Niobium oxide compounds

The Raman spectra of several niobium oxide compounds,... 

Figure 2 Raman spectra of bulk niobium oxide compounds.

Oxide superconductors have been known since the 1960s. Compounds such as niobium oxide [12034-57-0] NbO, TiO, SrTi02, and AWO, where A is an alkah or alkaline earth cation, were found to be superconducting at 6 K or below. The highest T observed in oxides before 1986 was 13 Kin the perovskite compound BaPb Bi O, x = 0.27. Then in 1986 possible superconductivity at 35 K in the La—Ba—Cu—O compound was discovered (21). The compound composition was later determined to be La 85 A the Y—Ba—Cu—O system was pubUshed in 1987 and reported a transition... 

Tantalum and niobium are added, in the form of carbides, to cemented carbide compositions used in the production of cutting tools. Pure oxides are widely used in the optical industiy as additives and deposits, and in organic synthesis processes as catalysts and promoters [12, 13]. Binary and more complex oxide compounds based on tantalum and niobium form a huge family of ferroelectric materials that have high Curie temperatures, high dielectric permittivity, and piezoelectric, pyroelectric and non-linear optical properties [14-17]. Compounds of this class are used in the production of energy transformers, quantum electronics, piezoelectrics, acoustics, and so on. Two of... 

The synthesis of tantalum and niobium fluoride compounds is, above all, related to the fluorination of metals or oxides. Table 3 presents a thermodynamic analysis of fluorination processes at ambient temperature as performed by Rakov [51, 52]. It is obvious that the fluorination of both metals and oxides of niobium and tantalum can take place even at low temperatures, whereas fluorination using ammonium fluoride and ammonium hydrofluoride can be performed only at higher temperatures. 

The stoichiometry of the prepared compounds depends not only on the composition of the initial mixture, but also on the initial oxide s fluorination activity. Unlike tantalum oxide, fluorination of niobium oxide by an ammonium hydrofluoride melt results in the formation of oxyfluoroniobates, but not of fluoroniobates. During the first step of Nb205 fluorination, (NH4)3NbOF6 is formed according to the following interaction [51, 52, 105, 111, 121, 122] ... 

Nickel and copper containing compounds have been prepared in a similar manner. The phases obtained by the simultaneous fluorination of niobium oxide and other bivalent metal oxides were MHNbOF5, M21,Nb03F3 and M4UNb209, where M11 = Co Ni, Cu [129, 131],... 

Simultaneous fluorination of niobium oxide and oxides of trivalent metals using an ammonium hydrofluoride melt leads only to oxide-type compounds, MinNbC>4 due to low thermal stability of fluoride or oxyfluoride compounds that contain both niobium and trivalent metals. 

One of the most important parameters that defines the structure and stability of inorganic crystals is their stoichiometry - the quantitative relationship between the anions and the cations [134]. Oxygen and fluorine ions, O2 and F, have very similar ionic radii of 1.36 and 1.33 A, respectively. The steric similarity enables isomorphic substitution of oxygen and fluorine ions in the anionic sub-lattice as well as the combination of complex fluoride, oxyfluoride and some oxide compounds in the same system. On the other hand, tantalum or niobium, which are the central atoms in the fluoride and oxyfluoride complexes, have identical ionic radii equal to 0.66 A. Several other cations of transition metals are also sterically similar or even identical to tantalum and niobium, which allows for certain isomorphic substitutions in the cation sublattice. 

The processing of tantalum and niobium begins with the fluorination of the raw material, which always consists of complex oxide compounds containing tantalum and niobium. The main types of tantalum- and niobium-containing minerals are discussed in Chapter 1, and typical compositions of such minerals are presented in Table 2. 

The fluorination process aims to decompose the material and convert tantalum and niobium oxides into complex fluoride compounds to be dissolved in aqueous solutions. The correct and successful performance of the decomposition process requires a clear understanding of the oxygen-fluorine substitution mechanism of the interaction itself. 

Since the fluorination enables to separate components of complex oxide compounds containing tantalum and niobium, it seems that it is applicable for... 

Ammonium hydrofluoride is relatively stable, even in the molten state. In addition to being in contact with tantalum or niobium oxide, the compound will initiate the fluorination process yielding complex tantalum or niobium fluoride compounds. There is no doubt that thermal treatment of the hydroxides at high temperatures and/or at a high temperature rate leads to the enhancement of the defluorination processes, which in turn results in an increase in fluorine content of the final oxides. 

Another promising method for the preparation of tantalum and niobium oxide precursors involves the precipitation of peroxoniobate and peroxotantalate compounds. 

Thermal treatment of the compounds obtained from the hydrolysis leads to their decomposition, yielding tantalum or niobium oxides and gaseous oxygen. The processes of thermal decomposition are given as follows [512] ... 

At temperatures above 45°C, however, (NRj MOs compounds decompose yielding gaseous ammonia, NH3, and oxygen as well as tantalum or niobium oxides ... 

To avoid explosion, the compounds can be decomposed via hydrolysis in liquid solution. Ultra-fine particles are obtained in water and water-ammonia media. Hydrolysis in HC1 and HN03 solutions leads to the precipitation of an agglomerated powder of both tantalum and niobium oxides. Agglomerates obtained are up to 12 pm in diameter, while the estimated diameter of the smallest ciystalline particles varies in the range of 0.01-0.5 pm [512]. 

S Fluorination of tantalum and niobium oxides by hydrofluorides of ammonium or alkali metals yields fluorotantalate or monooxy-fluoroniobate compounds. Fluorination of tantalum or niobium oxides in the presence of oxides of other metals yields complex fluoride compounds containing both tantalum or niobium and added metals. 

Modem refining technology uses tantalum and niobium fluoride compounds, and includes fluorination of raw material, separation and purification of tantalum and niobium by liquid-liquid extraction from such fluoride solutions. Preparation of additional products and by-products is also related to the treatment of fluoride solutions oxide production is based on the hydrolysis of tantalum and niobium fluorides into hydroxides production of potassium fluorotantalate (K - salt) requires the precipitation of fine crystals and finishing avoiding hydrolysis. Tantalum metal production is related to the chemistry of fluoride melts and is performed by sodium reduction of fluoride melts. Thus, the refining technology of tantalum and niobium involves work with tantalum and niobium fluoride compounds in solid, dissolved and molten states. 

Overview of the Chemistry of Niobium Chloride and Niobium Oxide Cluster Compounds 83... 

In contrast to chloride compounds, niobium oxides have a VEC of 14 electrons, due to an overall anti-bonding character of the a2u state, caused by a stronger Nb-O anti-bonding contribution. In some cases, the VEC cannot be determined unambiguously due to the uncertainty in the electron distribution between the clusters and additional niobium atoms present in the majority of the structures. The 14-electron compounds exhibit semiconducting properties and weak temperature-independent paramagnetism. Unlike niobium chlorides, the oxides do not exhibit a correlation between the electronic configuration and intra-cluster bond distances. 

The results of studies of niobates, tantalates, and mixed oxide compounds containing niobium(v) or tantalum(v) are summarized in Table 6. 

T able 6 Niobates, tan talates and mixed oxide compounds containing niobium (v)... 

Metal-rich binary systems (also referred to as metallic sub-oxides), however, exhibited slightly higher transition temperatures than the stoichiometric oxide compounds, but for these interstitials the Tc was never any higher than that of the superconducting metal. For example, Nb0 94O 06 was observed to have a Tc of only 9.02 K. Other interstitial niobium oxides had transition temperatures to 9.23 K, and similar tantalum oxides showed a maximum Tc value of 4.18 K. 

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