Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XXIII. Neue Bauelemente bei metastabilen Blockstrukturen im System Nb2O5/WO3 Elektronenmikroskopische Untersuchung in Hochauflösung

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.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XIV. Oxydationsprodukte von orthorhombischem Nb12O29 Elektronenoptische Untersuchung

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.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XIII. Oxydationsprodukte von monoklinem Nb12O29 Elektronenoptische Untersuchung

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.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XX. Metastabile Oxydation von Mischkristallreihen — ein Zugang zu W-reichen Blockstrukturen im System Nb2O5/WO3

Contributions to the Investigation of Inorganic Non-stoichiometric Compounds. XX. Metastable Oxidation of a Series of Solid Solutions — an Access to W-rich Block Structures in the System Nb₂O₅/WO₃ The characteristical region of existence of block structures with building elements that are limited in size in two directions ends in the system Nb₂O₅/WO₃, as was shown by previous investigations, under conditions of equilibrium at a maximum value of 2.654 O/ΣM. For the occurring phases with the ratios Nb₂O₅: WO₃ = 6:1, = 7:3, = 8:5 and = 9:8 as well we now were successful in substituting W for Nb. The original block structure and the corresponding ratio O/ΣM were preserved. The “9:8”-phase W_4/4[Nb₁₈W₇O₆₉], for example, forms solid solutions W_4/4[Nb₁₁W₁₄O₆₉] leaving the size of the building elements ([5 times; 5] blocks) unchanged. Hereby the ratio W/Nb is drastically enhanced from 0.444 to 1.364. By metastable oxidation of these solid solutions at temperatures of about 500°C, for instance in air, one comes back to the system Nb₂O₅/WO₃. In this way the region of existence of block structures could be expanded far beyond the limit at 2.654 O/ΣM to higher W/Nb values.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XLIV. Neue elektronenmikroskopische Untersuchung zur Realstruktur der metastabilen Nb2O5-Modifikation Ox1C

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 NbO_x 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 NbO_x 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.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XXXV [1, 2]. Reduktion von Blockstrukturen im Elektronenmikroskop - in situ - Beobachtung einer topotaktischen Reaktion im System Nb2O5/WO3

Contributions to the investigation of inorganic non-stoichiometric compounds. XXXV. Reduction of block structures by heating with the electron beam -- in situ investigation of a topotactic reaction in the system Nb₂O₅/WO₃ In quenched samples with the starting composition Nb₂O₅: WO₃ ≈? 1:1 we observed by using high resolution transmission electron microscopy (HRTEM) areas with large blocks of [5 × n] M–O octahedra (n = 6, 7, 8, 9; M = Nb, W). Upon heating with the electron beam a structural change occurs as an in-situ reaction. The original [5 × n] blocks are splitting up mostly in two [5 × 1/2n] blocks (n even) or when n is odd into one block with [5 × 1/2(n + 1)] and one with [5 × 1/2(n--1)] M–O octahedra. The splitting up of blocks forces some corner sharing octahedra to become edge sharing octahedra. This change of connections constitutes a partial reduction of the sample.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XXXIV. Fehlgeordnete Strukturen mit Großen Blöcken im System Nb2O5/WO3 — Elektronenmikroskopische Untersuchung

Contributions to the Investigation of Inorganic Non-stoichiometric Compounds. XXXIV. Disordered Structures Consisting of Large Blocks in the System Nb₂O₅/WO₃. An Electronmicroscopical Investigation The real structures of samples which have been prepared by quenching procedures using the composition Nb₂O₅: WO₃ = 10:11 are in most cases heavily disordered; some areas show extremly large blocks. The electron microscopic investigation revealed that the blocks consist of [n × m] M? O octahedra and have edge lengths of n = 5 to 14 and of m = 5 to 13 and in one case we even found [n × m] = [5 × 32]. In comparison, samples that were heated below the melting point for a longer time, showed a less disordered structure. Block sizes of [5 × 6] to [5 × 9] in a matrix of [5 × 5] blocks could be observed.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer verbindungen. XV. Weitere metastabile Nb2O5-Modifikationen,Produkte der langsamen Oxydation von NbOx-Phasen

Contributions to the Investigation of Inorganic Non-stoichiometric Compounds. XV. Some Further Metastable Nb₂O₅-Modifications, Products of the Slow Oxidation of the NbO_x Phases If in contrast to previous investigations the blue-black NbO_x phases (2.4 < x < 2.5) are not oxidized in air, but in a rarefied oxygen atmosphere or with steam, five further metastable Nb₂O₅ forms can be obtained in addition to the numerous already known Nb₂O₅ modifications. Nb₁₂O₂₉ (mon. and orh.) and Nb₄₇O₁₁₆ lead to one new Nb₂O₅ form each. Nb₂₂O₅₄ yields two new Nb₂O₅ modifications. It can be deduced from the thermal behaviour that in addition to unexspected transitions between the known and the new metastable modifications in all cases H-Nb₂O₅ appears as final product at high temperature. The electron optical investigation of the new oxidation products of Nb₁₂O₂₉ (mon. and orh.) shows that their structures are determined by R-type tunnels as the characteristic structure element. By this they clearly differ from the already known oxidation products. With this for the first time sodium free niobium oxide structures occur whose structural concept is substantially shaped by R-type tunnels which are known from NaNb₁₃O₃₃.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XLIII. Darstellung und elektronenmikroskopische Untersuchung von (Cr,Nb)12O29

Contributions to the Investigation of Inorganic Non-Stoichiometric Compounds. XLIII. Preparation and Electron Microscopic Investigation of (Cr, Nb)₁₂O₂₉ Transport experiments in the system Cr/Nb/O yielded the compound (Cr, Nb)₁₂O₂₉ as crystalline green needles. The lattice parameters of the monoclinic cell are a = 31.162(8) Å, b = 3.8324(6) Å, c = 20.579(6) Å, β = 113.22(3)°. (Cr, Nb)₁₂O₂₉ is isotypic with monoclinic Nb₁₂O₂₉ as shown by Guinier diagrams and high resolution transmission electron microscopy. Characteristic structural building elements are [3 × 4]-blocks which are columnar sections from the ReO₃ structure. In the real structure one finds numerous defects. Under the influence of the electron beam we observed reversible changes of contrast which indicates that the positions of the M-particles (M = Cr, Nb) have shifted.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XXVI. Darstellung und elektronenmikroskopische Untersuchung von V16W9O65

Contributions to the Investigation of Inorganic Non-Stoichiometric Compounds. XXVI. Preparation and Electron Optical Investigation of V₁₆W₉O₆₅ The mixed vanadium-tungsten oxide with the composition V₁₆W₉O₆₅ (V_0.64W_0.36O_2.60) was prepared by chemical transport reactions. The dimensions of the tetragonal unit cell are a = 25.074 Å; c = 3,714 Å, determined by the X-ray-Guinier method. The probable space group is 14/mmm. The electron microscopical investigation directly reveals the block structure of the new compound. The blocks are made up of [5 × 5 × ∞] corner sharing M-O-octahedra. Other unusual block sizes are observed as defects. The blocks are connected by common corners like in the related compound (V_0.65W_0.35)₂O₅ with [4 × 4 × ∞] blocks.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XXXVIII. Quaternäre Nioboxidfluoride des Cadmiums und Mangans mit LiNb6O15F-Struktur

Contributions to the Investigation of Inorganic Non-stoichiometric Compounds. XXXVIII. Quaternary Niobium Oxide Fluorides of Cadmium and Manganese with LiNb₆O₁₅F structure For the first time we observed an occupation of the canals in the LiNb₆O₁₅F structure by bivalent metal ions. We obtained wellshaped crystals of M_xNb₆(O, F)₁₆ (M ? Cd, Mn) by heating mixtures of MF₂ and Nb₂O₅. Cd_xNb₆(O, F)₁₆ (Mn_xNb₆(O, F)₁₆) crystallizes in the orthorhombic space group Pmma with a = 16.686 (16.677), b = 3.951 (3.952) and c = 8.907 (8.902) Å. The structure of the cadmium compound was refined to give R = 3.33% and R_w = 2.90%. The resulting formula for the investigated crystal was Cd_0.25Nb₆O_14.5F_1.5.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XXX. Elektronenmikroskopische Untersuchung in Hochauflösung an metastabilen Niob-Wolfram-Oxiden Vergleich mit der rechnerischen Simultation

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)O_x, 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.     

Beiträge zur Untersuchung anorganischer nichstöchiometrischer Verbindungen. X. Zum thermischen Verhalten metastabiler H-Ta2O5-Varianten im System Ta2O5-TiO2

Contributions to the study of Inorganic Nonstoichiometric Compounds. X. Thermal Behaviour of Metastable H-Ta₂O₅ Variants in the system Ta₂O₅- TiO₂ Quenched samples of the high temperature form of Ta₂O₅ with Ti contents of 0 until 6.7 at-% (ΣMe = 100%) were investigated in the metastable region from 20 to 1400°C with a continuously registrating guinier-camera which was equiped with a special sample heating device: There are 3 roomtemperature-phases: H(triclinic), H1(monoclinic), H2(monoclinic), and 3 high temperature phases: H′ (triclinic), H2′ (monoclinic) and H3(tetragonal). In the regions between H and H1 as well as H1 and H2 diagrams of both phases could be observed together on the X-ray photograph; these regions disappeare at temperatures higher than approximately 310°C. With increasing temperatures the following phase transitions occure: H → H′ → H2′ → H3, H1 → H → H2′ → H3, H2 → H1 → H2′ → H3, H2 → H2′ → H3. Electronmicroscopic investigations of a sample with 6.7 at-% Ti gave no indication to the existence of “shear planes”. By means of the present results various possibilities of the incorporation of Ti in the H-Ta₂O₅ lattice are discussed.