3,582,266 United States Patent Office Patented June 1, 1971 2 size of barium ferrite is of the order of 0.5-1.0 micron, 3,582,266 particles larger than this would have multi-domain struc PROCESS FOR PRODUCING BARUM FERRITE ture, resulting in the production of permanent magnets of Samuel W. Sopp and Leo F. Heneghan, San Mateo, Calif., and Jack R. Anderson, Whippany, N.J., assignors to considerably lessened magnetic strength. The extensive Merck & Co., Inc., Rahway, N.J. ball-milling of the sintered clinkers required by the prior No Drawing. Filed Sept. 24, 1968, Ser. No. 762,154 art process does not always result in the production of Int, C. C01f 11/00, C01g 49/00 barium ferrite powder within the particle size range in U.S. C. 23-51. 6 Claims dicated above. The present invention departs significantly from the ac O cepted procedures and practices heretofore employed in ABSTRACT OF THE DISCLOSURE the production of powdered ferrites such as barium fer Barium ferrite is prepared by reacting a ferrous sulfate rite. In accordance with the process of the present inven Solution with a carbonate precipitating agent to produce a tion barium ferrite particles of single domain size are ferrous hydroxycarbonate slurry which is filtered. Barium consistently obtained without resorting to the inefficient carbonate is added to form a barium-iron carbonate co 5 and expensive comminution employed by the prior art. By slurry which is dried and conveted to the ferrite by calci utilizing chemical precipitation processes of the present nation. In another embodiment, barium chloride is added invention it is possible to achieve a high degree of homo to the ferrous hydroxycarbonate and a carbonate added geneity of the pre-calcined material. This intimacy be to precipitate barium carbonate on the hydroxycarbonate tween the barium and iron cations prior to the solid state particles. The addition of a carbonate to a solution of 20 reaction allows for the lowering of calcining temperatures barium chloride and ferric chloride to precipitate an iron and/or times. Also, by controlling the reaction tempera barium hydroxycarbonate co-precipitate is also disclosed. ture, the critical particle size of the resulting barium fer Calcination of the co-precipitate yields barium ferrite. rite can be maintained wtihin the 0.5-1.0 micron range in indicated above. As indicated previously, this has the 25 effect of eliminating the necessity of ball-milling the fired This invention relates to a method of making perma materials to desired particle size. According to the pre nent magnets and is directed particularly to magnetically cipitation processes of the present invention, the barium anisotropic permanent magnets of ferritic composition. A and iron cations are inherently in closer proximity after ferrite is a crystalline material which is a compound of precipitation than is possible to achieve by the mere me the reaction product of a metal oxide and iron oxide hav 30 chanical mixing of barium carbonate and ferric oxide ing the empirical formula MFeO4 wherein M represents powders. Moreover, the closer proximity of the metal ca a bivalent metal. It has previously been proposed to use tions not only permits for employing milder conditions barium ferrite of hexagonal crystalline structure of the during the reaction to barium ferrite but, in addition, the general formula BaFe2O1 in the manufacture of perma intimacy and homogeneity of the barium ferrite prepared nent magnets. Barium ferrite powder is conventionally according to the precipitation techniques of the inven utilized as the magnetic component in a variety of ap tion prevents formation of undesirable by-products such plications. Magnets produced employing this material as barium ferrate and c-Fe2O3. Furthermore, commercial procedures commonly used in the preparation of barium have been found to have extraordinary high coercive force. ferrite powders are highly dependent upon the purity of the The barium ferrite powders are employed in the produc 40 tion of flexible magnets wherein the ferrrite powder is raw materials in order to obtain in satisfactory product. incorporated into flexible non-magnetic elastomeric ma According to the present invention a highly purified trices by procedures well known in the art followed by ex barium ferrite product is achieved employing raw ma posing the formed piece to a magnetic field. Conventional terials that could not otherwise be utilized in the com means for practicing these techniques are discussed, for 45 merical processes. In addition, a dried product is achieved example, in United States Patents 2,959,832; 3,119,158; which can be selectively calcined to varying, but con and 3,359,152. The flexible magnets may be used for a trolled, particle sizes without employing harsh comminu variety of applications including magnetic sealing gaskets, tion techniques. This, along with milder reaction condi switches and toys, etc. In addition, the barium ferrite tions, serves to significantly reduce costs in the manufac powders have been wet-mixed with a binder, pressed into 50 turing operation leading to the production of ferrite the desired shape in a magnetic field and fixed at the ap powders of magnetic strength as high and in most in propriate temperature to form barium ferrite ceramic per stances higher than the commercially available materials. manent magnets. It should be noted that although the invention shall be The commonly practiced method for the production of described with reference to barium ferrite, the inventive barium ferrite magnets is to first mill particles of barium 55 processes are applicable for the preparation of other mag carbonate and ferric iron oxide together to a fine state netic ferrites such as strontium and lead. of subdivision. Extensive wet ball milling is required to In accordance with the method of the present invention, achieve as intimate a mixture as possible. Thereafter a ferrous sulfate solution of from about 5% to about 15% homogeneous mixture of the milled particles in the stoi concentration is reacted with a carbonate precipitating chiometric amount required for BaO 6Fe2O3 is prepared, 60 agent such as ammonium or an alkali metal carbonate and finally the mixture is calcined to transform the barium such as sodium carbonate of from about 5% to about carbonate to barium oxide with concomitant in-situ for 15% concentration to produce a ferrous hydroxycar mation of barium ferrite. The calcined sintered product bonate slurry which is filtered and washed with water. is then ball milled to a fine state of subdivision to obtain Barium carbonate of from about 10% to about 50% con BaC.6FeO in powdered form of desired particle size. 65 centration is added to form a barium-iron carbonate co However, ball-milling of the raw materials in accordance slurry which is then aged prior to drying. Although any with the prior art techniques does not achieve an in of the conventional drying techniques well known in the timacy in the precalcined mixture which is conducive to art may be employed, spray drying at a temperature rapid and complete reaction to barium ferrite. Moreover, range from about 100-150° C. and the procedure of stick it is well known that magnetic properties of the hexagonal 70 drying were found to be the preferred methods. The age barium ferrite are dependent upon compositional purity, of the slurry prior to drying may influence the grain crystallinity and particle size. Since the magnetic domain growth during subsequent calcination to barium ferrite. 3,582,266 3 4. Aging of the co-slurry for about 1-5 days with continuous 140 C. The spray dried product is an orange to brown agitation is preferred. The dried product is then con free-flowing powder. verted to barium ferrite by calcination. The selection of the temperature of the calcination procedure is determined EXAMPLE I by the particle size desired in the final barium ferrite The ferrous hydroxycarbonate slurry is prepared in product. It has been determined that temperatures within 5 the manner described in Example I. To 15 gallons of the range 900-1200° C. result in the preparation of a the ferrous hydroxycarbonate slurry containing 1.038 kg. highly satisfactory barium ferrite material. In the prac of iron as Fe (18.6 moles) is added a solution containing tice of the process identified above, efficient filtration and 416 g. of BaCl2.2H2O (1.7 moles). The resulting co sulfate removal may be achieved by employing an excess 10 slurry is agitated for 30 minutes and is then treated with a of sodium carbonate. A 10-20% excess of 10% sodium Solution containing 212 g. (2 moles) of sodium carbonate. carbonate solution resulted in efficient filtration per The resulting co-slurry which consists of a precipitate of formance. It has also been observed that the period of barium carbonate-ferrous hydroxycarbonate is filtered and time between precipitation of the ferrous hydroxycar Washed with deionized water to remove sodium and bonate material and the filtration of this material may chlorine ions. After repulping to a convenient viscosity have an effect on the efficiency of the filtration and sub which may vary from about 150 to about 2000 cps., the sequent washing operation. The filtration and washing co-slurry is spray dried in accordance with the procedure operation becomes less efficient when the period in ques of Example I. tion exceeds 2% hours. EXAMPLE III In another embodiment of the present invention, the 20 Fifteen gallons of a solution containing 21.8 moles ferrous hydroxycarbonate slurry is prepared in the man (3.54 kg.) FeCl3 is mixed with a 2 gallon solution con ner described above. However, in the place of barium taining 2.0 moles (0.488 kg.) BaCl-2HO. The com carbonate, a solution containing from about 5% to about bined solutions are then filtered to remove insoluble par 40% barium chloride is added to the ferrous hydroxy ticles. 42 moles of Na2CO3 (4453 g.) is added with agita carbonate slurry. After agitation of the slurry a solution tion to completely precipitate the iron-barium hydroxy of 5-15% sodium or ammonium carbonate is added to carbonate co-precipitate. The co-precipitated slurry is precipitate barium carbonate on the ferrous hydroxycar then filtered and washed with deionized water to remove bonate particles. The co-slurry is then filtered, washed, Sodium and chlorine ions. After repulping the filter cake, dried and subsequently converted to barium ferrite by the homogeneous slurry is spray dried in accordance with calcination. 30 the procedure of Example I. The product is a dark red A further aspect of the invention involves the reaction dish-brown powder. of FeCls of from about 5% to about 50% concentration The spray dried products obtained in Examples I, II with BaCl2. The filtered solution is treated with NaCO or (NH4)2CO3 in order to precipitate the iron-barium and III are converted to barium ferrite by calcination hydroxycarbonate co-precipitate. The co-precipitated 35 at a temperature of 1100° C. After calcination is complete, slurry is then filtered, washed and dried and calcined in the powder is cooled to ambient temperatures and screened a manner similar to the procedures discussed above. It through 270 mesh to break up any agglomerates. The has been further determined that accelerated aging by Specific gravity of barium ferrite powders obtained in aeration of the spray drier feed results in a calcined this manner ranged from 4.5 to 5.3 g/cc. powder of improved properties. The preferred procedure 40 The barium ferrite powders prepared according to the is to aerate to pH of from about 8 to 8.4. present invention can be formulated into flexible mag The identification of the powder prepared by each of nets according to methods known to the art. The follow the three routes discussed above as being barium ferrite ing is an example of such a formulation. (BaFe1g019) was confirmed by X-ray diffraction and Plaskon No. 4 formulation electron micrographs. Parts It shall be readily apparent to one skilled in the art that Plaskon CPE 102 ------100 soluble ferrous, ferric or barium salts other than those Paraplex G-54 ------25 specifically exemplified may be employed in the process Paraplex G-62 stabilizer ------5 of the invention. For example, ferrous chloride or ferrous Mark WSX stabilizer ------3.5 nitrate among others may be utilized in place of the fer 50 Stearic acid ------2 rous Sulfate material. The choice of the particular salt Barium ferrite to >60% by volume (about 90% by shall generally be dictated by the prevailing cost of the weight). material since the class of soluble ferric, ferrous or barium salts are functionally equivalent with respect to their re The barium ferrite is added to the binder on a conventional spective performance in the process. rubber mill having differentially speeded rolls. After mill The invention will be described in greater detail with ing to a uniform sheet, the sheet is stripped off and can reference to the following illustrative examples. be extruded or molded prior to magnetization. This same technique may be employed in incorporating the ferrite EXAMPLE I powder into well known flexible non-magnetic elastomeric 60 matrices such as rubber and polymer materials. Converse Ferrous sulfate solution (10% FeSO4.7HO) and 10% ly, the formulation can be mixed by other conventional Sodium carbonate solution are fed simultaneously into means, and extruded. a baffled reactor which is vigorously agitated. The flow While the principles of the invention have been de rate is controlled so as to obtain an excess of 20% so Scribed above in connection with specific embodiments, dium carbonate. Following a five minute retention time 65 and particular modifications thereof, it is to be clearly in the reactor the gray-green ferrous hydroxycarbonate understood that this description is made only by way of slurry is filtered and washed with de-ionized water. The example and not as a limitation on the scope of the cake is then repulped with a sufficient quantity of water invention. It will be evident to those skilled in the art that to produce a homogenous slurry. Analysis of this par many modifications and variations of this process may ticular repulped slurry reveals that 56 lbs. of the slurry 70 be carried out without departing from the spirit of the contains 1.34 kg. of Fe. 0.434 kg. of barium carbonate invention as defined in the following claims. slurry (2.20 moles) is added slowly with vigorous agita We claim: tion to the repulped material. The co-slurry that forms 1. A method of producing barium ferrite adapted for is aged three days with continuous agitation. The aged use in the preparation of permanent magnets which com co-slurry is then spray dried at a product temperature of 5 prises reacting a ferrous sulfate solution of 5-15% con 3,582,266 5 6 centration and a solution of sodium or ammonium car ferrite by calcination at temperatures from about 900 bonate of 5-15% concentration to form a ferrous hy 1200° C. droxycarbonate precipitate, filtering and treating said 5. The method of claim 4 wherein an excess of sodium precipitate with a solution of barium carbonate of 10-50% carbonate is employed. concentration to form barium carbonate-ferrous hydroxy 6. The method of claim 5 wherein the time between carbonate which is then dried and converted to barium precipitation and filtration of the ferrous hydroxycar ferrite by calcination at temperatures from about 900 bonate should not exceed about 2% hours. 1200°C. 2. The method of claim 1 wherein an excess of sodium References Cited carbonate is employed. 0. UNITED STATES PATENTS 3. The method of claim 2 wherein the time between precipitation and filtration of the ferrous hydroxycarbonate 3,049,404 8/1962 Wade ------23-50 should not exceed about 2% hours. 3,155,623 11/1964 Erickson et al. --- 252-62.63X 4. A method of producing barium ferrite adapted for 3,378,335 4/1968 Ellis et al. ------23-51 use in the preparation of permanent magnets which com 15 FOREIGN PATENTS prises reacting a solution of ferrous sulfate of 5-15% 739,069 10/1955 Great Britain ------23-51. concentration and a solution of sodium or ammonium car 866,420 4/1961 Great Britain ------23-51 bonate of 5-15% concentration to form a ferrous hydroxy carbonate precipitate and treating said precipitate with a HERBERTT. CARTER, Primary Examiner barium chloride solution of 5-40% concentration and a 20 Solution of sodium or ammonium carbonate of 5-15% U.S. C. X.R. concentration to form barium carbonate-ferrous hydroxy 148-101 carbonate which is then dried and converted to barium