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1.
Some New Nb2O5 Modifications, Metastable Oxidation Products of NbOx Phases (2.4 <x< 2.5) The blue-black NbOx Phases (2.4 <x< 2.5) are oxidized metastable in air to colourless (partly yellowish) Nb2O5 modifications already at temperatures about 200°C. At further heating stepwise and monotropic phase transformations are noticed; as final product the well known stable H modification appears. Some of the 15 new metastable Nb2O5 modifications obtained in this way appear in series. Therewith Nb12O29 (orh. and mon.) changes into two each, Nb22O54 and Nb47O116 into four each, Nb25O62 into two and Nb53O132 into one Nb2O5 phase. During oxidation and the following phase transformations at higher temperatures both the character of single crystal and the principle of building (block structure) of the starting material are maintained. This is especially proven from the electronoptical and X-ray investigations of Nb12O29 (orh. and mon.) and its products obtained by oxidation and further heating.  相似文献   

2.
Contributions to the Investigation of Inorganic Non-Stoichiometric Compounds. XLIV. New Electron Microscopic Investigation of the Metastable Nb2O5 Modification Ox1C Oxidation of the blue-black NbOx phases (2.4 < x < 2.5) in air or a diluted oxygen atmosphere leads all together to 21 metastable colourless (partly yellowish) Nb2O5 modifications. These can be described as compounds having block structures like the NbOx phases themselves. At 200°C the oxidation process to the metastable phases proceeds quite slowly; at higher temperatures all polymorphs are finally transformed to H? Nb2O5. Electron diffraction patterns of the polymorph, which can be obtained by heating crystals of Nb22O54 in atmospheric environment at about 200°C (Ox1C), show extra spots in the c* direction compared to Nb22O54. This oxidation product is quite sensitive to the focused electron beam, so the reduction of the crystals back to Nb22O54 can only be avoided by reducing its intensity. Finally HRTEM images of thin crystal areas showing a superstructure were obtained. Comparing those characteristic image contrasts to calculated images of different point defect models one finds, that mainly one point defect is responsible for the superstructure. By migration of one Niobium atom two interstitial oxygen sites are created. So a structure model can be achieved leading to the formula Nb44O110.  相似文献   

3.
Die Reduktion der metastabilen Oxydationsprodukte der NbOx-Phasen (2,4 < x < 2,5) mit H2O/H2-Mischungen wurde untersucht. Bei niedrigerer Temperatur (≈300°C) ist die Reduktionswirkung noch gering, sie nimmt mit steigender Temperatur beträchtlich zu. Dabei zeigen die Oxydationsprodukte der Zusammensetzung Nb2O5 ein gewisses ?Erinnerungsvermögen”?; in allen Fällen läft die Reduktion bis zu den ursprünglichen NbOx-Phasen zurück. Man gelangt bei um so niedrigerer Reduktionstemperatur zur Zusammensetzung x des jeweiligen Ausgangsprodukts NbOx zurück, je kleiner die Differenz 2,50?x ist. Bemerkenswert ist, daß die Rückreduktion zum monoklinen Nb12O29 über eine Zwischenstufe der Zusammensetzung 2,439?2,447 O/Nb verläuft. An dieser Stelle liegt eine neue, metastabile NbOx-Phase mit einem charakteristischen Guinierdiagramm vor. Contributions on the Investigation of Inorganic Non-stoichiometric Compounds. XII. Reduction of Metastable Nb2O5 Modifications, Oxidation Products of NbOx Phases (2.4 < x < 2.5) The reduction of metastable oxidation products of the NbOx phases (2.4 < x < 2.5) by H2O/H2 mixtures was investigated. At lower temperatures (ca 300°C) the effect of the reduction was slight. It increased considerably with rising temperature. Samples oxidized to the composition Nb2O5 showed a certain “memory of structure”. The original NbOx phases can be obtained in all cases from the oxidized products. The smaller the difference 2.50?x the lower the reaction temperature at which the composition x of the corresponding starting material NbOx is regained. It is remarkable that the re-reduction to the monoclinic Nb12O29 proceeds by way of the intermediate composition 2.439?2.447 O/Nb. At this ratio O/Nb a new metastable NbOx phase with a characteristic x-ray diagram exists.  相似文献   

4.
A metastable Nb2O5 modification, obtained by fast and complete oxidation of the monoclinic form of Nb12O29, is transformed into the stable HNb2O5, modification by heating in air above 700° C whereas the reduction of the metastable Nb2O5 modification at comparable temperatures leads to the compound NbO2.44 which is also metastable. The electron optical investigation shows that the reaction products have “block structures” which are heavily disordered.Typical structural defects recognizable in the products of both types of reactions are a “zipper-like” sequence of blocks, connections with R-tyue tunnels and characteristic structural elements of the initial structure of the metastable Nb2O5 modification. An irregular sequence of structural elements of Nb12O29 and Nb25O62 is characteristic of NbO2.44.  相似文献   

5.
Contributions to the Investigation of Inorganic Non-stoichiometric Compounds. XIII. Oxidation Products of Monoclinic Nb12O29, Electron Optical Investigation The electron optical investigation shows that the starting material Nb12O29(mon.) is well ordered and that the oxidation products Nb2O5(Ox1BI) and Nb2O5(Ox2BI) have different structures. Nb2O5(Ox1BI) has a similar structure as Nb12O29(mon.), however differs from the latter by characteristic point defects, which in the electron microscope easily disappear by reduction. Nb2O5(Ox2BI) has not a well ordered structure; characteristic are rows of [2×n]-blocks which on the average are separated by five [3×n]-blocks. The average block length is n = 4 octahedra. The observed composition O/Nb = 2.500 can be explained by a structure model with unoccupied tetrahedral sites of Nb.  相似文献   

6.
Thermochemical Investigations in the System V/Nb/O. II. Chemical Transport in the Region V2O5/Nb2O5/VO2/NbO2 Transport experiments were used to support the phase relationships of the V2O5/Nb2O5/VO2/NbO2 system, which were established by annealing experiments of powder mixtures. The phase relations were studied in the NbO2-rich region of the system by means of X-ray and ESMA methods. The NbO2-rich section is characterized by the following two phase and three phase regions: Two phase region: V3Nb9O29/rutile mixed crystal V1?xNbxO2 Two phase region: BI-mixed crystal/VxNb1?xO2 Three phase region: V3Nb9O29/solubility limit LG1 (V1?xNbxO2)/BI-mixed crystal Three phase region: solubility limit LG1 (V1?xNbxO2)/BI-mixed crystal/solubility limit LG2 (VxNb1?xO2). The composition of the solubility limits LG1 and LG2 was ascertained by means of ESMA-investigation: LG1: 57.5 ± 5 mol% NbO2/43.5 ± 5 mol% VO2 LG2: 22.5 ± 5 mol% NbO2/78.5 ± 5 mol% VO2?  相似文献   

7.
Contributions to the Investigation of Inorganic Non-stoichiometric Compounds. XXX. High Resolution Electron Microscopy Investigation of Metastable Niobium Tungsten Oxides. Comparison with Computer Simulated Images . Starting with solid solution series (Nb, W)Ox, where WO3 + NbO2 was substituted for Nb2O5, a gentle oxidation leads from the original block sizes of [3 × 4], [4 × 4], [4 × 5] or [5 × 5] octahedra to a doubling of blocks in the new ternary oxides, e. g. 2 × [5 × 5] → [5 × 10]. As HRTEM of the oxidation products revealed, these new larger blocks are connected in a special way including so-called “L-type-tunnels”. Using a LaB6-cathode with our electron microscope, we now for the first time can directly see the positions of these tunnels.  相似文献   

8.
Chemical transport reactions with HgCl2 as transport agent were used to prepare crystals (l = 1–2 mm) of the phases Nb22O54, Nb47O116, Nb25O62 and Nb53O132. Due to the high temperature applied (T ≈ 1250 to 1280°C) a new NbOx phase was formed. Without a transport agent the temperature had to be even higher (≈ 1350°C). The complicated block structure of the new phase corresponding to the ideal composition Nb25O62 was revealed by HRTEM. The structure visible by this method remained unchanged on oxidation to Nb2O5.  相似文献   

9.
Contributions to the Investigation of Inorganic Non-stoichiometric Compounds. XXIII. New Building Elements of Metastable Block Structures in the System Nb2O5/WO3, Investigation by High Resolution Electron Microscopy Under equilibrium conditions the region of existence of block structures in the system Nb2O5/WO3 ends with a phase having the composition 9 Nb2O5:8 WO3 corresponding to values of O/ΣM = 2.654 (M = Nb, W) and W/Nb = 0.44. We now investigated to what extent this region of existence of block structures could be expanded towards a higher content of WO3. Starting out from the known phases Nb2O5:WO3 = 6:1, 7:3, 8:5 and 9:8 in which Nb and W are present in their maximum states of oxidation, we obtained series of solid solutions by substituting W for Nb. Thereby the initial structure (block sizes [3×4], [4×4], [4×5] and [5×5] M–O-octahedra) and also the respective O/ΣM remained unchanged. Upon complete oxidation of these series of solid solutions which led into reduced systems (e. g. NbO2/Nb2O5/WO3) at ~500°C metastable products were gained, which also have block structures. Corresponding to the extent of substitution of the initial series of solid solution and the resulting ratio O/ΣM of the oxidation products the new structures are to a wide extent built of large blocks that have an extension (at maximum [5X15] M–O-octahedra) we have not observed so far. These blocks could be seen using high resolution transmission electron microscopy. The investigations on the oxidation products of the solid solutions of thc 8:5 and 9:8 series and illso it model concerning the mechanism of oxidation are described.  相似文献   

10.
Na(V3?xNbx)Nb6O14 — A Novel Oxoniobate with [Nb6O12] and [M2O9] Clusters Goldcolored single crystals and black powders of Na(V3?xNbx)Nb6O14 have been prepared by heating a pellet containing a mixture of NaNbO3, NbO2, NbO, VO2 and NaF or Na2B4O7 (as mineralizers) at 900°C in a sealed gold capsule. The analytically determined Nb : V ratio is 5 : 1 and means that x is about 1.5. The compound crystallizes in P63/m with a = 603.4(1), c = 1807.9(5) pm and Z = 3. The crystal structure can be described in terms of common close packing of sheets of O and Na atoms together with Nb6 octahedra. Characteristic building groups of the new structure type are [Nb6O12] clusters, [M2O9] clusters and NbO5 bipyramids. V atoms are distributed only on the positions of the Nb atoms within the trigonal bipyramids or the [M2O9] clusters. The [Nb6O12] clusters show characteristicaly short distances dNb-Nb = 279.4 and 281.3 pm, respectively. In the [M2O9] units, which are built from two MO6 octahedra that share a common face, V or Nb atoms form M–M dumbbells with dM–M = 255.9 pm. The electronic structure is discussed using Extended Hückel calculations.  相似文献   

11.
The thermal decomposition of lithium-inserted NbO2F was studied by differential scanning calorimetry. Samples of LixNbO2F (Ox ⩽ 1.8) were heated to 800 and 950 K. The thermograms revealed that decomposition started within the temperature range 640–780 K followed by a second step at approximately 900 K. The products were characterized by X-ray powder diffraction and electron diffraction patterns and by high resolution electron microscopy. The following phases were obtained at 800 K: LiF, NbO2F, the low pressure form of Nb3O7F, and lithium-enriched forms of PNb2O5, NbO2 and LiNbO3. At 950 K, NbO2F disappeared, and LiNb3O8 and the high pressure form of Nb3O7F coexisted with the other phases obtained at 800 K. The formation of structures built up of approximately hexagonally close-packed anion arrangements is discussed, as well as the role of lithium as a stabilizing component.  相似文献   

12.
Contributions to the Investigation of Inorganic Non-stoichiometric Compounds. XIV. Oxidation Products of Orthorhombic Nb12O29, Electron Optical Investigation An electron optical investigation shows that the orthorhombic starting material Nb12O29(BII) is well ordered. The oxidation products Nb2O5(Ox1BII) and Nb2O5(Ox2BII) are different from each other in structures as well as in their reactions. Nb2O5(Ox1BII) is unstable in the electron beam and differs from BII by characteristic point-defects. The radiation load can lead to the reduction to BII or to a transition into a defect structure with R-type-tunnels. The not well ordered structure of Nb2O5(Ox2BII) is stable in the electron beam. Characteristic is the sequence of [2×5] and [3×4] blocks, the latter in two different orientations. The observed composition O/Nb = 2.500 can be described by the present structural modell assuming vacant niobium tetrahedral sites. The large structural differences between the oxidation products of the orthorhombic and the monoclinic Nb12O29 are remarkable.  相似文献   

13.
Polymorphism of SrTa2O6 Orthorhombic SrTa2O6 is a new low temperature modification related to orthorhombic CaTa2O6. SrTa2O6(orh.) was obtained when the wellknown modification SrTa2O6(TTB) which is related to the tetragonal tungsten bronzes was heated in the presence of a transporting agent (chlorine) or a mineralizer (melt of B2O3) at temperatures below 1150°C. It could be prepared by the reaction of a 1:1 mixture of Sr(NO3)2 or SrCO3 with Ta2O5 in a sealed quartz glass tube as well. SrTa2O6(orh.) also occurred as an intermediate phase of the reaction of the corresponding 1:2 mixture at temperatures below 900°C (e. g. 840°C). Indexing of Guinier powder patterns led to the following unit cell: a = 11.006 Å, b = 7.638 Å, c = 5.622 Å. At temperatures above 1220°C SrTa2O6(orh.) changes (in air) to SrTa2O6(TTB). A reversal of this transition could not be achieved without the presence of a mineralizer or a transporting agent. CaxSr1?xTa2O6 solid solutions of the low temperature form could not definitely be established. However, at 1300°C solid TTB solutions of CaxSr1?xTa2O6 were formed. For x > 0.05 the TTB unit cells are orthorhombically distorted. For x ≥ 0.85 the x-ray powder patterns of the solid solutions looked like the one of CaTa2O6(orh.) and no TTB-structure was observed at 1300°C.  相似文献   

14.
A nonstoichiometric block structure oxide, Nb22O54 (NbO2.455), with monoclinic symmetry was characterized following in situ oxidation in a controlled environment, high-resolution electron microscope. This instrument is based on a JEOL 4000EX electron microscope equipped with a gas reaction cell. The oxidation reaction was carried out by introducing ca. 20 mb of oxygen gas to the specimen region and heating the specimen by means of a focussed electron beam. The resulting structures obtained after the oxidation reaction were not totally homogeneous. (1) Mainly microdomains of Nb10O25 were found, which consists of [3×3] blocks of octahedra linked through tetrahedrally coordinated sites—such a structure is isostructural with PNb9O25. Nb10O25 seems to be a metastable phase in the Nb-O system, and was found here for the first time as extended domains. (2) A highly disordered structure was observed in some areas of the crystal after oxidation, with a corresponding electron diffraction pattern similar to an “X” phase interpreted as two-dimensionally disordered H-Nb2O5. Very clear lamellar defects were also found after oxidation.  相似文献   

15.
On Some New Oxide Fluoride Phases of Tetragonal Tungsten Bronze Structure Six new oxide fluorides of tetragonal tungsten bronze type structure have been obtained by partial substitution of oxygen by fluorine in the ABCNb5O15 compounds (A = Ca, Sr, Ba; B = Ca, Sr, Ba; C = Na, K): CaK2Nb5O14F, SrK2Nb5O14F, SrKNaNb5O14F, BaK2Nb5O14F, BaKNaNb5O14F and BaNa2Nb5O14F. An investigation on Sr2?xK1+xNb5O15?xFx and Ba2?xNa1+xNb5O15?xFx solid solutions characterizes ferroelectric behaviour. Replacement of oxygen by fluorine decreases the Curie temperature, but for a small oxygenfluorine substitution rate an increase of the dielectric constant is observed.  相似文献   

16.
Phase relationships in TiNb2O7 and Ti2Nb10O29 reductions at 1400°C were investigated by means of X-ray microanalytical electron microscopy and high-resolution transmission electron microscopy (TEM). Compositions of phases present in equilibrium were obtained by applying thin-crystal approximation by which NbTi ratios in different phases were determined; their oxygen content was inferred from structural considerations. In this manner, phase relationships in that portion of the TiO2NbO2NbO2.5 equilibrium diagram with 2.417 ≥ x (in MeOx) ≥ 2 were defined. Data obtained, in combination with high-resolution electron microscopy observations, confirmed that the reduction reaction, in part, is a heterogeneous process controlled by outward diffusion of both metal and oxygen atoms. Recombination of the diffused particles leads to the formation of separate crystals. The original block structure phase undergoes transformation in a quasihomogeneous manner either to an isomorphous phase in the binary NbO system or to a structurally related lower composition oxide. A new superstructure Me25O60(Ti7.16Nb42.84O120) has been detected as an intermediate metastable phase, generated in the reduction of TiNb2O7 to stable Me12O29(Ti1.53Nb10.47O29) and MeO2(Ti0.52Nb0.48O2) phases. Consideration of phase relationships among Me25O60, Me12O29, and MeO2 suggests a chemical mechanism for the reaction concerned. The Me25O60 superstructure has a monoclinic symmetry with cell parameters a = 19.0 Å, b = 3.8 Å, c = 26.6 Å, α = 90°, β = 90°, γ = 78.5°, as determined from the structure image calculations.  相似文献   

17.
Interpretation of the reduction path of TiNb24O62 is complicated by uncertainty about both the stoichiometric ranges of the possible block structures and the formation of TiNb solid solutions. Reduction forms the Me12O29 phase, probably from the outset, with an initial composition close to Ti2Nb10O29, thereby rapidly depleting the Me25O62 phase of titanium. When log pO2 (atm) has dropped to ?9.62, a phase approximately Ti0.95Nb11.05O29 is in equilibrium with titanium-free Nb25O62 at its lower composition limit (NbO2.471). Nb25O62 is then reduced to Nb47O116 without change in the Me12O29. At ?9.62>log pO2 (atm) > ?10.0, niobium is transferred to the Me12O29 phase and Nb47O116 is consumed. A second univariant equilibrium is set up as Nb47O116 is reduced to Nb22O54. This is consumed in turn, to increase the niobium content of the Me12O29 until, at log pO2 close to ?10.8, monophasic Ti0.48Nb11.52O29 is formed. The (Ti,Nb)O2 solid solution then appears and the final product is Ti0.04Nb0.96O2, with the rutile superstructure cell reported for NbO2.  相似文献   

18.
Na3Al2Nb34O64 and Na (Si, Nb) Nb10O19. Cluster Compounds with Isolated Nb6-Octahedra Hexagonal ormolu coloured plates of the new compounds Na3Al2Nb34O64 ( I ) and Na(Si, Nb)Nb10O19 ( II ) were prepared by heating pellets of NaF, Al2O3, NbO2 and NbO (3:1:8:2) and NaF, NbO2 and NbO (1:4:2), respectively, at approx. 850°C. I was contained in a sealed gold capsule, II in a silica tube. The Si incorporated in II originates from the container material. Both compounds crystallize in R 3 , I with a = 784.4(1), c = 7065(1) pm, Z = 3 and II with a = 784.1(1), c = 4221.8(5) pm, Z = 6. I and II represent new structure types. They contain the same characteristic structural units, namely discrete Nb6O12 clusters (dNb–Nb = 283 ± 4 pm) and Nb2O10 units with Nb–Nb dumbells (dNb–Nb ≈? 269 pm) in edgesharing coordination octahedra. In addition NbO6 octahedra containing Nb in the oxidation state + 5 and NaO12 cube-octahedra occur in both compounds besides AlO4 and SiO4 tetrahedra in I and II , respectively. The structures can be described in terms of a common closepacking of O and Na atoms together with Nb6 octahedra.  相似文献   

19.
In this paper, the electronic structures of NbO2 and Nb2O5 are theoretically and experimentally analyzed. The oxides in the samples are mainly consisted of NbO2 and NbO, whereas the outmost layer of the samples is NbO2. After exposure to air, the outermost layer on all niobium samples is Nb2O5. The photoelectrons from the first 2–4 Å contribute to the spectra, so the valence band structure of NbO2 and Nb2O5 can be confirmed from ultraviolet photoelectron spectroscopy (UPS). By comparing the UPS with density of state results, the electronic structure of NbO2 and Nb2O5 can be distinguished from each other, and then the electronic structure was deconvoluted into several electronic states. The agreement between experimental result and theory is, in the best case, satisfactory. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

20.
The IR spectrum of V4Nb18O55 has been compared with the IR spectra of selected niobates of known structures to show structural relations between these compounds. This comparison shows that V4Nb18O55 has crystal structure related to T-Nb2O5, W16Nb18O94 and Ba2NaNb5O15. On the other hand, reaction between V2O5 and H-Nb2O5 yields a solid solution of V2O5 in VNb9O25. It has been proposed two models of synthesized solid solution with formulas V1+xNb9-xO25 or V1+xNb9O25+5x/2.Independently of Nb2O5 polymorph, used for synthesis, the metastable compound VNbO5 cannot be synthesized in the solid state below 650°C   相似文献   

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