Tantalum-containing systems

Iuchi and Matsuchima [305] and Zui Bin-Sin, Lushnaya and Konstantinov [306] investigated the melting diagram of the ternary system K2TaF7 - KF -KC1 and observed the compound K3TaF7Cl along with its initial components. 

Kovalev, Kartsev, Ioffe and Leonov [310] investigated melting in the ternary system K2TaF7 - KF - NaF, which is also characterized by the formation of K3TaF8. 

An analysis of the melting diagram led to the conclusion that, in fluoride and fluoride-chloride melts, tantalum forms the complex ions TaFg3 or TaF7Cl3, respectively [37, 306], 

Projections of the crystallization surfaces of the ternary systems K2TaF7 - KF - NaF (bottom). Reproduced from [310], F. V. Kovalev, V. E. Kartsev, V. M. Ioffe, M. E. Leonov, Zh. Neorg. Khim. 18 (1973) 1352, Copyright 1973, with permission of Nauka (Russian Academy of Sciences) publishing. 

It was assumed that tantalum, when added to the melt in the form of potassium heptafluorotantalate, K2TaF7, interacts with KF or KC1 to form a compound with an increased tantalum coordination number of up to eight. The compound is present in the melt in its dissociated form, yielding potassium ions and octa-coordinated complexes of tantalum, namely TaFg3 or TaF7Cl3  

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The same analysis of the properties of niobium-containing melts [316, 317] shows that the KF - NbFs system exhibits behavior similar to that of the tantalum-containing melts. 

Table 55 presents the results discussed above. Fluoride melts containing tantalum contain two types of complex ions, namely TaF6 and TaF72 . The equilibrium between the complexes depends on the concentration of fluoride ions in the system, but mostly upon the nature of the outer-sphere cations. The complex ionic structure of the melts can be adjusted by adding cations with a certain polarization potential. For instance, the presence of low polarization potential cations, such as cesium, leads primarily to the formation of TaF72 complexes, while the addition of cations with relatively high polarization potentials, such as lithium or sodium, shifts the equilibrium towards the formation of TaF6 ions. 

Phase transition irreversible, 225 order - disorder, 224-228 reversible, 225, 229, Physicochemical properties of ammonium hydrofluoride, 39 deviations from ideal, 149 ideal system, 148 NbF5 and TaFs, 25 niobium containing melts, 150 tantalum containing melts, 151 M5Nb3OFlg, 234-235 Piezoelectric properties, 245-247 Plasma chemical decomposition equipment, 311... 

As illustrated in Figure 12, the reaction mixture contains mono-, di-, and tri-brominated glycols, hydrobromic acid, and water. The mixture is extremely corrosive, and the reactor is operated at a temperature just above the freezing point of the product. The key to successfully sampling this mixture was the use of a corrosion-resistant tantalum sampling system. In addition, the sample line was continuously flushed with reactor solvent except during sampling. 

MCM-41 and silicalite-1 can be synthesized in the presence of niobium- and tantalum-containing compounds. The results indicated that Nb(V) and Ta(V) are well dispersed in the framework of silicalite-1 and in the amorphous walls of MCM-41 y-irradiation of activated niobium and tantalum molecular sieves show two radiation induced hole centers (V centers) located on Si-O-Si and M-O-Si (M = Nb, Ta) units. True isomorphous substitution as suggested in the literature for Ti(IV), however, is unlikely to be present Nevertheless, interesting chemical and catalytic properties can be expected from these systems and are subject to further studies... 

Thus we are fully justified in observing that spontaneous interaction between nickel and tantalum containing chloride, chloride-fluoride, and fluoride melts results in the predominant formation of NisTa intermetallic compound on the surface of the nickel samples. This corresponds with the published thermodynamics and kinetics data for the nickel-tantalum system. 

Tantalum is not resistant to substances that can react with the protective oxide layer. The most aggressive chemicals are hydrofluoric acid and acidic solutions containing fluoride. Fuming sulfuric acid, concentrated sulfuric acid above 175°C, and hot concentrated aLkaU solutions destroy the oxide layer and, therefore, cause the metal to corrode. In these cases, the corrosion process occurs because the passivating oxide layer is destroyed and the underlying tantalum reacts with even mild oxidising agents present in the system. 

Tantalum-Titanium Bishop examined the corrosion resistance of this alloy system in hydrochloric, sulphuric, phosphoric and oxalic acids and found that alloys containing up to about 50% titanium retained much of the superlative corrosion resistance of tantalum. Under more severe conditions, a titanium content of below 30% appears advisable from the standpoint of both corrosion resistance and hydrogen embrittlement, although contacting or alloying the material with noble metals greatly decreases the latter type of attack. Tantalum-titanium alloys cost less than tantalum because titanium is much cheaper than tantalum, and because the alloys are appreciably lower in density. These alloys are amenable to hot and cold work and appear to have sufficient ductility to allow fabrication. 

In the second part of the 20th century, the tantalum capacitor industry became a major consumer of tantalum powder. Electrochemically produced tantalum powder, which is characterized by an inconsistent dendrite structure, does not meet the requirements of the tantalum capacitor industry and thus has never been used for this purpose. This is the reason that current production of tantalum powder is performed by sodium reduction of potassium fluorotantalate from molten systems that also contain alkali metal halides. The development of electronics that require smaller sizes and higher capacitances drove the tantalum powder industry to the production of purer and finer powder providing a higher specific charge — CV per gram. This trend initiated the vigorous and rapid development of a sodium reduction process. 

The first comprehensive investigation of the TaF5 - HF - H2O system was performed by Buslaev and Nikolaev [292]. Based on the analysis of solubility isotherms, and on conductometric and potentiometric titrations, the authors concluded that in this solution, tantalum forms oxyfluorotantalic acid, H2TaOF5, similar to the formation of H NbOFs in solutions containing NbF5. 

Three conceptual steps can be discerned in the definition of the ionic structure of fluoride melts containing tantalum or niobium. Based on the very first thermodynamic calculations and melting diagram analysis, it was initially believed that the coordination numbers of tantalum and niobium, in a molten system containing alkali metal fluorides, increase up to 8. 

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