Magnetic phase diagram of dysprosium

We have studied the magnetic phase diagram of single crystal dysprosium (Dy) below the Néel temperature. The recent study by Andrianov et al. showed that magnetic phase diagram of Dy for applied magnetic field along the b-axis, contains four regions: I—helical antiferromagnetic phase, II—angular phase, III—fan phase and IV—collinear ferromagnetic phase. In our study we have used magnetization measurements to construct the magnetic phase diagram of Dy in the H–T plane (H is the applied magnetic field, T is the temperature). Our magnetic phase diagram of Dy for H along the b-axis is very similar to that of Andrianov et al.     

The magnetic structure of TbNiSiD1.78

TbNiSiD_1.78 has been studied by powder neutron diffraction below 100 K. The compound takes the hexagonal room temperature structure at 100 and 50 K (P6₃/mmc). At 2 K, below the antiferromagnetic ordering temperature of 10 K, there is a small orthorhombic distortion of the lattice. The refined unit-cell dimensions at 2 K (space group Pnma) are a=7.9505(2), b=4.02502(14), c=6.9823(2) Å. The magnetic moments of Tb are 8.71(6) μ_B, and are ordered antiferromagnetically along a.     

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.     

New Zr6CoAs2-type compounds: Y6CoBi2, Ho6CoBi2 and Tm6CoBi2

Results of a powder X-ray diffraction investigation of new ternary compounds are reported. The compounds Y₆CoBi₂ [a=0.8312(1) nm, c=0.4144(1) nm], Ho₆CoBi₂ [a=0.8246(2) nm, c=0.4095(1) nm], and Tm₆CoBi₂ [a=0.8155(2) nm, c=0.4066(1) nm] crystallize in the hexagonal Zr₆CoAs₂-type structure (space group P6b2m No. 189). The Zr₆CoAs₂-type structure is a superstructure of the Fe₂P-type structure.     

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.     

The molybdenum diphosphate Mo1.3O(P2O7), containing Mo2 and Mo3 clusters

A novel molybdenum diphosphate, Mo_1.3O(P₂O₇), was obtained by electrochemical lithium deintercalation. The diphosphate crystallises in space group I2/a with the lattice parameters a=22.88(1), b=22.94(2), c=4.832(1) Å, γ=90.36°, Z=8. Its original framework is built up from MoO₆ octahedra, P₂O₇ groups and also from MoO₄, Mo₂O₄ and Mo₃O₈ units containing Mo₂ and Mo₃ clusters. These polyhedra delimit large octagonal and z-shaped tunnels running along c, in which the inserted cations may be located.     

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.     

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.     

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).     

Crystal structures of the Ag4HgGe2S7 and Ag4CdGe2S7 compounds

The crystal structures of the Ag₄HgGe₂S₇ and Ag₄CdGe₂S₇ compounds were investigated using X-ray powder diffraction. These compounds crystallize in the monoclinic Cc space group with the lattice parameters a=1.74546(8), b=0.68093(2), c=1.05342(3) nm, β=93.398(3)° for Ag₄HgGe₂S₇ and a=1.74364(8), b=0.68334(3), c=1.05350(4) nm, β=93.589(3)° for Ag₄CdGe₂S₇. Atomic parameters were refined in the isotropic approximation (R_I=0.0761 and R_I=0.0727, respectively).     

Determination of magnetic phase transitions in holmium using magnetoresistance measurements

The magnetic phase diagram of Holmium in the field–temperature plane has been determined using electrical resistance and longitudinal magnetoresistance measurements along the b-axis. Our H–T phase diagram below 70 K agrees quite well with that of Jensen and Mackintosh. We observed a splitting of the Néel temperature above approximately 1 T. This study shows that fairly simple magnetoresistance measurements can be used to establish magnetic phase diagrams of rare earth single crystals.     

Structural studies of high-pressure Ba---Rh---O phases

Three different phases in the Ba---Rh---O system were prepared under high-pressure/high-temperature conditions. The black crystalline product was studied by X-ray diffraction techniques and the space groups for several phases were obtained. The first phase, the 4H polytype BaRhO₃, has already been reported in the literature, but in addition two new phases were isolated and their structures determined. The second high-pressure Ba---Rh---O product, previously reported to be an 18R polytype, was observed to be isostructural with BaIrO₃. This phase was found to be non-stoichiometric with a deficiency in rhodium in octahedral sites, with a stoichiometry of BaRh_0.92O₃. The space group is C2/m and the unit cell parameters are a = 10.005(2), b = 5.764(1), c = 14.937(3) Å, β = 102.99° and Z = 12. The third phase isolated in this study was observed to possess a hollandite-type structure with space group I2/m, where the RhO₆ octahedra share edges and vertices. Its unit cell parameters are a = 9.435(2), b = 3.1041(5), c = 10.399(2) Å, β = 94.45(1)° and Z = 1. Refinement of the structure generated the composition Ba_1.72Rh₈O₁₆.     

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).     

Crystal field splitting and anomalous thermal expansion in YbVO4

We have investigated the Yb³⁺ crystal-field-level structure in YbVO₄ using inelastic magnetic neutron-scattering measurements and crystal-field model calculations. We determined the temperature dependence of the a and c lattice parameters of the tetragonal unit cell by neutron diffraction and observed a minimum at ca. 120 K in the c lattice parameter. This anomaly in the thermal expansion is interpreted as arising from a coupling of the anisotropic low-lying crystal-field states of the Yb³⁺ ions and the crystal lattice at low temperatures.     

High-pressure synthesis and crystal structures of two new polyphosphides, NaP5 and CeP5

Two novel polyphosphides, NaP₅ and CeP₅, were prepared in a BN crucible by the reaction of elemental components under a high pressure of 3 GPa at 800–950 °C. The X-ray structural analysis showed that NaP₅ crystallizes in an orthorhombic space group Pnma with a=10.993(2) Å, b=6.524(1) Å, c=6.903(1) Å, Z=4 and CeP₅ in the monoclinic group P2₁/m with a=4.9143(5) Å, b=9.6226(8) Å, c=5.5152(4) Å, β=104.303(6)°, Z=2. The crystal structure of NaP₅ consists of a three-dimensional framework _∞³[P₅]¹⁻ constructed by P---P bonds among four crystallographically inequivalent phosphorus sites, with large channels hosting the sodium cations, while CeP₅ is a layered compound containing _∞²[P₅]³⁻ polyanionic layers that are separated by Ce³⁺ ions. NaP₅ exhibits the diamagnetic behavior, while the temperature-dependent magnetic susceptibility of CeP₅ essentially follows the Curie–Weiss law.     

Structural, thermodynamic, and electrochemical properties of TixZr1−x(VNiCrMnCoAl)2 C14 Laves phase alloys

The crystal structure of the monoclinic phase η-Al₁₁Cr₂ of the space group C2/c, a ≈ 1.76 nm, b ≈ 3.05 nm, c ≈ 1.76 nm, β ≈ 90° [L.A. Bendersky, R.S. Roth, J.T. Ramon, D. Shechtman, Metall. Trans. A 22A (1991) 5] has been determined by single-crystal X-ray diffraction. The structure model, refined to a final R value of 0.0441, has the composition of Al_83.8Cr_16.2. a = 1.77348(10) nm, b = 3.04555(17) nm, c = 1.77344(10) nm, monoclinic angle β = 91.0520(12)°. There are 80 (66Al + 14Cr) independent atomic positions in a unit cell, of which all Cr atom sites and 8 Al atom sites have icosahedral coordination. These icosahedra are interconnected forming icosahedral chains along , (1 0 1) icosahedral layer blocks as well as a three-dimensional icosahedral structure.     

Materials with layered structures X: subsolidus phase diagram of the system FeIn2S4–FeIn2Se4

The system (1−x)FeIn₂S₄–xFeIn₂Se₄ has been investigated by X-ray powder methods. The subsolidus phase diagram is constructed in the temperature interval 600–1000°C. The spinel type FeIn₂S₄ exhibits a phase width up to the composition FeIn₂S₃Se and the layered FeIn₂Se₄ is formed for 1≥x≥0.65. A new layered compound is formed for 0.55≥x≥0.4 which crystallizes at temperatures below 850°C in an -FeGa₂S₄ structure with a=363.6 pm and c=1207.1 pm (x=0.5) for the hexagonal cell and at higher temperatures in the MgAl₂S₄-type with a=393.9 pm and c=3843.2 pm (x=0.5) for the hexagonal cell. Both structures have been refined by the Rietveld-method. All phase boundaries are nearly independent from temperature.     

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.     

Sr3GeMgN4: new quaternary nitride containing Mg

A new Mg-containing quaternary nitride, Sr₃GeMgN₄, was obtained as single crystals from constituent elements in molten Na. It crystallizes in space group Pnna (No. 52) with a=5.939(1) Å, b=10.320(2) Å, c=9.618(2) Å, and Z=6. It is isostructural with Sr₃Ga₂N₄, both of which contain one-dimensional chains of edge-sharing tetrahedra.     

New RRh5Ge3 compounds of the new SmRh5Ge3 structure type and their magnetic properties (R=Sm, Gd, Tb)

Powder X-ray diffraction results and macroscopic magnetic properties of new ternary RRh₅Ge₃ compounds (R=Sm, Gd, Tb) are reported. The compounds SmRh₅Ge₃ (a=2.2744(4) nm, c=0.3888(1) nm), GdRh₅Ge₃ (a=2.2711(5) nm, c=0.3872(1) nm) and TbRh₅Ge₃ (a=2.2628(7) nm, c=0.3851(1) nm) crystallize in the hexagonal SmRh₅Ge₃-type structure (space group P6₃/m; No. 176). The GdRh₅Ge₃ and TbRh₅Ge₃ compounds are Curie–Weiss paramagnets down to 5 K.