Pyrochlore properties

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). 

Literature on flotation of gold, PGMs, rare earths and various oxides is rather limited, compared to literature on treatment of sulphide-bearing ores. As mentioned earlier, the main problem arises from the presence of gangue minerals in the ore, which have flotation properties similar to those of valuable minerals. These minerals have a greater floatability than that of pyrochlore or columbite. In the beneficiation of oxide minerals, finding a selectivity solution is a major task. 

The treatment process and flotation properties of pyrochlore are very much dependent on the gangue composition of the ore. The selective flotation of pyrochlore from carbonatite ore is not possible since calcite and dolomite have similar flotation properties as pyrochlore. In addition, in the presence of carbonates, the stable pH required for flotation of pyrochlore (i.e. 5.0-5.5) cannot be maintained. 

From disseminated ores contained in mineral lenses, the recovery of bastnaesite and monazite is accomplished using flotation. The flotation properties of bastnaesite and monazite are similar to the gangue minerals contained in the bastnaesite and monazite, such as calcite, barite, apatite, tourmaline, pyrochlore and others, which represent difficulties in selective flotation. However, in recent years, significant progress has been made in the flotation of both monazite and bastnaesite [2,3]. 

Oxide pyrochlores of the general formula A2B2O7 show interesting electronic properties (Subramanian et al, 1983). Ferromagnetic pyrochlores of rare earths have also been described (Subramanian et al., 1988). A composition-dependent metal-semiconductor transition has been found in A2(Ru2 (AJ07 j, where A = Bi or Pb (Beyerlein et al., 1988). 

The crystal structure of cadmium rhenium(V) oxide, as determined by single-crystal technique,1 is of the face-centered cubic pyrochlore type (a = 10.219 A.). The only positional parameter for the 48 (/) oxygens is x = 0.309 0.007 when rhenium is at the origin. The density, determined pycnometrically, is 8.82 0.03 g./cc., compared with the theoretical value of 8.83 g./cc. for Z = 8. The resistivity between 4.2 K and room temperature is very low (10-3-10-4 J2-cm.) and has a positive temperature coefficient. Over the same temperature range the magnetic susceptibility is low and temperature-independent. These properties indicate that cadmium rhenium(V) oxide exhibits metallic conductivity. 

As discussed in Section 5.7.2, in the case of niobium-containing perovskites it is necessary to avoid the formation of pyrochlore-type phases if reproducible and optimum dielectric and piezoelectric properties are to be achieved. G. Roberts et al. [13] developed a modification of the B-site precursor ( columbite process) route to produce high quality PNN-PZT ceramics. 

The redox properties of ceria-zirconia mixed oxides are interesting, because these materials find applications as electrolytes for solid oxide fuel cells, supports for catalysts for H2 production, and components in three-way automobile exhaust conversion catalysts. The group of Kaspar and Fornasiero (Montini et al., 2004, 2005) used TPR/TPO-Raman spectroscopy to identify the structural features of more easily reducible zirconia-ceria oxides and the best method for their preparation by suitable treatments. TPR/TPO experiments and Raman spectra recorded during redox cycles demonstrated that a pyrochlore-type cation ordering in Ce2Zr2Og facilitates low temperature reduction. 

Polymorphism including also the formation of metastable and amorphous phases is widely observed. The properties of respective phases are strongly dependent on the particular structure and on temperature. Careful investigations of phase transitions may lead to a better understanding of the conditions necessary for the synthesis of new phases. A well-known example comes from the pyrochlore form of FeF3, which was first prepared in the pioneering days of what is nowadays called chimie douce . 

At first sight, the catalytic behaviour and the surface properties of pyrochlore Al(OH,F)3 does not fit this model since the pyrochlore structure (cf Fig. 9(c)) is a more open one than the HTB-A1F3 structure. However, since aluminium hydroxofluoride is susceptible to thermal decomposition, it is in fact no longer pyrochlore Al(OH,F)3 under the temperature conditions employed for the catalytic reactions. Thus, the behaviour of this phase in heterogeneous catalytic halogen exchange can be explained by the presence of amorphous alumina which determines the surface characteristics at the initial stage. Consequently, this phase acts in a manner similar to alumina and not until the surface becomes completely fluorinated does it reach its full catalytic activity. 

The stoichiometric pyrochlore transition metal oxides exhibit a wide range of magnetic and electronic transport properties. These properties are, of course, dependent on the d electron count of the B cation. Electrical conductivity may be insulating... 

Several kinds of conduction mechanisms are operative in ceramic thermistors, resistors, varistors, and chemical sensors. Negative temperature coefficient (NTC) thermistors make use of the semiconducting properties of heavily doped transition metal oxides such as tf-type Fe2 Ty03 and type Ni1 LyO. Thick film resistors are also made from transition-metal oxide solid solutions. Glass-bonded By 2 Pb2yRu207 having the pyrochlore [12174-36-6] structure is typical. 

It shows a huge fhistration index of 150 with a spin freezing Tf = 3.4 K for a sample with 90% coverage of the pyrochlore slabs by Cr +. Several anomalous properties appear in the specific heat that are still not understood in detail bnt point to the possible involvement of spin singlets in the ground state... 

Niobium (formerly called columbium) and tantalum are Transition Metals having a considerable affinity for oxygen donor groups they are thus called oxophilic see Oxophilic Character). They occur as mixed-metal oxides such as columbites (Fe/Mn)(Nb/Ta)206 and pyrochlore NaCaNb206p. Their discovery in minerals extends back to the beginning of the nineteenth century, when they were believed to be identical and called tantalum. Rose showed that at least two different elements were involved in the minerals, and named the second one niobium. Their separation was resolved around 1866, especially by Marignac. These metals often display similar chemical behavior as a result of nearly identical atomic radii (1.47 A) due to the lanthanide contraction see Periodic Table Trends in the Properties of the Elements)... 

Bae, J.M. and Steele, B.C.H., Properties of pyrochlore ruthenate cathodes for intermediate temperature solid oxide fuel cells. Journal of Electroceramics, 1999, 3, 37-46. 

The ferroelectric Pb(Mgy3Nb2/3)03 (PMN) ceramic has been the snbject of extensive investigations due to its high dielectric coefficient and high electrostrictive coefficient, which renders it suitable for use in capacitors and electrostrictive actuators. However, the successful exploitation of this material is limited by the difficulty of producing a single-phase material with the perovskite structnre. Conventional solid state synthesis techniques invariably resnlt in the formation of one or more pyrochlore phases, which exhibit poor dielectric properties. 

---