X-ray investigations of ternary R3Pd4Ge4 samples

Ternary R₃Pd₄Ge₄ samples (R=Nd, Eu, Er) were investigated by means of X-ray single crystal (four circle diffractometer Philips PW1100, MoK radiation) and powder diffraction (MX Labo diffractometer, CuK radiation). The Er₃Pd_3.68(1)Ge₄ compound belongs to the Gd₃Cu₄Ge₄ structure type, space group Immm, a=4.220(2) Å, b=6.843(2) Å, c=14.078(3) Å, R₁=0.0484 for 598 reflections with F_o>4σ(F_o) from X-ray single crystal diffraction data. No ternary R₃Pd₄Ge₄ compound when R is Nd or Eu was observed. The Nd and Eu containing samples appeared to be multiphase. Ternary phases observed in the Nd₃Pd₄Ge₄ and Eu₃Pd₄Ge₄ alloys and their crystallographic characteristics are the following: NdPd₂Ge₂, CeGa₂Al₂ structure type, space group I4/mmm, a=4.3010(2) Å, c=10.0633(2) Å (X-ray powder diffraction data); NdPd_0.6Ge_1.4, AlB₂ structure type, space group P6/mmm, a=4.2305(2) Å, c=4.1723(2) Å (X-ray powder diffraction data); Nd(Pd_0.464(1)Ge_0.536(1))₂, KHg₂ structure type, space group Imma, a=4.469(2) Å, b=7.214(2) Å, c=7.651(3) Å, R₁=0.0402 for 189 reflections with F_o>4σ(F_o) (X-ray single crystal diffraction data); Eu(Pd,Ge)₂, AlB₂ structure type, space group P6/mmm, a=4.311(2) Å, c=4.235(2) Å; EuPdGe, EuNiGe structure type, space group P2₁/c, and ternary compound with unknown structure (X-ray powder diffraction data).     

Peculiarities of the R3(Fe,Si)29 phase formation in the Sm---Fe---Si system

The phase content of the Sm(Fe_1−xSi_x)_y alloys (0.05≤x≤0.15; 8.5≤y≤12) has been studied by X-ray diffraction using micromonocrystals. The compounds Sm₂(Fe,Si)₁₇, Sm(Fe,Si)₁₂ and a novel Sm₃(Fe,Si)₂₉ compound with a monoclinic unit cell are found. The lattice parameters of Sm₃(Fe,Si)₂₉ are: a=1.056 nm, b=0.850 nm, c=0.966 nm, β=96.8°. This compound forms as a result of a solid state transformation from the high-temperature Sm₂(Fe,Si)₁₇ phase. Diffuse effects observed in rocking photographs suggest transition structures arising from this transformation. The Curie temperatures of Sm₃(Fe,Si)₂₉ vary in the interval 496–521 K.     

Crystal structure and magnetism of the Y2Pd14B5 compound

The crystal structure of the ternary boride Y₂Pd₁₄B₅, space group I4₁/amd, a=8.484(2) Å, c=16.490(3) Å, V=1186.98 ų, Z=4, was refined down to R=0.0475, wR2=0.1276 from single crystal X-ray diffraction data. Two types of coordination for boron atoms were observed: the coordination sphere for the B1 atom is a trigonal prism with one additional atom; the B2 atom has only four neighboring atoms which form a square. No boron–boron contact was observed. Analysis of the Y₂Pd₁₄B₅ crystal structure shows the existence of a correlation between this structure and the Sc₄Ni₂₉B₁₀ structure type. Magnetization and AC susceptibility measurements indicate that there is no superconducting or magnetic transition in Y₂Pd₁₄B₅ down to 2 K.     

Crystal structures of new ternary rare earth silicides Sc3Pr2Si4, Sc1.26Pr3.74Si4 and Sc3.96Nd1.04Si4 with ordered and partially ordered rare earth sites

The crystal structures of three new ternary silicides Sc₃Pr₂Si₄, Sc_1.26Pr_3.74Si₄ and Sc_3.96Nd_1.04Si₄ were determined by single crystal X-ray diffraction. The title compounds crystallize with three different substitution derivatives of the Sm₅Ge₄ structure type (orthorhombic space group Pnma) containing various distributions of rare earth atoms on the three Sm sites. Crystal chemistry analysis shows that these distributions are controlled by the atomic size factor.     

Effect of hydrogenation on the crystal structure of La2Pd2In

The paper is focusing on the modification of the crystal lattice upon the hydrogenation of La₂Pd₂In and hydrogen desorption from La₂Pd₂In hydrides. The synthesis at 1 bar of hydrogen produces a crystalline hydride with 1.5 H atoms per formula unit and the volume expansion of ΔV/V = 6.0%. The synthesis at 10 and 100 bar H₂ pressures leads to an amorphous state and with 4 + δ H atoms/f.u. The uptake of hydrogen leads to the decrease of the Debye temperature of La₂Pd₂In and modification of the optical phonon spectrum.     

Ba3YB3O9: phase transition and crystal structure

A new modification of the compound Ba₃YB₃O₉, β phase, has been attained through solid phase transition from phase at 1125–1134 °C. β-Ba₃YB₃O₉ crystallizes in the hexagonal space group with cell parameters a=13.0529(8) Å, c=9.5359(9) Å. The crystal structure of -Ba₃YB₃O₉ has been determined from powder X-ray diffraction (XRD) data. The refinement was carried out using the Rietveld methods and the final refinement converged with R_p=8.8%, and R_wp=11.8% with R_exp=5.65%. In its structure, the isolated [BO₃]³⁻ anionic groups are parallel to each other and distributed layer upon layer along the c-axis. The Y atoms are six-coordinated by the O atoms to form octahedra. The result of IR spectrum confirmed the existence of [BO₃]³⁻ triangular groups.     

Ce2Ir5B2, a new structure type of ternary borides

The crystal structure of a new ternary boride Ce₂Ir₅B₂, space group , a=5.477(2) Å, c=31.518(5) Å, Z=6, V=818.79 Å, was refined down to R=0.0484, wR₂=0.1211 from single crystal X-ray diffraction data. This is the first representative of a new structure type of intermetallic compounds (an ordered variant of the binary Er₂Co₇ compound). The structure of Ce₂Ir₅B₂ is the stacking variant of the MgCu₂- and CeCo₃B₂-type slabs and belongs to the structural series with the general formula R_2+nM_4+3nX_2n (n=2).     

A new ternary compound YbZn2As2 with mixed valency of Yb

A new compound with chemical formula YbZn₂As₂ and ‘anti’-La₂O₃-type crystal structure (space group P3m1) has been synthesized for the first time. The trigonal lattice constants of the compound are a=0.4157 and c=0.6954 nm. In the temperature range 77–500 K, the magnetic susceptibility of YbZn₂As₂ follows the Curie–Weiss law, indicating antiferromagnetic interactions of the Yb ions and yielding a Curie temperature θ=−52.8 K and an effective magnetic moment μ_eff=2.35 μ_B (the Bohr magneton) per Yb ion. This means that a part of the Yb ions has valency 3+, instead of 2+ for all the Yb ions, as would be expected from their formal oxidation number, i.e. YbZn₂As₂ is a compound with mixed valency of Yb. YbZn₂As₂ exhibits p-type conductivity with a room temperature electrical resistivity of 0.15 Ω cm which decreases when lowering temperature and reaches a practically constant value of 0.08 Ω cm below 20 K.     

Crystal structure of the R3Si1.25Se7 (R = Pr, Nd and Sm) compounds

The crystal structure of new ternary R₃Si_1.25Se₇ (R = Pr, Nd and Sm) compounds (Dy₃Ge_1.25S₇ structure type, Pearson symbol hP22.5, space group P6₃, a = 1.05268 (3) nm, c = 0.60396 (3) nm, R_I = 0.0897 for Pr₃Si_1.25Se₇; a = 1.04760 (3) nm, c = 0.60268 (3) nm, R_I = 0.0891 for Nd₃Si_1.25Se₇; a = 1.04166 (6) nm, c = 0.59828 (6) nm for Sm₃Si_1.25Se₇) was determined using X-ray powder diffraction. The nearest neighbours of the R and Si atoms are exclusively Se atoms. The latter form distorted trigonal prisms around the R atoms, octahedra around the Si1 atoms and tetrahedra around the Si2 atoms. Tetrahedral surrounding exists for Se1 and Se3 atoms. Six neighbours surround every Se2 atom.     

Single crystal preparation and crystal structure of the Cu2Zn/Cd,Hg/SnSe4 compounds

Single crystals of Cu₂Zn/Cd/SnSe₄ were grown using a solution-fusion method. The crystal structure of the Cu₂Zn/Cd,Hg/SnSe₄ compounds were investigated using X-ray powder diffraction. These compounds crystallize in the stannite structure (space group I 2m) with the lattice parameters: a=0.56882(9), c=1.13378(9) nm, c/a=1.993 (Cu₂ZnSnSe₄), a=0.58337(2), c=1.14039(4) nm, c/a=1.955 (Cu₂CdSnSe₄) and a=0.58288(1), c=1.14179(2) nm, c/a=1.959 (Cu₂HgSnSe₄). Atomic parameters were refined in the isotropic approximation (R_I=0.0517, R_I=0.0511 and R_I=0.0695 for Cu₂ZnSnSe₄, Cu₂CdSnSe₄ and Cu₂HgSnSe₄, respectively).     

Structural investigation of ternary RIr3B2 compounds (R=Ce and Pr)

Structural studies were performed for the ternary RIr₃B₂ compounds (R=Ce and Pr) from as cast samples. The crystal structure of the ternary boride CeIr₃B₂ (CeCo₃B₂ structure type, space group P6/mmm, a=5.520(3) Å, c=3.066(2) Å, Z=1, V=80.91 ų, ρ_x=15.154 g cm⁻³) was refined to R₁=0.0470, wR₂=0.1240 from single-crystal X-ray diffraction data. The new ternary boride PrIr₃B₂ was found to be isostructural with the CeIr₃B₂ compound. Its lattice parameters a=5.5105(2) Å, c=3.1031(1) Å were obtained from a Rietveld refinement of X-ray powder diffraction data.     

Crystal structure, thermal expansion and magnetic properties of new compound Dy1.2Fe4Si9.8

The new ternary compound Dy_1.2Fe₄Si_9.8 have been prepared and studied by means of X-ray powder diffraction technique and vibrating sample magnetometer. The ternary compound Dy_1.2Fe₄Si_9.8 crystallizes in the hexagonal Er_1.2Fe₄Si_9.8-type structure, space group P6₃/mmc (no. 194) with lattice parameters a = 0.39415(1) nm and c = 1.52771(3) nm. The crystal structural refinement of the compound Dy_1.2Fe₄Si_9.8 has been performed by using Rietveld method. Lattice thermal expansion studies on the compound were carried out in the temperature range from 298 to 1013 K. The variation of the unit cell parameters shows that the unit cell parameters increase with the increase in temperature. The coefficients of average lattice thermal expansion along various axes in the temperature range from 298 to 1013 K are , and . The temperature dependence of the magnetization for the compound was also investigated in the range from 90 to 300 K. The experimentally determined magnetic effective paramagnetic moment is μ_eff = 11.3μ_B per formula unit (10.3μ_B per Dy atom).     

Synthesis and properties of Ba3NaRu2O9−δ and Ba3(Na, R)Ru2O9−δ (R=rare earth) crystals

Crystals of Ba₃NaRu₂O_9−δ (δ≈0.5) and Ba₃(Na, R)Ru₂O_9−δ (R=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb) were grown by an electrochemical method, and their crystallographic, magnetic, and electric properties were studied. All crystals have a hexagonal structure of space group P6₃mmc. Ba₃NaRu₂O_9−δ and Ba₃(Na, R)Ru₂O_9−δ (except Ce) have a negative asymptotic Curie temperature suggesting the existence of an antiferromagnetic order; however, they are paramagnetic at temperatures above 1.7 K. Ba₃NaRu₂O_9−δ has an effective magnetic moment P_eff of 0.91 μ_B, while P_eff of Ba₃(Na, R)Ru₂O_9−δ (except Ce) reflects the large free-ion moment of the rare earth ions. Ba₃(Na, Ce)Ru₂O_9−δ shows peculiar magnetic behavior that differs from the magnetism of other Ba₃(Na, R)Ru₂O_9−δ crystals. The resistivity of all crystals exhibits an activation-type temperature dependence with an activation energy in the range of 0.10.2 eV.     

Synthesis and crystal structure of Ba3Si4C2

SiC powder prepared by the Na flux method at 1023 K for 24 h and Ba were used as starting materials for synthesis of tribarium tetrasilicide acetylenide, Ba₃Si₄C₂. Single crystals of the compound were obtained by heating the starting materials with Na at 1123 K for 1 h and by cooling to 573 K at a cooling rate of −5.5 K/h. The single crystal X-ray diffraction peaks were indexed with tetragonal cell dimensions of a = 8.7693(4) and c = 12.3885(6) Å, space group I4/mcm (No.140). Ba₃Si₄C₂ has the Ba₃Ge₄C₂ type structure which can be described as a cluster-replacement derivative of perovskite (CaTiO₃), and contains isolated anion groups of slightly compressed [Si₄]⁴⁻ tetrahedra and [C₂]²⁻ dumbbells. The electrical conductivity measured for a not well-sintered polycrystalline sample was 2.6 × 10⁻²–7 × 10⁻³ S cm⁻¹ in the temperature range of 370–600 K and slightly increased with increasing temperature. The Seebeck coefficient showed negative values of around −200 to −300 μV K⁻¹.     

Crystal structure of the Nd(Ru0.6Ge0.4)2 and ErRuGe compounds

Using X-ray powder and single crystal diffraction, the crystal structures of the Nd(Ru_0.6Ge_0.4)₂ and ErRuGe compounds were investigated. The compounds belong to the KHg₂ and TiNiSi type structure, respectively.     

Antiferromagnetic transition in ternary rare-earth metal silicide Er5Ir4Si10 single crystal

In the present paper the electric field dependence of the permittivity of (Ba, Sr)TiO₃ ceramics is reported. Single phase Ba_1−xSr_xTiO₃ (x = 0.20 and 0.30) ceramics were obtained by powders synthesized by a modified Pechini method. The dc-tunability at room temperature is higher for the ceramic with lower strontium content as this composition is ferroelectric at room temperature, whereas the composition corresponding to the higher strontium content is paraelectric. The data are well described by the Johnson's approximation for the ferroelectric state and by an additional “extrinsic” contribution due to the polar clusters in the case of the paraelectric state (Ba, Sr)TiO₃ ceramic.     

Magnetocrystalline anisotropy and exchange interactions in the novel R3(Fe, V)29 compounds (R = Y, Nd, Sm)

A type of magnetocrystalline anisotropy and exchange interactions of the novel ternary R₃(Fe, V)₂₉ compounds (R = Y, Nd, Sm) have been investigated. The compounds are uniaxial ferromagnets with easy magnetization direction along the [ 0 1] axis of the monoclinic lattice at room temperature. The temperature variations of the magnetic moment and the first anisotropy constant for Y₃(Fe, V)₂₉ are presented. The first order magnetization process along the hard magnetization direction takes place for Sm₃(Fe, V)₂₉ at T < 120 K. A magnetic anomaly is detected in the temperature dependence of the a.c. susceptibility for Nd₃(Fe, V)₂₉ which can be related to a spin reorientation.     

Magnetic properties and magnetic structure of the Mn5Si3-type Tb5Si3 compound

Neutron diffraction and magnetization measurements have been performed on the Tb₅Si₃ compound (hexagonal Mn₅Si₃-type, hP16, P6₃/mcm) to understand its magnetic structure and magnetic properties. The temperature-dependent neutron diffraction results prove that this intermetallic phase shows a complex flat spiral magnetic ordering, presenting three subsequent changes in magnetization at on cooling. However, the magnetization data depict two transitions at 72 K (T_N1) and 55 K (T_N2). The extended temperature range between and over which the neutron diffraction patterns slowly evolve might correspond to the high-temperature antiferromagnetic transition at T_N1 and low-temperature antiferromagnetic transition at T_N2 of the magnetic data. Between Tb₅Si₃ shows a flat spiral antiferromagnetic ordering with a propagation vector K₁ = [0,0, ±1/4]; then, between the flat spiral type ordering is conserved, but by two coexisting propagation vectors K₁ = [0,0, ±1/4] and K₂ = [0,0, ±0.4644(3)]. The terbium magnetic moments arrange in the XY(ab) plane of the unit cell. Below the magnetic component with K₁ = [0,0, ±1/4] vanishes and magnetic structure of Tb₅Si₃ is a flat spiral with K₂ = [0,0, ±0.4644(3)], only. Low field magnetization measurements confirm the occurrence of complex, multiple magnetic transitions. The field dependence of the magnetization indicates a metamagnetic transition at a critical field of 3 T.     

Neutron diffraction studies of the magnetic structure of Ho3Pd4Ge4

Ho₃Pd₄Ge₄ crystallizes in the orthorhombic Gd₆Cu₈Ce₈-type of structure (space group Immm) in which the Ho atoms occupy two nonequivalent crystallographic positions: 2a and 4j. Neutron diffraction measurements indicate that the Ho moments in the 4j site below 6.7 K form a collinear antiferromagnetic structure with the magnetic moments parallel to the a axis, whereas the Ho moments in the 2a site below 5 K form a sine-wave modulated structure with the magnetic moments parallel to the c axis.     

Synthesis, crystal structure and X-ray excited luminescent properties of LuBa3B9O18

A new compound LuBa₃B₉O₁₈ has been prepared by a high-temperature solid-state reaction and its crystal structure was determined by powder X-ray diffraction methods. The results of Rietveld refinement show that it is isotypic to YBa₃B₉O₁₈. The X-ray excited luminescent properties of LuBa₃B₉O₁₈ were investigated. It shows a broad emission band in the wavelength range of 300–550 nm with peak center at 385 nm. Its room temperature fluorescent decay profile exhibits a single-exponent shape with decay time of 15 ns. It is believed that the lattice defects have played an important role on the luminescent performances of LuBa₃B₉O₁₈ powders and its thermal luminescence measurement confirmed the existence of lattice defects in it. Considering the emission wavelength, luminescence intensity, decay time, melting point, density and non-hygroscopic property of LuBa₃B₉O₁₈, one has reason to assume that it might find an application as a new scintillation material.