CN110136908A - A kind of rare earth permanent magnet composite material and preparation method - Google Patents

A kind of rare earth permanent magnet composite material and preparation method Download PDF

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CN110136908A
CN110136908A CN201910375538.3A CN201910375538A CN110136908A CN 110136908 A CN110136908 A CN 110136908A CN 201910375538 A CN201910375538 A CN 201910375538A CN 110136908 A CN110136908 A CN 110136908A
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rare earth
permanent magnet
earth permanent
composite material
matrix
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CN110136908B (en
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李明
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Ningbo Co Star Materials Hi Tech Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032Magnets 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
    • H01F1/04Magnets 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
    • H01F1/047Alloys characterised by their composition
    • H01F1/053Alloys characterised by their composition containing rare earth metals
    • H01F1/055Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032Magnets 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
    • H01F1/04Magnets 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
    • H01F1/047Alloys characterised by their composition
    • H01F1/053Alloys characterised by their composition containing rare earth metals
    • H01F1/055Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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
    • H01F41/14Apparatus 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 applying magnetic films to substrates
    • H01F41/18Apparatus 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 applying magnetic films to substrates by cathode sputtering

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Hard Magnetic Materials (AREA)
  • Manufacturing Cores, Coils, And Magnets (AREA)
  • Thin Magnetic Films (AREA)

Abstract

The present invention relates to a kind of rare earth permanent magnet composite material and preparation methods, belong to permanent-magnet material technical field, rare earth permanent magnet composite material includes rare earth permanent magnet matrix, surface transition thin layer and surface SmCo thin layer, successively adhere to one layer of transition zone and one layer of SmCo layer in matrix surface by specific preparation method, and make SmCo layer obtain the coercivity of superelevation by specific heat treatment process, finally prepare the rare earth permanent magnet composite material of high-coercive force.

Description

A kind of rare earth permanent magnet composite material and preparation method
Technical field
The present invention relates to a kind of rare earth permanent magnet composite material and preparation methods, belong to permanent-magnet material technical field.
Background technique
In recent years, the development of functional material effectively promotes the social progress of human society, and rare earth permanent-magnetic material is magnetic One of sexual function material is a kind of highest permanent-magnet material of currently known comprehensive performance, it is higher than the magnetic property of magnet steel More than 100 times, much than ferrite, alnico superior performance.Due to the use of rare earth permanent-magnetic material, permanent magnet devices are not only promoted To miniaturization, the performance of product is improved, and promotes the generation of certain particular devices, so rare earth permanent-magnetic material one goes out It is existing, cause the very big attention of various countries immediately, develops extremely rapid.Rare earth permanent-magnetic material can be divided mainly by ingredient: 1. cobalt-baseds are dilute Native permanent-magnet material, including Rare-Earth Cobalt (1-5 type) permanent-magnet material SmCo5With Rare-Earth Cobalt (2-17 type) permanent-magnet material Sm2Co17Two is big Class;2. neodymium base rare earth permanent magnet material, NdFeB permanent-magnet material.
Cobalt-based rare earth permanent-magnetic material is that a kind of excellent heat-resisting material is rectified since its Curie temperature is high (700-900 DEG C) Stupid power is high (> 25kOe), and temperature stability is good, therefore have in high temperature and high stability field can not for cobalt-based rare earth permanent-magnetic material The effect of substitution is still widely used for the fields such as rail traffic, military affairs and aerospace at present.But cobalt-based rare earth permanent-magnetic material Room temperature magnetic energy product it is relatively low (generally below 32MGOe), at present prepare high-performance cobalt-based rare earth permanent-magnetic material main method improve The theoretical remanent magnetism of the iron content of magnet, the cobalt-based rare earth permanent-magnetic material of high Fe content (iron content is greater than 20wt.%) can be up to 14kGs, theoretical magnetic energy product may be up to 49MGOe.But iron content, after raising, the microstructure of magnet is seriously damaged, and is passed through Traditional heat treatment process can not obtain ideal institutional framework, and it is serious that this causes the coercivity of magnet to deteriorate.
Neodymium base rare earth permanent magnet material is the strongest magnetic material of magnetism at present, is known as " magnetic king ", since its is excellent Magnetic property, have a wide range of applications in automotive field, energy saving household electrical appliances, elevators field and computer field etc..Neodymium base rare earth is forever Although magnetic material remanent magnetism and magnetic energy product are higher, high temperature demagnetization is the big restriction that temperature sensitivity is its application, especially The fields such as new-energy automobile, wind-power electricity generation, compressor, high-temperature stability requirement of the working condition to neodymium base rare earth permanent magnet material It is high, that is, require magnet to have higher intrinsic coercivity.It is well known that being formulated design aspect in neodymium base rare earth permanent magnet material, add Add heavy rare earth element such as Dy, Tb of part can greatly improve magnet intrinsic coercivity can significantly improve magnet high temperature it is steady It is qualitative.But, on the one hand, heavy rare earth element Dy, Tb resource are extremely rare and expensive, and the life of enterprise will be significantly greatly increased after addition Cost is produced, on the other hand, the magnetic energy product of magnet can be substantially reduced after addition heavy rare earth element Dy, Tb.Based on considerations above, exploitation The thinking progress that magnetic energy product should not be greatly reduced in line with that can improve intrinsic coercivity in high-temperature stability magnet again.Therefore, herein On the basis of, heavy rare earth surface penetration technology is come into being, and gradually becomes one of the hot spot of industry research, because it is saving weight It can be realized while rare earth β-diketone complex, Tb and increase substantially intrinsic coercivity in magnetic body without being substantially reduced magnetic energy product.Currently, surface Infiltration technology mainly includes surface coating technology, vacuum evaporation process and magnetron sputtering technique etc., and no matter which kind of technique is all that will weigh Rare earth β-diketone complex, Tb or its alloy are attached to neodymium base rare earth permanent magnet material matrix surface, then finally obtain in height by DIFFUSION TREATMENT Report coercitive neodymium base rare earth permanent magnet material.
Although heavy rare earth surface penetration technology improves the intrinsic coercivity of magnet magnetic energy product is not greatly reduced, still There are shortcomings.First is that there is still a need for use rare and expensive heavy rare earth Dy and Tb;Second is that the utilization rate of heavy rare earth is not high, with compared with For mature magnetron sputtering technique, the utilization rate of Dy and Tb target only has 50% or so, sputtered from target and It is attached to product surface heavy rare earth element only accounts for consumption target 80% or so, there is also about 20% to be wasted in magnetron sputtering stove On baffle, the utilization rate of entire magnetron sputtering process only has 40%.If counting Post isothermal treatment process and target preparation process in Middle heavy rare earth loss, heavy rare earth utilization rate can be lower, although usage amount is few in magnet, preparation process loss is very big.
Therefore, it in order to save heavy rare earth resource, while realizing and increasing substantially intrinsic coercivity in magnetic body without obviously dropping Low magnetic energy product, we still need to new technical solution.
Summary of the invention
In view of the above problems, the present invention provide it is a kind of have excellent performance, rare earth permanent magnet composite wood applied widely Material and preparation method thereof.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of rare earth permanent magnet composite material, the composite material include rare earth permanent magnet matrix, surface transition thin layer and surface SmCo thin layer.
Preferably, the demagnetizing factor PC value of the rare earth permanent magnet matrix is less than 1.5.Magnet is in demagnetization, due to itself The influence of demagnetizing field, magnet surface are equivalent to by bigger opposing magnetic field effect, and often surface is first by magnetic reversal.The present invention It is to improve the anti-demagnetization capability of magnet surface by improving the coercivity of magnet surface.And the permanent magnetism for isolating (single) Body, PC value are only related with the geomery of magnet.When the demagnetizing factor PC value of magnet is larger, magnet surface is first compared to internal It is not obvious by the feature of magnetic reversal, so the coercivity that the method provided through the invention is promoted is very limited, therefore matrix Preferential selection geomery of the demagnetizing factor PC value less than 1.5.
Preferably, the rare earth permanent magnet matrix includes neodymium base rare earth permanent magnet matrix, one in cobalt-based rare earth permanent magnet matrix Kind or two kinds.
Further preferably, the component molecules formula of the neodymium base rare earth permanent magnet matrix is (Nd1-xRx)11-18(Fe1-yMy)balB5-6.5, wherein R is one of Y, La, Ce, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a variety of, the range of x For 0-0.8;M is one of Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Al, In, Sn, Ag, Au, Mo, Nb, Zr, Hf, Ta, W or more Kind, the range of y is 0-0.2.
Further preferably, the cobalt-based rare earth permanent magnet matrix is the cobalt-based rare earth permanent magnet matrix of high Fe content low-coercivity, Its component molecules formula is (Sm1-xRx)(Co1-y-zFeyMz)b, R Y, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, The range of one of Lu or a variety of, x are 0-0.8;M be Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Al, In, Sn, Ag, Au, Mo, One of Nb, Zr, Hf, Ta, W, Si or a variety of, the range of z are 0-0.2, and the range of y is 0.28-0.5;The range of b is 6.5- 8.5;The cobalt-based rare earth permanent magnet matrix is 2:17 type samarium-cobalt material, and coercivity is lower than 15kOe, can pass through traditional powder smelting Gold process preparation.
Further preferably, in the component molecules formula of the cobalt-based rare earth permanent magnet matrix, 0.32≤y < 0.45.As 0.28≤y When < 0.32, cobalt-based rare earth permanent-magnetic material is generally 5-15kOe by magnet coercivity prepared by traditional preparation process, if logical The coercivity of 15-25kOe can also be obtained by crossing special and harsh heat treatment process.Therefore, the preparation method is in 0.28≤y < Advantage is not particularly evident in 0.32 composition range section, so select higher iron content, i.e. 0.32≤y < 0.45.
Preferably, the surface transition thin layer is between rare earth permanent magnet matrix and surface SmCo thin layer, be one layer or The metal layer of multilayer.
Further preferably, the metal layer includes one of layers of copper, iron layer, nickel layer or a variety of.
Further preferably, the metal layer is layers of copper.In the follow-up heat treatment process, transition zone can be to matrix and surface The diffusion of SmCo thin layer, copper not will lead to the coercitive deterioration of the two after diffusing to matrix and surface SmCo thin layer, instead There is gain effect to the coercivity of matrix and surface SmCo thin layer.In addition, copper is plastic material, it can be relieved in preparation process and generate Stress, increase the binding force between surface SmCo layer and matrix, so preferably layers of copper is surface depletion layer (i.e. metal Layer).
Further preferably, the surface transition thin layer with a thickness of 0-20 μm.
Further preferably, the thickness of the surface transition thin layer is also related with the material of rare earth permanent magnet matrix.
Further preferably, when rare earth permanent magnet matrix be neodymium base rare earth permanent magnet matrix when, surface transition thin layer with a thickness of 0.05-4μm.Because excessively thin transition zone is unfavorable for preventing the mutual extension between matrix and SmCo thin layer, this counterdiffusion can be tight The coercivity of the two is reduced again, and surface depletion layer is blocked up by the magnetic coupling being unfavorable between matrix and surface SmCo thin layer work With.
Further preferably, when rare earth permanent magnet matrix be cobalt-based rare earth permanent magnet matrix when, surface transition thin layer with a thickness of 0-4 μm.It is can choose at this time without transition zone, since matrix and SmCo superficial layer are all SmCos, and ferro element is molten in 1:5 SmCo Xie Du is very low, and counterdiffusion between the two is not very big to coercivity impact effect, and surface depletion layer is blocked up to be unfavorable for Magnetic coupling interaction between matrix and surface SmCo thin layer.
Preferably, the material of the surface SmCo thin layer is the 1:5 type SmCo of high-coercive force.Because 1:5 type SmCo exists The coercivity of ideal institutional framework and superelevation is easily obtained in attaching process and subsequent heat treatment process.
Preferably, the surface SmCo thin layer with a thickness of 0.005-50 μm.
Further preferably, the surface SmCo thin layer with a thickness of 1-10 μm.Thickness is too thin, and it is unknown that coercivity promotes effect Aobvious, thickness is too thick, and preparation time is long and cost advantage is unobvious, therefore preferential 1-10 μm of selection.
Preferably, the coercivity of the surface SmCo thin layer is greater than 25kOe.
The present invention is improved on the basis of neodymium base rare earth permanent magnet material (matrix) or cobalt-based rare earth permanent-magnetic material (matrix) The coercivity of magnet entirety, to achieve the purpose that save the cost and improve magnetic property.Rare earth permanent magnet composite material be by rare earth forever The surface SmCo thin layer of magnetic basis material, surface transition thin layer and high-coercive force forms, and wherein rare earth permanent magnet basis material can be with It is commercially available the cobalt-based rare earth permanent-magnetic material of rare-earth iron-based permanent-magnetic material or high Fe content low-coercivity, surface depletion layer can inhibit The phase counterdiffusion of matrix element and surface SmCo layer element in high-temperature heat treatment process, while can be relieved heat treatment heating and drop The stress generated during temperature increases the binding force between surface SmCo layer and matrix;The SmCo layer of high-coercive force is very big Ground improves the anti-demagnetization capability of rare earth permanent magnet matrix surface, and then improves the coercivity and temperature tolerance of magnet entirety, in addition Due to the protective effect of surface transition thin layer and surface SmCo thin layer, the corrosion resistance of rare earth permanent magnet composite material can obtain bright Aobvious raising.The present invention successively adheres to one layer of transition zone and one layer of SmCo layer in matrix surface by specific method, and passes through Specific heat treatment process makes SmCo layer obtain the coercivity of superelevation, finally obtains the rare earth permanent magnet composite wood of high-coercive force Material.
The present invention additionally provides another technical solution while reasonable selection material mixture ratio:
A kind of preparation method of rare earth permanent magnet composite material, described method includes following steps:
S1: surface transition thin layer is attached to rare earth permanent magnet matrix surface and obtains rare earth permanent magnet composite A;
S2: surface SmCo thin layer is attached to rare earth permanent magnet composite A surface and obtains rare earth permanent magnet composite material B;
S3: rare earth permanent magnet composite material B is carried out to be heat-treated to obtain rare earth permanent magnet composite material.
Preferably, attachment described in S1, S2 is all made of one or both of magnetron sputtering technique, electroplating technology.
Further preferably, attachment described in S1 uses one of magnetron sputtering technique, electroplating technology, it is highly preferred that using Magnetron sputtering technique.Because comparing electroplating technology, magnetron sputtering technique can obtain thickness of coating and consistency more evenly, and The material transfer process involved in technique preparation process is less.
Further preferably, the current density of the electroplating technology of S1 is 0.1-0.5A/dm2, electroplating time 0.1-8h, formation Surface transition thickness of thin layer be 1-20 μm.
Further preferably, the magnetron sputtering technique of S1 carries out in argon atmosphere, power 6-100KW, and the time is 0.1-10h, the surface transition thickness of thin layer of formation are 0.005-20 μm.
Further preferably, the magnetron sputtering technique that S1 is used is also related with the material of rare earth permanent magnet matrix.
Further preferably, when rare earth permanent magnet matrix is neodymium base rare earth permanent magnet matrix, the magnetron sputtering plating time is 0.2- 2h, surface depletion layer thickness range are 0.05-2 μm.
Further preferably, when rare earth permanent magnet matrix is cobalt-based rare earth permanent magnet matrix, the magnetron sputtering plating time is 0-2h, Surface depletion layer thickness range is 0-2 μm.
Further preferably, attachment described in S2 uses magnetron sputtering technique, and S2 magnetron sputtering technique is in argon atmosphere It carries out, power 6-100KW, time 0.1-25h, the surface transition thickness of thin layer of formation is 0.005-50 μm.
Further preferably, in S2 magnetron sputtering technique plated film time be 1-10h, surface SmCo thin layer with a thickness of 1-10 μ m。
Preferably, being heat-treated described in S3 specifically: rare earth permanent magnet composite material B is warming up to 800-950 DEG C, and is kept the temperature Then 0.5-10h is cooled to room temperature with 20-200 DEG C/min.
Further preferably, it is heat-treated described in S3 also related with the material of rare earth permanent magnet matrix.
Further preferably, when matrix is neodymium base rare earth permanent magnet matrix, rare earth permanent magnet composite material B is warming up to 850- 920 DEG C, and 0.5-2h is kept the temperature, it is then cooled to room temperature with 20-200 DEG C/min, then rare earth permanent magnet composite material B is warming up to 450-550 DEG C, and 3-8h is kept the temperature, then quickly cooling to room temperature, obtains rare earth permanent magnet composite material.850-920 DEG C and 450-550 DEG C this Two temperature ranges are respectively the first order heat treatment temperature section and second level aging temp section of neodymium base rare earth permanent magnet matrix, I the study found that have already passed through two-stage heat treatment neodymium base rare earth permanent magnet magnet, then carry out two-stage heat treatment will not destroy base The institutional framework and the original coercivity of deterioration of body, therefore commercially available neodymium base rare earth permanent magnet material can choose by two-stage two-stage Magnet after heat treatment also can choose without the magnet after two-stage treatment.In addition, 850-920 DEG C of temperature range is also The aging temp section of 1:5 type SmCo is heat-treated in this temperature, can restore that 1:5 type SmCo skin layer is original to be rectified Stupid power even improves original coercivity, I also found that the 1:5 type surface SmCo thin layer after Wetted constructures exists again at research Heat preservation is carried out at 450-550 DEG C will not destroy its coercivity, therefore entire rare earth permanent magnet composite material exhibits is finally made to go out surface The feature (surface coercivity is obviously higher) of " hardening ".The soaking time of 0.5-2h is selected primarily to guaranteeing 1:5 type samarium Cobalt shortens heat treatment time under the premise of abundant timeliness as far as possible.
Further preferably, when matrix is cobalt-based rare earth permanent magnet matrix, rare earth permanent magnet composite material B is warming up to 800- 850 DEG C, and 0.5-2h is kept the temperature, it is then cooled to room temperature with 20-200 DEG C/min, obtains rare earth permanent magnet composite material.The temperature range It is both the heat treatment temperature section and the aging temp section of 1:5 type SmCo of cobalt-based rare earth permanent-magnetic material, therefore in this temperature Section will not destroy the institutional framework of matrix and deteriorate original coercivity, while it is former to restore 1:5 type SmCo skin layer The coercivity come even improves original coercivity, and entire rare earth permanent magnet composite material exhibits is made to go out the feature of surface " hardening " (surface coercivity is obviously higher).The soaking time of 0.5-2h is selected primarily to guaranteeing 1:5 type SmCo in abundant timeliness Under the premise of shorten heat treatment time as far as possible.
Compared with other materials, the present invention has the advantage that
(1) present invention is substantially reduced the use of expensive heavy rare earth (2000-5000 member/kg), and final preparation cost is obvious It reduces, has saved valuable rare earth resources.
(2) neodymium base rare earth permanent magnet composite material of the invention (matrix is neodymium base rare earth permanent magnet material) is since surface is attached to Transition thin layer and surface SmCo thin layer, the anticorrosion effect of both thin layers is preferable, can significantly improve the corrosion resistant of material entirety Lose characteristic.
(3) neodymium base rare earth permanent magnet composite material (matrix is neodymium base rare earth permanent magnet material) is difficult through traditional powder metallurgy Technique preparation, although can be prepared with heavy rare earth surface penetration technology, higher cost, preparation method provided by the invention at Originally it can substantially reduce.
(4) cobalt-based rare earth permanent magnet composite material of the invention (matrix is cobalt-based rare earth permanent-magnetic material) overcomes high Fe content to rectify The relatively low deficiency of stupid power, preparation process through the invention can prepare iron content and be up to 23wt% or more, and remanent magnetism is greater than 12kGs, magnetic energy product is greater than 35MGOe very-high performance samarium-cobalt magnet, and this superelevation magnetic property samarium-cobalt magnet is non-using traditional handicraft Batch is often difficult to prepare.
(5) rare earth permanent magnet composite material magnetic property provided by the invention is high (compared to trade mark product), cheap, preparation Process is easily operated, is convenient for industrialization.
Specific embodiment
The following is specific embodiments of the present invention, and technical scheme of the present invention will be further described, but the present invention is simultaneously It is not limited to these embodiments.
Embodiment 1
S1: selection rare earth permanent magnet matrix is neodymium base rare earth permanent magnet matrix N50M, and ingredient is (Nd78.7Pr20.1Dy1.2)13.7 (Fe97.64Co1.4Al0.3Cu0.13Zr0.06Ga0.23)80.53B5.77, matrix is having a size of 30mm × 20mm × 1.5mm, the direction 1.5mm Magnetizing direction, PC value are 0.12, and the remanent magnetism Br of material is 14.63kGs, and coercivity H j is 14.89kOe, magnetic energy product (BH)mFor 52.18MGOe carries out magnetron sputtering transition thin copper layer on above-mentioned matrix, and target is selected as copper target material, and plated film atmosphere is argon Gas shielded atmosphere, plated film power are 40KW, and plated film time 1h, coating film thickness is 2 μm, obtains rare earth permanent magnet composite A;
S2: attachment SmCo skin layer, target choosing are sputtered on rare earth permanent magnet composite A surface using magnetron sputtering technique It selects 1:5 type samarium-cobalt material (coercivity be greater than 25kOe), plated film atmosphere is argon atmosphere, and plated film power is 40KW, when plated film Between be 5h, coating film thickness be 10 μm, obtain rare earth permanent magnet composite material B;
S3: being warming up to 880 DEG C for rare earth permanent magnet composite material B and keep the temperature 2h, then quick with 30 DEG C/min cooling velocity It is cooled to room temperature, is then warming up to 490 DEG C again and keeps the temperature 5h, obtain rare earth permanent magnet composite material.
Embodiment 2
S1: selection rare earth permanent magnet matrix is neodymium base rare earth permanent magnet matrix N48SH, and ingredient is (Nd74.55Pr19.08Dy2.38Ho3.99)13.30(Fe97.16Co1.37Al1.05Cu0.19Zr0.06Ga0.17)80.94B5.76, matrix having a size of The direction 20mm × 20mm × 2mm, 2mm is magnetizing direction, and PC value is 0.19, and the remanent magnetism Br of material is 13.94kGs, coercivity H j For 20.01kOe, magnetic energy product (BH)mFor 47.61MGOe, magnetron sputtering transition thin copper layer, target choosing are carried out on above-mentioned matrix It is selected as copper target material, plated film atmosphere is argon atmosphere, and plated film power is 40KW, and plated film time 1h, coating film thickness is 2 μm, Obtain rare earth permanent magnet composite A;
S2: attachment SmCo skin layer, target choosing are sputtered on rare earth permanent magnet composite A surface using magnetron sputtering technique It selects 1:5 type samarium-cobalt material (coercivity be greater than 25kOe), plated film atmosphere is argon atmosphere, and plated film power is 40KW, when plated film Between be 4h, coating film thickness be 5 μm, obtain rare earth permanent magnet composite material B;
S3: being warming up to 880 DEG C for rare earth permanent magnet composite material B and keep the temperature 2h, then quick with 30 DEG C/min cooling velocity It is cooled to room temperature, is then warming up to 490 DEG C again and keeps the temperature 5h, obtain rare earth permanent magnet composite material.
Embodiment 3
S1: selection rare earth permanent magnet matrix is cobalt-based rare earth permanent magnet matrix, ingredient Sm (CobalFe0.32Cu0.055Zr0.02)7.85, matrix is magnetizing direction having a size of 25mm × 20mm × 2mm, the direction 2mm, and PC value is 0.17, the remanent magnetism Br of material are 12.10kGs, and coercivity H j is 14.01kOe, magnetic energy product (BH)mFor 32.10MGOe, above-mentioned Magnetron sputtering transition thin copper layer is carried out on matrix, target is selected as copper target material, and plated film atmosphere is argon atmosphere, plated film function Rate is 40KW, and plated film time 0.5h, coating film thickness is 1 μm, obtains rare earth permanent magnet composite A;
S2: attachment SmCo skin layer, target choosing are sputtered on rare earth permanent magnet composite A surface using magnetron sputtering technique It selects 1:5 type samarium-cobalt material (coercivity be greater than 25kOe), plated film atmosphere is argon atmosphere, and plated film power is 40KW, when plated film Between be 4h, coating film thickness be 8 μm, obtain rare earth permanent magnet composite material B;
S3: being warming up to 840 DEG C for rare earth permanent magnet composite material B and keep the temperature 2h, then quick with 30 DEG C/min cooling velocity It is cooled to room temperature, obtains rare earth permanent magnet composite material.
Embodiment 4
S1: selection rare earth permanent magnet matrix is cobalt-based rare earth permanent magnet matrix, ingredient Sm (CobalFe0.36Cu0.055Zr0.02)7.85, matrix is magnetizing direction having a size of 25mm × 20mm × 2mm, the direction 2mm, and PC value is 0.17, the remanent magnetism Br of material are 12.35kGs, and coercivity H j is 11.82kOe, magnetic energy product (BH)mFor 31.03MGOe, above-mentioned Magnetron sputtering transition thin copper layer is carried out on matrix, target is selected as copper target material, and plated film atmosphere is argon atmosphere, plated film function Rate is 40KW, and plated film time 0.5h, coating film thickness is 1 μm, obtains rare earth permanent magnet composite A;
S2: attachment SmCo skin layer, target choosing are sputtered on rare earth permanent magnet composite A surface using magnetron sputtering technique It selects 1:5 type samarium-cobalt material (coercivity be greater than 25kOe), plated film atmosphere is argon atmosphere, and plated film power is 40KW, when plated film Between be 4h, coating film thickness be 8 μm, obtain rare earth permanent magnet composite material B;
S3: being warming up to 835 DEG C for rare earth permanent magnet composite material B and keep the temperature 2h, then quick with 30 DEG C/min cooling velocity It is cooled to room temperature, obtains rare earth permanent magnet composite material.
Embodiment 5
Difference with embodiment 4 is only that, the non-cohesive surface transition thin layer of embodiment 5.
Embodiment 6
Difference with embodiment 1 is only that, the non-cohesive surface transition thin layer of embodiment 6.
Embodiment 7
Difference with embodiment 1 is only that, 7 surface transition thin layer of embodiment with a thickness of 0.04 μm.
Embodiment 8
Difference with embodiment 1 is only that, 8 surface transition thin layer of embodiment with a thickness of 5 μm.
Embodiment 9
Difference with embodiment 3 is only that, 9 surface transition thin layer of embodiment with a thickness of 5 μm.
Comparative example 1
Difference with embodiment 1 is only that comparative example 1 is heat-treated without S3.
Comparative example 2
Difference with embodiment 1 is only that comparative example 2 only carries out the cooling that heats up for the first time, protects without second of heating Temperature, i.e., without " and then be warming up to 490 DEG C again and keep the temperature 5h " operation.
Comparative example 3
Difference with embodiment 1 is only that comparative example 3 is without S2 processing.
Comparative example 4
Difference with embodiment 1 is only that having a size of 30mm × 20mm × 15mm, the direction 15mm is the matrix of comparative example 4 Magnetizing direction, PC value are 1.63.
Comparative example 5
Difference with embodiment 1 is only that for the matrix of comparative example 5 having a size of 30mm × 20mm × 8mm, the direction 8mm is to fill Magnetic direction, PC value are 0.75.
Comparative example 6
Difference with embodiment 3 is only that comparative example 6 is without S2 processing.
Comparative example 7
Difference with embodiment 3 is only that comparative example 7 is heat-treated without S3.
The rare earth permanent magnet composite material that embodiment 1-9 and comparative example 1-7 is obtained carries out magnetism testing, as a result such as table 1 It is shown:
Table 1: the technological parameter and magnetic property of composite material in embodiment 1-9 and comparative example 1-7
The Magnetic Test of product is directly tested by sample size, and direction of magnetization height presses lamination side less than 4mm product Formula carries out test magnetic property, although the standard specimen test relative to D10x10 has error, error is smaller, does not influence sxemiquantitative and sentences It is fixed.
As can be seen from Table 1:
According to embodiment 1 as a result, preparation method provided by the invention is passed through in discovery, remanent magnetism and magnetic energy product are slightly decreased, It is basically unchanged, the coercivity of magnet improves 5.26kOe, reaches the magnetic property standard of N50SH.
According to embodiment 2 as a result, preparation method provided by the invention is passed through in discovery, remanent magnetism and magnetic energy product are slightly decreased, It is basically unchanged, the coercivity of magnet improves 5.03kOe, has reached the magnetic property standard of N48UH.
According to embodiment 3 as a result, preparation method provided by the invention is passed through in discovery, remanent magnetism is slightly decreased, is basically unchanged, The coercivity of magnet improves 5.79kOe, and magnetic energy product also improves 2.66MGOe, and coercivity is promoted to 19.80kOe, has reached one As requirement.
According to embodiment 4 as a result, preparation method provided by the invention is passed through in discovery, remanent magnetism is slightly decreased, is basically unchanged, The coercivity of magnet improves 5.31kOe, and magnetic energy product also improves 4.86MGOe, and coercivity is promoted to 17.13kOe, has reached one As requirement.
Embodiment 4 and embodiment 5 are compared, the coercivity of rare earth permanent magnet composite material prepared by discovery embodiment 5 is promoted Amplitude is slightly more, and difference is little, illustrates when matrix is cobalt-based rare earth permanent-magnetic material, can be with non-cohesive transition zone.This is because base Body and SmCo superficial layer are all SmCos, and ferro element solubility in 1:5 SmCo is very low, and counterdiffusion between the two is to coercive Power impact effect is not very big.
Embodiment 1 and embodiment 6 are compared, it is found that when matrix is neodymium base rare earth permanent magnet material, transition zone is not dilute The coercivity of native permanent-magnetic composite materials does not increase, and reduces instead, this is because counterdiffusion causes between matrix and SmCo superficial layer The result that coercivity deteriorates.
Embodiment 1 and comparative example 1 are compared, it is found that when matrix is neodymium base rare earth permanent magnet material, be without S3 processing The coercivity for the rare earth permanent magnet composite material not being heat-treated can not be improved.
Embodiment 1 and comparative example 2 are compared, it is found that when matrix is neodymium base rare earth permanent magnet material, do not carry out second level heat The coercivity of the rare earth permanent magnet composite material of i.e. 490 DEG C heat preservation 5h of processing does not rise anti-reduction.
Embodiment 1 and comparative example 3 are compared, it is found that when matrix is neodymium base rare earth permanent magnet material, unattached surface The coercivity of the neodymium base rare earth permanent magnet composite material of SmCo layer does not increase substantially.
Embodiment 1 and comparative example 4 are compared, when the PC value of discovery neodymium base rare earth permanent magnet material is 1.63, material It is very faint that coercivity promotes effect.
Embodiment 1 and comparative example 5 are compared, when the PC value of discovery neodymium base rare earth permanent magnet material is 0.75, material Coercivity promotes amplitude and there was only 2.18kOe, promotes effect and is substantially reduced.
Embodiment 3 and comparative example 6 are compared, it is found that when matrix is cobalt-based rare earth permanent-magnetic material, unattached surface The coercivity of the cobalt-based rare earth permanent magnet composite material of SmCo layer cannot be improved.
Embodiment 3 and comparative example 7 are compared, it is found that when matrix is cobalt-based rare earth permanent-magnetic material, at S3 The coercivity for managing the cobalt-based rare earth permanent magnet composite material not being heat-treated cannot be improved.
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited For technical staff, as long as it is obvious for can making various changes or correct without departing from the spirit and scope of the present invention.

Claims (10)

1. a kind of rare earth permanent magnet composite material, which is characterized in that the composite material includes that rare earth permanent magnet matrix, surface transition are thin Layer and surface SmCo thin layer.
2. a kind of rare earth permanent magnet composite material according to claim 1, which is characterized in that the rare earth permanent magnet matrix moves back Magnetic system number PC value is less than 1.5.
3. a kind of rare earth permanent magnet composite material according to claim 1, which is characterized in that the rare earth permanent magnet matrix includes One or both of neodymium base rare earth permanent magnet matrix, cobalt-based rare earth permanent magnet matrix.
4. a kind of rare earth permanent magnet composite material according to claim 1, which is characterized in that the surface transition thin layer between It is one or more layers metal layer between rare earth permanent magnet matrix and surface SmCo thin layer.
5. a kind of rare earth permanent magnet composite material according to claim 4, which is characterized in that the metal layer include layers of copper, One of iron layer, nickel layer are a variety of.
6. a kind of rare earth permanent magnet composite material according to claim 1 or 4, which is characterized in that the surface transition thin layer With a thickness of 0-20 μm.
7. a kind of rare earth permanent magnet composite material according to claim 1, which is characterized in that the thickness of the surface SmCo thin layer Degree is 0.005-50 μm.
8. a kind of preparation method of rare earth permanent magnet composite material, which is characterized in that described method includes following steps:
S1: surface transition thin layer is attached to rare earth permanent magnet matrix surface and obtains rare earth permanent magnet composite A;
S2: surface SmCo thin layer is attached to rare earth permanent magnet composite A surface and obtains rare earth permanent magnet composite material B;
S3: rare earth permanent magnet composite material B is carried out to be heat-treated to obtain rare earth permanent magnet composite material.
9. a kind of preparation method of rare earth permanent magnet composite material according to claim 8, which is characterized in that described in S1, S2 Attachment is all made of one or both of magnetron sputtering technique, electroplating technology.
10. a kind of preparation method of rare earth permanent magnet composite material according to claim 8, which is characterized in that heat described in S3 Processing specifically: rare earth permanent magnet composite material B is warming up to 800-950 DEG C, and keeps the temperature 0.5-10h, then with 20-200 DEG C/ Min is cooled to room temperature.
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Publication number Priority date Publication date Assignee Title
CN113451038A (en) * 2021-06-07 2021-09-28 杭州永磁集团有限公司 Preparation method of samarium-cobalt permanent magnet suitable for high-temperature high-pressure pure hydrogen environment

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JPS5848608A (en) * 1981-09-18 1983-03-22 Tohoku Metal Ind Ltd Production of permanent magnet of rare earths
JPS61170004A (en) * 1985-01-24 1986-07-31 Namiki Precision Jewel Co Ltd Permanent magnetic body
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CN113451038A (en) * 2021-06-07 2021-09-28 杭州永磁集团有限公司 Preparation method of samarium-cobalt permanent magnet suitable for high-temperature high-pressure pure hydrogen environment
CN113451038B (en) * 2021-06-07 2023-05-02 杭州永磁集团有限公司 Preparation method of samarium cobalt permanent magnet suitable for high-temperature high-pressure pure hydrogen environment

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