Processing of Soft Ferrites by the Citrate Precursor Method

"Processing of ferrites has gained tremendous importance in recent times to meet the high performance demands on ferrites in keeping with the fast emerging· technologies. The quality of ferrite powders has strong influence on ·the performance of final device. Fabrication· of high performing ferrite components requires starting ferrite powders of precise stoichiometry, purity and microstructure. It is difficult to obtain these attributes by the conventional ceramic method. The key to obtaining quality powders lies in the· solution techniques. With this in view soft ferrites have been prepared by a wet chemical process, known as the citrate precursor method, which involves the formation of citrate complexes of the constituent cations. The advantages of this process are the ease of preparation and close control of composition, homogeneity, purity and particle size. Electrical and magnetic measurements on lithium ferrites have shown resistivity higher by more than two orders of magnitude compared to that observed for samples prepared by the conventional ceramic method, and low magnetic losses, making the ferrites specially suitable for high frequency applications.IntroductionProperties of ferrites are known to be sensitive to .their processing technique. A small deviation in the compositional stoichiometry of the ferrite affects its properties greatly. Soft ferrites such as Ni-Zn, Mn-Zn and Mg-Mn. are well known ferrites covering wide-ranging applications [1,2]. Lithiiim ferrites have also assumed technological importance for microwave applications and are potential substitutes for the expensive garnets [3]. Lithium ferrites are often doped with zinc to tailor the saturation magnetization required at high frequencies. Lithium and lithium-zinc ferrites, however, present difficulty to processing due to the volatile nature of both the cation components, namely Li and Zn. These ions are volatile at temperatures > 1000°C which makes their processing difficult. One of the main considerations of high frequency performance of ferrites is the high eddy current losses which prevent the interaction of the magnetic field with the ferrite component and hence impair device performance. These losses can be reduced by having a material of high resistivity. Electrical conductivity in lithium ferrite has been attributed to electron hopping [4] between the two vaience states of iron, Fe2+ <=> Fe3+, on octahedral sites. Maintaining the + 3 valence state of otahedral- Fe ions is thus a prerequisite for achieving high resistivity. The resistivity of ferrites is normally found to be low when processed by the conventional solid-state or the ceramic method [5]. This is attributed to (a) extensive ball-milling employed in the method to mix the component oxides results in non-stoichiometric compositions due to introduction of additional Fe ions on abrasion of steel balls during milling, (b) high processing temperatures involved which result in significant volatilization of Li and Zn ions creating thereby oxygen non-stoichiometry which results in reduction of Fe3 + to Fe2 +, (c) large and non-uniform grain sizes. In the present work, preparation of Li and Li-Zn ferrites by a non-conventional method known as a citrate precursor method [6, 7] which requires lower processing temperatures and duration is reported. The method gives stoichiometric compositions on account of homogeneous atomic-scale mixing of the constituent cations via the formation of metal-citrate complexes mixed in solution state. The method is also capable of giving small grain size which aids the oxidation ofFe2+ ions."