Institute of Metals Division - Influence of Additives in the Production of High Coercivity Ultra-Fine Iron Powder

The effects of several additives upon the reduction characteristics of hydrogen-reduced ferrous formate are described. The various additives inhibit sintering of the reduced iron particles by apparently different mechanisms. The magnetic properties of the low density compacts produced from the resulting ultra-fine iron powders were improved markedly. THE permanent magnetic characteristics of ultra-fine iron powder prepared by various means have been a subject of considerable interest and experimentation in the past few years. When such particles are small enough to show single domain behavior, they possess' 1—permanent saturation magnetization, and 2—high coercive force. In the absence of domain boundaries, the only magnetization changes in a particle occur through spin rotation which is opposed by relatively large anisotropy forces. With decreasing particle size, the coercive force tends to increase to a maximum and then decrease because of the instability in magnetization associated with thermal fluctuations. Kittel' has calculated the critical diameter at which a spherical particle of iron can no longer sustain domain boundaries or walls to be approximately 1.5x10-' cm. Stoner and Wohlfarthr in England and Neel4,6 in France have shown from purely theoretical calculations that the high coercive force expected from single domain particles is dependent upon crystal anisotropy, shape anisotropy, or strain anisotropy contributions. Further work by Weil, Bertaut,' and many others has contributed much to the understanding of fine particle theory. Neel and Meikeljohn" have demonstrated that a decrease in particle size below a critical value of approximately 160A leads to a quite rapid decrease in coercive force because of the prevention of stable magnetization by thermal agitation. Lih1, working with powders prepared by the reduction of formate and oxalate salts of iron, has shown the marked influence of powder purity upon magnetic properties. Maximum coercive force was obtained in powders of approximately 65 pct metallic iron content while the maximum energy product, (BxH) occurred in powders of 85 pct metallic iron content. Careful consideration of the preceding theoretical considerations and experimental results has led to the manufacture of permanent magnets from ultra-fine ferromagnetic powders by powder metallurgy techniques. Such work has been done by Dean and Davis," the Ugine Co. of France, and Kopelman." The aforementioned work of Kopelman and the Ugine Co. was concerned somewhat with the effect of various additives upon the properties of hydrogen-reduced ferrous formate. Virtually no work, however, has been published on the effects of additives on the reduction rates of metal formates, although unpublished work by Ananthanarayanan16 howed promise of improved energy product in ultra-fine iron compacts prepared by the hydrogen reduction of a coprecipitated mixture of magnesium and ferrous formate. After consideration of the preceding information, it was hoped that a better balance between the metallic iron content and particle size of the reduced iron powder could be accomplished by a prevention of the attendant sintering of the partially reduced iron powder during the reduction reaction. It appeared possible that magnesium oxide might interpose a mechanical barrier between adjacent iron particles and prevent their sintering together, while metallic cadmium and metallic tin would interpose a liquid barrier which might accomplish the same purpose. The degree to which these materials were effective in accomplishing the foregoing objective and the experimental details associated with the work are reported in the following sections of this paper. Experimental Procedure Preparation of Formate and Oxide Mixtures: To obtain ferrous formate of reproducible reduction characteristics, a slight modification' was made in the technique of Fraioli and Rhoda." A supersaturated solution of ferrous formate was mixed with an equal volume of 95 pct ethyl alcohol and the formate crystals precipitated by stirring and screened to —325 mesh. These crystals were in the shape of elongated hexagons, approximately 4x10 micron in dimension. Various preparations of such ferrous formate, designated as lot 111, were reduced for 2 hr, yielding ultra-fine iron particles of exceedingly reproducible size, metallic iron content, and magnetic properties. The magnesium and cadmium formates were prepared by the reaction of dilute formic acid with their respective carbonates, while the tin formate was prepared by the reaction of dilute formic acid with stannous hydroxide. To evaluate the effect of metallic formate additives in intimate mixture with the ferrous formate, varying amounts of magnesium, cadmium, and tin formates were coprecipitated with the latter. The designations of these materials and their chemical compositions are given in Table I. Due to the differing solubilities of the various formates in aqueous media,