HfFe6Ge6-type YbMn6Ge6−xGax compounds (0.07≤x<0.72) with large magnetocrystalline anisotropy

The HfFe₆Ge₆-type YbMn₆Ge_6−xGa_x solid solution (0.07≤x≤0.72) has been studied by X-ray diffraction, microprobe analysis and powder magnetization measurements. All the compounds order antiferromagnetically between T_N=481 K for x=0.07 and T_N=349 K for x=0.72 and display more or less pronounced spontaneous magnetization at lower temperature. The corresponding Curie points increase from 40 K for x=0.07 to 319 K for x=0.72. The maximum magnetization values of the Ga-rich compounds (M≈5 μ_B/f.u. at 6 K) is compatible with a ferrimagnetic order of the Mn and Yb sublattices whereas the smaller values measured in the Ga-poor compounds suggest the stabilization of non-colinear magnetic structures. All the studied compounds are characterized by rather large coercive fields at low temperature (4.0≤H_c≤8.2 kOe).     

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.     

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 YMn6Ge6 and room temperature magnetic structure of LuMn6Sn6 obtained from neutron diffraction study

Neutron diffraction measurements have been performed on the ternary compounds YMn₆Ge₆ and LuMn₆Sn₆ of HfFe₆Ge₆-type structure (space group, P6/mmm). This structure can be described as a filled derivative of the CoSn-B35-type structure. Each of the rare earth (R) and Mn atoms are successively distributed in alternate layers, stacked along the c axis with the sequence Mn---R---Mn---Mn---R---Mn. At 300 K, both compounds exhibit collinear antiferromagnetic arrangements and the magnetic structures consist of a stacking of ferromagnetic (001) layers of Mn with the coupling sequence Mn(+)---R---Mn(−)---Mn(−)---R---Mn(+) (μ_Mn ≈ 1.33(1)μ_B and 1.82(3)μ_B for LuMn₆Sn₆ and YMn₆Ge₆ respectively). For LuMn₆Sn₆, the magnetic moments lie in the (001) plane, while they are along the c axis in YMn₆Ge₆. At low temperature, a spin reorientation process occurs in both compounds, yielding incommensurate antiferromagnetic arrangements. For YMn₆Ge₆ (T_t ≈ 80 K), the Mn moments form a double-cone structure with a periodicity of about 105 Å (μ_Mn = 1.95(4)μ_B at 2 K), while only preliminary results are available for LuMn₆Sn₆ below about 200 K. The results are compared with those obtained on the CoSnB35-type structure binary compounds FeSn and FeGe, on one hand, and the RMn₆Sn₆ compounds, on the other hand.     

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.     

Evolution of magnetic hardness in the HfFe6Ge6-type RMn6Sn6−xGax and RMn6Sn6−xInx compounds (R=Tb, Dy; 0.2≤x≤1.4)

The HfFe₆Ge₆-type RMn₆Sn_6−xX_x′ solid solutions (R=Tb, Dy, X′=Ga, In; x≤1.4) have been studied by powder magnetization measurements. All the series are characterized by ferrimagnetic ordering and by a decrease in Curie temperatures with the substitution (ΔT_c/Δx≈−39 K for X′=Ga and ΔT_c/Δx≈−75 K for X′=In). The RMn₆Sn_6−xGa_x systems are characterized by a strong decrease in the spin reorientation temperature with substitution (ΔT_t/Δx≈−191 K and −78 K for R=Tb and Dy, respectively) while this transition almost does not change in systems containing indium. The coercive fields drastically decrease with the substitution in the TbMn₆Sn_6−xGa_x system while the substitution of In for Sn has a weaker effect. The coercive fields of the Dy compounds do not vary greatly with the substitution in both series. The behaviour of the TbMn₆Sn_6−xGa_x is compared with the evolutions observed in the TmMn₆Sn_6−xGa_x series. This comparison strongly suggests that the replacement of Sn by Ga changes the sign of the A₀² crystal field parameter.     

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.     

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.     

Neutron diffraction studies of CaMn2Ge2 and BaMn2Ge2 compounds: first examples of antiferromagnetic Mn planes in ThCr2Si2-type structure compounds

The magnetic properties of ThCr₂Si₂-type structure CaMn₂Ge₂ and BaMn₂Ge₂ compounds have been investigated by neutron diffraction experiments. In the whole temperature range studied (2–270 K), both compounds are purely collinear antiferromagnets (not detected by bulk magnetometric measurements) characterized by a stacking of antiferromagnetic (001) Mn planes. This peculiar Mn-sublattice magnetic behaviour seems to be related to the valency of the large metal. At 2 K, the total Mn moments are about 2.7 μ_B and 3.6 μ_B for CaMn₂Ge₂ and BaMn₂Ge₂, respectively. The results are compared with those of closely related RMnSi and RMnGe compounds and the isotypic alkali-metal manganese pnictides. The magnetic properties of the ThCr₂Si₂-type structure RMn₂X₂ (XSi, Ge) compounds are discussed.     

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.     

Magnetic ordering in ternary RMn2Ge2 compounds (R = Tb, Ho, Er, Tm, Lu) from neutron diffraction study

The compounds RMn₂Ge₂ (R = Tb, Ho, Er, Tm, Lu) have been investigated by neutron diffraction. TbMn₂Ge₂ is a collinear ferrimagnet with the Mn and Tb moment aligned along the c axis (μ_TB = 8.81(59) μ_B: μ_Mn = 2.21(44) μ_B). HoMn₂Ge₂ exhibits incommensurale ordering below 2.1 K characterized by two wavevectors at 1.3 K: q₁ = (0.1543(4), 0.1543(4), 0) and q₂ = (0.210(1), 0.007(1), 0). The Mn sublattice remains antiferromagnetic down to 1.3 K (μ_Mn = 2.38(6) μ_B). The Er moments order ferromagnetically below 5.5 K in ErMn₂Ge₂ (μ_Mn = 6.81(31) μ_B). The moments are perpendicular to the c axis. The Mn sublattice remains antiferromagnetic down to 1.8 K (μ_Mn = 2.34(18) μ_B). The magnetic structure of TmMn₂Ge₂ is characterized by the propagation vector (0.0.1/2). the Tm moments lying in the basal plane. The ordering of the Tm moments yields a canting of the Mn moments (τ = 21(3)°); μ_Tm = 6.63(18) μ_B; μ_Mn = 2.28(27) μ_B). The antiferromagnetic structure of LuMn₂Ge₂ has been determined (μ_Mn = 2.32(14) μ_B). The evolution of the magnetic properties of the heavy rare earth compounds RMn₂Ge₂ is discussed.     

Gibbs free energy of formation of the ternary oxide Nd3RuO7

The Gibbs free energy of formation of Nd₃RuO₇(s) has been determined using solid-state electrochemical cell employing oxide ion conducting electrolyte. The electromotive force (e.m.f.) of the following solid-state electrochemical cell has been measured, in the temperature range from 929.3 to 1228.6 K.

Cell: (−)Pt/{Nd₃RuO₇(s) + Nd₂O₃(s) + Ru(s)}//CSZ//O₂(p(O₂) = 21.21 kPa)/Pt(+)

The Gibbs free energy of formation of Nd₃RuO₇(s) from elements in their standard state, calculated by the least squares regression analysis of the data obtained in the present study, can be given by:

{Δ_fG°(Nd₃RuO₇, s)/(kJ mol⁻¹) ± 1.6} = −3074.3 + 0.6097(T/K); (929.3 ≤ T/K ≤ 1228.6).

The uncertainty estimate for Δ_fG°(T) includes the standard deviation in e.m.f. and the uncertainty in the data taken from the literature. The intercept and the slope of the above equation correspond to the enthalpy of formation and entropy, respectively, at the average experimental temperature of T_av. = 1079 K.     

Changes in the phase structure and magnetic characteristics of Gd5Si2Ge2 when alloyed with Mn

Gd₅Si₂Ge₂ parent compounds were alloyed with Mn in order to understand the underlying relation between the structural phases and the magnetic behavior of the pseudo ternary compounds formed. The alloying mechanism in Gd₅Si₂Ge₂ causes simultaneous substitution of the nonmagnetic Si and Ge atoms from the (Si + Ge) sublattice in equal amounts. No subsequent heat treatment was made on alloyed compounds. X-ray powder diffraction, magnetization versus temperature and isothermal magnetization measurements were carried out. X- ray diffraction patterns were used to qualitatively determine the existence of different structural phases in the alloys. It was observed that the starting, as-melted alloy with z = 0 has Gd₅Si₄-type orthorhombic structure at room temperature with traces of 1:1 stoichiometry phase which transforms totally to a Gd₅Si₂Ge₂-type monoclinic phase when heat treated. Similarly, increase in the Mn content leads to an increase in the monoclinic phase content of the originally orthorhombic compounds. Curie temperatures were determined from M(T) measurements and the magnetocaloric characterization was made using M(H) measurements by plotting the magnetic entropy change values against temperature. No giant magnetocaloric effect was observed for non heat treated samples.     

Structure, hyperfine interactions and magnetization studies of mechanically alloyed Fe50Ge50 and Fe62Ge38

X-ray diffraction, Mössbauer spectroscopy and magnetization measurements were used to study the structure and some magnetic properties of Fe₅₀Ge₅₀ and Fe₆₂Ge₃₈ prepared by mechanical alloying from the elemental powders. In both cases in the early stages of milling the intermediate paramagnetic FeGe₂ phase was formed. The mechanical alloying process of Fe₅₀Ge₅₀ resulted in the formation of the paramagnetic FeGe (B20) phase with an average crystallite size of about 15 nm. In the case of the Fe₆₂Ge₃₈, the ferromagnetic Fe₅Ge₃ (β) phase with a Curie temperature of about 430 K was obtained. The average crystallite size was about 9 nm. The average hyperfine magnetic field of about 16 T allowed it to determine that more than four germanium atoms exist in the nearest environment of the ⁵⁷Fe isotopes in the Fe₅Ge₃ phase.     

Magnetic ordering in Th3P4-type Tb4Sb3 compound

The nature of the magnetic ordering of Tb₄Sb₃ compound (Th₃P₄-type, cubic; cI28, space group , No. 220, a = 0.91518(7) nm) has been investigated by using the techniques of magnetization and neutron diffraction. AC and DC magnetisation measurements indicate antiferromagnetic ordering at 108 K in zero magnetic field that is accompanied by a field-induced metamagnetic transition to a ferromagnetic state, in fields above 0.3 T. Neutron diffraction experiment in zero applied magnetic field shows that below T_N = 112(4) K Tb₄Sb₃ exhibits an antiferromagnetic flat spiral-type ordering with propagation vector K₁ = [±1/8, ±1/8, ±1/8]. The magnetic moment of Tb atoms is found to be M_Tb = 6.7(3) μ_B at 80 K. The magnetic moment of Tb atoms lie in the (1 1 1) plane of Tb₄Sb₃ unit cell (the cone axis arranges along [1 1 1] direction with cone angle β = 90°). Below T_N2  50 K, Tb₄Sb₃ shows second antiferromagnetic transition with K₂ = [1/2, 1/2, 1/2] with possible re-orientation of Tb magnetic moments.     

Phase relationships and crystallography in the pseudobinary system Gd5Si4---Gd5Ge4

A study of phase relationships and crystallography in the pseudobinary system Gd₅(Si_xGe_1−x)₄ revealed: (1) that both terminal binary compounds Gd₅Si₄ and Gd₅Ge₄ crystallize in the Sm₅Ge₄-type orthorhombic structure, and (2) the appearance of an intermediate (ternary) phase with a monoclinic crystal structure which is similar to both Gd₅Si₄ and Gd₅Ge₄. The formation of the monoclinic phase at 0.24≤x≤0.5 [between Gd₅(Si_0.96Ge_3.03)Gd₅(Si₁Ge₃) and Gd₅(Si₂Ge₂)] is probably due to the large difference in bonding characteristics of Si and Ge in the Gd₅Si₄-Gd₅Ge₄ pseudobinary system which limits the ability of the mutual substitution of Si for Ge and vice versa without a change of the crystal structure. For the composition Gd₅(Si₂Ge₂) the lattice parameters of the monoclinic structure (space group P112₁/a) are a=7.580865), b=14.802(1), c=7.7799(5)Å, γ=93.190(4)°. A distinct difference in the magnetic behaviors of the alloys from three different phase regions in this system follows the distinct difference in the crystal structures observed for the alloys from the three phase regions.     

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).     

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.     

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.     

Thermal and conductometric studies of the CeBr3–MBr binary systems (M = Li, Na)

DSC was used to investigate phase equilibrium in the CeBr₃–MBr (M = Li, Na) systems. They represent typical examples of simple eutectic systems. The eutectic composition and eutectic temperature, x(CeBr₃) = 0.249, T_eut = 709 K and x(CeBr₃) = 0.372, T_eut = 692 K, were found for CeBr₃–LiBr and CeBr₃–NaBr systems, respectively.

The electrical conductivity of CeBr₃–MBr liquid mixtures, together with that of pure components was measured down to temperatures below solidification. Results obtained are discussed in term of possible complex formation.