WO2020015389A1 - 一种高韧性、高矫顽力含Ce烧结稀土永磁体及其制备方法 - Google Patents

一种高韧性、高矫顽力含Ce烧结稀土永磁体及其制备方法 Download PDF

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WO2020015389A1
WO2020015389A1 PCT/CN2019/081439 CN2019081439W WO2020015389A1 WO 2020015389 A1 WO2020015389 A1 WO 2020015389A1 CN 2019081439 W CN2019081439 W CN 2019081439W WO 2020015389 A1 WO2020015389 A1 WO 2020015389A1
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phase
cerium
phase alloy
permanent magnet
alloy
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French (fr)
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李安华
冯海波
李卫
席龙龙
谭敏
赵扬
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钢铁研究总院
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Priority to US17/047,229 priority Critical patent/US11195645B2/en
Priority to JP2021502796A priority patent/JP7170833B2/ja
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
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    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered
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    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
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    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
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    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0573—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes obtained by reduction or by hydrogen decrepitation or embrittlement
    • H—ELECTRICITY
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
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    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/0536—Alloys characterised by their composition containing rare earth metals sintered
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    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing
    • H—ELECTRICITY
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    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0273—Imparting anisotropy
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    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0293—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets
    • H—ELECTRICITY
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F7/00—Magnets
    • H01F7/02—Permanent magnets [PM]

Definitions

  • the invention belongs to the technical field of rare earth permanent magnet materials, and particularly relates to a sintered rare earth permanent magnet containing Ce with high toughness and high coercivity and a preparation method thereof.
  • the anisotropy field H A of the Ce 2 Fe 14 B compound is much lower than that of Nd 2 Fe 14 B, so the coercivity of the cerium-containing magnet is low.
  • the literatures [Journal of Applied Physics, 1985, 57: 4146] and [Journal of Applied Physics, 1994, 75: 6268] reported that when using 5% Ce-15% Pr-Nd, the intrinsic coercive force is 10.2kOe, The magnetic energy product is 40MGOe, and when using 40% Ce-10% Pr-50% Nd, the intrinsic coercive force is 9.2kOe and the magnetic energy product is 28.2MGOe. In order to improve the coercive force of cerium-containing magnets, those skilled in the art have made unremitting efforts.
  • the cerium-containing sintered magnet prepared by the dual main phase method described in Chinese patent application CN102436892A does not contain heavy rare earth elements, and the intrinsic coercive force Hcj of the magnet is about 11-12 kOe.
  • the Chinese patent application CN102800454A which is prepared by a dual main phase process, is named (Ce x , Re 1-x ) Fe 100-abc B b TM c sintered magnet.
  • Re is one of the elements Nd, Pr, Dy, Tb, Ho One or more kinds
  • the intrinsic coercive force Hcj of the magnet is about 12 to 13 kOe.
  • the sintered cerium magnet compounded with Gd and Ce described in Chinese patent application CN104900360A has an intrinsic coercive force Hcj of about 10 kOe to 12 kOe.
  • Chinese patent application CN104575920A uses a single main phase method to prepare sintered cerium magnets. In a narrow range of cerium content (cerium accounts for 24 to 32 wt.% Of total rare earth content), the intrinsic coercivity Hcj of the magnet is 12kOe to 13kOe When the magnet alloy formula contains 3 wt.% Dy, the internal coercive force Hcj of the internal alloy reaches about 15-16 kOe.
  • Chinese patent application CN107275026A discloses a cerium-rich rare earth permanent magnet using lanthanum in bulk.
  • the intrinsic coercive force Hcj of the magnet is about 9.0kOe to 12kOe.
  • the Chinese patent application CN101694797A of McGerman Magnetics (Tianjin) Co., Ltd. proposes a new NdFeB magnetic material with a Ce substitution amount of 10 to 40% of Nd. %, Used for the production of rapidly quenched bonded neodymium iron boron magnetic powder.
  • the intrinsic coercive force Hcj of this magnet is about 7kOe ⁇ 9kOe.
  • the object of the present invention is to provide a Ce-containing sintered rare earth permanent magnet with high toughness and high coercivity and a preparation method thereof.
  • the present invention provides the following technical solutions:
  • the invention provides a sintered rare earth permanent magnet containing Ce with high toughness and high coercivity, which is prepared through the steps of raw material preparation, rapid solidification smelting, hydrogen crushing and jet milling powder, orientation molding, sintering and heat treatment.
  • the raw materials are main phase alloy powder and cerium additive phase alloy powder.
  • the cerium additive phase is a magnetic phase or a non-magnetic liquid phase alloy; the cerium additive phase alloy accounts for 5% to 30% of the total mass of the permanent magnet, and the rest is the main phase.
  • the alloy composition of the main phase is expressed as [(Nd, Pr) 1-x1 RE x1 ] 29.5 ⁇ 32 Fe bal.
  • the intrinsic coercive force Hcj of the permanent magnet is 17 to 28.73 kOe, and the fracture toughness K IC is 4.5 to 5.0 MPa ⁇ m 1/2 .
  • the final product of the permanent magnet has a cerium oxide flocculent phase.
  • the permanent magnet when the cerium additive phase is a magnetic phase, the permanent magnet is a bimagnetic main phase alloy; when the cerium additive phase is a non-magnetic liquid phase alloy, the cerium additive phase forms a grain boundary phase.
  • a method for preparing a high-toughness, high-coercivity Ce-containing sintered rare earth permanent magnet includes (1) raw material preparation, (2) rapid solidification smelting, (3) hydrogen crushing and jet milling powder, and (4) orientation Forming, (5) sintering and heat treatment steps.
  • step (1) the mass percentage is [(Nd, Pr) 1-x1 RE x1 ] 29.5 ⁇ 32 Fe bal. -B 0.9 ⁇ 1.05 TM 1.0 ⁇ 3.0 , ((Nd, Pr) 1-xy Re x Ce y ) 33 ⁇ 60 Fe bal.
  • the cerium additive phase is a magnetic phase or a non-magnetic liquid alloy
  • step (2) a main-phase alloy quick-setting sheet and a cerium-added phase alloy quick-setting sheet are separately prepared;
  • step (3) the main phase quick-setting zone and the cerium-added phase quick-setting zone are mixed in a mass percentage of 30 to 5% of the cerium-added phase quick-setting zone, and the rest of the main-phase quick-setting zone are mixed, and then hydrogen is carried out.
  • Crushing and jet milling powder during the jet milling stage, a certain concentration of oxygen is added to the inert gas, so that the final magnet has an oxygen content of 1500 to 2500 ppm.
  • the method includes the following steps:
  • the powder made in the main phase alloy quick-set sheet and the cerium-added phase alloy quick-set sheet prepared in step (2) or the main-phase alloy quick-set sheet and the cerium-added phase alloy quick-set sheet is mixed in a certain proportion, and then hydrogenated. Crushed, dehydrogenated, air-milled powder to make magnetic powder; or,
  • the main-phase alloy quick-setting flakes and cerium-added phase alloy quick-setting flakes obtained in step (2) were respectively subjected to hydrogen crushing and dehydrogenation treatment, and then the dehydrogenated main-phase alloy powder and cerium-added phase alloy powder were processed according to certain conditions. Proportional mixing, magnetic powder produced by jet milling; or,
  • the main-phase alloy quick-setting flakes and cerium-added phase alloy quick-setting flakes obtained in step (2) were separately hydrogen-broken, dehydrogenated, and jet-milled to make main-phase alloy magnetic powder and cerium-added phase alloy magnetic powder, and then Mix the main phase alloy magnetic powder and the cerium additive phase alloy magnetic powder in a certain proportion;
  • the average particle size of the magnetic powder made by jet milling is 2.0-5.0 ⁇ m;
  • Orientation molding orientation-molding the magnetic powder obtained in step (3) in a magnetic field press, and then cold isostatic pressing to form a blank, with a density of 3.8 to 5.0 g / cm 3 ;
  • Sintering and heat treatment Put the blank prepared in step (4) into a high-vacuum sintering furnace, and evacuate to less than 10E-1Pa to start heating; keep the temperature at 400 ° C, 650 ° C, and 830-880 ° C for 0.5. Degassing treatment for ⁇ 1 hour; then vacuum sintering at 1020 °C ⁇ 1100 °C, sintering time is 2 ⁇ 5 hours, and then tempering heat treatment at 800 ⁇ 920 °C and 400 ⁇ 650 °C respectively for 2 ⁇ 5 hours, and finally obtain High coercivity sintered rare earth permanent magnet containing cerium.
  • the linear speed of the water-cooled copper roll is 1.0 to 2.0 m / s, and a quick-setting sheet having an average thickness of 0.28 to 0.32 mm is prepared.
  • the concentration of oxygen added in the inert gas is 50-80 ppm in the jet milling stage.
  • the average particle size of the magnetic powder made by jet milling is 2.5-3.5 ⁇ m.
  • the sintering temperature is from 1050 ° C to 1080 ° C.
  • the final magnet has a cerium oxide floc phase.
  • the sintered rare earth permanent magnet containing Ce with high toughness and high coercive force according to the present invention includes a main phase and an cerium additive phase, wherein the cerium additive phase may be a magnetic phase or a non-magnetic liquid phase alloy.
  • the cerium-added phase alloy of the present invention has a higher total rare earth content and a lower melting point, which can optimize the grain boundary structure of the main phase, and the rare earth Ce rarely enters the main phase.
  • the magnet of the present invention is in the air-flow milling powder stage and in an inert gas grinding medium. A certain concentration of oxygen is added to the final, and the oxygen content of the final magnet is 1500 to 2500 ppm.
  • a cerium oxide flocculent phase is formed in the magnet, which plays a role of strengthening and toughening.
  • the cerium-containing sintered permanent magnet prepared by the present invention has high toughness and high coercive force, its intrinsic coercive force Hcj reaches 17-28.73kOe, and its fracture toughness value is increased by 10% -30% compared with the traditional sintered neodymium-iron-boron magnet.
  • the magnet of the present invention can be applied to high-end fields such as wind power generation and new energy vehicles, and the application field of cerium-containing magnets is greatly expanded.
  • FIG. 1 is a microstructure diagram of a sintered rare earth permanent magnet containing Ce with high toughness and high coercivity according to the present invention.
  • the arrow indicates the cerium oxide floc phase.
  • the sintered rare earth permanent magnet containing Ce with high toughness and high coercive force according to the present invention is prepared through the steps of raw material preparation, rapid solidification smelting, hydrogen crushing and jet milling powder, orientation molding, sintering and heat treatment.
  • the raw materials of the permanent magnet are Main phase alloy powder and cerium additive phase alloy powder, wherein the cerium additive phase is a magnetic phase or a non-magnetic liquid phase alloy; the main phase accounts for 70% to 95% of the total mass of the permanent magnet, and the cerium additive phase accounts for the total mass of the permanent magnet.
  • the composition of the main phase alloy is expressed as [(Nd, Pr) 1-x1 RE x1 ] 29.5 to 32 Fe bal.
  • the alloy composition of the phase is expressed as ((Nd, Pr) 1-xy Re x Ce y ) 33 ⁇ 60 Fe bal. B 0.15 ⁇ 1.05 TM 0.5 ⁇ 2.0 , where: RE is in Dy, Tb, Ho, Gd Re is one or more of La, Gd, Y, TM is one or more of Co, Ga, Al, Cu, Nb, Zr, 0.05 ⁇ x1 ⁇ 0.28, 0 ⁇ x ⁇ 0.15, 0.3 ⁇ y ⁇ 0.8;
  • the final product of the permanent magnet has a cerium oxide flocculent phase.
  • the permanent magnet when the cerium additive phase is a magnetic phase, the permanent magnet is a bimagnetic main phase alloy; when the cerium additive phase is a non-magnetic liquid phase alloy, the cerium additive phase forms a grain boundary phase.
  • the method for preparing a high-toughness, high-coercivity Ce-containing sintered rare earth permanent magnet includes (1) raw material preparation, (2) rapid solidification smelting, (3) hydrogen crushing and jet milling powder, (4) Orientation molding, (5) sintering and heat treatment steps, the specific steps are as follows:
  • TM 0.5 ⁇ 2.0 Configure the main phase alloy and cerium additive phase alloy raw materials, where: RE is one or more of Dy, Tb, Ho, Gd, and Re is La , Gd, Y or one or more, TM is one or more of Co, Ga, Al, Cu, Nb, Zr, 0.05 ⁇ x1 ⁇ 0.28, 0 ⁇ x ⁇ 0.15, 0.3 ⁇ y ⁇ 0.8 ; Wherein the cerium additive phase is a magnetic phase or a non-magnetic liquid alloy;
  • step (3) Hydrogen crushing and jet milling powder:
  • the two quick-setting flakes (or powders made from quick-setting flakes) prepared in step (2) are mixed in a certain proportion, and charged into a hydrogen-breaking furnace. Crushing, dehydrogenating, and air milling to obtain magnetic powder with an average particle size of 2.0-5.0 ⁇ m;
  • the oxygen concentration is 50 to 80 ppm.
  • Orientation molding orientation-molding the magnetic powder obtained in step (3) in a magnetic field press, and then cold isostatic pressing to form a blank, with a density of 3.8 to 5.0 g / cm 3 ;
  • Sintering and heat treatment Put the blank prepared in step (4) into a high-vacuum sintering furnace, and evacuate to less than 10E-1Pa to start heating; keep the temperature at 400 °C, 650 °C, and 830 °C ⁇ 880 °C, respectively. Degassing treatment for 0.5 to 1 hour to remove the adsorbed gas, antioxidants and lubricants; then vacuum sintering at 1020 ° C to 1100 ° C, sintering time is 2 to 5 hours, and then at 800 to 920 ° C and 400 to 650 ° C, respectively. Each is subjected to tempering heat treatment for 2 to 5 hours, and finally a sintered rare earth permanent magnet containing cerium containing high coercivity is obtained.
  • the mixing of the main phase and the cerium added phase may be performed before hydrogen crushing, or after hydrogen crushing, or may be mixed after jet milling.
  • the linear speed of the water-cooled copper roll is 1.0 to 2.0 m / s, and a quick-setting sheet having an average thickness of 0.28 to 0.32 mm is prepared.
  • step (3) a certain concentration of oxygen is added in the inert gas in the jet milling stage.
  • the average particle size of the jet magnetic powder in step (3) is 2.5-3.5 ⁇ m.
  • the sintering temperature in step (5) is from 1050 ° C to 1080 ° C.
  • the cerium additive phase is a magnetic phase or a non-magnetic liquid phase alloy: when the Re content in the cerium additive phase alloy is relatively low, the magnetic phase is obtained, and the permanent magnet is a dual main phase permanent magnet alloy; when cerium is added When the content of Re in the phase alloy is relatively high, the cerium additive phase is a non-magnetic liquid phase alloy, and aggregates at the grain boundary of the main phase to form a grain boundary phase.
  • the final magnet has a cerium oxide flocculent phase.
  • Step 1 Preparation of raw materials: Main phase alloy raw materials are prepared according to mass percentage (Nd, Pr) 23.5 RE 8.0 Fe bal. B 1.05 TM 3.0 , and cerium is prepared according to mass percentage (Nd, Pr) 23 Ce 10 Fe bal. B 1.0 TM 0.5 Add phase alloy raw materials, RE is one or more of Dy, Tb, Ho, TM is one or more of Co, Ga, Al, Cu, Zr.
  • Step 2 Rapid solidification smelting: The prepared main phase alloy raw materials and cerium addition phase alloy raw materials are separately melted to prepare a rapid solidification zone. First put the raw materials into the crucible of the rapid solidification furnace, and perform vacuum induction melting under the protection of argon. After the raw materials are fully melted to form the alloy, maintain the temperature of 1400-1500 ° C, and cast the alloy liquid to a linear speed of 1.0-2.0 m / s. A quick-setting sheet having an average thickness of 0.28 to 0.32 mm was prepared on a water-cooled copper roll. The main phase quick-setting zone and the cerium-added phase quick-setting zone were mixed in a proportion of 90%: 10% by mass.
  • Step 3 Hydrogen crushing and air-flow milling powder: The quick-setting tablets mixed in proportion in step 2 are subjected to hydrogen crushing, dehydrogenation, and air-flow milling to obtain magnetic powder with an average particle size of 2.5-3.5 ⁇ m. During the jet milling process, a small amount of O 2 is added to the jet milling media (inert gas such as N 2 ), and the O 2 concentration is 50 ppm.
  • Step 4 Orientation molding and pressing: Orient and shape the magnetic powder obtained in step 3 in a magnetic field press, and then perform cold isostatic pressing to form a blank with a density of 4.5 to 5.0 g / cm 3 ;
  • Step 5 Sintering and heat treatment: Put the blank prepared in step 4 into a high-vacuum sintering furnace, evacuate to less than 10E-1Pa, and start heating; keep the temperature at 400 °C, 650 °C, and 830 ⁇ 880 °C for 0.5 ⁇ Degassing treatment is performed for 1 hour to remove adsorbed gases, antioxidants and lubricants; and then sintered at 1080 ° C for 2 to 5 hours, and then sintered at 920 ° C and 400 to 650 ° C for 2-5 hours each. Tempering heat treatment finally obtains a sintered rare-earth permanent magnet containing cerium with high coercivity, and the final magnet has an oxygen content of 1500 ppm.
  • the composition design of the main phase alloy and the cerium additive phase alloy of the sintered rare earth permanent magnet and the preparation method of the sintered rare earth permanent magnet are basically the same as those in Example 1.
  • the difference is that the main phase alloy and the cerium additive phase alloy are The mass percentage is 70%: 30%, the magnet sintering temperature is 1070 ° C, and the final oxygen content of the magnet is 1800ppm.
  • Step 1 Preparation of raw materials: Prepare the main phase alloy raw materials by mass percentage (Nd, Pr) 26 RE 5.0 Fe bal. B 0.97 TM 2.5 , and by mass percentage (Nd, Pr) 12 Re 4.5 Ce 17 Fe bal. B 1.05 TM 2.0 Prepare cerium additive phase alloy raw materials, RE is one or more of Dy, Tb, Ho, Re is one or more of La, Gd, Y, TM is Co, Ga, Al, Cu, Nb One or more.
  • Step 2 Smelt the prepared main phase alloy raw material and the cerium additive phase alloy raw material to prepare a rapid solidification zone, respectively.
  • a quick-setting sheet having an average thickness of 0.28 to 0.32 mm was prepared on a water-cooled copper roll.
  • the main phase quick-setting zone and the cerium-added phase quick-setting zone were mixed in a proportion of 90%: 10% by mass.
  • Step 3 crushing and pulverizing: the quick-setting tablets mixed in proportion in step 2 are crushed by hydrogen, dehydrogenated, and air-milled to obtain magnetic powder with an average particle size of 2.5-3.5 ⁇ m.
  • a small amount of O 2 is added to the jet milling media (inert gas such as N 2 ), and the O 2 concentration is 50 ppm.
  • Step 4 Orientation molding and pressing: Orient and shape the magnetic powder obtained in step 3 in a magnetic field press, and then perform cold isostatic pressing to form a blank with a density of 4.5 to 5.0 g / cm 3 ;
  • Step 5 Sintering and heat treatment: Put the blank prepared in step 4 into a high-vacuum sintering furnace, evacuate to less than 10E-1Pa, and start heating; keep the temperature at 400 °C, 650 °C, and 830 ⁇ 880 °C for 0.5 ⁇ Degassing treatment is performed for 1 hour to remove adsorbed gases, antioxidants and lubricants; and then sintered at 1070 ° C for 2 to 5 hours, and then sintered at 920 ° C and 400 to 650 ° C for 2-5 hours each. Tempering heat treatment finally obtains a sintered rare earth permanent magnet containing cerium with high coercivity, and the final magnet has an oxygen content of 1800 ppm.
  • Step 1 Preparation of raw materials: Prepare the main phase alloy raw materials according to mass percentage (Nd, Pr) 29 RE 1.5 Fe bal. B 0.92 TM 1.0 and 6 Re 6 Ce 48 Fe bal. B 0.15 TM 1.0 according to mass percentage (Nd, Pr) Preparation of cerium additive phase alloy raw materials, RE is one or more of Dy, Tb, Ho, Gd, Re is one or more of La, Gd, Y, TM is Co, Ga, Al, Cu, Zr One or more of them.
  • Step 2 Smelt the prepared main phase alloy raw material and the cerium additive phase alloy raw material to prepare a rapid solidification zone, respectively.
  • a quick-setting sheet having an average thickness of 0.28 to 0.32 mm was prepared on a water-cooled copper roll.
  • the main phase quick-setting zone and the cerium-added phase quick-setting zone are mixed in a proportion of 95%: 5% by mass.
  • Step 3 crushing and pulverizing: the quick-setting tablets mixed in proportion in step 2 are crushed by hydrogen, dehydrogenated, and air-milled to obtain magnetic powder with an average particle size of 2.5-3.5 ⁇ m.
  • a small amount of O 2 is added to the jet milling media (inert gas such as N 2 ), and the O 2 concentration is 80 ppm.
  • Step 4 Orientation molding and pressing: Orient and shape the magnetic powder obtained in step 3 in a magnetic field press, and then perform cold isostatic pressing to form a blank with a density of 4.5 to 5.0 g / cm 3 ;
  • Step 5 Sintering and heat treatment: Put the blank prepared in step 4 into a high-vacuum sintering furnace, evacuate to less than 10E-1Pa, and start heating; keep the temperature at 400 °C, 650 °C, and 830 ⁇ 880 °C for 0.5 ⁇ Perform degassing treatment for 1 hour to remove the adsorbed gas, antioxidants and lubricants; then vacuum sinter at 1075 ° C for 2 to 5 hours, and then perform 2-5 hours at 900 ° C and 400-650 ° C respectively. Tempering heat treatment finally obtains a sintered rare-earth permanent magnet containing cerium with high coercivity, and the final magnet has an oxygen content of 2500 ppm.

Abstract

本发明涉及一种高韧性、高矫顽力含Ce烧结稀土永磁体及其制备方法，属于稀土永磁材料技术领域。该磁体是通过原料配制、速凝熔炼、氢破碎和气流磨制粉、取向成型、烧结和热处理步骤制备获得，该永磁体的原料为主相合金粉末和铈添加相合金粉末，其中，铈添加相为磁性相或非磁性液相合金；铈添加相合金占永磁体总质量的5％～30％，其余为主相；在气流磨制粉阶段，在惰性气体中添加一定浓度氧，最终磁体的氧含量为1500～2500ppm。本发明制备的含铈双合金磁体具有高矫顽力，其内禀矫顽力Hcj达到17kOe～28.73kOe，本发明磁体具有良好的断裂韧性，其断裂韧性值比传统的烧结钕铁硼磁体提高10％～30％。本发明磁体可应用于风力发电、新能源汽车等高端领域，大幅度拓宽了含铈磁体的应用领域。

Description

一种高韧性、高矫顽力含Ce烧结稀土永磁体及其制备方法 技术领域
本发明属于稀土永磁材料技术领域，特别涉及一种高韧性、高矫顽力含Ce烧结稀土永磁体及其制备方法。
背景技术
随着新一代高丰度铈磁体的规模化生产获得成功，用Ce取代Nd制备高丰度稀土永磁体，不仅能够大幅度降低稀土永磁体的原材料成本、而且对于缓解我国日益突出的稀土资源严重浪费与环境污染问题，及实现稀土资源高效平衡利用,有着极为重要的战略意义。
众所周知，Ce 2Fe 14B化合物的各向异性场H A均远低于Nd 2Fe 14B，因此导致含铈磁体矫顽力偏低。文献[Journal of Applied Physics,1985,57:4146]和[Journal of Applied Physics,1994,75:6268]报道，当使用5％Ce-15％Pr-Nd时，内禀矫顽力为10.2kOe、磁能积为40MGOe，而使用40％Ce-10％Pr-50％Nd时，内禀矫顽力为9.2kOe、磁能积为28.2MGOe。为了提高含铈磁体的矫顽力，本领域的科技人员进行了不懈的努力。
中国专利申请CN102436892A所述的采用双主相方法制备的含铈烧结磁体，不含重稀土元素，该磁体的内禀矫顽力Hcj为11～12kOe左右。中国专利申请CN102800454A所述采用双主相工艺制备的名义成为(Ce x,Re 1-x)Fe 100-a-b-cB bTM c烧结磁体，Re为Nd、Pr、Dy、Tb、Ho元素中的一种或几种，该磁体的内禀矫顽力Hcj为12～13kOe左右。中国 专利申请CN104900360A所述的复合添加Gd、Ce的烧结铈磁体，其内禀矫顽力Hcj在10kOe～12kOe左右。中国专利申请CN104575920A采用单主相方法制备烧结铈磁体，在较窄的铈含量范围(铈占总稀土含量在24～32wt.％之间)，该磁体的内禀矫顽力Hcj在12kOe～13kOe左右；当磁体合金配方含3wt.％Dy时，其内禀内禀矫顽力Hcj达到15～16kOe左右。中国专利申请CN107275026A公布了一种批量应用镧的富铈稀土永磁体，该磁体的内禀矫顽力Hcj在9.0kOe～12kOe左右。麦格昆磁(天津)有限公司的中国专利申请CN101694797A提出了Ce替代量为10～40％的Nd的一种新型钕铁硼磁性材料，其总稀土含量(Ce+Nd)的重量百分比为27％,用于快淬粘结钕铁硼磁粉的生产,该磁体的内禀矫顽力Hcj为7kOe～9kOe左右。总之，到目前为止，含铈磁体的矫顽力总体偏低，极大地限制了含铈磁体的应用领域，而永磁体的力学性能，尤其是断裂韧性对于其抗冲击振动性能和可加工性能有重要影响，对材料的实际应用有重要意义。
发明内容
本发明的目的在于提供一种高韧性、高矫顽力含Ce烧结稀土永磁体及其制备方法。
为了实现上述目的，本发明提供了如下技术方案：
本发明提供一种高韧性、高矫顽力含Ce烧结稀土永磁体，是通过原料配制、速凝熔炼、氢破碎和气流磨制粉、取向成型、烧结和热处理步骤制备获得，该永磁体的原料为主相合金粉末和铈添加相合金粉末，其中，铈添加相为磁性相或非磁性液相合金；铈添加相合金占永磁体总质量的5％～30％，其余为主相；所述主相的合金成分按质量百分 比表示为[(Nd,Pr) 1-x1RE x1] 29.5～32Fe bal.B 0.9～1.05TM 1.0～3.0,所述铈添加相的合金成分按质量百分比表示为((Nd,Pr) 1-x-yRe xCe y) 33～60Fe bal.B 0.15～1.05TM 0.5～2.0；其中，RE为Dy、Tb、Ho、Gd中的一种或者几种，Re为La、Gd、Y中的一种或者几种，TM为Co、Ga、Al、Cu、Nb、Zr中的一种或者几种，0.05≤x1≤0.28，0≤x≤0.15，0.3≤y≤0.8；其中：
在气流磨制粉阶段，在惰性气体中添加一定浓度氧，使得最终磁体的氧含量为1500～2500ppm；
该永磁体的内禀矫顽力Hcj＝17～28.73kOe，断裂韧性K ⅠC＝4.5～5.0MPa·m 1/2。
该永磁体的最终产品中具有氧化铈絮状相。
该永磁体的最终产品中，当铈添加相为磁性相时，该永磁体为双磁性主相合金；当铈添加相为非磁性液相合金时，该铈添加相形成晶界相。
所述含铈高矫顽力烧结稀土永磁体具有如下磁性能：剩磁Br＝11.98～13.35kGs，磁能积(BH) max＝35.16～43.68MGOe。
一种高韧性、高矫顽力含Ce烧结稀土永磁体的制备方法，该方法包括(1)原料准备、(2)速凝熔炼、(3)氢破碎和气流磨制粉、(4)取向成型、(5)烧结和热处理步骤。
在步骤(1)中，分别按照质量百分比为[(Nd,Pr) 1-x1RE x1] 29.5～32Fe bal.-B 0.9～1.05TM 1.0～3.0，((Nd,Pr) 1-x-yRe xCe y) 33～60Fe bal.B 0.15～1.05TM 0.5～2.0配置主相合金原料和铈添加相合金原料，其中：RE为Dy、Tb、Ho、Gd中的一种或者几种，Re为La、Gd、Y中的一种或者几种，TM为Co、Ga、Al、Cu、Nb、Zr中的一种或者几种，0.05≤x1≤0.28，0≤x≤0.15，0.3≤y≤0.8； 其中，铈添加相为磁性相或非磁性液相合金；
在步骤(2)中，分别制备主相合金速凝薄片和铈添加相合金速凝薄片；
在步骤(3)中，将主相速凝带和铈添加相速凝带按照质量百分比为铈添加相速凝带占30～5％、其余为主相速凝带的比例混合，然后进行氢破碎和气流磨制粉；其中，在气流磨制粉阶段，在惰性气体中添加一定浓度氧，使得最终磁体的氧含量为1500～2500ppm。
该方法包括如下步骤：
(2)速凝熔炼：将步骤(1)中配置好的主相合金原料和铈添加相合金原料分别放入速凝炉坩埚内，在氩气保护下进行真空感应熔炼，待原料充分融化后，保持1300～1500℃温度，将合金液浇注到线速度为1.0～3.0米/秒的水冷铜辊上，分别制备平均厚度为0.20～0.50mm的主相合金速凝薄片和铈添加相合金速凝薄片；
(3)氢破碎和气流磨制粉：
将步骤(2)中制得的主相合金速凝薄片和铈添加相合金速凝薄片或主相合金速凝薄片和铈添加相合金速凝薄片制成的粉末按照一定比例混合后，经氢破碎、脱氢、气流磨制粉制成磁粉；或者，
分别将步骤(2)中制得的主相合金速凝薄片和铈添加相合金速凝薄片分别进行氢破碎和脱氢处理，然后将脱氢的主相合金粉末和铈添加相合金粉末按照一定比例混合，经气流磨制粉制成磁粉；或者，
分别将步骤(2)中制得的主相合金速凝薄片和铈添加相合金速凝薄片分别进行氢破碎、脱氢、气流磨制粉制成主相合金磁粉和铈添加相合金磁粉，然后将主相合金磁粉和铈添加相合金磁粉按照一定比例混合；
其中，在气流磨制粉阶段，在惰性气体中添加一定浓度氧；经气流磨制粉制成的磁粉的平均粒度为2.0～5.0μm；
(4)取向成型：将步骤(3)中制得的磁粉在磁场压机中取向成型，再进行冷等静压制成毛坯，其密度为3.8～5.0g/cm 3；
(5)烧结和热处理：将步骤(4)中制得的毛坯放入高真空的烧结炉中，抽真空到小于10E-1Pa开始升温；分别在400℃、650℃和830～880℃保温0.5～1小时进行脱气处理；然后在1020℃～1100℃真空烧结，烧结时间2～5小时，然后分别在800～920℃和400～650℃各进行2～5小时的回火热处理，最终得到含铈高矫顽力烧结稀土永磁体。
所述步骤(2)中，水冷铜辊的线速度为1.0～2.0米/秒，制备平均厚度为0.28～0.32mm的速凝片。
所述步骤(3)中，在气流磨制粉阶段，在惰性气体中添加的氧浓度为50～80ppm。
所述步骤(3)中，经气流磨制成的磁粉的平均粒度为2.5～3.5μm。
所述步骤(5)中，烧结温度为1050℃～1080℃。
最终磁体的氧含量为1500～2500ppm，且具有如下磁性能：剩磁Br＝11.98～13.35kGs，磁能积(BH) max＝35.16～43.68MGOe，内禀矫顽力Hcj＝17～28.73kOe，断裂韧性K ⅠC＝4.5～5.0MPa·m 1/2。
最终磁体中有氧化铈絮状相。
与现有技术相比，本发明的有益效果在于：
本发明高韧性、高矫顽力含Ce烧结稀土永磁体，包括主相和铈添加相，其中：铈添加相可以是磁性相，也可以是非磁性液相合金。本发明铈添加相合金的总稀土含量较高，其熔点较低，可以优化主相晶 界结构，而稀土Ce较少进入主相；本发明磁体在气流磨制粉阶段，在惰性气体研磨介质中添加一定浓度氧，最终磁体的氧含量在1500～2500ppm，在磁体中形成氧化铈絮状相，起到补强增韧的作用。本发明制备的含铈烧结永磁体具有高韧性和高矫顽力，其内禀矫顽力Hcj达到17～28.73kOe，其断裂韧性值比传统的烧结钕铁硼磁体提高10％～30％。本发明磁体可应用于风力发电、新能源汽车等高端领域，大幅度拓宽了含铈磁体的应用领域。
附图说明
图1为本发明高韧性、高矫顽力含Ce烧结稀土永磁体的微观结构图。
其中，箭头所指为氧化铈絮状相。
具体实施方式
下面结合附图和实施例对本发明进行进一步说明。
本发明的高韧性、高矫顽力含Ce烧结稀土永磁体，是通过原料配制、速凝熔炼、氢破碎和气流磨制粉、取向成型、烧结和热处理步骤制备获得，该永磁体的原料为主相合金粉末和铈添加相合金粉末，其中，铈添加相为磁性相或非磁性液相合金；所述主相占永磁体总质量的70％～95％，铈添加相占永磁体总质量的5％～30％；所述主相合金的成分按质量百分比表示为[(Nd,Pr) 1-x1RE x1] 29.5～32Fe bal.B 0.9～1.05TM 1.0～3.0,所述铈添加相的合金成分按质量百分比表示为((Nd,Pr) 1-x-yRe xCe y) 33～60Fe bal.B 0.15～1.05TM 0.5～2.0，其中：RE为Dy、Tb、Ho、Gd中的一种或者几种，Re为La、Gd、Y中的一种或者几种，TM为Co、Ga、Al、Cu、Nb、Zr中的一种或者几种，0.05≤x1≤0.28，0≤x≤0.15， 0.3≤y≤0.8；该含铈的双合金磁体具有高矫顽力，其内禀矫顽力Hcj达到17kOe～28.73kOe，磁体具有良好的断裂韧性，断裂韧性K ⅠC＝4.5～5.0MPa·m 1/2，其断裂韧性值比传统的烧结钕铁硼磁体提高10％～30％。
该永磁体的最终产品中具有氧化铈絮状相。
在气流磨制粉阶段，在惰性气体中添加一定浓度氧，最终磁体的氧含量为1500～2500ppm。
所述含铈高矫顽力烧结稀土永磁体还具有如下磁性能：剩磁Br＝11.98～13.35kGs，磁能积(BH) max＝35.16～43.68MGOe。
该永磁体的最终产品中，当铈添加相为磁性相时，该永磁体为双磁性主相合金；当铈添加相为非磁性液相合金时，该铈添加相形成晶界相。
本发明的高韧性、高矫顽力含Ce烧结稀土永磁体的制备方法，该方法包括(1)原料准备、(2)速凝熔炼、(3)氢破碎和气流磨制粉、(4)取向成型、(5)烧结和热处理步骤，具体步骤如下：
(1)原料准备：分别按照质量百分比为[(Nd,Pr) 1-x1RE x1] 29.5～32Fe bal.-B 0.9～1.05TM 1.0～3.0，((Nd,Pr) 1-x-yRe xCe y) 33～60Fe bal.B 0.15～1.05TM 0.5～2.0配置主相合金和铈添加相合金原料,其中：RE为Dy、Tb、Ho、Gd中的一种或者几种，Re为La、Gd、Y中的一种或者几种，TM为Co、Ga、Al、Cu、Nb、Zr中的一种或者几种，0.05≤x1≤0.28，0≤x≤0.15，0.3≤y≤0.8；其中，铈添加相为磁性相或非磁性液相合金；
(2)速凝熔炼：将步骤(1)中配置好的主相合金和铈添加相合金原料分别放入速凝炉坩埚内，在氩气保护下进行真空感应熔炼，待原料充分融化后，保持1300～1500℃温度，将合金液浇注到线速度为1.0～3.0米/秒的水冷铜辊上，制备平均厚度为0.20～0.50mm的主相合金 速凝薄片和铈添加相合金速凝薄片。
(3)氢破碎、气流磨制粉：将步骤(2)中制得的将两种速凝薄片(或速凝片制成的粉末)按照一定比例混合，装入氢破炉中，经氢破碎、脱氢、气流磨制粉，获得平均粒度为2.0～5.0μm的磁粉；
在气流磨制粉阶段，在惰性气体中添加一定浓度氧；氧浓度为50～80ppm。
(4)取向成型：将步骤(3)中制得的磁粉在磁场压机中取向成型，再进行冷等静压制成毛坯，其密度为3.8～5.0g/cm 3；
(5)烧结和热处理：将步骤(4)中制得的毛坯放入高真空的烧结炉中，抽真空到小于10E-1Pa开始升温；分别在400℃、650℃和830℃～880℃保温0.5～1小时进行脱气处理，脱去吸附的气体及防氧化剂、润滑剂；然后在1020℃～1100℃真空烧结，烧结时间2～5小时，然后分别在800～920℃和400～650℃各进行2～5小时的回火热处理，最终得到含铈高矫顽力烧结稀土永磁体。
所述含铈高矫顽力永磁体制备方法，主相和铈添加相混合可以在氢破碎之前，或氢破碎之后进行，也可以在气流磨之后进行混合。
优选地，步骤(2)中水冷铜辊的线速度为1.0～2.0米/秒，制备平均厚度为0.28～0.32mm的速凝片。
步骤(3)中，在气流磨制粉阶段，在惰性气体中添加一定浓度氧。
优选地，步骤(3)中气流磨磁粉的平均粒度为2.5～3.5μm。
优选地，步骤(5)中烧结温度为1050℃～1080℃。
最终磁体的氧含量为1500～2500ppm，且具有如下磁性能：剩磁Br＝11.98～13.35kGs，磁能积(BH) max＝35.16～43.68MGOe，内禀矫顽力Hcj＝17～28.73kOe，断裂韧性K ⅠC＝4.5～5.0MPa·m 1/2。
最终磁体中，所述铈添加相为磁性相或非磁性液相合金：当铈添加相合金中Re含量比较低时，得到的是磁性相，永磁体为双主相永磁合金；当铈添加相合金中Re含量比较高时，铈添加相为非磁性液相合金，且聚集在主相晶界处，形成晶界相；最终磁体中具有氧化铈絮状相。
实施例1
步骤1：原料准备：按质量百分比(Nd,Pr) 23.5RE 8.0Fe bal.B 1.05TM 3.0配制主相合金原料，按质量百分比(Nd,Pr) 23Ce 10Fe bal.B 1.0TM 0.5配制铈添加相合金原料，RE为Dy、Tb、Ho中的一种或者几种，TM为Co、Ga、Al、Cu、Zr中的一种或几种。
步骤2：速凝熔炼：将配好的主相合金原料和铈添加相合金原料分别熔炼制备速凝带。首先将原材料放入速凝炉坩埚内，在氩气保护下进行真空感应熔炼，待原料充分融化形成合金后，保持1400～1500℃温度，将合金液浇注到线速度为1.0～2.0米/秒的水冷铜辊上，制备平均厚度为0.28～0.32mm的速凝片。将主相速凝带和铈添加相速凝带按照质量百分比为90％：10％的比例混合。
步骤3：氢破碎、气流磨制粉：将步骤2中按比例混合好的速凝片，经氢破碎、脱氢、气流磨制粉，得到平均粒度为2.5～3.5μm的磁粉。在气流磨制粉过程中，在气流磨研磨介质(N 2等惰性气体)中加入少量O 2,O 2浓度为50ppm。
步骤4：取向成型和压制：将步骤3中制得的磁粉在磁场压机中取向成型，再进行冷等静压制成毛坯，其密度为4.5～5.0g/cm 3；
步骤5：烧结和热处理：将步骤4中制得的毛坯放入高真空的烧结炉中，抽真空到小于10E-1Pa开始升温；分别在400℃，650℃，和 830～880℃保温0.5～1小时进行脱气处理，脱去吸附的气体及防氧化剂、润滑剂；然后在1080℃真空烧结，烧结时间2～5小时，然后分别在920℃和400～650℃各进行2-5小时的回火热处理，最终得到含铈高矫顽力烧结稀土永磁体，最终磁体的氧含量为1500ppm。
所得磁体的磁性能为Br＝11.98kGs,Hcj＝28.73kOe,(BH) max＝35.16MGOe；断裂韧性K ⅠC＝4.5MPa·m 1/2。
实施例2
本实施例中烧结稀土永磁体的主相合金和铈添加相合金的成分设计，以及该烧结稀土永磁体的制备方法基本与实施例1相同，所不同的是主相合金与铈添加相合金是按照质量百分比为70％：30％的比例混合，磁体烧结温度为1070℃，最终磁体的氧含量为1800ppm。
所得磁体的磁性能为Br＝12.30kGs,Hcj＝25.19kOe,(BH) max＝37.06MGOe；断裂韧性K ⅠC＝5.0MPa·m 1/2。
实施例3
步骤1：原料准备：按质量百分比(Nd,Pr) 26RE 5.0Fe bal.B 0.97TM 2.5配制主相合金原料，按质量百分比(Nd,Pr) 12Re 4.5Ce 17Fe bal.B 1.05TM 2.0配制铈添加相合金原料，RE为Dy、Tb、Ho中的一种或者几种，Re为La、Gd、Y中的一种或者几种，TM为Co、Ga、Al、Cu、Nb中的一种或几种。
步骤2：将配好的主相合金原料和铈添加相合金原料分别熔炼制备速凝带。首先将原材料放入速凝炉坩埚内，在氩气保护下进行真空感应熔炼，待原料充分融化形成合金后，保持1400～1500℃温度，将合金液浇注到线速度为1.0～2.0米/秒的水冷铜辊上，制备平均厚度为 0.28～0.32mm的速凝片。将主相速凝带和铈添加相速凝带按照质量百分比为90％：10％的比例混合。
步骤3：破碎制粉：将步骤2中按比例混合好的速凝片，经氢破碎、脱氢、气流磨制粉，得到平均粒度为2.5～3.5μm的磁粉。在气流磨制粉过程中，在气流磨研磨介质(N 2等惰性气体)中加入少量O 2,O 2浓度为50ppm。
步骤4：取向成型和压制：将步骤3中制得的磁粉在磁场压机中取向成型，再进行冷等静压制成毛坯，其密度为4.5～5.0g/cm 3；
步骤5：烧结和热处理：将步骤4中制得的毛坯放入高真空的烧结炉中，抽真空到小于10E-1Pa开始升温；分别在400℃，650℃，和830～880℃保温0.5～1小时进行脱气处理，脱去吸附的气体及防氧化剂、润滑剂；然后在1070℃真空烧结，烧结时间2～5小时，然后分别在920℃和400～650℃各进行2-5小时的回火热处理，最终得到含铈高矫顽力烧结稀土永磁体，最终磁体的氧含量为1800ppm。
所得磁体的磁性能为Br＝12.72kGs,Hcj＝23.86kOe,(BH) max＝39.64MGOe；断裂韧性K ⅠC＝4.8MPa·m 1/2。
实施例4
步骤1：原料准备：按质量百分比(Nd,Pr) 29RE 1.5Fe bal.B 0.92TM 1.0配制主相合金原料，按质量百分比(Nd,Pr) 6Re 6Ce 48Fe bal.B 0.15TM 1.0配制铈添加相合金原料，RE为Dy、Tb、Ho、Gd中的一种或者几种，Re为La、Gd、Y中的一种或者几种，TM为Co、Ga、Al、Cu、Zr中的一种或几种。
步骤2：将配好的主相合金原料和铈添加相合金原料分别熔炼制备速凝带。首先将原材料放入速凝炉坩埚内，在氩气保护下进行真空感应熔炼，待原料充分融化形成合金后，保持1400～1500℃温度，将合金 液浇注到线速度为1.0～2.0米/秒的水冷铜辊上，制备平均厚度为0.28～0.32mm的速凝片。将主相速凝带和铈添加相速凝带按照质量百分比为95％：5％的比例混合。
步骤3：破碎制粉：将步骤2中按比例混合好的速凝片，经氢破碎、脱氢、气流磨制粉，得到平均粒度为2.5～3.5μm的磁粉。在气流磨制粉过程中，在气流磨研磨介质(N 2等惰性气体)中加入少量O 2,O 2浓度为80ppm。
步骤4：取向成型和压制：将步骤3中制得的磁粉在磁场压机中取向成型，再进行冷等静压制成毛坯，其密度为4.5～5.0g/cm 3；
步骤5：烧结和热处理：将步骤4中制得的毛坯放入高真空的烧结炉中，抽真空到小于10E-1Pa开始升温；分别在400℃，650℃，和830～880℃保温0.5～1小时进行脱气处理，脱去吸附的气体及防氧化剂、润滑剂；然后在1075℃真空烧结，烧结时间2～5小时，然后分别在900℃和400～650℃各进行2-5小时的回火热处理，最终得到含铈高矫顽力烧结稀土永磁体，最终磁体的氧含量为2500ppm。
所得磁体的磁性能为Br＝13.35kGs,Hcj＝18.52kOe,(BH) max＝43.68MGOe；断裂韧性K ⅠC＝4.85MPa·m 1/2。
表1本发明实施例与高矫顽力钕铁硼磁体的磁性能和断裂韧性对比
Figure PCTCN2019081439-appb-000001
Figure PCTCN2019081439-appb-000002

Claims (12)

  1. 一种高韧性、高矫顽力含Ce烧结稀土永磁体，是通过原料配制、速凝熔炼、氢破碎和气流磨制粉、取向成型、烧结和热处理步骤制备获得，其特征在于：该永磁体的原料为主相合金粉末和铈添加相合金粉末，其中，铈添加相为磁性相或非磁性液相合金；铈添加相合金占永磁体总质量的5％～30％，其余为主相；所述主相的合金成分按质量百分比表示为[(Nd,Pr) 1-x1RE x1] 29.5～32Fe bal.B 0.9～1.05TM 1.0～3.0,所述铈添加相的合金成分按质量百分比表示为((Nd,Pr) 1-x-yRe xCe y) 33～60Fe bal.B 0.15～1.05TM 0.5～2.0；其中，RE为Dy、Tb、Ho、Gd中的一种或者几种，Re为La、Gd、Y中的一种或者几种，TM为Co、Ga、Al、Cu、Nb、Zr中的一种或者几种，0.05≤x1≤0.28，0≤x≤0.15，0.3≤y≤0.8；其中：
    在气流磨制粉阶段，在惰性气体中添加一定浓度氧，使得最终磁体的氧含量为1500～2500ppm；
    该永磁体的内禀矫顽力Hcj＝17～28.73kOe，断裂韧性K ⅠC＝4.5～5.0MPa·m 1/2。
  2. 根据权利要求1所述的高韧性、高矫顽力含Ce烧结稀土永磁体，其特征在于：该永磁体的最终产品中具有氧化铈絮状相。
  3. 根据权利要求1所述的高韧性、高矫顽力含Ce烧结稀土永磁体，其特征在于：该永磁体的最终产品中，当铈添加相为磁性相时，该永磁体为双磁性主相合金；当铈添加相为非磁性液相合金时，该铈添加 相形成晶界相。
  4. 根据权利要求1所述的高韧性、高矫顽力含Ce烧结稀土永磁体，其特征在于：所述含铈高矫顽力烧结稀土永磁体具有如下磁性能：剩磁Br＝11.98～13.35kGs，磁能积(BH) max＝35.16～43.68MGOe。
  5. 一种权利要求1所述的高韧性、高矫顽力含Ce烧结稀土永磁体的制备方法，该方法包括(1)原料准备、(2)速凝熔炼、(3)氢破碎和气流磨制粉、(4)取向成型、(5)烧结和热处理步骤，其特征在于：
    在步骤(1)中，分别按照质量百分比为[(Nd,Pr) 1-x1RE x1] 29.5～32Fe bal.-B 0.9～1.05TM 1.0～3.0，((Nd,Pr) 1-x-yRe xCe y) 33～60Fe bal.B 0.15～1.05TM 0.5～2.0配置主相合金原料和铈添加相合金原料，其中：RE为Dy、Tb、Ho、Gd中的一种或者几种，Re为La、Gd、Y中的一种或者几种，TM为Co、Ga、Al、Cu、Nb、Zr中的一种或者几种，0.05≤x1≤0.28，0≤x≤0.15，0.3≤y≤0.8；其中，铈添加相为磁性相或非磁性液相合金；
    在步骤(2)中，分别制备主相合金速凝薄片和铈添加相合金速凝薄片；
    在步骤(3)中，将主相速凝带和铈添加相速凝带按照质量百分比为铈添加相速凝带占30～5％、其余为主相速凝带的比例混合，然后进行氢破碎和气流磨制粉；其中，在气流磨制粉阶段，在惰性气体中添加一定浓度氧，使得最终磁体的氧含量为1500～2500ppm。
  6. 根据权利要求5所述的制备方法，其特征在于：该方法包括如 下步骤：
    (2)速凝熔炼：将步骤(1)中配置好的主相合金原料和铈添加相合金原料分别放入速凝炉坩埚内，在氩气保护下进行真空感应熔炼，待原料充分融化后，保持1300～1500℃温度，将合金液浇注到线速度为1.0～3.0米/秒的水冷铜辊上，分别制备平均厚度为0.20～0.50mm的主相合金速凝薄片和铈添加相合金速凝薄片；
    (3)氢破碎和气流磨制粉：
    将步骤(2)中制得的主相合金速凝薄片和铈添加相合金速凝薄片或主相合金速凝薄片和铈添加相合金速凝薄片制成的粉末按照一定比例混合后，经氢破碎、脱氢、气流磨制粉制成磁粉；或者，
    分别将步骤(2)中制得的主相合金速凝薄片和铈添加相合金速凝薄片分别进行氢破碎和脱氢处理，然后将脱氢的主相合金粉末和铈添加相合金粉末按照一定比例混合，经气流磨制粉制成磁粉；或者，
    分别将步骤(2)中制得的主相合金速凝薄片和铈添加相合金速凝薄片分别进行氢破碎、脱氢、气流磨制粉制成主相合金磁粉和铈添加相合金磁粉，然后将主相合金磁粉和铈添加相合金磁粉按照一定比例混合；
    其中，在气流磨制粉阶段，在惰性气体中添加一定浓度氧；经气流磨制粉制成的磁粉的平均粒度为2.0～5.0μm；
    (4)取向成型：将步骤(3)中制得的磁粉在磁场压机中取向成型，再进行冷等静压制成毛坯，其密度为3.8～5.0g/cm 3；
    (5)烧结和热处理：将步骤(4)中制得的毛坯放入高真空的烧结炉中，抽真空到小于10E-1Pa开始升温；分别在400℃、650℃和830～880℃保温0.5～1小时进行脱气处理；然后在1020℃～1100℃真空烧 结，烧结时间2～5小时，然后分别在800～920℃和400～650℃各进行2～5小时的回火热处理，最终得到含铈高矫顽力烧结稀土永磁体。
  7. 根据权利要求6所述的制备方法，其特征在于：所述步骤(2)中，水冷铜辊的线速度为1.0～2.0米/秒，制备平均厚度为0.28～0.32mm的速凝片。
  8. 根据权利要求6所述的制备方法，其特征在于：所述步骤(3)中，在气流磨制粉阶段，在惰性气体中添加的氧浓度为50～80ppm。
  9. 根据权利要求6所述的制备方法，其特征在于：所述步骤(3)中，经气流磨制成的磁粉的平均粒度为2.5～3.5μm。
  10. 根据权利要求6所述的制备方法，其特征在于：所述步骤(5)中，烧结温度为1050℃～1080℃。
  11. 根据权利要求6所述的制备方法，其特征在于：最终磁体的氧含量为1500～2500ppm，且具有如下磁性能：剩磁Br＝11.98～13.35kGs，磁能积(BH) max＝35.16～43.68MGOe，内禀矫顽力Hcj＝17～28.73kOe，断裂韧性K ⅠC＝4.5～5.0MPa·m 1/2。
  12. 根据权利要求6所述的制备方法，其特征在于：最终磁体中有氧化铈絮状相。
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