CN105489332A - Permanent magnet material containing multiple rare earth phases and preparation method - Google Patents
Permanent magnet material containing multiple rare earth phases and preparation method Download PDFInfo
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- CN105489332A CN105489332A CN201610001429.1A CN201610001429A CN105489332A CN 105489332 A CN105489332 A CN 105489332A CN 201610001429 A CN201610001429 A CN 201610001429A CN 105489332 A CN105489332 A CN 105489332A
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- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
- C23C8/26—Nitriding of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
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- 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
-
- 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
- B22F2003/248—Thermal after-treatment
Abstract
The invention provides a permanent magnet material containing multiple rare earth phases and a preparation method. The permanent magnet material is high in magnetic energy product; the preparation method is simple in process, low in production cost and suitable for industrial production. The permanent magnet material containing the multiple rare earth phases comprises the following components in percentage by mass: 15-20% of Nd, 3-4% of Y, 4.5-6% of La, 6.0-8.0% of Ce, 3-4% of Pr, 0.15-0.20% of Pd, 0.3-0.4% of Sm, 2-5% of B, 0.45-0.60% of Co, 0.01-0.04% of Mn, 0.01-0.04% of Mo and the balance of Fe; the mass ratio of Pd to Co in the permanent magnet material is 1:3; the mass ratio of Nd to Y to La to Ce to Pr to Pd to Sm is 10:2:3:4:2:0.1:0.2; and the permanent magnet material also comprises 0.15-0.55% of N in percentage by mass.
Description
Technical field
The invention belongs to metal material field, relate to a kind of many rare-earth phases permanent magnetic material and preparation method.
Background technology
CN201410730163.5 application relates to a kind of high-performance rare-earth permanent magnet material, this material belongs to R-T-B system alloy, the general formula of this alloy is R<sub>x</subGrea tT.GreaT.GTT<sub>100-x-y-zLEs sT.LTssT.LT/sub>M<subGreatT.G reaT.GTy</sub>Q< sub>z</sub>, in formula, R comprises one or more in all rare earth elements of Y, T is Fe, Co, one or more in Ni, M is Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, one or more in Ga, Q is B, N, one or more in C, wherein x, y, z meets: 10≤x≤13 atom %, 0≤y≤5 atom %, 0.9≤z≤2 atom %.But the magnetic energy product of this material is high not enough.
Summary of the invention
Object of the present invention is exactly for above-mentioned technological deficiency, and provide a kind of many rare-earth phases permanent magnetic material, this material has high magnetic energy product.
Another object of the present invention is to provide a kind of many rare-earth phases permanent magnetic material preparation method, and this preparation method's technique is simple, and production cost is low, is suitable for suitability for industrialized production.
The object of the invention is to be achieved through the following technical solutions:
A kind of many rare-earth phases permanent magnetic material, in this permanent magnetic material, the mass percent of each composition is: Nd15-20%, Y3-4%, La4.5-6%, Ce6.0-8.0%, Pr3-4%, Pd0.15-0.20%, Sm0.3-0.4%, B2-5%, Co0.45-0.60%, Mn0.01-0.04%, Mo0.01-0.04%, all the other are Fe; In this permanent magnetic material, the mass ratio of Pd and Co is 1:3; The mass ratio of Nd, Y, La, Ce, Pr, Pd, Sm is 10:2:3:4:2:0.1:0.2, and also containing mass percent in this permanent magnetic material is the N of 0.15-0.55%.
A preparation method for many rare-earth phases permanent magnetic material, the method comprises the steps:
1) waste disposal:
A) Nd-Fe-B permanent magnet waste material (mass fraction is 10-15%) Na is got
2cO
3oil in solution removing waste material, Na
2cO
3be (0.01-0.03) with the mass ratio of waste material: 1, the waste material after process dries 1-2 hour after filtration and after water washing 3 times in 120-125 DEG C of baker, and must deoil waste material; Then the waste material that will deoil is placed in (mass concentration is 25-30%) concentrated sulfuric acid, and the mass ratio of deoil waste material and the concentrated sulfuric acid is 1: (1.0-1.3), immerses and is filtered after 2-3 hour, and with tap water 3 times, filter residue abandons, and filtrate and washing lotion merge; The feed liquid of above-mentioned merging is placed in stirred reactor, stirs 1-2 hour at 150-200 DEG C, then evenly add sodium sulphate and stir and form double salt precipitation thing in 1-2 hour, the addition of sodium sulphate is the 13-16% of waste material quality of deoiling; Oxalic acid being made concentration is that the solution of 125-180g/L puts into stirred reactor, after being raised to 80-90 DEG C, evenly add described double salt precipitation thing, make it be converted into oxalate compound to separate out, the consumption of oxalic acid is the 45-55% of quality of waste material of deoiling, and after filtration and after washing 2-5 time, solution discards, collecting precipitation thing is dried 1 hour at the temperature of 120 DEG C, obtains sediment A stand-by after cooling;
B) polishing powder waste material is placed in baking furnace and carries out preliminary treatment in 500-650 DEG C, insulation 1-2 hour, is milled to 20-80 micron, obtains processing rear waste material after cooling; Then rear for process waste material being joined concentration is in the sulfuric acid of 6-10mol/L, after process, the mass ratio of waste material and sulfuric acid is (1-2): 1, by mixture first at 260-300 DEG C of insulation 1-1.5 hour, then at 310-340 DEG C of insulation 1-1.5 hour, wash 3-5 time with water logging more afterwards, collecting precipitation thing is dried 1 hour at the temperature of 120 DEG C, obtains sediment B after cooling, for subsequent use;
C) by sediment A and sediment B 1:1-2 mixing in mass ratio, be incubated 1-1.5 hour under being placed in the temperature of 1050-1100 DEG C, after cooling, be precipitated rare earth oxide;
2) grinding batching: Nd, Y, La, Ce, Pr, Pd, Sm assay is carried out to above-mentioned precipitating rare earth oxide, measure in backward precipitating rare earth oxide and add corresponding oxide (yittrium oxide powder, lanthana powder, cerium oxide powder, oxidation spectrum powder, neodymia powder, palladium oxide powder, samarium oxide powder) and carry out composition adjustment, in sediment rare earth oxide after adjustment, the mass ratio of Nd, Y, La, Ce, Pr, Pd, Sm is 10:2:3:4:2:0.1:0.2, and after adjusting, mixing is ground to particle diameter is that 0.5-0.8mm obtains RE oxide powder;
3) electrolytic preparation mixed rare earth alloy: above-mentioned RE oxide powder is put into electrolytic furnace, wherein electroanalysis solvent is LiF-ZnF
2-CaF
2-K
2siF
6, LiF, ZnF in electroanalysis solvent
2, CaF
2, K
2siF
6mass percent be respectively containing 55-60%, 13-16%, 14-16%, all the other; The mass ratio of electroanalysis solvent and RE oxide powder is (4-5): 1, and the current strength of electrolytic furnace is 75A, working temperature is 990-1180 DEG C; After electrolysis 20-30 minute, obtain mixed rare earth alloy;
4) many rare-earth phases permanent magnetic material alloy pig is prepared: prepare burden according to following mass percent: Nd15-20%, Y3-4%, La4.5-6%, Ce6.0-8.0%, Pr3-4%, Pd0.15-0.20%, Sm0.3-0.4%, B2-5%, Co0.45-0.60%, Mn0.01-0.04%, Mo0.01-0.04%, all the other are Fe, and the mass ratio of control Pd and Co is 1:3 simultaneously; Wherein Co, Mn, Mo add in simple metal mode, and B is to be that the ferroboron mode of 25% adds containing B mass percent, and surplus Fe adds in simple metal mode; The mixed rare earth alloy form that Nd, Y, La, Ce, Pr, more than Pd walk preparation adds, and wherein the mass ratio of Nd, Y, La, Ce, Pr, Pd, Sm is 10:2:3:4:2:0.1:0.2; The raw material prepared joins in the crucible of vaccum sensitive stove, and heating reaches 1500-1590 DEG C, is incubated and pours in ingot mould after 20 minutes, and cooling obtains many rare-earth phases permanent magnetic material alloy pig naturally.
5) band, nitriding, powder process, die mould, sintering is made: above-mentioned many rare-earth phases permanent magnetic material alloy pig is made band, namely nitriding, powder process, compressing, sintering processes obtain many rare-earth phases permanent magnetic material.
Further design of the present invention is:
In step 5), during system band, the remelting tubular type crucible that the many rare-earth phases permanent magnetic material alloy pig first step 4) obtained puts into vacuum induction forming furnace carries out remelting, remelting temperature is 1530-1580 DEG C, the bottom of remelting tubular type crucible is placed in 2-4mm place on vacuum induction quick quenching furnace runner wheel rim, above-mentioned alloy pig is placed in tubular type crucible and melts, the runner EDGE CONTACT of ejection and rotation from the hole of crucible bottom under ar gas acting after alloy molten, formation thickness is 670-750 μm, width is the alloy strip of 12-15mm, the linear velocity of runner wheel rim is 18-21m/s.
In step 5), when nitriding, powder process, will close and state gold bar band and put into nitriding furnace, the ammonia flow of nitriding furnace is 5-10L/min, is warming up to 550-650 DEG C, insulation 8-12min; Take out with after stove cooling, after band is stirred, put into nitriding furnace again, be warming up to 550-650 DEG C, insulation 8-12min, the ammonia flow of stove is 5-10L/min, after the coarse crushing to 3-6mm of cooled nitro-alloy band, then prepares by airflow milling the powder that particle mean size is 2.8-3.2 μm.
In step 5), during compressing, sintering processes, first above-mentioned powder is put into press die, type is made at 2-3T pressure, the sintering furnace that compacting base is placed in 1170-1190 DEG C is sintered 2-4 hour, sintering furnace vacuum level requirements is less than 0.1Pa, and finally at 400-450 DEG C, vacuum level requirements is less than heat treatment 2-3 hour under the condition of 0.1Pa; And then magnet is placed in the heat-treatment furnace that magnetic field intensity is 6-8T, cools with stove be incubated 2-3h in 1080-1150 DEG C of vacuum environment after, namely obtain many rare-earth phases permanent magnetic material.
compared with prior art, remarkable advantage of the present invention is:
Owing to there being the existence of multiple rare earth element in material of the present invention, therefore form Nd in the tissue
2fe
14b, (Nd, La)
2fe
14b, Ce
2fe
14b, Pr
2fe
14b, Y
2fe
14multiple magnetic principal phase such as B.When these magnetic principal phases are 10:2:3:4:2:0.1:0.2 by the mass ratio of Nd, Y, La, Ce, Pr, Pd, Sm, Nd
2fe
14can by the different principal crystalline phase of other as Ce between B crystal grain
2fe
14b phase, Y
2fe
14b is equal to be separated, and can change the direct exchange interaction between single main phase grain.In sintering process, main phase grain border to be magnetic particle pinning by another one, and this effect can make magnet coercive force improve, and can hinder growing up of main phase grain simultaneously, easily realizes high density, compact grained Sintered NdFeB magnet is formed.
Nitrogen occupies specific gap crystal site in the structure, can regulate the crystal field effect of rare earth 4f electronics and the band structure of iron 3d electronics delicately, thus the atomic magnetic moment of iron is increased, and makes the crystal field effect generation basic change of rare earth 4f electronics.In material of the present invention, N and Sm forms another one principal phase Sm
2fe
17nx, has given full play to the complementary effect of B and N.Having under Mo existent condition, rare earth and N can form new principal phase.
Nonmagnetic Nd-rich phase in magnetic material plays a part to dilute whole magnet magnetic moment, and its existence in magnet actually reduces the magnetic property of the unit volume of permanent magnet.And La, Ce, Pr and the Mn in material of the present invention can make uniform crystal particles, refinement, regularization.This makes nonmagnetic Nd-rich phase can be evenly distributed on the crystal boundary of principal phase, avoids Nd-rich phase with large block appearance.
Being added in of Co and Bd is conducive to elevated temperature strength, structural stability and corrosion resistance when mass ratio is 1:3 and all significantly improves, and the brittle phenomenon easily produced during long-term work under high temperature can be avoided.Cobalt itself has high stability, has high-temperature oxidation resistance.Add cobalt element significantly to improve the temperature stability of alloy and expand operating temperature range.Cobalt and palladium combine the corrosion resistance not only can improving material, and can improve exchange coupling pinning field H, ensure the stability of material.
Compared with prior art, permanent magnetic material of the present invention has uniform tissue, and strong strong structure, both can improve the anti-corrosion capability of material, and magnetic property makes moderate progress.
This material obtains in the process of the present invention, this simple and effective anti-oxidation method, can make magnet surface and inner oxygen content difference less, make acquisition high-performance rare-earth permanent magnet material become possibility.
Permanent magnetic material of the present invention has good stability and practicality, can be widely used in the every field such as electronic device, aeronautical and space technology, computer equipment, magnetic separator, communication apparatus, Medical Devices, electric bicycle, electronic toy.
The preparation method of permanent magnetic material of the present invention takes full advantage of waste material and directly produces alloy raw materials, composition proportion is flexible, quality control puts in place, and can reduce costs, technique utilizes hyperoxic powder scrap simply, fully, environmental protection, effectively environmental protect, have very high social value.
Accompanying drawing explanation
Fig. 1 is many rare-earth phases permanent magnetic material tissue that the embodiment of the present invention one prepares.
As seen from the figure, material structure dense uniform.
Embodiment
Raw materials used as follows in various embodiments of the present invention:
1, Nd-Fe-B permanent magnet waste material used derives from the waste material that manufacturer production Nd-Fe-B permanent magnet product produces.
In this waste material, the mass fraction of each composition is: neodymium 29%-32.5%, boron 2.8-3.6%, protactinium 0.6-1.2%, palladium 0.05-0.08%, and surplus is iron.
2, polishing powder waste material used derive from recovery polishing powder 739 use after waste material.
Rare earth composition percentage in this polishing powder waste material is: La
2o
35-7%, Y
2o
30.2-0.6%, Pr
6o
111-2%, Nd
2o
35-7%, Sm
2o
30.2-0.4%, all the other are CeO
2.
embodiment one:
The preparation method of the present invention's many rare-earth phases permanent magnetic material, the method comprises the steps:
1) waste disposal:
A) getting Nd-Fe-B permanent magnet waste material mass fraction is 15%Na
2cO
3oil in solution removing waste material, Na
2cO
3be 0.03:1 with the mass ratio of waste material, the waste material after process is dried 2 hours after filtration and after water washing 3 times in 125 DEG C of bakers, and must deoil waste material; Then the waste material that deoils is placed in the concentrated sulfuric acid that mass concentration is 30%, the mass ratio of deoil waste material and the concentrated sulfuric acid is 1: 1.2, immerses and is filtered after 3 hours, and with tap water 3 times, filter residue abandons, and filtrate and washing lotion merge; The feed liquid of above-mentioned merging is placed in stirred reactor, stirs 2 hours at 200 DEG C, then evenly add sodium sulphate and stir 2 hours formation double salt precipitation things, the addition of sodium sulphate is 16% of waste material quality of deoiling; Oxalic acid being made concentration is that the solution of 180g/L puts into stirred reactor, after being raised to 90 DEG C, evenly add described double salt precipitation thing, make it be converted into oxalate compound to separate out, the consumption of oxalic acid be deoil waste material quality 55%, after filtration and washing 5 times after, solution discards, collecting precipitation thing is dried 1 hour at the temperature of 120 DEG C, obtains sediment A stand-by after cooling;
B) polishing powder waste material is placed in baking furnace and carries out preliminary treatment in 650 DEG C, be incubated 2 hours, after cooling, be milled to 20-80 micron, obtain processing rear waste material; Then rear for process waste material being joined concentration is in the sulfuric acid of 10mol/L, after process, the mass ratio of waste material and sulfuric acid is 2:1, by mixture first 300 DEG C of insulations 1.5 hours, then 340 DEG C of insulations 1.5 hours, 5 times are washed again afterwards with water logging, collecting precipitation thing is dried 1 hour at the temperature of 120 DEG C, obtains sediment B after cooling, for subsequent use;
C) by sediment A and sediment B 1:2 mixing in mass ratio, be incubated 1.5 hours under being placed in the temperature of 1100 DEG C, after cooling, be precipitated rare earth oxide;
2) grinding batching: Nd, Y, La, Ce, Pr, Pd, Sm assay is carried out to above-mentioned precipitating rare earth oxide, measure in backward precipitating rare earth oxide and add corresponding oxide (yittrium oxide powder, lanthana powder, cerium oxide powder, oxidation spectrum powder, neodymia powder, palladium oxide powder, samarium oxide powder) and carry out composition adjustment, in sediment rare earth oxide after adjustment, the mass ratio of Nd, Y, La, Ce, Pr, Pd, Sm is 10:2:3:4:2:0.1:0.2, and after adjusting, mixing is ground to particle diameter is that 0.5-0.8mm obtains RE oxide powder;
3) electrolytic preparation mixed rare earth alloy: above-mentioned RE oxide powder is put into electrolytic furnace, wherein electroanalysis solvent is LiF-ZnF
2-CaF
2-K
2siF
6(LiF, ZnF in electroanalysis solvent
2, CaF
2, K
2siF
6mass percent be respectively containing 55-60%, 13-16%, 14-16%, all the other); The mass ratio of electroanalysis solvent and RE oxide powder is 5:1, and the current strength of electrolytic furnace is 75A, working temperature is 1180 DEG C; Electrolysis, after 30 minutes, obtains mixed rare earth alloy;
4) prepare many rare-earth phases permanent magnetic material alloy pig: prepare burden according to following mass percent: Nd15%, Y3%, La4.5%, Ce6.0%, Pr3%, Pd0.15%, Sm0.3%, B2%, Co0.45%, Mn0.01%, Mo0.01%, all the other are Fe.The mass ratio of control Pd and Co is 1:3 simultaneously; Wherein Co, Mn, Mo add in simple metal mode, and B is to be that the ferroboron mode of 25% adds containing B mass percent, and surplus Fe adds in simple metal mode; The mixed rare earth alloy form that Nd, Y, La, Ce, Pr, more than Pd walk preparation adds, and wherein the mass ratio of Nd, Y, La, Ce, Pr, Pd, Sm is 10:2:3:4:2:0.1:0.2; The raw material prepared joins in the crucible of vaccum sensitive stove, and heating reaches 1590 DEG C, is incubated and pours in ingot mould after 20 minutes, and cooling obtains many rare-earth phases permanent magnetic material alloy pig naturally.
5) band, nitriding, powder process, die mould, sintering is made: above-mentioned many rare-earth phases permanent magnetic material alloy pig is made band, namely nitriding, powder process, compressing, sintering processes obtain many rare-earth phases permanent magnetic material.
During system band, the remelting tubular type crucible that the many rare-earth phases permanent magnetic material alloy pig first step 4) obtained puts into vacuum induction forming furnace carries out remelting, remelting temperature is 1580 DEG C, the bottom of remelting tubular type crucible is placed in 2-4mm place on vacuum induction quick quenching furnace runner wheel rim, above-mentioned alloy pig is placed in tubular type crucible and melts, the runner EDGE CONTACT of ejection and rotation from the hole of crucible bottom under ar gas acting after alloy molten, formation thickness is 670-750 μm, width is the alloy strip of 12-15mm, and the linear velocity of runner wheel rim is 20m/s.
When nitriding, powder process, will close and state gold bar band and put into nitriding furnace, the ammonia flow of nitriding furnace is 5L/min, is warming up to 650 DEG C, insulation 12min; Take out with after stove cooling, after band is stirred, then put into nitriding furnace, be warming up to 650 DEG C, insulation 12min, the ammonia flow of stove is 5L/min, after the coarse crushing to 3-6mm of cooled nitro-alloy band, then prepare by airflow milling the powder that particle mean size is 2.8-3.2 μm.In material after process, N mass percentage is 0.15%.
During compressing, sintering processes, first above-mentioned powder is put into press die, type is made at 3T pressure, the sintering furnace that compacting base is placed in 1190 DEG C is sintered 4 hours, sintering furnace vacuum level requirements is less than 0.1Pa, last at 450 DEG C, vacuum level requirements to be less than under the condition of 0.1Pa heat treatment 3 hours; And then magnet is placed in the heat-treatment furnace that magnetic field intensity is 8T, cools with stove be incubated 3h in 1150 DEG C of vacuum environments after, namely obtain many rare-earth phases permanent magnetic material.
embodiment two:
The preparation method of the present invention's many rare-earth phases permanent magnetic material, the method comprises the steps:
1) waste disposal:
A) getting Nd-Fe-B permanent magnet waste material mass fraction is the Na of 10%
2cO
3oil in solution removing waste material, Na
2cO
3be 0.02:1 with the mass ratio of waste material, the waste material after process is dried 1 hour after filtration and after water washing 3 times in 120 DEG C of bakers, and must deoil waste material; Then the waste material that deoils is placed in the concentrated sulfuric acid that mass concentration is 25%, the mass ratio of deoil waste material and the concentrated sulfuric acid is 1: 1.0, immerses and is filtered after 2 hours, and with tap water 3 times, filter residue abandons, and filtrate and washing lotion merge; The feed liquid of above-mentioned merging is placed in stirred reactor, stirs 1 hour at 150 DEG C, then evenly add sodium sulphate and stir 1-2 hour formation double salt precipitation thing, the addition of sodium sulphate is 13% of waste material quality of deoiling; Oxalic acid being made concentration is that the solution of 125g/L puts into stirred reactor, after being raised to 80 DEG C, evenly add described double salt precipitation thing, make it be converted into oxalate compound to separate out, the consumption of oxalic acid be deoil waste material quality 50%, after filtration and washing 2 times after, solution discards, collecting precipitation thing is dried 1 hour at the temperature of 120 DEG C, obtains sediment A stand-by after cooling;
B) polishing powder waste material is placed in baking furnace and carries out preliminary treatment in 550 DEG C, be incubated 1 hour, after cooling, be milled to 20-80 micron, obtain processing rear waste material; Then rear for process waste material being joined concentration is in the sulfuric acid of 8mol/L, after process, the mass ratio of waste material and sulfuric acid is 1:1, by mixture first 260 DEG C of insulations 1 hour, then 320 DEG C of insulations 1 hour, 3 times are washed again afterwards with water logging, collecting precipitation thing is dried 1 hour at the temperature of 120 DEG C, obtains sediment B after cooling, for subsequent use;
C) by sediment A and sediment B 1:1 mixing in mass ratio, be incubated 1 hour under being placed in the temperature of 1080 DEG C, after cooling, be precipitated rare earth oxide;
2) grinding batching: Nd, Y, La, Ce, Pr, Pd, Sm assay is carried out to above-mentioned precipitating rare earth oxide, measure in backward precipitating rare earth oxide and add corresponding oxide (yittrium oxide powder, lanthana powder, cerium oxide powder, oxidation spectrum powder, neodymia powder, palladium oxide powder, samarium oxide powder) and carry out composition adjustment, in sediment rare earth oxide after adjustment, the mass ratio of Nd, Y, La, Ce, Pr, Pd, Sm is 10:2:3:4:2:0.1:0.2, and after adjusting, mixing is ground to particle diameter is that 0.5-0.8mm obtains RE oxide powder;
3) electrolytic preparation mixed rare earth alloy: above-mentioned RE oxide powder is put into electrolytic furnace, wherein electroanalysis solvent is LiF-ZnF
2-CaF
2-K
2siF
6(LiF, ZnF in electroanalysis solvent
2, CaF
2, K
2siF
6mass percent be respectively containing 55-60%, 13-16%, 14-16%, all the other); The mass ratio of electroanalysis solvent and RE oxide powder is 4:1, and the current strength of electrolytic furnace is 75A, working temperature is 990 DEG C; Electrolysis, after 20 minutes, obtains mixed rare earth alloy;
4) prepare many rare-earth phases permanent magnetic material alloy pig: prepare burden according to following mass percent: Nd20%, Y4%, La6%, Ce8.0%, Pr4%, Pd0.20%, Sm0.4%, B5%, Co0.60%, Mn0.04%, Mo0.04%, all the other are Fe.The mass ratio of control Pd and Co is 1:3 simultaneously; Wherein Co, Mn, Mo add in simple metal mode, and B is to be that the ferroboron mode of 25% adds containing B mass percent, and surplus Fe adds in simple metal mode; The mixed rare earth alloy form that Nd, Y, La, Ce, Pr, more than Pd walk preparation adds, and wherein the mass ratio of Nd, Y, La, Ce, Pr, Pd, Sm is 10:2:3:4:2:0.1:0.2; The raw material prepared joins in the crucible of vaccum sensitive stove, and heating reaches 1550 DEG C, is incubated and pours in ingot mould after 20 minutes, and cooling obtains many rare-earth phases permanent magnetic material alloy pig naturally.
5) band, nitriding, powder process, die mould, sintering is made: above-mentioned many rare-earth phases permanent magnetic material alloy pig is made band, namely nitriding, powder process, compressing, sintering processes obtain many rare-earth phases permanent magnetic material.
During system band, the remelting tubular type crucible that the many rare-earth phases permanent magnetic material alloy pig first step 4) obtained puts into vacuum induction forming furnace carries out remelting, remelting temperature is 1550 DEG C, the bottom of remelting tubular type crucible is placed in 2-4mm place on vacuum induction quick quenching furnace runner wheel rim, above-mentioned alloy pig is placed in tubular type crucible and melts, the runner EDGE CONTACT of ejection and rotation from the hole of crucible bottom under ar gas acting after alloy molten, formation thickness is 670-750 μm, width is the alloy strip of 12-15mm, and the linear velocity of runner wheel rim is 18m/s.
When nitriding, powder process, will close and state gold bar band and put into nitriding furnace, the ammonia flow of nitriding furnace is 10L/min, is warming up to 550 DEG C, insulation 8min; Take out with after stove cooling, after band is stirred, then put into nitriding furnace, be warming up to 550 DEG C, insulation 8min, the ammonia flow of stove is 10L/min, after the coarse crushing to 3-6mm of cooled nitro-alloy band, then prepare by airflow milling the powder that particle mean size is 2.8-3.2 μm.In material after process, N mass percentage is 0.55%.
During compressing, sintering processes, first above-mentioned powder is put into press die, type is made at 2T pressure, the sintering furnace that compacting base is placed in 1180 DEG C is sintered 2 hours, sintering furnace vacuum level requirements is less than 0.1Pa, last at 400 DEG C, vacuum level requirements to be less than under the condition of 0.1Pa heat treatment 3 hours; And then magnet is placed in the heat-treatment furnace that magnetic field intensity is 8T, cools with stove be incubated 3h in 1150 DEG C of vacuum environments after, namely obtain many rare-earth phases permanent magnetic material.
embodiment three:
In this example, prepare many rare-earth phases permanent magnetic material alloy pig: prepare burden according to following mass percent: Nd18%, Y3.6%, La5.4%, Ce7.2%, Pr3.6%, Pd0.18%, Sm0.36%, B3%, Co0.54%, Mn0.03%, Mo0.03%, all the other are Fe.All the other preparation conditions and process are with embodiment one.In material after process, N mass percentage is 0.35%.
embodiment four: this example proportioning components is not in scope of design of the present invention
In this example, prepare many rare-earth phases permanent magnetic material alloy pig: prepare burden according to following mass percent: Nd12%, Y2.4%, La3.6%, Ce4.8%, Pr2.4%, Pd0.12%, Sm0.24%, B1.5%, Co0.40%, Mn0.005%, Mo0.005%, all the other are Fe.All the other preparation conditions and process are with embodiment one.In material after process, N mass percentage is 0.10%.
embodiment five: this example proportioning components is not in scope of design of the present invention
In this example, prepare many rare-earth phases permanent magnetic material alloy pig: prepare burden according to following mass percent: Nd22%, Y4.4%, La6.6%, Ce8.8%, Pr4.4%, Pd0.22%, Sm0.44%, B6%, Co0.66%, Mn0.06%, Mo0.06%, all the other are Fe.All the other preparation conditions and process are with embodiment two.In material after process, N mass percentage is about 0.65%.
Material property of the present invention sees the following form:
As can be seen from the above table, material of the present invention increases with Nd, Y, La, Ce, Pr, Pd, Sm, Co, Mn, Mo, B, N, and the magnetic performance of material is all in raising.But the mutual restraint between element can be caused too much, have impact on the combination property of material on the contrary.
Claims (5)
1. the permanent magnetic material of rare-earth phase more than, is characterized in that: in this permanent magnetic material, the mass percent of each composition is: Nd15-20%, Y3-4%, La4.5-6%, Ce6.0-8.0%, Pr3-4%, Pd0.15-0.20%, Sm0.3-0.4%, B2-5%, Co0.45-0.60%, Mn0.01-0.04%, Mo0.01-0.04%, all the other are Fe; In this permanent magnetic material, the mass ratio of Pd and Co is 1:3; The mass ratio of Nd, Y, La, Ce, Pr, Pd, Sm is 10:2:3:4:2:0.1:0.2, and also containing mass percent in this permanent magnetic material is the N of 0.15-0.55%.
2. a preparation method for the permanent magnetic material of rare-earth phase more than, is characterized in that: the method comprises the steps:
1) waste disposal:
A) Nd-Fe-B permanent magnet waste material Na is got
2cO
3oil in solution removing waste material, Na
2cO
3be (0.01-0.03) with the mass ratio of waste material: 1, the waste material after process dries 1-2 hour after filtration and after water washing 3 times in 120-125 DEG C of baker, and must deoil waste material; Then the waste material that will deoil is placed in the concentrated sulfuric acid, and the mass ratio of deoil waste material and the concentrated sulfuric acid is 1: (1.0-1.3), immerses and is filtered after 2-3 hour, and with tap water 3 times, filter residue abandons, and filtrate and washing lotion merge; The feed liquid of above-mentioned merging is placed in stirred reactor, stirs 1-2 hour at 150-200 DEG C, then evenly add sodium sulphate and stir and form double salt precipitation thing in 1-2 hour, the addition of sodium sulphate is the 13-16% of waste material quality of deoiling; Oxalic acid being made concentration is that the solution of 125-180g/L puts into stirred reactor, after being raised to 80-90 DEG C, evenly add described double salt precipitation thing, make it be converted into oxalate compound to separate out, the consumption of oxalic acid is the 45-55% of quality of waste material of deoiling, and after filtration and after washing 2-5 time, solution discards, collecting precipitation thing is dried 1 hour at the temperature of 120 DEG C, obtains sediment A stand-by after cooling;
B) polishing powder waste material is placed in baking furnace and carries out preliminary treatment in 500-650 DEG C, insulation 1-2 hour, after cooling, ball milling obtains processing rear waste material; Then waste material after process is joined in sulfuric acid, after process, the mass ratio of waste material and sulfuric acid is (1-2): 1, by mixture first at 260-300 DEG C of insulation 1-1.5 hour, then at 310-340 DEG C of insulation 1-1.5 hour, wash 3-5 time with water logging more afterwards, collecting precipitation thing is dried 1 hour at the temperature of 120 DEG C, obtains sediment B after cooling, for subsequent use;
C) by sediment A and sediment B 1:1-2 mixing in mass ratio, be incubated 1-1.5 hour under being placed in the temperature of 1050-1100 DEG C, after cooling, be precipitated rare earth oxide;
2) grinding batching: Nd, Y, La, Ce, Pr, Pd, Sm assay is carried out to above-mentioned precipitating rare earth oxide, measure and add corresponding oxide in backward precipitating rare earth oxide and carry out composition adjustment, in sediment rare earth oxide after adjustment, the mass ratio of Nd, Y, La, Ce, Pr, Pd, Sm is 10:2:3:4:2:0.1:0.2, and after adjusting, RE oxide powder is ground to obtain in mixing;
3) electrolytic preparation mixed rare earth alloy: above-mentioned RE oxide powder is put into electrolytic furnace, wherein electroanalysis solvent is LiF-ZnF
2-CaF
2-K
2siF
6; The mass ratio of electroanalysis solvent and RE oxide powder is (4-5): 1, and the current strength of electrolytic furnace is 75A, working temperature is 990-1180 DEG C; After electrolysis 20-30 minute, obtain mixed rare earth alloy;
4) many rare-earth phases permanent magnetic material alloy pig is prepared: prepare burden according to following mass percent: Nd15-20%, Y3-4%, La4.5-6%, Ce6.0-8.0%, Pr3-4%, Pd0.15-0.20%, Sm0.3-0.4%, B2-5%, Co0.45-0.60%, Mn0.01-0.04%, Mo0.01-0.04%, all the other are Fe, and the mass ratio of Pd and Co is 1:3 simultaneously; Wherein Co, Mn, Mo add in simple metal mode, and B is to be that the ferroboron mode of 25% adds containing B mass percent, and surplus Fe adds in simple metal mode; The mixed rare earth alloy form that Nd, Y, La, Ce, Pr, more than Pd walk preparation adds; The raw material prepared joins in the crucible of vaccum sensitive stove, and heating reaches 1500-1590 DEG C, is incubated and pours in ingot mould after 20 minutes, and cooling obtains many rare-earth phases permanent magnetic material alloy pig naturally;
5) band, nitriding, powder process, die mould, sintering is made: above-mentioned many rare-earth phases permanent magnetic material alloy pig is made band, namely nitriding, powder process, compressing, sintering processes obtain many rare-earth phases permanent magnetic material.
3. the preparation method of many rare-earth phases permanent magnetic material according to claim 2, it is characterized in that: in step 5), during system band, the remelting tubular type crucible that the many rare-earth phases permanent magnetic material alloy pig first step 4) obtained puts into vacuum induction forming furnace carries out remelting, remelting temperature is 1530-1580 DEG C, the bottom of remelting tubular type crucible is placed in 2-4mm place on vacuum induction quick quenching furnace runner wheel rim, above-mentioned alloy pig is placed in tubular type crucible and melts, the runner EDGE CONTACT of ejection and rotation from the hole of crucible bottom under ar gas acting after alloy molten, formation thickness is 670-750 μm, width is the alloy strip of 12-15mm, the linear velocity of runner wheel rim is 18-21m/s.
4. the preparation method of many rare-earth phases permanent magnetic material alloy according to claim 3, is characterized in that: in step 5), when nitriding, powder process, to close and state gold bar band and put into nitriding furnace, the ammonia flow of nitriding furnace is 5-10L/min, is warming up to 550-650 DEG C, insulation 8-12min; Take out with after stove cooling, after band is stirred, put into nitriding furnace again, be warming up to 550-650 DEG C, insulation 8-12min, the ammonia flow of stove is 5-10L/min, after the coarse crushing to 3-6mm of cooled nitro-alloy band, then prepares by airflow milling the powder that particle mean size is 2.8-3.2 μm.
5. the preparation method of many rare-earth phases permanent magnetic material alloy according to claim 4, it is characterized in that: in step 5), during compressing, sintering processes, first above-mentioned powder is put into press die, make type at 2-3T pressure, the sintering furnace that compacting base is placed in 1170-1190 DEG C is sintered 2-4 hour, and sintering furnace vacuum level requirements is less than 0.1Pa, last at 400-450 DEG C, vacuum level requirements is less than heat treatment 2-3 hour under the condition of 0.1Pa; And then magnet is placed in the heat-treatment furnace that magnetic field intensity is 6-8T, cools with stove be incubated 2-3h in 1080-1150 DEG C of vacuum environment after, namely obtain many rare-earth phases permanent magnetic material.
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| CN111418034A (en) * | 2017-12-05 | 2020-07-14 | 三菱电机株式会社 | Permanent magnet, method for manufacturing permanent magnet, and rotary machine |
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| CN111418034B (en) * | 2017-12-05 | 2021-08-13 | 三菱电机株式会社 | Permanent magnet, method for manufacturing permanent magnet, and rotary machine |
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