CN107170543A - The preparation method of Sm Co based alloy block shaped magnets - Google Patents

The preparation method of Sm Co based alloy block shaped magnets Download PDF

Info

Publication number
CN107170543A
CN107170543A CN201710456082.4A CN201710456082A CN107170543A CN 107170543 A CN107170543 A CN 107170543A CN 201710456082 A CN201710456082 A CN 201710456082A CN 107170543 A CN107170543 A CN 107170543A
Authority
CN
China
Prior art keywords
alloy
magnetic
block shaped
shaped magnet
heat treatment
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
CN201710456082.4A
Other languages
Chinese (zh)
Other versions
CN107170543B (en
Inventor
孙继兵
韩续豪
李英
韩瑞平
崔春翔
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.)
Hebei University of Technology
Original Assignee
Hebei University of Technology
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 Hebei University of Technology filed Critical Hebei University of Technology
Priority to CN201710456082.4A priority Critical patent/CN107170543B/en
Publication of CN107170543A publication Critical patent/CN107170543A/en
Application granted granted Critical
Publication of CN107170543B publication Critical patent/CN107170543B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • H01F1/0552—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 with a protective layer
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • 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
    • H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

The preparation method of Sm Co based alloy block shaped magnets of the present invention, it is related to rare earth cobalt-base permanent magnet material, it is a kind of preparation method of the nanocrystalline Sm Co based alloy block shaped magnets with obvious magnetocrystalline anisotropy, the full amorphous powder of Sm Co based alloys is prepared by carrying out high-energy ball milling to Sm Co based alloys fast quenching thin strap, then block is pressed under hydraulic press, finally the Sm Co based alloy blocks suppressed are put into magnetic heat treatment furnace and carry out magnetic-field heat treatment, amorphous phase is set to be recrystallized in heating process along magnetic direction, so as to which the nanocrystalline Sm Co based alloy block shaped magnets with obvious magnetocrystalline anisotropy are made, overcoming prior art can only be orientated to crystallite dimension in micron-sized Sm Co based alloy block shaped magnets, and the defect of the nanocrystalline Sm Co based alloy block shaped magnets with obvious preferred orientation can not be prepared.

Description

The preparation method of Sm-Co based alloy block shaped magnets
Technical field
Technical scheme is related to rare earth cobalt-base permanent magnet material, specifically Sm-Co based alloys block shaped magnet Preparation method.
Background technology
Rare earth permanent-magnetic material is a kind of important basic functional material, and wherein Sm-Co base permanent magnetic alloys are because with excellent Permanent magnetism performance and high-temperature stability and have irreplaceable status in high-temperature applications.The biography of Sm-Co base permanent magnetic alloys System preparation technology be：Melting-powder processed-magnetic aligning shaping-sintering, but the crystal grain of block shaped magnet that this method is obtained is micron Level.For permanent-magnet alloy, coercitive size depends on material internal and forms the complexity on reverse farmland, and the crystalline substance of magnet It is higher that formation of the particle size to reverse farmland serves the smaller coercivity of conclusive effect, i.e. crystal grain, therefore, by Sm-Co bases forever The trend of magnetic alloy nano-crystallization is increasingly strengthened.
In recent years, the research of nanocrystalline Sm-Co base permanent magnetic alloys received the concern of researchers generally.Quick quenching technique and Mechanical attrition method is the main method for preparing nanocrystalline Sm-Co based permanent magnetic materials, wherein, high-energy ball milling be prepare it is nanocrystalline SmCo5The powerful measure of permanent-magnet alloy.(root ball millings SmCo is protected in Zhang Jian, Shen by Zhang Jian and Shen Baogen5Nanocrystalline structure and magnetic properties [J] Metallic Functional Materials, 2001,8 (3):10-12.) by SmCo5Ball milling 5h is made non-on high energy ball mill after ingot casting is broken Crystalline flour end, then anneal 30min in the range of 450 DEG C~800 DEG C, finds the sample average crystallite dimension after being annealed through 700 DEG C For 22nm, then powder after 700 DEG C are annealed is mixed with the Instant cement that the trade mark is CH-914, prepares isotropic bonded magnet, It was found that coercivity is up to 28672Oe.Cui et al. (Cui B Z, Gabay A M, Li W F, et al.Anisotropic SmCo5nanoflakes by surfactant-assisted high energy ball milling[J].Journal of Applied Physics,2010,107(9):465701.) having prepared thickness by surfactant auxiliary ball grinding technique is 8nm~80nm, length is 0.5 μm~8 μm, and average grain size is 8nm SmCo5Nanometer sheet, then uses epoxy resin system Standby bonded permanent magnet, and be orientated under 19kOe magnetic field, obtain the SmCo that coercivity is 17.7kOe5Nanocrystalline bonded permanent magnet, The magnet has obvious anisotropy.Zuo et al. (Zuo W L, Zhao X, Xiong J F, et al.Strong textured SmCo5nanoflakes with ultrahigh coercivity prepared by multistep (three steps)surfactant-assisted ball milling.[J].Scientific Reports,2015,5: 13117.) SmCo that coercivity is 26.2kOe has been prepared out by multistage ball milling method5Nanometer sheet, they are using normal heptane as ball milling Medium, the oleic acid-oleyl amine for adding 20% is surfactant, has then carried out the ball milling of three phases again：(1) 150rpm's Ball milling 4h under speed；(2) the ball milling 8h under 200rpm speed；(3) the ball milling 16h under 250rpm speed.Finally by ball milling Obtained nanometer sheet is orientated after being mixed with epoxy resin under 20kOe magnetic field, has prepared the high magnetocrystalline of high-coercive force different The SmCo of property5Magnet.Cruse et al. (Crouse C A, Michel E, Shen Y, et al.Effect of surfactant molecular weight on particle morphology of SmCo5prepared by high energy ball milling[J].Journal of Applied Physics,2012,111(7):07A724.) by SmCo5Alloy ball milling During add different organic acids and make surfactant and studied, find compared with the oleic acid commonly used, using relative point The positive valeric acid that protonatomic mass is smaller, boiling point is lower is minimum as the crystallite dimension obtained after surfactant and ball milling 1h, and coercive Power is up to 20kOe, simultaneously as the boiling point of positive valeric acid is relatively low, so be easier to remove after ball milling.CN101265529 is public A kind of preparation method of Sm-Co based alloys block shaped magnet is opened, i.e., carrying out ball milling to Sm-Co based alloys fast quenching thin strap obtains amorphous State alloy powder, then carries out Fast Sintering using discharge plasma sintering (SPS) technology, obtains crystallite dimension less than 100nm Sm-Co based alloy block shaped magnets, although the patent document does not announce obtained nanocrystalline Sm-Co based alloys block shaped magnet Crystallite dimension, but (permitted firm, Yang Jianjun, Zhang Dongtao wait block-shaped nano-crystal SmCos according to other pertinent literatures delivered5Burn Tie the structure and its magnetic property [J] China YouSe Acta Metallurgica Sinicas of magnet, 2009,19 (7):1305-1309.) learn its last system It is 30nm for average grain size is gone out, coercivity is 29184Oe (2.28MA/m) nanocrystalline SmCo5Block shaped magnet.But, this The nanocrystalline Sm-Co based alloys block shaped magnet that the method for kind is prepared does not have obvious preferred orientation, is isotropic. CN102766835A discloses a kind of preparation method for preparing high-coercive force Sm-Co based alloy block shaped magnets, i.e., in traditional handicraft Multistage aging technique is added afterwards, and is continuously added into steady magnetic field environment in ag(e)ing process, has been prepared coercivity and has been existed More than 27097Oe (2117kA/m) Sm-Co based alloy block shaped magnets, but this technique does not reduce crystallite dimension, prepares Sm-Co based alloy block shaped magnet crystal grain out is still micron-sized.
In a word, it can effectively reduce the crystallite dimension of Sm-Co based alloy magnets using high-energy ball-milling process, lift Sm- The coercivity of Co based alloy magnets, but the magnet that the technique is prepared is powdered, or need to be further added by bonding process and add Bonded permanent magnet is prepared with orientation；Although nanocrystalline Sm-Co based alloys block shaped magnet can be prepared with discharge plasma sintering method, But this block shaped magnet is isotropic, without obvious preferred orientation.Preparation there is no to have obvious magnetocrystalline each so far The document report of the nanocrystalline Sm-Co based alloys block shaped magnet of anisotropy.
The content of the invention
The technical problems to be solved by the invention are：The preparation method of Sm-Co based alloy block shaped magnets is provided, is a kind of tool There is the preparation method of the nanocrystalline Sm-Co based alloys block shaped magnet of obvious magnetocrystalline anisotropy, by Sm-Co based alloy fast quenchings Strip carries out high-energy ball milling and prepares the full amorphous powder of Sm-Co based alloys, and block is then pressed under hydraulic press, finally will pressure The Sm-Co based alloy blocks made, which are put into magnetic heat treatment furnace, carries out magnetic-field heat treatment, makes amorphous phase edge in heating process Magnetic direction is recrystallized, so that the nanocrystalline Sm-Co based alloys block shaped magnet with obvious magnetocrystalline anisotropy is made, is overcome Prior art can only be orientated to crystallite dimension in micron-sized Sm-Co based alloys block shaped magnet, and can not prepare has The defect of the nanocrystalline Sm-Co based alloys block shaped magnet of obvious preferred orientation.
The present invention solves the technical scheme that is used of the technical problem：The preparation method of Sm-Co based alloy block shaped magnets, Key is will to carry out magnetic-field heat treatment after the full amorphous powder briquet of Sm-Co based alloys, make amorphous phase edge in heating process Magnetic direction is recrystallized, so that the nanocrystalline Sm-Co based alloys block shaped magnet with obvious magnetocrystalline anisotropy is made, specific step It is rapid as follows：
The first step, preparation raw material：
According to element composition formula Sm (Co1-xCux)5Atomic ratio carry out dispensing, wherein, x=0~0.3, weighing needs quality Pure Sm, pure Co and pure Cu prepared, the Sm mass ratio actually weighed is higher by 2wt% by the quality of theoretical calculation during dispensing ~10wt%, the volatilization of Sm during melting and fast quenching is made up with this, preparation raw material is thus completed；
Second step, prepares Sm-Co base mother alloy ingots：
The raw material that the first step is prepared all is put into the crucible of vacuum arc melting furnace or vacuum induction melting furnace, right Body of heater is vacuumized, and vacuum in stove is less than 5 × 10-2Pa, furnace temperature is elevated above more than feed metal Co fusing point, makes raw material complete Running down is simultaneously sufficiently mixed, and Sm-Co base mother alloy ingots are made；
3rd step, prepares Sm-Co based alloy fast quenching thin straps：
Sm-Co bases mother alloy ingot made from second step is placed in fast melt-quenching stove, vacuum in stove is evacuated to 5 × 10- 2Below Pa, again melts mother alloy ingot, is then melted on the disk roller of the peripheral speed rotation with 30m/s~50m/s Body fast quenching, is made Sm-Co based alloy fast quenching thin straps；
4th step, prepares the full amorphous powder of Sm-Co based alloys：
Sm-Co based alloy fast quenching thin straps made from 3rd step are put into ball grinder and carry out ball milling using high energy ball mill, Ordered crystal structure in strip is destroyed completely, form full amorphous, that is, the full amorphous powder of Sm-Co based alloys is made；
5th step, is pressed into Sm-Co based alloy blocks：
The full amorphous powder of Sm-Co based alloys made from 4th step is put into mould and is pressed into Sm-Co bases using hydraulic press Alloy block；
6th step, prepares Sm-Co based alloy block shaped magnet products：
Sm-Co based alloy blocks made from 5th step are put into magnetic heat treatment furnace and carry out magnetic-field heat treatment, method is： Sm-Co based alloy blocks made from 5th step are directly placed into magnetic heat treatment furnace and magnetic heat treatment furnace vacuum is evacuated to 5 ×10-2Below Pa first will place into magnetic-field heat treatment after the anti-oxidation processing of Sm-Co based alloys block progress made from the 5th step In stove, then in 500 DEG C~850 DEG C scope inside holding 0.5h~10h, while adding 4kOe~60kOe's in heating process Magnetic field, makes amorphous phase be recrystallized in heating process along magnetic direction, is thus made different with high-coercive force and high magnetocrystalline The nanocrystalline Sm-Co based alloys block shaped magnet product of property, the vibrating specimen magnetometer or external magnetic field for being 20kOe with external magnetic field be 90kOe comprehensive physical performance measurement instrument measurement magnetic property, when measurement magnetic direction is put down with magnetic-field heat treatment externally-applied magnetic field direction During row, the magnetic property of the product is：Coercivity be 6171.2Oe~48243.3Oe, remanent magnetization be 20.4emu/g~ 60.1emu/g, saturation magnetization is 27.4emu/g~78.0emu/g.
The preparation method of above-mentioned Sm-Co based alloys block shaped magnet, the use high energy ball mill carries out ball milling, used in ball milling Ratio of grinding media to material uses 5~20:1, liquid medium is made of normal heptane wet-milling is carried out to strip, liquid medium pair is done with No. 120 aero oils Strip carries out wet-milling or makees medium with argon gas strip is dry grinded, and Ball-milling Time is 8~40h.
The preparation method of above-mentioned Sm-Co based alloys block shaped magnet, the use hydraulic press is pressed into Sm-Co based alloy blocks Body, the pressing speed of hydraulic press is 80~120kN/min, pressure 50kN, dwell time 3min, and the Sm-Co bases after ball milling are closed Golden full amorphous powder is pressed into a diameter of 1cm, the cylindrical Sm-Co based alloys block highly for 1.5mm.
The preparation method of above-mentioned Sm-Co based alloys block shaped magnet, the anti-oxidation processing, its method is included to the 5th step system The Sm-Co based alloys block obtained carries out the processing of pipe envelope or anti-oxidation in Sm-Co based alloys block surface coating made from the 5th step Coating.
The preparation method of above-mentioned Sm-Co based alloys block shaped magnet product, used raw material be all by commercially available, Used equipment is known chemical industry equipment, and used process operation is those skilled in the art institute It is well known.
Beneficial effects of the present invention are as follows：
Compared with prior art, the present invention has prominent substantive distinguishing features as follows：
(1) relevant research shows that high-energy ball milling is the effective means for preparing nanocrystalline material, but the material prepared is then It is isotropic nanoscale or micron particles shape magnet.The substantive distinguishing features of the protrusion of the inventive method are：By Sm-Co bases Alloy fast quenching thin strap ball milling helps amorphous powder, rather than manocrystalline powders, and the full amorphous powder is pressed into using hydraulic press Block, then applies an externally-applied magnetic field in heating process, amorphous phase is recrystallized in heating process along magnetic direction, so that Obtain high-coercive force and the Sm-Co based alloy block shaped magnet products of high magnetocrystalline anisotropy.
(2) although Sm-Co based alloys inherently have high anisotropy field, because Cu is nonmagnetic elements, Cu's In the presence of the magnetocrystalline anisotropy field of magnet in itself can be improved, exactly because also improving magnetocrystalline anisotropy field, add Cu elements can strengthen magnetocrystalline anisotropy, therefore add a small amount of Cu in dispensing prepared by Sm-Co based alloys block shaped magnet, make Obtain Sm-Co based alloy block shaped magnets to be easier to be oriented during magnetic-field heat treatment, promote crystal grain to be given birth to along [001] direction It is long, so that the coercivity and magnetic anisotropy of Sm-Co based alloy block shaped magnets are improved.
(3) document (Cui B Z, Gabay A M, Li W F, et al.Anisotropic SmCo5nanoflakes by surfactant-assisted high energy ball milling[J].Journal of Applied Physics, 2010,107(9):465701；Zuo W L,Zhao X,Xiong J F,et al.Strong textured SmCo5nanoflakes with ultrahigh coercivity prepared by multistep(three steps) surfactant-assisted ball milling[J].Scientific Reports,2015,5:13117.) reported in The nanocrystalline SmCo of anisotropy5Magnet is to prepare bonded permanent magnet after the nanometer sheet after ball milling is mixed with binding agent and taken To being substantially still to belong to the category of magnetic Nano piece, rather than block shaped magnet truly；And SPS sintering is prepared Bulk nanometer be then isotropic, no preferred orientation.It is of the invention then be that Sm-Co based alloys have been directly prepared into bright The nanocrystalline Sm-Co based alloys block shaped magnet product of aobvious preferred orientation.
Compared with prior art, the present invention has following marked improvement：
(1) to pure SmCo made from prior art5For block shaped magnet, the externally-applied magnetic field when measuring magnetic direction with compacting Magnetic property is when direction is parallel：Its coercivity is 6000Oe at room temperature, and remanent magnetization is 18.6emu/g, saturated magnetization Intensity is 35.1emu/g, and Sm-Co based alloys block shaped magnet product made from the inventive method, in external magnetic field shaking for 20kOe Dynamic sample magnetometer and external magnetic field show for 90kOe comprehensive physical performance measurement instrument test, when measurement magnetic direction and magnetic field Its magnetic property is when heat treatment externally-applied magnetic field direction is parallel：Its coercivity is 6171.2Oe~48243.3Oe at room temperature, remaining The intensity of magnetization is 20.4emu/g~60.1emu/g, and saturation magnetization is 27.4emu/g~78.0emu/g, and magnetic property is obtained Significantly increase.
(2) with crystallite dimension made from prior art in micron-sized Sm-Co based alloys block shaped magnet compared with, the present invention The Sm-Co based alloy block shaped magnet crystallite dimensions prepared are only 16.7nm~68.6nm, and the reduction of crystallite dimension is to magnetic The lifting of energy serves obvious action.
(3) nanocrystalline Sm-Co based alloys block shaped magnet produced by the present invention has obvious magnetocrystalline anisotropy, overcomes Prior art can only be orientated to crystallite dimension in micron-sized Sm-Co based alloys block shaped magnet, and can not prepare non-stick The defect of the nanocrystalline Sm-Co based alloys block shaped magnet of the high magnetocrystalline anisotropy of junction type high-coercive force.
(4) preparation method of Sm-Co based alloy block shaped magnets of the invention, it is adaptable to SmCo5Type, SmCo7Type and Sm2Co17 The preparation of all Sm-Co based permanent magnetic materials such as type.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is SmCo made from embodiment 15The X ray diffracting spectrum of alloy fast quenching thin strap.
Fig. 2 is SmCo made from embodiment 15The X ray diffracting spectrum of the full amorphous powder of alloy.
Fig. 3 is SmCo made from embodiment 15The transmission electron microscopy figure of the full amorphous powder of alloy.
Fig. 4 is SmCo made from embodiment 15The SEAD figure of the full amorphous powder of alloy.
Fig. 5 is SmCo made from embodiment 15The X ray diffracting spectrum of alloy block shaped magnet product.
Fig. 6 is SmCo made from embodiment 15Alloy block shaped magnet product is additional in measurement magnetic direction and magnetic-field heat treatment Hysteresis curve when magnetic direction is parallel.
Fig. 7 is SmCo made from embodiment 15Alloy block shaped magnet product is additional in measurement magnetic direction and magnetic-field heat treatment Hysteresis curve when magnetic direction is vertical.
Fig. 8 is SmCo made from embodiment 25The X ray diffracting spectrum of alloy block shaped magnet product.
Fig. 9 is SmCo made from embodiment 25Alloy block shaped magnet product is additional in measurement magnetic direction and magnetic-field heat treatment Hysteresis curve when magnetic direction is parallel.
Figure 10 is SmCo made from embodiment 25Alloy block shaped magnet product is outside measurement magnetic direction and magnetic-field heat treatment Plus magnetic direction it is vertical when hysteresis curve.
Figure 11 is Sm (Co made from embodiment 30.8Cu0.2)5The X ray diffracting spectrum of alloy block shaped magnet product.
Figure 12 is Sm (Co made from embodiment 30.8Cu0.2)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel.
Figure 13 is Sm (Co made from embodiment 40.8Cu0.2)5The X ray diffracting spectrum of alloy block shaped magnet product.
Figure 14 is Sm (Co made from embodiment 40.8Cu0.2)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel.
Figure 15 is Sm (Co made from embodiment 50.9Cu0.1)5The X ray diffracting spectrum of alloy block shaped magnet product.
Figure 16 is Sm (Co made from embodiment 50.9Cu0.1)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel.
Figure 17 is Sm (Co made from embodiment 60.9Cu0.1)5The X ray diffracting spectrum of alloy block shaped magnet product.
Figure 18 is Sm (Co made from embodiment 60.9Cu0.1)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel.
Figure 19 is Sm (Co made from embodiment 70.9Cu0.1)5The X ray diffracting spectrum of alloy block shaped magnet product.
Figure 20 is Sm (Co made from embodiment 70.9Cu0.1)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel.
Figure 21 is Sm (Co made from embodiment 80.8Cu0.2)5The X ray diffracting spectrum of alloy block shaped magnet product.
Figure 22 is Sm (Co made from embodiment 80.8Cu0.2)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel.
Figure 23 is Sm (Co made from embodiment 90.8Cu0.2)5The product X ray diffracting spectrum of alloy block shaped magnet.
Figure 24 is Sm (Co made from embodiment 90.8Cu0.2)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel.
Figure 25 is Sm (Co made from embodiment 100.7Cu0.3)5The X ray diffracting spectrum of alloy block shaped magnet product.
Figure 26 is Sm (Co made from embodiment 100.7Cu0.3)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel.
Embodiment
Embodiment 1
The first step, preparation raw material：
According to element composition formula SmCo5Atomic ratio carry out dispensing, weighing needs the pure Sm and pure Co of quality to be prepared, The Sm mass ratio actually weighed is higher by 5wt% by the quality of theoretical calculation during dispensing, and melting and fast quenching process are made up with this Middle Sm volatilization；
Second step, prepares SmCo5Mother alloy ingot：
The raw material that the first step is prepared all is put into the crucible of vacuum arc melting furnace, and body of heater is vacuumized, and makes stove Interior vacuum is less than 5 × 10-2Pa, furnace temperature is elevated above more than feed metal Co fusing point, raw material is completely melt and is fully mixed Close, SmCo is made5Mother alloy ingot；
3rd step, prepares SmCo5Alloy fast quenching thin strap：
By SmCo made from second step5Mother alloy ingot is placed in fast melt-quenching stove, and vacuum in stove is evacuated into 5 × 10-2Pa Hereinafter, mother alloy ingot is melted again, then carries out fast melt-quenching on the disk roller of the peripheral speed rotation with 40m/s, make Obtain SmCo5Alloy fast quenching thin strap；
Fig. 1 shows SmCo made from the present embodiment5The X ray diffracting spectrum of alloy fast quenching thin strap, it is visible molten by the figure There was only single SmCo after body fast quenching in strip5Phase, while it can be seen that in the presence of the diffusing scattering peak of a small amount of amorphous phase, showing that this is thin Containing a certain amount of amorphous phase in band, and the strength ratio I of fast quenching thin strap easy magnetizing axis and main peak002/I111=0.256, with standard Peak I002/I111=0.24 compares without too big difference, and this shows the effect that the process of fast melt-quenching is not orientated to strip.
4th step, prepares SmCo5The full amorphous powder of alloy：
By SmCo made from the 3rd step5Alloy fast quenching thin strap is put into ball grinder carries out ball milling using high energy ball mill, makes Ordered crystal structure is destroyed completely in strip, forms full amorphous, that is, SmCo is made5The full amorphous powder of alloy, ball milling balls material Than using 5: 1, liquid medium is made of normal heptane wet-milling is carried out to strip, Ball-milling Time is 40h；
Fig. 2 shows SmCo made from the present embodiment5The X of the full amorphous powder of gained is penetrated after alloy fast quenching thin strap ball milling 40h Ray diffraction diagram is composed, compared to Fig. 1 before ball milling, its diffraction maximum severe weakness and widthization, only has a bulge at 40 °~45 ° And without obvious diffraction maximum, show that strip alloy after high-energy ball milling is in full noncrystalline state, because in the process of high-energy ball milling In, strip is under the repeated stock of abrading-ball and ball grinder, and size is less and less, is gradually converted into micron order even nano level powder End, with the further progress of ball milling, the defect concentration in crystal grain persistently increases, and causes severe lattice to distort, atom have left Equilbrium position, so as to cause alloy to be changed into amorphous state completely.
Fig. 3 shows SmCo made from the present embodiment5The transmission electron microscopy figure of the full amorphous powder of alloy, can be seen by the figure Go out, gained powder diameter is 1.3 μm~3.7 μm after ball milling 40h.
Fig. 4 shows SmCo made from the present embodiment5The SEAD collection of illustrative plates of the full amorphous powder of alloy, the electronics spreads out Penetrate spectrum and show the SmCo after ball milling5Alloy powder is amorphous state.
5th step, is pressed into SmCo5Alloy block：
By SmCo made from the 4th step5The full amorphous powder of alloy is put into mould is pressed into SmCo using hydraulic press5Alloy block Body, pressing speed is 80kN/min, pressure 50kN, dwell time 3min, by the SmCo after ball milling5The full amorphous powder compacting of alloy The cylindrical SmCo for being into a diameter of 1cm, highly 1.5mm5Alloy block；
6th step, prepares SmCo5Alloy block shaped magnet product：
By SmCo made from the 5th step5Alloy block, which is put into magnetic heat treatment furnace, carries out magnetic-field heat treatment, and method is：Will SmCo made from 5th step5Alloy block is directly placed into magnetic heat treatment furnace and magnetic heat treatment furnace vacuum is evacuated into 5 × 10- 2Below Pa, is then incubated 0.5h at 500 DEG C, while adding 4kOe magnetic field in heating process, makes amorphous phase in heating process It is middle to be recrystallized along magnetic direction, the nanocrystalline SmCo with high-coercive force and high magnetocrystalline anisotropy is thus made5Alloy is block Magnet product.
Fig. 5 is SmCo made from the present embodiment5The X ray diffracting spectrum of alloy block shaped magnet product.It can be seen by the figure Obvious diffusing scattering peak, shows still there is more amorphous phase in the alloy, and have SmCo certainly5Phase, illustrates that the alloy is block Magnet thing phase composition is that Amorphous Phase coexists with crystalline phases, its principal crystalline phase SmCo5Average grain size be 17.8nm, easy magnetization The strength ratio I of axle and main peak002/I111=0.468, show the SmCo after magnetic-field heat treatment5Alloy block shaped magnet forms edge [001] preferred orientation.With reference to the SmCo5Knowable to the X ray diffracting spectrum of alloy block shaped magnet, SmCo made from the present embodiment5 There is obvious anisotropy in alloy block shaped magnet product.
Fig. 6 is SmCo made from the present embodiment5Alloy block shaped magnet product is outside measurement magnetic direction and magnetic-field heat treatment Plus magnetic direction it is parallel when hysteresis curve, it is shown SmCo made from the present embodiment5Alloy block shaped magnet product is additional Magnetic field is measures magnetic property on 20kOe vibrating specimen magnetometer, when measurement magnetic direction and magnetic-field heat treatment externally-applied magnetic field side To it is parallel when, its coercivity be 6171.2Oe, remanent magnetization is 21.2emu/g, and saturation magnetization is 35.1emu/g.
Fig. 7 is SmCo made from the present embodiment5Alloy block shaped magnet product is outside measurement magnetic direction and magnetic-field heat treatment Plus magnetic direction it is vertical when hysteresis curve, its show when measurement magnetic direction it is vertical with magnetic-field heat treatment externally-applied magnetic field direction When, its coercivity is 4176.3Oe, and remanent magnetization is 10.6emu/g, and saturation magnetization is 25.2emu/g.
Embodiment 2
The first step, preparation raw material：
According to element composition formula SmCo5Atomic ratio carry out dispensing, weighing needs the pure Sm and pure Co of quality to be prepared, The Sm mass ratio actually weighed is higher by 8wt% by the quality of theoretical calculation during dispensing, and melting and fast quenching process are made up with this Middle Sm volatilization；
Second step, prepares SmCo5Mother alloy ingot：
Be the same as Example 1；
3rd step, prepares SmCo5Alloy fast quenching thin strap：
By SmCo made from second step5Mother alloy ingot is placed in fast melt-quenching stove, and vacuum in stove is evacuated into 5 × 10-2Pa Hereinafter, mother alloy ingot is melted again, then carries out fast melt-quenching on the disk roller of the peripheral speed rotation with 50m/s, make Obtain SmCo5Alloy fast quenching thin strap；
4th step, prepares SmCo5The full amorphous powder of alloy：
By SmCo made from the 3rd step5Alloy fast quenching thin strap is put into ball grinder carries out ball milling using high energy ball mill, makes Ordered crystal structure is destroyed completely in strip, forms full amorphous, that is, SmCo is made5The full amorphous powder of alloy, ball milling balls material Than using 8: 1, liquid medium is made of normal heptane wet-milling is carried out to strip, Ball-milling Time is 30h；
5th step, is pressed into SmCo5Alloy block：
Be the same as Example 1；
6th step, prepares SmCo5Alloy block shaped magnet product：
By SmCo made from the 5th step5Alloy block, which is put into magnetic heat treatment furnace, carries out magnetic-field heat treatment, and method is：First By SmCo made from the 5th step5Alloy block carries out the pipe envelope processing of anti-oxidation processing, and concrete operations are by the SmCo5Alloy block Body is sealed in quartz ampoule, and vacuum is evacuated to 5 × 10 in pipe-2Below Pa, is then placed into magnetic heat treatment furnace, in 500 DEG C of guarantors Warm 0.5h, while adding 28kOe magnetic field in heating process, makes amorphous phase be recrystallized in heating process along magnetic direction, Thus high-coercive force and the nanocrystalline SmCo of high magnetocrystalline anisotropy is made5Alloy block shaped magnet product.
Fig. 8 is SmCo made from the present embodiment5The X ray diffracting spectrum of alloy block shaped magnet product.It can be seen by the figure Obvious diffusing scattering peak, shows still there is more amorphous phase in the alloy, and have SmCo certainly5Phase, illustrates that the alloy is block Magnet thing phase composition is that Amorphous Phase coexists with crystalline phases, its principal crystalline phase SmCo5Average grain size be 16.7nm, easy magnetization The strength ratio I of axle and main peak002/I111=0.542, show the SmCo after magnetic-field heat treatment5Alloy block shaped magnet forms edge [001] preferred orientation.With reference to the SmCo5Knowable to the X ray diffracting spectrum of alloy block shaped magnet, SmCo made from the present embodiment5 There is obvious anisotropy in alloy block shaped magnet product.
Fig. 9 is SmCo made from the present embodiment5Alloy block shaped magnet product is outside measurement magnetic direction and magnetic-field heat treatment Plus magnetic direction it is parallel when hysteresis curve, it is shown SmCo made from the present embodiment5Alloy block shaped magnet is in externally-applied magnetic field To measure magnetic property on 20kOe vibrating specimen magnetometer, when measurement magnetic direction is put down with magnetic-field heat treatment externally-applied magnetic field direction During row, its coercivity is 6848.6Oe, and remanent magnetization is 24.5emu/g, and saturation magnetization is 39.0emu/g.
Figure 10 is SmCo made from the present embodiment5Alloy block shaped magnet product is outside measurement magnetic direction and magnetic-field heat treatment Plus magnetic direction it is vertical when hysteresis curve, its show when measurement magnetic direction it is vertical with magnetic-field heat treatment externally-applied magnetic field direction When, its coercivity is 3635.4Oe, and remanent magnetization is 10.7emu/g, and saturation magnetization is 27.3emu/g.
Embodiment 3
The first step, preparation raw material：
According to element composition formula Sm (Co0.8Cu0.2)5Atomic ratio carry out dispensing, weigh the pure Sm for needing quality, pure Co and Pure Cu is prepared, and the Sm mass ratio actually weighed is higher by 6wt% by the quality of theoretical calculation during dispensing, is made up with this molten Sm volatilization during refining and fast melt-quenching；
Second step, prepares Sm (Co0.8Cu0.2)5Mother alloy ingot：
The raw material that the first step is prepared all is put into the crucible of vacuum arc melting furnace, and body of heater is vacuumized, and makes stove Interior vacuum is less than 5 × 10-2Pa, furnace temperature is elevated above more than feed metal Co fusing point, raw material is completely melt and is fully mixed Close, Sm (Co are made0.8Cu0.2)5Mother alloy ingot；
3rd step, prepares Sm (Co0.8Cu0.2)5Alloy fast quenching thin strap：
By Sm (Co made from second step0.8Cu0.2)5Mother alloy ingot is placed in fast melt-quenching stove, and vacuum in stove is evacuated into 5 ×10-2Below Pa, again melts mother alloy ingot, then carries out melt on the disk roller of the peripheral speed rotation with 30m/s Fast quenching, is made Sm (Co0.8Cu0.2)5Alloy fast quenching thin strap；
4th step, prepares Sm (Co0.8Cu0.2)5The full amorphous powder of alloy：
By Sm (Co made from the 3rd step0.8Cu0.2)5Alloy fast quenching thin strap is put into ball grinder to be carried out using high energy ball mill Ball milling, is totally disrupted ordered crystal structure in strip, forms full amorphous, that is, Sm (Co are made0.8Cu0.2)5The full amorphous of alloy Powder, ratio of grinding media to material used in ball milling uses 10:1, liquid medium is made of normal heptane wet-milling is carried out to strip, Ball-milling Time is 25h；
5th step, is pressed into Sm (Co0.8Cu0.2)5Alloy block：
By Sm (Co made from the 4th step0.8Cu0.2)5The full amorphous powder of alloy is put into briquetting mold to be used using hydraulic press The mode of vertical steel molding is pressed into Sm (Co0.8Cu0.2)5Alloy block, pressing speed is 100kN/min, pressure 50kN, pressurize Time 3min, by the Sm (Co after ball milling0.8Cu0.2)5The full amorphous powder of alloy is pressed into a diameter of 1cm, the circle highly for 1.5mm Cylindricality Sm (Co0.8Cu0.2)5Alloy block；
6th step, prepares Sm (Co0.8Cu0.2)5Alloy block shaped magnet product：
By Sm (Co made from the 5th step0.8Cu0.2)5Alloy block, which is put into magnetic heat treatment furnace, carries out magnetic-field heat treatment, Method is：By Sm (Co made from the 5th step0.8Cu0.2)5Alloy block is directly placed into magnetic heat treatment furnace and by magnetic field Re Chu Reason stove vacuum is evacuated to 5 × 10-2Below Pa, is then incubated 4h at 600 DEG C, while adding 8kOe magnetic field in heating process, makes Amorphous phase is recrystallized in heating process along magnetic direction, and high-coercive force and the nanocrystalline Sm of high magnetocrystalline anisotropy is thus made (Co0.8Cu0.2)5Alloy block shaped magnet product.
Figure 11 is Sm (Co made from the present embodiment0.8Cu0.2)5The X ray diffracting spectrum of alloy block shaped magnet product.By this Figure is it can be seen that the alloy block shaped magnet thing phase composition is Sm (Co, Cu)5、Sm(Co,Cu)7、Sm2(Co,Cu)7And Sm2O3, its oikocryst Phase Sm (Co, Cu)5Average grain size be 23.6nm, the strength ratio I of easy magnetizing axis and main peak002/I111=0.458, show Sm (the Co after magnetic-field heat treatment0.8Cu0.2)5Alloy block shaped magnet forms the preferred orientation along [001].With reference to the Sm (Co0.8Cu0.2)5Knowable to the X ray diffracting spectrum of alloy block shaped magnet, Sm (Co made from the present embodiment0.8Cu0.2)5Alloy is block There is obvious anisotropy in magnet product.
Figure 12 is Sm (Co made from the present embodiment0.8Cu0.2)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel, it is shown Sm (Co made from the present embodiment0.8Cu0.2)5Alloy block Shape magnet product externally-applied magnetic field for 90kOe comprehensive physical performance measurement instrument on measure magnetic property, when measurement magnetic direction with When magnetic-field heat treatment externally-applied magnetic field direction is parallel, its coercivity is 25468.7Oe, and remanent magnetization is 36.3emu/g, saturation The intensity of magnetization is 51.5emu/g.
Embodiment 4
The first step, preparation raw material：
According to element composition formula Sm (Co0.8Cu0.2)5Atomic ratio carry out dispensing, weigh the pure Sm for needing quality, pure Co and Pure Cu is prepared, and the Sm mass ratio actually weighed is higher by 2wt% by the quality of theoretical calculation during dispensing, is made up with this molten Sm volatilization during refining and fast melt-quenching；
Second step, prepares Sm (Co0.8Cu0.2)5Mother alloy ingot：
Be the same as Example 3；
3rd step, prepares Sm (Co0.8Cu0.2)5Alloy fast quenching thin strap：
Be the same as Example 3；
4th step, prepares Sm (Co0.8Cu0.2)5The full amorphous powder of alloy：
By Sm (Co made from the 3rd step0.8Cu0.2)5Alloy fast quenching thin strap is put into ball grinder to be carried out using high energy ball mill Ball milling, is totally disrupted ordered crystal structure in strip, forms full amorphous, that is, Sm (Co are made0.8Cu0.2)5The full amorphous of alloy Powder, ratio of grinding media to material used in ball milling uses 8:1, do liquid medium with No. 120 aero oils and wet-milling is carried out to strip, Ball-milling Time is 10h；
5th step, is pressed into Sm (Co0.8Cu0.2)5Alloy block：
Be the same as Example 3；
6th step, prepares Sm (Co0.8Cu0.2)5Alloy block shaped magnet product：
By Sm (Co made from the 5th step0.8Cu0.2)5Alloy block, which is put into magnetic heat treatment furnace, carries out magnetic-field heat treatment, Method is：First by Sm (Co made from the 5th step0.9Cu0.1)5Alloy block carries out the pipe envelope processing of anti-oxidation processing, concrete operations It is by the Sm (Co0.8Cu0.2)5Alloy block is sealed in quartz ampoule, and vacuum is evacuated to 5 × 10 in pipe-2Below Pa, is then placed into In magnetic heat treatment furnace, 10h is incubated at 600 DEG C, while adding 30kOe magnetic field in heating process, makes amorphous phase in heating During recrystallized along magnetic direction, the nanocrystalline Sm (Co of high-coercive force and high magnetocrystalline anisotropy are thus made0.8Cu0.2)5 Alloy block shaped magnet product.
Figure 13 is Sm (Co made from the present embodiment0.8Cu0.2)5The X ray diffracting spectrum of alloy block shaped magnet product.By this Figure is it can be seen that the alloy block shaped magnet thing phase composition is Sm (Co, Cu)5、Sm(Co,Cu)7、Sm2(Co,Cu)7And Sm2O3, its oikocryst Phase Sm (Co, Cu)5Average grain size be 68.6nm, the strength ratio I of easy magnetizing axis and main peak002/I111=0.531, show Sm (the Co after magnetic-field heat treatment0.8Cu0.2)5Alloy block shaped magnet forms the preferred orientation along [001].With reference to the Sm (Co0.8Cu0.2)5Knowable to the X ray diffracting spectrum of alloy block shaped magnet, Sm (Co made from the present embodiment0.8Cu0.2)5Alloy is block There is obvious anisotropy in magnet product.
Figure 14 is Sm (Co made from the present embodiment0.8Cu0.2)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel, it is shown Sm (Co made from the present embodiment0.8Cu0.2)5Alloy block Shape magnet product measures magnetic property on the vibrating specimen magnetometer that externally-applied magnetic field is 20kOe, when measurement magnetic direction and magnetic field When heat treatment externally-applied magnetic field direction is parallel, its coercivity is 17577.3Oe, and remanent magnetization is 27.9emu/g, saturated magnetization Intensity is 38.6emu/g.
Embodiment 5
The first step, preparation raw material：
According to element composition formula Sm (Co0.9Cu0.1)5Atomic ratio carry out dispensing, weigh the pure Sm for needing quality, pure Co and Pure Cu is prepared, and the Sm mass ratio actually weighed is higher by 10wt% by the quality of theoretical calculation during dispensing, is made up with this Sm volatilization during melting and fast melt-quenching；
Second step, prepares Sm (Co0.9Cu0.1)5Mother alloy ingot：
The raw material that the first step is prepared all is put into the crucible of vacuum induction melting furnace, and body of heater is vacuumized, and makes stove Interior vacuum is less than 5 × 10-2Pa, furnace temperature is elevated above more than feed metal Co fusing point, raw material is completely melt and is fully mixed Close, Sm (Co are made0.9Cu0.1)5Mother alloy ingot；
3rd step, prepares Sm (Co0.9Cu0.1)5Alloy fast quenching thin strap：
By Sm (Co made from second step0.9Cu0.1)5Mother alloy ingot is placed in fast melt-quenching stove, and vacuum in stove is evacuated into 5 ×10-2Below Pa, again melts mother alloy ingot, then carries out melt on the disk roller of the peripheral speed rotation with 35m/s Fast quenching, is made Sm (Co0.9Cu0.1)5Alloy fast quenching thin strap；
4th step, prepares Sm (Co0.9Cu0.1)5The full amorphous powder of alloy：
By Sm (Co made from the 3rd step0.9Cu0.1)5Alloy fast quenching thin strap is put into ball grinder to be carried out using high energy ball mill Ball milling, is totally disrupted ordered crystal structure in strip, forms full amorphous, that is, Sm (Co are made0.9Cu0.1)5The full amorphous of alloy Powder, ratio of grinding media to material used in ball milling uses 8:1, liquid medium is made of normal heptane wet-milling is carried out to strip, Ball-milling Time is 16h；
5th step, compacting Sm (Co0.9Cu0.1)5Alloy block：
By Sm (Co made from the 4th step0.9Cu0.1)5The full amorphous powder of alloy is put into mould is pressed into Sm using hydraulic press (Co0.9Cu0.1)5Alloy block, pressing speed is 110kN/min, pressure 50kN, dwell time 3min, by the Sm after ball milling (Co0.9Cu0.1)5The full amorphous powder of alloy is pressed into a diameter of 1cm, the cylindrical Sm (Co highly for 1.5mm0.9Cu0.1)5Alloy Block；
6th step, prepares nanocrystalline Sm (Co0.9Cu0.1)5Alloy block shaped magnet product：
By Sm (Co made from the 5th step0.9Cu0.1)5Alloy block is directly placed into magnetic heat treatment furnace and by magnetic field Re Chu Reason stove vacuum is evacuated to 5 × 10-2Below Pa, is then incubated 3h at 650 DEG C, while adding 8kOe magnetic field in heating process, makes Amorphous phase is recrystallized in heating process along magnetic direction, and high-coercive force and the nanocrystalline Sm of high magnetocrystalline anisotropy is thus made (Co0.9Cu0.1)5Alloy block shaped magnet product.
Figure 15 is Sm (Co made from the present embodiment0.9Cu0.1)5The X ray diffracting spectrum of alloy block shaped magnet product.By this Figure is it can be seen that the alloy block shaped magnet thing phase composition is Sm (Co, Cu)5、Sm(Co,Cu)7、Sm2(Co,Cu)7And Sm2O3, its oikocryst Phase Sm (Co, Cu)5Average grain size be 26.8nm, the strength ratio I of easy magnetizing axis and main peak002/I111=0.521, show Sm (the Co after magnetic-field heat treatment0.9Cu0.1)5Alloy block shaped magnet forms the preferred orientation along [001].With reference to the Sm (Co0.9Cu0.1)5Knowable to the X ray diffracting spectrum of alloy block shaped magnet, Sm (Co made from the present embodiment0.9Cu0.1)5Alloy is block There is obvious anisotropy in magnet product.
Figure 16 is Sm (Co made from the present embodiment0.9Cu0.1)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel, it is shown Sm (Co made from the present embodiment0.9Cu0.1)5Alloy block Shape magnet product externally-applied magnetic field for 90kOe comprehensive physical performance measurement instrument on measure magnetic property, when measurement magnetic direction with When magnetic-field heat treatment externally-applied magnetic field direction is parallel, its coercivity is 31446.7Oe, and remanent magnetization is 38.5emu/g, saturation The intensity of magnetization is 55.8emu/g.
Embodiment 6
The first step, preparation raw material：
According to element composition formula Sm (Co0.9Cu0.1)5Atomic ratio carry out dispensing, weigh the pure Sm for needing quality, pure Co and Pure Cu is prepared, and the Sm mass ratio actually weighed is higher by 4wt% by the quality of theoretical calculation during dispensing, is made up with this molten Sm volatilization during refining and fast melt-quenching；
Second step, prepares Sm (Co0.9Cu0.1)5Mother alloy ingot：
Be the same as Example 5；
3rd step, prepares Sm (Co0.9Cu0.1)5Alloy fast quenching thin strap：
By Sm (Co made from second step0.9Cu0.1)5Mother alloy ingot is placed in fast melt-quenching stove, and vacuum in stove is evacuated into 5 ×10-2Below Pa, again melts mother alloy ingot, then carries out melt on the disk roller of the peripheral speed rotation with 40m/s Fast quenching, is made Sm (Co0.9Cu0.1)5Alloy fast quenching thin strap；
4th step, prepares Sm (Co0.9Cu0.1)5The full amorphous powder of alloy：
By Sm (Co made from the 3rd step0.9Cu0.1)5Alloy fast quenching thin strap is put into ball grinder to be carried out using high energy ball mill Ball milling, is totally disrupted ordered crystal structure in strip, forms full amorphous, that is, Sm (Co are made0.9Cu0.1)5The full amorphous of alloy Powder, ratio of grinding media to material used in ball milling uses 10:1, liquid medium is made of normal heptane wet-milling is carried out to strip, Ball-milling Time is 8h；
5th step, compacting Sm (Co0.9Cu0.1)5Alloy block：
Be the same as Example 5；
6th step, prepares nanocrystalline Sm (Co0.9Cu0.1)5Alloy block shaped magnet product：
By Sm (Co made from the 5th step0.9Cu0.1)5Alloy block, which is put into magnetic heat treatment furnace, carries out magnetic-field heat treatment, Method is：First by Sm (Co made from the 5th step0.9Cu0.1)5Alloy block carries out the pipe envelope processing of anti-oxidation processing, concrete operations It is by the Sm (Co0.8Cu0.2)5Alloy block is sealed in quartz ampoule, and vacuum is evacuated to 5 × 10 in pipe-2Below Pa, is then placed into In magnetic heat treatment furnace, 4h is incubated at 650 DEG C, while adding 4kOe magnetic field in heating process, makes amorphous phase heated Recrystallized in journey along magnetic direction, high-coercive force and the nanocrystalline Sm (Co of high magnetocrystalline anisotropy is thus made0.9Cu0.1)5Close Golden block shaped magnet product.
Figure 17 is Sm (Co made from the present embodiment0.9Cu0.1)5The X ray diffracting spectrum of alloy block shaped magnet product.By this Figure is it can be seen that the alloy block shaped magnet thing phase composition is Sm (Co, Cu)5、Sm2(Co,Cu)17And Sm2O3, its principal crystalline phase Sm (Co, Cu)5Average grain size be 28.7nm, the strength ratio I of easy magnetizing axis and main peak002/I111=0.573, show through magnetic field heat SmCo after processing5The preferred orientation of alloy block shaped magnet product formation along [001].With reference to the Sm (Co0.9Cu0.1)5Alloy is block The X ray diffracting spectrum of magnet understands that it shows Sm (Co made from the present embodiment0.9Cu0.1)5Alloy block shaped magnet product is present Obvious anisotropy.
Figure 18 is Sm (Co made from the present embodiment0.9Cu0.1)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel, it is shown Sm (Co made from the present embodiment0.9Cu0.1)5Alloy block Shape magnet product externally-applied magnetic field for 90kOe comprehensive physical performance measurement instrument on measure magnetic property, when measurement magnetic direction with When magnetic-field heat treatment externally-applied magnetic field direction is parallel, its coercivity is 32909.2Oe, and remanent magnetization is 43.5emu/g, saturation The intensity of magnetization is 61.8emu/g.
Embodiment 7
The first step, preparation raw material：
According to element composition formula Sm (Co0.9Cu0.1)5Atomic ratio carry out dispensing, weigh the pure Sm for needing quality, pure Co and Pure Cu is prepared, and Sm actual mass is higher by 5wt% than Theoretical Mass during dispensing, and melting and fast melt-quenching are made up with this During Sm volatilization；
Second step, prepares Sm (Co0.9Cu0.1)5Mother alloy ingot：
Be the same as Example 5；
3rd step, prepares Sm (Co0.9Cu0.1)5Alloy fast quenching thin strap：
By Sm (Co made from second step0.9Cu0.1)5Mother alloy ingot is placed in fast melt-quenching stove, and vacuum in stove is evacuated into 5 ×10-2Below Pa, again melts mother alloy ingot, then carries out melt on the disk roller of the peripheral speed rotation with 50m/s Fast quenching, is made Sm (Co0.9Cu0.1)5Alloy fast quenching thin strap；
4th step, prepares Sm (Co0.9Cu0.1)5The full amorphous powder of alloy：
By Sm (Co made from the 3rd step0.9Cu0.1)5Alloy fast quenching thin strap is put into ball grinder to be carried out using high energy ball mill Ball milling, is totally disrupted ordered crystal structure in strip, forms full amorphous, that is, Sm (Co are made0.9Cu0.1)5The full amorphous of alloy Powder, ratio of grinding media to material used in ball milling uses 20:1, liquid medium is made of normal heptane wet-milling is carried out to strip, Ball-milling Time is 35h；
5th step, compacting Sm (Co0.9Cu0.1)5Alloy block：
Be the same as Example 5；
6th step, prepares Sm (Co0.9Cu0.1)5Alloy block shaped magnet product：
By Sm (Co made from the 5th step0.9Cu0.1)5Alloy block, which is put into magnetic heat treatment furnace, carries out magnetic-field heat treatment, Method is：First by Sm (Co made from the 5th step0.9Cu0.1)5Alloy block carries out anti-oxidation processing, i.e., in Sm (Co0.9Cu0.1)5Close The antioxidizing paint that the golden block surface coating trade mark is 202, then places into magnetic heat treatment furnace, is incubated 4h at 650 DEG C, together When in heating process add 12kOe magnetic field, amorphous phase is recrystallized in heating process along magnetic direction, thus be made height Nanocrystalline Sm (the Co of coercivity and high magnetocrystalline anisotropy0.9Cu0.1)5Alloy block shaped magnet product.
Figure 19 is Sm (Co made from the present embodiment0.9Cu0.1)5The X ray diffracting spectrum of alloy block shaped magnet product.By this Figure is it can be seen that the alloy block shaped magnet thing phase composition is Sm (Co, Cu)5、Sm2(Co,Cu)17And Sm2O3, its principal crystalline phase Sm (Co, Cu)5Average grain size be 27.5nm, the strength ratio I of easy magnetizing axis and main peak002/I111=1.240, show through magnetic field heat Sm (Co after processing0.9Cu0.1)5The preferred orientation of alloy block shaped magnet product formation along [001].With reference to the Sm (Co0.9Cu0.1)5 Knowable to the X ray diffracting spectrum of alloy block shaped magnet, Sm (Co made from the present embodiment0.9Cu0.1)5Alloy block shaped magnet product is deposited In obvious anisotropy.
Figure 20 is Sm (Co made from the present embodiment0.9Cu0.1)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel, it is shown Sm (Co made from the present embodiment0.9Cu0.1)5Alloy block Shape magnet product externally-applied magnetic field for 90kOe comprehensive physical performance measurement instrument on measure magnetic property, when measurement magnetic direction with When magnetic-field heat treatment externally-applied magnetic field direction is parallel, its coercivity is 40044.5Oe, and remanent magnetization is 47.8emu/g, saturation The intensity of magnetization is 65.6emu/g.
Embodiment 8
The first step, preparation raw material：
According to element composition formula Sm (Co0.8Cu0.2)5Atomic ratio carry out dispensing, weigh the pure Sm for needing quality, pure Co and Pure Cu is prepared, and the Sm mass ratio actually weighed is higher by 8wt% by the quality of theoretical calculation during dispensing, is made up with this molten Sm volatilization during refining and fast melt-quenching；
Second step, prepares Sm (Co0.8Cu0.2)5Mother alloy ingot：
The raw material that the first step is prepared all is put into the crucible of vacuum arc melting furnace, and body of heater is vacuumized, and makes stove Interior vacuum is less than 5 × 10-2Pa, furnace temperature is elevated above more than feed metal Co fusing point, raw material is completely melt and is fully mixed Close, Sm (Co are made0.8Cu0.2)5Mother alloy ingot；
3rd step, prepares Sm (Co0.8Cu0.2)5Alloy fast quenching thin strap：
By Sm (Co made from second step0.8Cu0.2)5Mother alloy ingot is placed in fast melt-quenching stove, and vacuum in stove is evacuated into 5 ×10-2Below Pa, again melts mother alloy ingot, then carries out melt on the disk roller of the peripheral speed rotation with 40m/s Fast quenching, is made Sm (Co0.8Cu0.2)5Alloy fast quenching thin strap；
4th step, prepares Sm (Co0.8Cu0.2)5The full amorphous powder of alloy：
By Sm (Co made from the 3rd step0.8Cu0.2)5Alloy fast quenching thin strap is put into ball grinder to be carried out using high energy ball mill Ball milling, is totally disrupted ordered crystal structure in strip, forms full amorphous, that is, Sm (Co are made0.8Cu0.2)5The full amorphous of alloy Powder, ratio of grinding media to material used in ball milling uses 10:1, make medium with argon gas and strip is dry grinded, Ball-milling Time is 15h；
5th step, compacting Sm (Co0.8Cu0.2)5Alloy block：
By Sm (Co made from the 4th step0.8Cu0.2)5The full amorphous powder of alloy is put into mould is pressed into Sm using hydraulic press (Co0.8Cu0.2)5Alloy block, pressing speed is 100kN/min, pressure 50kN, dwell time 3min, by the Sm after ball milling (Co0.8Cu0.2)5The full amorphous powder of alloy is pressed into a diameter of 1cm, the cylindrical Sm (Co highly for 1.5mm0.8Cu0.2)5Alloy Block；
6th step, prepares Sm (Co0.8Cu0.2)5Alloy block shaped magnet product：
By Sm (Co made from the 5th step0.8Cu0.2)5Alloy block is put into progress magnetic field Re Chu in vacuum magnetic heat treatment stove Manage, method is：First by Sm (Co made from the 5th step0.8Cu0.2)5Alloy block carries out anti-oxidation processing, i.e. Sm (Co0.8Cu0.2)5 The antioxidizing paint that the alloy block surface coating trade mark is 202, then places into magnetic heat treatment furnace, 2h is incubated at 700 DEG C, 30kOe magnetic field is added in heating process simultaneously, amorphous phase is recrystallized in heating process along magnetic direction, is thus made Nanocrystalline Sm (the Co of high-coercive force and high magnetocrystalline anisotropy0.8Cu0.2)5Alloy block shaped magnet product.
Figure 21 is Sm (Co made from the present embodiment0.8Cu0.2)5The X ray diffracting spectrum of alloy block shaped magnet product.By this Figure is it can be seen that the alloy block shaped magnet thing phase composition is Sm (Co, Cu)5And Sm2O3Phase, its principal crystalline phase Sm (Co, Cu)5Average crystalline substance Particle size is 32.4nm, easy magnetizing axis and main peak strength ratio I002/I111=1.619, show the Sm after magnetic-field heat treatment (Co0.8Cu0.2)5The preferred orientation of alloy block shaped magnet product formation along [001].With reference to the Sm (Co0.8Cu0.2)5Alloy is block Knowable to the X ray diffracting spectrum of magnet, Sm (Co made from the present embodiment0.8Cu0.2)5Alloy block shaped magnet product exists obvious Anisotropy.
Figure 22 is Sm (Co made from the present embodiment0.8Cu0.2)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel, it is shown Sm (Co made from the present embodiment0.8Cu0.2)5Alloy block Shape magnet product externally-applied magnetic field for 90kOe comprehensive physical performance measurement instrument on measure magnetic property, when measurement magnetic direction with When magnetic-field heat treatment externally-applied magnetic field direction is parallel, its coercivity is 42922.1Oe, and remanent magnetization is 53.6emu/g, saturation The intensity of magnetization is 73.7emu/g.
Embodiment 9
The first step, preparation raw material：
According to element composition formula Sm (Co0.8Cu0.2)5Atomic ratio carry out dispensing, weigh the pure Sm for needing quality, pure Co and Pure Cu is prepared, and the Sm mass ratio actually weighed is higher by 5wt% by the quality of theoretical calculation during dispensing, is made up with this molten Sm volatilization during refining and fast melt-quenching；
Second step, prepares Sm (Co0.8Cu0.2)5Mother alloy ingot：
Be the same as Example 8；
3rd step, prepares Sm (Co0.8Cu0.2)5Alloy fast quenching thin strap：
By Sm (Co made from second step0.8Cu0.2)5Mother alloy ingot is placed in fast melt-quenching stove, and vacuum in stove is evacuated into 5 ×10-2Below Pa, again melts mother alloy ingot, then carries out melt on the disk roller of the peripheral speed rotation with 50m/s Fast quenching, is made Sm (Co0.8Cu0.2)5Alloy fast quenching thin strap；
4th step, prepares Sm (Co0.8Cu0.2)5The full amorphous powder of alloy：
By Sm (Co made from the 3rd step0.8Cu0.2)5Alloy fast quenching thin strap is put into ball grinder to be carried out using high energy ball mill Ball milling, is totally disrupted ordered crystal structure in strip, forms full amorphous, that is, Sm (Co are made0.8Cu0.2)5The full amorphous of alloy Powder, ratio of grinding media to material used in ball milling uses 15:1, liquid medium is made of normal heptane wet-milling is carried out to strip, Ball-milling Time is 20h；
5th step, compacting Sm (Co0.8Cu0.2)5Alloy block：
Be the same as Example 8；
6th step, prepares Sm (Co0.8Cu0.2)5Alloy block shaped magnet product：
By Sm (Co made from the 5th step0.8Cu0.2)5Alloy block is put into progress magnetic field Re Chu in vacuum magnetic heat treatment stove Manage, method is：First by Sm (Co made from the 5th step0.8Cu0.2)5Alloy block carries out anti-oxidation processing, i.e. Sm (Co0.8Cu0.2)5 The antioxidizing paint that the alloy block surface coating trade mark is 202, then places into magnetic heat treatment furnace, 3h is incubated at 700 DEG C, 60kOe magnetic field is added in heating process simultaneously, amorphous phase is recrystallized in heating process along magnetic direction, is thus made Nanocrystalline Sm (the Co of high-coercive force and high magnetocrystalline anisotropy0.8Cu0.2)5Alloy block shaped magnet product.
Figure 23 is Sm (Co made from the present embodiment0.8Cu0.2)5The X ray diffracting spectrum of alloy block shaped magnet product.By this Figure is it can be seen that the alloy block shaped magnet thing phase composition is Sm (Co, Cu)5And Sm2O3Phase, its principal crystalline phase Sm (Co, Cu)5Average crystalline substance Particle size is 30.1nm, easy magnetizing axis and main peak strength ratio I002/I111=2.012, show the Sm after magnetic-field heat treatment (Co0.8Cu0.2)5The preferred orientation of alloy block shaped magnet product formation along [001].With reference to the Sm (Co0.8Cu0.2)5Alloy is block Knowable to the X ray diffracting spectrum of magnet, Sm (Co made from the present embodiment0.8Cu0.2)5Alloy block shaped magnet product exists obvious Anisotropy.
Figure 24 is Sm (Co made from the present embodiment0.8Cu0.2)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel, it is shown Sm (Co made from the present embodiment0.8Cu0.2)5Alloy block Shape magnet product externally-applied magnetic field for 90kOe comprehensive physical performance measurement instrument on measure magnetic property, when measurement magnetic direction with When magnetic-field heat treatment externally-applied magnetic field direction is parallel, its coercivity is 48243.3Oe, and remanent magnetization is 60.1emu/g, saturation The intensity of magnetization is 78.0emu/g.
Embodiment 10
The first step, preparation raw material：
According to element composition formula Sm (Co0.7Cu0.3)5Atomic ratio carry out dispensing, weigh the pure Sm for needing quality, pure Co and Pure Cu is prepared, and the Sm mass ratio actually weighed is higher by 10wt% by the quality of theoretical calculation during dispensing, is made up with this Sm volatilization during melting and fast melt-quenching；
Second step, prepares Sm (Co0.7Cu0.3)5Mother alloy ingot：
The raw material that the first step is prepared all is put into the crucible of vacuum induction melting furnace, and body of heater is vacuumized, and makes stove Interior vacuum is less than 5 × 10-2Pa, furnace temperature is elevated above more than feed metal Co fusing point, raw material is completely melt and is fully mixed Close, Sm (Co are made0.7Cu0.3)5Mother alloy ingot；
3rd step, prepares Sm (Co0.7Cu0.3)5Alloy fast quenching thin strap：
By Sm (Co made from second step0.7Cu0.3)5Mother alloy ingot is placed in fast melt-quenching stove, and vacuum in stove is evacuated into 5 ×10-2Below Pa, again melts mother alloy ingot, then carries out melt on the disk roller of the peripheral speed rotation with 35m/s Fast quenching, is made Sm (Co0.7Cu0.3)5Alloy fast quenching thin strap；
4th step, prepares Sm (Co0.7Cu0.3)5The full amorphous powder of alloy：
By Sm (Co made from the 3rd step0.7Cu0.3)5Alloy fast quenching thin strap is put into ball grinder to be carried out using high energy ball mill Ball milling, is totally disrupted ordered crystal structure in strip, forms full amorphous, that is, Sm (Co are made0.7Cu0.3)5The full amorphous of alloy Powder, ratio of grinding media to material used in ball milling uses 5:1, liquid medium is made of normal heptane wet-milling is carried out to strip, Ball-milling Time is 20h；
5th step, compacting Sm (Co0.7Cu0.3)5Alloy block：
By Sm (Co made from the 4th step0.7Cu0.3)5The full amorphous powder of alloy is put into mould is pressed into Sm using hydraulic press (Co0.7Cu0.3)5Alloy block, pressing speed is 120kN/min, pressure 50kN, dwell time 3min, by the Sm after ball milling (Co0.7Cu0.3)5The full amorphous powder of alloy is pressed into a diameter of 1cm, the cylindrical Sm (Co highly for 1.5mm0.7Cu0.3)5Alloy Block；
6th step, prepares Sm (Co0.7Cu0.3)5Alloy block shaped magnet product：
By Sm (Co made from the 5th step0.7Cu0.3)5Alloy block, which is put into magnetic heat treatment furnace, carries out magnetic-field heat treatment, Method is：By Sm (Co made from the 5th step0.7Cu0.3)5Alloy block is directly placed into magnetic heat treatment furnace and by magnetic field Re Chu Reason stove vacuum is evacuated to 5 × 10-2Below Pa, is then incubated 1h at 850 DEG C, while adding 4kOe magnetic field in heating process, makes Amorphous phase is recrystallized in heating process along magnetic direction, and nanocrystalline Sm (Co are thus made0.7Cu0.3)5Alloy block shaped magnet is produced Product.
Figure 25 is Sm (Co made from the present embodiment0.7Cu0.3)5The X ray diffracting spectrum of alloy block shaped magnet product.By this Figure is it can be seen that the alloy block shaped magnet thing phase composition is Sm (Co, Cu)5、Sm2(Co,Cu)17And Sm2O3, its principal crystalline phase Sm (Co, Cu)5Average grain size be 35.0nm, the strength ratio I of easy magnetizing axis and main peak002/I111=0.323, show through magnetic field heat Sm (Co after processing0.7Cu0.3)5Preferred orientation of the alloy block shaped magnet product formation along [001].With reference to the Sm (Co0.7Cu0.3)5Close Knowable to the X ray diffracting spectrum of golden block shaped magnet, Sm (Co made from the present embodiment0.7Cu0.3)5Alloy block shaped magnet product is present Obvious anisotropy.
Figure 26 is Sm (Co made from embodiment 100.7Cu0.3)5Alloy block shaped magnet product is in measurement magnetic direction and magnetic field Hysteresis curve when heat treatment externally-applied magnetic field direction is parallel, it is shown Sm (Co made from the present embodiment0.7Cu0.3)5Alloy block Shape magnet product measures magnetic property on the vibrating specimen magnetometer that externally-applied magnetic field is 20kOe, when measurement magnetic direction and magnetic field When heat treatment externally-applied magnetic field direction is parallel, its coercivity is 17203.8Oe, and remanent magnetization is 20.4emu/g, saturated magnetization Intensity is 27.4emu/g.
In above-described embodiment, it by commercially available, used equipment is knownization that used raw material, which is all, Construction equipment, used process operation is known to those skilled in the art.

Claims (4)

  1. The preparation method of 1.Sm-Co based alloy block shaped magnets, it is characterised in that：Key is by the full amorphous powder of Sm-Co based alloys Magnetic-field heat treatment is carried out after briquet, amorphous phase is recrystallized in heating process along magnetic direction, so as to be made with bright The nanocrystalline Sm-Co based alloys block shaped magnet of aobvious magnetocrystalline anisotropy, is comprised the following steps that：
    The first step, preparation raw material：
    According to element composition formula Sm (Co1-xCux)5Atomic ratio carry out dispensing, wherein, x=0 ~ 0.3, weighing needs the pure of quality Sm, pure Co and pure Cu are prepared, during dispensing the Sm mass ratio actually weighed by the quality of theoretical calculation be higher by 2wt% ~ 10wt%, the volatilization of Sm during melting and fast quenching is made up with this, preparation raw material is thus completed；
    Second step, prepares Sm-Co base mother alloy ingots：
    The raw material that the first step is prepared all is put into the crucible of vacuum arc melting furnace or vacuum induction melting furnace, to body of heater Vacuumize, vacuum in stove is less than 5 × 10-2Pa, furnace temperature is elevated above more than feed metal Co fusing point, raw material is melted completely Change and be sufficiently mixed, Sm-Co base mother alloy ingots are made；
    3rd step, prepares Sm-Co based alloy fast quenching thin straps：
    Sm-Co bases mother alloy ingot made from second step is placed in fast melt-quenching stove, vacuum in stove is evacuated to 5 × 10-2Pa with Under, mother alloy ingot is melted again, it is fast then to carry out melt on the disk roller of the peripheral speed rotation with 30m/s ~ 50m/s Quench, Sm-Co based alloy fast quenching thin straps are made；
    4th step, prepares the full amorphous powder of Sm-Co based alloys：
    Sm-Co based alloy fast quenching thin straps made from 3rd step are put into ball grinder and carry out ball milling using high energy ball mill, are made thin Destroyed completely with interior ordered crystal structure, form full amorphous, that is, the full amorphous powder of Sm-Co based alloys is made；
    5th step, is pressed into Sm-Co based alloy blocks：
    The full amorphous powder of Sm-Co based alloys made from 4th step is put into mould and is pressed into Sm-Co based alloys using hydraulic press Block；
    6th step, prepares Sm-Co based alloy block shaped magnet products：
    Sm-Co based alloy blocks made from 5th step are put into magnetic heat treatment furnace and carry out magnetic-field heat treatment, method is：
    Sm-Co based alloy blocks made from 5th step are directly placed into magnetic heat treatment furnace and magnetic heat treatment furnace vacuum is taken out To 5 × 10-2Below Pa first will place into magnetic field Re Chu after the anti-oxidation processing of Sm-Co based alloys block progress made from the 5th step Manage in stove, then in 500 DEG C ~ 850 DEG C scope inside holding 0.5h ~ 10h, while adding 4kOe ~ 60kOe magnetic in heating process , amorphous phase is recrystallized in heating process along magnetic direction, being thus made has high-coercive force and high magnetocrystalline anisotropy Nanocrystalline Sm-Co based alloys block shaped magnet product, the vibrating specimen magnetometer or external magnetic field for being 20kOe with external magnetic field be 90kOe comprehensive physical performance measurement instrument measurement magnetic property, when measurement magnetic direction is put down with magnetic-field heat treatment externally-applied magnetic field direction During row, the magnetic property of the product is：Coercivity be 6171.2Oe ~ 48243.3Oe, remanent magnetization be 20.4emu/g ~ 60.1emu/g, saturation magnetization is 27.4emu/g ~ 78.0emu/g.
  2. 2. the preparation method of Sm-Co based alloys block shaped magnet according to claim 1, it is characterised in that：The use high energy Ball mill carries out ball milling, and ratio of grinding media to material used in ball milling uses 5 ~ 20:1, liquid medium is made of normal heptane wet-milling, use are carried out to strip No. 120 aero oils do liquid medium and wet-milling are carried out to strip or makees medium with argon gas strip is dry grinded, Ball-milling Time for 8 ~ 40h。
  3. 3. the preparation method of Sm-Co based alloys block shaped magnet according to claim 1, it is characterised in that：The use hydraulic pressure Machine is pressed into Sm-Co based alloy blocks, and the pressing speed of hydraulic press is 80 ~ 120kN/min, pressure 50kN, dwell time 3min, The full amorphous powder of Sm-Co based alloys after ball milling is pressed into a diameter of 1cm, the cylindrical Sm-Co based alloys highly for 1.5mm Block.
  4. 4. the preparation method of Sm-Co based alloys block shaped magnet according to claim 1, it is characterised in that：The anti-oxidation place Reason, its method includes carrying out Sm-Co based alloys block made from the 5th step the processing of pipe envelope or in Sm-Co bases made from the 5th step Alloy block surface coats antioxidizing paint.
CN201710456082.4A 2017-06-16 2017-06-16 The preparation method of Sm-Co based alloy block shaped magnets Active CN107170543B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710456082.4A CN107170543B (en) 2017-06-16 2017-06-16 The preparation method of Sm-Co based alloy block shaped magnets

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710456082.4A CN107170543B (en) 2017-06-16 2017-06-16 The preparation method of Sm-Co based alloy block shaped magnets

Publications (2)

Publication Number Publication Date
CN107170543A true CN107170543A (en) 2017-09-15
CN107170543B CN107170543B (en) 2018-10-12

Family

ID=59818772

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710456082.4A Active CN107170543B (en) 2017-06-16 2017-06-16 The preparation method of Sm-Co based alloy block shaped magnets

Country Status (1)

Country Link
CN (1) CN107170543B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108899150A (en) * 2018-09-10 2018-11-27 重庆科技学院 A kind of Nd-Fe-B/Sm-Co compoiste adhering magnet and preparation method thereof
CN110379579A (en) * 2019-06-20 2019-10-25 杭州永磁集团有限公司 The preparation method of high resistivity 2:17 type samarium cobalt permanent magnet body
CN113496816A (en) * 2020-03-18 2021-10-12 中国科学院宁波材料技术与工程研究所 Production method of samarium-cobalt-based permanent magnet block and samarium-cobalt-based permanent magnet block
CN116344191A (en) * 2023-03-28 2023-06-27 燕山大学 Method for improving effective deformation of magnetic powder material
CN116425206A (en) * 2023-04-06 2023-07-14 中国科学院宁波材料技术与工程研究所 Improve SrFe 12 O 19 Method for magnetic performance of ferrite

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103586465A (en) * 2013-11-12 2014-02-19 河北工业大学 Method for preparing Sm-Co based magnetic nano-material
CN106710764A (en) * 2017-03-27 2017-05-24 河北工业大学 SmCo5-based permanent magnet thin strip magnet and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103586465A (en) * 2013-11-12 2014-02-19 河北工业大学 Method for preparing Sm-Co based magnetic nano-material
CN106710764A (en) * 2017-03-27 2017-05-24 河北工业大学 SmCo5-based permanent magnet thin strip magnet and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J.C. TE´LLEZ-BLANCO等: "Structure and magnetic properties of SmCo5-xCuxalloys", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
苏艳锋: "SmCo5/α-Fe 纳米复合永磁材料的制备及其磁性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅱ辑》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108899150A (en) * 2018-09-10 2018-11-27 重庆科技学院 A kind of Nd-Fe-B/Sm-Co compoiste adhering magnet and preparation method thereof
CN108899150B (en) * 2018-09-10 2020-10-16 重庆科技学院 Nd-Fe-B/Sm-Co composite bonded magnet and preparation method thereof
CN110379579A (en) * 2019-06-20 2019-10-25 杭州永磁集团有限公司 The preparation method of high resistivity 2:17 type samarium cobalt permanent magnet body
CN113496816A (en) * 2020-03-18 2021-10-12 中国科学院宁波材料技术与工程研究所 Production method of samarium-cobalt-based permanent magnet block and samarium-cobalt-based permanent magnet block
CN116344191A (en) * 2023-03-28 2023-06-27 燕山大学 Method for improving effective deformation of magnetic powder material
CN116344191B (en) * 2023-03-28 2024-05-03 燕山大学 Method for improving effective deformation of magnetic powder material
CN116425206A (en) * 2023-04-06 2023-07-14 中国科学院宁波材料技术与工程研究所 Improve SrFe 12 O 19 Method for magnetic performance of ferrite

Also Published As

Publication number Publication date
CN107170543B (en) 2018-10-12

Similar Documents

Publication Publication Date Title
CN107170543B (en) The preparation method of Sm-Co based alloy block shaped magnets
CN102800454B (en) Low-cost double-main phase Ce permanent-magnet alloy and preparation method thereof
CN106128668B (en) A kind of preparation method of Nanocomposite rare earth permanent-magnetic material
CN103680919B (en) A kind of preparation method of the high anti-corrosion sintered Nd-Fe-B permanent magnet of tough height of high-coercive force
CN102543341B (en) Method for preparing anisotropic nanocrystalline rare-earth permanent magnet block material
Zakotnik et al. Hydrogen decrepitation and recycling of NdFeB-type sintered magnets
JPS62276803A (en) Rare earth-iron permanent magnet
CN100559519C (en) Sintered Nd-Fe-B permanent magnetic material with holmium to substitute dysprosium
JP5686213B1 (en) R-T-B permanent magnet
CN101673605B (en) Anisotropic nano/amorphous complex phase block permanent-magnetic material and preparation method thereof
CN103875047A (en) Rare earth permanent magnet and method for producing rare earth permanent magnet
CN105513738B (en) A kind of hot pressing nitrogenizes the preparation method of magnet
CN107622852A (en) A kind of preparation method of high-coercive force manganese gallium magnetic
JP5686212B1 (en) R-T-B permanent magnet
CN109754970B (en) Rare earth magnet and preparation method thereof
Jurczyk et al. Application of high energy ball milling to the production of magnetic powders from NdFeB-type alloys
Lv et al. Coercivity enhancement in Dy-free HDDR Nd-Fe-B powders by the grain boundary diffusion of Zn
CN111863369A (en) Magnetic binder and preparation method thereof, and preparation method of composite permanent magnetic material
TW202235640A (en) Main-auxiliary alloy series ndfeb magnet material and preparation method
JPH01171209A (en) Manufacture of permanent magnet
Zhao et al. Structure and performance of anisotropic nanocrystalline Nd-Fe-B magnets fabricated by high-velocity compaction followed by deformation
JP2013016628A (en) Method for producing rare-earth magnet
JP4240988B2 (en) Rare earth alloy granulated powder manufacturing method, rare earth alloy granulated powder manufacturing apparatus, and rare earth alloy sintered body manufacturing method
WO2024108851A1 (en) Samarium-iron-based rare earth permanent magnet material containing grain boundary phase, and preparation method therefor and use thereof
CN112466651B (en) Preparation method of rare earth-free high-performance composite 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