Transition ferrites

Fig. 3. An overview of atomistic mechanisms involved in electroceramic components and the corresponding uses (a) ferroelectric domains capacitors and piezoelectrics, PTC thermistors (b) electronic conduction NTC thermistor (c) insulators and substrates (d) surface conduction humidity sensors (e) ferrimagnetic domains ferrite hard and soft magnets, magnetic tape (f) metal—semiconductor transition critical temperature NTC thermistor (g) ionic conduction gas sensors and batteries and (h) grain boundary phenomena varistors, boundary layer capacitors, PTC thermistors.

The site preference of several transition-metal ions is discussed in References 4 and 24. The occupation of the sites is usually denoted by placing the cations on B-sites in stmcture formulas between brackets. There are three types of spinels normal spinels where the A-sites have all divalent cations and the B-sites all trivalent cations, eg, Zn-ferrite, [Fe ]04j inverse spinels where all the divalent cations are in B-sites and trivalent ions are distributed over A- and B-sites, eg, Ni-ferrite, Fe Fe ]04 and mixed spinels where both divalent and trivalent cations are distributed over both types of sites,... 

Unfortunately considerably less is known about MMCT in other solids. This does not mean that it is not of importance. Consider for example, the ferrites. Those with only Fe(III) are brown-red colored like Fe203, LiFcgOg, MgFe204. However, MnFe204, CoFe204 and NiFe204 are black. This is undoubtedly due to a MMCT transition of the type M(II) + Fe(III) M(III) -1- Fe(II) in the near infrared. 

Oxides play many roles in modem electronic technology from insulators which can be used as capacitors, such as the perovskite BaTiOs, to the superconductors, of which the prototype was also a perovskite, Lao.sSro CutT A, where the value of x is a function of the temperature cycle and oxygen pressure which were used in the preparation of the material. Clearly the chemical difference between these two materials is that the capacitor production does not require oxygen partial pressure control as is the case in the superconductor. Intermediate between these extremes of electrical conduction are many semiconducting materials which are used as magnetic ferrites or fuel cell electrodes. The electrical properties of the semiconductors depend on the presence of transition metal ions which can be in two valence states, and the conduction mechanism involves the transfer of electrons or positive holes from one ion to another of the same species. The production problem associated with this behaviour arises from the fact that the relative concentration of each valence state depends on both the temperature and the oxygen partial pressure of the atmosphere. 

Few comparative studies have been made on the reductive dissolution of different mineral phases. In one such study, the order of reaction with seven organic and transition metal reductants was found to be the same hematite (a-Fe203)>magnetite (FejO,/,)>nickel ferrite (NiFe204) (43). Magnetite is an interesting case, since both Fe(III) and Fe(II) are present in the lattice prior to reaction. Evidence indicates that Fe(IIl) sites reduced to Fe(II) sites by redox reaction dissolve more quickly than Fe(II) sites originally present in the mineral lattice (6). 

The number of Bohr magnetons contributed by various divalent transition metal ions are summarized below. Since the trivalent ions are equally distributed between half of the occupied octahedral sites (8) and all the occupied tetrahedral sites (8), their moments cancel out, and the net magnetic moment of a ferrite can be predicted from the moment of the divalent ions that occupy the remainder of the octahedral sites (8). 

Carbon monoxide in the product is not inert and may change the stoichiometry and properties of transition metal oxide pigment or magnetic ferrites, such as Fe203. 

Most transition elements are available in a pure state as metals which can be dissolved in acids. A mixture of nitrates can be evaporated to dryness and calcined to form precursor oxide mixtures for the preparation of spinel and garnet ferrites. Alternatively, mixed oxides, carbonates or oxalates can be precipitated. Microwave ferrites that are required to be of high purity can be prepared by one of these chemical routes. 

Step cooling will not simulate embrittlement of 1 WCM Mb, though it occurs (e.g., a 100°F [38°C] increase in transition temperature was reported after 8 y at 930° F [500° C]). This is because the embrittlement in 11/iCr-1 Mo is caused by precipitation of carbides in the ferrite phase rather than segregation of impurities to the grain boundaries. Temper embrittlement can be reversed by heating at 1,150°F (620°C) for 2 h per inch of thickness. 

Reactions during cooling. The liquid crystallizes, giving mainly aluminate and ferrite. Polymorphic transitions of the alite and belite occur. 

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