Bull. Mater. Sci., Vol. 24, No. 1, February 2001, pp. 39–45. © Indian Academy of Sciences. Synthesis of ferrite grade g-Fe2O3 K S RANE* and V M S VERENKAR Department of Chemistry, Goa University, Goa 403 206, India MS received 3 October 2000 Abstract. Iron(II) carboxylato–hydrazinates: Ferrous fumarato–hydrazinate (FFH), FeC4H2O4×2N2H4; ferrous succinato–hydrazinate (FSH), FeC4H4O4×2N2H4; ferrous maleato–hydrazinate (FEH), FeC4H2O4×2N2H4; ferrous malato–hydrazinate (FLH), FeC4H4O5×2N2H4; ferrous malonato–hydrazinate (FMH), FeC3H2O4×1×5N2H4×H2O; and ferrous tartrato–hydrazinate (FTH), FeC4H4O6×N2H4×H2O are being synthesized for the first time. These decompose (autocatalytically) in an ordinary atmosphere to mainly g-Fe2O3, while the unhydrazinated iron(II) carboxylates in air yield a-Fe2O3, but the controlled atmosphere of moisture requires for the oxalates to stabi- lize the metastable g-Fe2O3. The hydrazine released during heating reacts with atmospheric oxygen liberating enormous energy, N2H4 + O2 ® N2 + H2O; DH2O = – 621 kJ/mol, which enables to oxidatively decompose the dehydrazinated complex to g-Fe2O3. The reaction products N2 + H2O provide the necessary atmosphere of moisture needed for the stabilization of the metastable oxide. The synthesis, characterization and thermal decomposition (DTA/TG) of the iron(II) carboxylato–hydrazinates are discussed to explain the suitability of g-Fe2O3 in the ferrite synthesis. Keywords. Carboxylate; hydrazine; metastable oxide; ferrite. 1. Introduction ide with vacancy ordered structure of unit cell structure, 3+ 3+ (Fe )8 [Fe40/3 o8/3]O32, where ( ), [ ] and o represent Technologically important ferrites of general formula, tetrahedral, octahedral and vacant sites, respectively. MFe2O4 (M = divalent metal) are generally synthesized by This defective cubic oxide reacts easily with the cubic a solid state reaction between Fe2O3 and MO. The solid MO giving cubic spinel easily. And, such enhanced reac- state reactions are normally sluggish in nature, and hence, tivity of g-Fe2O3 in ferrite, MgFe2O4 synthesis has been in ceramic technique granulations are done to get reactive realized by us (Verenkar 1997; Sawant 1998; Rane et al fine particles of the starting materials, compacted and 1999) that confirms the fact that cubic defective iron then heat treated to very high temperatures, > 1000°C. oxide, g-Fe2O3, is a better starting material in ferrites Many a times the repeated grinding and heat treatments manufacture. This is also in conformity with certain solid are given to achieve a single phase ferrite of desired com- state reactions which are favoured if they are carried out position. Reactivity of sluggish solid state reactions are at the phase transformation temperature of one of the enhanced by choosing defective starting materials by reactants (Hedvaall effect); formation of CoAl2O4 is easier intentionally adding foreign impurities called as doping. at the g ® a transformation of Al2O3. Thus, the enhanced Structural compatibility also plays an important role. In reactivity of cubic g-Fe2O3 is the combined effect of its ferrites synthesis the iron oxide in hexagonal corundum structural compatibility, defective structure and its trans- structure form, a-Fe2O3, is made to react with the cubic formation to a-Fe2O3 during the heat treatment with cubic divalent metal oxides, MO, to get cubic spinel, MFe2O4. MO. In the synthesis of LiMn ferrite it was observed Here, at high temperatures the a-Fe2O3 transforms into (Sano and Tamaura 1999) that g-Fe2O3 is more suitable cubic spinel magnetite, Fe3O4, which then reacts easily than even other cubic spinel oxide, magnetite, Fe3O4, 3+ 3 + 2 + with the cubic MO resulting into cubic spinel. However, it (Fe )8 [Fe8 Fe8 ]O32, may be because it is not defective. has been observed (Huhn 1987; Tuan et al 1992; Shrotri Considering the importance of g-Fe2O3 in the synthesis et al 1992) that the iron oxide in cubic spinel form, g- of ferrites, we (Rane et al 1981; Moye et al 1993; Veren- Fe2O3, as a starting material in ferrites synthesis enhances kar 1997; Sawant 1998) have been investigating an easier the solid state reaction and a better quality material could method of preparation of this oxide from various precur- be obtained. The cubic spinel, g-Fe2O3, is a defective ox- sors such as iron(II) oxalate, formate, iron hydroxides and iron oxyhydroxides and their hydrazinates. Especially the iron(II) carboxylate, ferrous oxalate dihydrate, *Author for correspondence FeC2O4×2H2O, is a widely studied precursor in the synthe- 39 40 K S Rane and V M S Verenkar sis of Fe2O3. In air the ferrous oxalate decomposes to a- Ferrous tartrate was prepared from ferrous ammonium Fe2O3, while in a controlled atmosphere of a known par- sulphate and sodium tartrate and the dry ferrous tartrate tial pressure of moisture the decomposed product is was then equilibrated over hydrazine atmosphere by sto- mainly g-Fe2O3. However, the ferrous oxalate on hydra- ring in a petri dish in a desiccator containing hydrazine zination yields complexes of known composition such as hydrate. (Caution: hydrazine and hydrazine derivatives FeC2O4×2N2H4, FeC2O4×N2H4×2H2O and these decompose were carcinogenic. They were handled carefully in a fume autocatalytically at an ordinary temperature and pressure cupboard.) into mainly g-Fe2O3. This easy formation of the g-Fe2O3 has also been observed (Sawant 1998) in iron(II) formates. 2.2 Characterization Hydrazine method has opened up a new area of coordi- nation chemistry involving metals ranging from transition, Hydrazine content of all the complexes and the inter- lanthanides to actinides (Athavale and Padmanabh Iyer mediate thermal products was analyzed titrimetrically 1967; Ferrari et al 1966; Braibanti et al 1968; Sharov using KIO . The percentage of iron, carbon and hydrogen 1977; Sharov et al 1977; Ravindranathan and Patil 1987; 3 was estimated by standard analytical techniques. Infrared Kikkawa et al 1995; Goto et al 1996; Patil et al 1997; band regions were detected using a FTIR spectrometer Yasodhai and Govindarajan 1999). The thermal products (Shimadzu FTIR, model 8101A) of complexes and their of hydrazinated complexes produce high reactivity metal/ thermal intermediate products. Pyknometric density of the mixed metal oxides due to explosive decomposition. complexes was also determined. The metal carboxylates are in general pyrophoric in nature and the decomposition at low temperatures involves the release of enormous amount of volatile gas products 2.3 Thermal decomposition: isothermal, DTA/TG leading them to very fine oxide products of high surface area. The hydrazination of the oxalates further makes Simultaneous differential thermal analysis (DTA) and them to explosively decompose giving still finer oxide thermogravimetric (TG) analysis were done on STA 1500 products. Since we observed the easy formation of g- instrument from room temperature (RT) to 700°C. Iso- Fe2O3 from the hydrazinated iron(II) oxalate as compared thermal weight loss studies were carried out at various to the rigorous temperature and atmosphere control need temperatures established based on DTA/TG traces. All for the formation of the oxide from the unhydrazinated hydrazinate complexes decomposed autocatalytically when carboxylate, we have been studying hydrazine method to the samples were spread in a petri dish and a burning prepare the oxide from other iron(II) carboxylates: ferrous splinter brought near to it. Initially a glow was formed fumarate, ferrous succinate, ferrous malonate, ferrous which then spread throughout the bulk, thereby, comple- tartrate, ferrous malate and ferrous maleate. ting the decomposition in an ordinary atmosphere. Weight The ferrous-fumarate, -succinate, -malonate and tartrate loss studies of these were also done. are found to decompose to mainly a-Fe2O3 in air (Ven- kataraman et al 1987, 1989; Rahman et al 1988; Venkata- 2.4 Phase identification, microstructure (SEM) and raman and Mukhedkar 1990; Nikumbh et al 1993) and magnetic characteristics like ferrous oxalate (Rane et al 1981) they too decompose to g-Fe O in a controlled atmosphere of moisture. We 2 3 X-ray powder diffraction (XRD) studies of all the thermal present here preparation and decomposition of hydrazine products were carried out on Rigaku D MAX II diffracto- complexes of these and two other (ferrous malate and meter using Cu and Fe targets. Phase identification was maleate complexes), prepared for the first time. done by comparing the observed dhkl values with the JCPDS file Nos 24–81 and 25–1402. Scanning electron micrographs (SEM) of all the thermal products were taken 2. Preparation and characterization on Cambridge Stereoscan S 250 MK III. Saturation mag- netization values, J , in emu/g of the thermal products 2.1 Preparation: Solution and equilibration method S were measured on a high field hysteresis loop trace described by Likhite et al (1965) and supplied by M/s A requisite quantity of sodium salts of fumaric, succinic, Arun Electronics, Mumbai. maleic and malic acid was added to a known amount of hydrazine hydrate (95–99%) in an inert atmosphere of nitrogen and stirred well for 2–3 h and then a freshly pre- 3. Results and discussion pared ferrous chloride was run down till the precipitation was complete. The contents were further stirred for 3.1 Chemical formula another 60 min in the N2 atmosphere. The precipitate was then filtered, washed with alcohol and then dried. Malonic Important infrared band positions, chemical contents of acid was used in the preparation