Niobium carbonates

The Pourbaix-Ellingham diagram of the tantalum-carbon-oxygen (Ta-C-O) system indicates fewer sequential steps between the oxide and the metal as compared to the niobium-carbon-oxygen system ... 

Insertions of isocyanide into niobium-carbon bonds follow a path similar to that with vanadium, resulting in the formation of the 7]2-iminoacyl complexes, which can then be involved in further chemistry.175 176 The reaction of acetone with cyclopentadienyl complex 110 under a carbon monoxide atmosphere gives the if -acetone compound 111. Complex 111 subsequently undergoes either stepwise insertion of two isocyanides via 112 or double insertion of the isocyanide to give complex 113 (Scheme 48).177... 

Figure 3 Section of phase diagrams of the group 5 transition metal-carbon systems, (a) vanadium-carbon (b) niobium-carbon (c) tantalum-carbon. (Reprinted from Ref. 22. 1998, with permission from Elsevier)...

Martynenko, V. M., and Borovinskaya, I. P., Some characteristic features of the combustion in system niobium-carbon. In Combustion Processes in Chemical Engineering and Metallurgy (Russ.) (A. G. Merzhanov, ed.). USSR Academy of Science, Chemogolovka, Russia, 1975, p. 127. 

Atmospheric pressure CVD of NbCi-yN, using NbCl, NH3, and CH4 has been employed in three separate approaches toward the optimization of reaction characteristics [69]. These were (i) simultaneous deposition of niobium, carbon, and nitrogen by hydrogen reduction of NbCls with decomposition of methane and ammonia at a temperature of 900-1000°C (ii) deposition of a niobium amide complex derived from NbCl.s/NHi in nitrogen as a carrier gas at 250-350 °C, and subsequent conversion in ammonia/methane at 1 000-1 100 °C (iii) separate deposition of elemental niobium or NbCl.3 by hydrogen reduction at 500-1000°C and subsequent conversion to NbCi yNy in an ammonia/methane atmosphere at 1000-1 100°C. The results of these three approaches are given below. 

Mo1vbdenum-Carbon and Niobium-Carbon Bond Dissociation Enthalpies... 

C. He and G. C. Stangle, The mechanism and kinetics of the niobium-carbon reaction under self-propagating synthesis-like conditions, J. Mater. Res. 1995,10, 2829-2841. 

Smi] Smith, J.F., Carlson, O.N., de Avillez, R.R., The Niobium-Carbon System a Review , J. Nucl. Mater., 148(1), 1 -16 (1987) (Crys. Structure, Phase Diagram, Phase Relations, Review, 116)... 

The element is found in niobite (or columbite), niobite-tantalite, parochlore, and euxenite. Large deposits of niobium have been found associated with carbonatites (carbon-silicate rocks), as a constituent of parochlore. Extensive ore reserves are found in Canada, Brazil, Nigeria, Zaire, and in Russia. 

Nitrogen and carbon are the most potent solutes to obtain high strength in refractory metals (55). Particulady effective ate carbides and carbonitrides of hafnium in tungsten, niobium, and tantalum alloys, and carbides of titanium and zirconium in molybdenum alloys. 

Opa.nte. There are two methods used at various plants in Russia for loparite concentrate processing (12). The chlorination technique is carried out using gaseous chlorine at 800°C in the presence of carbon. The volatile chlorides are then separated from the calcium—sodium—rare-earth fused chloride, and the resultant cake dissolved in water. Alternatively, sulfuric acid digestion may be carried out using 85% sulfuric acid at 150—200°C in the presence of ammonium sulfate. The ensuing product is leached with water, while the double sulfates of the rare earths remain in the residue. The titanium, tantalum, and niobium sulfates transfer into the solution. The residue is converted to rare-earth carbonate, and then dissolved into nitric acid. 

The reaction of chlorine gas with a mixture of ore and carbon at 500—1000°C yields volatile chlorides of niobium and other metals. These can be separated by fractional condensation (21—23). This method, used on columbites, is less suited to the chlorination of pyrochlore because of the formation of nonvolatile alkaU and alkaline-earth chlorides which remain in the reaction 2one as a residue. The chlorination of ferroniobium, however, is used commercially. The product mixture of niobium pentachloride, iron chlorides, and chlorides of other impurities is passed through a heated column of sodium chloride pellets at 400°C to remove iron and aluminum by formation of a low melting eutectic compound which drains from the bottom of the column. The niobium pentachloride passes through the column and is selectively condensed the more volatile chlorides pass through the condenser in the off-gas. The niobium pentachloride then can be processed further. 

The reaction of finely ground ores and an excess of carbon at high temperatures produces a mixture of metal carbides. The reaction of pyrochlore and carbon starts at 950°C and proceeds vigorously. After being heated to 1800—2000°C, the cooled friable mixture is acid-leached leaving an insoluble residue of carbides of niobium, tantalum, and titanium. These may be dissolved in HF or may be chlorinated or burned to oxides for further processing. 

Fused-salt electrolysis of K2NbFy is not an economically feasible process because of the low current efficiency (31). However, electrowinning has been used to obtain niobium from molten alkaU haUde electrolytes (32). The oxide is dissolved in molten alkaU haUde and is deposited in a molten metal cathode, either cadmium or zinc. The reaction is carried out in a ceramic or glass container using a carbon anode the niobium alloys with the cathode metal, from which it is freed by vacuum distillation, and the niobium powder is left behind. 

Niobium pentoxide can be reduced with carbon in a two-step process, called the Balke process. Formation of the carbide is the first step. The oxide is mixed with the stoichiometric amount of lamp black, placed in a carbon cmcible, and heated in vacuum to 1800°C ... 

Addition of niobium to austenitic stainless steels inhibits intergranular corrosion by forming niobium carbide with the carbon that is present in the steel. Without the niobium addition, chromium precipitates as a chromium carbide film at the grain boundaries and thus depletes the adjacent areas of chromium and reduces the corrosion resistance. An amount of niobium equal to 10 times the carbon content is necessary to prevent precipitation of the chromium carbide. 

Niobium Pent chloride. Niobium pentachloride can be prepared in a variety of ways but most easily by direct chlorination of niobium metal. The reaction takes place at 300—350°C. Chlorination of a niobium pentoxide—carbon mixture also yields the pentachloride however, generally the latter is contaminated with niobium oxide trichloride. The pentachloride is a lemon-yeUow crystalline soHd that melts to a red-orange Hquid and hydrolyzes readily to hydrochloric acid and niobic acid. It is soluble in concentrated hydrochloric and sulfuric acids, sulfur monochloride, and many organic solvents. 

Niobium Oxide Tribromide. Niobium oxide tribromide, NbOBr, is a yeUowbrown soHd which is readily hydrolyzed by moist air. It is prepared by reaction of bromine with a mixture of niobium pentoxide and carbon at 550°C. It decomposes in vacuum to the pentabromide and pentoxide at 320°C. 

Niobic Acid. Niobic acid, Nb20 XH2O, includes all hydrated forms of niobium pentoxide, where the degree of hydration depends on the method of preparation, age, etc. It is a white insoluble precipitate formed by acid hydrolysis of niobates that are prepared by alkaH pyrosulfate, carbonate, or hydroxide fusion base hydrolysis of niobium fluoride solutions or aqueous hydrolysis of chlorides or bromides. When it is formed in the presence of tannin, a volurninous red complex forms. Freshly precipitated niobic acid usually is coUoidal and is peptized by water washing, thus it is difficult to free from traces of electrolyte. Its properties vary with age and reactivity is noticeably diminished on standing for even a few days. It is soluble in concentrated hydrochloric and sulfuric acids but is reprecipitated on dilution and boiling and can be complexed when it is freshly made with oxaHc or tartaric acid. It is soluble in hydrofluoric acid of any concentration. 

Lithium niobate [12031 -63-9] Nb20 or LiNbO, is prepared by the soHd-state reaction of lithium carbonate with niobium pentoxide. After... 

---