Pyrochlores

4 Pyrochlores - The pyrochlores are a group of materials with the general formula A2B2O7. They have been mentioned as a material for catalytic combustion. The structure allows vacancy at the A site and the O sites to some extend. The A position can be a rare earth metal or an element with lone pair of electrons and the B position can be a transition metal or a post-transition metal. This make the structure rather flexible as the oxidation state of the transition metal B can be varied as well as the nature of the A and B metal ions. Subramanian and Castro et al. have prepared several pyrochlores. When studying the thermal stability of different complex oxides, Zwinkels et al. have shown that La2Zr207 pyrochlores have a surface area lower than 5 m g , already after calcination at 1000 °C. Hence, such materials are probably not suitable for high temperature applications unless the preparation method is improved. However, pyrochlore compounds have been patented for catalytic combustion applications, see Section 5.5. 

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There is often a wide range of crystalline soHd solubiUty between end-member compositions. Additionally the ferroelectric and antiferroelectric Curie temperatures and consequent properties appear to mutate continuously with fractional cation substitution. Thus the perovskite system has a variety of extremely usehil properties. Other oxygen octahedra stmcture ferroelectrics such as lithium niobate [12031 -63-9] LiNbO, lithium tantalate [12031 -66-2] LiTaO, the tungsten bron2e stmctures, bismuth oxide layer stmctures, pyrochlore stmctures, and order—disorder-type ferroelectrics are well discussed elsewhere (4,12,22,23). 

Zaire, Norway, and the United States (14). It also occurs with calcite, dolomite, apatite, magnetite, and some siUcates. The density of pyrochlore is ca 4.0—4.4 g/cm. The tantalum content usually is low, ca 0.1—0.3% on a metal basis. 

Direct attack by hot 70—80 wt % hydrofluoric acid, sometimes with nitric acid (qv), is effective for processiag columbites and tantalo-columbites. Yields are >90 wt%. This method, used in the first commercial separation of tantalum and niobium, is used commercially as a lead-in to solvent extraction procedures. The method is not suited to direct processiag of pyrochlores because of the large alkaU and alkaline-earth oxide content therein, ie, ca 30 wt %, and the corresponding high consumption of acid. 

Concentrated sulfuric acid (97 wt %) at 300—400°C has been used to solubili2e niobium from columbite and pyrochlore (18,19). The exothermic reaction is performed in iron or siUcon-iron cmcibles to yield a stable sulfato complex. The complex is filtered free of residue and is hydroly2ed by dilution with water and boiling to yield niobic acid which is removed by filtration as a white coUoidal precipitate. 

Fusion with caustic soda at 500—800°C in an iron cmcible is an effective method for opening pyrochlores and columbites (20). The reaction mixture is flaked and leached with water to yield an insoluble niobate which can be converted to niobic acid in yields >90 wt% by washing with hydrochloric 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. 

The niobium-tantalum weight ratio in North American pyrochlores is 100-150 1, while in Russian ores the ratio varies between 8 1 and 1 20 [21 ]. 

The compounds characterized by X Me = 3.5 have a common formula of M2Me205F2 and crystallize either in a pyrochlore [192] or a veberite [229] type structure. According to X-ray powder diffraction patterns, the structure of Na2Nb205F2 can be regarded as a super-structure of pyrochlore, which is made up of octahedrons connected in layers and arranged in the (111) direction. The layers are linked via octahedrons so that each octahedron in one layer shares three vertexes with an octahedron in the adjacent layer. 

Known oxyfluoroniobates (-tantalates) with compositions that correspond to X Me = 3 crystallize in typical structures of ReC>3, pyrochlore, and hexagonal and tetragonal tungsten bronze. Table 35 presents structural parameters of such compounds. 

The compounds of the MMe205F type, where Me = Nb or Ta M = Rb, Cs, Tl, crystallize in cubic symmetry and correspond to a pyrochlore-type structure [235-237]. This structure can be obtained from a fluorite structure by replacing half of the calcium-containing cubic polyhedrons with oxyfluoride octahedrons. 

Perovskite, pyrochlore, tungsten (Re03, Ti02, aPb02, NaCl etc.)... 

The second group is the group of oxyfluorides that are derived from ferroelectric oxides by means of fluorine-oxygen substitution. The basic oxides are usually perovskite, tetragonal tungsten bronze, pyrochlore, lithium tantalate etc. [400]. 

Bayan Obo, China Bastnasite, monazite, magnetite, pyrochlore... 

Table 4.3 Details of ferroniobium production from pyrochlore by aluminothermic reduction.

Complex oxides Chromite niobite-tantalite pyrochlore ilmenite wolframite scheelite... 

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