共查询到20条相似文献,搜索用时 0 毫秒
1.
R.A. Secco H. LiuN. Imanaka G. AdachiM.D. Rutter 《Journal of Physics and Chemistry of Solids》2002,63(3):425-431
Impedance spectroscopy measurements and synchrotron X-ray diffraction studies of Sc2(WO4)3 at 400°C have been carried out as a function of pressure up to 4.4 GPa. Ionic conductivity shows normal decrease with increase in pressure up to 2.9 GPa, but then increases at higher pressures. The XRD results show that Sc2(WO4)3 undergoes pressure-induced amorphization at pressures coincident with the reversal in conductivity behavior. The loss of crystal structure at high pressure is consistent with growing evidence of pressure-induced amorphization in negative thermal expansion materials, such as Sc2(WO4)3. The increase in conductivity in the amorphized state is interpreted as the result of an increase in structural entropy and a concomitant reduction of energy barriers for ionic transport. 相似文献
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3.
Eriko Ohshima Keiji KusabaSinji Onodera Masae Kikuchi 《Journal of Physics and Chemistry of Solids》2002,63(3):419-423
High-pressure phase transition of Ta2NiO6 with the trirutile-type structure was investigated from the viewpoint of crystal chemistry. A new quenchable high-pressure phase was found in the pressure range higher than 7 GPa and 900°C. The high-pressure phase has an orthorhombic cell (a=4.797(1) Å, b=5.153(2) Å and c=14.85(1) Å and space group; Abm2), and it is more dense by 9.6% than the trirutile-structured phase. Infrared spectra of the trirutile-type phase and the high-pressure phase show that Ni2+ ions in the high-pressure phase are still in octahedral sites. The crystal structure of the high-pressure phase is considered as a cation-ordering trifluorite-type structure, which can be stabilized by a crystal field effect of Ni2+ ions. 相似文献
4.
Vladimir Dmitriev Vitaly Sinitsyn Denis Machon Eugeny Ponyatovsky Hans Peter Weber 《Journal of Physics and Chemistry of Solids》2003,64(2):307-312
The effect of pressure on the phase transformations in Sm2(MoO4)3, Gd2(MoO4)3 and Eu2(MoO4)3 crystals has been studied in situ using synchrotron radiation. All three isostructural compounds undergo a structural phase transition at 2.2-2.8 GPa to a new phase, which is interpreted as a possible precursor of amorphization. Amorphization in these crystals occurs irreversibly over a wide pressure range, and its mechanism, interpreted as a chemical decomposition, is found to be weakly affected by the degree of hydrostaticity. 相似文献
5.
A laser-heated sample in a diamond anvil cell and synchrotron X-ray radiation was used to carry out structural characterization of the phase transformation of Fe2O3 at high pressures (30-96 GPa) and high temperature. The Rh2O3(II) (or orthorhombic perovskite) structure transforms to a new phase, which exhibits X-ray diffraction data that are indicative of a CaIrO3-type structure. The CaIrO3-type structure exhibited an orthorhombic symmetry (space group: Cmcm) that was stable at temperatures of 1200-2800 K and pressure of 96 GPa (the highest pressure used). Unambiguous assignment of such a structure requires experimental evidence for the presence of two Fe species. Based on the equation of state of gold, the phase boundary of the CaIrO3-type phase transformation was P (GPa)=59+0.0022×(T−1200) (K). 相似文献
6.
Paul M Forster 《Journal of Physics and Chemistry of Solids》2004,65(1):11-16
A novel layered hydrotalcite-like material, Co7(H2O)2(OH)12(C2H4S2O6), has been prepared hydrothermally and the structure determined using single crystal X-ray diffraction (a=6.2752(19) Å, b=8.361(3) Å, c=9.642(3) Å, α=96.613(5)°, β=98.230(5)°, γ=100.673(5)°, R1=0.0551). The structure consists of brucite-like sheets where 1/6 of the octahedral sites are replaced by two tetrahedrally coordinated Co(II) above and below the plane of the layer. Ethanedisulfonate anions occupy the space between layers and provide charge balance for the positively charged layers. The compound is ferrimagnetic, with a Curie temperature of 33 K, Curie-Weiss θ of −31 K, and a coercive field of 881 Oe at 5 K. 相似文献
7.
Aqueous electrochemical insertion of M+ (Na+ and H+) species into WO3(4,4′-bipyridyl)0.5 has been carried out. The chemical states and structure of the resulting product were analysed by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). XPS showed the presence of W6+ as well as the usual reduced W species (W5+) which is responsible for a change in colour. Moreover, the presence of these intercalates correlates with the evolution of the reduced W species. The bulk structure of the layered hybrid, as determined by powder X-ray diffraction, showed no alteration after electrochemistry, in contrast to the same measurements on tungsten trioxide (WO3). This however concurs with single-crystal X-ray studies, which show little change in lattice parameters with Na+ insertion. Four-probe resistance measurements of the layered hybrid coated film display a drop in resistance after electrochemistry, which can be attributed to the injection of charge-carriers into the conduction band. 相似文献
8.
Lakshmi Vijayan 《Journal of Physics and Chemistry of Solids》2011,72(6):613-619
Nano-crystallites of Li1.3Ti1.7Al0.3(PO4)2.9(VO4)0.1 NASICON type material are prepared by means of solid-state reaction of a stoichiometric mixture after milling it for 22 and 55 h. The milling reduces the average crystallite size of the ceramic to 80 and 60 nm, respectively. Mechanical milling changes structural parameters and the strain induced at the grain-boundaries plays a major role in improving electrical conductivity. An order of magnitude increase in electrical conductivity is observed in the material milled for 55 h compared to the unmilled material, which is also reflected in permittivity loss. Modulus and permittivity representations substantiate the constriction effect of grain-boundaries observed in the complex impedance representation. 相似文献
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A. Martínez-de la Cruz F.E. Longoria Rodríguez 《Journal of Physics and Chemistry of Solids》2008,69(4):830-834
Electrochemical lithium insertion into (PO2)4(WO3)2m, where m=9 and 10, has allowed the determination of several phases Lix(PO2)4(WO3)2m between 3.4 and 0.01 V vs Li+/Li0. After the first cycle the electrochemical system was unable to maintain the high specific capacity of the cells (540 Ah/kg) due to irreversible processes. Nevertheless at high voltage values, above 1.4 V vs Li+/Li0, the lithium insertion proceeded through a reversible mechanism. By means of X-ray diffraction experiments we have detected the nature of different phases Lix(PO2)4(WO3)2m formed and we have established a correlation with the reversible/irreversible processes detected during the electrochemical insertion. 相似文献
10.
A.N. Papathanassiou 《Journal of Physics and Chemistry of Solids》2005,66(10):1849-1850
A power law used to describe the AC conductivity from 299 to 393 K of the mixed crystal (NH4)3H(SO4)1.42(SeO4)0.58 led to fractional exponent values ranging from 1.08 to 0.91, depending on structural changes induced on temperature variation [B. Louati, M. Gargouri, K. Guidara and T. Mhiri, J. Phys. Chem. Solids 66 (2005) 762]. In the present note, we suggest that the fractional law exhibits features of lattice relaxation. Despite the structural changes, the parameters of the power law are mutually interconnected to yield a temperature independent phenomenon. Such behavior is probably of general validity and characterizes the universal fractional dispersion of the AC conductivity, as it was also observed in glasses of different composition. 相似文献
11.
?brahim Uçar Necmi Dege Bünyamin Karabulut Ahmet Bulut 《Journal of Physics and Chemistry of Solids》2007,68(8):1540-1548
The single crystal of [Ni(ina)2(H2O)4]·(sac)2, (NINS), (ina is isonicotinamide and sac is saccharinate) complex has been prepared and its structural, spectroscopic and thermal properties have been determined. The title complex crystallizes in monoclinic system with space group P21/c, Z=2. The octahedral Ni(II) ion, which rides on a crystallographic centre of symmetry, is coordinated by two monodentate ina ligands through the ring nitrogen and four aqua ligands to form discrete [Ni(ina)2(H2O)4] unit, which captures two saccharinate ions in up and down positions, each through intermolecular hydrogen bands. The magnetic environment of copper(II) doped NINS crystal has also been identified by electron paramagnetic resonance (EPR) technique. The g and A values of Cu2+ doped NINS single crystal were calculated from the EPR spectra recorded in three mutually perpendicular planes. These values indicated that the paramagnetic centre has a rhombic symmetry with the Cu2+ ion having distorted octahedral environment. The complex exhibits only metal centred electroactivity in the potential range of −2.00, 1.25 V versus Ag/AgCl reference electrode. 相似文献
12.
Composite electrolytes in the system [(KCl)0.9:(NaCl)0.1]1−y:(ZrO2)y were prepared and their ionic conductivities were studied. In our previous study on the mixed halide system (KCl)1−x:(NaCl)x, maximum conductivity (∼50 times that of the base KCl matrix) was found when x=0.1. The matrix (KCl)0.9:(NaCl)0.1 was dispersed with different concentration of ZrO2 (powder) for the preparation of composites and their conductivities were determined. The maximum conductivity was developed for the composite having composition y=0.5. The matrices were prepared by melt-quench technique and the dispersion of ZrO2 was carried out in liquid medium. The conductivity measurements of the composites were carried out by impedance spectroscopy technique. The composite [(KCl)0.9:(NaCl)0.1]0.5:(ZrO2)0.5 was characterized by X-ray diffraction (XRD) analysis, differential thermal analysis (DTA), thermogravimetric analysis (TG) and scanning electron microscopy (SEM). The conductivity of the composite [(KCl)0.9:(NaCl)0.1]0.5:(ZrO2)0.5 as a function of temperature was also studied. The conductivity increase in the composite could be attributed to enhancement of defect concentration in the space charge region created at the interface between the host halide and the dispersoid. 相似文献
13.
A new compound, K4(SO4)(HSO4)2(H3AsO4) was synthesized from water solution of KHSO4/K3H(SO4)2/H3AsO4. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å3, Z=2 and ρcal=2.466 g cm−3. The refinement of 3760 observed reflections (I>2σ(I)) leads to R1=0.0394 and wR2=0.0755. The structure is characterized by SO42−, HSO4− and H3AsO4 tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O4−?S(1)O42− and H(12)S(2)O4−?H3AsO4). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H3AsO4 group to build the chain S(1)O4?H3AsO4 which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K4(SO4)(HSO4)2(H3AsO4) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature. 相似文献
14.
The crystal structure of a layered ternary carbide, Ti3(Si0.43Ge0.57)C2, was studied with single-crystal X-ray diffraction. The compound has a hexagonal symmetry with space group P63/mmc and unit-cell parameters a=3.0823(1) Å, c=17.7702(6) Å, and V=146.21(1) Å3. The Si and Ge atoms in the structure occupy the same crystallographic site surrounded by six Ti atoms at an average distance of 2.7219 Å, and the C atoms are octahedrally coordinated by two types of symmetrically distinct Ti atoms, with an average C-Ti distance of 2.1429 Å. The atomic displacement parameters for C and Ti are relatively isotropic, whereas those for A (=0.43Si+0.57Ge) are appreciably anisotropic, with U11 (=U22) being about three times greater than U33. Compared to Ti3SiC2, the substitution of Ge for Si results in an increase in both A-Ti and C-Ti bond distances. An electron density analysis based on the refined structure shows that each A atom is bonded to 6Ti atoms as well as to its 6 nearest neighbor A site atoms, whether the site is occupied by Si or Ge, suggesting that these bond paths may be significantly involved with electron transport properties. 相似文献
15.
Dongbin Hou Jianguo Du Jinyuan Yan Hongyang Zhu 《Journal of Physics and Chemistry of Solids》2010,71(11):1571-1575
The high-pressure behavior of rhenium disulfide (ReS2) has been investigated to 51.0 GPa by in situ synchrotron X-ray diffraction in a diamond anvil cell at room temperature. The results demonstrate that the ReS2 triclinic phase is stable up to 11.3 GPa, at which pressure the ReS2 transforms to a new high-pressure phase, which is tentatively identified with a hexagonal lattice in space group P6?m2. The high-pressure phase is stable up to the highest pressure in this study (51.0 GPa) and not quenchable upon decompression to ambient pressure. The compressibility of the triclinic phase exhibits anisotropy, meaning that it is more compressive along interlayer directions than intralayer directions, which demonstrates the properties of the weak interlayer van der Waals interactions and the strong intralayer covalent bonds. The largest change in the unit cell angles with increasing pressures is the increase of β, which indicates a rotation of the sulfur atoms around the rhenium atoms during the compression. Fitting the experimental data of the triclinic phase to the third-order Birch-Murnaghan EOS yields a bulk modulus of KOT=23±4 GPa with its pressure derivative KOT′= 29±8, and the second-order yields KOT=49±3 GPa. 相似文献
16.
Andrzej Grzechnik Vladimir Dmitriev 《Journal of Physics and Chemistry of Solids》2005,66(10):1769-1774
Dilithium zirconium hexafluoride, Li2ZrF6 (, Z=1), is studied at high pressures using synchrotron angle-dispersive X-ray powder diffraction in a diamond anvil cell at room temperature. At atmospheric conditions, it has a structure with all the cations octahedrally coordinated to fluorine atoms. Above 10 GPa it transforms reversibly to a new polymorph (C2/c, Z=4), in which the coordination polyhedron of the Zr atoms is a distorted square antiprism, while the Li atoms are in the octahedral coordination. The LiF6 octahedra form layers parallel to (100) that are connected by zig-zag chains of the edge-sharing Zr polyhedra running in the [001] direction. The relative change in volumes per one formula unit for both polymorphs is 6% at 11.8 GPa. The relations to other A2BX6-type structures are discussed. 相似文献
17.
A novel mixed cadmium zirconium cesium oxalate with an open architecture has been synthesized from precipitation methods at room pressure. It crystallizes with an hexagonal symmetry, space group P3112 (no. 151), a=9.105(5) Å, c=23.656(5) Å, V=1698(1) Å3 and Z=3. The structure displays a [CdZr(C2O4)4]2− helicoidal framework built from CdO8 and ZrO8 square-based antiprisms connected through bichelating oxalates, which generates channels along different directions. Cesium cations, hydronium ions and water molecules are located inside the voids of the anionic framework. They exhibit a dynamic disorder which has been further investigated by 1H and 133Cs solid-state NMR. Moreover a phase transition depending both upon ambient temperature and water vapor pressure was evidenced for the title compound. The thermal decomposition has been studied in situ by temperature-dependent X-ray diffraction and thermogravimetry. The final product is a mixture of cadmium oxide, zirconium oxide and cesium carbonate. 相似文献
18.
High tap density Li3V2(PO4)3 cathode materials were synthesized using mixed LiF and LiNO3 as lithium precursors, LiNO3 was used as the sintering agent. Rietveld refinement results show that no impurities phases are detected in products. Particle size distribution and tap density measurement results show that particle size and tap density of products can be increased by the addition of LiNO3. Electrochemical characterization results show that electrochemical performance of products is declined with the increase in contents of LiNO3 in the lithium precursors. Only a small amount of LiNO3 added in the lithium precursors (mole ratio of LiNO3 to LiF is 1:9) can increase the tap density and also retain the good performance of products. Scanning electron microscopy (SEM) images indicate that the samples prepared by mixed lithium precursors present particles agglomerate, and the particle size increased with increase in contents of LiNO3. Large amount of LiNO3 added in the lithium precursors induces the particles to become spheric and smooth, which worsens the performance. The particles obtained with the mole ratio of LiNO3 to LiF in 1:9 show a flake-like shape with a high specific surface area, which leads to good electrochemical performance. 相似文献
19.
Z. Aloui 《Journal of Physics and Chemistry of Solids》2004,65(5):923-926
Chemical preparation and crystal structure are given for a new cyclotetraphosphate: [3,5-(CH3)2C6H3NH3]4P4O12·3H2O. This compound is triclinic P with the following unit-cell parameters: a=8.298(3), b=8.299(3), c=17.242(7)Å, α=97.13(3), β=102.72(3), γ=64.55(3)°, Z=1 and V=1045.2(8)Å3. The crystal structure has been solved and refined to R=0.040 using 6086 independent reflections. The atomic arrangement can be described as layers organization. Layers built by P4O12 ring anions, ammonium groups and water molecules parallel to the plan (001), between which the organic groups are located. Characterization by X-ray diffraction, IR absorption, and thermal analysis are described. 相似文献
20.
Local structural order and temperature-dependent structural variation have been studied in the molecular-based layer ferrimagnet (n-C4H9)4N FeIIFeIII(C2O4)3 by EXAFS and high resolution X-ray powder diffraction. The EXAFS spectra measured at the Fe K-edge are successfully modelled by successive O, C, O and metal shells, showing that even when there is extensive structural disorder due to stacking faults, the local structural order in this class of ferrimagnets is fully retained. In this salt, which shows remarkable negative magnetisation at low temperature (Néel class Q), the EXAFS Debye-Waller factor has a discontinuity at 40 K, corresponding to one found in the magnetisation. At the same temperature there is also a change in the expansion of the lattice as evidenced by the high resolution X-ray powder diffraction. 相似文献