CN108015293A - A kind of dual alloy Fe-B rare-earth permanent magnet and its manufacture method - Google Patents

A kind of dual alloy Fe-B rare-earth permanent magnet and its manufacture method Download PDF

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CN108015293A
CN108015293A CN201711396990.5A CN201711396990A CN108015293A CN 108015293 A CN108015293 A CN 108015293A CN 201711396990 A CN201711396990 A CN 201711396990A CN 108015293 A CN108015293 A CN 108015293A
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permanent magnet
parts
rare
alloy
phase alloy
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CN108015293B (en
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赵渭敏
于博
赵胤杰
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Ningbo Jinlun Magnetic Material Technology Co Ltd
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Ningbo Jinlun Magnetic Material Technology Co Ltd
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    • 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
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • 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
    • B22F9/023—Hydrogen absorption
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/241—Chemical after-treatment on the surface
    • B22F2003/242—Coating
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Abstract

The invention discloses a kind of dual alloy Fe-B rare-earth permanent magnet and its manufacture method, solves a kind of dual alloy Fe-B rare-earth permanent magnet and is easily aoxidized in atmosphere, and corrosion resistance is poor, its key points of the technical solution are that：A kind of dual alloy Fe-B rare-earth permanent magnet, the permanent magnet include main-phase alloy and auxiliary phase alloy according to 15:The magnetic body that 1 mixed sintering forms；The surface of magnetic body is also plated with the Ni-based layer of anti-corrosion and acrylic acid protective layer, is played a protective role by coating to permanent magnet, improves the corrosion resistance of permanent magnet.

Description

A kind of dual alloy Fe-B rare-earth permanent magnet and its manufacture method
Technical field
The present invention relates to permanent-magnet material, more particularly to a kind of dual alloy Fe-B rare-earth permanent magnet and its manufacture method.
Background technology
Neodymium-iron-boron magnetic material is the alloy of praseodymium neodymium metal, ferro-boron etc., and also known as magnet steel, neodymium iron boron have high magnetic energy product With strong power, more and more applied with the magnetic property that its is excellent, be widely used in the Magnetic resonance imaging of medical treatment, computer Hard disk drive, sound equipment, mobile phone etc.；With energy saving and low-carbon economy requirement, Nd-Fe-B rare earth permanent magnetic material starts in vapour again Car parts, household electrical appliance, energy saving and control motor, hybrid vehicle, field of wind power generation application.
Neodymium in Nd-Fe-B permanent magnet is a kind of rare earth element, and chemism is very strong, its standard equilibration current potential is- 2.431V, is easily aoxidized, corrosion resistance is poor in atmosphere.And in sintered Nd-Fe-B permanent magnetic material richness B phases, rich-Nd phase, The electrochemical potentials of Nd2Fe14B phases is different, and the electrode potential of rich-Nd phase is defeated by matrix Nd2Fe14B phases, quantity on crystal boundary Numerous rich neodymium phases, forms corrosion micro cell in damp and hot environment, constitutes many big cathode (Nd2Fe14B phases) and primary anode The micro cell group of (Nd phases) composition.Rich-Nd phase is corroded first, forms intercrystalline corrosion, when serious, produces the oxide of a large amount of Nd Make material dusting with hydride, so as to cause magnetic property to decline.
The content of the invention
First purpose of the present invention is to provide a kind of dual alloy Fe-B rare-earth permanent magnet, and permanent magnet is risen by coating To protective effect, the corrosion resistance of permanent magnet is improved.
The present invention above-mentioned technical purpose technical scheme is that：
A kind of dual alloy Fe-B rare-earth permanent magnet, the permanent magnet include main-phase alloy and auxiliary phase alloy according to 15:1 mixing is burnt Tie the magnetic body formed；
Main-phase alloy is (Pr1-xNdx)29Co3Zr0.2Fe66.8B1, 0 ＜ x ＜ 1；
Auxiliary phase alloy is (Pr1-yNdy)10Dy20Co2Al8Ga4Fe55B1, 0 ＜ y ＜ 1；
The surface of magnetic body is also plated with the Ni-based layer of anti-corrosion.
By using above-mentioned technical proposal, using PrNd alloys compared to directly utilizing Nd simple substance to sinter, its cost is significantly Decline；In main-phase alloy, the addition of Co can strengthen exchange-coupling interaction, improve magnet temperature stability, improve Nd2Fe14The ratio of B phases, to improve the performances such as magnet remanent magnetism, magnetic energy product；The addition of Zr can crystal grain thinning, reduce soft, Hard Magnetic The crystallization temperature difference of phase；The addition of Dy improves each diversity of hard magnetic phase, increases magnet coercivity；The addition of Al and Ga can promote It is uniformly distributed into precipitate size, improves magnet micro-structure, improves the summation performance of magnet；The compound addition of Dy, Ga, Al and Co The corrosion resistance of permanent magnet can be improved；The Ni-based layer of anti-corrosion is stronger to the adhesive force of magnet, the hardness and wearability of coating compared with It is good, and permanent magnet and external environment condition can be isolated, play a protective role to permanent magnet, so as to improve the corrosion-resistant of permanent magnet Property.
Second object of the present invention is to provide a kind of manufacture method of dual alloy Fe-B rare-earth permanent magnet.
The present invention above-mentioned technical purpose technical scheme is that：
A kind of manufacture method of dual alloy Fe-B rare-earth permanent magnet, includes following steps：
Step1, main-phase alloy and auxiliary phase alloy smelting ingot casting；
Step2, main-phase alloy ingot casting is quick-fried by carrying out hydrogen after high annealing；
Step3, it is quick-fried to carry out hydrogen by auxiliary phase alloy ingot casting；
Step4, powder is broken into by main-phase alloy ingot casting of the hydrogen after quick-fried and auxiliary phase alloy ingot casting, and is sieved；
Step5, by the main-phase alloy powder after screening and auxiliary phase alloy powder according to 15：Added after 1 mixing and account for main-phase alloy powder The lubricant of last and auxiliary phase alloy powder gross mass 0.01% carries out batch mixing；
Step6, after the completion of batch mixing, by vacuum-sintering and is heat-treated, obtains magnetic body；
Step7, is located at permanent magnet surfaces by chemical plating plating by nickel-plating liquid, forms the Ni-based layer of anti-corrosion.
By using above-mentioned technical proposal, the presence of α-Fe phases in ingot casting can be reduced using high annealing；HD process It is in polyhedral that can make powder, improves size distribution, improves intrinsic coercivity；The addition of lubricant can lift mixing process In processing performance, improve material between dispersiveness, make mixing process more uniform；Pass through heat treatment, it is possible to increase magnet Coercivity.
Preferably, in Step5, lubricant is preferably 1500 mesh silicon powders.
By using above-mentioned technical proposal, silicon powder is used for the scattered of material and stablizes, meanwhile, Si elements can improve non- The stability in crystal zone, enhancing Grain-Boundary Phase is formed and enrichment, reduces the situation that permanent magnet cracks in sintering.
Preferably, nickel-plating liquid adds the Nd for accounting for Nickel in Nickel Sulphate Plating Bath gross mass 0.2%, 0.1% Zr simultaneously before chemical plating Pass through ultrasonic disperse.
By using above-mentioned technical proposal, the combination power of magnet and coating is capable of in the addition of Nd and Zr, while plays toughness reinforcing Effect, by ultrasonic disperse, can be such that Nd and Zr is more dispersed in nickel-plating liquid, plated film is kept continuous, more uniform.
Preferably, after the Ni-based layer of chemical plating anti-corrosion, which has further included Step8, in the Ni-based layer table of anti-corrosion Bread covers acrylic acid protective layer.
By using above-mentioned technical proposal, acrylic acid protective layer has excellent water proofing property, resistance to chemical attack and bonding Performance, there is the higher degree of cross linking can fill up the hole in the Ni-based layer of anti-corrosion for it, improves compactness, further improves permanent magnet Corrosion resistance.
Preferably, acrylic acid protective layer is formed by metal protection liquid coating, metal protection liquid includes component A and B groups Point, component A includes 27-30 parts of methyl methacrylate, 6-8 parts of n-BMA, 30-40 parts of styrene, propylene 2-5 parts sour, 2-5 parts of n-butyl acrylate, 10-20 parts of aqueous epoxy resins, 0.2-0.8 parts of ammonium persulfate, lauryl mercaptan 0.2-0.8 parts, 1.2-2.0 parts of ammonium hydroxide, 1.2-3.0 parts of polyoxyethylene ether, 50-80 parts of deionized water；B component includes epoxy and consolidates Agent.
By using above-mentioned technical proposal, the addition of epoxy resin can improve the hardness and strength of system, improve at the same time Adhesion strength, wearability is preferable, and lauryl mercaptan and ammonium persulfate can be used as initiator and chain-transferring agent to make acrylic acid And autohemagglutination or outer poly- occurs for acrylate, improves the degree of cross linking of system, while react with epoxy resin, improve system Tensile strength and impact strength.
Preferably, epoxy hardener is made of polyamide, diethylenetriamine and benzoyl peroxide, wherein polyamide：Two Ethene triamine：Benzoyl peroxide mass ratio is 5:3:2.
By using above-mentioned technical proposal, polyamide has good toughening effect to curing, reduces cracking, diethylenetriamine Addition can speed up solidification process.
Preferably, component A has further included 10-15 parts of magnesium hydroxide, 10-15 parts of titanium dioxide, 3-5 parts of aluminium hydroxide.
By using above-mentioned technical proposal, both magnesium hydroxide and aluminium hydroxide, which can act synergistically, improves flame retardant effect, And titanium dioxide can improve the heat-resisting effect of system, so that the defects of density polyamide heat resistance is low.
Preferably, component A has further included 0.3-0.5 parts of silane coupling agents.
By using above-mentioned technical proposal, silane coupling agent can change magnesium hydroxide, aluminium hydroxide and titanium dioxide surface Property, improve magnesium hydroxide, aluminium hydroxide and titanium dioxide and the adhesive property of system.
To sum up, the invention has the advantages that：
1st, the dual alloy Fe-B rare-earth permanent magnet plays permanent magnet protection by the Ni-based layer of anti-corrosion and acrylic acid protective layer and makees With improving the corrosion resistance of permanent magnet；
2nd, the dual alloy NdFeB rear-earth adds in chemical nickel plating bath in preparation process and accounts for Nickel in Nickel Sulphate Plating Bath gross weight 0.2% Nd, 0.1% Zr and by ultrasonic disperse, improve the bond strength of the Ni-based layer of anti-corrosion and magnetic body；
3rd, the dual alloy NdFeB rear-earth improves third in preparation process by adding magnesium hydroxide, aluminium hydroxide, titanium dioxide The heat resistance of olefin(e) acid protective layer, so as to improve protecting effect of the acrylic acid protective layer to the Ni-based layer of anti-corrosion.
Brief description of the drawings
Fig. 1 is the structure diagram of permanent magnet；
Fig. 2 is the manufacture method flow chart of permanent magnet.
In figure, 1, magnetic body；2nd, the Ni-based layer of anti-corrosion；3rd, acrylic acid protective layer.
Embodiment
The present invention is described in further detail below in conjunction with attached drawing.
Embodiment 1
Referring to Fig. 1, a kind of dual alloy Fe-B rare-earth permanent magnet, includes magnetic body 1, is located at magnetic body 1 by chemical plating plating The Ni-based layer 2 of outer anti-corrosion and the acrylic acid protective layer 3 for being coated on Ni-based 2 periphery of layer of anti-corrosion.
Embodiment 2a
Referring to Fig. 2, a kind of manufacture method of dual alloy Fe-B rare-earth permanent magnet, includes following steps：
Step1.1, chooses the Pr-Nd alloys that purity is more than 99.8%, and wherein Pr accounts for the 20% of Pr-Nd alloy gross weights；Choose Purity is more than 99.8%B-Fe alloys, and wherein B accounts for the 20% of B-Fe alloy gross weights；
Step1.2.1, weighs the Pr-Nd alloys of 29 parts by weight, the Co of 3 parts by weight, the Zr of 0.2 parts by weight, 61.8 parts by weight Fe, the B-Fe alloys of 5 parts by weight, add Fe, B-Fe alloy, Pr-Nd alloys, Co, Zr, in argon gas in vacuum smelting furnace successively Atmosphere, 1300 DEG C of smelting ingot castings, not blow-on natural cooling, obtains main-phase alloy ingot casting；
Step1.2.2, weighs the Pr-Nd alloys of 10 parts by weight, the Dy of 20 parts by weight, the Co of 2 parts by weight, the Al of 8 parts by weight, and 4 The B-Fe alloys of the Ga of parts by weight, the Fe of 50 mass parts and 5 mass parts, added successively in vacuum smelting furnace Fe, B-Fe alloy, Pr-Nd alloys, Dy, Co, Al, Ga, in argon atmosphere, 1300 DEG C of smelting ingot castings, blow-on takes ingot, obtains auxiliary phase alloy ingot casting；
Step2.1, heats the vacuum smelting furnace in Step1.2.1 again, smelly to be evacuated to 2.5 × 10-2After Pa, heating is opened up, 6 DEG C/min is warming up to 850 DEG C, keeps the temperature 1h, and 6 DEG C/min is continuously heating to 1080 DEG C, is evacuated to 5 × 10-2When Pa insulations 8 are small, Natural cooling, takes out main-phase alloy ingot casting；
Step2.2,50 × 50 × 50mm is cut into by the main-phase alloy ingot casting that Step2.1 is obtained3Square block, be sent into XZHD-500 types hydrogen blasting furnace carries out the quick-fried processing of hydrogen；
Step3, the auxiliary phase alloy ingot casting that Step1.2.2 is obtained are cut into 50 × 50 × 50mm3Square block, be sent into XZHD-500 types hydrogen blasting furnace carries out the quick-fried processing of hydrogen；
Step4.1,100 mesh are taken to the main-phase alloy of 500 mesh by the main-phase alloy ingot casting of the quick-fried processing of hydrogen by Mechanical Crushing, screening Powder；Step4.2, takes 100 mesh to be harmonious to 500 purposes are auxiliary on the auxiliary phase alloy ingot casting of the quick-fried processing of hydrogen by Mechanical Crushing, screening Bronze end；Step5.1, by main-phase alloy powder and auxiliary phase alloy powder according to 15：It is finely ground to after 1 mixing by airflow milling Powder size is less than 2000 mesh；
Step5.2, adds the 1500 mesh silicon powders for accounting for main-phase alloy powder and auxiliary phase alloy powder gross mass 0.01% in batch mixing Nitrogen atmosphere, 100r/min batch mixings 2h in machine；
Step6.1, is pressed into base after the completion of batch mixing by static pressure machine, adds in vacuum sintering furnace, and 6/min is started to warm up, heating To 250 DEG C of insulations 1h, 500 DEG C of insulations 2h, 700 DEG C of insulations 2h, 1100 DEG C of insulation 5h；
Step6.2, is naturally cooling to 800 DEG C of insulations 2h, 600 DEG C of insulation 3h；Cooled to room temperature, obtains permanent magnet；
Step7, from the chemical nickel-plating solution of Sai Qi Science and Technology Ltd.s of Shenzhen purchase model 903, carries out chemical nickel plating.
Embodiment 2b- embodiments 2e is roughly the same with the manufacture method of embodiment 2a, and difference lies in embodiment 2b- implementations for it The content that example 2e accounts for Pr-Nd alloy gross weights from the Pr of Pr-Nd alloys in embodiment 2a is different.Concrete content see the table below (single Position：%)：
Embodiment 2a Embodiment 2b Embodiment 2c Embodiment 2d Embodiment 2e
Principal phase Pr contents 20 10 30 40 0
Auxiliary phase Pr contents 20 90 30 40 100
(numerical value accounts for the percentage of Pr-Nd alloy gross weights for Pr in upper table)；
Embodiment 3
Embodiment 3 is roughly the same with the manufacture method of embodiment 2a, and difference lies in 903 chemical nickel plating is molten in embodiment 3a for it Liquid adds the Nd for accounting for Nickel in Nickel Sulphate Plating Bath gross weight 0.2%, 0.1% Zr and passes through ultrasonic disperse before plating.
Permanent magnet will be made by embodiment 2a- embodiments 2e, embodiment 3 and do not carried out using embodiment 2a step7 as Comparative example 2a carries out following experiment：
Permanent magnet is put into chamber, the sodium chloride solution by atomizer to experiment household sprays 0.1mol/L, keeps Visibility ＜ 5m under the vaporific state of laboratory's inner salt, 37 DEG C of sprinkling 48h, observe and pass through made from embodiment 2a- embodiments 2e forever Whether whether the Ni-based layer surface of anti-corrosion of magnet the Ni-based layer of rust staining, anti-corrosion occurs occurs coming off, whether magnetic body surface becomes rusty Spot.
Test result see the table below：
Salt-fog resistant test
Embodiment 2a The Ni-based layer surface of anti-corrosion is without rust staining, the Ni-based layer of anti-corrosion there are slight crack, magnetic body without rust staining
Embodiment 2b The Ni-based layer surface of anti-corrosion is without rust staining, the Ni-based layer segment of anti-corrosion comes off, magnetic body is without rust staining
Embodiment 2c The Ni-based layer surface of anti-corrosion is without rust staining, the Ni-based layer of anti-corrosion there are slight crack, magnetic body without rust staining
Embodiment 2d The Ni-based layer surface of anti-corrosion is without rust staining, the Ni-based layer of anti-corrosion there are slight crack, magnetic body without rust staining
Embodiment 2e The Ni-based layer surface of anti-corrosion is without rust staining, the Ni-based layer segment of anti-corrosion comes off, magnetic body is without rust staining
Embodiment 3 The Ni-based layer surface of anti-corrosion is without rust staining, the Ni-based layer of anti-corrosion without trace, magnetic body without rust staining
Comparative example 2a There is rust staining in magnetic body
To sum up, the Ni-based layer of anti-corrosion can improve the corrosion resistance of permanent magnet, and magnetic body is protected, meanwhile, by ultrasonic disperse, The bond strength between the Ni-based layer of anti-corrosion and magnetic body can be improved, makes the Ni-based layer of anti-corrosion not easily to fall off.
Embodiment 4a
Embodiment 4a is roughly the same with the manufacture method of embodiment 3, and difference lies in further included step8, in the Ni-based layer of anti-corrosion for it Surface coats acrylic acid protective layer；Acrylic acid protective layer includes component A and B component：
Component A includes 27 parts of methyl methacrylate, 6 parts of n-BMA, 30 parts of styrene, 2 parts of acrylic acid, third 2 parts of olefin(e) acid N-butyl, 10 parts of aqueous epoxy resins, 0.2 part of ammonium persulfate, 0.2 part of lauryl mercaptan, 1.2 parts of ammonium hydroxide, polyoxy 1.2 parts of vinethene, 50 parts of deionized water；
B component is made of polyamide, diethylenetriamine and benzoyl peroxide, wherein polyamide：Diethylenetriamine：Benzoyl peroxide Mass ratio is 5:3:2.
Embodiment 4b- embodiments 4e is roughly the same with the manufacture method of embodiment 4a, its content ginseng difference lies in component A Number, specific content parameter see the table below：
Embodiment 2a Embodiment 2b Embodiment 2c Embodiment 2d Embodiment 2e
Methyl methacrylate 27 30 28 29 27.5
N-BMA 6 8 7 6.5 7.5
Styrene 30 40 32 35 38
Acrylic acid 2 5 3 4 2.5
N-butyl acrylate 2 5 2.5 3 4
Aqueous epoxy resins 10 20 12.5 17.5 15
Ammonium persulfate 0.2 0.8 0.6 0.4 0.5
Lauryl mercaptan 0.2 0.8 0.3 0.6 0.4
Ammonium hydroxide 1.2 2.0 1.5 1.8 1.6
Polyoxyethylene ether 1.2 3.0 2.0 2.5 1.8
Deionized water 50 80 60 70 75
Permanent magnet made from embodiment 4a- embodiments 4e is put into chamber, by atomizer to experiment household sprays The sodium chloride solution of 0.1mol/L, keeps the visibility ＜ 5m under the vaporific state of laboratory's inner salt, sprays 72h, design temperature 37 DEG C, 60 DEG C, 80 DEG C, observation whether become rusty by the Ni-based layer surface of anti-corrosion of permanent magnet made from embodiment 4a- embodiments 4e Whether the Ni-based layer of spot, anti-corrosion, which occurs, comes off, whether magnetic body surface rust staining occurs
Test result see the table below：
To sum up, protection effect of the Ni-based layer of anti-corrosion to magnetic body can be improved compared to embodiment 3, the design of acrylic acid protective layer Fruit, makes at 37 DEG C in salt-fog resistant test the Ni-based layer surface of anti-corrosion without trace.
Embodiment 5a- embodiments 5e is roughly the same with the manufacture method of embodiment 4c, its content ginseng difference lies in component A Number, specific content parameter see the table below：
Embodiment 5a Embodiment 5b Embodiment 5c Embodiment 5d Embodiment 5e
Methyl methacrylate 27.5 27.5 27.5 27.5 27.5
N-BMA 7.5 7.5 7.5 7.5 7.5
Styrene 38 38 38 38 38
Acrylic acid 2.5 2.5 2.5 2.5 2.5
N-butyl acrylate 4 4 4 4 4
Aqueous epoxy resins 15 15 15 15 15
Ammonium persulfate 0.5 0.5 0.5 0.5 0.5
Lauryl mercaptan 0.4 0.4 0.4 0.4 0.4
Ammonium hydroxide 1.6 1.6 1.6 1.6 1.6
Polyoxyethylene ether 1.8 1.8 1.8 1.8 1.8
Deionized water 75 75 75 75 75
Magnesium hydroxide 10 15 12 13 14
Titanium dioxide 10 15 12 13 14
Aluminium hydroxide 5 3 4 3.5 4.5
KH-570 0.3 0.5 0.35 0.45 0.4
Permanent magnet made from embodiment 5a- embodiments 5e is equally subjected to salt-fog resistant test at 37 DEG C, 60 DEG C, 80 DEG C, is tested As a result see the table below：
To sum up, the salt spray resistance of permanent magnet can be further improved by the addition of magnesium hydroxide, titanium dioxide, aluminium hydroxide.
This specific embodiment is only explanation of the invention, it is not limitation of the present invention, people in the art Member as needed can make the present embodiment the modification of no creative contribution after this specification is read, but as long as at this All protected in the right of invention be subject to Patent Law.

Claims (9)

1. a kind of dual alloy Fe-B rare-earth permanent magnet, it is characterised in that the permanent magnet includes main-phase alloy and auxiliary phase alloy According to 15:The magnetic body that 1 mixed sintering forms（1）；
Main-phase alloy is（Pr1-xNdx）29Co3Zr0.2Fe66.8B1, 0 ＜ x ＜ 1；
Auxiliary phase alloy is（Pr1-yNdy）10Dy20Co2Al8Ga4Fe55B1, 0 ＜ y ＜ 1；
Magnetic body（1）Surface be also plated with the Ni-based layer of anti-corrosion（2）.
2. a kind of manufacture method of dual alloy Fe-B rare-earth permanent magnet, it is characterised in that include following steps：
Step1, main-phase alloy and auxiliary phase alloy smelting ingot casting；
Step2, main-phase alloy ingot casting is quick-fried by carrying out hydrogen after high annealing；
Step3, it is quick-fried to carry out hydrogen by auxiliary phase alloy ingot casting；
Step4, powder is broken into by main-phase alloy ingot casting of the hydrogen after quick-fried and auxiliary phase alloy ingot casting, and is sieved；
Step5, by the main-phase alloy powder after screening and auxiliary phase alloy powder according to 15：Added after 1 mixing and account for main-phase alloy powder The lubricant of last and auxiliary phase alloy powder gross mass 0.01% carries out batch mixing；
Step6, by vacuum-sintering and is heat-treated after the completion of batch mixing, obtains magnetic body（1）；
Step7, is located at permanent magnet surfaces by plating by nickel-plating liquid, forms the Ni-based layer of anti-corrosion（2）.
A kind of 3. manufacture method of dual alloy Fe-B rare-earth permanent magnet according to claim 2, it is characterised in that in Step5, Lubricant is preferably 1500 mesh silicon powders.
4. the manufacture method of a kind of dual alloy Fe-B rare-earth permanent magnet according to claim 2, it is characterised in that nickel-plating liquid exists Added before chemical plating and account for the Nd of Nickel in Nickel Sulphate Plating Bath gross mass 0.2%, 0.1% Zr and pass through ultrasonic disperse.
5. the manufacture method of a kind of dual alloy Fe-B rare-earth permanent magnet according to claim 3, it is characterised in that in chemical plating The Ni-based layer of anti-corrosion（2）Afterwards, which has further included Step8, in the Ni-based layer of anti-corrosion（2）Surface coats acrylic acid protective layer （3）.
6. the manufacture method of a kind of dual alloy Fe-B rare-earth permanent magnet according to claim 5, it is characterised in that acrylic acid is protected Sheath（3）Formed by metal protection liquid coating, metal protection liquid includes component A and B component, and component A includes metering system Sour methyl esters 27-30 parts, 6-8 parts of n-BMA, 30-40 parts of styrene, 2-5 parts of acrylic acid, n-butyl acrylate 2-5 Part, 10-20 parts of aqueous epoxy resins, 0.2-0.8 parts of ammonium persulfate, 0.2-0.8 parts of lauryl mercaptan, 1.2-2.0 parts of ammonium hydroxide, 1.2-3.0 parts of polyoxyethylene ether, 50-80 parts of deionized water；B component includes epoxy hardener.
A kind of 7. manufacture method of dual alloy Fe-B rare-earth permanent magnet according to claim 6, it is characterised in that curable epoxide Agent is made of polyamide, diethylenetriamine and benzoyl peroxide, wherein polyamide：Diethylenetriamine：Benzoyl peroxide mass ratio For 5:3:2.
8. the manufacture method of a kind of dual alloy Fe-B rare-earth permanent magnet according to claim 7, it is characterised in that component A is also Include 10-15 parts of magnesium hydroxide, 10-15 parts of titanium dioxide, 3-5 parts of aluminium hydroxide.
9. the manufacture method of a kind of dual alloy Fe-B rare-earth permanent magnet according to claim 8, it is characterised in that component A is also Include 0.3-0.5 parts of silane coupling agents.
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