Europaisches Patentamt European Patent Office Office europeen des brevets Publication number : 0 B1 2 0 2 8 3 4

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EUROPEAN

PATENT S P E C I F I C A T I O N

(45) Date of publication of patent specification : 27.07.88 (21) Application number : 86303573.9 (22) Date of filing : 12.05.86

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(54) Permanent magnet alloy.

(m) Priority : 20.05.85 US 736017 @ Date of publication of application : 26.11.86 Bulletin 86/48 (45) Publication of the grant of the patent : 27.07.88 Bulletin 88/30 @ Designated contracting states : U NL SE AT BE CH OE FR GB IT LI L (56) References cited : GB-A- 2 100 286 CHEMICAL ABSTRACTS, vol. 102, no. 6, February 11, 1985, Columbus, Ohio, USA, YUTAKA at al., "Permanent magnet materials", page 606, abstract no. 54959n CHEMICAL ABSTRACTS, vol. 100, no. 24, June 11, 1984, Columbus, OHIO; USA, MASATO et al.: "Magnetic materials and permanent magnets", page 668, abstract no. 202266k

(73) Proprietor : CRUCIBLE MATERIALS CORPORATION P.O. Box 88 Parkway West & Route 60 Pittsburgh Pennsylvania 15230 (US) nventor : Narasimnan, Kaiatnur a.v.L. 131 Mayberry Drive Monroeville Pennsylvania 15146 (US) nventor : Willman, Carol J. 5406 Churchill Road Bethel Park Pennsylvania 15102 (US) nventor : Dulis, Edward J. 1775 Hastings Mill Road Upper SL Clair Pennsylvania 15241 (US) (74) Representative : Sheader, Brian N. et al ERIC POTTER & CLARKSON 27 South Street Reading Berkshire, RG1 4QU (GB)

CO CM o CM o Ill Note : Within nine months from the publication of the mention of the grant of tne turopean patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid (Art. 99(1 ) European patent convention). Jouve, 18, rue St-Denis, 75001 Pans, France

0 202 8 3 4 Description This invention relates to permanent magnet alloys. Permanent magnets produced from alloys containing iron in combination with at least one rare earth element and boron provide magnets having maximum energy product, which may be of the order of 45 MGOe. Energy product, as is well known, is a measure of the usefulness of a magnet and therefore 5 magnets of these alloys are of significant commercial value. It has been found, however, that these ironcontaining magnets do not exhibit physical stability under heat and humidity. In most commercial applications heat and humidity are present. Under these conditions iron-containing permanent magnets react with the hydrogen present in the humid atmosphere and the hydrogen absorbed by the alloys of the magnet result in the disintegration of the magnet. Specifically, the reaction is initiated on the surface of 10 the magnet with the surface thereof providing active sites for the catalytic decomposition of water and resultant absorption of hydrogen. It is accordingly a primary object of the present invention to provide a magnet alloy that may be used for the production of permanent magnets that will resist hydrogen absorption and decomposition when used in applications of humidity and heat. 15 This and other objects of the invention as well as a more complete understanding thereof may be obtained from the following description and specific examples : Broadly, in the practice of the invention, a magnet alloy consisting of, in weight percent, 30 to 36 of at least one rare earth element, 60 to 66 iron, and balance boron and added thereto oxygen within the range of 6,000 to 35,000 ppm, preferably 9,000 to 30,000 ppm. The rare earth element content may comprise at 20 least one of the rare earth elements neodymium and dysprosium. Although the oxygen may be added to the alloy in any effective manner it has been found that by jet milling in an oxygen containing atmosphere the oxygen content of the alloy in powder form may be effectively produced within the limits necessary for the invention. 25 Example 1* An alloy of composition in weight percent 33 neodymium, 66 iron, 1 boron was melted, crushed and milled to a particle size of 5 microns. The powder was oriented in a magnetic field and sintered at 1 0501 10QC to form magnets and cooled to room temperature. The magnetic properties of these magnets were as follows : Table I 35 r (G) " 12,600 12,900 40 12,600 B H c (Oe) 8,800 9,500 9,300 H ci (Oe) 10,600 10,600 11,200 H. K (Oe) 6,900 8,500 7,700 BH max (MGOe) 35.8 38.4 37.4

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The analyzed composition of the magnet had an oxygen content of 2,000 ppm as an integral part of the alloy. These magnets were exposed to a high temperature and humidity utilizing an autoclave. The steam temperature was maintained at 315 F (157 C) for 16 hours. This test provides a means of accelerated testing of long term stability. After this test, the magnets were totally disintegrated. Example 2* To verify whether the rare earth content has any controlling effect on the distintegration of the magnets, a series of alloys were prepared with varying rare earth content and processes by similar procedures described above into magnets. The magnetic properties of the magnets are shown in Table II. * 1 Gauss = 10-4 Tesla 1 Oe = 0,0796 kA/m

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0 202 8 3 4 The oxygen content of these magnets before the autoclave test was 2,000 parts per million. Exemple 3 5 Having determined that the variation of rare earth content does not improve the stability of these magnets, a controlled amount of oxygen was added during processing to increase the oxygen content to 8,000 ppm from the previously used 2,000 ppm of oxygen for the specimens reported in Table II. Magnets were made and subjected to the autoclave test. Figure 5 shows the results of this test. The properties of these magnets before and after the autoclave test are shown in Table III. Table III* Magnetic properties on autoclave tested magnets (Before refers to the properties on the magnets before the test was made) 15 Condition 20 Before After Before After 25 Before After Before After Br (G) 11,200 11,300 10,900 10,800 11,200 11,100 11,000 11,100 Hci (Oe) 20,000 19,500 19,200 18,900 20,200 20,000 18,700 18,400 Hc (Oe) 10,900 10,900 10,500 10,500 10,900 10,700 10,600 10,700 Hk (Oe) 17,900 15,900 15,900 14,800 18,000 16,000 15,100 15,100 BHmax (MGOe) 30.6 31.4 28.9 28.1 30.5 29.4 28.9 29.3

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From this test it is clear that increasing the oxygen content improves the stability of the magnets under high-temperature, humid conditions. Example 4 In order to ascertain the lower and upper limits of oxygen, a series of magnets were prepared from the composition and processing conditions set forth in Example 1 with varying oxygen content. These magnets were then exposed to temperature and humidity in the autoclave test. The results of this experiment are shown graphically in the Figure. The grading for the magnets was given by visually inspecting these magnets. The proportion of the solid magnet remaining compared to the power produced by the disintegration process was used as a measure of classifying into fully disintegrated (020% solid), partially disintegrated (20-80% solid), and excellent resistance (80-100% solid). Claims

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1. A permanent magnet alloy characterised in consisting essentially of, in weight percent, 30 to 36 of at least one rare earth element, 60 to 66 iron, 6,000 to 35,000 ppm oxygen and balance boron. 2. An alloy according to claim 1, wherein said at least one rare earth element is neodymium. 3. An alloy according to claim 1 or 2, wherein sait at least one rare earth element is dysprosium. 4. An alloy according to claim 1, 2 or 3, containing, in weight percent, 9,000 to 30,000 ppm oxygen. Patentanspruche 1. Dauermagnet-Legierung, dadurch gekennzeichnet, da(3 sie im wesentlichen aus 30 bis 36 Gew.-% wenigstens eines Elementes aus der Gruppe seltenen Erden, 60 bis 66 Gew.-% Eisen, 6 000 bis 35 000 ppm Sauerstoff und dem Rest Bor besteht. 2. Legierung nach Anspruch 1, bei der das wenigstens eine Element aus der Gruppe der seltenen Erden Neodym ist. 3. Legierung nach Anspruch 1 Oder 2, bei dem das wenigstens eine Element aus der Gruppe der seltenen Erden Dysprosium ist. 4. Legierung nach Anspruch 1, 2 Oder 3, die in Gew.-% 9 000 bis 30 000 ppm Sauerstoff enthalt. 4

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0 202 8 3 4 Revendications 1. Alliage pour aimant permanent, caracterise en ce qu'il contient essentiellement, en pourcentage en poids, 30 a 36 d'au moins un element des terres rares, 60 a 66 de fer, 6 000 a 35 000 ppm d'oxygene et 5 le reste en bore. 2. Alliage selon la revendication 1, dans lequel I'element des terres rares est le neodyme. 3. Alliage selon la revendication 1 ou la revendication 2, dans lequel I'element des terres rares est le dysprosium. 4. Alliage selon la revendication 1, 2 ou 3, contenant, en pourcentage en poids, 9 000 a 30 000 ppm 10 d'oxygene.

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Wt. % Oxygen In The

Magnet