Tantalum fluoride reduction

The best described case is the one of potassium tantalum fluoride reduction. This salt is currently obtained in the Marignac separation, from the potassium columbium oxyfluoride, by crystallization. The fully dried salt is mixed with clean sodium chips, pressed lightly in a steel bomb which is sealed and heated externally with gas. After the flash the cooled bomb is drilled out and the cake is treated with alcohol, water, and various acids. The powder obtained is processed to compact metal by pressing in bars and high vacuum sintering. 

Fluorides are nonhygroscopic, and their melting points are higher than those of the corresponding chlorides. Besides, the fluoride reduction reactions are considerably more exothermic. The prime examples of the use of fluorides as intermediates are the reduction of uranium tetrafluoride by calcium or magnesium the reduction of rare earth fluorides by calcium, reduction of beryllium fluoride by magnesium and the reduction of potassium tantalum double fluoride by sodium. 

Neither calcium nor magnesium is used as the reducing agent in the production of tantalum by fluoride reduction. The intermediate used is potassium tantalum fluoride (K2TaF7), and the reducing agent is sodium. The choice of sodium is primarily guided by the need to produce tantalum in the powder form. The pertinent reaction is ... 

Aluminium alloys well with up to about 3-5 per cent, of tantalum, which has no effect, however, on the mechanical strength, ductility, and working properties of aluminium.3 Reduction of tantalum pentoxide by the thermite process yields hard, brittle alloys.1 A substance the composition of which corresponds with the formula TaAls has been obtained by reducing potassium tantalum fluoride, K2TaF7, with aluminium filings at a high temperature. It is described as an iron-grey crystalline powder, of density 7-02, which is scarcely attacked by acids.5... 

Fio. 9.11, Extraction of tantalum (fluoride dissolution, re rystallization of double fluoride, sodium reduction process). 

A slight excess of calcium is used and the exothermic reaction, carried out in a tantalum cmcible, is initiated at - 900° C. After physical separation of the upper layer of immiscible fluoride slag, vacuum distillation removes unreacted volatile Ca. Cerium can also be made by the electrolytic reduction of fused chloride. 

For a long period of time, molten salts containing niobium and tantalum were widely used for the production by electrolysis of metals and alloys. This situation initiated intensive investigations into the electrochemical processes that take place in molten fluorides containing dissolved tantalum and niobium in the form of complex fluoride compounds. Well-developed sodium reduction processes currently used are also based on molten salt media. In addition, molten salts are a suitable reagent media for the synthesis of various compounds, in the form of both single crystals and powdered material. The mechanisms of the chemical interactions and the compositions of the compounds depend on the structure of the melt. 

Tantalum powder is produced by reduction of potassium heptafluoro-tantalate, K2TaF7, dissolved in a molten mixture of alkali halides. The reduction is performed at high temperatures using molten sodium. The process and product performance are very sensitive to the melt composition. There is no doubt that effective process control and development of powders with improved properties require an understanding of the complex fluoride chemistry of the melts. For instance, it is very important to take into account that changes both in the concentration of potassium heptafluorotantalate and in the composition of the background melt (molten alkali halides) can initiate cardinal changes in the complex structure of the melt itself. 

The production of tantalum and niobium metals by reduction of fluoride melts... 

Only two processes of tantalum metal production are of worldwide commercial significance. These are the electrolysis of fluoride-chloride melts containing potassium heptafluorotantalate, K TaF , and tantalum oxide, Ta20s, and the reduction with sodium of K-salt or K—salt that is dissolved in potassium fluoride-chloride melts. 

An ongoing debate continues among researchers regarding the mechanism of the electrochemical reduction of tantalum in fluoride melts. No unified model exists for the process. Espinola et al. [545] concluded, based on an investigation of the electrochemical reduction of tantalum from a molten LiF-NaF-KF eutectic solution, that the process takes place in two stages. The first, reversible step involves the transfer of two electrons ... 

The majority of researchers, however, are inclined to believe that the tantalum reduction process takes place in a single step. Experimental results and discussions confirm that tantalum is reduced from fluoride, fluoride-chloride and oxyfluoride melts containing K2TaF7, via a single stage in which five electrons are transfered [546 - 548] ... 

Single-stage reduction of tantalum seems to be typical mostly for fluoride complexes due to the ionic nature of the bonds. 

Substitution of the fluoride ligands by ions that lead to higher covalence of the bonds can alter the mechanism of tantalum reduction. For instance, the investigation of pure chloride systems containing tantalum pentachloride,... 

Another application of the electrolysis of tantalum and niobium in fluoride melts is in the preparation of intermetalic compounds as a result of the interaction between the electrochemically precipitating metal and the cathode material. Based on an investigation of the electrochemical reduction of K2TaF7 or K2NbF7 in a LiF - NaF melt on nickel cathodes, Taxil and Qiao [565] determined the appropriate conditions for the formation of TaNi3 or NbNi3 in the form of stable phases in the bulk of the obtained layer. 

The sodium reduction process was first implemented in Germany by Siemens and Halske A.G. and it remained a principally European method, while the American tantalum industry was founded exclusively on the electrolysis of molten fluorides [28, 576]. The production of tantalum by sodium reduction has gained worldwide acceptance and currently, nearly 90% of the world s tantalum is produced by the sodium reduction method [538]. 

It is, therefore, required that all initial compounds be dried properly prior to performing the reduction. This procedure is not at all trivial and refers, first of all, to the diluent salts, and especially to potassium fluoride, KF, which is characterized by a strong hygroscopic property and a tendency to form stable crystal hydrates. The problem of contamination due to hydrolytic processes can usually be resolved in two manners. The first is to apply another tantalum-containing complex fluoride compound that does not undergo hydrolysis. The second involves the adjustment of the reduction process parameters and use of some additives that will "collect" the oxygen present, in the form of water, hydroxyl groups or other compounds. 

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. 

Bulk holmium metal is prepared by reduction of holmium chloride or fluoride by sodium, calcium, or magnesium in a tantalum crucible under argon atmosphere ... 

Lanthanum in purified metallic state may be obtained from its purified oxide or other salts. One such process involves heating the oxide with ammonium chloride or ammonium fluoride and hydrofluoric acid at 300° to 400° C in a tantalum or tungsten crucible. This is followed by reduction with alkali or alkaline earth metals at 1,000°C under argon or in vacuum. 

In most recovery processes, scandium oxide is converted to its fluoride salt. The fluoride salt is the end product. The fluoride is converted to metallic scandium by heating with calcium in a tantalum crucible at elevated temperatures. A similar reduction is carried out with most rare earths. The metal is purified by distillation at 1,650 to 1,700°C under high vacuum in a tantalum crucible. 

Another example is the silicidizing of tantalum, basically an oxidation— reduction reaction. The packing is sodium fluoride and silicon. After deposition, the coating diffuses continuously into the substrate, according to the following reactions ... 

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