Syntheses and single-crystal structures of La3AgSnS7, Ln3MxMS7 (Ln = La, Ho, Er; M = Ge, Sn; 1/4 ≤ x ≤ 1/2)

In our investigation of non-centrosymmetric rare earth sulfides in the La₃AgSnS₇/KBr, LaAlGeS₅/NaBr, HoAlGeS₅/KBr, ErAlGeS₅/NaBr, Er₃AgGeS₇/KBr and La₃NaSnS₇/NaBr systems, five compounds belonging to the R₆B₂C₂Q₁₄ family have been obtained. These compounds crystallize in the P6₃ space group, and the crystal data are as follows—La₃AgSnS₇: a = 10.3780(15) Å, c = 5.9900(12) Å, Z = 2; La₃Ge_0.25GeS₇: a = 10.2970(15) Å, c = 5.8120(12) Å, Z = 2; Ho₃Ge_0.272(10)GeS₇: a = 9.6480(14) Å, c = 5.7920(12) Å, Z = 2; Er₃Ge_0.330(10)GeS₇: a = 9.5930(14) Å, c = 5.8490(12) Å, Z = 2; La₃Sn_0.25SnS₇: a = 10.2770(15) Å, c = 6.0030(12) Å, Z = 2. Single-crystal analysis indicated that the crystal structures consist of three types of building block: LnS_n, MS₄, and AgS₃ (for La₃AgSnS₇) or MS₆ units (for Ln₃M_xMS₇, Ln = La, Ho, Er; M = Ge, Sn; 1/4 ≤ x ≤ 1/2), as any other compounds belonging to the R₆B₂C₂Q₁₄ family. Ln₃M_xMS₇ (Ln = La, Ho, Er; M = Ge, Sn; 1/4 ≤ x ≤ 1/2) are deficient compounds with the B sites occupied partly by M(II), and/or M(IV).     

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.     

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.     

Ce(Au,Sb)2 with UHg2 structure type, a new member of the AlB2 family

A new ternary compound Ce(Au,Sb)₂, with a homogeneity range has been observed from X-ray powder diffraction of as cast alloys, a = 4.743–4.712 Å, c = 3.567–3.768 Å. Its crystal structure was investigated by X-ray diffraction from Ce(Au_1−xSb_x)₂ (x = 0.266) single crystal: CAD-4 automatic diffractometer, Mo K radiation, a = 4.7256(6) Å, c = 3.6711(6) Å, P6/mmm space group, V = 70.997(17) Å³, Z = 1, ρ = 10.732 Mg/m³, μ = 76.369 mm⁻¹, R₁ = 0.0415, wR₂ = 0.0793 for 99 reflections with I > 2σ(I₀). The coordination polyhedron of X (X = 0.734Au + 0.266Sb) atom is a full-capped trigonal prism [XCe₆X₃X₂]. Ce atom is coordinated by 14 atoms: [CeX₁₂Ce₂]. The compound is isotypic with UHg₂ structure, a deformation derivative of AlB₂ structure type. It forms isostructural compounds with La and Pr.     

Power factor of La1−xSrxFeO3 and LaFe1−yNiyO3

The electrical conductivity (σ), Seebeck coefficient (S), and power factor (σS²) of perovskite-type LaFeO₃, La_1−xSr_xFeO₃ [0.1 ≤ x ≤ 0.4] and LaFe_1−yNi_yO₃ [0.1 ≤ y ≤ 0.6] were investigated in the temperature range of 300–1100 K to explore their possibility as thermoelectric materials. The electrical conductivity of LaFeO₃ showed semiconducting behavior, and its Seebeck coefficient changed from positive to negative around 650 K with increasing temperature. The electrical conductivity of LaFeO₃ increased with the substitutions of Sr and Ni atoms, while its Seebeck coefficient decreased. The Seebeck coefficient of La_1−xSr_xFeO₃ was positive, whereas that of LaFe_1−yNi_yO₃ changed from positive to negative with increasing Ni content. The substitutions of Sr and Ni were effective in increasing the power factor of LaFeO₃; 0.0053 × 10⁻⁴ Wm⁻¹ K⁻² for LaFeO₃ (1050 K), 1.1 × 10⁻⁴ Wm⁻¹ K⁻² for La_1−xSr_xFeO₃ (x = 0.1 at 1100 K) and 0.63 × 10⁻⁴ Wm⁻¹ K⁻² for LaFe_1−yNi_yO₃ (y = 0.1 at 1100 K).     

An investigation of the structures of the compounds in the tin-rich part of the Dy–Sn system: Crystal structure of Dy5Sn11 and Dy5Sn13

The structural properties of the compounds in the tin-rich part of the dysprosium–tin system have been studied by X-ray powder diffraction. The crystal structures of six compounds DySn_2+x (0 < x < 1) have been characterized. There are four compounds with known structural types: DySn₂ with the ZrSi₂ structure, Dy₃Sn₇ with the Gd₃Sn₇ structure, Dy₂Sn₅ with the Er₂Ge₅ structure, DySn₃ with the DyGe₃ structure and two compounds characterized by new body-centred orthorhombic types (Immm): Dy₅Sn₁₁ (a = 4.411 Å, b = 42.50 Å and c = 4.328 Å) and Dy₅Sn₁₃ (a = 4.341 Å, b = 48.05 Å and c = 4.405 Å) which result from various insertions of AuCu₃ and Po slabs into the ZrSi₂ structure. The relationships and structural evolution are discussed.     

Ba4In2−x(CO3)1+xO6−2.5x and Ba4In0.8Cu1.6(CO3)0.6O6.2—new indium oxycarbonates closely related to n=3 Ruddlesden–Popper phases

Investigations of phase relations in the Ba-rich part of the In₂O₃–BaO(CO₂)–CuO pseudo-ternary system at 900 °C have revealed the existence of new indium–copper oxycarbonate – Ba₄In_0.8Cu_1.6(CO₃)_0.6O_6.2. Rietveld refinement of the X-ray powder diffraction data combined with infrared studies gives evidence that this phase is a oxycarbonate crystallising in the tetragonal structure (space group I4/mmm) with unit cell parameters: a=4.0349(1) Å and c=29.8408(15) Å. In the binary part of the In₂O₃–BaO(CO₂) system we have identified the occurrence of Ba₄In_2−x(CO₃)_1+xO_6−2.5x oxycarbonate solid solution showing a crystal structure also described by I4/mmm space group, but with the unit cell parameters: a=4.1669(1) Å and c=29.3841(11) Å for x=1. The existence range of this phase, −0.153<x<0.4, includes chemical compositions of earlier found phases: Ba₅In_2+xO_8+0.5x with 0≤x≤0.45 (known as the -solid solution), as well as the binary Ba₄In₂O₇ phase. The crystal structures of both new oxycarbonates are isomorphic and related to n=3 member of the Ruddlesden–Popper family.     

Characterization and hydrogenation of CeNi5−xCrx (x = 0, 1, 2) alloys

The effect of partial substitution of Ni by Cr in CeNi₅ intermetallic compound has been studied by pressure–composition isotherm measurements for different temperatures. The samples were prepared of high purity materials using the standard arc melting technique in argon atmosphere. The structure and the elemental composition of different alloys have been investigated by means of XRD, SEM and EDX techniques. The unit cell volume of the alloy was found to increase with increasing Cr content. In order to calculate the hydrogen storage capacity pressure–composition isotherm has been investigated for CeNi_5−xCr_x (x = 1, 2) alloys in the temperature and pressure ranges of 293 ≤ T ≤ 333 K and 0.5 ≤ P ≤ 35 bar, respectively. The P–C–T isotherm for different alloys clearly shows the presence of three regions ,  + β and β. The enthalpy and entropy for the systems has also been calculated using Van’t Hoff plot. The variation of enthalpy and entropy with hydrogen content has also been studied.     

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.     

Synthesis and characterization of LiGaxMn2−xO4 (0 ≤ x ≤ 0.05) by triethanolamine-assisted sol–gel method

Spinel LiGa_xMn_2−xO₄ (0 ≤ x ≤ 0.05) cathode materials with phase-pure particles and nano-sized distribution were synthesized by sol–gel method using triethanolamine as the chelating agent. The effects of heat treatment on the physicochemical properties of the spinel LiGa_xMn_2−xO₄ powders were examined with thermogravimetric and differential thermal analysis (TG/DTA), powder X-ray diffraction (XRD) and scanning electron micrograph (SEM). The LiGa_xMn_2−xO₄ (0 ≤ x ≤ 0.05) electrodes were characterized electrochemically by charge/discharge experiments under a current rate of 0.5C at 55 °C. Although the Ga-doped spinel electrode showed smaller initial discharge capacity, it exhibited better cycling performance than the undoped-LiMn₂O₄ electrode. The dQ/dV versus potential plots at 55 °C revealed that the improvement in cycling performance of the Ga-doped spinel electrode is attributed to stabilization of the spinel structure by the presence of gallium ion.     

Dependency of c-lattice parameter, activation energy and its magnetic power constant on x in Y1−xYbx/2Gdx/2Ba2Cu3O7−y superconductors

To investigate the effect of x on c-lattice parameter, the activation energy, and the magnetic power constant of activation energy, the nominal composition of Y_1−xYb_x/2Gd_x/2Ba₂Cu₃O_7−y superconducting samples for x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0 were prepared by solid-state reaction technique. c-Lattice parameters of the samples were calculated using XRD data. From the resistivity curves which were obtained under 11 different magnetic fields from 0 up to 5 T in the temperature range from 70 to 100 K steps by 0.25 K in zero field cooling regime, the activation energies of the samples were determined using Arrhenius activation energy law. The magnetic power constants of activation energy of the samples were calculated from the slopes of the plots ln U versus ln H. The results showed that the value of c-lattice parameters of samples x = 0 (Y123), and x = 1.0 (YbGd123) are in good agreement with the reported works. It was found that c-lattice parameter decreased with the increasing the content x except samples of x = 0.4 and 1.0. It was thought that the origin of the separation from the linearity comes from the lack of Y in nominal composition for x = 1.0. As for the sample x = 0.4, it was thought to be due to the fact that Y, Yb and Gd atoms affect the superconductivity properties dominantly. On the other hand, there is a similarity among U(0 T), U(1 T), its magnetic power constant and the c-lattice parameter with increasing content x. The desired activation energy and its magnetic field dependency constant can be controlled with x and then this can be useful for the superconducting applications.     

Crystal structure, magnetic behaviour and valence state of ytterbium in the Yb4Ni10+xGa21−x phase

The ternary phase Yb₄Ni_10+xGa_21−x has been synthesised from the elements by high frequency melting in argon atmosphere. The homogeneity region has been established from X-ray powder data and confirmed by EDX analysis for 0.3≤x≤1. The crystal structure of Yb₄Ni_10+xGa_21−x has been estimated from X-ray single crystal data: space group C2/m (no. 12), Z=2, a=20.6815(9) Å, b=4.0560(4) Å, c=15.3520(7) Å, β=124.800(3)°, R(F)=0.023 for 1701 symmetry independent reflections with F(hkl)>4σ(F). A special feature of the structure is the local disorder within the gallium/nickel network. Neglecting atomic disorder in the region of the Ga9 and Ga11 positions, the Yb₄Ni_10+xGa_21−x structure is an occupation variant of the Ho₄Ni₁₀Ga₂₁ type with nickel atoms partially replacing the Ga atoms in the 2d sites at the centers of distorted icosahedra. From magnetic susceptibility and from L_III-XAS spectra, the valence state of ytterbium is near 3+.     

Influence of tin on the electrochemical and gas phase hydrogen sorption in Mg2−xSnxNi (x = 0, 0.1, 0.3)

Mg_2−xSn_xNi (x = 0, 0.1, 0.3) alloys were synthesized by reactive ball milling under protective Ar atmosphere and liquid n-heptane. The microstructure and the morphology of the powders were determined by X-ray diffraction and scanning electron microscopy. The as-milled alloys consist of Mg₂Ni nanocrystals with an average grain size in the range 3–7 nm, depending on the alloy composition. Sn containing phases were not detected even in the Sn-rich alloy. Obviously, Sn is dissolved in the Mg₂Ni intermetallic compound. Gas phase sorption of hydrogen was not observed in the alloys containing Sn (Mg_2−xSn_xNi; x = 0.1, 0.3). It was suggested that Sn impedes the process of hydrogen molecules decomposition. The as-milled alloys absorbed reversibly hydrogen electrochemically. Mg₂Ni alloy showed the highest discharge capacity of 300 mAh/g. The capacity of Mg_1.9Sn_0.1Ni and Mg_1.7Sn_0.3Ni was about 260 mAh/g. It was found that Sn improved the cycle life of the electrode.     

Preparation and structural characterization of perovskite-type LaxLn1−x″CoO3 by the thermal decomposition of heteronuclear complexes, LaxLn1−x″| Co(CN)6| · nH2O (Ln″ = Sm and Ho)

Perovskite-type La_xLn_1−x″CoO₃ oxides are prepared by the thermal decomposition of La_xLn_1−x″ [Co(CN)₆] · nH₂O hetero-nuclear complexes. Except for LaCoO₃ (hexagonal), the structures observed for La_xSm_1−xCoO₃ are othorhombic. While the perovskite-type oxide HoCoO₃ is not formed by decomposition at 1000°C of the corresponding hexacyano complex, the partial replacing of Ho with La is effective in forming the pervoskite-type oxide having an orthorhombic structure containing Ho even at 800°C. A monotonous correlation (quasi-linear relationship) was found between the b- and c-lattice constants of the orthorhombic structures of the perovskite-type oxides and the effective radii of Ln ions, defined as r_eff = xr_1.a + (1 − x)r_1.0″. The distortion parameter for the orthorhombie cell (3″a/b−1) increaseswith decrease in r_eff and is expected to be 0.270 for perovskite-type HoCoO₃. The crystal structure of the La_xLn_1−x″, CoO₃ oxides is mainly controlled by the effective radii of Ln ions.     

Magnetic properties and spin-reorientation transition in DyFe10−xNixSi2 compounds

The magnetic properties of DyFe_10−xNi_xSi₂ compounds with x = 0, 1, 2, 3, 4, 6, 9 and 10 have been investigated by means of X-ray diffraction and magnetic measurements. Substitution of Ni for Fe leads to a decrease in the lattice constants a, c and the unit-cell volume V. The Curie temperature reaches a maximum of 590 K at x = 2, then decreases strongly for x ≥ 2. The spin reorientations are observed for the compounds with x = 0, 1, 2 and 3. The spin reorientation temperature decreases strongly from 255 to 60 K as the Ni content is increased from x = 0 to 3. Below the spin reorientation temperature, the compounds exhibit ferrimagnetic ordering. For the Ni-rich compounds with x = 9 and 10, the magnetization of the Dy sublattice decreases strongly since the magnetization of the Dy sublattice is strongly affected by the molecular field produced by the 3d sublattice.     

Spin glass state and its correlations with the magnetic and electrical properties as well as with the defectiveness in the spinels CuCr2X4 (X = S, Se) doped with Sb

High degree of defectiveness both in the stoichiometric CuCr_2−xSb_xS₄ (x = 0.3, 0.4, 0.5) and nonstoichiometric Cu_1 + xCr_1.5 + ySb_0.5 + zSe_4 + t (where: −0.02 ≤ x ≤ 0.01, 0.03 ≤ y ≤ 0.35, −0.2 ≤ z ≤ −0.02, 0.01 ≤ t ≤ 0.08) spinels doped with Sb has been determined with the aid of the vacancy model. From the analysis carried out of the effective magnetic moments and the exchange integrals, it follows that in the spinels with sulphur mainly the cation subarrays are defected whereas in the spinels with selenium the defectiveness appears mainly in the anion subarrays. It turned out that in the spinels with sulphur the ferromagnetic cluster spin glass states appear accompanied by the large negative magnetoresistance, whereas in the spinels with selenium the corresponding clusters are antiferromagnetic and the giant magnetoresistance has been observed both positive and negative. A jump-like phase transition was here observed changing both the sign and the measured value of the magnetoresistance from −4433% at 153.2 K up to +980% at 154.24 K. Moreover, in the spinels with selenium both semiconductor–metal and metal–semiconductor phase transitions have been observed from the temperature dependence of the resistance.     

Nd11Pd4In9 compound – A new member of the homological series based on AlB2 and CsCl types

The Nd₁₁Pd₄In₉ compound was prepared by arc melting of pure metals under an argon atmosphere. Crystal structure was refined from X-ray single crystal diffractometer data (space group Cmmm, a = 14.843(3), b = 22.284(3), c = 3.7857(6) Å, Z = 2, R_I = 0.0584, 653 F₂ values). It has own structure type and together with Mn₂AlB₂, Cr₃AlB₄, Mo₂FeB₂ and Lu₅Ni₂In₄ structure types belongs to homological series based on AlB₂ and CsCl structure types with common formula R_m+nM_2nX_m.     

X-ray diffraction and Mössbauer study of (Fe1−xNix)4N (0.2 ≤ x ≤ 0.6) films

Single phase (Fe_1−xNi_x)₄N compounds (0.2 ≤ x ≤ 0.6) have been synthesized by reactive evaporation and investigated by X-ray diffraction and Mössbauer spectrometry. The lattice parameters of the nitrides decrease from 3.796 to 3.774 Å with increasing Ni concentration. The fitting results of Mössbauer spectra indicate that the average hyperfine field have the same changing tendency with lattice parameter and the nickel atoms have a tendency to be located at the corner site.     

Subsolidus phase relation in the system ZnO–Li2O–MoO3

The subsolidus phase relation of the system ZnO–Li₂O–MoO₃ has been investigated by X-ray diffraction (XRD) analyses. The phase diagram has been constructed. There are six binary compounds and one ternary compound in this system. The phase diagram comprises nine three-phase regions. The ternary compound Li₂Zn₂(MoO₄)₃ is refined by the Rietveld method. It belongs to an orthorhombic system with space group Pnma and lattice constants a = 5.1114 Å, b = 10.4906 Å, c = 17.6172 Å.     

Synthesis and crystal structure of CaAgBi and BaAg1.837Bi2

Two ternary alkali earth silver bismuthides, CaAgBi and BaAg_1.837Bi₂, have been synthesized by solid-state reactions of the corresponding metals in welded Nb tubes at high temperature. Their structures have been established by single-crystal X-ray diffraction studies. CaAgBi crystallizes in the hexagonal space group P6₃mc (No.186) with cell parameters of a = b = 4.8113(4) Å, c = 7.8273(9) Å, V = 156.92(3) Å³, and Z = 2. BaAg_1.837Bi₂ belongs to tetragonal space group P4/nmm (No.129) with cell parameters of a = b = 4.9202(2) Å, c = 11.628(1) Å, V = 281.50(3) Å³, and Z = 2. The structure of CaAgBi is of the LiGaGe type, and features a three-dimensional four-connected (3D4C) anionic network with Ca²⁺ encapsulated in the channels formed by [Ag₃Bi₃] six-membered rings. BaAg_1.837Bi₂ is isostructural with CaBe₂Ge₂, a variant of the tetragonal ThCr₂Si₂-type structure. Its structure exhibits a three-dimensional anionic network built of (0 0 1) and (0 0 2) puckered [Ag₂Bi₂] layers interconnected via additional Ag–Bi bonds along the c-axis. BaAg_1.837Bi₂ is metallic based on band structure calculations.