WO2014190558A1 - 稀土永磁粉、包括其的粘结磁体及应用该粘结磁体的器件 - Google Patents

稀土永磁粉、包括其的粘结磁体及应用该粘结磁体的器件 Download PDF

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WO2014190558A1
WO2014190558A1 PCT/CN2013/076605 CN2013076605W WO2014190558A1 WO 2014190558 A1 WO2014190558 A1 WO 2014190558A1 CN 2013076605 W CN2013076605 W CN 2013076605W WO 2014190558 A1 WO2014190558 A1 WO 2014190558A1
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Prior art keywords
rare earth
permanent magnet
earth permanent
magnet powder
powder
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PCT/CN2013/076605
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English (en)
French (fr)
Inventor
李红卫
罗阳
于敦波
李扩社
闫文龙
李世鹏
袁永强
彭海军
Original Assignee
北京有色金属研究总院
有研稀土新材料股份有限公司
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Application filed by 北京有色金属研究总院, 有研稀土新材料股份有限公司 filed Critical 北京有色金属研究总院
Priority to JP2016515594A priority Critical patent/JP6163258B2/ja
Priority to PCT/CN2013/076605 priority patent/WO2014190558A1/zh
Priority to DE112013007128.2T priority patent/DE112013007128T5/de
Priority to US14/651,560 priority patent/US10079085B2/en
Priority to KR1020157017182A priority patent/KR101687981B1/ko
Priority to CN201380057909.4A priority patent/CN104823249B/zh
Publication of WO2014190558A1 publication Critical patent/WO2014190558A1/zh

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    • 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
    • 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
    • H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
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    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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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
    • 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
    • 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
    • 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
    • H01F1/0551—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • 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
    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0558—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together bonded together
    • 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
    • H01F1/06—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 in the form of particles, e.g. powder
    • H01F1/08—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 in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/083—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 in the form of particles, e.g. powder pressed, sintered, or bound together in a bonding agent
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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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/20—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 soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/22—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 soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F2998/10—Processes characterised by the sequence of their steps
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    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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Definitions

  • the present invention relates to a rare earth magnetic material, and in particular to a rare earth permanent magnet powder, a bonded magnet including the same, and a bonded magnet using the same Device.
  • a bonded rare earth permanent magnet is a combination of a rare earth permanent magnet powder and a bonding material, and various permanent magnet devices are directly injected or molded according to user requirements.
  • the magnets have the advantages of high dimensional accuracy, good magnetic uniformity, good corrosion resistance, high yield, easy processing into complex shapes, and are widely used in home appliances, micro-motors, automated office equipment, instrumentation, medical devices, In automobiles, magnetic machinery and other devices and equipment.
  • the bonded rare earth permanent magnet powder mainly includes neodymium iron boron magnetic powder and nitride rare earth magnetic powder.
  • Nitride rare earth magnetic powders have been gradually applied due to their high magnetic properties and good corrosion resistance. Widely, how to improve the performance of nitride rare earth magnetic powder to meet the needs of the application has become the focus of research.
  • the nitride rare earth magnetic powder is mainly obtained by nitriding the rare earth alloy powder through a certain temperature and time.
  • the preparation method of the rare earth alloy powder includes various methods, which can be performed by mechanical alloying method or by rapid quenching methods such as CN1196144C and JP2002057017.
  • Disclosed is an isotropic SmFeN powder magnet material for producing a resin bonded magnet, the crystal structure being TbCu 7 type, which is prepared by rapidly quenching a molten alloy and directly nitriding the obtained alloy powder in a nitrogen-containing gas. .
  • No. 5,750,044 discloses a nitride rare earth powder which is also obtained by rapid quenching and then nitriding.
  • the magnetic powder has TbCu 7 or Th 2 Zn 17 or Th 2 Ni 17 and a soft magnetic phase structure, and the soft magnetic phase ratio is 10 ⁇ . 60%.
  • the nitride rare earth powder improves the magnetic properties of the nitride rare earth magnetic powder to some extent, but in order to meet the requirements of customers for high quality products, further research is needed to better improve the magnetic properties of the rare earth permanent magnet powder.
  • the present invention is directed to a rare earth permanent magnet powder, a bonded magnet, and a device using the same, to improve the magnetic properties of the rare earth permanent magnet powder.
  • a rare earth permanent magnet powder comprising 70 to 99 vol% of a hard magnetic phase and 1 to 30 vol% of a soft magnetic phase, and a hard magnetic phase having a TbCu 7 structure.
  • grain The particle size is 5 ⁇ 100nm; the soft magnetic phase is the Fe phase with bcc structure, the average grain size of the soft magnetic phase is l ⁇ 30nm, and the standard deviation of the particle size is less than 0.5 ⁇ .
  • the grain size distribution of the hard magnetic phase in the rare earth permanent magnet powder is in the range of 5 to 80 nm, and preferably, the grain size distribution of the hard magnetic phase is in the range of 5 to 50 nm.
  • the soft magnetic phase of the rare earth permanent magnet powder accounts for 3 to 30 vol% of the total volume of the rare earth permanent magnet powder, and preferably, the soft magnetic phase accounts for 5 to 15 vol% of the total volume of the rare earth permanent magnet powder.
  • the average grain size of the soft magnetic phase in the rare earth permanent magnet powder is 1 to 20 nm.
  • the standard deviation of the grain size of the soft magnetic phase in the rare earth permanent magnet powder is 0.3 ⁇ or less.
  • the above rare earth permanent magnet powder is composed of RTMA, wherein R is a combination of Sm or Sm and other rare earth elements, T is a combination of Fe or Fe and P Co, and M is Ti, V, Cr, Zr, Nb, Mo, Ta At least one of W, Si or Hf, A is N and/or C.
  • the rare earth permanent magnet powder has an R content of 5 to 12 at.%, A of 10 to 20 at.%, and M of 0 to 10 at.%. , the balance is T.
  • the rare earth permanent magnet powder has an R content of 5 to 10 at.%.
  • the atomic number content of S in R is 80 to 100 at.%.
  • T is a combination of Fe and Co
  • the atomic content of Co in T is
  • the rare earth permanent magnet powder has a thickness of 5 to 50 ⁇ m.
  • a bonded magnet which is obtained by bonding a rare earth permanent magnet powder as described above to a binder.
  • a device to which the above-described bonded magnet is applied is provided.
  • a method for preparing the above rare earth permanent magnet powder comprising the steps of supplying a molten raw material to a rotating roller for rapid quenching to form a flake alloy powder, and heat treating the flake alloy powder
  • the step of rapidly quenching to form the flake alloy powder comprises: spraying the molten raw material onto the rotating roller to lx l0 5 ° C / s ⁇ 80 x l 0 5
  • the cooling rate of °C/s is cooled to 850 °C -950 °C, and once cooled; then cooled to 250 °C ⁇ 350 °C at a cooling rate of 0.5 °C / s ⁇ 5 °C / s, for the second
  • the secondary cooling is performed to obtain a flake alloy powder.
  • the flake alloy powder is heated at a rate of 10 ° C / S ⁇ 30 ° C / s, heated to 600 ⁇ 900 ° C and then heat treated for 10 ⁇ 150 min, preferably, sheet
  • the alloy powder is heated at a rate of 10 ° C / s to 20 ° C / s.
  • the rare earth permanent magnet powder provided by the invention mainly comprises a dual phase magnetic powder composed of a hard magnetic phase having a TbCu 7 structure and a soft magnetic phase having an ⁇ -Fe structure, and the dual phase magnetic powder has a uniform microstructure, which can ensure The soft and hard magnetic phases are uniformly coupled to improve the magnetic properties of the rare earth permanent magnet powder.
  • the microstructure of the rare earth permanent magnet powder plays an important role in the properties of the material.
  • the certain microstructure determines the coupling between the magnetic material grains, the formation of magnetic domains, the stability of the structure, etc., and ultimately Affect the magnetic properties of the material.
  • the inventors of the present invention have conducted extensive research on the microstructure thereof, and proposed the following technical solutions.
  • the rare earth permanent magnet powder provided by the invention comprises 70 ⁇ 99 vol% hard magnetic phase and 1-30 vol% soft magnetic phase, wherein the hard magnetic phase has a TbCu 7 structure and the grain size is 5 ⁇ 100 nm; the soft magnetic phase is The Fe phase having a bcc structure, the soft magnetic phase has an average grain size of 1 to 30 nm, and the standard deviation of the particle size is 0.5 ⁇ or less.
  • the rare earth permanent magnet powder provided by the present invention is mainly composed of a dual phase magnetic powder composed of a hard magnetic phase having a TbCu 7 structure and a soft magnetic phase having an ⁇ -Fe structure.
  • the hard magnetic phase having the TbCu 7 structure in the rare earth permanent magnet powder has more excellent magnetic properties than the already widely used Th 2 Zn 17 structure and the ThMn 12 structure nitride magnetic powder, which is advantageous for further improving the prepared
  • the magnetic properties of rare earth permanent magnet powder at the same time, the soft magnetic phase of the Fe phase with bcc structure and the hard magnetic phase with TbCu 7 structure can couple, thereby inhibiting the conversion of TbCu 7 structure to Th 2 Zn 17 and other structures.
  • the rare earth permanent magnet powder is prevented from being transformed into a phase of Th 2 Zn 17 and 1 ⁇ 1 12 in the stages of crystallization and nitriding to deteriorate the magnetic properties.
  • the Fe phase with bcc structure also has a certain remanence enhancement effect as a soft magnetic phase, which tempers the sensitivity of the magnetic powder to temperature and makes the preparation process wider.
  • the particle size of the hard magnetic phase crystal grains in the rare earth permanent magnet powder of the present invention is preferably 5 to 100 nm. This is because, in the rare earth permanent magnet powder, the average grain size of the hard magnetic phase is less than 5 nm, which is disadvantageous for obtaining a coercive force of 5 kOe or more, and also causes great difficulty in preparation, resulting in low yield.
  • the hard magnetic phase grain size distribution is in the range of 5 to 80 nm, and more preferably in the range of 5 to 50 nm.
  • the volume content of the soft magnetic phase in the rare earth permanent magnet powder of the present invention is preferably from 1 to 30 vol%. Controlling the volume of the soft magnetic phase within this range is advantageous for suppressing the structural transformation of the TbCu 7 structure to Th 2 Zn 17 and the like, and improving the magnetic properties of the prepared rare earth permanent magnet powder. If the content of the soft magnetic phase is less than 1 vol%, the effect of suppressing the occurrence of other miscellaneous phases may be deteriorated. If the content of the soft magnetic phase is more than 30 vol%, the formation of other hetero phases such as Th 2 Zn 17 may be suppressed, but excessive The presence of the soft magnetic phase greatly reduces the coercivity of the material, which is detrimental to the overall performance improvement.
  • the soft magnetic phase ratio is preferably from 3 to 30 vol%, more preferably from 5 to 15 vol%.
  • the average grain size ⁇ of the soft magnetic phase is preferably from 1 to 30 nm, and the average grain size ⁇ of the soft magnetic phase is controlled within the range, which has the effect of remanence enhancement, and improves the prepared rare earth permanent magnet powder. Magnetic properties. If the average grain size ⁇ of the soft magnetic phase is too large, the effect of remanence enhancement cannot be exerted, and not only the above, but also the coercive force of the magnetic powder may be lowered.
  • the soft magnetic phase of the rare earth permanent magnet powder has an average grain size of 1 to 20 nm.
  • the standard deviation of the grain size of the soft magnetic phase is less than 0.5 ⁇ .
  • the distribution of soft magnetic phase in magnetic powder is also a key factor affecting the magnetic properties of magnetic powder. Uniform structure can make the soft and hard magnetic phases evenly match, and the coupling is better, which is beneficial to the improvement of magnetic properties.
  • the soft and hard magnetic phases can be uniformly matched, and then good coupling can be performed to obtain a uniform fine structure. If the standard deviation of the grain size of the soft magnetic phase is higher than 0.5 ⁇ , since the grain distribution is too wide, a uniform fine structure cannot be obtained, which easily causes a decrease in the exchange interaction between the particles in the magnetic powder, resulting in a residual The reduction of the magnetic (Br), and thus the coupling between the hard magnetic phase and the remanence enhancement, does not result in good magnetic properties.
  • the standard deviation of the grain size of the soft magnetic phase in the rare earth permanent magnet powder of the present invention is preferably 0.3 ⁇ .
  • a rare earth permanent magnet powder is composed of RTMA, wherein R is a combination of ⁇ or ⁇ with other rare earth elements, ⁇ is Fe or a combination of Fe and Co, and M is Ti, V, At least one of Cr, Mn, Ni, Cu, Zr, Nb, Mo, Ta, W, Al, Ga, Si or Hf, and A is N and/or.
  • the rare earth permanent magnet powder has an R content of 5 to 12 at.%, A of 10 to 20 at.%, an M content of 0 to 10 at.%, and a balance of T.
  • the R element is a combination of Sm or Sm and other rare earth elements, and R is a combination of Sm or Sm and other rare earth elements, wherein R must contain Sm, which is a TbCu 7 structure hard magnetic field.
  • the content of the R element is preferably in the range of 5 to 12 & 1.%, more preferably in the range of 5 to 10 & 1.%.
  • the rare earth permanent magnet powder if the atomic content of R is less than 5 at.%, the relative ⁇ -Fe soft magnetic phase will be formed relatively more, and further The coercive force of the prepared magnetic powder is lowered; if the R content is higher than 12 at%, relatively more structures similar to the yttrium-rich phase are formed, both of which are disadvantageous for the improvement of magnetic properties.
  • the atomic number of Sm is 80-100 at.%, and part of Sm can be replaced by rare earth elements such as Ce and Y, and the substitution ratio cannot exceed 20%, and a certain amount of other rare earth elements can be improved.
  • the molding properties of the material reduce the melting point of the material. At this time, the content of Ce and La needs to be less than 5 at.%, and the addition of Nd and Y improves the coercive force.
  • the lanthanum element is Fe or a combination of Fe and Co, and preferably T is a combination of Fe and Co.
  • a certain amount of Co addition is beneficial to the improvement of the remanence and temperature stability of the nitrogen-containing magnetic powder, and at the same time, the metastable TbCu 7 phase structure can be stabilized, and the wettability in the preparation process can be improved.
  • the atomic content of Co in T is 0 to 30 at.%, and when the Co content is 0 or 1%, it means that Co is not contained in the composition.
  • M element may be added.
  • M is an element having a melting point higher than that of rare earth Sm. The addition of these high melting point elements is advantageous for refining crystal grains, and the key is to form a uniform microstructure.
  • the rare earth permanent magnet powder is more important in suppressing the uneven growth of crystal grains in the crystallization nitriding process, so that the standard deviation of the grain size of the magnetic powder in the present invention is within a certain range.
  • M mainly include, but are not limited to, one or more of Ti, V, Cr, Mn, Zr, Nb, Mo, Ta, W, Si, Hf, and the addition of the M element can refine grains and improve coercivity. Magnetic properties such as remanence. Meanwhile, the atomic content of the M element in the rare earth permanent magnet powder is preferably selected within 0 to 10 at%, and if the atomic content of the M element is greater than 10 at.%, magnetic properties such as remanence may be lowered. In the rare earth permanent magnet powder composed of RTMA of the present invention, element A may be added, and A is N and/or C. The addition of element A to the rare earth iron compound may have a great influence on its performance, which is called a gap atomic effect.
  • the interstitial atomic effect can increase the Curie temperature, saturation magnetization and anisotropy field of the compound.
  • the rare earth permanent magnet powder composed of RTMA of the present invention it is preferable to contain A of 10 to 20% of atoms, and A can be obtained within this range.
  • the magnetic powder with excellent magnetic properties, the content of less than 10% indicates that the nitriding/carbonization is insufficient, the composition is not uniform, and the magnetic properties are degraded; too high is liable to cause decomposition of the hard magnetic phase, which is also disadvantageous for the improvement of magnetic properties.
  • a rare earth permanent magnet powder is composed of a hard magnetic phase having a TbCu 7 structure and a Fe phase having a bcc structure, wherein the soft magnetic phase of the bcc structure is mainly an ⁇ -Fe phase,
  • the number of diffraction peaks in which the ratio of the peak intensity of the 2 ⁇ angle between 65° and 75° to the intensity of the strongest peak is greater than 10% in the X-ray diffraction pattern of the magnetic powder using the Cu target is less than one.
  • the number of diffraction peaks satisfying this condition is 1 or 0, the grain size and distribution in the prepared bonded magnetic powder are within the limits defined by the present invention, and have an optimum matching performance.
  • the rare earth permanent magnet powder has a thickness of less than 50 ⁇ m. Controlling the thickness of the magnetic powder is advantageous for uniformly distributing the phases in the magnetic powder, thereby optimizing the magnetic powder squareness and the like of the magnetic powder. If the thickness exceeds 50 ⁇ m, the crystals of the phases in the display material are not easily distributed uniformly, which may eventually deteriorate the properties such as the squareness of the magnetic powder. At the same time, it is not conducive to the penetration of nitrogen or carbon into the crystal of the material during the nitriding process.
  • the rare earth permanent magnet powder has a thickness of 5 to 50 ⁇ m, and a too low thickness causes great difficulty in preparation, and is more amorphous, which is disadvantageous for the consistency of the subsequent crystallization nitridation process.
  • the above-mentioned rare earth permanent magnet powder is prepared by a rapid quenching method, and those skilled in the art, under the teachings of the present application, have the ability to prepare a rare earth permanent magnet powder meeting the above requirements.
  • a common preparation method comprises the following steps: (1) After melting various raw material components, such as R, ⁇ , ⁇ , ⁇ , etc., through a nozzle, spray onto a rotating roller, and obtain the roller by the roller.
  • the main preparation steps include the steps of rapidly quenching the molten raw material to form a flake alloy powder, and subjecting the flake alloy powder to heat treatment, followed by nitriding or carbonizing to obtain a rare earth permanent magnet powder.
  • the step of rapidly quenching to form the flake-shaped alloy powder comprises: spraying the molten raw material onto the rotating roller, and cooling to 850 ° C at a cooling rate of lxl 0 5 ° C/s to 80 x 10 5 ° C/s.
  • cooling is performed once; then, it is cooled to 250 ° C to 350 ° C at a cooling rate of 0.5 ° C / s to 5 ° C / s, and a second cooling is performed to obtain the flake alloy powder.
  • the step of rapid quenching process of generating a sheet-like alloy powder comprising: spraying the molten material to the melting point of the roller in the range of 900 ° C to 5 xl 0 5 ° C / s ⁇ 80x l 0 5 ° C /
  • the cooling rate of s is cooled to 880 ° C ⁇ 920 ° C, and once cooled; then cooled to 280 ° C ⁇ 320 ° C at a cooling rate of 0.5 ° C / s ⁇ 3 ° C / s, for the second cooling , secondary cooling is performed to obtain the flake alloy powder.
  • the molten steel liquid is processed by the rotating roller, and is rapidly cooled to 850 to 950 ° C.
  • the rapid cooling rate is lxl 0 5 ° C/s to 80 x l 5 5 ° C. /s, by this cooling rate, the equilibrium phase is too late to form, and the grain size is not as long as it grows.
  • the molten steel is processed and then flew out, and after secondary cooling, in order to achieve a cooling rate of 0.5 ° C / s to 5 ° C / s, as a preferred embodiment of the present invention, the guide baffle is increased in the direction in which the flake powder flies out, The distance between the guide baffle and the starting point of the flake powder is controlled, the temperature of the baffle is guided, and the like to adjust the cooling rate of the flake powder.
  • the preparation method of the rare earth permanent magnet powder provided by the invention can obtain fine structure by using a two-step cooling quenching treatment step, and at the same time, the crystal is ensured by the slow cooling rate during the secondary cooling of the material.
  • the stability of the grain size makes the grain size of the rare earth alloy powder not excessively unevenly grow during the heat treatment, and the magnetic properties of the final rare earth permanent magnet powder are ensured.
  • the flake alloy powder in the heat treatment process of the method for preparing the rare earth permanent magnet powder, is heated at a rate of 10 ° C / s to 30 ° C / s, and the temperature is raised to 600 ⁇ 900 ° C, preferably 600 to 850 ° C, and then heat-treated for 10 to 150 minutes, preferably, the flake alloy powder is heated at a rate of 10 ° C / s to 20 ° C / s.
  • Heating at a certain speed is beneficial to maintain the stability of the entire heating zone, so that the powder grows uniformly, the rate is too low, and the powder is too long in the heating phase, which is not conducive to controlling the heat treatment process; the rate is too high, and the powder heating is uneven.
  • the heat treatment temperature is preferably 600 to 900 ° C. If the temperature is too high, the crystal grains are excessively grown, and if the temperature is too low, the heat treatment effect cannot be obtained.
  • the roller material preferably includes, but is not limited to, Cu, Mo, Cu alloy; in the step of nitriding or carbonizing, the time of nitriding or carburizing process is preferably 3 ⁇ 30h;
  • the nitrogen source is preferably industrial pure nitrogen, a mixed gas of hydrogen and ammonia, and the like.
  • the above rare earth permanent magnet powder may be prepared by bonding with a binder to form a bonded magnet.
  • Such a bonded magnet can be prepared by mixing the rare earth permanent magnet powder of the present invention (the main phase is a ferroniobium powder of a TbCu 7 structure) with a resin, and by molding, injection, calendering or extrusion.
  • the bonded magnet prepared may be in the form of a block, a ring or the like.
  • the bonded magnet can be applied to the preparation of a corresponding device, by which a high-performance neodymium iron magnetic powder and a magnet can be prepared, which is advantageous for further miniaturization of the device.
  • the high temperature resistance and corrosion resistance of the magnetic powder is beneficial to the use of the device under special circumstances.
  • the application of rare earth lanthanum is also beneficial to the balanced application of rare earth resources.
  • the composition, grain size, crystal grain distribution, magnetic powder property, magnet properties, and the like of the rare earth permanent magnet powder of the present invention will be described in the manner of carrying out the specific examples, and the advantageous effects of the present invention will be further explained.
  • the rare earth alloy magnetic powder component is a smelted ferroniobium alloy powder which is formed by nitriding.
  • the composition is the composition of the magnetic powder after nitriding, and the composition is expressed by atomic percentage.
  • n is not less than 5 (L)
  • VSM detection vibrating sample magnetometer
  • Hcj is the intrinsic coercive force, the unit is kOe;
  • (BH)m is the magnetic energy product, the unit is MGOe.
  • the alloy powder obtained was measured by XRD, and the Cu target was used as a target to investigate the phase structure of the magnetic powder.
  • the rare earth permanent magnet powder prepared in the following Examples 1-38 was detected by the following XRD peak, and the ratio of the peak intensity to the strongest peak intensity at a 2 ⁇ angle between 65 ° and 75 ° in the diffraction pattern was greater than 10% of the diffraction peak. The number is 1 or 0
  • Thickness ⁇ Thickness is measured by a spiral micrometer, and the thickness unit is ⁇ Examples 1 to 8 (M is 1 to 2 elements) Preparation method:
  • the alloy ingot is coarsely crushed and placed in a quenching furnace for rapid quenching.
  • the shielding gas is Ar gas
  • the injection pressure is 80 kPa
  • the nozzle diameter is 0.8 mm
  • the water-cooling roller linear velocity is 55 m/s. Flaky alloy powder.
  • the performance of the soft magnetic phase has a higher standard deviation distribution ⁇ ⁇ 0.5 ⁇ , and the highest performance when ⁇ ⁇ 0.3 ⁇ .
  • the hard magnetic phase grains are all in the range of 5 to 50 nm, which is high. Magnetic properties.
  • the grain size distribution of the hard magnetic phase is in the range of 5 to 80 nm, and it is particularly preferable that the magnetic grain size distribution of the hard magnetic phase is better in the range of 5 to 50 nm.
  • the overall use of a plurality of M additions is relatively lower than the addition of 1 to 2 M elements, mainly because the saturation magnetic moment of the transition elements is lower than that of Fe and Co.
  • the addition of more elements loses its saturation magnetic moment, which slightly reduces some of the magnetic properties.
  • the grain size and distribution deviate from the protection range, the coercive force is greatly reduced.
  • the a-Fe soft magnetic phase exists in the magnetic powder, the crystallites are coarse and unevenly distributed, and the residual magnetization is not improved. , but it has decreased.
  • the alloy ingot is coarsely crushed and placed in a quenching furnace for rapid quenching.
  • the shielding gas is Ar gas
  • the injection pressure is 100 kPa
  • the nozzle diameter is 0.8 mm
  • the water-cooling roller linear velocity is 55 m/s. Flaky alloy powder.
  • the alloy ingot is coarsely crushed and placed in a quenching furnace for rapid quenching.
  • the shielding gas is Ar gas
  • the injection pressure is 80 kPa
  • the nozzle diameter is 0.7 mm
  • the water cooling roller linear velocity is 55 m/s
  • the copper roller diameter is 300mm
  • a flake alloy powder is obtained.
  • the above alloy was treated under Ar gas treatment at 700 ° C for 70 min, and then subjected to nitriding under N 2 atmosphere of 1 atm.
  • the treatment condition was 450 ° C for 6 hours to obtain a nitride magnetic powder.
  • the prepared rare earth permanent magnet powder (the composition of the material is shown in Table 7) was subjected to detection of magnetic properties, grain size, grain distribution, and comparative examples; as shown in Table 8, S represents an example, D Indicates the comparison.
  • the alloy ingot is coarsely crushed and placed in a quenching furnace for rapid quenching.
  • the shielding gas is Ar gas
  • the injection pressure is 80 kPa
  • the nozzle diameter is 0.8 mm
  • the water cooling roller linear velocity is 50 m/s
  • the copper roller diameter is 300mm, after quenching, a flake alloy powder is obtained.
  • Example 31 38 In the present invention, the preparation method of the rare earth permanent magnet powder is mainly used for preparing Sm 8 . 5 Fe bal C 0l 6 Zr 8 N 12. 5 bonded magnetic powder, and the main preparation steps are as follows:
  • heating rate unit is °C / s
  • cooling rate unit is ° C / s
  • fast quenching wheel speed unit is m / s
  • crystallization temperature and nitriding temperature unit C
  • crystallization time unit is minute min
  • nitriding time unit is hour h.
  • the rare earth permanent magnet powder provided by the invention can be formed by a rapid quenching method, and those skilled in the art can reasonably apply the conventional quenching method to adjust the parameters of each step to form the rare earth permanent magnet powder protected by the present application, for example, the above embodiment The method used in S1-S30.
  • a fine structure can be obtained by a quenching treatment step using two-step cooling, and at the same time due to the secondary cooling of the material. After slower cooling and cooling, the stability of the grain size is ensured, so that the grain size of the rare earth alloy powder does not grow unevenly during the heat treatment process.
  • the prepared material has a grain distribution ⁇ 0.5 ⁇ , and good magnetic properties are obtained.
  • the main phase provided by the present invention is a material which is a composite of a TbCu 7 structure and a bcc soft magnetic phase structure, and the magnetic properties of the material are improved by controlling the grain size and distribution.
  • a bonded magnet can be prepared by mixing the above magnetic powder with a binder, and is applied to a motor, an acoustic, a measuring instrument, or the like.

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Abstract

本发明公开了一种稀土永磁粉、包括其的粘结磁体及应用该粘结磁体的器件。该稀土永磁粉包括70~99vol%的硬磁相和1~30vol%的软磁相，硬磁相具有TbCu7结构，且晶粒粒度为5~100nm；软磁相为具有bcc结构的Fe相，软磁相的晶粒平均粒度为1~30nm，且粒度的标准偏差低于0.5σ。这种稀土永磁粉主要由具有TbCu7结构的硬磁相和具有α-Fe结构的软磁相结合组成的双相磁粉，该双相磁粉具有均匀的微观组织，能够保证软硬磁相均匀耦合，进而提高磁性能。

Description

稀土永磁粉、 包括其的粘结磁体及应用该粘结磁体的器件 技术领域 本发明涉及稀土磁性材料， 具体而言， 涉及一种稀土永磁粉、 包括其的粘结磁体 及应用该粘结磁体的器件。 背景技术 粘结稀土永磁体是由稀土永磁粉末和粘结材料相结合而成， 按用户要求直接注射 或模压成型各种永磁器件。 该类磁体具有尺寸精度高、 磁均匀性好、 耐蚀性好、 成品 率高、 易加工成形状复杂的器件等优点， 广泛应用于家电、 微电机、 自动化办公设备、 仪器仪表、 医疗器件、 汽车、 磁力机械等装置和设备中。 目前， 粘结稀土永磁粉主要包括钕铁硼磁粉以及氮化物稀土磁粉等。 近年来， 随 着电动车、 风力发电、 磁悬浮列车的发展， 对高性能高稳定性的稀土永磁体提出了更 高的要求.氮化物稀土磁粉由于磁性能高、 耐腐性好等优点应用逐渐广泛， 而如何提高 氮化物稀土磁粉的性能从而满足应用的需求成为研究的重点。 氮化物稀土磁粉主要通过将稀土合金粉末经过一定温度和时间的氮化处理而得 到， 稀土合金粉的制备方法包括多种， 可通过机械合金化方法， 或者通过快淬方法， 比如 CN1196144C 和 JP2002057017 均公开了一种生产树脂粘结磁体的各向同性 SmFeN粉末磁体材料， 晶体结构是 TbCu7型， 该粉末通过将熔融合金快淬并且将所得 的合金粉在含氮气体中直接渗氮来制备的。
US5750044公开了一种氮化物稀土粉， 该磁粉也是通过快淬然后氮化处理获得， 该磁粉具有 TbCu7或者 Th2Zn17或者 Th2Ni17以及软磁相结构，软磁相比例为 10~60%。 这种氮化物稀土粉在一定程度上提高了氮化物稀土磁粉的磁性能， 但为了满足客户对 高品质产品的要求， 仍需进一步研究， 以更好地提高稀土永磁粉的磁性能。 发明内容 本发明旨在提供一种稀土永磁粉、 粘结磁体及应用该粘结磁体的器件， 以提高稀 土永磁粉的磁性能。 为了实现上述目的， 根据本发明的一个方面， 提供了一种稀土永磁粉， 该稀土永 磁粉包括 70~99vol%的硬磁相和 l~30vol%的软磁相， 硬磁相具有 TbCu7结构， 且晶粒 粒度为 5~100nm; 软磁相为具有 bcc结构的 Fe相，软磁相的晶粒平均粒度为 l~30nm， 且粒度的标准偏差低于 0.5σ。 进一步地， 上述稀土永磁粉中硬磁相的晶粒粒度分布在 5~80nm范围内， 优选地， 硬磁相的晶粒粒度分布在 5~50nm范围内。 进一步地， 上述稀土永磁粉中软磁相占稀土永磁粉总体积的 3~30vol%， 优选地， 软磁相占稀土永磁粉总体积的 5~15vol%。 进一步地， 上述稀土永磁粉中软磁相的平均晶粒粒度为 l~20nm。 进一步地， 上述稀土永磁粉中软磁相的晶粒粒度标准偏差在 0.3σ以下。 进一步地， 上述稀土永磁粉由 R-T-M-A组成， 其中 R为 Sm或 Sm与其他稀土元 素的组合， T为 Fe或者 Fe禾 P Co的组合， M为 Ti、 V、 Cr、 Zr、 Nb、 Mo、 Ta、 W、 Si或 Hf中至少一种， A为 N和 /或 C， 优选地， 稀土永磁粉中 R含量为 5~12at.%， A 为 10~20at.%， M为 0~10at.%， 余量为 T。 进一步地， 上述稀土永磁粉中 R含量为 5~10at.%。 进一步地， 上述稀土永磁粉中 R中 Sm的原子数含量为 80~100at.% 进一步地， 上述稀土永磁粉中 T为 Fe和 Co的组合， 且 T中 Co的原子数含量为
0~30at.%。 进一步地， 上述稀土永磁粉中永磁粉厚度为 5~50μιη。 根据本发明的第二个方面， 提供了一种粘结磁体， 该粘结磁体为上述的稀土永磁 粉与粘结剂粘结而成。 根据本发明的第三个方面， 提供了一种器件， 该器件应用了上述的粘结磁体。 根据本发明的第四个方面， 提供了一种上述稀土永磁粉的制备方法， 包括将熔融 原料供应到旋转的辊轮上进行快淬处理生成片状合金粉的步骤， 将片状合金粉热处理 后进行氮化或碳化处理得到稀土永磁粉的步骤， 其中， 快淬处理生成片状合金粉的步 骤包括:将熔融原料喷到旋转辊轮上，以 l x l05°C/s~80x l05°C/s的冷却速度冷却至 850°C -950 °C , 进行一次冷却； 再以 0.5°C/s~5°C/s的冷却速度冷却至 250°C~350°C， 进行第 二次冷却以获得片状合金粉。 进一步地， 上述制备方法在热处理过程中， 片状合金粉以 10°C/S~30°C/s的速度进 行升温， 升温至 600~900°C后热处理 10~150min， 优选地， 片状合金粉以 10°C/s~20°C /s的速度进行升温。 本发明所提供的这种稀土永磁粉主要由具有 TbCu7结构的硬磁相和具有 α-Fe结构 的软磁相结合组成的双相磁粉， 该双相磁粉均有均匀的微观组织， 能够保证软硬磁相 均匀耦合， 提高稀土永磁粉的磁性能。 具体实施方式 需要说明的是， 在不冲突的情况下， 本申请中的实施例及实施例中的特征可以相 互组合。 下面将结合实施例来详细说明本发明。 在稀土永磁粉的微观组织对材料的性能起着十分重要的作用， 一定的微观组织决 定着磁性材料晶粒之间的耦合作用， 磁畴的形成， 结构的稳定性等多个方面， 并最终 影响到材料的磁性能。 本发明发明人为了改善稀土永磁粉的磁性能， 对其微观结构进 行了大量研究， 并提出了以下技术方案。 本发明提供的稀土永磁粉由 70~99vol%的硬磁相和 l~30vol%的软磁相组成，其中， 硬磁相具有 TbCu7结构， 且晶粒粒度为 5~100nm; 软磁相为具有 bcc结构的 Fe相， 该 软磁相的晶粒平均粒度为 l~30nm， 且粒度的标准偏差在 0.5σ以下。 本发明所提供的这种稀土永磁粉主要由具有 TbCu7结构的硬磁相和具有 α-Fe结构 的软磁相结合组成的双相磁粉。 这种稀土永磁粉中具有 TbCu7结构的硬磁相相对于已 经广泛使用的 Th2Zn17结构与 ThMn12结构的氮化物磁粉而言，具有更加优异的磁性能， 有利于进而提高所制备的稀土永磁粉的磁性能； 同时， 具有 bcc结构的 Fe相的软磁相 与具有 TbCu7结构的硬磁相之间能够产生耦合作用， 进而抑制 TbCu7结构向 Th2Zn17 等结构转化的性能， 避免该稀土永磁粉在晶化及氮化等阶段转化形成 Th2Zn17与 1 ^1 12等相而恶化其磁性能。 另外， 具有 bcc结构的 Fe相作为软磁相还具有一定的 剩磁增强效应， 钝化了磁粉对温度的敏感性， 使之制备工艺区间更宽。 为了充分实现以上软硬磁相耦合的效果， 在本发明稀土永磁粉中硬磁相晶粒的粒 度优选为 5~100nm。这是因为，在稀土永磁粉中硬磁相的平均晶粒粒度如果小于 5nm， 一来不利于得到 5kOe 以上的矫顽力， 二来也为制备造成了很大的难度， 导致成品率 低下。 如果硬磁相的平均晶粒粒度大于 lOOnm, 不但会降低硬磁相的剩磁， 而且， 此 时该具有 TbCu7结构的硬磁相无法与 α-Fe相发生耦合作用此时， α-Fe不但起不到抑制 TbCu7结构向 Th2Zn17等结构转化的效果， 而且还会成为劣化其性能的相。为了更好地 提高本发明稀土永磁粉的磁性能， 硬磁相晶粒粒度分布在 5~80nm范围内， 更加优选 分布在 5~50nm范围内。 在本发明稀土永磁粉中软磁相的体积含量优选为 l~30vol%。将软磁相的体积控制 在该范围内， 有利于抑制 TbCu7结构向 Th2Zn17等结构转化， 提高所制备稀土永磁粉 的磁性能。 如果软磁相的含量小于 lvol%， 会导致对其他杂相出现的抑制效果变差， 如果软磁相的含量大于 30vol%， 虽然能够抑制 Th2Zn17等其他杂相的生成， 但是过多 的软磁相存在大幅降低材料的矫顽力的问题， 这不利于总体性能的提高。 为了更好地 提高本发明稀土永磁粉的磁性能，软磁相比例优选为 3~30vol%，更加优选为 5~15vol%。 在本发明稀土永磁粉中软磁相的平均晶粒粒度 σ优选为 l~30nm， 将软磁相的平 均晶粒粒度 σ控制在该范围内， 具有剩磁增强的效果， 提高所制备稀土永磁粉的磁性 能。 如果软磁相的平均晶粒粒度 σ过大则不能起到剩磁增强的作用， 不但如此， 而且 还可能会降低磁粉的矫顽力。 如果软磁相的平均晶粒粒度 σ过小则制备困难。 更为优 选地， 该稀土永磁粉中软磁相的平均晶粒粒度为 l~20nm。 在本发明稀土永磁粉中软磁相的晶粒粒度标准偏差低于 0.5σ。 磁粉中软磁相分布 情况也是影响磁粉磁性的一个关键因素， 均匀的组织能让软硬磁相均匀配合， 耦合得 更好， 有利于磁性能的提高。 在本发明稀土永磁粉中通过将软磁相的平均晶粒粒度标 准偏差控制在 0.5σ以下， 能够使得软硬磁相均匀配合， 进而进行良好的耦合， 得到均 匀精细的组织。 如果软磁相的晶粒粒度标准偏差高于 0.5σ， 由于晶粒分布过宽， 进而 无法得到均匀精细的组织， 这就容易造成磁粉中各颗粒之间起作用的交换相互作用降 低， 导致剩磁 （Br) 的降低， 进而起不到与硬磁相之间耦合与剩磁增强的效果， 最终 无法得到良好的磁性能。在本发明稀土永磁粉中软磁相的晶粒粒度标准偏差优选 0.3σ。 在本发明的一种优选的实施方式中， 一种稀土永磁粉由 R-T-M-A组成， 其中 R为 γ或 γ与其他稀土元素的组合， Τ为 Fe或者 Fe和 Co的组合， M为 Ti、 V、 Cr、 Mn、 Ni、 Cu、 Zr、 Nb、 Mo、 Ta、 W、 Al、 Ga、 Si或 Hf中至少一种， A为 N和 /或。。 优 选地， 该稀土永磁粉中 R含量为 5~12at.%， A为 10~20at.%， M含量为 0~10at.%， 余 量为 T。 在本发明由 R-T-M-A组成的稀土永磁粉中 R元素为 Sm或 Sm与其他稀土元素的 组合， R为 Sm或者 Sm与其他稀土元素的组合，其中 R必须含有 Sm，这是形成 TbCu7 结构硬磁相并保证磁性能的必要条件。 R元素的含量优选在 5~12&1.%范围内， 更为优选在 5~10&1.%范围内。 在该稀土永 磁粉中如果 R的原子含量低于 5at.%， 相对的 α-Fe软磁相相的形成会相对较多， 进而 会降低所制备的磁粉的矫顽力； 如果当 R含量高于 12at%， 相对的会形成较多的类似 于富钐相的结构， 这两种情况都不利于磁性能的提高。 优选地， 在本发明稀土永磁粉 中 Sm的原子数含量为 80~100at.%， 部分 Sm可以被 Ce、 Y等稀土元素替代， 替代比 例不能超过 20%， 一定量的其他稀土元素加入可以改善材料成型性能， 如 Ce、 La的 加入降低材料熔点， 此时 Ce、 La的含量需小于 5at.%， Nd、 Y的加入改善矫顽力等。 在本发明由 R-T-M-A组成的稀土永磁粉中 Τ元素为 Fe或者 Fe和 Co的组合， 优 选 T为 Fe和 Co的组合。一定量的 Co加入有利于含氮磁粉剩磁和温度稳定性的提高， 同时可以稳定亚稳的 TbCu7相结构， 改善制备过程中的润湿性等效果。 考虑到成本等 原因， T中 Co的原子数含量为 0~30at.%， 其中当 Co含量为 0&1%时， 表示成分中不 含 Co。 在本发明由 R-T-M-A组成的稀土永磁粉中可以加入 M元素， 本发明中 M均为熔 点高于稀土 Sm的元素， 这些高熔点元素的加入有利于细化晶粒， 关键是形成均匀微 观组织的稀土永磁粉， 更重要的是在晶化氮化过程中抑制晶粒的不均匀长大， 从而使 本发明中的磁粉晶粒尺寸的标准偏差在一定范围内。这些 M主要包括但不限于 Ti、 V、 Cr、 Mn、 Zr、 Nb、 Mo、 Ta、 W、 Si、 Hf中一种或多种， 该 M元素的加入可以细化晶 粒， 提高矫顽力、 剩磁等磁性能。 同时， 该稀土永磁粉中 M元素的原子含量优选选取 0~10at%内， 如果 M元素的原子含量大于 10at.%， 可能会降低剩磁等磁性能。 在本发明由 R-T-M-A组成的稀土永磁粉中可以加入 A元素， A为 N和 /或 C， A 元素加入稀土铁化合物中会对其性能产生较大的影响， 称为间隙原子效应。 间隙原子 效应能提高化合物的居里温度、 饱和磁化强度及各向异性场， 在本发明由 R-T-M-A组 成的稀土永磁粉中优选含有原子数 10~20 ％的 A， A在该范围之内可以得到优异磁性 能的磁粉， 含量低于 10 ％表明氮化 /碳化不充分， 成分不均匀， 磁性能下降； 过高易 造成硬磁相的分解， 同样不利于磁性能的提高。 在本发明的一种优选的实施方式中， 一种稀土永磁粉由具有 TbCu7结构的硬磁相 与具有 bcc结构的 Fe相组成， 其中 bcc结构的软磁相主要为 α-Fe相， 该磁粉采用 Cu 靶进行 X射线衍射图谱中 2Θ角在 65°~75°之间的峰强度与最强峰强度之比大于 10% 的衍射峰的数量低于 1个。 将符合这种条件的衍射峰个数在为 1个或 0个时， 所制备 的粘结磁粉中晶粒尺寸及分布在本发明限定的范围之内， 并具有最优的匹配性能。 在本发明的一种优选的实施方式中，一种稀土永磁粉的厚度低于 50μιη。控制磁粉 的厚度有利于使得磁粉中各相的均匀分布， 进而优化磁粉的磁粉方形度等性能。 如果 厚度超过 50μιη， 显示材料中各相结晶不易均匀分布， 会最终恶化磁粉方形度等性能， 同时也不利于氮化过程中氮或者碳向材料晶体中渗透。 优选地， 稀土永磁粉的厚度为 5~50μιη, 太低的厚度给制备造成很大的难度， 同时非晶较多， 不利于后续晶化氮化工 艺的一致性。 本发明中上述稀土永磁粉是通过快淬的方法制备而成， 本领域技术人员在本申请 所给出的教导下， 有能力制备出符合上述要求的稀土永磁粉。 目前， 一种常见的制备 方法， 包括如下步骤： （1 )将各原料成分， 例如 R、 Τ、 Μ、 Α等经过融化后， 通过喷 嘴喷到旋转的辊轮上， 对由辊轮， 得到片状合金粉； （2) 将片状合金粉在 600~900°C 热处理 10~150min; ( 3 ) 热处理后的合金粉在 350~550°C左右渗氮或者渗碳处理， 得 到稀土永磁粉。 本领域技术人员有能力根据上述制备方法制备出本发明所保护的稀土永磁粉， 但 为了简化工艺操作难度， 以及提高所制备的稀土永磁粉的性能， 在本申请的一种优选 实施方式中， 还提供了一种上述稀土永磁粉的制备方法， 其主要制备步骤包括将熔融 原料快淬处理生成片状合金粉， 将片状合金粉热处理后进行氮化或碳化处理得到稀土 永磁粉的步骤。 其中， 快淬处理生成片状合金粉的步骤包括： 将熔融原料喷到旋转辊 轮上， 以 l x l 05°C/s~80x l 05°C/s的冷却速度冷却至 850°C~950°C， 进行一次冷却； 然后 以 0.5 °C/s~5 °C/s的冷却速度冷却至 250°C~350°C， 进行第二次冷却以获得所述片状合 金粉。 作为本发明的优选， 快淬处理生成片状合金粉的步骤包括： 将熔融原料喷到辊轮 在熔点到 900°C范围内以 5 x l 05°C/s~80x l 05°C/s的冷却速度冷却至 880°C~920°C， 进行 一次冷却；； 然后以 0.5 °C/s~3 °C/s的冷却速度冷却至 280°C~320°C， 进行第二次冷却， 进行二次冷却以获得所述片状合金粉。 本发明中， 熔融钢液经过旋转的辊轮处理后飞出， 迅速冷却到 850~950°C， 在这 个过程中， 迅速冷却的速率在 l x l 05°C/s~80x l 05°C/s， 通过该冷却速率， 使平衡相来不 及形成， 晶粒尺寸来不及长大。 钢液经过处理后飞出， 经过二次冷却， 为了达到 0.5 °C /s~5 °C/s 的冷却速度， 作为本发明的一个优选， 在片状粉末飞出方向增加引导挡板， 通过控制引导挡板与片状粉末飞出起点之间的间距， 引导挡板的温度等来调节片状粉 末的冷却速度。 本发明所提供的这种稀土永磁粉的制备方法通过采用两步冷却的快淬处理步骤， 可以获得精细的组织， 同时由于材料二次冷却过程中经过较慢的冷速冷却， 从而保证 了晶粒尺寸的稳定性， 使稀土合金粉的晶粒尺寸在热处理过程中不至于过度不均匀长 大， 保证了最终稀土永磁粉的磁性能。 在本发明的一种优选的实施方式中， 上述稀土永磁粉的制备方法中热处理过程， 片状合金粉以 10°C/s~30°C/s的速度进行升温， 升温至 600~900°C， 优选为 600~850°C， 然后热处理 10~150min， 优选地， 片状合金粉以 10°C/s~20°C/s的速度进行升温。 以一 定的速度升温有利于保持整个加热区间的稳定性， 从而使粉末均匀长大， 速率过低， 粉末在加热阶段时间过长， 不利于控制热处理过程； 速率过高， 粉末加热不均匀。 本 发明优选热处理温度在 600~900°C， 过高则晶粒过度长大， 过低则不能起到热处理的 效果。 在本发明上述所提供的稀土永磁粉材料中， 辊轮材质优选包括但不限于 Cu， Mo, Cu合金； 氮化或碳化的步骤中， 渗氮或者渗碳过程的时间优选为 3~30h; 氮源优选为 工业纯氮， 氢气和氨气的混合气等。 在本发明的一种优选实施方式中， 上述稀土永磁粉可以通过与粘结剂粘结制备形 成粘结磁体。 这种粘结磁体可以通过将本发明所述稀土永磁粉 （主相为 TbCu7结构的 钐铁氮粉末） 与树脂进行混合， 并通过模压， 注射， 压延或挤出等方法制备而成。 所 制备的粘结磁体可以为块状， 环状等其他形式。 在本发明的一种优选实施方式中， 上述粘结磁体可以应用到相应器件的制备中， 通过该方法可以制备出高性能的钐铁氮磁粉以及磁体， 有利于器件的进一步小型化， 该系列磁粉高的耐温性耐蚀性有利于器件在特殊环境下的使用， 稀土钐的应用也有利 于稀土资源的平衡运用。 以下将以实施具体实施例的方式， 说明本发明稀土永磁粉的成分、 晶粒大小、 晶 粒分布、 磁粉性能、 磁体性能等， 进而说明本发明的有益效果。
( 1 ) 稀土永磁粉成分 稀土合金磁粉成分为熔炼的钐铁系列合金粉经过渗氮而成， 成分为渗氮后磁粉的 成分， 成分用原子百分比表示。
(2) 晶粒粒度 σ 平均晶粒粒度表示方法： 采用电子显微镜拍摄材料的微观组织照片， 从照片中观 测硬磁相 TbCu7结构晶粒， 以及软磁相 α-Fe相晶粒， 具体方法是统计 n个同种类型晶 粒的总横截面积 S， 然后将横截面积 S等效成一个圆的面积， 求出圆的直径即为平均 晶粒粒度 σ， 单位为 nm， 计算公式如下： σ = 2 ― s
V m
(3 ) 晶粒分布 晶粒分布采用标准偏差表示， 相应计算公式如下:
Figure imgf000009_0001
其中 t为标准偏差， ^为第 i个晶粒大小。 在本发明中， 为了考虑统计的准确性以及测试情况， 选取 n不小于 5(L
(4) 磁粉性能 磁粉性能通过振动样品磁强计 （ VSM检测） t 其中 Br为剩磁， 单位为 kGs;
Hcj为内禀矫顽力， 单位为 kOe; (BH)m为磁能积， 单位为 MGOe。
( 5 ) 相比例卩％ 相比例通过对磁性材料金相照片进行面积分析得到， 测得横断面面积比， 可以得 到体积比。
(6) XRD峰 所得到的合金粉通过 XRD测量， 采用 Cu靶为靶材， 考察获得磁粉的相结构。 在如下实施例 1-38中所制备的稀土永磁粉通过如下 XRD峰检测， 衍射图谱中 2Θ 角在 65°~75°之间的峰强度与最强峰强度之比大于 10%的衍射峰的数量均为 1个或 0
(7) 厚度 λ 厚度采用螺旋测微器测量， 厚度单位为 μι^ 实施例 1~8 (M为 1~2个元素） 制备方法：
( 1 ) 按比例将表 1各实施例列出的金属混合后放入感应熔炼炉中， 在 Ar气保护 下进行熔炼得到合金铸锭；
(2) 将合金铸锭粗破碎后放入快淬炉中进行快淬， 保护气体为 Ar气， 喷射压力 为 80kPa， 喷嘴直径为 0.8mm， 水冷辊线速度为 55m/s， 快淬后得到片状合金粉。
(3 )将上述合金粉在 Ar气保护下于 750°C处理 55min后进入 1个大气压的 N2气 下进行氮化， 处理条件为 460°C， 7小时， 得到氮化物磁粉。 检测： 将所制备得到的稀土永磁粉 （材料的成分如表 1所示） 进行磁性能、 晶粒 大小、 晶粒分布、 相比例的检测； 检测如表 2所示， S表示实施例， D表示对比例。 表 1 材料成分
Figure imgf000010_0001
表 2 材料组织及性能
硬磁相 软磁相 磁粉性能
样 λ(μ
P o(nm P% P% o(nm t Br(kG Hcj(kO (BH)m(MG ΒΠ m)
) ) s) e) Oe)
SI 20 47 83 14 17 6.5 9.5 8.1 17.2
S2 15 8 89 8 8 1.3 9.6 8.9 18.6
S3 11 30 82 15 11 3.6 9.3 8.6 17.2
S4 19 45 85 13 1 0.9 9.1 8.4 17.7
S5 17 24 85 14 15 5.6 9.3 8.3 17.3 S6 15 25 87 11 9 2.6 9.6 8.2 18.7
S7 18 41 93 5 8 1.1 9.7 8.1 18.8
S8 19 33 89 10 9 3.8 9.3 8.3 17.5
S9 20 57 82 16 13 4.1 9.2 8.0 17.1
S10 22 71 80 18 15 4.9 9.1 7.9 17.0
Dl 21 65 85 14 32 11 7.3 3.5 14.2
D2 20 68 83 16 13 10 7.1 4.5 13.5
D3 61 103 86 9 23 12 6.8 5.2 13.2 从以上实施例可以看出， 当磁粉的晶粒粒度及分布在本发明要求保护的范围之内 时， 可以获得较高的磁性能， 其中主要体现在矫顽力与磁能积上。 与 D1和 D2对比可 以看出， 当晶粒粒度及分布偏离保护范围时， 即使 α-Fe软磁相存在于磁粉中， 但由于 晶粒粗大， 分布不均， 剩磁不但没有提高， 反而有所降低， 且矫顽力也会出现大幅度 的降低。 其中 D1软磁相的晶粒大于 30nm， D2的 ί≥0.5σ， 磁性能均大幅降低。 同时 从实施例中可以看出， 软磁相的晶粒标准偏差分布 ί≤0.5σ时性能较高， 当 ί≤0.3σ性能 最高。 同时， 由本申请实施例与 D3 的对比可以看出， 当硬磁相晶粒过大， 相应磁性 也会大幅降低， 本实施例中硬磁相晶粒均在 5~50nm范围内， 具有较高的磁性能。 其 中，硬磁相的晶粒粒度分布在 5~80nm范围内，尤其优选硬磁相晶粒粒度分布在 5~50nm 范围内磁性能较好。 实施例 9~13 (M为多个元素混合） 制备方法：
( 1 ) 按比例将表 3各实施例列出的金属混合后放入感应熔炼炉中， 在 Ar气保护 下进行熔炼得到合金铸锭； (2) 将合金铸锭粗破碎后放入快淬炉中进行快淬， 保护气体为 Ar气， 喷射压力 为 80kPa， 喷嘴直径为 0.8， 水冷辊线速度为 55m/s， 快淬后得到片状合金粉。
( 3 )将上述合金在 Ar气保护下于 750°C处理 55min后进入 1个大气压的 N2气下 进行氮化， 处理条件为 460°C， 7小时， 得到氮化物磁粉。 检测： 将所制备得到的稀土永磁粉 （材料的成分如表 3所示） 进行磁性能、 晶粒 大小、 晶粒分布、 相比例的检测； 检测如表 4所示， S表示实施例， D表示对比例。 表 3 材料成分
成分 （bal表示剩余部分）
S9 Sm8.5FebaiCo4.2Zr2.4Gai.iCri.5Ni3.5 S10 Sm9.3FebaiCo8.iHfo.5Mn0.8Nio.5Ni2.5
Sl l Sm5.oFebaiCoi5.7 r3.iWo.7Alo.2Nio.6
S12 Sm6.2FebalCOll.9Hf4.3CU3.5V2.2Nl2.3
S13 Sm7.3FebaiCo2i.o ri.3Tao.2Sio.2Ni2.5
D4 Sm6.2FebalCOll.9Hfo.5Cul.5Vo.2Nl2.3
D5 Sm7.3FebaiCo2i.o ri.3Tao.2Sio.2Ni2.5 表 4 材料组织及性能
Figure imgf000012_0001
从以上实施例及对比例可以看出， 总体上采用多个 M添加相对于 1~2个 M元素 添加内禀磁性能相对稍低， 主要是因为过渡族元素的饱和磁矩比 Fe和 Co低， 更多的 元素加入会损失其饱和磁矩， 从而稍微降低了部分磁性能。 同样的，当晶粒粒度及分布偏离保护范围时，矫顽力出现大幅度的降低，虽然 a-Fe 软磁相的存在与磁粉中， 但由于晶粒粗大， 分布不均， 剩磁没有提高， 反而有所降低。 且由表 4中数据可以看出， 软磁相的晶粒标准偏差分布 ί≤0.5σ时性能较高， 当 ί≤0.3σ 性能最高。 实施例 14~16(SmFeN型永磁粉） 制备方法：
( 1 ) 将表 5各实施例中 SmFe合金按照一定比例混合后放入感应熔炼炉中， 在 Ar气保护下进行熔炼得到合金铸锭；
(2) 将合金铸锭粗破碎后放入快淬炉中进行快淬， 保护气体为 Ar气， 喷射压力 为 100kPa， 喷嘴直径为 0.8mm， 水冷辊线速度为 55m/s， 快淬后得到片状合金粉。
( 3 )将上述合金在 Ar气保护下于 730°C处理 60min后进入 1个大气压的 N2气下 进行氮化， 处理条件为 440°C， 8小时， 得到氮化物磁粉。 检测： 将所制备得到的稀土永磁粉 （材料的成分如表 5所示） 进行磁性能、 晶粒 大小、 晶粒分布、 相比例的检测； 检测如表 6所示， S表示实施例， D表示对比例。 表 5 材料成分
Figure imgf000013_0001
表 6 材料组织及性能
Figure imgf000013_0002
从表 6中数据可以看出， 所制备的磁粉在不添加 Co与过渡族金属 M的情况下， 软磁相晶粒稍高，磁性能比添加的也稍低，但是仍然满足晶粒分布1≤0.5。时性能较高， 当1≤0.30性能最高。 实施例 17~21 ( SmRFeCoMN型磁粉） 制备方法： ( 1 )将表 7中各实施例中相关稀土及过渡族金属按照一定比例混合后放入感应熔 炼炉中， 在 Ar气保护下进行熔炼得到合金铸锭；
(2) 将合金铸锭粗破碎后放入快淬炉中进行快淬， 保护气体为 Ar气， 喷射压力 为 80kPa， 喷嘴直径为 0.7mm， 水冷辊线速度为 55m/s， 铜辊直径为 300mm， 快淬后 得到片状合金粉。 ( 3 )将上述合金在 Ar气保护下于 700°C处理 70min后进入 1个大气压的 N2气下 进行氮化， 处理条件为 450°C， 6小时， 得到氮化物磁粉。 检测： 将所制备得到的稀土永磁粉 （材料的成分如表 7所示） 进行磁性能、 晶粒 大小、 晶粒分布、 相比例的检测； 检测如表 8所示， S表示实施例， D表示对比例。 表 7材料成分
Figure imgf000014_0001
表 8 材料组织及性能
Figure imgf000014_0002
从表 8中数据可以看出， 所制备的磁粉添加稀土元素 R会使剩磁产生一定程度的 降低， 但各方面性能仍然满足晶粒分布 ί≤0.5σ时性能较高， 当 ί≤0.3σ ( S18和 S20) 性能最高。 从 S19可以看出， 由于稀土含量高， 相应的剩磁和磁能积下降较多， 但是 矫顽力稍高。 实施例 22 30 (含碳永磁粉） 制备方法
( 1 ) 按比例将高纯度金属混合后放入感应熔炼炉中， 在 Ar气保护下进行熔炼得 到合金铸锭；
(2) 将合金铸锭粗破碎后放入快淬炉中进行快淬， 保护气体为 Ar气， 喷射压力 为 80kPa， 喷嘴直径为 0.8mm， 水冷辊线速度为 50m/s， 铜辊直径为 300mm， 快淬后 得到片状合金粉。
( 3 )将上述合金在 Ar气保护下于 710°C处理 70min后，磁粉经过粗破碎至 ΙΟΟμιη 以下， 破碎后的粉与碳粉混合经过 480°C7小时处理得到碳化物磁粉。 检测： 将所制备得到的稀土永磁粉 （材料的成分如表 9所示） 进行磁性能、 晶粒 大小、 晶粒分布、 相比例的检测； 检测如表 10所示， S表示实施例， D表示对比例。 表 9 材料成分
Figure imgf000015_0001
表 10材料组织及性能
Figure imgf000015_0002
由如上表 10中数据可知， 当所制备的稀土永磁粉中添加 C元素， 其仍然具有较 高的磁性能，磁能积在 15MGOe以上，同时满足晶粒分布 ί≤0.5σ时性能较高，当 ί≤0.3σ 性能最高。 实施例 31 38 在本发明中稀土永磁粉的制备方法主要用于制备 Sm8.5FebalC0l 6Zr 8N12.5粘结磁 粉， 其主要制备步骤如下：
( 1 ) 按表 11 中各实施例的比例将高纯度金属混合后放入感应熔炼炉中， 在 Ar 气保护下进行熔炼得到合金铸锭； (2) 将合金铸锭粗破碎后放入快淬炉中进行快淬， 保护气体为 Ar气， 控制喷嘴 喷射压力为 80kPa， 喷嘴直径为 0.8mm， 喷到旋转的辊轮上一次冷却， 进一步通过设 置挡板经二次冷却后得到片状合金粉； （辊轮的材质、轮速、一次冷却的温度和二次冷 却温度如表 11所示。）
(3 ) 将上述合金在 Ar气保护下将片状合金粉升温， 升温后， 持温进行热处理; (升温速度、升温后温度，热处理时间如表 11所示）；磁粉经过粗破碎至 ΙΟΟμιη以下， 破碎后的粉在 Ν2气氛中处理得到碳氮化合物磁粉（氮化温度、氮化时间如表 11所示）。 检测： 将所制备得到的稀土永磁粉（材料的成分如表 11所示）进行磁性能、 晶粒 大小、 晶粒分布、 相比例的检测； 检测如表 10所示， S表示实施例， D表示对比例。 工艺中所涉及到的检测数据的单位： 升温速率单位为 °C/s; 冷却速率单位为 °C/s; 快淬轮速单位为 m/s; 晶化温度和氮 化温度单位为。 C ; 晶化时间单位为分钟 min; 氮化时间单位为小时 h。
11.该磁粉的具体制备以及最终磁粉的磁性能
Figure imgf000016_0001
5x l05°C/s~
S37 0.5-5 °C/s Mo 55 20 730-780 50 420 24 8x l06°C/s
l x l05°C/s~
S38 0.5-5 °C/s Mo 55 30 850-900 10 350 30 5x l05°C/s
5x l06°C/s~
Dl l 0.2-0.5 °C/s Mo 65 15 700-750 60 440 18 l x l07°C/s
l x l05°C/s~
D12 0.2-0.5 °C/s BeCu 53 9 590-630 180 440 18 5x l05°C/s 表 12材料组织及性能
Figure imgf000017_0001
本发明所提供的稀土永磁粉采用快淬方法制备即可形成， 本领域技术人员可以合 理地运用常规快淬方法， 调节其各步骤参数以形成本申请所保护的稀土永磁粉， 例如 如上实施例 S1-S30中所采用的方法。 在本发明中优选采用两步冷却的快淬处理步骤， 由上述表 11-12中数据可知， 通过采用两步冷却的快淬处理步骤， 可以获得精细的组 织， 同时由于材料二次冷却过程中经过较慢的冷速冷却， 从而保证了晶粒尺寸的稳定 性， 使稀土合金粉的晶粒尺寸在热处理过程中不至于过渡不均匀长大， 从以上工艺中 可以看出， 结合二次冷却， 结合后续的热处理和氮化工艺， 使制备的材料晶粒分布 ΐ≤0.5σ, 获得了较好的磁性能。 由上述内容可知， 本发明所提供的主相为 TbCu7结构与 bcc软磁相结构复合的材 料， 通过控制晶粒大小及分布， 改善了材料的磁性能。 此外， 根据本发明， 可用以上 的磁粉与粘结剂混合进行粘结制备粘结磁体， 在马达、 音响、 测量仪器等场合得到应 用。 以上所述仅为本发明的优选实施例而已， 并不用于限制本发明， 对于本领域的技 术人员来说， 本发明可以有各种更改和变化。 凡在本发明的精神和原则之内， 所作的 任何修改、 等同替换、 改进等， 均应包含在本发明的保护范围之内。

Claims

权 利 要 求 书 一种稀土永磁粉， 其特征在于， 所述稀土永磁粉包括 70~99vol%的硬磁相和 l~30vol%的软磁相， 所述硬磁相具有 TbCu7结构， 且晶粒粒度为 5~100nm; 所 述软磁相为具有 bcc结构的 Fe相， 所述软磁相的晶粒平均粒度为 l~30nm， 且 粒度的标准偏差低于 0.5σ。 根据权利要求 1所述的稀土永磁粉， 其特征在于， 所述硬磁相的晶粒粒度分布 在 5~80nm范围内， 优选地， 所述硬磁相的晶粒粒度分布在 5~50nm范围内。 根据权利要求 1或 2所述的稀土永磁粉， 其特征在于， 所述软磁相占所述稀土 永磁粉总体积的 3~30vol%， 优选地， 所述软磁相占所述稀土永磁粉总体积的 5~15vol% o 根据权利要求 1至 3中任一项所述的稀土永磁粉， 其特征在于， 所述软磁相的 平均晶粒粒度为 l~20nm。 根据权利要求 1至 4中任一项所述的稀土永磁粉， 其特征在于， 所述软磁相的 晶粒粒度标准偏差在 0.3σ以下。 根据权利要求 1至 5中任一项所述的稀土永磁粉， 其特征在于， 所述稀土永磁 粉由 R-T-M-A组成，其中 R为 Sm或 Sm与其他稀土元素的组合， T为 Fe或者 Fe禾 P Co的组合， M为 Ti、 V、 Cr、 Zr、 b、 Mo、 Ta、 W、 Si或 Hf中至少一 种， A为 N和 /或 C， 优选地， 所述稀土永磁粉中 R含量为 5~12at.%， A为 10~20at.%, M含量为 0~10at.%， 余量为 T。 根据权利要求 6所述的稀土永磁粉， 其特征在于， 所述稀土永磁粉中 R含量为 5~10at.%。 根据权利要求 7所述的稀土永磁粉， 其特征在于， 所述 R中 Sm的原子数含量 为 80~100at.% 根据权利要求 6所述的稀土永磁粉， 其特征在于， 所述 T为 Fe和 Co的组合， 且所述 T中 Co的原子数含量为 0~30at.%。 根据权利要求 1至 9中任一项所述的稀土永磁粉， 其特征在于， 所述稀土永磁 粉厚度为 5~50μιη。
11. 一种粘结磁体，其特征在于，所述粘结磁体由权利要求 1至 10中任一项所述的 稀土永磁粉与粘结剂粘结而成。
12. 一种器件， 其特征在于， 所述器件应用了权利要求 11所述的粘结磁体。
13. 一种权利要求 1至 10中任一项所述的稀土永磁粉的制备方法，包括将熔融原料 供应到旋转的辊轮上进行快淬处理生成片状合金粉的步骤， 将所述片状合金粉 热处理后进行氮化或碳化处理得到所述稀土永磁粉的步骤， 其特征在于， 所述 快淬处理生成片状合金粉的步骤包括： 将熔融原料喷到旋转辊轮上， 以 l x l05°C/s~80x l05°C/s的冷却速度冷却至 850°C~950°C， 进行一次冷却；
再以 0.5°C/s~5°C/s的冷却速度冷却至 250°C~350°C， 进行第二次冷却以获 得所述片状合金粉。
14. 利要求 13所述的制备方法， 其特征在于， 在所述热处理过程中， 所述片状合金 粉以 10°C/s~30°C/s的速度进行升温， 升温至 600~900°C后热处理 10~150min， 优选地， 所述片状合金粉以 10°C/S~20°C/s的速度进行升温。
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KR20150095714A (ko) 2015-08-21
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