CN111627631A - Preparation method of nano composite permanent magnetic material - Google Patents

Preparation method of nano composite permanent magnetic material Download PDF

Info

Publication number
CN111627631A
CN111627631A CN202010197633.1A CN202010197633A CN111627631A CN 111627631 A CN111627631 A CN 111627631A CN 202010197633 A CN202010197633 A CN 202010197633A CN 111627631 A CN111627631 A CN 111627631A
Authority
CN
China
Prior art keywords
powder
permanent magnetic
magnetic
nano composite
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010197633.1A
Other languages
Chinese (zh)
Other versions
CN111627631B (en
Inventor
王凤青
张健
李艳鹏
张耀
池建义
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Baotou Rare Earth R&d Center Chinese Academy Of Sciences
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Baotou Rare Earth R&d Center Chinese Academy Of Sciences
Ningbo Institute of Material Technology and Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Baotou Rare Earth R&d Center Chinese Academy Of Sciences, Ningbo Institute of Material Technology and Engineering of CAS filed Critical Baotou Rare Earth R&d Center Chinese Academy Of Sciences
Priority to CN202010197633.1A priority Critical patent/CN111627631B/en
Publication of CN111627631A publication Critical patent/CN111627631A/en
Application granted granted Critical
Publication of CN111627631B publication Critical patent/CN111627631B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01F1/0551—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • 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
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
    • 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
    • H01F1/0556—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together pressed
    • 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
    • H01F1/12—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
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15308—Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
    • 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
    • H01F1/12—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
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15316—Amorphous metallic alloys, e.g. glassy metals based on Co
    • 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
    • H01F1/12—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
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15333—Amorphous metallic alloys, e.g. glassy metals containing nanocrystallites, e.g. obtained by annealing
    • 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
    • H01F1/12—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
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15341—Preparation processes therefor
    • 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
    • H01F1/12—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
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15358—Making agglomerates therefrom, e.g. by pressing
    • 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
    • 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
    • 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
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Thermal Sciences (AREA)
  • Hard Magnetic Materials (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention relates to a method for preparing a nano composite permanent magnetic material, which adds R-Cu alloy into a SmCo/Fe (Co) amorphous structure and a crystallized substance, and realizes the improvement of the room-temperature coercive force of the SmCo/Fe (Co) nano composite material through the formation of Sm- (Co, Cu) crystallized phase and the enrichment of Sm and Cu elements among soft and hard magnetic crystal grains; cu enters into hard magnetic crystal lattices to form Sm- (Co, Cu) crystallization phases, so that the high-temperature stability of the coercive force of the SmCo/Fe (Co) composite material is improved, and the crystallization temperature and the preparation temperature of the SmCo/Fe (Co) composite material are reduced to be below 500 ℃ and can be as low as 400-425 ℃. The coercive force at room temperature and the high-temperature stability of the coercive force are improved, so that the preparation method has the preparation advantage of developing a high-magnetic energy product high-temperature-resistant nano composite permanent magnetic material; the preparation temperature is reduced, and the energy-saving preparation advantage of low energy consumption is achieved, so that the invention is very suitable for developing the high-temperature-resistant nano composite permanent magnetic material with high soft magnetism, low rare earth and high magnetic energy product under low energy consumption.

Description

Preparation method of nano composite permanent magnetic material
Technical Field
The invention relates to a preparation method of a nano composite permanent magnetic material, in particular to a preparation method of a SmCo/Fe (Co) nano composite permanent magnetic material with higher coercive force.
Background
Compared with the traditional hard magnetic single-phase permanent magnetic material, the isotropic nanocrystalline composite permanent magnetic material composed of the soft magnetic phase and the hard magnetic phase has the advantages of low rare earth content, short preparation period, high magnetic consistency, near net shaping and the like, and is widely applied to the application fields of various precise motors and micro special motors in information industry, office automation, consumer electronics, household appliances, sensors, automobiles and the like. The most widely used isotropic permanent magnetic material in the market is Nd-Fe-B/Fe type nano material, the magnetic energy product is usually 8-17 MGOe, and the Nd is applied2Fe14Influence of Curie temperature of phase B (T)c310 ℃) below 150 ℃, the magnetism of the permanent magnet is sharply reduced when the temperature is above 200 ℃, and the magnetism basically disappears when the temperature is above 300 ℃, so that the application requirement of the market on the high-temperature resistant permanent magnet above 200 ℃, especially above 300 ℃ is difficult to meet.
As an important isotropic nanocrystalline composite permanent magnet material, a SmCo/Fe (Co) permanent magnet material consisting of a Sm-Co hard magnetic phase and a Fe (Co) soft magnetic phase has higher Curie temperature (T) than the Nd-Fe-B nanocrystalline composite permanent magnet material commonly used in the marketc> 700 ℃) and can be obtained at a lower hard magnetic phase contentThe room temperature magnetic energy product (such as 18-19 MGOe), so the method has wide prospect in the aspects of room temperature and high temperature application.
However, the isotropic SmCo/fe (co) nanocomposite permanent magnet material prepared in the prior art is generally low in room-temperature coercivity and poor in high-temperature stability, and meanwhile, the phenomenon that the coercivity and the magnetic energy product are reduced more seriously due to high-temperature demagnetization when the room-temperature coercivity is lower exists, so that the high-temperature magnetic energy product of the existing isotropic SmCo/fe (co) nanocomposite permanent magnet material at 300 ℃ is far lower than the room-temperature magnetic energy product level thereof, and therefore, the isotropic SmCo/fe (co) nanocomposite permanent magnet material has a great challenge in meeting the use requirements of the market on high-temperature ferromagnetic materials. In addition, the energy consumption and the preparation cost can be greatly reduced by reducing the preparation temperature, and the preparation temperature is influenced by the type and the crystallization temperature of the SmCo/Fe (Co) nano composite material, so that the preparation temperature of the high-performance SmCo/Fe (Co) nano composite material of 18-19 MGOe is usually increased to over 500 ℃ and is difficult to control within 500 ℃, and the energy consumption problem caused by high preparation temperature is very serious.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a preparation method of a nano composite permanent magnetic material, which improves the coercivity at room temperature and the high-temperature stability of the coercivity and reduces the preparation temperature by adding an R-Cu alloy.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for preparing a nano composite permanent magnetic material is characterized by comprising the following steps:
(1) mixing R-Cu alloy powder, hard magnetic raw material powder and soft magnetic raw material powder according to a ratio, and carrying out high-energy ball milling on the obtained mixed material to obtain amorphous matrix mixed powder with non-crystallized hard magnetic grains and nano-scaled soft magnetic grains;
(2) and (2) heating and crystallizing the amorphous matrix mixed powder obtained in the step (1), and converting an amorphous phase in the amorphous matrix mixed powder into a crystallized state to obtain the nano composite permanent magnetic material.
The above-mentioned hard magnetic crystal grain amorphization includes all cases where hard magnetic crystal grains are amorphized and transformed, a part of hard magnetic crystal grains are amorphized and transformed, a trace amount of hard magnetic crystal grains are amorphized and transformed, and a part of hard magnetic crystal grain regions are amorphized and transformed.
In the above scheme, the R-Cu alloy is an alloy of a rare earth element and a Cu element. The Cu element and the rare earth element have the important function of improving the coercive force by magnetic pinning in the NdFeB magnet and the SmCo magnet, and according to the similar phase solubility principle, when the Cu element is mixed into the rare earth element which is the same as or similar to the main phase Sm element, the Cu element and the alloy are more beneficial to realizing the element exchange between the Cu element and the SmCo hard magnet, so that the uniform distribution of the doped phase in the main phase and the magnetic pinning improvement function are more beneficial to being improved; in addition, the melting point of the rare earth-Cu alloy is generally lower, the higher metal plasticity and deformability can be still maintained below 500 ℃, the full densification of the magnet at a lower temperature can be promoted, and the Cu element entering the hard magnetic lattice can also play a role in reducing the crystallization temperature of a nonmagnetic phase. Therefore, after the R-Cu alloy is added, the invention has high development potential in the aspects of improving the forming temperature of the two-phase magnet and improving the coercive force of the magnet, and is more beneficial to obtaining the nanocrystalline two-phase magnetic powder and the bulk magnet with more excellent magnetism at lower preparation temperature.
Preferably, the rare earth element is at least one element selected from Sm and Pr elements.
Preferably, the addition amount of the R-Cu alloy powder is as follows: the R-Cu alloy powder accounts for 0.1-15% of the total amount of the hard magnetic raw material powder and the soft magnetic raw material powder. If the addition amount of the R-Cu alloy powder is too small, the coercive force improvement effect is not obvious, and if the addition amount is too large, the remanence of the magnet is reduced too much.
More preferably, the addition amount of the R-Cu alloy powder is: the proportion of the R-Cu alloy powder to the total amount of the hard magnetic raw material powder and the soft magnetic raw material powder is 1 to 5 percent.
Preferably, the mass ratio of the hard magnetic raw material powder to the soft magnetic raw material powder is (10:0.1) to (5: 5).
Preferably, the hard magnetic phase in the hard magnetic raw material powder is SmCo2、SmCo3、Sm2Co7，SmCo5、SmCo7、 SmCo12、(Sm,Pr)Co5、Sm(Fe,Co)3、Sm(Fe,Co)7One or more of a type phase structure.
Preferably, the soft magnetic raw material powder is one or more of Fe, Co and Fe-Co soft magnetic powder, and the atomic percentage of Fe and Co elements is (100-x) x, wherein x is more than or equal to 0 and less than or equal to 100.
Preferably, the high-energy ball mill is used in an apparatus including, but not limited to, a one-dimensional or three-dimensional vibration ball mill, a planetary ball mill; the ball milling time, the ball material ratio and the rotating speed of the ball mill are matched with the technological parameters of the ball milling device, the material of the ball milling tank, the material of the grinding balls, the size of the grinding balls and the like, and the method is not limited. Preferably, the high-energy ball milling is carried out in a three-dimensional vibration ball mill, a ball milling tank is a hard alloy tank, grinding balls are hard alloy balls, the ball milling process is carried out under the protection of inert gas or under the vacuum condition, the rotating speed of the ball mill is higher than 400rpm, the ball-to-material ratio is (15:1) - (30:1), and the ball milling time is 2-5 hours. The heating crystallization treatment is a treatment mode of converting an amorphous phase in the amorphous matrix mixed powder into a crystallization state by using a heating mode; the treatment environment is anaerobic and comprises a vacuum environment or a high-purity inert gas environment; in the crystallization treatment, only heating may be performed, or crystallization control conditions such as a magnetic field and pressure may be applied while heating. The temperature of the heating crystallization treatment is 350-800 ℃, preferably below 650 ℃.
Preferably, the nano composite permanent magnetic material comprises nano composite permanent magnetic powder and a nano composite permanent magnetic block, when the nano composite permanent magnetic material is the nano composite permanent magnetic block, the preparation method further comprises a pressure forming treatment process, wherein in the process of heating and crystallizing the amorphous matrix powder or after the heating and crystallizing are completed, the pressure of 1-2600 MPa is applied to the powder to obtain a low-density or full-density composite permanent magnetic block; the nano composite permanent magnet block can also be a bonded magnet formed by mixing and pressing crystallized powder and non-magnetic materials such as epoxy resin and the like.
When the heating crystallization process does not relate to compression molding, the prepared material is permanent magnet powder; when the heating crystallization process is combined with the pressing molding process, the prepared material is a permanent magnet block. The heating crystallization process may be combined with the compression molding process, and includes different combinations of the heating crystallization process and the compression molding process, for example, the amorphous matrix mixed powder is heated and crystallized first and then heated and pressurized for molding, the amorphous matrix mixed powder is simultaneously subjected to amorphous crystallization and compression molding under the heating and pressurizing conditions, the amorphous matrix mixed powder is compressed and molded first and then heated for crystallization, and the like.
Preferably, the permanent magnet blocks may be subjected to a thermal annealing treatment to improve the uniformity of the permanent magnet blocks or to achieve a further increase in the magnetic energy product of the permanent magnet blocks.
The invention also comprises a non-pressure treatment process, and the nano composite permanent magnetic powder is directly obtained after the ball-milled magnetic powder is heated and crystallized.
Compared with the prior art, the invention has the advantages that: according to the invention, the R-Cu alloy is added into a SmCo/Fe (Co) amorphous structure and a crystal, and a Sm- (Co, Cu) crystal phase and an Sm and Cu element are enriched among soft and hard magnetic crystal grains by entering a Cu element into a hard magnetic crystal lattice, so that the room-temperature coercive force and the high-temperature stability of a magnet of the SmCo/Fe (Co) nano composite material are improved; the preparation temperature of the SmCo/Fe (Co) composite magnetic powder and the full-density magnet is reduced to 500 ℃ or below, and can be as low as 400-425 ℃ at most by reducing the crystallization temperature of amorphous hard magnetic and improving the low-temperature plasticity and deformability of the powder. The room-temperature coercive force of the nano composite magnet is improved, and the high-temperature stability is improved, so that the preparation method has the preparation advantage of developing a high-performance high-temperature-resistant nano composite permanent magnet material; the preparation temperature is reduced, so that the preparation method has the advantages of energy saving and low cost; particularly, in the low-cost low-rare earth high-soft magnetic nano composite material with the soft magnetic content of 15-30%, the preparation temperature can be reduced, the room-temperature coercive force can be increased, a high magnetic energy product material reaching 21-23 MGOe can be obtained, and the material is obviously higher than neodymium iron boron isotropic permanent magnetic powder and permanent magnetic block bodies which are widely used in the market and have the magnetic energy product of 8-19 MGOe, so that the invention is also very suitable for developing the high-temperature resistant nano composite permanent magnetic material with high soft magnetic, low rare earth and high magnetic energy product under low energy consumption.
Drawings
FIG. 1 is a graph showing a comparison of magnetic properties of materials prepared in example 1 of the present invention and comparative example 1;
FIG. 2 is a graph showing another comparison of magnetic properties of the materials prepared in example 1 of the present invention and comparative example 1.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
the preparation method of the nano composite permanent magnetic material comprises the following steps:
(1) in an inert gas glove box filled with high-purity Ar gas, SmCo is weighed according to the proportion of 7.5:2.55Hard magnetic raw material powder and Fe soft magnetic raw material powder, and 5% of Sm by mass70Cu30Alloy raw material powder, uniformly mixing the raw material powder, and then filling the mixture and grinding balls into a hard alloy ball-milling tank for sealing, wherein the grinding balls are made of hard alloy materials, the ball-material ratio is 25:1, and the grinding balls have two sizes of 6mm and 9 mm;
(2) placing the sealed ball milling tank on a Spex-8000 ball mill for ball milling for 3h to obtain amorphous matrix mixed powder with non-crystallized hard magnetic grains and nano-scaled soft magnetic grains;
(3) sealing the amorphous matrix mixed powder in a quartz tube, and placing in a muffle furnace for vacuum heating annealing at 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C for 30min, wherein the annealing vacuum degree is higher than 3 × 10-3Pa, after annealing, taking the powder out of the quartz tube to obtain the isotropic SmCo/FeCo nano composite permanent magnetic powder.
Comparative example 1:
the comparative example was prepared in substantial agreement with example 1, except that: sm in step 1 of this comparative example70Cu30The addition amount of the alloy is 0, namely no R-Cu alloy is added.
Fig. 1 and 2 are graphs comparing the magnetic properties of SmCo/FeCo nanocomposite permanent magnetic powder prepared by different processes in example 1 and comparative example 1 of the present invention, wherein x is 5% of the material prepared in example 1; x ═ 0 is the material prepared in comparative example 1. Magnetic properties of the magnetic powder were measured by a vibrating sample magnetometer, lakeshore 7410, usa, at a maximum magnetic field of 2.1T at room temperature, the magnetic powder was embedded in epoxy resin and magnetized by a 7-8T pulsed magnetic field before the test.
As can be seen from the figure, the addition of the Sm-Cu alloy can improve the room-temperature coercive force of the isotropic SmCo/Fe (Co) nano composite powder, effectively prepare high-performance magnetic powder with the highest magnetic energy product of 23MGOe, and reduce the preparation temperature of the high-performance SmCo/Fe (Co) nano composite powder to 450-500 ℃, so that the superiority of the preparation method in the aspects of improving the room-temperature coercive force and reducing the preparation temperature of the isotropic SmCo/Fe (Co) nano composite powder is proved, and the superiority of the preparation method in the aspects of preparing a high-soft-magnetic and high-performance SmCo/Fe (Co) nano composite permanent magnetic material is also proved.
Example 2:
the preparation method of the nano composite permanent magnetic material comprises the following steps:
(1) in an inert gas glove box filled with high-purity Ar gas, SmCo is weighed according to the proportion of 8.0:2.05Hard magnetic raw material powder and Fe soft magnetic raw material powder, and adding Sm70Cu30Alloy raw material powder, the raw material powder is evenly mixed and then is put into a hard alloy ball milling tank together with grinding balls for sealing, the grinding balls are made of hard alloy materials, the ball material ratio is 25:1, and the size of the grinding balls is 9 mm;
(2) placing the sealed ball milling tank on a Spex-8000 ball mill for ball milling for 3h to obtain amorphous matrix mixed powder with non-crystallized hard magnetic grains and nano-scaled soft magnetic grains;
(3) coating a molybdenum disulfide release agent on a pressing mold, filling amorphous matrix mixed powder into the mold in an inert gas glove box, applying 700MPa pressure on the powder for prepressing at room temperature, placing the prepressed blank and the mold in a hot pressing furnace for vacuumizing until the vacuum degree reaches 1.9 × 10-3And starting a heating program when the temperature is below Pa, and applying pressing pressure to the powder between 250 ℃ and the highest temperature to simultaneously perform amorphous crystallization and press molding on the powder under the conditions of heating and pressurizing to obtain the isotropic SmCo/FeCo nano composite permanent magnet block directly formed by the crystallized powder through press molding.
Comparative example 2:
the comparative example was prepared in substantially the same manner as example 2, except thatIn the following steps: sm in step 1 of this comparative example70Cu30The addition amount of the alloy is 0, namely no R-Cu alloy is added.
Table 1 shows the room temperature magnetic performance data of SmCo/FeCo permanent magnet blocks prepared in example 2 and comparative example 2. The magnetic performance of the permanent magnet block is measured by a vibration sample magnetometer (lakeshore 7410) of the United states under the condition of 2.1T of maximum magnetic field at room temperature, and the block is magnetized in a 7-8T pulse magnetic field before the test.
Table 1 room temperature magnetic properties of permanent magnet blocks prepared in example 2 and comparative example 2
Figure BDA0002418188530000051
Example 3:
the preparation method of the nano composite permanent magnetic material comprises the following steps:
(1) in an inert gas glove box filled with high-purity Ar gas, SmCo is weighed according to the proportion of 7.5:2.55Adding 5% of RCu alloy powder by total mass into hard magnetic raw material powder and Fe soft magnetic raw material powder, uniformly mixing the raw material powder, and then putting the raw material powder and grinding balls into a hard alloy ball milling tank for sealing, wherein the grinding balls are made of hard alloy materials, the ball-to-material ratio is 15:1, and the size of the grinding balls is 12 mm;
(2) placing the sealed ball milling tank on a Spex-8000 ball mill for ball milling for 4h to obtain amorphous matrix mixed powder with non-crystallized hard magnetic grains and nano-scaled soft magnetic grains;
(3) coating a molybdenum disulfide release agent on a pressing mold, filling amorphous matrix mixed powder into the mold in an inert gas glove box, applying 600MPa pressure on the powder for prepressing at room temperature, placing the prepressed blank and the mold in a hot pressing furnace for vacuumizing until the vacuum degree reaches 2.9 × 10-3And starting a heating program when the pressure is lower than Pa, and performing compression molding on the magnetic powder at the maximum temperature of 475 ℃ to obtain the isotropic SmCo/FeCo nano composite permanent magnet block directly formed by compression molding of the crystallized magnetic powder.
Comparative example 3:
the comparative example was prepared in substantial agreement with example 3, except that: the amount of the R-Cu alloy added in step 1 of this comparative example was 0, i.e., no R-Cu alloy was added.
Table 2 shows the data of the change in magnetic properties of the permanent magnet blocks obtained in example 3 and comparative example 3. The magnetic performance of the permanent magnet block is measured by a vibration sample magnetometer (lakeshore 7410) of the United states under the condition of 2.1T of maximum magnetic field at room temperature, and the block is magnetized in a 7-8T pulse magnetic field before the test.
Table 2 room temperature magnetic properties of permanent magnet blocks prepared in example 3 and comparative example 3
Figure BDA0002418188530000061
Example 4:
the preparation method of the nano composite permanent magnetic material comprises the following steps:
(1) weighing SmCo in proportion in an inert gas glove box filled with high-purity Ar gas5Hard magnetic raw material powder, Fe soft magnetic raw material powder and Sm70Cu30Alloy powder, uniformly mixing the raw material powder, and then putting the mixture and grinding balls into a hard alloy ball-milling tank for sealing, wherein the grinding balls are made of hard alloy materials, the ball material ratio is 30:1, and the size of the grinding balls is 12 mm;
(2) placing the sealed ball milling tank on a Spex-8000 ball mill for ball milling for 4h to obtain amorphous matrix mixed powder with non-crystallized hard magnetic grains and nano-scaled soft magnetic grains;
(3) coating a molybdenum disulfide release agent on a pressing mold, filling amorphous matrix mixed powder into the mold in an inert gas glove box, applying 800MPa pressure on the powder for prepressing at room temperature, placing the prepressed blank and the mold in a hot pressing furnace for vacuumizing until the vacuum degree reaches 1.7 × 10-3And starting a heating program when the temperature is below Pa, and applying pressing pressure to the powder between 290 ℃ and the highest temperature to simultaneously perform amorphous crystallization and pressing molding on the powder under the heating and pressing conditions to obtain the isotropic SmCo/FeCo nano composite permanent magnet block.
Comparative example 4:
the comparative example was prepared in substantial agreement with example 4,the only difference is that: sm in step 1 of this comparative example70Cu30The addition amount of the alloy is 0, namely no R-Cu alloy is added.
Table 3 shows the room temperature magnetic properties of the permanent magnet blocks obtained under the preparation conditions of example 4 and comparative example 4. The magnetic performance of the permanent magnet block is measured by a vibration sample magnetometer (lakeshore 7410) of the United states under the condition of 2.1T of maximum magnetic field at room temperature, and the block is magnetized in a 7-8T pulse magnetic field before the test.
Table 3 room temperature magnetic properties of permanent magnet blocks obtained in example 4 and comparative example 4
Figure BDA0002418188530000071
It can be seen from tables 1, 2 and 3 that the room-temperature coercive force of the isotropic SmCo/Fe (Co) nano composite permanent magnet block can be effectively improved by adding the R-Cu alloy on the premise of not obviously changing the magnetic energy product of the magnet, and the preparation temperature of the high-performance SmCo/Fe (Co) nano composite block is reduced to below 500 ℃ and is as low as 400-425 ℃, so that the superiority of the method in the aspects of improving the room-temperature coercive force of the isotropic SmCo/Fe (Co) nano composite permanent magnet material and reducing the preparation temperature of the isotropic SmCo/Fe (Co) nano composite permanent magnet material is proved, and the superiority of the method in the aspects of preparing the high-soft-magnetism low-rare earth, high-magnetic energy product and high-temperature-resistant SmCo/Fe (Co) nano composite permanent magnet block under the condition of low energy consumption is proved.
It should be noted that the present invention is not limited to the above-mentioned embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the present invention.

Claims (10)

1. A method for preparing a nano composite permanent magnetic material is characterized by comprising the following steps:
(1) mixing R-Cu alloy powder, hard magnetic raw material powder and soft magnetic raw material powder according to a ratio, and performing high-energy ball milling on the obtained mixed powder to obtain amorphous matrix mixed powder with non-crystallized hard magnetic grains and nano-scaled soft magnetic grains;
(2) and (2) heating and crystallizing the amorphous matrix mixed powder obtained in the step (1), and converting an amorphous phase in the amorphous matrix mixed powder into a crystallized state to obtain the nano composite permanent magnetic material.
2. The method for preparing a nanocomposite permanent magnetic material according to claim 1, characterized in that: the R-Cu alloy is an alloy of a rare earth element and a Cu element, and in the R-Cu alloy, the addition ratio of the R to the Cu element is (100-y): y is more than or equal to 0 and less than or equal to 100.
3. The method of preparing a nanocomposite, permanent magnetic material of claim 2, characterized in that: the rare earth element is at least one of Sm and Pr elements.
4. The method for preparing a nanocomposite permanent magnetic material according to claim 1, characterized in that: the addition amount of the R-Cu alloy powder is as follows: the R-Cu alloy powder accounts for 0.1-15% of the total amount of the hard magnetic raw material powder and the soft magnetic raw material powder.
5. The method for preparing a nanocomposite permanent magnetic material according to claim 4, characterized in that: the addition amount of the R-Cu alloy powder is as follows: the R-Cu alloy powder accounts for 0.5 to 5 percent of the total amount of the hard magnetic raw material powder and the soft magnetic raw material powder.
6. The method for preparing a nanocomposite permanent magnetic material according to any of claims 1 to 5, characterized in that: the mass ratio of the hard magnetic raw material powder to the soft magnetic raw material powder is (10:0.1) - (5: 5).
7. The method for preparing a nanocomposite permanent magnetic material according to any of claims 1 to 5, characterized in that: the hard magnetic phase in the hard magnetic raw material powder is SmCo2、SmCo3、Sm2Co7，SmCo5、SmCo7、SmCo12、(Sm,Pr)Co5、Sm(Fe,Co)3、Sm(Fe,Co)7One or more of a type phase structure.
8. The method for preparing a nanocomposite permanent magnetic material according to any of claims 1 to 5, characterized in that: the soft magnetic raw material powder is one or more of Fe, Co and Fe-Co soft magnetic powder, the atomic percentage of Fe and Co elements is (100-x) x, and x is more than or equal to 0 and less than or equal to 100.
9. The method for preparing a nanocomposite permanent magnetic material according to any of claims 1 to 5, characterized in that: the high-energy ball milling process is carried out under the protection of inert gas or under the vacuum condition; the heating crystallization treatment is carried out under the anaerobic condition, wherein the anaerobic condition comprises a vacuum condition, an inert gas condition and a reducing gas condition.
10. The method for preparing a nanocomposite permanent magnetic material according to any of claims 1 to 5, characterized in that: the nano composite permanent magnetic material comprises nano composite permanent magnetic powder and a nano composite permanent magnetic block, and when the nano composite permanent magnetic material is the nano composite permanent magnetic block, the nano composite permanent magnetic block is a low-density/full-density composite permanent magnetic block obtained by applying a pressure of 1-2600 MPa to amorphous matrix powder in a heating crystallization process or after heating crystallization is completed, or a bonded magnet formed by mixing and pressing crystallized powder and a non-magnetic material.
CN202010197633.1A 2020-03-19 2020-03-19 Preparation method of nano composite permanent magnetic material Expired - Fee Related CN111627631B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010197633.1A CN111627631B (en) 2020-03-19 2020-03-19 Preparation method of nano composite permanent magnetic material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010197633.1A CN111627631B (en) 2020-03-19 2020-03-19 Preparation method of nano composite permanent magnetic material

Publications (2)

Publication Number Publication Date
CN111627631A true CN111627631A (en) 2020-09-04
CN111627631B CN111627631B (en) 2022-07-05

Family

ID=72273157

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010197633.1A Expired - Fee Related CN111627631B (en) 2020-03-19 2020-03-19 Preparation method of nano composite permanent magnetic material

Country Status (1)

Country Link
CN (1) CN111627631B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120021219A1 (en) * 2010-07-21 2012-01-26 Alexander Gabay Magnetic nanoflakes
CN102496437A (en) * 2011-11-17 2012-06-13 中国科学院宁波材料技术与工程研究所 Anisotropic nanocrystal complex-phase compact block neodymium-iron-boron permanent-magnet material and preparation method thereof
CN104078175A (en) * 2014-06-12 2014-10-01 嘉兴市鹏程磁钢有限公司 Samarium-cobalt-base nanocrystalline permanent magnet material and preparation method thereof
CN106531382A (en) * 2015-09-10 2017-03-22 燕山大学 Permanent magnet material and preparation method therefor
CN108962523A (en) * 2018-08-14 2018-12-07 徐靖才 A kind of preparation method for the SmCo base nanocomposite permanent magnets adulterating SmCu alloy

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120021219A1 (en) * 2010-07-21 2012-01-26 Alexander Gabay Magnetic nanoflakes
CN102496437A (en) * 2011-11-17 2012-06-13 中国科学院宁波材料技术与工程研究所 Anisotropic nanocrystal complex-phase compact block neodymium-iron-boron permanent-magnet material and preparation method thereof
CN104078175A (en) * 2014-06-12 2014-10-01 嘉兴市鹏程磁钢有限公司 Samarium-cobalt-base nanocrystalline permanent magnet material and preparation method thereof
CN106531382A (en) * 2015-09-10 2017-03-22 燕山大学 Permanent magnet material and preparation method therefor
CN108962523A (en) * 2018-08-14 2018-12-07 徐靖才 A kind of preparation method for the SmCo base nanocomposite permanent magnets adulterating SmCu alloy

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李晨浩: "球磨时间和硬相成分对SmCo/α-Fe(Co)系磁体微结构和磁性能的影响", 《中国优秀硕士学位论文全文数据库工程科技Ⅱ辑》 *

Also Published As

Publication number Publication date
CN111627631B (en) 2022-07-05

Similar Documents

Publication Publication Date Title
CN107424695B (en) Double-alloy nanocrystalline rare earth permanent magnet and preparation method thereof
CN105957673B (en) A kind of isotropism rare earth permanent magnet powder and preparation method thereof
CN106531382B (en) A kind of permanent-magnet material and preparation method thereof
CN110060833B (en) High-remanence and high-coercivity R-T-B permanent magnet material and preparation method thereof
CN104599802A (en) Rare earth permanent magnetic material and preparation method thereof
WO2018126738A1 (en) Mn-ga alloy and magnetic hardening method therefor
CN108899150B (en) Nd-Fe-B/Sm-Co composite bonded magnet and preparation method thereof
CN108831659B (en) Method for preparing nano neodymium iron nitrogen permanent magnetic powder and nano permanent magnetic powder
He et al. Effects of grain boundary diffusion process on magnetic properties enhancement and microstructure evolution of hot-deformed Nd-Fe-B magnets
CN203791590U (en) Preparation device for bonded NdFeB permanent magnet material
CN116612956A (en) Cerium-containing neodymium-iron-boron magnet with core-shell structure and preparation method and application thereof
CN111627631B (en) Preparation method of nano composite permanent magnetic material
Popov et al. Preparation of sintered Nd-Fe-B magnets by pressless process
CN115938771B (en) SmFe (zinc oxide) x M 12-x Preparation method of nanocrystalline permanent magnet material
Korent et al. Magnetic properties and microstructure evolution of hot-deformed Nd-Fe-B magnets produced by low-pressure spark-plasma sintering
CN114156031A (en) Neodymium-iron-boron magnet and preparation method thereof
CN110895984A (en) Strong texture SmCo5Base nano composite permanent magnetic material and its preparation method
CN103779026A (en) Cohesive NdFeB permanent magnet material and preparation equipment thereof
Cook et al. Rare-earth iron boron supermagnets
CN104576022B (en) The preparation method of rare-earth permanent magnet
Strnat Permanent magnets based on 4f-3d compounds
CN103413668B (en) A kind of method for preparing dysprosium iron neodymium iron boron magnetic body
CN109637768A (en) A kind of rare earth permanent-magnetic material and preparation method thereof containing yttrium
CN112466651B (en) Preparation method of rare earth-free high-performance composite magnet
JPH04143221A (en) Production of permanent magnet

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20220705