Metamagnetism in DyBaCo2O5+x, x≈0.5

The temperature dependence of the paramagnetic susceptibility χ_m(T) taken in 2500 Oe, the resistivity ρ(T), and the thermoelectric power α(T) of DyBaCo₂O_5+x, which has Ba and Dy ordered into alternate (001) planes of an oxygen-deficient perovskite, have revealed a phase segregation in the compositional range 0.3?x<0.5. Orthorhombic DyBaCo₂O_5.51 has, in addition, oxygen vacancies ordered into alternate rows of the DyO_0.51 (001) planes; a cold-pressed polycrystalline sample exhibits a first-order insulator-metal transition at T_IM=320 K, a Curie temperature T_C=300 K, and a broadened metamagnetic transition temperature T_M≈265 K in 2500 Oe. A ferromagnetic M-H hysteresis curve fails to saturate at 5 T, and a minority ferromagnetic phase below T_M has a volume fraction that decreases with decreasing temperature, vanishing below 50 K. Oxygen vacancies in the DyBaCo₂O_5.5 phase suppress the metallic state; interstitial oxygen does not. A thermoelectric power α(T)>0 of DyBaCo₂O_5.51 changing continuously across T_IM is interpreted to manifest a metallic minority phase crossing a percolation threshold; α(T) also provides evidence for a progressive excitation of higher-spin Co(III) with increasing temperature from below 50 K to above T_IM. A previous model of the RBaCo₂O_5.5 phase is extended to account for the Ising spin configuration below T_C, the magnetic order in the presence of higher-spin octahedral-site Co(III), and the α(T) data.     

Structural, magnetic, and electrochemical studies on lithium insertion materials LiNi1−xCoxO2 with 0≤x≤0.25

The structural, magnetic, and electrochemical properties of the LiNi_1−xCo_xO₂ samples with x= 0, 0.05, 0.1, and 0.25 have been investigated by powder X-ray diffraction analyses, magnetic susceptibility (χ) measurements, and electrochemical charge and discharge test in non-aqueous lithium cell. According to the structural analyses using a Rietveld method, the occupancy of the Ni ions in the Li layer was estimated to be below 0.01 for all the samples and was eventually independent of x. The temperature (T) dependence of χ⁻¹ obtained with the magnetic field H=10 kOe indicated that all the samples are a Curie-Weiss paramagnet down to . At low T, all the samples entered into a spin-glass-like phase below T_f. The magnitude of T_f was found to decrease almost linearly with x, as in the case for the x dependences of the lattice parameters of a_h- and c_h-axes, Weiss temperature, and effective magnetic moment. It is, therefore, found that the change of the magnetic properties with x is simply explained by a dilution effect due to the increase of the quantity of Co³⁺ ions. On the other hand, the electrochemical measurements demonstrated that the irreversible capacity at the initial cycle is drastically decreased by the small amount of Co ions. Furthermore, the discharge capacity (Q_dis) for the x=0.05 and 0.1 samples are larger than that for the x=0 sample; namely, Q_dis=180 mAh g⁻¹ for x=0, Q_dis=217 mAh g⁻¹ for x=0.05, and Q_dis=206 mAh g⁻¹ for x=0.1. Comparing with the past results, the amount of Ni ions in the Li layer is found to play a significant role for determining the magnetic and electrochemical properties of LiNi_1−xCo_xO₂.     

Thermoelectric and microstructural properties of Pb0.9−xSn0.1GexTe compounds prepared by spinodal decomposition

Three samples of Pb_0.9−xSn_0.1Ge_xTe with x=0.25, 0.35, 0.6 were prepared by heating the mixtures above the melting point of the constituent elements followed by quenching in water. The x=0.6 sample is close to the center of the immiscibility region, while the x=0.25 and 0.35 samples are in the Pb rich region inside the spinodal miscibility gap. Microstructural investigations using Powder X-ray Diffraction, Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy revealed both GeTe-rich and PbTe-rich phases. The samples were uniaxially hot pressed and the thermoelectric properties were characterized in the temperature range 2-400 K using a commercial apparatus and from 300 to 650 K with a custom designed setup. The best sample (x=0.6) reached zT≈0.6 at 650 K, while the x=0.25 and 0.35 samples showed thermal instability at elevated temperatures.     

Polaron morphologies in SrFe1−xTixO3−δ

The morphologies of the charge carriers in the perovskite system SrFe_1−xTi_xO_3−δ are explored by transport and magnetic measurements. Oxygen vacancies are present in all samples, but they do not trap out the Fe³⁺ ions they introduce. The x=0.05 composition was prepared with three different values of δ. They all show small-polaron conduction above 225 K; but where there is a ratio c=Fe⁴⁺/Fe<0.5, the polaron morphology appears to change progressively with decreasing temperature below 225 K to two-Fe polarons that become ferromagnetically coupled in an applied magnetic field at lower temperatures; With an applied field of 2500 Oe, divergence of the paramagnetic susceptibility for zero-field-cooled and field-cooled samples manifests a greater stabilization of ferromagnetic pairs on cooling in the applied field. With a c>0.5, the data are consistent with a disproportionation reaction 2Fe⁴⁺=Fe³⁺+Fe(V)O_6/2 that inhibits formation of two-Fe polarons and, on lowering the temperature, creates Fe³⁺-Fe(V)-Fe³⁺ superparamagnetic clusters.     

Tolerance factor rules for Sr1−x−yCaxBayMnO3 perovskites

Synthesis of new perovskite Sr_1−x−yCa_xBa_yMnO_3−δ compounds is described in detail and dependence of their phase stability and structural distortions on the tolerance factor is discussed. Oxygen contents have been measured over extended temperature and composition ranges. Neutron powder diffraction was used to precisely measure the A-O and Mn-O bond lengths and derive accurate interatomic distances [Ca-O], [Sr-O], [Ba-O], and [Mn-O]. By using these parameters instead of tabulated ionic radii we have derived the functional dependence of the tolerance factor t=t(x,y,T,δ) on composition, temperature, and oxygen content. At a fixed oxygen content, the tolerance factor is an increasing function of temperature as a result of greater thermal expansion of the average 〈A-O〉 bond relative to the 〈Mn-O〉 bond. We find that the stability of the perovskite phase at high temperature is governed, as expected, by the magnitude of tolerance factor (t?1) which can be adjusted by controlling the oxygen content 3−δ. This dependence of the tolerance factor on oxygen content and temperature can be utilized to design synthesis conditions for the controlled formation of the new, kinetically stable, perovskite phases.     

Phase stability and chemical composition dependence of the thermoelectric properties of the type-I clathrate Ba8AlxSi46−x (8≤x≤15)

Phase stability of the type-I clathrate compound Ba₈Al_xSi_46−x and the thermoelectric property dependence on chemical composition are presented. Polycrystalline samples were prepared by argon arc melting and annealing. Results of powder X-ray diffraction and electron microprobe analysis show that the type-I structure is formed without framework deficiency for 8≤x≤15. Lattice constant a increases linearly with the increase of x. Thermoelectric properties were measured for x=12, 14 and 15. The Seebeck coefficients are negative, with the absolute values increasing with x. The highest figure of merit zT=0.24 was observed for x=15 at T=1000 K, with carrier electron density n=3×10²¹ cm⁻³. A theoretical calculation based on the single parabolic band model reveals the optimum carrier concentration to be n∼4×10²⁰ cm⁻³, where zT∼0.7 at T=1000 K is predicted.     

Structure, Stoichiometry, and Properties of the Chimney-Ladder Phases Ru2Ge3+x (0<x<1)

The preparation and physical characterization of non-stoichiometric Ru₂Ge_3+x (0≤x≤1) are reported for the first time. The defect TiSi₂-type chimney-ladder structure is maintained for the full stoichiometry range. The resistivity of Ru₂Ge_3+x increases systematically with x from 300 mΩ cm, x=0 -3 Ω cm, x=1 at 300 K. The temperature dependence is consistent with a variable range-hopping mechanism for x≥0.6. The Seebeck coefficients of samples do not evolve simply with x. A low thermal conductivity (κ_{300 K}=0.03 W/K cm) suggests that Ru₂Ge₃ has some of the properties of a phonon-glass-electron-crystal. The low value of the thermoelectric figure of merit ZT=3.2×10⁻³ (T=300 K) calculated for Ru₂Ge₃ is due primarily to a low conductivity.     

Eu doping effects on structural and magnetic properties of (Sr2−xEux)FeMoO6 compounds

Double perovskite compounds (Sr_2−xEu_x)FeMoO₆ (0≤x≤0.3) were prepared by solid-state reaction at high temperature. Crystal structure, magnetic and transport properties of the compounds were investigated. The crystal structure of the compounds changes from an I4/m lattice to an Fm3¯m lattice around x=0.1. The unit-cell volume decreases with the doping level in both the I4/m lattice and the Fm3¯m lattice. The resistivity of the compounds shows a metal-semiconductor transition, and the transition temperature T_M-S increases with the doping level. However, Curie temperature (T_C) of the compounds exhibits a weak dependence on the doping level. The saturation magnetization (M_S) at 100 K varies almost linearly with the anti-site defect concentration and agrees well with the simple FIM model. In contrast to the Ce-, Pr-, Nd- and Sm-doped Sr₂FeMoO₆, the difference of M_S of (Sr_2−xEu_x)FeMoO₆ between 5 and 100 K indicates that the moment of Eu³⁺ is antiparellel to that of Fe³⁺ at low temperature.     

Crystal structure, thermal expansion and conductivity of anisotropic La1−xSrxGa1−2xMg2xO3−y (x=0.05, 0.1) single crystals

Crystal structure and anisotropy of the thermal expansion of single crystals of La_1−xSr_xGa_1−2xMg_2xO_3−y (x=0.05 and 0.1) were measured in the temperature range 300-1270 K. High-resolution X-ray powder diffraction data obtained by synchrotron experiments have been used to determine the crystal structure and thermal expansion. The room temperature structure of the crystal with x=0.05 was found to be orthorhombic (Imma, Z=4, a=7.79423(3) Å, b=5.49896(2) Å, c=5.53806(2) Å), whereas the symmetry of the x=0.1 crystal is monoclinic (I2/a, Z=4, a=7.82129(5) Å, b=5.54361(3) Å, c=5.51654(4) Å, β=90.040(1)°). The conductivity in two orthogonal directions of the crystals has been studied. Both, the conductivity and the structural data indicate three phase transitions in La_0.95Sr_0.05Ga_0.9Mg_0.1O_2.92 at 520-570 K (Imma-I2/a), 770 K (I2/a-R3c) and at 870 K (R3c-R-3c), respectively. Two transitions at 770 K (I2/a-R3c) and in the range 870-970 K (R3c-R-3c) occur in La_0.9Sr_0.1Ga_0.8Mg_0.2O_2.85.     

Superconductivity and crystal structure of the solid solutions of Ba8−δSi46−xGex (0?x?23) with Type I clathrate structure

The solid solutions of barium containing Type I clathrate, Ba_8−δSi_46−xGe_x (0?x?23) were prepared under high-pressure and high-temperature conditions of 3 GPa at 800°C. All the solid solutions showed superconductivity, and the transition temperature (T_c) decreased from 8.0 to 2.0 K as the germanium content increased from x=0 to 23 in Ba_8−δSi_46−xGe_x. The single crystals with five different compositions were obtained and the structures, compositions, and site occupancies were determined from X-ray single-crystal analysis. A slight barium deficiency was observed at Ba1 (2a) sites for all the clathrates. The Ge atoms replaced the Si atoms at the Si3 (24k) site in the composition range of x<8, and then at the Si2 (16i) site. The crystals had a slight deficiency in the covalent (Si, Ge) network and the deficiency increased with the increase of the Ge content.     

Comparison of the Chemical Stability of Li1−xCoO2 and Li1−xNi0.85Co0.15O2 Cathodes

The chemical stability of the layered Li_1−xCoO₂ and Li_1−xNi_0.85Co_O.15O₂ cathodes is compared by monitoring the oxygen content with lithium content (1−x) in chemically delithiated samples. The Li_1−xCoO₂ system tends to lose oxygen from the lattice at deep lithium extraction while the Li_1−xNi_0.85Co_0.15O₂ system does not lose oxygen at least for (1−x)>0.3. This difference seems to result in a lower reversible (practical) capacity (140 mA h/g) for LiCoO₂ compared to that for LiNi_0.85Co_0.15O₂ (180 Ma h/g). The loss of significant amount of oxygen leads to a sliding of oxide layers and the formation of a major P3 and a minor O1 phase for the end member CoO_2−δ with δ=0.33. In contrast, Ni_0.85Co_0.15O_2−δ with a small amount of δ=0.1 maintains the initial O3 layer structure.     

Crystal structure and physical properties of the novel ternary intermetallics URuSi3−x and U3Ru2Si7

Two novel ternary intermediate phases, namely URuSi_3−x (x=0.11) and U₃Ru₂Si₇ were found in the Si-rich part of the U-Ru-Si phase diagram. Single crystal X-ray diffraction measurements, carried out at room temperature, indicated that URuSi_3−x crystallizes in its own tetragonal type structure (space group P4/nmm, no. 129; unit cell parameters: a=12.108(1) Å and c=9.810(1) Å), being a derivative of the BaNiSn₃-type structure. U₃Ru₂Si₇ adopts in turn a disordered orthorhombic La₃Co₂Sn₇-type structure (space group Cmmm, no. 65; unit cell parameters: a=4.063(1) Å, b=24.972(2) Å and c=4.072(1) Å). As revealed by magnetization, electrical resistivity and specific heat measurements, both compounds order magnetically at low temperatures. Namely URuSi_3−x is a ferromagnet with T_C=45 K, and U₃Ru₂Si₇ shows ferrimagnetic behavior below T_C=29 K.     

Magnetic properties of La0.5−xLnxSr0.5MnO3 (Ln=Pr, Nd, Gd and Y)

Magnetic and electron transport properties of four series of manganates of the composition La_0.5−xLn_xSr_0.5MnO₃ (Ln=Pr, Nd, Gd and Y) have been investigated to examine how the ferromagnetic metallic nature of the parent La compound changes over to antiferromagnetic insulating behavior, with change in Ln and x due to the associated changes in the A-site cation radius as well as the size disorder. When Ln=Pr and Nd, there is a transition from the tetragonal I4/mcm structure to the orthorhombic Immm and Imma structures at x=0.2 and 0.35, respectively. There is a gradual evolution of the properties from those of La_0.5Sr_0.5MnO₃ to those of Pr_0.5Sr_0.5MnO₃ or Nd_0.5Sr_0.5MnO₃ with increase in x. Thus, when x>0.2 and >0.35, respectively, the Pr- and Nd-substituted manganates show ferromagnetic transitions followed by antiferromagnetic transitions at low temperatures, with the ferromagnetic T_C decreasing with increasing x. The Gd and Y series of compounds are all orthorhombic and show a decrease in T_C with the increase in x, the ferromagnetism disappearing at high x. At a value of x corresponding to the A-site cation radius of Pr_0.5Sr_0.5MnO₃, the Gd and Y series of compounds exhibit ferromagnetism in the 250-300 K region and undergo an antiferromagnetic transition on cooling. The T_C−T_N gap is sensitive to the disorder arising from the size mismatch.     

Crystal structure of Bi1−xTbxFeO3 from high-resolution neutron diffraction

Samples of Bi_1−xTb_xFeO₃, with x=0.05, 0.10, 0.15, 0.20 and 0.25, have been synthesised by solid state reaction. The crystal structures of the perovskite phases, characterised via Rietveld analysis of high resolution powder neutron diffraction data, reveal a structural transition from the R3c symmetry of the parent phase BiFeO₃ to orthorhombic Pnma symmetry, which is complete for x=0.20. The x=0.10 and 0.15 samples are bi-phasic. The transition from a rhombohedral to orthorhombic unit cell is suggested to be driven by the dilution of the stereochemistry of the Bi³⁺ lone pair at the A-site. The G-type antiferromagnetic spin structure, the size of the ordered magnetic moment (∼3.8 μ_B) and the T_N (∼375 °C) are relatively insensitive to increasing Tb concentrations at the A-site.     

An investigation of magnetocaloric effect and its implementation in critical behavior study of La1−xNdxMn2Si2 compounds

The magnetic properties of La_1−xNd_xMn₂Si₂ (x = 0.30–0.45) compounds are studied over the temperature range 5 K ≤ T ≤ 375 K. We report inverse and conventional magnetic entropy change values of La_1−xNd_xMn₂Si₂ (x = 0.35 and 0.40) compounds over the temperature range 5 ≤ T ≤ 375 K. In addition, we study critical behavior of La_1−xNd_xMn₂Si₂ (x = 0.35 and 0.40) compounds around their Curie temperatures. The field dependence of the magnetic entropy change is brought out and implemented to deduce the critical exponents. The critical behavior study shows that the magnetic interactions for the x = 0.35 sample have the same behavior below and above T_C. However, for the x = 0.40 sample has different behavior below and above T_C. Thus, the x = 0.40 sample behaves as a multiphase compound.     

Electrical properties in the system (La1−xCax)CoO3 (0.1 ≦ x ≦ 0.5)

The electrical resistivity of (La_1?xCa_x)CoO₃ (0.1 ≦ x ≦ 0.5) was measured in the temperature range from 80 to 300K. Cobaltite with x ≦ 0.15 is a semiconductor, but the specimen with chemical composition 0.2 ≦ x ≦ 0.5 is metallic. The change of temperature dependence of electrical resistivity has a break point around T_c. The value of the logarithm of the specific electrical resistivity (log ?) at 300K has a minimum at x = 0.4, and this result is explained by the Zener double-exchange mechanism.     

Heat capacity measurements of MnxFe3−xO4

Heat capacities of Mn_xFe_3?xO₄ with the composition x = 1.0, 1.5, and 2.0 were measured from 200 to 740 K. λ-type heat capacity anomalies due to the ferri-paramagnetic transition were observed for all the compositions. The transition temperatures were 577, 471, and 385 K for the composition x = 1.0, 1.5 and 2.0, respectively, which are in good agreement with the results of magnetic measurements. The difference in heat capacities between the different samples was small except for the temperature range of the transition. The magnetic contribution to the observed heat capacity was obtained by assuming that the heat capacity can be expressed by the sum of the lattice heat capacity C_v (l), the dilation contribution C(d), and the magnetic contribution C(m). Entropy changes due to the transition were obtained from C(m) as 55.5, 50.7 and 49.2 J K^?1 mole^?1 for the composition x = 1.0, 1.5, and 2.0, respectively. The entropy changes were also calculated by assuming the randomization of unpaired electron spins on each ion, but they were from 6 to 10 J K^?1 mole^?1 smaller than the observed ones. The difference between the experimental and the calculated values is roughly explained by taking into account the cation exchange reaction between the tetrahedral and the octahedral sites in the spinel structure.     

Magnetic properties of the chemically delithiated LixMn2O4 with 0.07≤x≤1

Magnetism for the Li_xMn₂O₄ samples with 0.07≤x≤1, which are prepared by a chemical reaction in HNO₃ solution, is investigated by direct current susceptibility (χ) and muon-spin rotation/relaxation (μSR) measurements. The effective magnetic moment (μ_eff) of Mn ions decreases monotonically with decreasing x, indicating that Mn³⁺ ions with S=2 () are oxidized to Mn⁴⁺ ions with S=3/2 () with decreasing x. On the other hand, as x decreases from 1 to 0.6, the Curie-Weiss temperature (Θ_p) increases monotonically from ∼−260 to −100 K, and then levels off to −100 K with further decreasing x. This indicates that the antiferromagnetic interaction is dominant in the whole x range. For the x=0.48 sample, the temperature dependence of χ in field-cooling mode clearly deviates from that in zero-field-cooling mode below ∼63 K (=T_m). Furthermore, the hysteresis loop is observed in the magnetization vs. field curve at 5 K. Since the zero-field μSR spectrum is well fitted by a strongly damped oscillation function, the Mn moments for the x=0.48 sample are in a highly disordered fashion down to the lowest temperature measured.     

Neutron diffraction studies of RSn1+xGe1−x (R=Tb-Er) compounds

The magnetic structures of RSn_1+xGe_1−x (R=Tb, Dy, Ho and Er, x≈0.1) compounds have been determined by neutron diffraction studies on polycrystalline samples. The data recorded in a paramagnetic state confirmed the orthorhombic crystal structure described by the space group Cmcm. These compounds are antiferromagnets at low temperatures. The magnetic ordering in TbSn_1.12Ge_0.88 is sine-modulated described by the propagation vector k=(0.4257(2), 0, 0.5880(3)). Tb magnetic moment equals 9.0(1) μ_B at 1.62 K. It lies in the b-c plane and form an angle θ=17.4(2)° with the c-axis. This structure is stable up to the Nèel temperature equal to 31 K. The magnetic structures of RSn_1+xGe_1−x, where R are Dy, Ho and Er at low temperatures are described by the propagation vector k=(1/2, 1/2, 0) with the sequence (++−+) of magnetic moments in the crystal unit cell. In DySn_1.09Ge_0.91 and HoSn_1.1Ge_0.9 magnetic moments equal 7.25(15) and 8.60(6) μ_B at 1.55 K, respectively. The moments are parallel to the c-axis. For Ho-compound this ordering is stable up to T_N=10.7 K. For ErSn_1.08Ge_0.92, the Er magnetic moment equals 7.76(7) μ_B at T=1.5 K and it is parallel to the b-axis. At T_t=3.5 K it tunes into the modulated structure described by the k=(0.496(1), 0.446(4), 0). With the increase of temperature there is a slow decrease of k_x component and a quick decrease of k_y component. The Er magnetic moment is parallel to the b-axis up to 3.9 K while at 4 K and above it lies in the b-c plane and form an angle 48(3)° with the c-axis. In compounds with R=Tb, Ho and Er the magnetostriction effect at the Nèel temperature is observed.     

Crystal structure and magnetic properties of Ce7Ni5±xGe3±xIn6 and Pr7Ni5±xGe3±xIn6

The indides Ce₇Ni_5±xGe_3±xIn₆ and Pr₇Ni_5±xGe_3±xIn₆ were synthesized from the elements by arc-melting of the components. Single crystals were grown via special annealing sequences. Both structures were solved from X-ray single crystal diffraction data: new structure type, P6/m, Z=1, a=11.385(2), c=4.212(1) Å, wR₂=0.0640, 634F² values, 25 variables for Ce₇Ni_4.73Ge_3.27In₆ and a=11.355(6), c=4.183(2) Å, wR₂=0.0539, 563F² values, 25 variables for Pr₇Ni_4.96Ge_3.04In₆. Both indides show homogeneity ranges through Ni/Ge mixing (M sites). This new structure type can be derived from the AlB₂ structure type by a substitution of the Al and B atoms by CeM₁₂ and NiIn₆Ce₃ polyhedra (tricapped trigonal prism). Magnetic susceptibility measurements on a polycrystalline sample of Ce₇Ni₅Ge₃In₆ indicated Curie-Weiss like paramagnetic behavior down to 1.71 K with the effective magnetic moment slightly reduced in relation to the value expected for trivalent cerium ions. No magnetic ordering is evident.