High-resolution electron microscopic study of V6O13

High-resolution structure images of V₆O₁₃ were taken with a 1-MV electron microscope with a cutoff resolution of 0.14 nm. Individual V atom rows, as well as tunnels in the structure, were resolved. The effect of the electronic state on the structure image was investigated by comparing the observed image with the simulated images calculated by assuming various ionized states to the constituent atoms. The neutral-state model interpreted the observed image more satisfactorily than the ionized-state models. A modification of V₆O₁₃ was displayed as an image. In order to interpret the image, a structure model was proposed, which is orthorhombic with lattice parameters a = 1.1922, b = 1.19912, and c = 0.3680 nm and belongs to the space group Cmma. This structure is derived from the V₂O₅ structure by removing all the atoms on every third (001) oxygen atom plane and then introducing crystallographic shear $\text{1}\text{2}\text{[0}\text{1}\text{1}\text{]}$, instead of $\text{1}\text{6}\text{[10}\text{3}\text{]}$ in the case of normal V₆O₁₃.     

Heat capacities of the tungsten oxides WO3, W20O58, W18O49 and WO2

The heat capacities of the tungsten oxides WO₃, W₂₀O₅₈, W₁₈O₄₉ and WO₂ have been measured over the temperature range 340–999 K using differential scanning calorimetry. The lower oxides were prepared by controlled reduction of WO₃ in H₂/H₂O gas atmospheres. Previous calorimetric work on WO₃ is confirmed in the temperature range 340–800 K, however, significant increases in heat capacity were observed in the range 800–999 K prior to the orthorhombic—tetragonal phase transition. W₂₀O₅₈ is shown to behave similarly to WO₃. A high temperture phase change is evident, however, this appears to be complete by 970–990 K. The measured values of heat capacity for W₁₈O₄₉ are in close agreement with estimated data for W₁₈O₄₉. There is no evidence of any phase transitions for this oxide in the temperature range studied. The heat capacity data for WO₂ confirm previous drop calorimetry measurements and give no evidence of any phase changes for WO₂ in the temperature range 340–990 K.     

High-resolution electron microscopy of microsyntactic intergrowth in VnO2n−1

Structural features of the Magnéli phases V_nO_2n?1 were studied by means of high-resolution transmission electron microscopy. Microsyntactic intergrowth on a unit cell scale of several phases with neighboring n were frequently observed in arc-melted specimens, and this was ascribed to the structural compensation of the local composition fluctuation. Also observed were periodic microsyntaxy, where two neighboring phases intergrow periodically, and the crystallographic shear (CS) structure with laterally displaced CS planes. The origin of this microsyntactic intergrowth is discussed from the standpoint of the CS plane interaction.     

Electron microscopy studies of W18O49. 1. Crystals formed by gaseous reduction of WO3

W₁₈O₄₉ samples were prepared by reduction of WO₃ crystals at various temperatures (at about 1170, 1270, and 1370K) by equilibration with a gaseous buffer of controlled oxygen pressure. The samples were studied by high-resolution electron microscopy. The results show that an amorphous phase is an intermediary step in the formation of W₁₈O₄₉. Defects are very rarely observed in as-reduced W₁₈O₄₉, which differs in this respect from other tungsten oxides. Apart from twinning, however, three types of extended defects have been observed occasionally, and these are interpreted and discussed.     

High resolution electron microscopy of TiO2·7Nb2O5

The defect structure of TiO₂·7Nb₂O₅ has been examined at about 0.3 nm resolution in an electron microscope. Under suitable conditions of crystal orientation and objective lens defocus, the contrast in images from very thin fragments can be interpreted directly in terms of structure. Proposed structures for Wadsley intergrowth defects and displacements are confirmed, and new observations of complex fault bands and grain boundaries are described. Microdomains of TiNb₁₄O₃₇, with the structure predicted by Wadsley, have also been found in this material.     

Crystal structure and charge carrier concentration of W18O49

The electrical resistivity of the tungsten oxide, W₁₈O₄₉, is 1.75 · 10^?3 Ω cm along the needle axis. The charge carrier density, as determined by reflectivity measurements, is 1.87 · 10²² cm^?3, thereby indicating that most of the charge carriers are delocalized. Hence the smaller conductivity along the needle axis than that expected for such charge carrier concentrations must be found in the structure, which has been refined using the data collected with an automatic diffractometer. The structure consists of WO₆ and WO₇ polyhedra which are linked along edges and/or corners. However, as the linkage parallel to b takes place only by sharing corners, an anisotropy in the electrical conductivity may be expected. Another explanation for the smaller conductivity may be found in the occurrence of defects such as tunnels in the structure, which may scatter the electrons. The refinement shows that the tungsten positions, determined by Magneli (Arkiv Kemi1, 223 (1950)), are essentially correct; but the positions of the oxygens, especially two of them, differ considerably. This results in one of the tungsten atoms getting an additional coordinating oxygen, the coordination number thereby becoming seven.     

Preparation and electron microscopy of intermediate phases in the interval Ce7O12Ce11O20

Crystals of CeO₂, grown from a flux of sodium tetraborate, were reduced in dry hydrogen to compositions in the interval CeO_1.714CeO_1.818. Selected compositions were studied using a high-resolution electron microscope. The phase CeO_1.714(Ce₇O₁₂) was confirmed to have the same unit cell as does Pr₇O₁₂ and Tb₇O₁₂. CeO_1.818(Ce₁₁O₂₀) was found to be isostructural with Tb₁₁O₂₀. Two new phases in the interval were established unequivocally. One of them, probably Ce₁₉O₃₄, is triclinic with a = 6.627, b = 11.478, c = 10.123, α = 100.9, β = 90.0, and γ = 95.5, has not previously been observed in any rare earth oxide system. Another, Ce₆₂O₁₁₂, appears to be isomorphous with Tb₆₂O₁₁₂. The two intermediate phases previously reported in this interval, Ce₉O₁₆ and Ce₁₀O₁₈, were not observed, nor was Ce₁₂O₂₂. Diffraction evidence also points to three additional phases in the interval not previously seen.     

Structure and antiferroelectric properties of cesium niobate, Cs2Nb4O11

The compound cesium niobate, Cs₂Nb₄O₁₁, is an antiferroelectric, as demonstrated by double hysteresis loops in the electric field versus polarization plot. The crystal structure refinement by X-ray diffraction at both 100 and 297 K shows it to have a centrosymmetric structure in point group mmm and orthorhombic space group Pnna, which is consistent with its antiferroelectric behavior. The 100-K structure data is reported herein. The lattice is comprised of niobium-centered tetrahedra and octahedra connected through shared vertices and edges; cesium atoms occupy channels afforded by the three-dimensional polyhedral network. Antiferroelectricity is produced by antiparallel displacements of niobium atoms along the c-axis at the phase transition temperature of 165 °C. The critical field for onset of ferroelectric behavior in a single-crystal sample is 9.5 kV/cm at room temperature.     

Preparation and comparison of the photoelectronic properties of Sr2Nb2O7 and Ba0.5Sr0.5Nb2O6

The two alkaline earth niobates Sr₂Nb₂O₇ and Ba_0.5Sr_0.5Nb₂O₆ have been prepared, their electronic properties measured, and their photoresponses compared. The indirect band gap in Sr₂Nb₂O₇ is 3.86 eV compared with 3.38 eV for Ba_0.5Sr_0.5Nb₂O₆. Hence, photoanodes composed of Sr₂Nb₂O₇ respond to much less of the “white” light spectrum than those made from Ba_0.5Sr_0.5Nb₂O₆. Nevertheless, their electrical outputs at an anode potential of 0.8 eV with respect to SCE in 0.2 M sodium acetate under “white” xenon arc irradiation of 1.25 W/cm² are comparable.     

Electron microscopy studies of W18O49. 2. Defects and disorder introduced by partial oxidation

W₁₈O₄₉ was oxidized in air at about 500K for different intervals of time. Defects of various kinds, related to structures of higher oxides, were observed. These were a coherent intergrowth of W₁₂O₃₄, {102}, and {103} crystallographic shear, and WO₃-type structures. A new type of TTB structure was also observed as a defect. Its formation mechanism is proposed and discussed.     

Heat capacity, enthalpy and entropy of strontium niobate Sr2Nb2O7 and calcium niobate Ca2Nb2O7

The heat capacity and the enthalpy increments of strontium niobate Sr₂Nb₂O₇ and calcium niobate Ca₂Nb₂O₇ were measured by the relaxation time method (2–300 K), DSC (260–360 K) and drop calorimetry (720–1370 K). Temperature dependencies of the molar heat capacity in the form C_pm = 248.0 + 0.04350T − 3.948 × 10⁶/T² J K⁻¹ mol⁻¹ for Sr₂Nb₂O₇ and C_pm = 257.2 + 0.03621T − 4.434 × 10⁶/T² J K⁻¹ mol⁻¹ for Ca₂Nb₂O₇ were derived by the least-square method from the experimental data. The molar entropies at 298.15 K, S_m°(298.15 K) = 238.5 ± 1.3 J K⁻¹ mol⁻¹ for Sr₂Nb₂O₇ and S_m°(298.15 K) = 212.4 ± 1.2 J K⁻¹ mol⁻¹ for Ca₂Nb₂O₇, were evaluated from the low-temperature heat capacity measurements.     

Some studies on the solid solutions in the systems Sr2Nb2O7Eu2Nb2O7 and Sr2Ta2O7Eu2Ta2O7

Preparation of new solid solutions containing divalent europium have been tried in the systems Eu₂Nb₂O₇Sr₂Nb₂O₇ and Eu₂Ta₂O₇Sr₂Ta₂O₇. These solid solutions described as Eu_2xSr_2(1?x)M₂O₇ (M = Nb and Ta) exist in a pure orthorhombic phase in a limited region of x from 0 to about 0.5. The compounds with compositions close to Eu₂M₂O₇ exist but techniques have not been found to prepare them in pure form.     

Extension of the La7Mo7O30 structural type with La7Nb3W4O30 and La7Ta3W4O30 compounds

Two compounds of formula La₇A₃W₄O₃₀ (with A=Nb and Ta) were prepared by solid-state reaction at 1450 and 1490 °C. They crystallize in the rhombohedric space group R-3 (No. 148), with the hexagonal parameters: , and , . The structure of the materials was analyzed from X-ray, neutron and electronic diffraction. These oxides are isostructural of the reduced molybdenum compound La₇Mo₇O₃₀, which are formed of perovskite rod along [111]. An order between (Nb, Ta) and W is observed.     

Unusual valences and fast electron exchange in MoFe2O4

The distribution of d electrons over the cations in MoFe₂O₄, which is represented by the formal valence assignment, is shown to be complicated by the equilibrium reactionsFe²⁺_B+Fe³⁺_A+Mo³⁺Fe³⁺_B+Fe²⁺_A+Mo⁴⁺We have used thermal treatment to confirm that the Mo are primarily on octahedral sites; Fe_A[Mo_BFe_B]O₄. K-shell absorption and Mössbauer data at T = 423 K > T_c demonstrate that the iron has an average valence near 2.5+ with fast electron transfer (τ_h < 10⁻⁸ sec) on both octahedral and tetrahedral sites. Paramagnetic susceptibility data give a Curie constant C_M = 7.95 ± 0.2 emu/mole and a Weiss constant θ_p = −445 K; magnetometer measurements confirm a compensation point near 160 K. Transport data give a surprisingly high electronic conductivity, but also give an activated mobility similar to that found in AlFe₂O₄ and CrFe₂O₄ where mixed Fe^3+/2+ valences on both A and B sites have been demonstrated. However, a positive Seebeck coefficient and a preexponential factor one order of magnitude higher in MoFe₂O₄ point to involvement of a fraction of the Mo atoms in electronic transport, which would be consistent with the observation of a τ_h < 10⁻⁸ sec on the A sites of a spinel. An energy diagram consistent with these data and other information about the relative redox potentials of these ions in oxides are proposed for this system.     

Evolution and characterization of fluorite-like nano-SrBi2Nb2O9 phase in the SrO-Bi2O3-Nb2O5-Li2B4O7 glass system

Transparent glasses of various compositions in the system (100−x)Li₂B₄O₇−x(SrO-Bi₂O₃-Nb₂O₅) (where x=10, 20, 30, 40, 50 and 60, in molar ratio) were fabricated via splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses. X-ray powder diffraction (XRD) and transmission electron microscopic studies confirmed the amorphous nature of the as-quenched and crystallinity in the heat-treated samples. Fluorite phase formation prior to the perovskite SrBi₂Nb₂O₉ phase was analyzed by both the XRD and high-resolution transmission electron microscopy. Dielectric and the optical properties (transmission, optical band gap and Urbach energy) of these samples have been found to be compositional dependent. Refractive index was measured and compared with the values predicted by Wemple-Didomemenico and Gladstone-Dale relations. The glass nanocomposites comprising nanometer-sized crystallites of fluorite phase were found to be nonlinear optic active.     

Electron microscopy of the perovskite-related phases 4H Ba0.1Sr0.9MnO2.96,5H Ba5Nb4O15 and 6H BaFeO2.79

Lattice images of 4H, 5H, and 6H perovskite polytypes have been obtained. With the electron beam parallel to 10 , the images are correlated directly with the projected structures of the polytypes. Stacking faults were found only in the 6H compound, and consisted of additional cubic close-packed AO₃ layers. Ordering of cation vacancies in the 5H material was evident in the lattice image as an array of white dots.     

Crystal structure determination of BaNd2Ti3O10 using high-resolution electron microscopy

The crystal structure of BaNd₂Ti₃O₁₀ has been determined by electron diffraction and high-resolution electron microscopy. The unit cell is monoclinic with P2₁/m as the most probable space group and not orthorhombic as previously found by X-ray diffraction. However, the structure has an orthorhomic pseudosymmetry, but due to the small Nd³⁺ cations the octahedra are titled and the structure is monoclinic. The cell dimensions based on X-ray data are: a_m = 7.7310 ± 0.0006 Å; b_m = 7.6661 ± 0.0007 Å; c_m = 14.210 ± 0.002 Å; β_m = 97.82 ± 0.01°.     

Crystal structure of Sr3Ir2O7 investigated by transmission electron microscopy

We report on the crystallographic structure of the layered perovskite iridate Sr₃Ir₂O₇, investigated using transmission electron microscopy. The space group was found to be Bbcb (, No. 68 in the International Tables for Crystallography) at 315 K. A very fine twin structure with 90° rotation with respect to the c-axis was observed. The crystal structure at temperatures lower than 285 K, where a phase transition from paramagnetism to weak ferromagnetism is known to occur, was also examined. There was no difference in the extinction rule for the diffraction patterns between the two phases. We conclude that there is no change in the space group for this magnetic transition. There still remains the possibility of a change in the rotation angle of IrO₆ octahedrons and a corresponding change in the interatomic distance between Ir and O, though.     

Les antimonites antiferromagnetiques MnSb2O4 et NiSb2O4

Neutron diffraction has been used to study the variation of antiferromagnetic order in the antimony isomorphous MnSb₂O₄ (T_N ～ 60 K) and NiSb₂O₄ (T_N ～ 46 K). The magnetic moments have been related to the Mn²⁺ and Ni²⁺ spins and magnetostrictive effects have been interpreted. The influence of the method of synthesis is mentioned: polycrystalline MnSb₂O₄ has been obtained from hydrothermal synthesis. Orthorhombic distortions are not connected with magnetic interactions but with structural defects.     

Nonstoichiometry and defects in V2O3

The structural mechanism which accommodates nonstoichiometry in V₂O₃ was investigated by transmission electron microscopy. The existence of distinct diffuse scattering was observed as the boundary of the homogeneity range was approached. The analysis of the diffuse scattering indicates the formation of one-dimensional microdomains in the c direction having a structure similar to VO₂. Orientation relations between V₂O₃ and V₃O₅ (which is formed from V₂O₃ by heat treatment in an oxidizing atmosphere) show that V₃O₅ is formed by redistribution of vanadium ions among the octahedral interstitial sites of common close-packed sublattice consisting of oxygen ions. Possible relations between the present observations and physical properties in nonstoichiometric V₂O_3+x are discussed.