WO2011032432A1

WO2011032432A1 - Rare earth permanent magnetic material and preparation method thereof

Info

Publication number: WO2011032432A1
Application number: PCT/CN2010/075594
Authority: WO
Inventors: Qing Gong; Xiaoxia Deng; Xin Du
Original assignee: Byd Company Limited
Priority date: 2009-09-15
Filing date: 2010-07-30
Publication date: 2011-03-24
Also published as: CN102024544A; EP2478528A4; EP2478528A1; CN102024544B; US20110062372A1; JP2013504881A; JP5426029B2

Abstract

A rare earth permanent magnetic material is provided, which is represented by the general formula of R_a-x-yHo_xDy_yFe_1-a-b-c-dCo_dM_cB_b, wherein x, y, a, b, c and d are weight percentages of corresponding elements, in which 28%≤ a ≤34%, 0.95%≤ b ≤1.3%, 0≤ c ≤1.5%, 1%≤ d ≤10%, 15%≤ x ≤20% and 3%≤ y ≤8%; wherein R is a rare earth element, which is selected from the group consisting of Nd, Pr, La, Ce, Gd, Tb and combinations thereof; and wherein M is selected from the group consisting of Al, Cu, Ti, V, Cr, Zr, Hf, Nb, Sn, Mo, Ga, Si and combinations thereof. A method for preparing the rare earth permanent magnetic material is also provided.

Description

RARE EARTH PERMANENT MAGNETIC MATERIAL AND PREPARATION METHOD THEREOF

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority, and benefits of Chinese Patent Application No.

200910190316.0 filed with the State Intellectual Property Office of P RC. on September 15, 2009, the entirety of which is incorporated herein by reference.

FIELD

The present disclosure relates to a rare earth permanent magnetic material and a method of preparing the same.

BACKGROUND

Because of their magnetic properties, low cost and ample reserves, Nd-Fe-B permanent magnetic materials are widely used in vehicles, computers, electronics, mechanical and medical devices, etc. In addition, because of their high performance/price ratio, Nd-Fe-B materials have been the ideal materials to produce magnetic devices with high efficiency, small volume and light mass. However, as the continuous expansion of application fields and the development of technology, requirements for performance, operating temperature and corrosion resistance of permanent magnetic materials become higher and higher.

Chinese patent CN101409121 discloses a rare earth permanent magnetic material, which comprises 24 wt% to 28 wt% of PrNd, 0.5 wt% to 7 wt% of Gd , 1 wt% to 5 wt% of Ho, 0 to 0.6 wt% of Dy, 0.9 wt% to 1.1 wt% of B, 0.1 wt% to 0.15 wt% of Cu , 0.2 wt% to 1.2 wt% of Al, 62.35 wt% to 66.5 wt% of Fe, 0.2 wt% to 1.5 wt% of Co, 0.2 wt% to 0.8 wt% of Nb, based on the weight of the rare earth permanent magnetic material. The patent also discloses a method of preparing the material comprising the steps of: mixing, melting, crushing, pressing, sintering and milling. According to embodiments of this patent, elements Gd and Ho are applied instead of one or more of PrNd, Gd, and Dy to form the rare earth permanent magnetic material with a coercivity of 17.65 kOe to 26.83 kOe and a maximum operating temperature of less than 200°C.

Chinese patent CN101404196 discloses a rare earth permanent magnetic material represented by the formula of Re_aHopB_YM_xNyFei-a-p-_Y-x-y, in which Re is a rare earth element including Nd, or a combination of Nd and an element selected from the group consisting of La, Ce, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc and combinations thereof; M is an additive including Co and Cu; N is an additive selected from the group consisting of Ti, V, Cr, Mn, Ni, Zn, Ga, Ge, Al, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Hf, Ta, W, Pd, Au, Pb, Bi, and combinations thereof; α, β, γ, x, and y are weight percentages of corresponding elements, in which: 29%<α<35%, 0.05%<β<0.5%, 0.95%<γ<1.2%, 0<x<10%, 0<y<1.5%; and Fe comprises Fe and an unavoidable impurity. The patent also discloses a method of preparing the material comprising the steps of: melting, casting, crushing, pressing and sintering. According to embodiments of this patent, the rare earth permanent magnetic material has a coercivity of 12.31 kOe to 27.08 kOe and a maximum operating temperature of less than 200°C. SUMMARY

In view thereof, the present disclosure is directed to provide a rare earth permanent magnetic material with high coercivity and high-temperature resistance, and further to provide a method of preparing the same.

According to an embodiment of the present disclosure, a rare earth permanent magnetic material may be provided, which may be represented by the general formula of Ra-x-yHOxDyyFei-a-b-c-dCodMcBb. x, y, a, b, c, and d may be weight percentages of corresponding elements, in which: 28%<a<34%, 0.95%<b<1.3%, 0<c<1.5%, l%<d<10%, 15%<x<20%, and 3%<y<8%; R may be a rare earth element, which may be selected from the group consisting of Nd, Pr, La, Ce, Gd, Tb, and combinations thereof; M may be selected from the group consisting of Al, Cu, Ti, V, Cr, Zr, Hf, Mn, Nb, Sn, Mo, Ga, Si, and combinations thereof.

According to an embodiment of the present disclosure, a method of preparing a rare earth permanent magnetic material as described above may be provided. The method may comprise the steps of: weighting and melting single metals of the rear earth permanent magnetic material to form a melted alloy which is casted to form an ingot or strip casted to form flakes; crushing and jet milling the ingot or the flakes to form a powder, followed by mixing thereof with an antioxidant to form a mixed powder; pressing the mixed powder in a magnetic field to form a parison of the rare earth permanent magnetic material; and sintering the parison under vacuum condition to obtain the rare earth permanent magnetic material.

According to the present disclosure, the rare earth permanent magnetic material, as manufactured by the method as described hereinabove may have a maximum operating temperature of 240 ^°C with a coercivity up to 28.52kOe.

Additional aspects and advantages of the embodiments of present disclosure will be given in part in the following descriptions, become apparent in part from the following descriptions, or be learned from the practice of the embodiments of the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENT

Reference will be made in detail to embodiments of the present invention. The embodiments described herein are explanatory and illustrative, which are used to generally understand the present invention. The embodiments shall not be construed to limit the present invention.

In a first aspect of the present disclosure, an embodiment thereof may provide a rare earth permanent magnetic material represented by the general formula of: Ra-x-yHOxDyyFei-a-b-c-dCodMcBb, in which x, y, a, b, c, and d are weight percentages of corresponding elements, in which: 28%<a<34%, 0.95%<b<1.3%, 0<c<1.5%, l%<d<10%, 15%<x<20%, and 3%<y<8%. R is a rare earth element, which is selected from the group consisting of Nd, Pr, La, Ce, Gd, Tb, and combinations thereof. M is selected from the group consisting of Al, Cu, Ti, V, Cr, Zr, Hf, Mn, Nb, Sn, Mo, Ga, Si, and combinations thereof.

In an alternative embodiment, a, b, c, d, x, and y may have the following range: 30%<a<33%,

0.97%<b<1.2%, 0.1%<c<1.3%, 1.5%<d<9%, 17%<x<19%, and 4.1%<y<7.7%. R may be selected from Nd, Tb, or combinations thereof. In a further alternative embodiment, R may comprise Nd and Tb with a weight ratio of about (5.6 : 1) to about (10.1 : 1).

It has been found by the inventors that, the introduction of Ho and Dy in the respective ranges as described above may effectively increase the coercivity and the maximum operating temperature of the rare earth permanent material. The maximum operating temperature mentioned above is the highest temperature at which a permanent material can be kept for about 2 hours with an irreversible magnetic flux loss less than 5%.

In another aspect of the present disclosure, an embodiment provides a method for preparing a rare earth permanent magnetic material, comprising the steps of: weighing and melting single metals to form a melted alloy which is casted to form an ingot or strip casted to form flakes; crushing and jet milling the ingot or the strip-casting flakes to form a powder, followed by mixing the powder with an antioxidant to form a mixed powder; pressing the mixed powder in a magnetic field to form a parison of the rare earth permanent magnetic material; and sintering the parison under vacuum condition to obtain the rare earth permanent magnetic material. In an embodiment, the rare earth permanent magnetic material may be represented by the following general formula: R_a-x-yHo_xDy_y Fei_-a-b-_c-d Cod M3_b, in which x, y, a, b, c, and d are weight ratios of corresponding elements, in which: 28%<a<34%, 0.95%<b<1.3%, 0<c<1.5%, l%<d<10%, 15%<x<20%, and 3%<y<8%. R is a rare earth element, which is selected from the group consisting of Nd, Pr, La, Ce, Gd, Tb, and combinations thereof. M is selected from the group consisting of Al, Cu, Ti, V, Cr, Zr, Hf, Mn, Nb, Sn, Mo, Ga, Si, and combinations thereof.

In an alternative embodiment, 30%<a<33%, 0.97%<b<1.2%, 0.1%<c<1.3%, 1.5%<d<9%,

17%<x<19%, and 4.1 %<y<7.7%. R may be selected from Nd, Tb, or combinations thereof. In a further alternative embodiment, R may comprise Nd and Tb with a weight ratio of about (5.6 : 1) to about (10.1 : 1). In an alternative embodiment, the method may further comprise a step of tempering the parision under vacuum condition.

The steps of the method will be described in detail in the follows.

First, single metals of the rare earth permanent magnetic material as described above are weighted and melted to form a melted alloy, and an ingot is casted or strip-casting flakes are formed.

The casting process may be those known in the art. In an embodiment, a melted alloy may be casted in a water-cooled copper mould and cooled accordingly to obtain the ingot. In some embodiments, the strip-casting flaking process may be those well known in the art, and may comprise the steps of: pouring a melted alloy onto the surface of a rotating copper roller having a water-cooled interior, with a rotating linear velocity of about 1 m/s to about 2 m/s, and then rapidly cooling the melted alloy to form flakes with a thickness of about 0.2 mm to about 0.5 mm.

Secondly, the ingot or the strip-casting flakes is or are crushed and jet milled to form a powder, followed by mixing the powder with an antioxidant to form a mixed powder.

In an embodiment, the crushing process may be a hydrogen decrepitation process or a mechanical crushing process using a crusher. In some embodiments, the hydrogen decrepitation process using a hydrogen decrepitation furnace may be those well known in the art, and may comprise, for example, the steps of placing the ingot or the strip-casting flakens into a stainless steel vessel, filling the vessel with high purity hydrogen until about one atmospheric pressure after vacuumizing, and then maintaining the pressure for about 20 minutes to about 30 minutes until the ingot or the strip-casting flakes decrepitates and the temperature of the vessel increases, which is resulted from the decrepitation of the ingot or the strip-casting flakes due to the formation of a hydride after the ingot or the strip-casting flakes absorbs hydrogen, and finally vacuumizing the vessel and dehydrogenating the hydride at a temperature of about 400°C to about 600°C for about 2 hours to about 10 hours to obtain powder particles. In some embodiments, the mechanical crushing process may be those well known in the art, and may comprise, for example, the steps of rough crushing the ingot or the strip-casting flakes in a jaw crusher, followed by secondary crushing the rough crushed ingot or the strip-casting flakes in a secondary crusher to obtain powder particles.

In some embodiments, the jet milling process may be those well known in the art, and may comprise the steps of accelerating the powder particles to a supersonic speed by airflow, and then causing the accelerated powder particles to collide with each other, thus breaking up the accelerated powder particles into more fine powder with an average particle diameter of about 2 microns to about 10 microns.

The mixing process may be those known in the art. For example, the powder may be mixed with an antioxidant uniformly in a mixer to form a mixed powder.

In an embodiment, the antioxidant is used in an amount of about 0.1 wt% to about 5 wt% of the powder. There are no special limitations on the antioxidant. For example, the antioxidant may be selected from polyethylene oxide alkyl ether, polyethylene oxide monofatty ester, polyethylene oxide alkenyl ether, and combinations thereof. In an embodiment, the antioxidant may be polyethylene oxide monofatty ester commercially available from the Shenzhen Deepocean Chemical Industry Co., Ltd., P R C.

Thirdly, the mixed powder may be oriented and pressed in a magnetic field to form a parison.

The pressing process may be achieved by a well known process. In an alternative embodiment, the mixed powder may be oriented and pressed in a magnetic field to form a parison. In some embodiments, the pressing step may be performed under a magnetic field intensity of about 1.2 T to about 2.0 T and an isostatic pressure of about 10 MPa to about 200 MPa for about 10 seconds to about 60 seconds.

Fourthly, the parison is sintered and tempered under a vacuum to obtain the rare earth permanent magnetic material.

The sintering and tempering steps may be those known in the art. In an alternative embodiment, the sintering step may be performed under vacuum. In some embodiments, the parison may be sintered under a vacuum of about 2*10^"2 Pa to 5 *10^"2 Pa and a temperature of about 1030°C to about 1120°C for a period of about 2 hours to about 4 hours, then tempered in a first tempering step at a temperature of about 800°C to about 920°C for a period of about 1 hour to about 3 hours, and finally tempered in a second tempering step under a vacuum of about 2*10^"2 Pa to 5*10^"2 Pa and a temperature of about 500°C to about 650°C for a period of about 2 hours to about 4 hours to obtain the rare earth permanent magnetic material. In the method according to the present disclosure, the tempering may be divided into a primary tempering or a secondary tempering. Compared with primary tempering, secondary tempering may enhance metallurgical structure stability with reduced internal stress, so that the magnetic performance of the magnetic material may be improved. According to an embodiment of the present disclosure, a secondary tempering may be adopted to improve the magnetic property of the rare earth permanent magnetic material.

The present disclosure will be described in detail with reference to the following examples. EXAMPLE 1

A method for preparing a rare earth permanent magnetic material comprises the following steps.

(1) Based on the weight of the rare earth permanent magnetic material, single metals: Pr, Nd, Dy, Tb, Ho, B, Fe_, Co, Al, Cu, Zr, and Ga with weight percentages of 0.46%, 2.02%, 2.80%, 0.20%, 17.91 %, 1%, 73.11%, 1.65%, 0.2%, 0.15%, 0.15%, and 0.1 % were weighed and placed in VI-200SC strip-casting furnace available from ULVAC Vacuum Furnace (Shenyang), Co., Ltd., P.R.C. to form strip-casting flakes with a thickness of about 0.3 mm. The surface of the copper roller in the strip- casting furnace had a rotating linear velocity of about 1.5 m/s.

(2) The flakes were crushed in a hydrogen decrepitation furnace, and jet milled to produce a powder with an average particle diameter of about 3.5 microns. Polyethylene oxide alkyl ether in an amount of about 3 wt% of the powder was added into the powder and mixed with the powder uniformly by V-25 mixer available from Wuxi Xinguang Powder Process Co., Ltd., P.R.C. to form a mixed powder.

(3) The mixed powder was pressed by FCY 300 magnetic press machine available from Shanxi Golden kaiyuan Co., Ltd., P.R.C. to form a parison. The intensity of the magnetic field was about 1.2 T, the pressure was about 200 MPa, and the pressing time was about 10 seconds.

(4) The parison was sintered under a vacuum of 2* 10^"2 Pa at a temperature of about 1080°C for about 3 hours, then tempered at about 850°C for about 2 hours, and finally tempered at about 550°C for about 3 hours to prepare a rare earth permanent magnetic material Tl represented by Pro.46Nd2.o2Dy2.8oTbo.2oHoi7.9iBiFe₇3.iiCoi.65Alo.2Cuo.i5Zro.i5Gao.i.

COMPARATIVE EXAMPLE 1 A method for preparing a rare earth permanent magnetic material by the single metals disclosed in EXAMPLE 6 of Chinese Patent No. CN 101409121 , which is substantially similar to the method of EXAMPLE 1 according to the present disclosure, comprises the following steps.

(1) Based on the weight of the rare earth permanent magnetic material, PrNd alloy, single metals: Ho, Dy, Gd, B, Cu, Al, Co, Nb, and Fe with weight percentages of 28%, 4%, 0.5%, 1.0%, 1%, 0.1%,

0.55%, 0.7%, 0.2%, and 63.95% respectively were weighed and placed in VI-200SC strip-casting furnace available from ULVAC Vacuum Furnace (Shenyang), Co., Ltd., P.R.C. to form strip-casting flakes with a thickness of about 0.3 mm. The surface of the copper roller in the strip-casting furnace had a rotating linear velocity of about 1.5 m/s.

(3) The mixed powder was pressed by FCY 300 magnetic press machine available from Shanxi

Golden kaiyuan Co., Ltd., P.R.C. to form a parison. The intensity of the magnetic field was about 1.2 T, the pressure was about 200 MPa, and the pressing time was about 10 seconds.

(4) The parison was sintered under a vacuum of 2* 10^"2 Pa at a temperature of about 1080°C for about 3 hours, then tempered at about 850°C for about 2 hours, and finally tempered at about 550°C for about 3 hours to prepare a rare earth permanent magnetic material CT1 represented by (PrNd)28Ho4Dyo.₅Gdi.oBiCuo.iAlo.55Coo.7Nbo.2Fe63.95.

EXAMPLE 2

A method for preparing a rare earth permanent magnetic material comprises the following steps. (1) Based on the weight of the rare earth permanent magnetic material, single metals: Pr, Nd, Dy,

Ho, B, Fe, and Co with weight percentages of 5.2%, 3.8%, 8%, 17%, 1%, 63.5%, and 1.5% respectively were weighed and placed in VI-200SC strip-casting furnace available from ULVAC Vacuum Furnace (Shenyang), Co., Ltd., P.RC. to form strip-casting flakes with a thickness of about 0.38 mm. The surface of the copper roller in the strip-casting furnace had a rotating linear velocity of about 1.2 m/s.

(2) The flakes were crushed in a hydrogen decrepitation furnace. After absorbing hydrogen to saturation at room temperature and being dehydrogenated at about 550°C for about 6 hours, the crushed flakes were jet milled to produce a powder with an average particle diameter of about 3.8 microns. Polyethylene oxide monofatty ester in an amount of about 0.2 wt% of the powder was added into the powder and mixed with the powder uniformly by V-25 mixer available from Wuxi Xinguang Powder Process Co., Ltd., P.R.C. to form a mixed powder.

Golden kaiyuan Co., Ltd., P.R.C. to form a parison. The intensity of the magnetic field was about 1.5 T, the pressure was about 150 MPa, and the pressing time was about 15 seconds.

(4) The parison was sintered under a vacuum of 2* 10^"2 Pa at a temperature of about 1085°C for about 3 hours, then tempered at about 880°C for about 2.5 hours, and finally tempered at about 580°C for about 2.5 hours to prepare a rare earth permanent magnetic material T2 represented by Pr5.2Nd₃.8Dy₈Hoi7BiFe63.5Coi.5.

EXAMPLE 3

Ho, B, Fe, Co, Al, Cu, Zr, and Ga with weight percentages of 1%, 6%, 6.5%, 18%, 0.95%, 61.95%, 5%, 0.2%, 0.15%, 0.15% and 0.1 % respectively were weighed and placed in VI-200SC strip-casting furnace available from ULVAC Vacuum Furnace (Shenyang), Co., Ltd., P.R.C. to form strip-casting flakes with a thickness of about 0.35 mm. The surface of the copper roller in the strip-casting furnace had a rotating linear velocity of about 1.4 m/s.

(2) The flakes were crushed in a hydrogen decrepitation furnace. After absorbing hydrogen to saturation at room temperature and being dehydrogenated at about 550°C for about 6 hours, the crushed flakes were jet milled to produce a powder with an average particle diameter of about 3.6 microns. Polyethylene oxide alkenyl ether in an amount of about 5 wt% of the powder was added into the powder and mixed with the powder uniformly by V-25 mixer available from Wuxi Xinguang Powder Process Co., Ltd., P.R.C. to form a mixed powder.

(3) The mixed powder was pressed by FCY 300 magnetic press machine available from Shanxi Golden kaiyuan Co., Ltd., P.RC. to form a parison. The intensity of the magnetic field was about 1.6 T, the pressure was about 140 MPa, and the pressing time was about 20 seconds.

(4) The parison was sintered under a vacuum of 2* 10^"2 Pa at a temperature of about 1090°C for about 3 hours, then tempered at about 900°C for about 2.5 hours, and finally tempered at about 540°C for about 3 hours to prepare a rare earth permanent magnetic material T3 represented by PriNd6Dy₆.5Hoi8Bo.95Fe6i.95Co₅Alo.2Cuo.i5Zro.i5Gao.i.

EXAMPLE 4

(1) Based on the weight of the rare earth permanent magnetic material, single metals: Nd, Dy, Ho, B, Fe, Co, Al, Cu, Zr, and Ga with weight percentages of 3.5%, 6%, 18.5%, 1%, 69.25%, 1 %, 0.3%, 0.15%, 0.15%, and 0.15% respectively were weighed and placed in VI-200SC strip-casting furnace available from ULVAC Vacuum Furnace (Shenyang), Co., Ltd., P.R.C. to form strip-casting flakes with a thickness of about 0.28 mm. The surface of the copper roller in the strip-casting furnace had a rotating linear velocity of about 2.2 m/s.

(2) The flakes were crushed in a hydrogen decrepitation furnace. After absorbing hydrogen to saturation at room temperature and being dehydrogenated at about 550°C for about 6 hours, the crushed flakes were jet milled to produce a powder with an average particle diameter of about 2 microns. Polyethylene oxide alkenyl ether in an amount of about 4.5 wt% of the powder was added into the powder and mixed with the powder uniformly by V-25 mixer available from Wuxi Xinguang Powder Process Co., Ltd., P.R.C. to form a mixed powder.

(3) The mixed powder was pressed by FCY 300 magnetic press machine available from Shanxi Golden kaiyuan Co., Ltd., P.R.C. to form a parison. The intensity of the magnetic field was about 2.0 T, the pressure was about 10 MPa, and the pressing time was about 50 seconds.

(4) The parison was sintered under a vacuum of 2* 10^"2 Pa at a temperature of about 1030°C for about 4 hours, then tempered at about 900°C for about 2 hours, and finally tempered at about 520°C for about 3 hours to prepare a rare earth permanent magnetic material T4 represented by Nd3.5Dy6Hoi8.5B1Fe69.25Co1Al0.3Cu0.15Zr0.15Ga0.15.

EXAMPLE 5

A method for preparing a rare earth permanent magnetic material comprises the following steps. (1) Based on the weight of the rare earth permanent magnetic material, single metals: Pr, Nd, Dy, Ho, B, Fe, Co, Al, Cu, Zr, and Ga with weight percentages of 1 %, 6.9%, 7.6%, 16%, 0.98%, 56.92%, 10%, 0.2%, 0.15%, 0.15%, and 0.1 % respectively were weighed and placed in VI-200SC strip- casting furnace available from ULVAC Vacuum Furnace (Shenyang), Co., Ltd., P.RC. to form strip- casting flakes with a thickness of about 0.42 mm. The surface of the copper roller in the strip-casting furnace had a rotating linear velocity of about 1 m/s.

(2) The flakes were crushed in a hydrogen decrepitation furnace. After absorbing hydrogen to saturation at room temperature and being dehydrogenated at about 560°C for about 6 hours, the crushed flakes were jet milled to produce a powder with an average particle diameter of about 4.2 microns. Polyethylene oxide alkenyl ether in an amount of about 3 wt% of the powder was added into the powder and mixed with the powder uniformly by V-25 mixer available from Wuxi Xinguang Powder Process Co., Ltd., P.R.C. to form a mixed powder.

(3) The mixed powder was pressed by FCY 300 magnetic press machine available from Shanxi Golden kaiyuan Co., Ltd., P.R.C. to form a parison. The intensity of the magnetic field was about 1.2

T, the pressure was about 200 MPa, and the pressing time was about 10 seconds.

(4) The parison was sintered under a vacuum of 2* 10^"2 Pa at a temperature of about 1065°C for about 3.5 hours, then tempered at about 870°C for about 2.5 hours, and finally tempered at about 540°C for about 2.5 hours to prepare a rare earth permanent magnetic material T5 represented by PriNd6.9Dy7.6Hoi6Bo.98Fe56.92CoioAlo.2Cuo.i5Zro.i₅Gao.i.

EXAMPLE 6

A method for preparing a rare earth permanent magnetic material comprises the following steps. (1) Based on the weight of the rare earth permanent magnetic material, single metals: Pr, Nd, Dy, Tb, Ho, B, Fe, Co, Al, Cu, and Zr with weight percentages of 1%, 5%, 4.1%, 0.5%, 19%, 1 %, 67.35%, 1.5%, 0.25%, 0.15%, and 0.15% respectively were weighed and placed in VI-200SC strip- casting furnace available from ULVAC Vacuum Furnace (Shenyang), Co., Ltd., P.R.C. to form strip- casting flakes with a thickness of about 0.45 mm. The surface of the copper roller in the strip-casting furnace had a rotating linear velocity of about 0.8 m/s.

(2) The flakes were crushed in a hydrogen decrepitation furnace. After absorbing hydrogen to saturation at room temperature and being dehydrogenated at about 550°C for about 6 hours, the crushed flakes were jet milled to produce a powder with an average particle diameter of about 4.5 microns. Polyethylene oxide alkenyl ether in an amount of about 4 wt% of the powder was added into the powder and mixed with the powder uniformly by V-25 mixer available from Wuxi Xinguang Powder Process Co., Ltd., P.R.C. to form a mixed powder. (3) The mixed powder was pressed by FCY 300 magnetic press machine available from Shanxi Golden kaiyuan Co., Ltd., P.R.C. to form a parison. The intensity of the magnetic field was about 1.4 T, the pressure was about 100 MPa, and the pressing time was about 60 seconds.

(4) The parison was sintered under a vacuum of 2* 10^"2 Pa at a temperature of about 1085°C for about 4 hours, then tempered at about 920°C for about 1 hour, and finally tempered at about 650°C for about 2 hours to prepare a rare earth permanent magnetic material T6 represented by Pr1Nd5Dy4.1Tb0.5Ho19B1Fe67.35Co1.5Al0.25Cu0.15 r0.15.

EXAMPLE 7

(1) Based on the weight of the rare earth permanent magnetic material, single metals: Pr, Nd, Dy, Tb, Ho, B, Fe, Co, Al, and Nb with weight percentages of 1.4%, 5.6%, 3%, 1 %, 20%, 1%, 65%, 1.5%, 0.3%, 1.2% respectively were weighed and placed in VI-200SC strip- casting furnace available from ULVAC Vacuum Furnace (Shenyang), Co., Ltd., P.R.C. to form strip-casting flakes with a thickness of about 0.5 mm. The surface of the copper roller in the strip-casting furnace had a rotating linear velocity of about 0.6 m/s.

(2) The flakes were crushed in a hydrogen decrepitation furnace. After absorbing hydrogen to saturation at room temperature and being dehydrogenated at about 550°C for about 6 hours, the crushed flakes were jet milled to produce a powder with an average particle diameter of about 4.8 microns. Polyethylene oxide alkenyl ether in an amount of about 3 wt% of the powder was added into the powder and mixed with the powder uniformly by V-25 mixer available from Wuxi Xinguang Powder Process Co., Ltd., P.R.C. to form a mixed powder.

(3) The mixed powder was pressed to by FCY 300 magnetic press machine available from Shanxi Golden kaiyuan Co., Ltd., P.R.C. to form a parison. The intensity of the magnetic field was about 1.6 T, the pressure was about 180 MPa, and the pressing time was about 30 seconds.

(4) The parison was sintered under a vacuum of 2* 10^"2 Pa at a temperature of about 1095°C for about 3 hours, then tempered at about 820°C for about 2.5 hours, and finally tempered at about 510°C for about 3.5 hours to prepare a rare earth permanent magnetic material T7 represented by Pri.4Nd5_.6Dy₃TbiHo₂oBiFe₆₅Coi_.5Alo_.3Nbi_.2.

EXAMPLE 8

A method for preparing a rare earth permanent magnetic material comprises the following steps. (1) Based on the weight of the rare earth permanent magnetic material, single metals: Nd, Dy, Ho, B, Fe, Co, Al, Cu, Zr and Ga with weight percentages of 5%, 5.2%, 19.3%, 1.3%, 67.6%, 1%, 0.2%, 0.15%, 0.15%, and 0.1% respectively were respectively were weighed and placed in VI- 50RLM melting furnace available from ULVAC Vacuum Furnace (Shenyang), Co., Ltd., P.R.C. to form a melted alloy. The melted alloy is casted and cooled accordingly in a water-cooled copper mould to form an ingot.

(2) The ingot was rough crushed in a jaw crusher, secondary crushed in a secondary crusher, and jet milled to produce a powder with an average particle diameter of about 10 microns. Polyethylene oxide alkyl ether in an amount of about 5 wt% of the powder was added into the powder and mixed with the powder uniformly by V-25 mixer available from Wuxi Xinguang Powder Process Co., Ltd., P.R.C. to form a mixed powder.

(4) The parison was sintered under a vacuum of 5*10^"2 Pa at a temperature of about 1120°C for about 2 hours, then tempered at about 800°C for about 3 hours, and finally tempered at about 500°C for about 4 hours to prepare a rare earth permanent magnetic material T8 represented by Nd₅Dy5.2Hoi9.3Bi.3Fe67.6CoiAlo.2Cuo.i5 ro.i₅Gao.i . COMPARATIVE EXAMPLE 2

A method for preparing a rare earth permanent magnetic material, which is substantially similar to the method disclosed in EXAMPLE 1 of Chinese Patent No. CN101409121, comprises the following steps.

(1) Based on the weight of the rare earth permanent magnetic material, about 100 kg of PrNd alloy, single metals: Gd, Ho, Dy, B, Cu, Al, Co, Nb, and Fe with weight percentages of 26%, 0.5%, 1%, 6.0%, 1%, 0.15%, 0.7%, 1.5%, 0.8%, and 62.35% respectively were weighed, placed in a medium frequency induction melting furnace with a single surface for cooling a copper mould according to the respective melting points of the single metals, and melted under a vacuum of about 5xl0^"2 Pa to form a steel ingot.

(2) The steel ingot was rough crushed and secondary crushed to form powder particles.

Dysprosium oxide (Dy₂03) in an amount of about 1 wt% of the powder particles was added into the powder particles and jet milled form a powder with an average particle diameter of about 3.5 microns to about 4.2 microns.

(3) The powder was pressed under a pressure of about 200 MPa in an isostatic press to form a parison.

(4) The parison was sintered in a sintering furnace under a vacuum of about 3 *10^"2 Pa at a temperature of about 1100°C for about 1 hour, then tempered at about 920°C for about 3 hours, and finally tempered at about 530°C for about 4 hours; and finally grounded to form a rare earth permanent magnetic material CT2 represented by (PrNd)28Ho Dyo.5Gdi.oBiCuo.iAlo.55Coo.7Nbo.2Fe₆3.95.

Test

Coercivities and irreversible magnetic flux losses at different maximum operating temperatures were tested for the rare earth permanent magnetic materials T1-T8, CTl and CT2 using a curve measurement system NTM200C (National Institute of Metrology, P.R.C.).

Test results were shown in Table 1.

Table 1

In Table 1 , the term "irr 200°C (%)" refers to the irreversible magnetic flux loss at a temperature of about 200°C, while the term "irr 240°C (%)" refers to the irreversible magnetic flux loss at a temperature of about 240°C. According to the results in Table 1 , the rare earth permanent magnetic materials according to embodiments of the present disclosure may have an irreversible magnetic flux loss of less than 5% at a temperature of 200°C, and can operate normally at a temperature of 240°C. For example, as shown in Table 1 , Tl may have a highest coercivity of about 28.54 kOe, an irreversible magnetic flux loss of about 1.2% at a temperature of 200°C, and an irreversible magnetic flux loss of about 3.6% at a temperature of 240°C, which indicates that the material of Example 1 may have a maximum operating temperature of 240°C. In another aspect, CTl has a highest coercivity of about 20.79 kOe and an irreversible magnetic flux loss of about 6.7% at a temperature of 200°C, and CT2 has a highest coercivity of about 26.83 kOe and an irreversible magnetic flux loss of about 5.2% at a temperature of 200°C, which indicates that both the materials of Comparative Example 1 and Comparative Example 2 may have a maximum operating temperature of less than 200°C. It can be seen from the results shown in Table 1 that, the rare earth permanent magnetic materials according to the embodiments of the present invention may have higher coercivities and maximum operating temperatures.

Although explanatory embodiments have been shown and described, it would be appreciated by those skilled in the art that changes, alternatives, and modifications all falling into the scope of the claims and their equivalents can be made in the embodiments without departing from spirit and principles of the disclosure.

Claims

WHAT IS CLAIMED IS:

1. A rare earth permanent magnetic material represented by the general formula of:

Ra-x-yHOxDyyFei-a-b-o-dCodMoBb

wherein x, y, a, b, c, and d are weight percentages of corresponding elements, in which: 28%<a<34%, 0.95%<b<1.3%, 0<c<1.5%, l%<d<10%, 15%<x<20%, and 3%<y<8%;

R is a rare earth element, which is selected from the group consisting of Nd, Pr, La, Ce, Gd, Tb, and combinations thereof;

M is selected from the group consisting of Al, Cu, Ti, V, Cr, Zr, Hf, Mn, Nb, Sn, Mo, Ga, Si, and combinations thereof.

2. The rare earth permanent magnetic material according to claim 1, wherein 30%<a<33%, 0.97%<b<1.2%, 0.1%<c<1.3%, 1.5%<d<9%, 17%<x<19%, 4.1%<y<7.7%.

3. The rare earth permanent magnetic material according to claim 1 , wherein R is selected from Nd, Tb, or combinations thereof.

4. The rare earth permanent magnetic material according to claim 3, wherein R comprises Nd and Tb with a weight ratio of about (5.6 : 1) to about (10.1 : 1).

5. The rare earth permanent magnetic material according to claim 1 , the rare earth permanent magnetic material is represented by the following formula:

Pro.46Nd2.o2Dy2.8oTbo.2oHoi7.9iBiFe₇3.iiCoi.65Alo.2Cuo.i5Zro.i5Gao.i.

6. A method of preparing a rare earth permanent magnetic material according to claim 1 , comprising the steps of:

weighting and melting single metals of the rear earth permanent magnetic material to form a melted alloy which is casted to form an ingot or strip casted to form flakes;

crushing and jet milling the ingot or the flakes to form a powder, followed by mixing thereof with an antioxidant to form a mixed powder;

pressing the mixed powder in a magnetic field to form a parison of the rare earth permanent magnetic material; and

sintering the parison under vacuum condition to obtain the rare earth permanent magnetic material.

7. The method according to claim 6, further comprising a step of tempering the parision under vacuum condition.

8. The method according to claim 6, wherein the rare earth permanent magnetic material powder has an average particle diameter of about 2 microns to about 10 microns.

9. The method according to claim 6, wherein the tempering step is performed under a temperature from about 500°C to about 920°C.

10. The method according to claim 6, wherein the antioxidant is selected from the group consisting of polyethylene oxide alkyl ether, polyethylene oxide monofatty ester, polyethylene oxide alkenyl ether, or combinations thereof.

11. The method according to claim 6, wherein the antioxidant is used in an amount of about 0.1 wt% to about 5 wt% of the powder.

12. The method according to claim 6, wherein the pressing step is performed under a magnetic field intensity ranging from about 1.2 T to about 2.0 T and a pressure of about 10 MPa to about 200

MPa for about 10 seconds to about 60 seconds.

13. The method according to claim 6, wherein the sintering step is performed under a vacuum degree of about 2x l 0^"2 to about 5x l O^"2 Pa and a temperature of about 1030°C to about 1120°C for about 2 hours to about 4 hours.

14. The method according to claim 6, wherein the tempering step is performed for about 2 hours to about 8 hours.

15. The method according to claim 6, wherein the tempering step is performed under a vacuum degree of about 2 ^χ 10^"2 Pa to 5 ^χ 10^"2 Pa.