Niobium hydroxide

Tantalum and niobium oxides dissolve very slowly in HF solutions. Thus, it is recommended to use a high concentration of HF or a mixture of HF and H2SO4 at a temperature of about 70-90°C. The best precursors for the preparation of fluoride solutions are hydroxides. Both tantalum hydroxide, Ta205 nH20, and niobium hydroxide, M Os-nHjO, dissolve well, even in diluted HF solutions. 

The second solution that results from the liquid-liquid extraction process is a high-purity niobium-containing solution. This solution is used in the preparation of niobium oxide, Nb205. The process is similar to the above-described process of tantalum oxide preparation and consists of the precipitation of niobium hydroxide and subsequent thermal treatment to obtain niobium oxide powder. 

Akimov and Chernyak [452] investigated and reported on the mechanism of the interaction between columbite and tantalite and sulfuric acid. The said interaction is presented as comprising two steps. The first step is related to the formation of iron and manganese sulfates and of tantalum and niobium hydroxides ... 

It is assumed that at the second step, tantalum and niobium hydroxides are converted into oxysulfate compounds, as represented by Equation (128) ... 

The results of a thermodynamic analysis of the interactions in Equations (127) and (128), as presented in [452], show that a coherent shell of tantalum and niobium hydroxides is formed on the surface of the columbite or tantalite during the interaction with sulfuric acid. The formation of the shell drives the process towards a forced thermodynamic equilibrium between the initial components and the products of the interaction, making any further interaction thermodynamically disadvantageous. It was also shown that, from a thermodynamic standpoint, the formation of a pseudomorphic structure on the surface of columbite or tantalite components is preferable to the formation of tantalum and niobium oxysulfates. Hence, the formation of the pseudomorphic phases catalyzes the interaction described by Equation (127) while halting that described by Equation (128). 

The filtrated solution can be successfully used for the precipitation of potassium heptafluoroniobate, K2NbF7 or niobium hydroxide. In addition, the solution is suitable for further purification by liquid-liquid extraction after adjustment of its acidity [118, 122]. 

Preparation of tantalum and niobium oxides based on the precipitation by ammonium solution of tantalum or niobium hydroxides from strip solutions is the most frequently used method in the industry and consists of several steps. Fig. 135 presents a flow chart of the process. 

Equations (141) and (142) describe the equilibrium between the hydrolysis of complex fluoride acids (shift to the right) and the fluorination of hydroxides (shift to the left). Near complete precipitation of hydroxides can be achieved by applying an excessive amount of ammonia. Typically, precipitation is performed by adding ammonia solution up to pH = 8-9. However, the precipitate that separates from the mother solution can be contaminated with as much as 20% wt. fluorine [490]. Analysis of niobium hydroxides obtained under different precipitation conditions showed that the most important parameter affecting the fluorine content of the resultant hydroxide is the amount of ammonia added [490]. Sheka et al. [491] found that increasing the pH to 9.6 toward the end of the precipitation process leads to a significant reduction in fluorine content of the niobium hydroxide. 

Thus, in order to achieve precipitation of tantalum and niobium hydroxides with minimal levels of fluorine contamination, it is recommended to perform the process at a pH no lower than 10. 

Brown et al. [494] developed a method for the production of hydrated niobium or tantalum pentoxide from fluoride-containing solutions. The essence of the method is that the fluorotantalic or oxyfluoroniobic acid solution is mixed in stages with aqueous ammonia at controlled pH, temperature, and precipitation time. The above conditions enable to produce tantalum or niobium hydroxides with a narrow particle size distribution. The precipitated hydroxides are calcinated at temperatures above 790°C, yielding tantalum oxide powder that is characterized by a pack density of approximately 3 g/cm3. Niobium oxide is obtained by thermal treatment of niobium hydroxide at temperatures above 650°C. The product obtained has a pack density of approximately 1.8 g/cm3. The specific surface area of tantalum oxide and niobium oxide is nominally about 3 or 2 m2/g, respectively. 

The opposite process, i.e. pouring the strip solution into the ammonia solution, significantly reduces the fluorine concentration in the hydroxides formed. Bludssus et al. [495] developed a process comprising the introduction of tantalum- or niobium-containing acid solution to an ammonia solution until achieving pH = 9. It is reported that this method enables the production of tantalum or niobium hydroxides with fluoride contents as low as 0.5% wt. with... 

Application of an excessive amount of ammonia solution in the precipitation of tantalum and niobium hydroxides from strip solutions usually ensures good quality of the products. Nevertheless, the method has two general problems. First, hydroxides containing low levels of fluorine contamination... 

Balabanov et al. [499] investigated the efficiency of different solutions for the washing of niobium hydroxide. The effectiveness of water and solutions of ammonia, NH4OH, ammonium acetate, CH3COONH4, and ammonium carbonate, (NH4)2C03, were tested. It was shown that ammonium acetate interacts with solid ammonium oxyfluoroniobates yielding niobium oxide even at temperatures as low as 125°C. The interaction that takes place between the solid components can be presented as follows (144) ... 

The most efficient washing of the hydroxide was achieved applying a three-step process using an ammonium carbonate solution as the first step, followed by an ammonia solution, and water as the final step. This washing process brings about a ten-fold reduction in the concentration of fluorine compared with laboratory and industrial experience, in which a 2-4 fold reduction in the fluorine content of tantalum or niobium hydroxides following a one-step washing process was obtained. 

Lapizki et al. [502] reported that niobium hydroxide can be completely dried by thermal treatment at 50-500°C. Titova et al. [503] argued that the number of water molecules incorporated with niobium in niobium hydroxide... 

Balabanov et al. [499] found an endothermic effect in the thermographic pattern of the decomposition of niobium hydroxide at 435°C that corresponds to complete removal of water. At the above temperature, amorphous niobium hydroxide also converts into amorphous niobium oxide. Ciystallization of the amorphous oxide occurs at a higher temperature with the release of energy [28]. Researchers [499] reported on another exothermal effect at 549°C that was attributed to the crystallization temperature of amorphous niobium oxide. Decomposition of tantalum hydroxide and its conversion into crystalline tantalum oxide occurs at about 710°C [502] or at 670-700°C according to another source [132]. 

Thus, tantalum and niobium hydroxides are converted into oxides following a two-step thermal treatment. The first step is usually performed at relatively low temperatures in the range of 100-200°C in order to dry the wet precursors. The second thermal treatment brings about the decomposition of hydroxides, removes the rest of the water and converts the material into crystalline oxides. The second thermal treatment is usually performed at temperatures as high as 900-1000°C. 

Uchino and Azuma [504] developed and proposed a two-step calcination process of tantalum and niobium hydroxides to obtain oxides. The first treatment is recommended to be performed at 500-700°C, and the second- at 750-1000°C. It is reported that the above method ensures the production of oxides that contain only negligible concentrations of fluorine and silicon impurities. 

Different procedures for the precipitation, washing and thermal treatment of hydroxides result in different fluorine contamination levels in the final products - tantalum and niobium oxides. Laboratory and industrial experience confirms some correlation between the initial concentration of fluorine in the dried hydroxides and the fluorine content in the final oxides obtained after appropriate thermal treatment. For instance, it is reported in [499] that if the initial concentration of fluorine in niobium hydroxide equals A%, then the fluorine content in the final niobium oxide can be estimated according to the thermal treatment temperature as follows ... 

Other methods exist for the precipitation of tantalum and niobium hydroxides for subsequent use as oxide precursors. Application of ammonium carbonate, (NH4)2C03, instead of ammonia solution, also seems to have potential for the precipitation of tantalum and niobium hydroxides. Ammonium carbonate is relatively stable in aqueous media at room temperature and does not initiate the precipitation of hydroxides. Increasing the temperature of the solution causes hydrolysis and decomposition of ammonium carbonate yielding hydroxyl ions and an increase in pH, as follows ... 

The interaction described in Equation (148), in which C02 separates from the solution and ammonia hydroxide is formed, reduces the acidity of the solution causing precipitation of tantalum or niobium hydroxide. The hydroxide powder precipitated using ammonium carbonate is usually coarser and has better filtering properties. Changing the ammonium carbonate concentration and temperature of the solution allows some control over the particle size and filtering properties of the precipitated hydroxides. 

Tantalum powder particle size, 334 production, 332 Thermal decomposition of CoNbOFj, 54,210 fluorotantalates, 195, 200 oxyfluoroniobates, 202-205,210 Nb02F, 25,210-211 niobium hydroxides, 300-303 niobium peroxide, 305-308 tantalum hydroxide, 300-303 tantalum peroxide, 305-308 Tributyl phosphate, 279-281... 

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