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1.
The new compounds U6Fe16Si7 and U6Fe16Si7C were prepared by arc-melting and subsequent annealing at 1500 °C. Single-crystal X-ray diffraction showed that they crystallize in the cubic space group (No. 225), with unit-cell parameters at room temperature a=11.7206(5) Å for U6Fe16Si7 and a=11.7814(2) Å for U6Fe16Si7C. Their crystal structures correspond to ordered variants of the Th6Mn23 type. U6Fe16Si7 adopts the Mg6Cu16Si7 structure type, whereas U6Fe16Si7C crystallizes with a novel “filled” quaternary variant. The inserted carbon is located in octahedral cages formed by six U atoms, with U-U interatomic distances of 3.509(1) Å. Insertion of carbon in the structure of U6Fe16Si7 has a direct influence on the U-Fe and Fe-Fe interatomic distances. The electronic properties of both compounds were investigated by means of DC susceptibility, electrical resistivity and thermopower. U6Fe16Si7 is a Pauli paramagnet. Its electrical resistivity and thermopower point out that it cannot be classified as a simple metal. The magnetic susceptibility of U6Fe16Si7C is best described over the temperature range 100-300 K by using a modified Curie-Weiss law with an effective magnetic moment of 2.3(2) μB/U, a paramagnetic Weiss temperature, θp=57(2) K and a temperature-independent term χ0=0.057(1) emu/mol. Both the electrical resistivity and thermopower reveal metallic behavior.  相似文献   

2.
The crystal structure of the Zr1−xYxNiSn half-Heusler solid solutions is synthesized and their crystal structure is determined. Electrical resistivity and thermoelectric Seebeck coefficient are measured in the 80-380 K temperature range, whereas magnetic susceptibility is measured at 290 K. It is established that substitution of Zr host atoms by Y in the ZrNiSn intermetallic semiconductor is equivalent to doping by acceptor impurities. Self-consistent ab initio calculations, based on the full potential local orbital (FPLO) minimum basis method, are performed to investigate the electronic and thermoelectric properties of these alloys. Spin polarized within the framework of the coherent potential approximation (CPA) are included.  相似文献   

3.
A new ternary compound, Ce2PdGa10, has been synthesized using Ga flux and characterized by single-crystal X-ray diffraction. Ce2PdGa10 adopts a tetragonal structure in the I4/mmm space group and is isostructural to Ce2NiGa10. Lattice parameters are , , , and Z=2. The compound is metallic (dρ/dT>0), with the resistance decreasing roughly linearly with temperature from 300 to 175 K. The magnetic susceptibility of Ce2PdGa10 is consistent with local-moment paramagnetism and no long-range magnetic ordering occurs down to 2 K. A large positive magnetoresistance over 200% is observed at 2 K for fields of 9 T. In this paper, we present the structure and physical properties of Ce2PdGa10 and compared them to CePdGa6.  相似文献   

4.
The new Chevrel phase Ti0.3Mo5RuSe8 has been synthesized and characterized by quantitative microprobe analysis, powder X-ray diffraction, and high-temperature thermoelectric properties measurements. The thermoelectric properties of this compound are compared to the previously reported data for other related Chevrel phases. We report also the results of Rietveld analysis of powder X-ray diffraction data for Ti0.3Mo5RuSe8. This compound adopts the rhombohedral Chevrel phase structure (space group , Z=3) with hexagonal lattice constants a=9.75430(25) Å and c=10.79064(40) Å. The low level of incorporation and low scattering power of Ti precluded the identification of the Ti positions, and Rietveld refinement was carried out only for the Mo5RuSe8 framework of Ti0.3Mo5RuSe8 (Rp=10.5%, Rwp=14.6%). Rietveld analysis was also used to refine the structure of the unfilled phase Mo5RuSe8 (, Z=3, a=9.63994(8) Å, c=10.97191(11) Å, Rp=8.0%, Rwp=10.5%). Comparisons between the two structures are made.  相似文献   

5.
The Ca2(ZnxFe2−x)O5 series was synthesized and characterized to determine the influence of zinc dopant on the brownmillerite structure for thermoelectric applications. All single-phase compounds exhibited Pnma symmetry at room temperature up to the solubility limit at x=0.10. High-temperature X-ray powder diffraction was used to show that the nature of the Pnma-Imma(0 0 γ)s00 transition in Ca2Fe2O5 is modified by the presence of zinc. While the Zn-free composition transitions to an incommensurate phase, the Zn-containing phases transition instead to a commensurate phase, Imma(0 0 γ)s00 with γ=1/2. Both the Néel temperature and the onset temperature of the Pnma-Imma(0 0 γ)s00 phase transition decreased with increasing zinc concentration. Rietveld analysis of the in situ diffraction pattern for the x=0 sample at 1300 °C demonstrates that the structure contains statistically disordered chain orientations as described by space group Imma. Thermoelectric properties were analyzed in air from 100 to 800 °C. The positive Seebeck coefficient revealed hole-type conduction for all compositions. Doped samples exhibited electrical conductivities up to 3.4 S/cm and thermal conductivity of 1.5 W/mK. Transport analysis revealed thermally activated mobility consistent with polaron conduction behavior for all compositions.  相似文献   

6.
Physical properties of NdPd2Ge2 and NdAg2Ge2, crystallizing with the tetragonal ThCr2Si2-type crystal structure, were investigated by means of magnetic, calorimetric, electrical transport as well as by neutron diffraction measurements. The specific heat studies and neutron diffraction measurements were performed down to 0.30 K and 0.47 K, respectively. Both compounds exhibit antiferromagnetic ordering below TN equal to 1.5 K for NdPd2Ge2 and 1.8 K for NdAg2Ge2. Neutron diffraction data for the latter germanide indicate antiferromagnetic collinear structure described by the propagation vector k=(0.5, 0, 0.5). The Nd magnetic moments equal to 2.24(5) μB at 0.47 K are aligned along the a-axis and have the +− sequence within the crystal unit cell. For NdPd2Ge2 only very small Bragg peaks of magnetic origin were observed in the neutron diffraction patterns measured below TN, thus hampering determination of the magnetic structure. Both compounds exhibit metallic-like electrical conduction. From the specific heat data the crystal electric field (CEF) levels schemes were determined. Difference between the overall CEF splitting in the two compounds is correlated with their structural parameters.  相似文献   

7.
A series of rare-earth metal–magnesium–germanides RE2MgGe2 (RE=Y, Nd, Sm, Gd–Tm, Lu) has been synthesized by reactions of the corresponding elements at high temperature. Their structures have been established by single-crystal and powder X-ray diffraction and belong to the Mo2FeB2 structure type (space group P4/mbm (No. 127), Z=2; Pearson symbol tP10). Temperature dependent DC magnetization measurements indicate Curie–Weiss paramagnetism in the high-temperature regime for all members of the family, excluding Y2MgGe2, Sm2MgGe2, and Lu2MgGe2. At cryogenic temperatures (ca. 60 K and below), most RE2MgGe2 phases enter into an antiferromagnetic ground-state, except for Er2MgGe2 and Tm2MgGe2, which do not undergo magnetic ordering down to 5 K. The structural variations as a function of the decreasing size of the rare-earth metals, following the lanthanide contraction, and the changes in the magnetic properties across the series are discussed as well.  相似文献   

8.
The crystal structures, synthesis and physical properties of ruthenium hollandites ALi2Ru6O12 (A=Na, K) with a new pseudo-hexagonal structure type are described. Analogous to tetragonal hollandites, the framework is made of MO6 octahedra in double chains that share corner oxygens with each other to create interstitial tunnels. The tunnels are either hexagonal or triangular in cross-section. Magnetic susceptibilities, low temperature specific heat, and electrical resistivities are reported. The data indicate that these materials are normal, low density of states metals. This new structure type can be extended from A=Group I to A=Group II ions with the synthesis of CaLi2Ru6O12 and SrLi2Ru6O12.  相似文献   

9.
Band structure calculations at the level of LMTO-ASA provide insight into the electronic structure of BaV10O15 and the origin of the structural phase transition. A crystal orbital Hamiltonian population/integrated crystal orbital Hamiltonian population analysis provides evidence that the crystallographic phase transition is driven by V-V bond formation. As well, the energy bands near the Fermi level are very narrow, <1 eV, consistent with the fact that the observed insulating behavior can be due to electron localization via either Mott-Hubbard correlation and/or Anderson disorder. The partial solid solution, BaV10−xTixO15, was examined to study the effect of Ti-doping at the V sites on the structure and electronic transport properties. In spite of the non-existence of “BaTi10O15”, the limiting x=8, as indicated by a monotonic increase in the cell volume and systematic changes in properties. This limit may be due to the difficulty of stabilizing Ti2+ in this structure. For x=0.5 both the first order structural phase transition and the magnetic transition at 40 K are quenched. The samples obey the Curie-Weiss law to x=3 with nearly spin only effective moments along with θ values which range from −1090 K (x=0.5) to −1629 K (x=3). For x>3 a very large, ∼2×10−3 emu/mol, temperature independent (TIP) contribution dominates. Conductivity measurements on sintered, polycrystalline samples show semiconducting behavior for all compositions. Activation energies for Mott hopping derived from high temperature data range from ∼0.1 eV for x=0-1 and fall to a plateau of 0.06 eV for x=3-7. Low temperature data for x=3, 5 and 7 show evidence for Mott variable range hoping (VRH) with a T1/4 law and in one case between 5 and 17 K, a Efros-Shklovskii correlated hopping, T1/2 law, was seen, in sharp contrast to BaV10O15 where only the E-S law was observed up to 75 K. Seebeck coefficients are small (<35 μV/K), positive, roughly TIP and increase with increasing x up to x=5. This may point to a Heikes hopping of holes but a simple single carrier model is impossible. The compositions for x>3 are remarkable in that local moment behavior is lost, yet a metallic state is not reached. The failure of this system to be driven metallic even at such high doping levels is not fully understood but it seems clear that disorder induced carrier localization plays a major role.  相似文献   

10.
A new ternary indide La8Co2In3 was prepared by arc-melting of the compact metals under an argon atmosphere. A subsequent high temperature treatment was used for single crystal growth. The crystal structure has been determined from X-ray single crystal data: own structure type, space group Pmn21, Pearson code oP26, Z = 2, a = 10.2646(11), b = 10.1802(12), c = 7.3235(8) Å, R1 = 0.0338, wR2 = 0.0458, for 1556 independent reflections with I > 2σ(I) and 71 variables. Similarly to intermetallic compound with a high rare earth content, atoms in the title structure have no high coordination numbers: 12–15 for lanthanum, 9 and 7 for cobalt, and 11 for indium. Strong Co–Co bonding is observed in the structure. The packing of In polyhedra can be represented as a complicated variant of the RuB2 structure type.  相似文献   

11.
Reported are the synthesis and the structural characterization of four new polar intermetallic phases, which exist only with mixed alkaline-earth and rare-earth metal cations in narrow homogeneity ranges. (Sr1-xCax)5In3Ge6 and (Eu1-xYbx)5In3Ge6 (x≈0.7) crystallize in the orthorhombic space group Pnma with two formula units per unit cell (own structure type, Pearson symbol oP56). The lattice parameters are as follows: a=13.109(3)-13.266(3) Å, b=4.4089(9)-4.4703(12) Å, and c=23.316(5)-23.557(6) Å. (Sr1-xCax)3In2Ge4 and (Sr1-xYbx)3In2Ge4 (x≈0.4-0.5) adopt another novel monoclinic structure-type (space group C2/m, Z=4, Pearson symbol mS36) with lattice parameters in the range a=19.978(2)-20.202(2) Å, b=4.5287(5)-4.5664(5) Å, c=10.3295(12)-10.3447(10) Å, and β=98.214(2)-98.470(2)°, depending on the metal cations and their ratio. The polyanionic sub-structures in both cases are based on chains of InGe4 corner-shared tetrahedra. The A5In3Ge6 structure (A=Sr/Ca or Sr/Yb) also features Ge4 tetramers, and isolated In atoms in nearly square-planar environment, while the A3In2Ge4 structure (A=Sr/Ca or Eu/Yb) contains zig-zag chains of In and Ge strings with intricate topology of cis- and trans-bonds. The experimental results have been complemented by tight-binding linear muffin-tin orbital (LMTO) band structure calculations.  相似文献   

12.
Single crystals of a new phosphate KCuFe(PO4)2 have been prepared by the flux method and its structural and physical properties have been investigated. This compound crystallizes in the monoclinic system with the space group P21/n and its parameters are: a=7.958(3) Å, b=9.931(2) Å, c=9.039(2) Å, β=115.59(3)° and Z=4. Its structure consists of FeO6 octahedra sharing corners with Cu2O8 units of edge-sharing CuO5 polyhedra to form undulating chains extending infinitely along the b-axis. These chains are connected by the phosphate tetrahedra giving rise to a 3D framework with six-sided tunnels parallel to the [101] direction, where the K+ ions are located. The Mössbauer spectroscopy results confirm the exclusive presence of octahedral Fe3+ ions. The magnetic measurements show the compound to be antiferromagnetic with Cm=5.71 emu K/mol and θ=−156.5 K. The derived experimental effective moment μex=6.76μB is somewhat higher than the theoretical one of μth=6.16μB, calculated taking only into account the spin contribution for Fe3+ and Cu2+ cations. Electrical measurements allow us to obtain the activation energy (1.22 eV) and the conductivity measurements suggest that the charge carriers through the structure are the potassium cations.  相似文献   

13.
The new compound U2Co6Al19 was prepared by reaction of the elemental components in an arc-melting furnace followed by a heat treatment at 1050°C for 500 h. Its chemical composition was checked by energy-dispersive X-ray analyses and its crystal structure was determined by single crystal X-ray diffraction experiments. It crystallizes with four formula units in the monoclinic space group C2/m in a unit cell of dimensions a=17.4617(3)Å, b=12.0474(2)Å, c=8.2003(1)Å, β=103.915(1)°. The crystal structure of U2Co6Al19 can be regarded as a superstructure of NdCo4−xGa9 structure type. This complex structure consists of a three-dimensional Co-Al framework delimiting tunnels where the U atoms reside. The shortest U-U distances are found in the c direction with alternating values of 3.98(1) and 4.22(1) Å. Temperature-dependent magnetization shows a first peak at 12.5 K and a weak ferromagnetic character below the temperature TC=8 K. Magnetization at 1.9 K reaches almost saturation in 5 T with the moment of 0.36 μB/U atom. The complex magnetic behavior of U2Co6Al19 may be ascribed to a canted spin structure resulting from an antiparallel arrangement of the magnetic moments not fully compensated at low temperature. At higher temperature, the compound displays simple paramagnetic behavior.  相似文献   

14.
Single crystals of NaCoO2 have been successfully synthesized for the first time by a flux method at 1323 K. A single-crystal X-ray diffraction study confirmed the trigonal space group and the lattice parameters , . The crystal structure has been refined to the conventional values R=1.9% and wR=2.1% for 309 independent observed reflections. The electron density distribution of NaCoO2 has been studied by the maximum entropy method (MEM) using single-crystal X-ray diffraction data obtained at 298 K. From the results of the MEM analysis, the strong covalent bonding was clearly observed between Co and O atoms, while no bonding was observed around Na atoms. We also calculated the electron density of NaCoO2 by first principles calculations. The electron density obtained experimentally is in good agreement with the theoretical one.  相似文献   

15.
Two types of strontium-, barium- and europium-containing germanides have been synthesized using high temperature reactions and characterized by single-crystal X-ray diffraction. All reported compounds also contain mixed-occupied Li and In atoms, resulting in quaternary phases with narrow homogeneity ranges. The first type comprises EuLi0.91(1)In0.09Ge2, SrLi0.95(1)In0.05Ge2 and BaLi0.99(1)In0.01Ge2, which crystallize in the orthorhombic space group Pnma (BaLi0.9Mg0.1Si2 structure type, Pearson code oP16). The lattice parameters are a=7.129(4)-7.405(4) Å; b=4.426(3)-4.638(2) Å; and c=11.462(7)-11.872(6) Å. The second type includes Eu2Li1.36(1)In0.64Ge3 and Sr2Li1.45(1)In0.55Ge3, which adopt the orthorhombic space group Cmcm (Ce2Li2Ge3 structure type, Pearson code oC28) with lattice parameters a=4.534(2)-4.618(2) Å; b=19.347(8)-19.685(9) Å; and c=7.164(3)-7.260(3) Å. The polyanionic sub-structures in both cases feature one-dimensional Ge chains with alternating Ge-Ge bonds in cis- and trans-conformation. Theoretical studies using the tight-binding linear muffin-tin orbital (LMTO) method provide the rationale for optimizing the overall bonding by diminishing the π-p delocalization along the Ge chains, accounting for the experimentally confirmed substitution of Li forIn.  相似文献   

16.
The new compound Bi2/3Ce1/3Rh2O5 has been discovered. It is currently the only known compound in the Bi-Ce-Rh-O system, and it crystallizes in a previously unknown structure type. The structure was established from single crystal X-ray diffraction data. Interatomic distances indicate the oxidation states as Bi2/33+Ce1/34+Rh23.33+O5. The structure indicates no ordering between Rh3+ and Rh4+. The lack of charge ordering is consistent with the metallic properties determined from electrical conductivity, Seebeck coefficient, and magnetic susceptibility measurements.  相似文献   

17.
The hydrothermal reaction of UO3, WO3, and CsIO4 leads to the formation of Cs6[(UO2)4(W5O21)(OH)2(H2O)2] and UO2(IO3)2(H2O). Cs6[(UO2)4(W5O21)(OH)2(H2O)2] is the first example of a hydrothermally synthesized uranyl tungstate. It's structure has been determined by single-crystal X-ray diffraction. Crystallographic data: tetragonal, space group Icm, , , Z=4, MoKα, , R(F)=2.84% for 135 parameters with 2300 reflections with I>2σ(I). The structure is comprised of two-dimensional anionic layers that are separated by Cs+ cations. The coordination polyhedra found in the novel layers consist of UO7 pentagonal bipyramids, WO6 distorted octahedra, and WO5 square pyramids. The UO7 polyhedra are formed from the binding of five equatorial oxygen atoms around a central uranyl, UO22+, unit. Both bridging and terminal oxo ligands are employed in forming the WO5 square pyramidal units, while oxo, hydroxo, and aqua ligands are found in the WO6 distorted octahedra. In the layers, four (UO2)O5 polyhedra corner share with equatorial oxygen atoms to form a U4O24 tetramer entity with a square site in the center; a tungsten atom populates the center of each of these sites to form a U4WO25 pentamer unit. The pentamer units that result are connected in two dimensions by edge-shared dimers of WO6 octahedra to form the two-dimensional [(UO2)4(W5O21)(OH)2(H2O)2]6- layers. The lack of inversion symmetry in Cs6[(UO2)4(W5O21)(OH)2(H2O)2] can be directly contributed to the WO5 square pyramids found in the pentamer units. In the structure, all of these polar polyhedra align their terminal oxygens in the same orientation, along the c axis, thus resulting in a polar compound.  相似文献   

18.
Single crystals of iron(II) pyroborate, Fe2B2O5, were prepared at 1000–1050 °C under an argon atmosphere. The crystals were transparent, yellowish in color and needle-like or columnar. The crystal structure of Fe2B2O5 was analyzed by single-crystal X-ray diffraction. Refined triclinic unit cell parameters were a=3.2388(2), b=6.1684(5), c=9.3866(8) Å, α=104.613(3)°, β=90.799(2)° and γ=91.731(2)°. The final reliability factors of refinement were R1=0.020 and wR2=0.059 [I > 2σ(I)]. Transmittance over 50% in the visible light region from 500 to 750 nm was observed for a single crystal of Fe2B2O5 with a thickness of about 0.3 mm. The light absorption edge estimated from a diffuse reflectance spectrum was at around 350 nm (3.6 eV). Magnetic susceptibility was measured for single crystals at 4–300 K. Fe2B2O5 showed antiferromagnetic behavior below the Néel temperature, TN≈70 K, and the Weiss temperature was TW=36 K. The effective magnetic moment of Fe was 5.3μB.  相似文献   

19.
Perovskite-type cobaltates in the system La2Co1+z(MgxTi1−x)1−zO6 were studied for z=0≤x≤0.6 and 0≤x<0.9, using X-ray and neutron powder diffraction, electron diffraction (ED), magnetic susceptibility measurements and X-ray absorption near-edge structure (XANES) spectroscopy. The samples were synthesised using the citrate route in air at 1350 °C. The space group symmetry of the structure changes from P21/n via Pbnm to Rc with both increasing Mg content and increasing Co content. The La2Co(MgxTi1−x)O6 (z=0) compounds show anti-ferromagnetic couplings of the magnetic moments for the Co below 15 K for x=0, 0.1 and 0.2. XANES spectra show for the compositions 0≤x≤0.5 a linear decrease in the L3/(L3+L2) Co-L2,3 edge branching ratio with x, in agreement with a decrease of the average Co ion spin-state, from a high-spin to a lower-spin-state, with decreasing nominal Co2+ ion content.  相似文献   

20.
The ternary rare-earth metal silicide borides RE5Si2B8 (RE=Y, Sm, Gd, Tb, Dy Ho) were prepared by arc melting the elemental components and subsequent annealing up to . The crystal structure was determined for each term of the series from single-crystal X-ray data: tetragonal symmetry, space group P4/mbm, Z=2; unit cell parameters a=7.2616(3), and a=7.1830(2), for Sm5Si2B8 and Ho5Si2B8, respectively. The structure is a new type and can be structurally described as an intergrowth of ThB4-like and U3Si2-like slabs of composition REB4 and RE3Si2, respectively, alternating along the c direction. The boron and silicon substructures are wholly independent and well ordered. The magnetic properties are as follows: Y5Si2B8 is a Pauli-type paramagnet above 1.8 K, Gd5Si2B8 undergoes a weak (canted) ferromagnetic-like order at 70 K followed by a colinear antiferromagnetic spin alignment at 44 K. Tb5Si2B8 and Dy5Si2B8 order antiferromagnetically at a Néel temperature of TN=45 and 28 K, respectively. In the paramagnetic regime, the effective moments are in good accord with the theoretical RE3+ free ion moments. The temperature dependence of the electrical resistivities for the Y, Gd, Tb, and Dy containing samples corroborates with the metallic state of the nonmagnetic (Y) and the magnetically ordered compounds. 11B, 29Si and 89Y nuclear magnetic resonance (NMR) spectroscopy on nonmagnetic Y5Si2B8 shows different signals, which correspond to the expected number of distinct crystallographic sites in the structure. 11B NMR on Y5Si2B8 indicates that the local magnetic susceptibilities are substantially different from the ones observed in the related compound YB4.  相似文献   

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