CN111210962A - Sintered neodymium iron boron containing SmFeN or SmFeC and preparation method thereof - Google Patents
Sintered neodymium iron boron containing SmFeN or SmFeC and preparation method thereof Download PDFInfo
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- CN111210962A CN111210962A CN202010077814.0A CN202010077814A CN111210962A CN 111210962 A CN111210962 A CN 111210962A CN 202010077814 A CN202010077814 A CN 202010077814A CN 111210962 A CN111210962 A CN 111210962A
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- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 77
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000005324 grain boundary diffusion Methods 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 239000000956 alloy Substances 0.000 claims abstract description 23
- 238000005121 nitriding Methods 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 238000009792 diffusion process Methods 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 229910016285 MxNy Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 30
- 238000003723 Smelting Methods 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000005266 casting Methods 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000010902 jet-milling Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 5
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052743 krypton Inorganic materials 0.000 claims description 4
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052704 radon Inorganic materials 0.000 claims description 4
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 4
- 238000007751 thermal spraying Methods 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000005488 sandblasting Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 238000007712 rapid solidification Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002131 composite material Substances 0.000 description 7
- 229910052692 Dysprosium Inorganic materials 0.000 description 6
- 229910052771 Terbium Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000004372 laser cladding Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- -1 Dy or Tb Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000009731 jinlong Substances 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- 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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
- C23C8/22—Carburising of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
- C23C8/26—Nitriding of ferrous surfaces
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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
- H01F41/026—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 protecting methods against environmental influences, e.g. oxygen, by surface treatment
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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
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- 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
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- 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
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Abstract
The invention discloses sintered neodymium iron boron containing SmFeN or SmFeC and a preparation method thereof, wherein the preparation method comprises the following steps: s1, forming Sm on the surface of the neodymium iron boron sintered body2Fe17‑xMxPerforming grain boundary diffusion treatment on the coating which is a diffusion source; s2, performing nitriding treatment or carbonizing treatment; wherein Sm is contained in the resulting alloy powder after nitriding treatment2Fe17‑ xMxNySintering neodymium iron boron; when carbonized, Sm-containing compounds are obtained2Fe17‑xMxCySintering neodymium iron boron; wherein M is one or more of Co, Mo, Cu, Zr, Ti and Al, and x is 0-2; y is 1 to 5. The sintered neodymium iron boron containing SmFeN or SmFeC has high coercive force, high temperature resistance and high resistance, the coercive force is increased greatly before and after grain boundary diffusion treatment, and the preparation method has simple operation and low cost.
Description
Technical Field
The invention relates to sintered neodymium iron boron containing SmFeN or SmFeC and a preparation method thereof.
Background
In the prior art, the coercive force of the sintered neodymium iron boron material can be increased by adding heavy rare earth elements such as dysprosium Dy or terbium Tb. For example, in the traditional metallurgical method, Dy or Tb is directly added into a main phase, but the method can cause the residual magnetism Br of the neodymium iron boron magnet to be sharply reduced. Further, for example, the grain boundary diffusion method is to make Dy or Tb penetrate into the Nd-rich phase to strengthen the Nd main phase2Fe14B, thereby improving the coercive force of the product, and although the method can reduce the use amount of heavy rare earth such as Dy or Tb, the requirements on diffusion equipment and a process method are harsh, and the price of the product is higher finally.
Since the SmFeN or SmFeC material is discovered, the SmFeN or SmFeC material has excellent intrinsic magnetic performance, such as Curie temperature (up to 750K), higher resistance, magnetocrystalline anisotropy field (2 times of NdFeB), and high remanence (theoretical Br is equivalent to NdFeB), so the SmFeN or SmFeC material has higher comprehensive performance.
In the prior art, for example, CN110444388A, NdFeB-SmFeN composite magnets were prepared, which discloses Sm is added2Fe17The alloy is made into a rod shape by spray casting and is made into a nanocrystalline powder alloy by high-energy ball milling, the nanocrystalline powder alloy is mixed with iron-based self-fluxing alloy nano powder and coated on a groove on the surface of the neodymium iron boron magnet, a laser cladding layer is prepared by laser heating cladding treatment, and a strong magnetic field and N are matched2And performing nitriding heat treatment in gas protection to obtain the neodymium iron boron magnet with high toughness and high stability. However, the preparation process of the method is complex, and suspension liquid needs to be prepared and laser cladding is carried out; and a strong magnetic field of more than 15T is needed, so that the requirement on equipment is strict, and the cost is high.
Disclosure of Invention
Aiming at the prior art, heavy rare earth elements are added for improving the coercive force of a neodymium iron boron magnet; or the process for preparing the NdFeB-SmFeN composite magnet is complex, the requirements for equipment are strict, and the cost is high. The sintered neodymium iron boron containing SmFeN or SmFeC has high coercive force, high temperature resistance and high resistance, the coercive force is increased greatly before and after grain boundary diffusion treatment, and the preparation method has simple operation and low cost.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of sintered neodymium iron boron containing SmFeN or SmFeC, which comprises the following steps:
s1, forming Sm on the surface of the neodymium iron boron sintered body2Fe17-xMxPerforming grain boundary diffusion treatment on the coating which is a diffusion source;
s2, performing nitriding treatment or carbonizing treatment; wherein Sm is contained in the resulting alloy powder after nitriding treatment2Fe17-xMxNySintering neodymium iron boron; when carbonized, Sm-containing compounds are obtained2Fe17-xMxCySintering neodymium iron boron;
wherein M is one or more of Co, Mo, Cu, Zr, Ti and Al, and x is 0-2; y is 1 to 5.
In the present invention, the neodymium iron boron sintered body may be conventional in the art.
Preferably, the raw materials of the neodymium iron boron sintered body comprise: r: 28-32%; fe: 65.5-70%; b: 0.90-1.2%; m: 0 to 5 percent; wherein the percentage is the mass percentage of the element in the total amount of the element; the R comprises Nd, Pr, La, Ce, Sm and RH, and the RH is a heavy rare earth element; and M is one or more of Cu, Co, Al, Ti, Nb, Zn, Hf, Zr and Ga.
In a preferred embodiment of the present invention, the raw materials of the neodymium iron boron sintered body include: PrNd: 29.7%, Ho: 1.5 percent; fe: 65.6 percent; b: 0.95 percent; cu: 0.2 percent; co: 1.2 percent; al: 0.6 percent; zr: 0.15 percent; ga: 0.1 percent, wherein the percentage of the element accounts for the mass percentage of the total mass.
Preferably, the neodymium iron boron sintered body is prepared by smelting, casting, hydrogen crushing, powder forming, magnetic field compression molding and sintering raw materials of the neodymium iron boron sintered body.
The smelting and casting equipment can be conventional in the field, and is generally a medium-frequency vacuum smelting furnace, such as a medium-frequency vacuum induction rapid hardening melt-spinning furnace.
The smelting temperature can be conventional in the art, and is preferably 1300-1700 ℃, and more preferably 1450-1550 ℃, for example 1450, 1500 or 1550 ℃.
The casting temperature may be conventional in the art, and is more preferably 1200-1600 ℃, and is preferably 1350-1500 ℃, for example 1350, 1400 or 1500 ℃.
The operation and conditions of the hydrogen-broken powder can be conventional in the field, and generally comprise a hydrogen breaking process and a jet milling process which are sequentially carried out.
Wherein the shaping may be conventional in the art. More preferably, the magnetic field is oriented vertically or parallel pressed, and the magnetic field strength during orientation pressing is 1.5T or more, for example, 1.8T.
The operation and conditions of the sintering may be conventional in the art, among others. More preferably, the sintering is performed under a vacuum of less than 0.05 Pa.
Wherein the sintering temperature is preferably 1000-1200 deg.C, such as 1000, 1050, 1080 or 1090 deg.C.
The sintering time is preferably 0.5-10 hours, such as 0.5, 5 or 10 hours.
Preferably, the thickness of the neodymium iron boron sintered body in the orientation direction is 0.1 to 10mm, more preferably 1 to 3mm, such as 1, 2 or 3 mm.
In a preferred embodiment of the present invention, it is known to those skilled in the art that in order to obtain a sheet-shaped sintered nd-fe-b body with an orientation thickness of 0.1 to 10mm, the sheet-shaped sintered nd-fe-b body (the orientation thickness is generally 5 to 70mm, more preferably 10 to 50mm, for example, 15, 30 or 45mm) needs to be sliced. After the sheet neodymium iron boron sintered body is obtained, in order to remove an oxide layer and a surface degradation layer on the surface of the sintered body and create conditions for the adhesion of a diffusion layer during subsequent grain boundary diffusion, the sheet neodymium iron boron sintered body is pretreated, and the pretreatment can be conventional in the field. Preferably, the neodymium iron boron sintered body is ground, sand-blasted and acid-washed for standby.
In a preferred embodiment of the invention, the inert gas and H are2Under the condition, the activity of the surface layer of the neodymium iron boron sintered body can be further excited by adopting a low-temperature hydrogen activation method. The activated Nd-Fe-B sintered body can absorb H2H is permeated by high temperature and inert gas pressure during subsequent grain boundary diffusion treatment2Sm is a rapidly escaping substance when heated2Fe17-xMxThe diffusion source provides more diffusion channels, the grain boundary diffusion speed and the grain boundary diffusion depth are increased, the coercivity of the neodymium iron boron magnet is further improved, and the neodymium iron boron magnet with more uniform overall coercivity is obtained through preparation.
Preferably, the neodymium iron boron sintered body is firstly put in inert gas and H2Sm is formed on the surface of the activated neodymium iron boron sintered body after being activated under the condition2Fe17-xMxIs a coating of a diffusion source.
More preferably, the inert gas is one or more of helium, neon, argon, krypton, xenon, and radon, such as argon.
Wherein, more preferably, the inert gas and H2The pressure of (A) is 0.01 to 1MPa, for example 0.05MPa, and said H2The mass percentage of the neodymium iron boron sintered body is 0.03-0.1%, for example 0.05%.
Wherein the activation temperature is more preferably 200-300 ℃, preferably 200-260 ℃, for example 200, 240 or 260 ℃.
Wherein the activation time is more preferably 0.1-2 h, preferably 0.2-0.8 h, such as 0.2, 0.4 or 0.8 h.
In the invention, the method of grain boundary diffusion is adopted, and Sm is adopted2Fe17-xMx(M is one or more of Co, Mo, Cu, Zr, Ti and Al, and x is 0-2) as a diffusion source. In the process of grain boundary diffusion, Sm2Fe17-xMxThe coating is dispersed along NdFeB crystal boundary, distributed along the crystal boundary in neodymium-rich phase, and dispersed Sm2Fe17-xMxSm is formed by subsequent nitriding or carbonizing treatment2Fe17-xMxNyOr Sm2Fe17-xMxCyAnd (5) structure. The prepared composite magnet has the advantages of high coercive force, good high-temperature performance, high resistance, high remanence and excellent comprehensive performance.
In the present invention, Sm is mentioned above2Fe17-xMxThe preparation process of (b) may be conventional in the art.
Preferably, Sm is the same as above2Fe17-xMxThe preparation method of (3) may comprise the steps of: will be Sm according to the nominal composition2Fe17- xMxThe raw materials are subjected to vacuum melting, casting, annealing, jaw crushing and jet milling to prepare the material.
Wherein, preferably, the smelting is carried out by adopting a melt rapid quenching method, and the prepared product has Th2Zn17Sm of structure2Fe17-xMxA master alloy.
The smelting and casting equipment can be conventional in the field, and is generally a medium-frequency vacuum smelting furnace, such as a medium-frequency vacuum induction rapid hardening melt-spinning furnace. The frequency of the medium frequency vacuum melting furnace can be conventional in the art, and is more preferably 1500-2500 Hz, such as 1500, 2000 or 2500 Hz.
The thickness of the alloy sheet obtained by melting is more preferably 0.1 to 0.6mm, preferably 0.2 to 0.4mm, for example 0.2, 0.3 or 0.4 mm.
The smelting temperature can be conventional in the art, and is preferably 1300-2000 ℃, more preferably 1500-1750 ℃, for example 1500, 1600 or 1750 ℃.
Wherein the casting temperature can be conventional in the art, more preferably 1200-1900 ℃, preferably 1450-1600 ℃, for example 1450, 1500 or 1600 ℃.
Preferably, the annealing is to place the alloy sheet obtained by smelting in a vacuum furnace at 400-600 ℃, for example, 400, 500 or 600 ℃; the heating time of the annealing is more preferably 1 to 10 hours, preferably 3 to 5 hours, for example 3, 4 or 5 hours, so that the components of the alloy sheet are more uniform and the stress of the alloy sheet is eliminated.
Wherein the jaw crushing is generally carried out in a jaw crusher. More preferably, the jaw is broken to yield Sm 0.2 to 2mm D50, e.g. 0.2, 1 or 2mm D502Fe17-xMxAnd (3) powder.
Wherein, the jet mill can be conventional in the field, and is preferably carried out under the condition of 0.1-2 MPa, preferably 0.5-0.7 MPa.
The gas flow in the jet mill is preferably an inert gas, including one or more of helium, neon, argon, krypton, xenon, and radon, such as argon.
More preferably, Sm 2 with a D50 of 2.0 to 5.0 μm, e.g., a D50 of 2.0, 3.0 or 5.0 μm is obtained after the jet milling2Fe17-xMxAnd (3) fine powder.
Wherein more preferably Sm is obtained after said jet milling2Fe17-xMxThe fine powder and Sm are respectively2Fe17-xMx0.5 to 1.5 weight percent of antioxidant and 0.8 to 1.2 weight percent of lubricant which are based on the mass of the fine powder are uniformly mixed, wherein the antioxidant and the lubricant are conventional in the field, and are preferably special antioxidant and lubricant for magnetic materials produced by new Tianjin Yuesheng material research institute.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 10.631 percent; fe: 89.369 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 89.264 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 11.052 percent; fe: 88.948 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 88.264 percent; mo: 1 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 87.564 percent; co: 0.1 percent; mo: 1 percent; cu: 0.1 percent; zr: 0.2 percent; ti: 0.1 percent; al: 0.2 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 88.564 percent; co: 0.1 percent; cu: 0.1 percent; zr: 0.2 percent; ti: 0.1 percent; al: 0.2 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In the present invention, the grain boundary diffusion treatment may be conventional in the art.
Wherein preferably Sm is formed on the surface of the activated neodymium iron boron sintered body by adopting a thermal spraying method, a coating method or a vapor deposition method2Fe17-xMxIs a coating of a diffusion source.
The thickness of the coating is preferably 0.1 to 5mm, more preferably 0.5 to 2mm, such as 0.5, 1 or 2 mm.
The temperature of the grain boundary diffusion treatment is preferably 800 to 1000 ℃, for example 800, 900 or 1000 ℃.
The time of the grain boundary diffusion treatment is preferably 4 to 20 hours, more preferably 6 to 15 hours, such as 6, 8 or 15 hours.
Preferably, before the grain boundary diffusion treatment, the furnace is vacuumized until the degree of vacuum in the furnace is lower than 0.05Pa, and then an inert gas, such as argon, is introduced, wherein the pressure of the grain boundary diffusion treatment is 0.01 to 0.1MPa, such as 0.01, 0.04, or 0.1 MPa.
In the invention, the Nd-Fe-B sintered body after the grain boundary diffusion treatment is subjected to nitriding treatment or carbonizing treatment to form Sm with high coercivity, good high-temperature performance, high resistance and high remanence2Fe17-xMxNyOr Sm2Fe17-xMxCyRealization of NdFeB magnet and Sm2Fe17-xMxNyOr Sm2Fe17-xMxCyThe composition of the magnet can also solve Sm2Fe17-xMxNyOr Sm2Fe17-xMxCyMagnet at high temperature>Easy decomposition at 600 ℃, can improve the comprehensive magnetic property of the base material NdFeB, does not need to add heavy rare earth Dy or Tb, and has simple preparation process and low cost.
Wherein the nitriding treatment is preferably performed in a rotary nitriding furnace.
Wherein the carbonization treatment is preferably performed in a rotary carbonization furnace.
The temperature of the nitriding treatment or the carbonizing treatment is preferably 400 to 600 ℃, more preferably 480 to 580 ℃, for example 550 ℃.
The time of the nitriding treatment or the carbonizing treatment is preferably 1 to 10 hours, more preferably 3 to 6 hours, such as 3, 5 or 6 hours.
The invention also provides sintered neodymium iron boron containing SmFeN or SmFeC, which is prepared by the preparation method.
The invention also relates toProvides a kind of Sm2Fe17-xMxA powder comprising, as raw materials: sm: 10-11.5%; fe: 87-90%, M: 0-2%; the percentage is the atomic percentage of the element in the total amount of the element; m is one or more of Co, Mo, Cu, Zr, Ti and Al, and x is 0-2.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 10.631 percent; fe: 89.369 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 89.264 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 11.052 percent; fe: 88.948 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 88.264 percent; mo: 1 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 87.564 percent; co: 0.1 percent; mo: 1 percent; cu: 0.1 percent; zr: 0.2 percent; ti: 0.1 percent; al: 0.2 percent; the percentage is the atomic percentage of the element in the total amount of the element.
In a preferred embodiment of the present invention, Sm is mentioned2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 88.564 percent; co: 0.1 percent; cu: 0.1 percent; zr: 0.2 percent; ti: 0.1 percent; al: 0.2 percent; the percentage is the atomic percentage of the element in the total amount of the element.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the NdFeB-SmFeN or NdFeB-SmFeC composite magnet structure with high temperature resistance, high resistance and high coercivity is prepared by nitriding or carbonizing the NdFeB-SmFe composite magnet and improving the matrix performance. The coercive force of the sintered neodymium iron boron is improved, and the problem that SmFeN or alloy SmFeC is easy to decompose at the temperature of over 600 ℃ can be avoided. The resistance and the high temperature resistance of the neodymium iron boron product are improved, and the application range of the neodymium iron boron magnet is widened.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Remanence (Br), coercive force (H) in examples and comparative examples of the present inventioncj) And square degree (H)k/Hcj) The magnetic property detection is carried out by using an NIM-62000 type rare earth permanent magnet measuring system of a Chinese measurement institute.
Example 1
Step 1: has the nominal component of Sm2Fe17-xMx(the formula components are shown in table 1), adding the raw materials into a medium-frequency vacuum induction rapid hardening melt-spun furnace with the frequency of 2000Hz, and preparing the material with Th by adopting a melt rapid quenching method2Zn17Sm of structure2Fe17-xMxThe smelting temperature of the master alloy is 1600 ℃, the casting temperature is 1500 ℃, and the thickness of an alloy sheet obtained by smelting is 0.3 mm; then carrying out homogenizing annealing, and placing the alloy sheet obtained by smelting in a vacuum furnace at 500 ℃; the heating time of annealing is 4 hours, so that the components of the alloy sheet are more uniform, and the stress of the alloy sheet is eliminated;
step 2: mixing Sm2Fe17-xMxSm of 1mm in the grain size D50 of master alloy broken by jaw2Fe17-xMxPowder is subjected to jet milling under the condition of 0.5-0.7 MPa under the protection of argon gas to prepare the powderSm 3.0 μm in terms of D502Fe17-xMxFine powder is milled by air flow to obtain Sm2Fe17-xMxThe fine powder and Sm are respectively2Fe17-xMxThe antioxidant and the lubricant which are 1.0 wt% of the fine powder are uniformly mixed, and the antioxidant and the lubricant are special for the magnetic material produced by new Tianjin Yuesheng material research institute.
And step 3: adding raw materials of a neodymium iron boron sintered body (the raw materials comprise 29.7 percent of PrNd, 1.5 percent of Ho, 65.6 percent of Fe, 0.95 percent of B, 0.2 percent of Cu, 1.2 percent of Co, 0.6 percent of Al, 0.15 percent of Zr and 0.1 percent of Ga in percentage by mass of the total mass) into a medium-frequency vacuum induction rapid hardening and casting furnace for smelting and casting, wherein the smelting temperature is 1500 ℃, and the casting temperature is 1400 ℃; then hydrogen crushing powder (hydrogen crushing process and airflow milling process which are sequentially carried out) is carried out; then, the magnetic field is oriented and vertically pressed for forming, and the magnetic field intensity is 1.8T during orientation pressing; sintering under the condition that the vacuum degree is lower than 0.05Pa, wherein the sintering temperature is 1080 ℃ and the sintering time is 5 h; cutting the obtained neodymium iron boron sintered body (30mm) into a sheet neodymium iron boron sintered body with the orientation thickness of 2mm, and carrying out pretreatment, namely, grinding, sand blasting, acid washing and other procedures for standby application;
and 4, step 4: putting the pretreated sheet neodymium iron boron sintered body in a diffusion furnace, introducing Ar gas, heating to 240 ℃, and introducing hydrogen (Ar and H) accounting for 0.05 percent of the weight of the charged neodymium iron boron sheet materials2The pressure of the sheet neodymium iron boron sintered body is 0.05MPa) and the sheet neodymium iron boron sintered body is activated at low temperature for 0.4 h;
and 5: after the low-temperature hydrogen activation is finished, vacuumizing the diffusion furnace until the vacuum degree is below 0.05Pa, refilling a certain amount of Ar gas, wherein the pressure in the furnace is 0.04MPa, and heating to 900 ℃ under the Ar gas. Then preparing Sm from the step 22Fe17-xMxAnd uniformly spraying the fine powder on the surface of the sheet neodymium iron boron sintered body under the thermal spraying process condition, wherein the thickness of the coating is 1mm, and carrying out grain boundary diffusion treatment for 8 hours at the temperature. Low temperature H by high temperature and inert gas pressure permeation2H absorbed by surface layer of sintered Nd-Fe-B body during activation treatment2Rapidly escaping as Sm2Fe17-xMxThe diffusion source provides a diffusion channel and increases the grain boundary diffusion speed and the grain boundary diffusion depth.
Step 6: NdFeB-Sm subjected to grain boundary diffusion treatment2Fe17-xMxThe composite magnet is placed in a rotary nitriding furnace, and is subjected to nitriding treatment at 550 ℃ for 5 hours to sinter Sm on the surface layer of the neodymium iron boron2Fe17-xMxThe alloy is fully nitrided to form Sm2Fe17-xMxNyStructure of (1), realization of NdFeB magnet and Sm2Fe17-xMxAnd (4) compounding the magnet.
Examples 2 to 6
Except for optional Sm2Fe17-xMxThe raw materials were formulated with different ingredient contents (as shown in table 1), and the parameters in the remaining preparation process were the same as those in example 1.
Example 7
Except for optional Sm2Fe17-xMxThe formula component content of the raw material (as shown in table 1) and the operation of step 6 are different, and the parameters in steps 1 to 5 are the same as the preparation process of example 1.
Step 6: NdFeB-Sm subjected to grain boundary diffusion treatment2Fe17-xMxThe composite magnet is placed in a rotary carbonization furnace, and is carbonized for 5 hours at the temperature of 550 ℃ to sinter Sm on the surface layer of the neodymium iron boron2Fe17-xMxThe alloy is fully nitrided to form Sm2Fe17-xMxCyStructure of (1), realization of NdFeB magnet and Sm2Fe17-xMxAnd (4) compounding the magnet.
Example 8
Except for optional Sm2Fe17-xMxThe raw materials have different formula component contents (shown in table 1), and the parameters in the steps 1-3 and 5-6 are the same as the preparation process of the example 1 except that the step 4 is not performed.
Comparative examples 9 to 10
Except for optional Sm2Fe17-xMxThe raw materials have different formula component contents (such asTable 1), the parameters in the remaining preparation process were the same as those of example 1.
Comparative example 11
Except for optional Sm2Fe17-xMxThe raw materials have different formula component contents (as shown in table 1), and the parameters in the steps 1-2 are the same as the preparation process of the example 1.
And step 3: mixing Sm2Fe17-xMxPutting the fine powder into a rotary nitriding furnace, and performing nitriding treatment at 550 ℃ for 5 hours to obtain Sm2Fe17-xMxNyAnd (5) fine powder for later use.
And 4, step 4: adding raw materials of a neodymium iron boron sintered body (the raw materials comprise 29.7 percent of PrNd, 1.5 percent of Ho, 65.6 percent of Fe, 0.95 percent of B, 0.2 percent of Cu, 1.2 percent of Co, 0.6 percent of Al, 0.15 percent of Zr and 0.1 percent of Ga according to the mass percent of the elements) into a medium-frequency vacuum induction rapid hardening melt-spun furnace for smelting and casting, wherein the smelting temperature is 1500 ℃, and the casting temperature is 1400 ℃; then hydrogen crushing powder (hydrogen crushing process and airflow milling process which are sequentially carried out) is carried out; then, the magnetic field is oriented and vertically pressed for forming, and the magnetic field intensity is 1.8T during orientation pressing; sintering under the condition that the vacuum degree is lower than 0.05Pa, wherein the sintering temperature is 1080 ℃ and the sintering time is 5 h; cutting the obtained neodymium iron boron sintered body into sheet neodymium iron boron sintered body with the orientation thickness of 2mm, and carrying out pretreatment, namely, grinding, sand blasting, acid washing and other procedures for standby application;
and 5: putting the pretreated sheet neodymium iron boron sintered body in a diffusion furnace, introducing Ar gas, heating to 240 ℃, and introducing hydrogen, Ar and H, which are 0.05 percent of the weight of the charged neodymium iron boron sheet material2The pressure of the sheet neodymium iron boron sintered body is 0.05MPa), and the sheet neodymium iron boron sintered body is activated at low temperature for 0.4 h;
step 6: after the low-temperature hydrogen activation is finished, vacuumizing the diffusion furnace until the vacuum degree is below 0.05Pa, refilling a certain amount of Ar gas, wherein the pressure in the furnace is 0.04MPa, and heating to 900 ℃ under the Ar gas. Then Sm is prepared by the step 32Fe17-xMxNyThe fine powder is evenly sprayed to the flaky neodymium iron boron for sintering under the condition of the thermal spraying processThe surface of the body is coated with 1mm of coating thickness, and the grain boundary diffusion treatment is carried out for 8h at the temperature.
TABLE 1 Sm2Fe17-xMxThe formula component content of the raw material
Comparative example 12
The sample in this comparative example is the sheet-like sintered nd-fe-b body prepared in step 3 of example 1.
Comparative example 13
The sample in this comparative example was a 42UH brand performance blank purchased from fujian province, changtian, jinlong rare earth ltd, containing more than 5 wt% Dy.
Effects of the embodiment
Table 2 shows the magnetic properties and resistivity of examples 1 to 7 and comparative examples 8 to 10.
TABLE 2 comparison of magnetic and resistivity of examples and comparative examples
From the above table it can be seen that:
the sintered neodymium iron boron containing SmFeN or SmFeC has high coercive force, the coercive force increase amplitude before and after grain boundary diffusion treatment is large (compared with the comparative example 11 in the embodiments 1-7), and the preparation method is simple to operate and low in cost.
Comparative example 10 Sm for example 1 to 72Fe17-xMxThe raw materials are prepared according to the ratio of 2:17, Sm loss is generated in the processes of smelting, jet milling and the like, and the component ratio of the obtained product is lower than 2:17, so that the Hcj of the product is greatly influenced.
Compared with the examples 1-8, the performance equivalent to that of the invention can be achieved only by adding more than 5 wt% of heavy rare earth element Dy into the neodymium iron boron magnet, and the cost is higher.
Claims (10)
1. A preparation method of sintered neodymium iron boron containing SmFeN or SmFeC is characterized by comprising the following steps:
s1, forming Sm on the surface of the neodymium iron boron sintered body2Fe17-xMxPerforming grain boundary diffusion treatment on the coating which is a diffusion source;
s2, performing nitriding treatment or carbonizing treatment; wherein Sm is contained in the resulting alloy powder after nitriding treatment2Fe17-xMxNySintering neodymium iron boron; when carbonized, Sm-containing compounds are obtained2Fe17-xMxCySintering neodymium iron boron;
wherein M is one or more of Co, Mo, Cu, Zr, Ti and Al, and x is 0-2; y is 1 to 5.
2. The method of claim 1, wherein the raw materials of the neodymium-iron-boron sintered body comprise: r: 28-32%; fe: 65.5-70%; b: 0.90-1.2%; m: 0 to 5 percent; wherein the percentage is the mass percentage of the element in the total amount of the element; the R comprises Nd, Pr, La, Ce, Sm and RH, and the RH is a heavy rare earth element; the M is one or more of Cu, Co, Al, Ti, Nb, Zn, Hf, Zr and Ga;
preferably, the raw materials of the neodymium iron boron sintered body comprise: PrNd: 29.7%, Ho: 1.5 percent; fe: 65.6 percent; b: 0.95 percent; cu: 0.2 percent; co: 1.2 percent; al: 0.6 percent; zr: 0.15 percent; ga: 0.1 percent, wherein the percentage of the element accounts for the mass percentage of the total mass;
and/or the neodymium iron boron sintered body is prepared by smelting, casting, hydrogen crushing powder, magnetic field compression molding and sintering raw materials of the neodymium iron boron sintered body;
and/or the thickness of the neodymium iron boron sintered body in the orientation direction is 0.1-10 mm, more preferably 1-3 mm, such as 1, 2 or 3 mm.
3. The method of claim 2, wherein the melting and casting is a medium frequency vacuum melting furnace, such as a medium frequency vacuum induction rapid solidification melt-spun furnace;
and/or the smelting temperature is 1300-1700 ℃, preferably 1450-1550 ℃, such as 1450, 1500 or 1550 ℃;
and/or the casting temperature is 1200-1600 ℃, preferably 1350-;
and/or the hydrogen crushing powder comprises a hydrogen crushing process and a gas flow milling process which are sequentially carried out;
and/or the magnetic field compression molding is magnetic field orientation vertical compression molding or parallel compression molding, and the magnetic field intensity during orientation compression is more than 1.5T, such as 1.8T;
and/or, the sintering is carried out under the condition that the vacuum degree is lower than 0.05 Pa;
and/or the sintering temperature is 1000-1200 ℃, such as 1000, 1050, 1080 or 1090 ℃;
and/or the sintering time is 0.5-10 h, such as 0.5, 5 or 10 h;
and/or grinding, sand blasting and acid washing the neodymium iron boron sintered body for later use.
4. The method of claim 1, wherein the sintered nd-fe-b body is first subjected to an inert gas and H2Sm is formed on the surface of the activated neodymium iron boron sintered body after being activated under the condition2Fe17-xMxA coating that is a diffusion source;
and/or, said Sm2Fe17-xMxThe preparation method of (3) may comprise the steps of: will be Sm according to the nominal composition2Fe17-xMxThe raw materials are subjected to vacuum melting, casting, annealing, jaw crushing and jet milling to prepare the material.
5. The method of claim 4, wherein the inert gas is one or more of helium, neon, argon, krypton, xenon, and radon, such as argon;
and/or, the inert gas and H2Is at a pressure of 0.01 to 1MPa, for example 0.05MPa, and the H2The mass percentage of the neodymium iron boron sintered body is 0.03-0.1%, for example 0.05%;
and/or the temperature of the activation is 200-300 ℃, preferably 200-260 ℃, such as 200, 240 or 260 ℃;
and/or the activation time is 0.1-2 h, preferably 0.2-0.8 h, such as 0.2, 0.4 or 0.8 h;
and/or the smelting is carried out by adopting a melt rapid quenching method;
and/or the smelting and casting equipment is a medium-frequency vacuum smelting furnace, such as a medium-frequency vacuum induction rapid hardening melt-spun furnace;
preferably, the frequency of the medium-frequency vacuum melting furnace is 1500-2500 Hz, such as 1500, 2000 or 2500 Hz;
and/or the thickness of the alloy sheet obtained by smelting is 0.1-0.6 mm, preferably 0.2-0.4 mm, such as 0.2, 0.3 or 0.4 mm;
and/or the smelting temperature is 1300-2000 ℃, preferably 1500-1750 ℃, such as 1500, 1600 or 1750 ℃;
and/or the casting temperature is 1200-1900 ℃, preferably 1450-1600 ℃, such as 1450, 1500 or 1600 ℃;
and/or the annealing is to place the alloy sheet obtained by smelting in a vacuum furnace at 400-600 ℃, for example, 400, 500 or 600 ℃;
and/or the heating time of the annealing is 1-10 h, preferably 3-5 h, for example 3, 4 or 5h,
and/or Sm 0.2-2 mm D50, e.g. 0.2, 1 or 2mm D50, is obtained after the jaw is broken2Fe17-xMxPowder;
and/or the jet mill is carried out under the condition of 0.1-2 MPa, preferably 0.5-0.7 MPa;
and/or the gas flow in the jet mill is inert gas, including one or more of helium, neon, argon, krypton, xenon and radon, such as argon;
and/or, after the jet milling, Sm with a D50 of 2.0-5.0 μm, for example a D50 of 2.0, 3.0 or 5.0 μm is obtained2Fe17- xMxFine powder;
and/or Sm obtained after the jet milling2Fe17-xMxThe fine powder and Sm are respectively2Fe17-xMx0.5 to 1.5 wt%, preferably 0.8 to 1.2 wt% of the fine powder of an antioxidant and a lubricant are uniformly mixed.
6. The process according to claim 1, wherein Sm is selected from the group consisting of2Fe17-xMxComprises the following raw materials: sm: 10.631 percent; fe: 89.369 percent; the percentage is the atomic percentage of the element in the total amount of the element;
or, Sm as the main component2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 89.264 percent; the percentage is the atomic percentage of the element in the total amount of the element;
or, Sm as the main component2Fe17-xMxComprises the following raw materials: sm: 11.052 percent; fe: 88.948 percent; the percentage is the atomic percentage of the element in the total amount of the element;
or, Sm as the main component2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 88.264 percent; mo: 1 percent; the percentage is the atomic percentage of the element in the total amount of the element;
or, Sm as the main component2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 87.564 percent; co: 0.1 percent; mo: 1 percent; cu: 0.1 percent; zr: 0.2 percent; ti: 0.1 percent; al: 0.2 percent; the percentage is the atomic percentage of the element in the total amount of the element;
or, Sm as the main component2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 88.564 percent; co: 0.1 percent; cu: 0.1 percent; zr: 0.2 percent; ti: 0.1 percent; al: 0.2 percent; the percentage is the atomic percentage of the element in the total amount of the element.
7. The method of claim 1, wherein Sm is formed on the surface of the activated sintered NdFeB body by thermal spraying, coating or vapor deposition2Fe17-xMxA coating that is a diffusion source;
and/or the thickness of the coating is 0.1 to 5mm, more preferably 0.5 to 2mm, such as 0.5, 1 or 2 mm;
and/or the temperature of the grain boundary diffusion treatment is 800-1000 ℃, such as 800, 900 or 1000 ℃;
and/or the time of the grain boundary diffusion treatment is 4-20 h, preferably 6-15 h, such as 6, 8 or 15 h;
and/or before the grain boundary diffusion treatment, vacuumizing, introducing inert gas such as argon when the vacuum degree in a furnace is lower than 0.05Pa, wherein the pressure of the grain boundary diffusion treatment is 0.01-0.1 MPa, such as 0.01, 0.04 or 0.1 MPa;
and/or the nitriding treatment is carried out in a rotary nitriding furnace;
and/or the carbonization treatment is carried out in a rotary carbonization furnace;
and/or the temperature of the nitriding treatment or the carbonizing treatment is 400-600 ℃, more preferably 480-580 ℃, for example 550 ℃;
and/or the nitriding treatment or the carbonizing treatment is carried out for 1 to 10 hours, preferably 3 to 6 hours, such as 3, 5 or 6 hours.
8. Sintered neodymium iron boron containing SmFeN or SmFeC, characterized in that it is prepared by the preparation method according to any one of claims 1 to 7.
9. Sm2Fe17-xMxPowder, characterized in that its raw materials comprise: sm: 10-11.5%; fe: 87-90%, M: 0-2%; the percentage is the atomic percentage of the element in the total amount of the element; m is one or more of Co, Mo, Cu, Zr, Ti and Al, and x is 0-2.
10. As claimed in claim9 Sm of2Fe17-xMxPowder, characterized in that Sm is2Fe17-xMxComprises the following raw materials: sm: 10.631 percent; fe: 89.369 percent; the percentage is the atomic percentage of the element in the total amount of the element;
or, Sm as the main component2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 89.264 percent; the percentage is the atomic percentage of the element in the total amount of the element;
or, Sm as the main component2Fe17-xMxComprises the following raw materials: sm: 11.052 percent; fe: 88.948 percent; the percentage is the atomic percentage of the element in the total amount of the element;
or, Sm as the main component2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 88.264 percent; mo: 1 percent; the percentage is the atomic percentage of the element in the total amount of the element;
or, Sm as the main component2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 87.564 percent; co: 0.1 percent; mo: 1 percent; cu: 0.1 percent; zr: 0.2 percent; ti: 0.1 percent; al: 0.2 percent; the percentage is the atomic percentage of the element in the total amount of the element;
or, Sm as the main component2Fe17-xMxComprises the following raw materials: sm: 10.736 percent; fe: 88.564 percent; co: 0.1 percent; cu: 0.1 percent; zr: 0.2 percent; ti: 0.1 percent; al: 0.2 percent; the percentage is the atomic percentage of the element in the total amount of the element.
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