icosahedral clusters. The lattice constant increases with the Mn concentration. The calculated XAFS curves of the center and the corner sites in the icosahedral clusters for the Mn K-edge are obtained by using the program . The fitting result for the corner site agrees much better with the observed XAFS spectrum than that for the center site. Therefore, the Mn site is determined to be the corner Co site in the icosahedral clusters of all the compounds. In comparison with the crystallographic parameters of LaCo₁₃, the icosahedral clusters composed of Mn atoms expand and the crystallographic Mn site is slightly more close to the La atom.     

Phase behavior and some properties of LaMn1−xRhxO3 solid solution

Structure and magnetic and electrical properties of the polycrystalline compounds LaMn_1−xRh_xO₃ (0 < x ≤ 1) have been investigated. The samples were characterized by X-ray diffraction and Rietveld refinement which confirmed the space group Pnma (No. 62) for all compositions at room temperature. A transformation from O′- to O-type orthorhombic structure is seen near x = 0.6 tending to make the phase unstable. The electrical conductivity measurement shows semiconducting property above room temperature with a rather low activation energy for Mn-rich compositions. Compounds in the region 0.1 ≤ x ≤ 0.9 show ferromagnetic property but the substitution of Rh³⁺ ion for Mn³⁺ ion suppresses the ferromagnetism that results in reducing the Curie temperature, T_C.     

The role of valence electron concentration in the cohesive properties of YBxN1−x, YCxN1−x and YNxO1−x compounds

The mechanical properties are not yet understood at basic levels. Previous works shows that the greatest hardness for rock-salt structures (such as TiC_xN_1−x) is attained for a valence electron concentration (VEC) of 4.2 electrons per atom. The present work is aimed to explore this concept for yttrium-based compounds. By means of first principles calculations we did a systematical investigation where nitrogen in YN (VEC = 4) was supplanted by either of B, C or O to reduce or increase its VEC, forming YB_xN_1−x, YC_xN_1−x and YN_1−xO_x ternary compounds. We have calculated the cohesive energy (E_O), cell volume (V_O), bulk modulus (B_O) and density of states (DoS) as a function of VEC. The Fermi level (E_f,) is shifted toward the valence band by substituting B or C in YN, and toward the conduction band by means of O. It is concluded that the optimal position for E_f (maximum B_O) is linked to the saturation of electronic states with e_g-symmetry. At this point the excess of electrons provided by O starts filling antibonding states with t_2g-symmetry. That is, B_O increases monotonically as a function of VEC until VEC  4.1, after that point B_O decrease.     

Electrical behaviour of hydridofluorides of potassium–calcium KCaH3−xFx with x = 1, 1.5, 2, 2.5

This paper reports the results of the electrical conductivity measurements for KCaH_3−xF_x series with (x = 1, 1.5, 2, 2.5) in the temperature range 298–503 K.The activation energy of the electrical conductivity for the studied compounds depends on hydrogen amount and Reau's criteria. Differential thermal analysis curves were measured in the same temperature range 298–503 K.Possible correspondence between preferential order given by X-ray diffraction, thermal behaviour and electrical properties are discussed.     

Structural and thermodynamic properties of the pseudo-binary TiCr2−xVx compounds with 0.0≤x≤1.2

The TiCr_2−xV_x compounds with 0.0≤x≤1.2 series have been synthesised and characterised by X-ray powder diffraction. X-Ray qualitative and quantitative phase analysis has been carried out on the as-cast alloys using the Rietveld method. The refinements of the structure shows that the materials crystallise either in the hexagonal or in the cubic Laves phase type for low V contents. For x>0.6, the system is found of b.c.c.-type structure only. The pressure–composition–temperature (P–C–T) isotherms measured at 298 K show that the as-cast alloys absorb large amounts of hydrogen, from 4 to 5.2 H/f.u. The P–C–T diagrams reveal also the presence of a relatively flat plateau, and a large hysterisis effect, and correspondingly the hydride cannot be completely dehydrogenated.     

Magnetic properties of Ce3−xGdxCo11B4 borides

The structure and magnetic properties of Ce_3−xGd_xCo₁₁B₄ borides have been studied by X-ray powder diffraction (XRPD), magnetization and differential scanning calorimetry (DSC) measurements. X-ray analysis reveals that the compounds crystallize in the hexagonal Ce₃Co₁₁B₄-type structure with P6/mmm space group. The substitution of Gd for Ce leads to an increase of the unit-cell parameter a and the unit-cell volume V, while the unit-cell parameter c decreases linearly. Magnetic measurements indicate that all samples are ordered magnetically below the Curie temperature. The Curie temperatures increase as Ce is substituted by Gd. The saturation magnetization at 4 K decreases upon the Gd substitution up to x = 1, and then increases.     

The effects of the combined substitution of Y and Ga on the crystallographic structure of Nd2−xYxFe17−yGay intermetallic compounds

The effects of the combined substitution of Y and Ga on the crystallographic structure of Nd_2−xY_xFe_17−yGa_y compounds with x = 0, 0.5, 1.0, 1.5 and y = 0, 1, 2, 3 have been investigated using X-ray and neutron powder diffractions. Rietveld refinements of the diffraction data indicate that all the samples crystallize in the rhombohedral Th₂Zn₁₇-type structure with only small amounts of alpha iron. It is found that the addition of Ga atoms lessens the decreasing rates of the a-axis and unit cell volume V on the Y content but almost does not affect the decreasing rates of the c-axis. However, the substitution of Y has a positive effect on the increasing rates of the a-axis and unit cell volume V on the Ga content but has a very slight effect on the increasing rate of the c-axis. The c/a ratio of Nd_2−xY_xFe_17−yGa_y as a function of Ga content exhibits a different increase for different Y content owe to the combined effects of Y and Ga on the crystallographic structure. The substitution of Y is found to have little effect on the site occupancy of Ga in Nd_2−xY_xFe_17−yGa_y. The combined effects of Y and Ga on the bond lengths and ASBL of Nd_2−xY_xFe_17−yGa_y indicate that more bonds detrimental to ferromagnetic exchange can be modulated into the desirable ferromagnetic exchange distance range through suitable combined substitution, which provides a valuable way to improve the magnetic properties of rare earth-transition intermetallic compounds.     

Magnetic properties of Pr1−xGdxMn2Ge2 compounds

The structure and magnetic properties of the Pr_1−xGd_xMn₂Ge₂ (0.0≤x≤1.0) compounds have been investigated by means of X-ray diffraction (XRD), differential scanning calorimetry (DSC) techniques and AC magnetic susceptibility measurements. All compounds crystallize in the ThCr₂Si₂-type structure with the space group I4/mmm. The lattice constants and the unit cell volume obey Vegard’s law. Samples in this alloy system exhibit a crossover from ferromagnetic ordering for PrMn₂Ge₂ to antiferromagnetic ordering for GdMn₂Ge₂ as a function of Gd concentration x. At low temperatures, the rare earth sublattice also orders and reconfigures the ordering in the Mn sublattice. The results are summarized in the x–T magnetic phase diagram.     

Solid solution Pb1−xSrxTiO3 and its thermal expansion

The solid solution limit of Pb_1−xSr_xTiO₃ was determined in the composition range of 0≤x≤1.0 at room temperature (RT). The phases were isolated and indexed in a tetragonal system with x<0.5 and in a cubic one with x≥0.5. The cell parameters of Pb_1−xSr_xTiO₃ continuously, but nonlinearly, change with solubility x. The intrinsic thermal expansions of the solid solution compounds Pb_1−xSr_xTiO₃ (x=0, 0.15, 0.20, 0.50, 0.90, 1.0) were obtained in the temperature range from RT to 1173 K with high-temperature X-ray powder diffraction. Negative thermal expansion coefficients of Pb_1−xSr_xTiO₃ (x=0, 0.15, 0.20) were found below the Curie points. The thermal expansions of these titanate ceramics were highly correlated with the solubility in the solid solution Pb_1−xSr_xTiO₃.     

Magnetic phase transitions in Nd1−xYxMn2Ge2 (0 ≤ x ≤ 0.6)

The structure and magnetic properties of Nd_1−xY_xMn₂Ge₂ (0.0≤x≤0.6) were studied by X-ray powder diffraction and magnetization measurements. All compounds crystallize in the ThCr₂Si₂-type structure with space group I4/mmm. Substitution of Y for Mn led to a linear decrease in the lattice constants and the unit cell volume. Increasing substitution of Y for Nd in NdMn₂Ge₂ shows a depression of ferromagnetic ordering and the gradual development of antiferromagnetic ordering.     

Composition-controlled synthesis, structure and magnetic properties of ternary FexCoyNi100−x−y alloys attached on carbon nanotubes

Fe_xCo_yNi_100−x−y alloy nanoparticles with controllable compositions attached on the surface of carbon nanotubes (CNTs) were synthesized using an easy two-step route including adsorption and reduction processes. The nanocomposites have been characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), energy-disperse X-ray spectroscopy (EDS) and vibrating sample magnetometer (VSM). The effect of the alloy composition on microstructure and magnetic properties of ternary FeCoNi alloys attached on carbon nanotubes have been studied. During the nominal composition range (x = 21, 24, 33, 37, 46 and y = 60, 46, 48, 48, 35), Fe_xCo_yNi_100−x−y alloy nanoparticles attached on CNTs are quasi-spherical, fcc–bcc dual phase, and the coercivity (H_c) and saturation magnetization (M_s) vary with the alloy composition. The H_c of Fe_xCo_yNi_100−x−y alloy nanoparticles attached on CNTs decreases and M_s increases with increasing Fe content. These demonstrate that the two-step route is promising for fabricating alloy nanoparticles attached on CNTs for magnetic storage and ultra high-density magnetic recording applications.     

Thermoelectric properties of novel skutterudites with didymium: DDy(Fe1−xCox)4Sb12 and DDy(Fe1−xNix)4Sb12

In order to improve the thermoelectric properties via efficient phonon scattering Didymium (DD), a mixture of Pr and Nd, was used as a new filler in ternary skutterudites (Fe_1−xCo_x)₄Sb₁₂ and (Fe_1−xNi_x)₄Sb₁₂. DD-filling levels have been determined from combined data of X-ray powder diffraction and electron microprobe analyses (EMPA). Thermoelectric properties have been characterized by measurements of electrical resistivity, thermopower and thermal conductivity in the temperature range from 4.3 to 800 K. The effect of nanostructuring in DD_0.4Fe₂Co₂Sb₁₂ was elucidated from a comparison of both micro-powder (ground in a WC-mortar, 10 μm) and nano-powder (ball-milled, 150 nm), both hot pressed under identical conditions. The figure of merit ZT depends on the Fe/Co and Ni/Co-contents, respectively, reaching ZT > 1. At low temperatures the nanostructured material exhibits a higher thermoelectric figure of merit. The Vickers hardness was measured for all samples being higher for the nanostructured material.