Structural chemistry, magnetism and thermodynamic properties of R2Pd2In

We report on magnetisation, resistivity and specific heat measurements of R₂Pd₂In compounds synthesised with the nominal composition R₄₀Pd₄₁In₁₉ (R=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y). Magnetic and thermodynamic measurements reveal antiferromagnetic order below 32 K for this series except for Y, La, Yb and Lu. An appreciably wide homogeneity range is found for Ce₂Pd_2+xIn_1−x where ferro- or antiferromagnetic order or both occur with typical features of a Kondo lattice. Yb₂Pd₂In exhibits intermediate valent behaviour and no magnetic order could be detected down to 0.3 K.     

Magnetic behaviour of two AlB2-related germanides: CePd0.63Ge1.37 and CeAu0.75Ge1.25

The title compounds were prepared from the elemental components by arc-melting and subsequent annealing at 1020 K and 1170 K. Both CePd_0.63Ge_1.37 and CeAu_0.75Ge_1.25 crystallize in the AlB₂ structure type with a statistical distribution of the transition metal and germanium atoms on the boron site. The structure of CeAu_0.75Ge_1.25 was refined from single crystal X-ray data: P6/mmm, a=433.5(1) pm, c=422.6(1) pm, V=0.0688(1) nm³, Z=1, wR2=0.0504 for 157 F² values and 7 variables. Magnetic susceptibility data for both compounds show a full cerium moment and ferromagnetic ordering at 6.0(5) K for CeAu_0.75Ge_1.25 and 3.0(5) K for CePd_0.63Ge_1.37. The crystal structure and properties of CeAu_0.75Ge_1.25 are compared with those of equiatomic CeAuGe which adopts the NdPtSb structure type, an ordered variant of AlB₂.     

Influence of HDDR treatment on magnetic properties of TbFe2- and DyFe2-based intermetallics

Magnetic properties of TbFe₂, DyFe₂, Tb(Fe_0.8M_0.2)₂ and Dy(Fe_0.8M_0.2)₂ with M=Co, Al, Si, Ga alloys affected by the Hydrogenation-Decomposition-Desorption-Recombination processing have been studied. After hydrogen treatment the coercive force H_c grows sharply, so HDDR-powders can be used as isotropic permanent magnets with the energy product up to 26 MG Oe at T=77 K. In Dy(Fe_0.8Al_0.2)₂ at T<10 K the stepwise magnetic reversal has been observed. The HDDR-treatment increases the critical field of magnetic reversal from 11 up to 18.4 kOe at 4.2 K. It is shown that the effect of the stepwise magnetic reversal is caused by a heat release in a sample during an avalanche motion of narrow domain walls.     

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.     

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.     

Low-temperature magnetic and electrical transport properties of some ternary Ce-Rh-Si compounds

Five novel cerium-based ternaries Ce₂Rh_3.1Si_0.9, Ce₄Rh₁₂Si, Ce₈Rh_21.9Si_3.1, CeRh_1.82Si_0.18 and CeRh₃Si_0.125 were studied by means of magnetic susceptibility and electrical resistivity measurements. All these phases were found to be Pauli paramagnets with metallic type of electrical conductivity.     

Magnetic ordering and magnetic properties of ErAuxNi1−xIn (0 ≤ x ≤ 1) solid solution

The ErAu_xNi_1−xIn (0 ≤ x ≤ 1) quasiternary compounds crystallize in the hexagonal layered crystal structure of ZrNiAl-type. ErAuIn was reported to be an antiferromagnet with T_N = 3 K and magnetic moments having triangular arrangement within the basal plane (the magnetic order is described by the propagation vector ). On the contrary ErNiIn is a ferromagnet with T_C = 9 K and magnetic moments pointing along the c-axis. The magnetic ordering in ErAu_xNi_1−xIn (0 < x < 1) solid solution, has been investigated by neutron diffractometry in the temperature range between 1.5 and 15 K. Moreover, bulk magnetic measurements have been carried out in the range 1.72–400 K. All alloys of intermediate composition were found to be antiferromagnets with T_N between 4.6 and 7 K. Below 2 K their magnetic order is described by the propagation vector and magnetic moments are aligned along the c-axis. However, for alloys with 0.2 ≤ x ≤ 0.7 the propagation vector was found to turn into with increasing temperature.     

Synthesis and properties of CaCd2Sb2 and EuCd2Sb2

High density polycrystalline CaCd₂Sb₂ and EuCd₂Sb₂ intermetallics are synthesized by Spark Plasma Sintering and their thermoelectric properties are investigated. X-ray diffraction measurements reveal both materials have a structure in space group, containing a small amount of CdSb as a second phase. Thermoelectric measurements indicate both are p-type conductive materials. The figure of merit value of CaCd₂Sb₂ is 0.04 at 600 K and that of EuCd₂Sb₂ is 0.60 at 617 K. Theoretical calculations show that CaCd₂Sb₂ is a degenerate semiconductor with a band gap of 0.63 eV, while EuCd₂Sb₂ is metallic with DOS of 13.02 electrons/eV. For deeper understanding of the better thermoelectric properties of EuCd₂Sb₂, its low temperature magnetic, transport and heat capacity properties are investigated. Its Nèel temperature is 7.22 K, convinced by heat capacity anomaly at 7.13 K. Hall effect convinced that it is a p-type conductive material. It has high Hall coefficient, high carrier concentration and high carrier mobility of +1.426 cm³/C, 4.38 × 10¹⁸/cm³ and 182.40 cm²/Vs, respectively. They are all in the magnitude of good thermoelectric materials. The Eu 4f level around Fermi energy and antiferromagnetic order may count for the better thermoelectric properties of EuCd₂Sb₂ than that of CaCd₂Sb₂.     

Magnetic and electrical properties of RCu5.1In6.9 compounds

Magnetic and electrical properties of the RCu_5.1In_6.9 compounds with R=Y, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho and Er were investigated in the temperature range 4.2–300 K. Additionally, for the compounds of Gd, Tb and Dy exhibiting magnetic anomalies at low temperatures, the magnetization versus magnetic field up to 14 T was measured at 4.2 K. Investigated compounds follow the Curie–Weiss law with relatively small values of the paramagnetic Curie temperature and the values of effective magnetic moment being in fair agreement with the values for the free ions. The electrical resistivity exhibits metallic character. The results are discussed in terms of the differences and similarities with other rare earth intermetallics.     

Coexistence of localized magnetism and itinerant ferromagnetism in a Gd5Y2Pd3 single crystal

Experimental results of the single-crystal X-ray diffraction, XPS, ac-magnetic susceptibility (ac-χ), dc-magnetization M(T), and electrical resistivity (ρ) measurements for the hexagonal Th₇Fe₃-type Gd₅Y₂Pd₃ single crystal are presented. Anomalies in (ac-χ), (T) and M(T)-curves have allowed to establish that Gd₅Y₂Pd₃ undergoes a long-range ferromagnetic-type ordering at T_C = 263 K, followed by a spin-reorientation below 190 K. The magnetization data indicate that there is an excess of the magnetic moment for the Gd³⁺ ions. The observed XPS, magnetic and electrical resistivity behaviour points to the coexistence of localized magnetism from the magnetic Gd³⁺ ions and itinerant ferromagnetism from 4d- and 5d-electron bands. We discuss the magnetic behaviour of the Gd_7−xY_xPd₃ solid solutions in terms of three competitive mechanisms: RKKY-interaction, magnetic frustration and spin-fluctuation.     

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.     

Crystal structure and magnetic behavior of novel R2PdIn8 (R = Pr, Nd, and Sm) compounds

A new series of R₂PdIn₈ intermetallics, where R = Pr, Nd, and Sm, was prepared by arc-melting the constituents under argon atmosphere and studied by means of X-ray diffraction and magnetic measurements. The compounds crystallize with a tetragonal structure of the Ho₂CoGa₈ type (space group P4/mmm). At very low temperatures, they order antiferromagnetically, and the Nd-based indide presumably exhibits an additional magnetic phase transition in the ordered region.     

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.     

Influence of the TbFe2 crystallization on the magnetic and magnetostrictive properties of (Fe3Ga/TbFe2)n heterostructures

In this work we have investigated (Fe₃Ga/TbFe₂)_n multilayers grown by sputtering at room temperature. These multilayers exhibit a large coercivity associated to the crystalline TbFe₂ Laves phase. To reduce the coercivity it is necessary to control the crystallization of that material. In this work, we focus on the analysis of the properties of the TbFe₂ layers. In the as-grown heterostructures we have found evidence of nanoaggregates in the TbFe₂ layers. The Fe₃Ga thickness and the thermal treatments have an influence on the volume of these nanoprecipitates. In the annealed samples, when increasing the Fe₃Ga thickness we observe a decrease in the nanoaggregate volume and thus in the coercivity. The experimental results indicate that the crystallization of the TbFe₂ depends on the Tb diffusion promoted by the thermal treatment and on the stiffness factor (Y/α) of the Fe₃Ga layer. The magnetostrictive properties are also strongly influenced by the crystallization of the TbFe₂. We have achieved a maximum magnetostriction constant of nearly 550 ppm with a coercive field close to 400 Oe.     

Effect of Cu on the magnetic properties and reducibility of Fe2TiO5

Ferrites have been studied for several years due to their wide use as magnetic materials for telecommunications, audio and video, power transformers and many other applications.

Equimolar mixtures of Fe₂O₃ and TiO₂ were fired in a muffle furnace at 1200 °C for 4 h. Mixed samples were prepared by replacing TiO₂ with calculated amounts of CuO (x = 0.2, 0.4, 0.6, 0.8 and 1 mol). The synthesized samples were characterized with X-ray diffraction and their magnetic properties were measured using vibrating-sample magnetometer. The microstructure of the sample was examined using reflected light microscope and scanning electron microscope. The formation of Fe₂TiO₅, Fe₅CuO₈, Cu₂TiO₃ and CuFeO₂ phases were detected whereas their magnetic properties increased with increasing the added mole ratio of Cu²⁺ ions. The isothermal reduction kinetics of synthesized nanocrystallites Ti–Cu mixed ferrite compacts were studied at 500 °C using hydrogen gas. It was found that the reduction rate and the reduction extent increased with increasing the extent of Cu²⁺ (0.2–1) whereas the maximum reduction extent (100%) was detected for pure Cu ferrite (Cu²⁺) while the minimum reduction extent (12%) was detected for pure iron titanate (Cu²⁺ = 0). The magnetic properties showed a drastic improvement upon reduction with hydrogen gas.     

Structural, dielectric and magnetic properties of Nd-doped Co2Z-type hexaferrites

Z-type hexaferrites doped with Nd³⁺, Ba_3−xNd_xCo₂Fe₂₄O₄₁ (x = 0, 0.05, 0.10, 0.15, and 0.25), were prepared by solid-state reaction. The effect of the Nd³⁺ ions substitution for Ba²⁺ ions on the microstructure and electromagnetic properties of the samples was investigated. The results reveal that an important modification of microstructure, complex permeability, complex permittivity, and static magnetic properties can be obtained by introducing a relatively small amount of Nd³⁺ instead of Ba²⁺. SEM image shows that the grains of the ferrites doped with Nd³⁺ were smaller, more perfect and homogeneous than that of the pure ferrite. The real part (?′) of complex permittivity and imaginary part (?″) increase at first, and then decrease with increasing Nd content. At low frequency, the imaginary part μ″ of complex permeability decreases with Nd content and then increases when frequency is above 7.0 GHz. The magnetization (M_s) and the coercivity (H_c) are 79.38 emu g⁻¹ and 36.94 Oe for Ba_2.75Nd_0.25Co₂Fe₂₄O₄₁. The data of magnetism show that the ferrite doped with Nd³⁺ ions is a better soft magnetic material due to the higher magnetization and lower coercivity.     

Mixed cerium valence and unusual Ce–Ru bonding in Ce23Ru7Cd4

The rare earth-rich compounds Ce₂₃Ru₇Cd₄ and Pr₂₃Ru₇Cd₄ were synthesized from the elements in sealed tantalum ampoules in an induction furnace. Both structures were refined on the basis of diffractometer data: P6₃mc, Z = 2, a = 988.7(3), c = 2241.6(5) pm, wR2 = 0.0439, 1976 F² values for Ce₂₃Ru₇Cd₄ and a = 992.7(2), c = 2236.4(7) pm, wR2 = 0.0466, 2528 F² values for Pr₂₃Ru₇Cd₄ with 74 variables per refinement. Striking structural motifs are ruthenium centered trigonal prisms RuCe₆ and RuPr₆ which are condensed via common edges and corners, building rigid three-dimensional networks. Larger voids within these networks are filled by slightly elongated Cd₄ tetrahedra. Five of the nine crystallographically independent cerium sites in Ce₂₃Ru₇Cd₄ show Ce–Ru distances which are shorter than the Pr–Ru distances in Pr₂₃Ru₇Cd₄. This strong hint for mixed cerium valence is supported by the magnetic behavior. Pr₂₃Ru₇Cd₄ shows Curie–Weiss behavior above 50 K with an experimental magnetic moment of 3.62 μ_B/Pr atom, indicating stable trivalent praseodymium. Complex magnetic ordering sets in at 13 K. Ce₂₃Ru₇Cd₄ shows a reduced magnetic moment of 2.05 μ_B/Ce atom. The trivalent cerium atoms show ferro- or ferrimagnetic ordering below T_C = 3.6 K.     

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.     

Magnetic properties of CeAg2Ge2

A.c. susceptibility and magnetization measurements of CAg₂Ge₂ are reported. Two phase transitions at T = 7 and 11 K are detected. The magnetization curve at T = 4.2 K has a two-step character.