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).     

Effect of addition of Cu into ZrOx film on its properties

The article reports on the effect of addition of Cu into the ZrO₂ film on its structure, physical and mechanical properties. The ZrO₂ and Zr–Cu–O films were reactively sputtered using a dc unbalanced magnetron from Zr (99.9) and ZrCu (90/10 at.%) targets in Ar + O₂ mixture at the substrate temperature T_s = 300, 400 and 550 °C and total sputtering gas pressure p_T = 1 Pa on steel, Si(100) and glass substrates. The structure of films was characterized by an X-ray diffraction (XRD) and mechanical properties, i.e. microhardness H, effective Young's modulus E* = E / (1 − ν²) and elastic recovery W_e, were measured using a microhardness tester; E and ν are the Young's modulus and the Poisson ratio, respectively. The film brittleness was characterized by the formation of cracks during the diamond indenter impression into it. 5 μm thick ZrO₂ films prepared in the oxide mode of sputtering are crystalline (m-ZrO₂) and exhibit relatively (i) high hardness H≈16 GPa and (ii) low ratio H³ / E*²≈0.11 GPa. The Zr–Cu–O films with low (≤ 2 at.%) Cu content exhibit (i) crystalline structure, (ii) higher H, (iii) lower (− 1.5 GPa) macrostress σ and (iv) higher ratio H³ / E*²≈0.14 GPa. On the contrary, the Zr–Cu–O films with high (24 to 44 at.%) Cu content exhibit (i) X-ray amorphous structure, (ii) lower H≈11 GPa and lower ratio H³ / E*²≈0.075 GPa. A special attention was devoted to the investigation of cracking of Zr–Cu–O films under high (0.5 and 1 N) loads of the diamond indenter. The relations between the film cracking and properties of the film and the substrate were used to assess the toughness of the Zr–Cu–O film. It was found that the film toughness increase with increasing H³ / E*² ratio. It was shown that the addition of Cu to ZrO₂ film can improve its toughness.     

Thermochemistry of GaBO3 and phase equilibria in the Ga2O3–B2O3 system

Employing a Tian-Calvet-type calorimeter operating in the scanning mode at temperatures from 1120 to 1220 K, the enthalpy change, Δ_dH, associated with the decomposition of GaBO₃ (=1/2β-Ga₂O₃+1/2B₂O₃(liq.)) and the corresponding decomposition temperature, T_d, were determined: Δ_dH=30.34±0.6 kJ/mol, T_d=1190±5 K. Using the transposed-temperature-drop method the thermal enthalpy, H(T)−H(295 K), of GaBO₃ was measured as a function of temperature, T, in the region from 760 to 1610 K; the results obtained are

[H(T)−H(295 K)]/(J/mol)=104.8·(T/K)−31 300 (760 K<T<1190 K),

[H(T)−H(295 K)]/(J/mol)=138.8·(T/K)−41 480 (1190 K<T<1590 K).

On the basis of the experimental results, the enthalpy and entropy of formation, Δ_fH and Δ_fS, respectively, of GaBO₃ from the component oxides were derived:

Δ_fH=−30.34 kJ/mol,Δ_fS=−25.50 J/(K·mol) at 1190 K,

Δ_fH=−10.55 kJ/mol,Δ_fS=−5.48 J/(K·mol) at 298 K.

The enthalpy versus temperature curve shows, apart from a step associated with the decomposition of GaBO₃, a further step at 1593 K which is attributed to a monotectic equilibrium.     

Transport and ultrasonic properties in La0.67Sr0.33Mn0.87Fe0.13O3 perovskite

The longitudinal and transverse ultrasonic sound velocity and attenuation, as well as electric resistance have been carefully measured in single-phase polycrystalline giant magnetoresistance perovskite La_0.67Sr_0.3Mn_0.87Fe_0.13O₃ at a frequency of 10 MHz, from 20 to 300 K. A big electric resistance peak was observed at 85 K (T_C). At the temperature above T_C, the resistivity can be fitted well by Mott’s law ρ=exp (T₀/T)^1/4 and both the longitudinal and transverse sound velocities show a lattice softening, which was accompanied by an attenuation peak. This simultaneous occurrence of electron and lattice softening implies electron–phonon coupling, known to exist for the octahedrally coordinated d⁴ ion, originating in the Jahn–Teller distortion. Below 55 K, pronounced sound-velocity softening for both longitudinal and transverse waves was observed; this may correspond to the formation of a spin-glass state.     

Magnetic entropy change in polycrystalline La1−xKxMnO3 perovskites

Polycrystalline samples of potassium doped lanthanum manganites having nanometric crystallite size have been synthesized by pyrophoric method. The Curie temperature (T_C) of the prepared samples is found to be strongly dependent on K content and spans between 260 and 309 K. Close to T_C, large change in magnetic entropy has been observed in all the samples. The maximum magnetic entropy change observed for samples with different concentration of K, exhibits a linear dependence with the applied magnetic field. Adiabatic temperature change at T_C at 1 T also increases with K doping and attains a maximum of 2.1 K for La_0.85K_0.15MnO₃. Estimated relative cooling power of La_1−xK_xMnO₃ compounds is nearly one-third of pure Gd. In addition to the tuneability of T_C between 260 and 310 K, higher chemical stability, lower eddy current heating and inexpensive preparation technique; the magnetic entropy change in La_0.85K_0.15MnO₃ compound at 1 T magnetic field is found to be 3.00 J/kg K and is 89% to that known for the prototype magnetic refrigerant (pure Gd). Our result on magnetocaloric properties suggests that La_1−xK_xMnO₃ compounds are attractive as a possible refrigerant for near room temperature magnetic refrigeration.     

Ba4In2−x(CO3)1+xO6−2.5x and Ba4In0.8Cu1.6(CO3)0.6O6.2—new indium oxycarbonates closely related to n=3 Ruddlesden–Popper phases

Investigations of phase relations in the Ba-rich part of the In₂O₃–BaO(CO₂)–CuO pseudo-ternary system at 900 °C have revealed the existence of new indium–copper oxycarbonate – Ba₄In_0.8Cu_1.6(CO₃)_0.6O_6.2. Rietveld refinement of the X-ray powder diffraction data combined with infrared studies gives evidence that this phase is a oxycarbonate crystallising in the tetragonal structure (space group I4/mmm) with unit cell parameters: a=4.0349(1) Å and c=29.8408(15) Å. In the binary part of the In₂O₃–BaO(CO₂) system we have identified the occurrence of Ba₄In_2−x(CO₃)_1+xO_6−2.5x oxycarbonate solid solution showing a crystal structure also described by I4/mmm space group, but with the unit cell parameters: a=4.1669(1) Å and c=29.3841(11) Å for x=1. The existence range of this phase, −0.153<x<0.4, includes chemical compositions of earlier found phases: Ba₅In_2+xO_8+0.5x with 0≤x≤0.45 (known as the -solid solution), as well as the binary Ba₄In₂O₇ phase. The crystal structures of both new oxycarbonates are isomorphic and related to n=3 member of the Ruddlesden–Popper family.     

Zur Kenntnis eines gemischtvalenten Lanthanoxovanadats: La11VV3O26

Single crystals of La₁₁V⁴⁺V₃⁵⁺O₂₆ were prepared by high temperature reactions in an N₂/H₂ mixture above the melting point of the initial oxides V₂O₅–La₂O₃. X-ray investigations of the dark blue crystals reveal triclinic symmetry, space group with = 7.088 Å, β = 10.213 Å, χ = 10.250 Å, = 89.59°, β = 71.10°, τ = 70.00°, Z = 1. The lanthanum-rich compound exhibits a new structure type characterized by a complicated La₁₁O₂₆^19- network with incorporated V⁴⁺/V⁵⁺ ions. The VO₄ tetrahedra are isolated from each other and occupied with V⁴⁺ and V⁵⁺ in a statistical manner.

Résumé

Einkristalle von La₁₁V⁴⁺V₃⁵⁺O₂₆ wurden durch Hochtemperaturreaktionen unter N₂/H₂-Mischungen oberhalb des Schmelzpunktes von V₂O₅-La₂O₃ dargestellt. Die röntgenographische Untersuchung der tiefblauen Kristalle führte zu trikliner Symmetrie, Raumgruppe mit = 7,088 Å, β = 10,213 Å, χ = 10,250 Å = 89,59°, β = 71,10°, τ=70,00°, Z = 1. Die lanthanreiche Verbindung bildet einen neuen Strukturtyp und zeichnet sich durch ein kompliziertes La₁₁O₂₆^19- Gerüst aus, in welches V⁴⁺/V⁵⁺-Ionen eingelagert sind. Die gebildeten VO₄-Tetraeder treten zueinander isoliert auf und sind statistisch mit V⁴⁺ und V⁵⁺ besetzt.     

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.     

Influence of A-site cation size-disorder on structural, magnetic and magnetocaloric properties of La0.7Ca0.3−xKxMnO3 compounds

The structural and magnetic properties of perovskite oxides La_0.7Ca_0.3−xK_xMnO₃ (0 ≤ x ≤ 0.15) have been investigated to explore the influence of the A-site cation size-disorder (σ²). The materials were prepared by the solid-state method and then characterized by X-ray diffraction (XRD). The XRD data have been analyzed by Rietveld refinement technique. For K doping concentration x ≤ 0.075, the samples crystallize in the orthorhombic structure, while for x ≥ 0.1, the structure becomes rhombohedral. The variation of the magnetization M as a function of the applied magnetic field μ₀H reveals the presence of a structural distortion leading to a reduction of the magnetization at low μ₀H values. When increasing μ₀H, the structural distortion decreases and for a high applied magnetic field, the M (μ₀H) curves saturate indicating the disappearance of the structural distortion. The influence of K doping concentration and the applied magnetic field on the magnetocaloric properties has been considered. A large magnetic-entropy change (|ΔS_M|  5 J/kg K) is obtained in all samples at Curie temperatures between 270 and 280 K for an applied magnetic field of 3 T. These results show that these materials can be used as candidates for magnetic refrigerants near room temperature.     

Lattice effect on the magnetic and magneto-transport properties of (La1/3Sm2/3)0.67Ba0.33−xSrxMnO3 (x = 0.0, 0.1, 0.2 and 0.33) compounds

The effect of substituting Sr for Ba on the magneto-transport and magnetic properties of (La_1/3Sm_2/3)_0.67Ba_0.33MnO₃ system, has been investigated. The samples, (La_1/3Sm_2/3)_0.67Ba_0.33−xSr_xMnO₃ (x = 0.0, 0.1, 0.2 and 0.33), synthesized by citrate gel route, crystallize in an orthorhombic structure (space group Pnma, no. 62). The unit cell volume decreases while the metal-insulator transition temperature (T_MI) increases with increasing Sr content. The localization of charge carriers occurs at low temperatures and becomes more pronounced with decreasing Sr content which leads to an enhancement of resistivity. This could be understood by the variation of MnOMn bond-distance and angle. Reappearance of semiconducting behavior (dρ/dT < 0) is observed only in samples with x = 0 and x = 0.1 below certain temperature (T < T_MI). These samples exhibit thermal irreversibility behavior for a field-cooled (FC) and zero-field-cooled (ZFC) magnetization data in a magnetic field of 100 Oe. This is ascribed to the competition between the superexchange and double exchange interactions. The change in physical properties has been correlated to chemical parameters such as ionic radii, tolerance factor, electronegativity and variation in MnOMn angle.     

LaMg2NiH7, a novel quaternary metal hydride containing tetrahedral [NiH4] complexes and hydride anions

A new ternary compound of composition LaMg₂Ni has been found and investigated with respect to structure and hydrogenation properties. It crystallizes with the orthorhombic MgAl₂Cu type structure (space group Cmcm, a=4.2266(6), b=10.303(1), c=8.360(1) Å; V=364.0(1) ų; Z=4) and absorbs hydrogen near ambient conditions (<200 °C, <8 bar) thereby forming the quaternary metal hydride LaMg₂NiH₇. Neutron powder diffraction on the deuteride revealed a monoclinic distorted metal atom substructure (LaMg₂NiD₇: space group P2₁/c, a=13.9789(7), b=4.7026(2), c=16.0251(8) Å; β=125.240(3)°, V=860.39(8) ų; Z=8) that contains two symmetry independent tetrahedral [NiD₄]⁴⁻ complexes with Ni–D bond lengths in the range 1.49–1.64 Å, and six D⁻anions in tetrahedral metal configuration with bond distances in the ranges 1.82–2.65 Å (Mg) and 2.33–2.59 Å (La). The compound constitutes a link between metallic ‘interstitial’ hydrides and non-metallic ‘complex’ metal hydrides.     

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.     

Hydriding kinetics of the La1.5Ni0.5Mg17–H system prepared by hydriding combustion synthesis

An experimental investigation of the hydrogen absorption rate in the two-phase (–β) region of La_1.5Ni_0.5Mg₁₇ powder under the condition of various pressures and temperatures is presented. The results are well interpreted using the Jander diffusion model, [1−(1−ξ)^1/3]²=k(T,P)t, which suggests that the rate-controlling step of hydrogen absorption in La_1.5Ni_0.5Mg₁₇ is three-dimensional diffusion. An apparent activation energy for such diffusion process of 90±1 kJ/mol H₂ has been obtained from the absorption data.     

Magnetoresistance studies on barium doped nanocrystalline manganite

An energetically attractive, simple, fast and a novel low temperature (300 °C) solution combustion route for the synthesis of crystalline and homogeneous nanoparticles of lanthanum barium manganese oxide La_0.9Ba_0.1MnO_3+δ (LBMO) is reported. Formation and homogeneity of the solid solutions have been confirmed by powder X-ray diffraction (PXRD) and energy dispersive X-ray analysis (EDS) respectively. The Rietveld analysis shows both as-formed as well as calcined samples are in cubic phase with space group pm3m. The microstructure and agglomerated particle size of the compounds are examined by scanning electron microscope. Infrared spectroscopy revealed that both MnOMn bending mode and MnO stretching mode are influenced by calcination temperature. The magnetoresistance measurement on sintered LBMO pellet exhibits a broad metal–insulator transition (T_M-I) at around 228 K. At 1 T applied magnetic field, LBMO shows magnetoresistance (MR) of 10%, whereas for 4 and 7 T, the negative magnetoresistance values are in the range 51 and 59% respectively at T_M-I. The experimental resistivity data of the present investigation are fitted to a simple empirical equation in order to understand conduction mechanism in this compound.     

Electrical, magnetic, thermal and thermoelectric properties of the “Bergman phase” Mg32(Al,Zn)49 complex metallic alloy

The Mg–Al–Zn system of intermetallics contains an exceptional crystalline phase Mg₃₂(Al,Zn)₄₉, named the Bergman phase, whose crystal structure is based on a periodic arrangement of icosahedral Bergman clusters within the giant-unit-cell, so that periodic and quasiperiodic atomic orders compete in determining the physical properties of the material. We have investigated electrical, magnetic, thermal and thermoelectric properties of a monocrystalline Bergman phase sample of composition Mg_29.4(Al,Zn)_51.6, grown by the Bridgman technique. Electrical resistivity is in the range ρ ≈ 40 μΩ cm and exhibits positive-temperature-coefficient with T² dependence at low temperatures and T at higher temperatures, resembling non-magnetic amorphous alloys. Magnetic susceptibility χ measurements revealed that the sample is a Pauli paramagnet with a significant Landau diamagnetic orbital contribution. The susceptibility exhibits a weak increase towards higher temperature. Combined analysis of the ρ(T) and χ(T), together with the independent determination of the Pauli susceptibility via the NMR Knight shift suggests that the observed temperature dependence originates from the mean-free-path effect on the orbital susceptibility. The electronic density of states (DOS) at the Fermi energy E_F was estimated by NMR and was found to amount 72% of the DOS of the fcc Al metal, with no evidence on the existence of a pseudogap. Thermal conductivity contains electronic, Debye and hopping of localized vibrations terms, whereas thermopower is small and negative. High structural complexity of the Bergman phase does not result in high complexity of its electronic structure.     

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.     

Orthorhombic Mg4IrD5 with disordered deuterium distribution

Mg₄IrH₅ and its deuteride was synthesized by the reaction of magnesium and iridium powders with hydrogen (deuterium) at high pressure (41–100 bar) and high temperature (723–783 K). The structure was determined by X-ray and neutron powder diffraction. This compound crystallizes with a new structure type with orthorhombic symmetry (space group Imma, cell parameters a = 4.8110(3) Å, b = 8.9624(6) Å, c = 10.8970(8) Å, Z = 4, hydride, T = 298 K). It contains two deuterium sites: one is disordered with an occupancy of 75% and surrounds iridium in a distorted square planar configuration with distances [Ir---D] = 1.69 Å; the other is ordered and is coordinated by magnesium in a distorted tetrahedral configuration.     

Properties of exchange biased Co/Co3O4 bilayer films

Co/Co₃O₄ bilayer films were fabricated by RF sputtering with Co and Co₃O₄ targets. Exchange bias effect in the bilayer films was observed at 80 K by vibrating sample magnetometer. The bias effect disappeared about 240 K slightly lower than the Néel point of CoO and much higher than the Néel temperature of Co₃O₄ about 40 K. To clarify the origin of the exchange bias effect, Auger and X-ray photoelectron spectroscopy were employed and CoO was found at a transition region from Co₃O₄ layer to Co layer due to oxygen diffusion during sputtering. The angular dependence of exchange bias field H_E was obtained to obey function of H_E(θ)=18.06 (kA/m)[−cos θ+0.22 cos 3θ+0.03 cos 5θ−0.01 cos 7θ+].     

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.     

Synthesis and structure of a potassium nitridoditungstenate (K6W2N4O3), a potassium digermanate (K6Ge2O7) and a rubidium digermanate (Rb6Ge2O7)

Light yellow single crystals of potassium nitridoditungstate (K₆W₂N₄O₃) and pale single crystals of potassium digermanate (K₆Ge₂O₇) were obtained by the reaction of the metal oxides WO₃ (molar ratio, 1 : 15.7) or GeO₂ (molar ratio, 1 : 2) in alkali metal amide melts in an autoclave at 530–600 °C for 6–8 days. Colourless single crystals of rubidium digermanate (Rb₆Ge₂O₇) were prepared by the reaction of GeO₂ with rubidium amide (molar ratio, 1 : 2) in ammonia at 350 °C in a high-pressure autoclave (H. Jacobs and D. Schmidt, in E. Kaldis (ed.), High-pressure Ammonolysis in Solid State Chemistry, Current Topics in Materials Science, Vol. 8, North Holland, Amsterdam, 1981, p. 379) (p(NH₃) = 5.5 kbar) for 10 days. In all three cases other nitrogen-containing products were present.

The structures of the title compounds were determined on the basis of single-crystal data. They are isotypic or structurally closely related to each other: K₆W₂N₄O₃: P2₁/n, a = 6.720(2) Å, b = 9.473(1) Å, c = 9.581(2) Å, β = 91.99(2)°, Z = 2, R/R_w = 0.040/0.048, N(I) > 3σ(I) 2057, N(Var.) = 71. K₆Ge₂O₇: Pn, a = 6.529(2) Å, b = 9.079(4) Å, c = 9.162(6)Å, β = 91.85(4)°, Z = 2, R/R_w = 0.022/0.024, N(I) 3σ(I) = 1486, N(Var.) = 135. Rb₆Ge₂O₇: P2₁/n, a = 6.839(4) Å, b = 9.437(6) Å, c = 9.460(6) Å, β = 91.53(5)°, Z = 2, R/R_w = 0.061/0.074, N(I) 3σ(I) = 1055, N(Var.) = 71.