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.     

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.     

Magnetic structure of the CeScSi-type RScGe compounds (R = Pr, Nd, Tb)

Subsequent magnetic transitions were recently reported for the CeScSi-type RScGe (R = rare earth) equiatomic intermetallic compounds. The compounds TbScGe and NdScGe order ferromagnetically at T_C = 216 K and T_C = 200 K, respectively whereas PrScGe orders antiferromagnetically at T_N = 140 K. In addition, PrScGe demonstrates two other magnetic transitions at T_C1 = 88 K and T_C2 = 80 K in an applied field of 5 kOe. An investigation by neutron diffraction has been now carried out on these phases in an attempt to solve the magnetic structures corresponding to each ordering, and in this article the results obtained are reported. Below the Curie point, the magnetic structure of TbScGe and NdScGe is collinear ferromagnetic. The magnetic moment of Tb atoms coincides with the Z-axis of CeScSi-type unit cell (M_Tb = 8.63μ_B at 2 K), whereas the magnetic moment of Nd atoms has the θ = 52(2)° angle with Z-axis (M_Nd = 3.53(2)μ_B at 2 K). Below the Néel temperature, T_N = 140 K the magnetic structure of PrScGe consists of antiferromagnetic (0 0 2) rare-earth double layers with magnetic moments of the rare earth atoms collinearly ordered. The magnetic moments of Pr atoms (M_Pr = 1.72(3)μ_B at 100 K) have the θ = 62(2)° angle with the Z-axis. Between T_C1 = 82 K and T_C2 = 62 K the conversion of the commensurate antiferromagnetic collinear type structure to the ferrimagnetic collinear type structure with propagation vector K = [0, 0, 1/2] was observed: the magnetic moments of Pr double layers became sine modulated along the Z-axis. Below T_C2 = 62 K the magnetic structure of PrScGe compound consists of ferrimagnetic (0 0 1/2) layers (amplitude of Pr magnetic moment M_Pr = 3.31(9)μ_B at 5 K).     

The crystal structure and magnetic properties of the Gd6Cr4Al43 compound

The crystal structure of intermetallic compound Gd₆Cr₄Al₄₃ has been investigated by means of X-ray diffraction data (Ho₆Mo₄Al₄₃ structure type, space group P6₃/mcm, Pearson symbol hP106, a = 10.9144(7) Å, c = 17.7361(13) Å).

SQUID magnetic measurements carried out for the title compound point to the existence of two antiferromagnetic phase transitions observed at T_N1 = 19.0(1) K and T_N2 = 6.8(1) K, respectively.     

Electrical transport in UNi0.5Sb2 single crystals

Single crystals of UNi₀.₅Sb₂ were investigated by means of Seebeck coefficient and Hall effect measurements in the temperature range 5–300 K. The results corroborated the occurrence of two magnetic phase transitions: from para- to antiferromagnetic state at T_N = 161.5 K and a spin-reorientation near T_t = 64 K. The first-order character of the latter feature was proved by studying in detail the electrical resistivity and the magnetic susceptibility of single-crystalline UNi₀.₅Sb₂ in the vicinity of T_t.     

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.     

Structural investigation of the alluaudite-like mixed-valence iron phosphate: Na1.25Mg1.10Fe1.90(PO4)3

A new mixed-valence iron phosphate Na_1.25Mg_1.10Fe_1.90(PO₄)₃ has been synthesized as single crystals by a flux technique and its structure has been refined from X-ray data to a residual R₁ = 0.032. The compound crystallizes in the monoclinic space group C2/c with the parameters: a = 11.7831(3) Å, b = 12.4740(3) Å, c = 6.3761(2) Å, β = 113.643(2)° and Z = 4. The structure belongs to the alluaudite structural type, and thus it obeys to the X(2)X(1)M(1)M(2)₂(PO₄)₃ general formula. The X(2) and X(1) sites are occupied by sodium while the M(1) and M(2) sites feature a statistical distribution of iron and magnesium.

Additional information about the cation distribution has been extracted from a Mössbauer spectroscopy study which confirmed the mixed valency of the compound. A magnetic susceptibility study has also been undertaken and has shown the compound to be antiferromagnetic with a Neel temperature of about 35 K.     

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.     

Magnetocaloric effect in Pr6Co1.67Si3 compound

Magnetic properties and magnetocaloric effects of Pr₆Co_1.67Si₃ compound have been investigated by magnetization measurements. The saturation moment at 5 K is found to be 10.7μ_B. The compound undergoes two magnetic transitions below Curie temperature T_C = 48 K and shows a reversible second-order magnetic transition around T_C. A magnetic entropy change ΔS = 6.9 J/(kg K) is observed for a magnetic field change from 0 to 5 T. The full width at half maximum of the ΔS peak is found to be about 38 K.     

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.     

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.     

UCo2Sn, UCo4Sn and UCo5Sn: a crystallographic and magnetic investigation

In our investigation of Co-rich alloys in the ternary U–Co–Sn system, we have identified three intermetallic compounds with composition UCo₂Sn, UCo₄Sn and UCo₅Sn, respectively. The existence and the crystal structure of the first compound, already known in the literature, have been confirmed, while the latter two compounds have been identified for the first time. The crystal structure of these compounds was determined by X-ray diffraction methods, performed both on powders (all samples) and single crystals (UCo₄Sn and UCo₅Sn). The crystal data are as follows (lattice constants from Guinier powder patterns): UCo₂Sn [UPd₂Sn-type, orthorhombic, oP16-Pnma, a = 9.402(3), b = 4.321(1), c = 6.615(2) Å], UCo₄Sn [MgCu₄Sn-type, cubic, , a = 6.992(2) Å] and UCo₅Sn [CeCu_4.38In_1.62-type, orthorhombic, oP56-Pnnm, a = 10.250(1), b = 16.012(2), c = 4.837(1) Å]. The physical properties of the compounds have been studied by electric transport (1.5–300 K), heat capacity (1.8–40 K) and magnetic measurements (1.8–300 K). The magnetisation data reveal weakly paramagnetic behaviour (with weak low temperature upturn due to parasitic impurity phases) in all the three alloys and absence of long-range magnetic ordering, despite the presence of uranium and a substantially high concentration of cobalt. The results for UCo₂Sn are in agreement with earlier reports in the literature. The magnitudes of the coefficients of the linear term in the heat capacity and the T² term in the low temperature resistivity track the room temperature magnetisation.     

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).     

Competing interactions and dimensional crossover in (Er0.5Y0.5)2Cu2O5 studied by EPR

Copper spin dynamics in (Er_0.5Y_0.5)₂Cu₂O₅ solid solution has been investigated by electron paramagnetic resonance (EPR) technique. The temperature dependence of the EPR integrated intensity of the resonance line has showed a pronounced maximum at low temperatures and has vanished at the transition to the antiferromagnetic ordering at T_N = 11 K. The temperature at which the EPR integrated intensity reaches maximum was different for the heating and cooling runs. Study of the product of integrated intensity and temperature has allowed determination of the dominating interactions in a particular temperature range. A model used previously to describe the AFM modes in the antiferromagnetic state of Y₂Cu₂O₅ was applied to explain the observed changes in the EPR spectra. A dimensional crossover from 2D to 3D magnetic behaviour was observed at 55 K and interpreted in terms of the spin correlation length.     

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.     

On the crystal structure of new series of compounds, RPt2+xSb2−y (x = 0.125, y = 0.25; R = La, Ce, Pr)

A new compound CePt_2+xSb_2−y (x = 0.125, y = 0.25) was synthesized by arc-melting of the elements. The chemical and structural characterizations were carried out at room temperature on as-cast samples using X-ray diffractometry, metallographic analysis and EDS-microanalysis. According to the results of X-ray single crystal diffraction this antimonide crystallizes in I4cm space group (no. 108), Z = 32, ρ = 12.19 Mg/m³, μ = 89.05 mm⁻¹ (a = 12.5386(3) Å, c = 21.4692(6) Å (crystal I) and a = 12.5455(2) Å, c = 21.4791(5) Å (crystal II)). The structure and composition were confirmed by powder X-ray diffraction (a = 12.4901(2) Å, c = 21.3620(4) Å) and EDS-microanalysis respectively. Isotypic compounds were observed with La and Pr from X-ray powder diffraction of as-cast alloys at room temperature (a = 12.6266(4) Å, c = 21.4589(6) Å for LaPt_2+xSb_2−y and a = 12.5184(5) Å, c = 21.4178(7) Å for PrPt_2+xSb_2−y). The CePt_2+xSb_2−y structure is derived from CaBe₂Ge₂ (a = 2a₀ − 2b₀, b = 2a₀ + 2b₀, c = 2c₀) and comprises a new atomic arrangement with both vacancy on 4(b) pyramidal site and substitution of antimony atoms (X) by platinum (B) in the B–XX–B layers (referring to the subcell structure) forming two B––1/2B1/2XX–3/4B and two X–BB–X layers per cell. The structure of CePt_2+xSb_2−y is compared with those reported before for URh_1.6As_1.9 and CeNi_1.91As_1.94.     

Single crystal study on UNi0.5Sb2

Single crystals of UNi_1−xSb₂ have been grown from an Sb-rich melt and studied by means of X-ray diffraction, magnetic and electrical transport measurements. Crystal structure refinements indicated significant deficiency on the transition metal sites in the tetragonal HfCuSi₂-type unit cell, yielding the actual composition UNi_0.5Sb₂. The single crystals studied order antiferromagnetically below T_N=161 K and exhibit another phase transition at T_t=60 K, presumably caused by a spin-reorientation. No crystal structure distortion could be detected at 10 K. Above T_N the electrical resistivity is dominated by a Kondo effect, whereas at lower temperatures it shows a behavior characteristic of antiferromagnets. The overall magnetic and electrical transport properties of UNi_0.5Sb₂ are highly anisotropic both in the ordered and paramagnetic states.     

Hydrothermal synthesis and characterization of a new layered compound Li2VGeO5

The new compound Li₂VGeO₅ with a layered structure has been synthesized at 580 °C via the hydrothermal method. The compound crystallizes in the space group P4/n of the tetragonal system with two formula units in a cell of dimensions a=6.5187(9) Å, c=4.5092(9) Å (T=298 K), V=191.61(5) Å³. The structure is composed of layers made of repeating [(VO₅)(GeO₄)]¹⁻ units. Li⁺ ions reside between the layers. The magnetic susceptibility data show an antiferromagnetic coupling below 5 K with C=0.47 emu K mol⁻¹, and θ=−13 K with μ_eff=1.89μ_B for each Li₂VGeO₅ unit.     

Crystallographic and magnetic properties of HfFe6Ge6-type REFe6Sn4Ge2 compounds (RE = Y, Gd–Er)

The REFe₆Sn₄Ge₂ (RE = Y, Gd–Er) compounds have been synthesized and studied by powder X-ray diffraction and magnetisation measurements. These compounds crystallize in the hexagonal HfFe₆Ge₆ structure although the parent ternary compounds REFe₆X₆ (X = Ge, Sn) display more complicated orthorhombic crystal structure. This evolution is discussed and interpreted on the basis of the relaxation of some RE–X contacts in the quaternary compounds. The iron sublattice order antiferromagnetically above room temperature (554 ≤ T_N ≤ 560 K) while the paramagnetic RE compounds display a second transition at low temperature (7.3 ≤ T_t ≤ 42.7 K). The magnetisation versus field curves display a metamagnetic behaviour at 4.2 K. The corresponding value of the magnetisation suggests a non-collinear ordering of the RE sublattice.     

Neutron diffraction studies of LaMn2Ge2Si2 and LaMn2Si2 compounds: evidence of dominant antiferromagnetic components within the Mn planes

The magnetic properties of ThCr₂Si₂-type structure LaMn₂Ge₂ and LaMn₂Si₂ compounds have been reinvestigated by neutron diffraction experiments. The ferromagnetic ordering previously proposed to take place on the manganese sublattice is revised. At high temperature, both compounds are purely collinear antiferromagnets (not detected by magnetic measurements), characterized by a stacking of antiferromagnetic (001) Mn planes. Below T_c=310 and 325 K for LaMn₂Ge₂ and LaMn₂Si₂, respectively, both compounds exhibit an easy-axis ferromagnetic behaviour. However, the occurrence of a dominant antiferromagnetic component within the (001) Mn planes yields a conical magnetic structure for the germanide (cone semi-angle =58° at 2 K) and a canted magnetic structure for the silicide (φ=49°). At 2 K, the total Mn moments are about 3.0 and 2.4 μ_B for LaMn₂Ge₂ and LaMn₂Si₂, respectively. The results are compared with those of closely related RMnSi and RMnGe compounds and the magnetic properties of the ThCr₂Si₂-type structure RMn₂X₂ (XSi, Ge) compounds are discussed.