CN101521068A - Rare earth permanent magnet and method of manufacturing the same - Google Patents
Rare earth permanent magnet and method of manufacturing the same Download PDFInfo
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- CN101521068A CN101521068A CNA2008101799497A CN200810179949A CN101521068A CN 101521068 A CN101521068 A CN 101521068A CN A2008101799497 A CNA2008101799497 A CN A2008101799497A CN 200810179949 A CN200810179949 A CN 200810179949A CN 101521068 A CN101521068 A CN 101521068A
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Abstract
A rare earth permanent magnet is prepared by disposing a powdered metal alloy containing at least 70 vol% of an intermetallic compound phase on a sintered body of R-Fe-B system, and heating the sintered body having the powder disposed on surface thereof below the sintering temperature of the sintered body in vacuum or in an inert gas for diffusion treatment. The advantages include efficient productivity, excellent magnetic performance, a minimal or zero amount of Tb or Dy used, an increased coercive force, and a minimized decline of remanence.
Description
Technical field
The present invention relates to a kind of R-Fe-B permanent magnet, wherein intermetallic compound combines with the sintered magnet body with the coercive force that improves it and simultaneously its remanent magnetism decline is reduced to minimum, and relates to its preparation method.
Background technology
Because excellent magnetism, the range of application of Nd-Fe-B permanent magnet enlarges day by day.The challenge that nearest environmental problem is brought expands to industrial equipment, electric automobile and wind-driven generator with the range of application of these magnets from electrical home appliances.This just requires further to improve the performance of Nd-Fe-B magnet.
The performance index of magnet comprise remanent magnetism (or residual magnetic flux density) and coercive force.Can be by improving Nd
2Fe
14The bulk factor of B compound and improve crystal orientation and realize that the remanent magnetism of Nd-Fe-B sintered magnet increases.For this reason, made a large amount of improvements.In order to improve coercive force, known have a diverse ways, comprises grain refinement, adopts the alloy composition with bigger Nd content and add and improve coercitive element such as Al and Ga.The most general current method is with the alloy composition that contains Dy or Tb instead of part Nd.
It is believed that the coercitive generation mechanism of Nd-Fe-B magnet is the nucleation type, wherein the nucleation of the reverse magnetic domain at crystal boundary place has determined coercive force.Usually, at crystal boundary or produce the unordered of crystal structure at the interface.If crystal structure is unordered at Nd
2Fe
14The near interface of B compound (it is the magnet primary phase) crystal grain extends some nanometers to depth direction, this generation that will cause the reduction of magnetocrystalline anisotropy and promote reverse magnetic domain so, thereby reduce coercive force and (see K.D.Durst and H.Kronmuller, " THE COERCIVE FIELD OFSINTERED AND MELT-SPUN NdFeB MAGNETS ", Journal of Magnetism and MagneticMaterials, 68 (1987), 63-75).Nd
2Fe
14Dy or Tb have improved the anisotropy field of this compound phase to the replacement of part Nd in the B compound, so have improved coercive force.Yet when adding Dy or Tb in a conventional manner, the loss of remanent magnetism is inevitably, because Dy or Tb replace the near interface that does not occur over just primary phase, and even occurs in the inside of primary phase.Must use the Tb of a certain amount of costliness and Dy also to produce other problem.
In addition, a large amount of trials have been carried out for the coercive force that improves the Nd-Fe-B magnet.A kind of exemplary trial is two alloyages: prepare the Nd-Fe-B magnet by mixing two kinds of different alloy powder and these mixtures of sintering of forming.The powder of alloy A is by R
2Fe
14The B primary phase is formed, and wherein R is mainly Nd and Pr.The powder of alloy B comprises various additional elements, comprises Dy, Tb, Ho, Er, Al, Ti, V and Mo, and the typical case is Dy and Tb.Then alloy A and B are mixed.Meticulous after this pulverizing, compacting in magnetic field, sintering and Ageing Treatment are prepared the Nd-Fe-B magnet thus.The sintered magnet generation high-coercive force that obtains like this makes remanent magnetism descend simultaneously and reduces to minimum, and this is because R
2Fe
14B compound primary phase crystal grain center does not exist Dy or Tb, on the contrary is positioned at (seeing JP-B 5-31807 and JP-A5-21218) near the crystal boundary such as the additional elements of Dy and Tb.Yet in this method, Dy or Tb diffuse into the inside of primary phase crystal grain during sintering, make that be positioned near the thickness that contains the layer of Dy or Tb the crystal boundary is equal to or greater than about 1 micron, the degree of depth that this significantly takes place greater than the reverse magnetic domain nucleation.It is very satisfied that such result still can not make us.
Recently, developed some kinds of methods make element-specific from the surface of R-Fe-B sintered body to diffusion inside so that improve magnet performance.In a kind of exemplary method, use evaporation or sputtering technology deposition of rare-earth metal (as Yb, Dy, Pr or Tb) or Al or Ta on the surface of Nd-Fe-B magnet, with after-baking.Referring to JP-A 2004-296973, JP-A 2004-304038, JP-A 2005-11973; K.T.Park, K.Hiraga and M.Sagawa, ＂ Effect of Metal-Coating and Consecutive HeatTreatment on Coercivity of Thin Nd-Fe-B Sintered Magnets, ＂ Proceedingsof the 16th International Workshop on Rare-Earth Magnets and TheirApplications.Sendai, p.257 (2000); And K.Machida, et al., ＂ GrainBoundary Modification of Nd-Fe-B Sintered Magnet and MagneticProperties, ＂ Abstracts of Spring Meeting of Japan Society of Powder andPowder Metallurgy, 2004, p.202.Another kind of exemplary method relates to the powder and the heat treatment of using rare earth inorganic compound such as fluoride or oxide on the surface of sintered body, as described in WO 2006/043348 A1.Use these methods, be arranged in the crystal boundary that the lip-deep element of sintered body (for example Dy or Tb) during heating treatment passes sintered body structure and diffuse into sintered body inside then.Therefore, Dy or Tb can be at the crystal boundary place or near the intragranular crystal boundary of sintered body primary phase with high concentration enrichment.Compare with above-described pair of alloyage, these methods produce desirable form.Because magnet character has been reacted this form, therefore realized minimizing and coercitive raising of remanent magnetism decline.Yet, utilize these methods of evaporation or sputter when extensive enforcement, to have the many problems relevant, and have bad productivity ratio with unit and step.
Summary of the invention
An object of the present invention is to provide a kind of R-Fe-B sintered magnet, this magnet prepares by the following method: use the dual alloy billet powder and implement DIFFUSION TREATMENT on sintered body, the feature of described magnet is that the coercive force and the minimized remanent magnetism of effective productivity ratio, excellent magnetism, few or zero Tb or Dy use amount, raising descends.Another purpose is to provide the method for this magnet of preparation.
The inventor finds, when by to R-Fe-B sintered body surface applied based on the alloy powder of the intermetallic compound phase of easy efflorescence and when implementing DIFFUSION TREATMENT and adjusting the R-Fe-B sintered body, the method raising that is improved compared to existing technology of the productivity ratio of this method, and the near interface enrichment of the component of this diffusion alloy primary phase crystal grain in sintered body makes coercive force improve and makes the remanent magnetism reduced minimum simultaneously.The present invention is based on this discovery.
The invention provides rare-earth permanent magnet and preparation method thereof, be defined as follows.
[1] a kind of method for preparing rare-earth permanent magnet may further comprise the steps:
Arrange alloy powder consisting of on the sintered body surface of Ra-T1b-Bc, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, and the b of surplus, described alloy powder consist of R
1 i-M
1 jAnd the intermetallic compound phase that comprises at least 70 volume %, wherein R
1Be at least a element that is selected from the rare earth element that comprises Y and Sc, M
1It is at least a element that is selected among Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, " i " and " j " expression atomic percentage and scope are: 15＜j≤99, the i of surplus, and
The sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is heat-treated, so that make the R in the powder
1And M
1In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside.
[2] method in [1], wherein said deposition step comprises: grind and consist of R
1 i-M
1 jAnd the alloy that comprises at least 70 volume % intermetallic compound phases, wherein R
1, M
1, i and j definition as above, grind to form the average particle size particle size powder of 500 μ m at the most, this powder is dispersed in organic solvent or the water, the slurry that obtains is applied in the sintered body surface, and dry.
[3] method in [1] or [2], wherein heat treatment step is included in 200 ℃ and heat-treats to the temperature between (Ts-10) ℃ and continue 1 minute to 30 hours, and wherein Ts represents the sintering temperature of sintered body.
[4] method in [1], [2] or [3], wherein the shape of sintered body comprises having the least part that size is equal to or less than 20mm.
[5] a kind of method for preparing rare-earth permanent magnet may further comprise the steps:
Consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of R
1 xT
2 yM
1 zAnd the intermetallic compound phase that comprises at least 70 volume %, wherein R
1Be at least a element that is selected from the rare earth element that comprises Y and Sc, T
2Be at least a element that is selected among Fe and the Co, M
1It is at least a element that is selected among Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, x, y and z represent that atomic percentage and scope are: 5≤x≤85,15＜z≤95, surplus be y and y greater than 0, and
The sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is heat-treated, so that make the R in the powder
1And M
1In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside.
[6] method in [5], wherein said deposition step comprises: grind and consist of R
1 xT
2 yM
1 zAnd the alloy that comprises the intermetallic compound phase of at least 70 volume %, wherein R
1, T
2, M
1, x, y and z definition as above, grind to form the average particle size particle size powder of 500 μ m at the most, this powder is dispersed in organic solvent or the water, the slurry that obtains is applied on the sintered body surface, and dry.
[7] method in [5] or [6], wherein heat treatment step is included in 200 ℃ and heat-treats to the temperature between (Ts-10) ℃ and continue 1 minute to 30 hours, and wherein Ts represents the sintering temperature of sintered body.
[8] method in [5], [6] or [7], wherein the shape of sintered body comprises having the least part that size is equal to or less than 20mm.
[9] a kind of rare-earth permanent magnet, it is prepared as follows: consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage table and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of R
1 i-M
1 jAnd the intermetallic compound phase that comprises at least 70 volume %,, R wherein
1Be at least a element that is selected from the rare earth element that comprises Y and Sc, M
1It is at least a element that is selected among Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, " i " and " j " expression atomic percentage and scope are: 15＜j≤99, the i of surplus, the sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is then heat-treated, wherein
R in the powder
1And M
1In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside, thereby the coercive force of described magnet brought up to the magnetic that is higher than former sintered body.
[10] a kind of rare-earth permanent magnet, it is prepared as follows: consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of R
1 xT
2 yM
1 zAnd the intermetallic compound phase that comprises at least 70 volume %, wherein R
1Be at least a element that is selected from the rare earth element that comprises Y and Sc, T
2Be at least a element that is selected among Fe and the Co, M
1It is at least a element that is selected among Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, x, y and z represent that atomic percentage and scope are: 5≤x≤85,15＜z≤95, surplus is y and greater than 0, the sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is then heat-treated, wherein
R in the powder
1And M
1In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside, thereby the coercive force of described magnet brought up to the magnetic that is higher than former sintered body.
[11] a kind of method for preparing rare-earth permanent magnet may further comprise the steps:
Consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of M
1 d-M
2 eAnd the intermetallic compound phase that comprises at least 70 volume %, wherein M
1And M
2Each is selected from least a element among Al, Si, C, P, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, M naturally
1With M
2Difference, " d " and " e " expression atomic percentage and scope are: 0.1≤e≤99.9, the d of surplus, then
The sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is heat-treated, so that make M and M in the powder
2In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside.
[12] method in [11], wherein said deposition step comprises: grind and consist of M
1 d-M
2 eAnd the alloy that comprises the intermetallic compound phase of at least 70 volume %, wherein M
1, M
2, d and e definition as above, grind to form the average particle size particle size powder of 500 μ m at the most, this powder is dispersed in organic solvent or the water, the gained slurry is administered to the surface of this sintered body, and dry.
[13] method in [11] or [12], wherein heat treatment step is included in 200 ℃ and heat-treated 1 minute to 30 hours to the temperature between (Ts-10) ℃, and wherein Ts represents the sintering temperature of sintered body.
[14] method in [11], [12] or [13], wherein the shape of sintered body comprises having the least part that size is equal to or less than 20mm.
[15] a kind of rare-earth permanent magnet, it is prepared as follows: consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of M
1 d-M
2 eAnd the intermetallic compound phase that comprises at least 70 volume %, wherein M
1And M
2Each is selected from least a element among Al, Si, C, P, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, M naturally
1With M
2Different, " d " and " e " expression atomic percentage and scope are: 0.1≤e≤99.9, the d of surplus, the sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is then heat-treated, wherein
M in the powder
1And M
2In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside, thereby the coercive force of this magnet brought up to the magnetic that is higher than former sintered body.
Benefit of the present invention
According to the present invention, the R-Fe-B sintered magnet is by the alloy powder of compound between using based on easy crushing metal on the sintered body and implements the DIFFUSION TREATMENT preparation.The advantage of gained magnet comprises that the coercive force and the minimized remanent magnetism of productivity ratio efficiently, excellent magnetism, few or zero Tb or Dy use amount, raising descend.
Embodiment
In brief, prepare the R-Fe-B sintered magnet in the following way according to the present invention: on sintered body, use the dual alloy billet powder and implement DIFFUSION TREATMENT.The advantage of the magnet that obtains comprises excellent magnetism and few Tb or Dy use amount or does not have Tb or Dy.
The parent material that the present invention uses is to consist of R
a-T
1 b-B
cSintered body, it is commonly called " female sintered body ".Here R is at least a element that is selected from the rare earth element that comprises scandium (Sc) and yttrium (Y), especially is selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb and Lu.Preferably, most of R are Nd and/or Pr.Preferably, comprise that the rare earth element of Sc and Y accounts for the 12-20 atom % (at%) of whole sintered body, and more preferably account for the 14-18at% of whole sintered body.T
1It is at least a element in chosen from Fe (Fe) and the cobalt (Co).B is a boron, and preferably accounts for the 4-7at% of whole sintered body.Especially, when B is 5-6at%, realized coercitive remarkable improvement by DIFFUSION TREATMENT.Surplus is by T
1Form.
Preparation is used for the alloy of female sintered body by the following method: at vacuum or inert gas atmosphere (preferred argon atmospher) deposite metal or alloy raw material, then with melt cast to flat mould, book mould or carry out Strip casting.A kind of possible replacement scheme is a so-called pair-alloyage, and this method comprises: preparation and the R that constitutes the associated alloys primary phase respectively
2Fe
14The B compound is formed approaching alloy and the rich rare earth alloy that serves as the liquid phase auxiliary agent under sintering temperature, with their fragmentations, weigh then and mix.Especially, form approaching alloy with primary phase and stand the homogenizing processing where necessary, so that improve this R
2Fe
14The amount of B compound phase, residual because primary crystal α-Fe has probably, this depends on cooldown rate and alloy composition between casting cycle.It is to continue at least one hour heat treatment down in 700-1200 ℃ in vacuum or Ar atmosphere that homogenizing is handled.As an alternative, can prepare the alloy that this is formed near primary phase by the Strip casting technology.For the rich rare earth alloy that serves as the liquid phase auxiliary agent, can use melt quenching and Strip casting technology and above-mentioned foundry engieering.
Usually the broken or corase grind size to 0.05 to 3mm with alloy, particularly 0.05 to 1.5mm.Broken step adopts Brown mill or hydrogenation to pulverize, and preferably adopts hydrogenation to pulverize for those alloys of Strip casting.Then, for example, on the jet mill that uses high pressure nitrogen, it is 0.2 to 30 μ m that the corase meal fine powder is broken to average particle size particle size, particularly 0.5 to 20 μ m.
Fine powder is pressed shape with forming press under magnetic field.Then, green compact are put into sintering furnace, in this sintering furnace, usually under 900-1250 ℃ of temperature, preferably under 1000-1100 ℃, in vacuum or inert gas atmosphere, carry out sintering.The agglomerate of Huo Deing comprises 60-99 volume % like this, the R of the tetragonal crystal system of preferred 80-98 volume %
2Fe
14The B compound is as primary phase, surplus be 0.5-20 volume % rich rare earth mutually and 0.1-10 volume % be selected from least a compound in the rare earth oxide, and deposit carbide, nitride and the hydroxide of impurity by chance, with and composition thereof or compound.
Can or be processed into reservation shape with the machine work of gained agglomerate.In the present invention, wait to be diffused into the R of sintered body inside
1And/or M
1And T
2, or M
1And/or M
2Provide from this sintered body surface.Therefore, if the part of this sintered body minimum has excessive size, purpose so of the present invention just can not realize.Therefore, described shape comprises that size is equal to or less than 20mm, preferably is equal to or less than 10mm, and lower limit is equal to or greater than the least part of 0.1mm.Described sintered body comprises the restricted especially largest portion of size, and the largest portion size wishes to be equal to or less than 200mm.
According to the present invention, alloy powder is arranged on the described sintered body and stands DIFFUSION TREATMENT.It is to consist of R
1 i-M
1 jOr R
1 xT
2 yM
1 zOr M
1 d-M
2 ePowder metallurgy.This alloy is commonly called " diffusion alloy ".R herein
1Be at least a element that is selected from the rare earth element that comprises Y and Sc, and preferred most of R
1Be Nd and Pr.M
1It is at least a element that is selected among Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi.At alloy M
1 d-M
2 eIn, M
1And M
2Different mutually, and be selected from the group that above-mentioned element constitutes.T
2Be Fe and/or Co.At alloy R
1 i-M
1 jIn, M
1(that is, j=15-99), surplus is R to account for 15-99at%
1At alloy R
1 xT
2 yM
1 zIn, M
1Account for 15-95at% (that is, z=15-95), and R
1(that is, x=5-85), surplus is T to account for 5-85at%
2In other words, y〉0, and T
2Be preferably 0.5-75at%.At alloy M
1 d-M
2 eIn, M
2Account for 0.1-99.9at%, in other words, the scope of e is: 0.1≤e≤99.9.M
1Be to remove M
2Remainder afterwards, promptly d is a surplus.
Described diffusion alloy can comprise idol and deposit impurity such as nitrogen (N) and oxygen (O), and the acceptable total amount of these impurity is equal to or less than 4at%.
The invention is characterized in that described diffusion alloy material comprises the intermetallic compound phase of at least 70 volume % in its structure.If described diffusion material is made of single metal or eutectic alloy, then be difficult for pulverizing, and need special technique, for example carry out efflorescence to obtain fine powder.On the contrary, described intermetallic compound is hard and frangible mutually usually in essence.When the alloy based on these intermetallic compound phases is used as diffusion material, can be simply by utilizing the alloy preparation or the reducing mechanism that in making the R-Fe-B sintered magnet, use easily to obtain fine powder.This is very favourable aspect productivity ratio.Because described diffusion alloy material is advantageously pulverized easily, therefore preferably comprise at least 70 volume % and the more preferably intermetallic compound phase of at least 90 volume %.Should be understood that term " volume % " can exchange with the area percentage of intermetallic compound in the alloy structure cross section.
Can by be prepared as follows comprise at least 70 volume % with R
1 i-M
1 j, R
1 xT
2 yM
1 zOr M
1 d-M
2 eThe diffusion alloy of intermetallic compound phase of expression, as the alloy of female sintered body as described in being used for: at vacuum or inert gas atmosphere (preferred argon atmospher) motlten metal or alloy raw material, then with melt cast in flat mould or book mould.Electric arc melting or Strip casting method also are acceptable.Then, utilize Brown mill or hydrogenation to pulverize with alloy broken or corase grind to the size of about 0.05-3mm, particularly about 0.05-1.5mm.Then, with the meticulous pulverizing of described corase meal, for example by ball mill, vibration milling or utilize the jet mill of high pressure nitrogen.Powder particle size is more little, and diffuser efficiency is high more.Described diffusion alloy comprises with R
1 i-M
1 j, R
1 xT
2 yM
1 zOr M
1 d-M
2 eThe intermetallic compound phase of expression, after powdered, preferred average particle size particle size is equal to or less than 500 μ m, more preferably is equal to or less than 300 μ m, and even more preferably is equal to or less than 100 μ m.Yet if described particle size is too little, the influence of surface oxidation just becomes significantly so, and operational hazards.Therefore the lower limit of average particle size particle size preferably is equal to or greater than 1 μ m.Can use the particle size distribution measuring instrument that for example relies on laser diffractometry or the like, press weight-average diameter D
50(particle diameter or median diameter when accumulating 50 weight %) measures " average particle size particle size " used herein.
After diffusion-alloyed powder was arranged on female sintered body surface, described female sintered body and diffusion-alloyed powder had been equal to or less than in the atmosphere of vacuum or inert gas such as argon (Ar) or helium (He) under the temperature of sintered body sintering temperature (be expressed as Ts unit be ℃) and are heat-treating.This heat treatment is called as " DIFFUSION TREATMENT ".By this DIFFUSION TREATMENT, the R in the diffusion alloy
1, M
1Or M
2Be diffused near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of described sintered body inside.
In the following way diffusion-alloyed powder is arranged on female sintered body surface: for example be dispersed in described powder in the water or in the organic solvent to form slurry, sintered body is immersed slurry, then by air-dry, the heated-air drying or the sintered body of dry dipping in a vacuum.Spraying also is fine.Described slurry can comprise the powder of 1-90 weight %, and the powder of preferred 5-70 weight %.
When the activity coefficient from the element of the diffusion alloy that is applied is minimum 1 volume %, preferably obtains better result during at least 10 volume %, described activity coefficient is with the mean value calculation in the sintered body surrounding space that is equal to or less than the 1mm distance that stretches out from the sintered body surface.The upper limit of activity coefficient is generally equal to or less than 95 volume %, and preferably is equal to or less than 90 volume %, although this is not important.
The condition of DIFFUSION TREATMENT changes with the type and the composition of diffusion alloy, and preferably selects to make at the crystal boundary place of sintered body inside and/or near the enrichment R intragranular crystal boundary of sintered body primary phase
1And/or M
1And/or M
2The temperature of DIFFUSION TREATMENT is equal to or less than the sintering temperature (be expressed as Ts unit ℃) of sintered body.If the temperature of DIFFUSION TREATMENT is higher than Ts, then following problem can take place: (1) thus the structure of sintered body may change make magnetic deterioration and (2) thus because thermal deformation can not keep mach size.Therefore, the temperature of DIFFUSION TREATMENT is equal to or less than Ts ℃ of sintered body, and preferably is equal to or less than (Ts-10) ℃.Can suitably select the lower limit of temperature, yet be typically at least 200 ℃, and preferably at least 350 ℃.The time of DIFFUSION TREATMENT is typically 1 minute to 30 hours.When being less than 1 minute, DIFFUSION TREATMENT is incomplete.If the processing time, then the structure of sintered body may change greater than 30 hours, thereby the component oxidation or the evaporation that take place inevitably make magnetic deterioration, perhaps M
1Or M
2Not only in the crystal boundary place and/or near the enrichment intragranular crystal boundary of sintered body primary phase of sintered body inside, and diffuse into the inside of primary phase crystal grain.The preferred time of DIFFUSION TREATMENT is 1 minute to 10 hours, more preferably 10 minutes to 6 hours.
By suitable DIFFUSION TREATMENT, be arranged in the component R of the lip-deep diffusion alloy of sintered body
1, M
1Or M
2Diffuse into sintered body, main simultaneously crystal boundary migration along sintered body structure inside.This causes following structure: R wherein
1, M
1Or M
2Be enriched near the crystal boundary place and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside.
So the coercive force of the permanent magnet that obtains is improved, because R
1, M
1Or M
2Thereby diffusion improved near the form the primary phase crystal boundary in this structure suppressed primary phase crystal boundary place magnetocrystalline anisotropy decline or produce cenotype at the crystal boundary place.Because described diffusion alloy element does not diffuse into the inside of primary phase crystal grain, therefore suppressed the decline of remanent magnetism.This magnet is high performance permanent magnet.
After the DIFFUSION TREATMENT, described magnet can further be accepted Ageing Treatment to improve coercitive enhancing under 200 to 900 ℃ temperature.
Embodiment
Provide embodiment below and further set forth the present invention, but the present invention is not limited to these embodiment.
Embodiment 1 and Comparative Examples 1
Be prepared as follows magnet alloy: use Nd, Fe and the Co metal of purity at least 99 weight %, and ferroboron, in argon atmospher medium-high frequency heat fused, then alloy melt is poured in the casting in bronze type.On the Brown mill, described alloy ground to form the particle size corase meal of 1mm at the most.
Subsequently, meticulous being ground into of described corase meal had the fine powder that the mass median particle diameter is 5.2 μ m utilizing on the jet mill of high pressure nitrogen.At about 300kg/cm
2Pressure under to described fine powder press just as the time at 1592kAm
-1Magnetic field in be orientated.Then, green compact are put into vacuum sintering furnace, in this vacuum sintering furnace under 1060 ℃ with its sintering 1.5 hours, obtain agglomerate.Use the diamond grinding instrument, on all surface, described agglomerate is machined to the shape of size 4 * 4 * 2mm.With alkaline solution, deionized water, nitric acid and deionized water it is cleaned successively, and dry, obtain to consist of Nd
16.0Fe
Ba1Co
1.0B
5.3Female sintered body.
Use the Nd of purity at least 99 weight % and Al metal and in argon atmospher electric arc melting, prepare and consist of Nd
33Al
67And mainly by intermetallic compound phase NdAl
2The diffusion alloy that constitutes.On ball mill, utilize organic solvent to be ground into the fine powder that the mass median particle diameter is 7.8 μ m with described alloy is meticulous.By electron probe microanalysis (EPMA) (EPMA), described alloy comprises the intermetallic compound phase NdAl of 94 volume %
2
The described diffusion-alloyed powder of 15g mixed forming slurry with 45g ethanol, under ultrasonic agitation, female sintered body immersed in the described slurry 30 seconds.Take out sintered body then and use heated-air drying immediately.
The sintered body that is coated with diffusion-alloyed powder carries out one hour DIFFUSION TREATMENT in a vacuum under 800 ℃, produce the magnet of embodiment 1.Do not having under the situation of diffusion-alloyed powder, described sintered body is being carried out one hour heat treatment separately in a vacuum under 800 ℃, producing the magnet of Comparative Examples 1.
Table 1 has gathered intermetallic compound main in the composition, diffusion alloy of female sintered body in embodiment 1 and the Comparative Examples 1 and diffusion alloy, the temperature and time of DIFFUSION TREATMENT.Table 2 shows the magnetic property of the magnet of embodiment 1 and Comparative Examples 1.As can be seen, the coercive force of the magnet of embodiment 1 (Hcj) is than the big 1300kAm of Comparative Examples 1
-1, and remanent magnetism (Br) decline only is 15mT.
Table 1
Table 2
| Br(T) | Hcj(kAm -1) | (BH) max(kJ/m 3) | |
| Embodiment 1 | 1.310 | 1970 | 332 |
| Comparative Examples 1 | 1.325 | 670 | 318 |
Embodiment 2 and Comparative Examples 2
Be prepared as follows magnet alloy: use Nd, Fe and the Co metal of purity at least 99 weight %, and ferroboron, in argon atmospher medium-high frequency heat fused, then alloy melt is poured in the casting in bronze type.On the Brown mill, described alloy ground to form the particle size corase meal of 1mm at the most.
Subsequently, meticulous being ground into of described corase meal had the fine powder that the mass median particle diameter is 5.2 μ m utilizing on the jet mill of high pressure nitrogen.At about 300kg/cm
2Pressure under to described fine powder press just as the time at 1592kAm
-1Magnetic field in be orientated.Then, green compact are put into vacuum sintering furnace, in this vacuum sintering furnace under 1060 ℃ with its sintering 1.5 hours, obtain agglomerate.Use the diamond grinding instrument, on all surface, described agglomerate is machined to the shape of size 4 * 4 * 2mm.With alkaline solution, deionized water, nitric acid and deionized water it is cleaned successively, and dry, obtain to consist of Nd
16.0Fe
Ba1Co
1.0B
5.3Female sintered body.
Utilize purity be Nd, Fe, Co and the Al metal of at least 99 weight % and in argon atmospher electric arc melting, prepare and have the Nd of consisting of
35Fe
25Co
20Al
20Diffusion alloy.On ball mill, utilize organic solvent to be ground into the fine powder that the mass median particle diameter is 7.8 μ m with described alloy is meticulous.Analyze by EPMA, described alloy comprises Nd (FeCoAl)
2, Nd
2(FeCoAl) and Nd
2(FeCoAl)
17Deng the intermetallic compound phase, has the intermetallic compound phase of 87 volume % altogether.
The described diffusion-alloyed powder of 15g mixed forming slurry with 45g ethanol, under ultrasonic agitation, female sintered body immersed in the described slurry 30 seconds.Take out sintered body then and use heated-air drying immediately.
The sintered body that is coated with diffusion-alloyed powder carries out one hour DIFFUSION TREATMENT in a vacuum under 800 ℃, produce the magnet of embodiment 2.Do not having under the situation of diffusion-alloyed powder, described sintered body is being carried out one hour heat treatment separately in a vacuum under 800 ℃, producing the magnet of Comparative Examples 2.
Table 3 has gathered intermetallic compound main in the composition, diffusion alloy of female sintered body in embodiment 2 and the Comparative Examples 2 and diffusion alloy, the temperature and time of DIFFUSION TREATMENT.Table 4 shows the magnetic property of the magnet of embodiment 2 and Comparative Examples 2.As can be seen, the coercive force of the magnet of embodiment 2 (Hcj) is than the big 1150kAm of Comparative Examples 2
-1, and its remanent magnetism decline only is 18mT.
Table 3
Table 4
| Br(T) | Hcj(kAm -1) | (BH) max(kJ/m 3) | |
| Embodiment 2 | 1.307 | 1820 | 330 |
| Comparative Examples 2 | 1.325 | 670 | 318 |
Embodiment 3
Be prepared as follows magnet alloy: use Nd, Fe and the Co metal of purity at least 99 weight %, and ferroboron, in argon atmospher medium-high frequency heat fused, then alloy melt is poured in the casting in bronze type.On the Brown mill, described alloy ground to form the particle size corase meal of 1mm at the most.
Subsequently, be ground into the fine powder that the mass median particle diameter is 5.2 μ m with described corase meal is meticulous utilizing on the jet mill of high pressure nitrogen.At about 300kg/cm
2Pressure under to described fine powder press just as the time at 1592kAm
-1Magnetic field in be orientated.Then, green compact are put into vacuum sintering furnace, in this vacuum sintering furnace under 1060 ℃ with its sintering 1.5 hours, obtain agglomerate.Utilize the diamond grinding instrument, on all surface, described agglomerate is machined to the shape (embodiment 3-1) of size 50 * 50 * 15mm or is of a size of the shape (embodiment 3-2) of 50 * 50 * 25mm.With alkaline solution, deionized water, nitric acid and deionized water it is cleaned successively, and dry, obtain to consist of Nd
16.0Fe
Ba1Co
1.0B
5.3Female sintered body.
Utilize purity be the Nd of at least 99 weight % and Al metal and in argon atmospher electric arc melting, prepare and consist of Nd
33Al
67And mainly by intermetallic compound phase NdAl
2The diffusion alloy of forming.On ball mill, utilize organic solvent to be ground into the fine powder that the mass median particle diameter is 7.8 μ m with described alloy is meticulous.Analyze by EPMA, described alloy comprises the intermetallic compound phase NdAl of 93 volume %
2
The 30g diffusion-alloyed powder is mixed the formation slurry with 90g ethanol, the female sintered body with embodiment 3-1 and 3-2 under ultrasonic agitation immersed respectively wherein 30 seconds.Take out sintered body then and use heated-air drying immediately.
The sintered body that is coated with diffusion-alloyed powder carries out 6 hours DIFFUSION TREATMENT in a vacuum under 850 ℃, produce the magnet of embodiment 3-1 and 3-2.
Table 5 has gathered main intermetallic compound, the temperature and time of DIFFUSION TREATMENT and the size of sintered body least part in the composition, diffusion alloy of the female sintered body of embodiment 3-1 and 3-2 and diffusion alloy.Table 6 shows the magnetic property of the magnet of embodiment 3-1 and 3-2.As can be seen, be of a size of among the embodiment 3-1 of 15mm 1584kAm at the sintered body least part
-1Coercive force show that DIFFUSION TREATMENT produces bigger effect.By contrast, sintered body least part size surpasses the sintered body of 20mm, for example is of a size of the sintered body of 25mm among the embodiment 3-2, and DIFFUSION TREATMENT produces less influence.
Table 5
Table 6
| Br(T) | Hcj(kAm -1) | (BH) max(kJ/m 3) | |
| Embodiment 3-1 | 1.305 | 1584 | 329 |
| Embodiment 3-2 | 1.305 | 653 | 308 |
Embodiment 4 to 52
Press embodiment 1, apply various female sintered bodies and carry out the DIFFUSION TREATMENT certain time at a certain temperature with various diffusion alloy.Table 7 and 8 has gathered the temperature and time of the type of compound between the composition, the major metal in the diffusion alloy of female sintered body and diffusion alloy and quantity, DIFFUSION TREATMENT.Table 9 and 10 shows the magnetic property of magnet.Notice that the amount of intermetallic compound is to adopt the EPMA assay determination in the diffusion alloy.
Table 7
Table 8
Table 9
| Br(T) | Hcj(kAm -1) | (BH) max(kJ/m 3) | |
| Embodiment 4 | 1.300 | 1871 | 327 |
| Embodiment 5 | 1.315 | 1831 | 333 |
| Embodiment 6 | 1.310 | 1879 | 331 |
| Embodiment 7 | 1.305 | 1966 | 329 |
| Embodiment 8 | 1.240 | 844 | 286 |
| Embodiment 9 | 1.260 | 1059 | 297 |
| Embodiment 10 | 1.280 | 892 | 304 |
| Embodiment 11 | 1.335 | 1059 | 339 |
| Embodiment 12 | 1.252 | 756 | 292 |
| Embodiment 13 | 1.245 | 780 | 288 |
| Embodiment 14 | 1.225 | 892 | 283 |
| Embodiment 15 | 1.220 | 1855 | 282 |
| Embodiment 16 | 1.265 | 1887 | 305 |
| Embodiment 17 | 1.306 | 1528 | 318 |
| Embodiment 18 | 1.351 | 1250 | 341 |
| Embodiment 19 | 1.305 | 1457 | 323 |
| Embodiment 20 | 1.348 | 1297 | 338 |
| Embodiment 21 | 1.311 | 1520 | 322 |
| Embodiment 22 | 1.308 | 1719 | 326 |
| Embodiment 23 | 1.298 | 1767 | 322 |
| Embodiment 24 | 1.304 | 1695 | 316 |
| Embodiment 25 | 1.306 | 1703 | 325 |
| Embodiment 26 | 1.273 | 1306 | 304 |
| Embodiment 27 | 1.265 | 1361 | 305 |
| Embodiment 28 | 1.292 | 1106 | 312 |
| Embodiment 29 | 1.254 | 1258 | 291 |
| Embodiment 30 | 1.325 | 1083 | 332 |
Table 10
| Br(T) | Hcj(kAm -1) | (BH) max(kJ/m 3) | |
| Embodiment 31 | 1.300 | 1910 | 324 |
| Embodiment 32 | 1.315 | 1871 | 329 |
| Embodiment 33 | 1.310 | 1934 | 328 |
| Embodiment 34 | 1.318 | 1958 | 330 |
| Embodiment 35 | 1.305 | 1966 | 326 |
| Embodiment 36 | 1.314 | 1974 | 328 |
| Embodiment 37 | 1.311 | 2006 | 330 |
| Embodiment 38 | 1.263 | 1528 | 297 |
| Embodiment 39 | 1.220 | 1130 | 269 |
| Embodiment 40 | 1.180 | 1186 | 251 |
| Embodiment 41 | 1.235 | 1051 | 278 |
| Embodiment 42 | 1.245 | 1146 | 289 |
| Embodiment 43 | 1.242 | 1154 | 286 |
| Embodiment 44 | 1.104 | 971 | 221 |
| Embodiment 45 | 1.262 | 1043 | 293 |
| Embodiment 46 | 1.173 | 1098 | 255 |
| Embodiment 47 | 1.307 | 971 | 311 |
| Embodiment 48 | 1.285 | 1178 | 309 |
| Embodiment 49 | 1.311 | 1226 | 325 |
| Embodiment 50 | 1.268 | 939 | 298 |
| Embodiment 51 | 1.252 | 1003 | 290 |
| Embodiment 52 | 1.352 | 860 | 341 |
Embodiment 53
Be prepared as follows magnet alloy: use Nd, Fe and the Co metal of purity at least 99 weight %, and ferroboron, in argon atmospher medium-high frequency heat fused, then alloy melt is poured in the casting in bronze type.On the Brown mill, described alloy ground to form the particle size corase meal of 1mm at the most.
Subsequently, be ground into the fine powder that the mass median particle diameter is 5.2 μ m with described corase meal is meticulous utilizing on the jet mill of high pressure nitrogen.At about 300kg/cm
2Pressure under to described fine powder press just as the time at 1592kAm
-1Magnetic field in be orientated.Then, green compact are put into vacuum sintering furnace, in this vacuum sintering furnace under 1060 ℃ with its sintering 1.5 hours, obtain agglomerate.Use the diamond grinding instrument, on all surface, described agglomerate is machined to the shape of size 4 * 4 * 2mm.With alkaline solution, deionized water, nitric acid and deionized water it is cleaned successively, and dry, obtain to consist of Nd
16.0Fe
Ba1Co
1.0B
5.3Female sintered body.
Utilize purity be the Al of at least 99 weight % and Co metal and in argon atmospher electric arc melting, prepare and consist of Al
50Co
50(atom %) and the diffusion alloy that mainly constitutes by intermetallic compound phase AlCo.On ball mill, utilize organic solvent to be ground into the fine powder that the mass median particle diameter is 8.5 μ m with described alloy is meticulous.Analyze by EPMA, described alloy comprises the intermetallic compound phase AlCo of 93 volume %.
The described diffusion-alloyed powder of 15g mixed forming slurry with 45g ethanol, under ultrasonic agitation, female sintered body immersed in this slurry 30 seconds.Take out sintered body then and use heated-air drying immediately.
The sintered body that is coated with diffusion-alloyed powder carries out DIFFUSION TREATMENT in a vacuum and continues for an hour under 800 ℃, produce the magnet of embodiment 53.
Table 11 has gathered the temperature and time of compound, DIFFUSION TREATMENT between the composition, the major metal in the diffusion alloy of female sintered body among the embodiment 53 and diffusion alloy.Table 12 shows the magnetic property of the magnet of embodiment 53.As can be seen, the coercive force of the magnet of embodiment 53 is than the Comparative Examples 1 big 1170kAm of front
-1, and remanent magnetism decline only is 20mT.
Table 11
Table 12
| Br(T) | Hcj(kAm -1) | (BH) max(kJ/m 3) | |
| Embodiment 53 | 1.305 | 1840 | 329 |
Embodiment 54 and Comparative Examples 3
Be prepared as follows magnet alloy: use Nd, Fe and the Co metal of purity at least 99 weight %, and ferroboron, in argon atmospher medium-high frequency heat fused, then alloy melt is poured in the casting in bronze type.On the Brown mill, described alloy ground to form the particle size corase meal of 1mm at the most.
Subsequently, be ground into the fine powder that the mass median particle diameter is 5.2 μ m with described corase meal is meticulous utilizing on the jet mill of high pressure nitrogen.At about 300kg/cm
2Pressure under to described fine powder press just as the time at 1592kAm
-1Magnetic field in be orientated.Then, green compact are put into vacuum sintering furnace, in this vacuum sintering furnace under 1060 ℃ with its sintering 1.5 hours, obtain agglomerate.Utilize the diamond grinding instrument, on all surface, agglomerate is machined to the shape (embodiment 54) of size 50 * 50 * 15mm or is of a size of the shape (Comparative Examples 3) of 50 * 50 * 25mm.With alkaline solution, deionized water, nitric acid and deionized water it is cleaned successively, and dry, obtain to consist of Nd
16.0Fe
Ba1Co
1.0B
5.3Female sintered body.
Utilize purity be the Al of at least 99 weight % and Co metal and in argon atmospher electric arc melting, prepare and consist of Al
50Co
50(atom %) and the diffusion alloy that mainly constitutes by intermetallic compound phase AlCo.On ball mill, utilize organic solvent to be ground into the fine powder that the mass median particle diameter is 8.5 μ m with described alloy is meticulous.Analyze by EPMA, described alloy comprises the intermetallic compound phase AlCo of 92 volume %.
The described diffusion-alloyed powder of 30g mixed forming slurry with 90g ethanol, under ultrasonic agitation, female sintered body of embodiment 54 and Comparative Examples 3 immersed in this slurry 30 seconds.Take out sintered body then and use heated-air drying immediately.
The sintered body that is coated with diffusion-alloyed powder is carried out DIFFUSION TREATMENT in a vacuum continue 6 hours under 850 ℃, produce the magnet of embodiment 54 and Comparative Examples 3.
Table 13 has gathered compound, the temperature and time of DIFFUSION TREATMENT and the size of sintered body least part between the composition, the major metal in the diffusion alloy of female sintered body of embodiment 54 and Comparative Examples 3 and diffusion alloy.Table 14 shows the magnetic property of the magnet of embodiment 54 and Comparative Examples 3.As can be seen, the sintered body least part is of a size of among the embodiment 54 of 15mm, 1504kAm
-1Coercive force demonstrate DIFFUSION TREATMENT and produced bigger effect.By contrast, when the least part of sintered body has size above 20mm, the size of 25mm in the Comparative Examples 3 for example, as coercive force almost increase confirm that DIFFUSION TREATMENT does not almost tell on.
Table 13
Table 14
| Br(T) | Hcj(kAm -1) | (BH) max(kJ/m 3) | |
| Embodiment 54 | 1.306 | 1504 | 328 |
| Comparative Examples 3 | 1.306 | 710 | 309 |
Embodiment 55 to 84
According to embodiment 53, apply different female sintered bodies and carry out the DIFFUSION TREATMENT of uniform temperature certain hour with different diffusion-alloyed powders.Table 15 has gathered the type mutually of compound between the composition, the major metal in the diffusion alloy of female sintered body and diffusion alloy and the temperature and time of quantity, DIFFUSION TREATMENT.Table 16 shows the magnetic property of magnet.Notice that the amount of intermetallic compound phase is to adopt the EPMA assay in the diffusion alloy.
Table 15
Table 16
| Br(T) | Hcj(kAm -1) | (BH) max(kJ/m 3) | |
| Embodiment 55 | 1.303 | 1815 | 327 |
| Embodiment 56 | 1.295 | 1847 | 320 |
| Embodiment 57 | 1.290 | 1982 | 319 |
| Embodiment 58 | 1.315 | 1902 | 334 |
| Embodiment 59 | 1.282 | 1688 | 310 |
| Embodiment 60 | 1.297 | 1815 | 324 |
| Embodiment 61 | 1.190 | 1664 | 268 |
| Embodiment 62 | 1.173 | 1258 | 260 |
| Embodiment 63 | 1.246 | 1186 | 290 |
| Embodiment 64 | 1.370 | 1473 | 350 |
| Embodiment 65 | 1.305 | 1528 | 327 |
| Embodiment 66 | 1.313 | 1401 | 329 |
| Embodiment 67 | 1.312 | 1656 | 325 |
| Embodiment 68 | 1.296 | 1449 | 317 |
| Embodiment 69 | 1.236 | 1640 | 288 |
| Embodiment 70 | 1.312 | 1576 | 330 |
| Embodiment 71 | 1.247 | 1656 | 295 |
| Embodiment 72 | 1.309 | 1775 | 320 |
| Embodiment 73 | 1.295 | 1369 | 323 |
| Embodiment 74 | 1.335 | 1290 | 340 |
| Embodiment 75 | 1.331 | 1242 | 337 |
| Embodiment 76 | 1.301 | 1178 | 322 |
| Embodiment 77 | 1.263 | 1297 | 295 |
| Embodiment 78 | 1.258 | 1098 | 292 |
| Embodiment 79 | 1.314 | 1616 | 330 |
| Embodiment 80 | 1.303 | 1703 | 322 |
| Embodiment 81 | 1.311 | 1560 | 326 |
| Embodiment 82 | 1.342 | 1210 | 342 |
| Embodiment 83 | 1.227 | 1043 | 280 |
| Embodiment 84 | 1.290 | 971 | 314 |
Embodiment 85 to 92 and Comparative Examples 4
Be prepared as follows magnet alloy: use Nd, Fe and the Co metal of purity at least 99 weight %, and ferroboron, in argon atmospher medium-high frequency heat fused, then alloy melt is poured in the casting in bronze type.On the Brown mill, described alloy ground to form the particle size corase meal of 1mm at the most.
Subsequently, be ground into the fine powder that the mass median particle diameter is 4.2 μ m with described corase meal is meticulous utilizing on the jet mill of high pressure nitrogen.Atmosphere is become inert gas atmosphere to suppress the oxidation of fine powder.Then, at about 300kg/cm
2Pressure under to described fine powder press just as the time at 1592kAm
-1Magnetic field in be orientated.Then, green compact are put into vacuum sintering furnace, in this vacuum sintering furnace,, obtain agglomerate 1060 ℃ of following sintering 1.5 hours.Utilize the diamond grinding instrument, on all surface, agglomerate is machined to the shape of size 4 * 4 * 2mm.With alkaline solution, deionized water, nitric acid and deionized water it is cleaned successively, and dry, obtain to consist of Nd
13.8Fe
Ba1Co
1.0B
6.0Female sintered body.
Utilize Dy, Tb, Nd, Pr, Co, Ni and the Al metal of purity at least 99 weight % and in argon atmospher electric arc melting, prepare the different diffusion alloy of forming (atom%) that have shown in table 17.On ball mill, utilize organic solvent to be ground into the fine powder that the mass median particle diameter is 7.9 μ m with each alloy is meticulous.Analyze by EPMA, each alloy all comprises the intermetallic compound phase of 94 volume %, and is shown in table 17.
The 15g diffusion-alloyed powder is mixed the formation slurry with 45g ethanol, under ultrasonic agitation, each female sintered body was immersed this slurry 30 seconds.Take out this sintered body then and use heated-air drying immediately.
The sintered body that is coated with diffusion-alloyed powder is carried out 10 hours DIFFUSION TREATMENT in a vacuum under 840 ℃, produce the magnet of embodiment 85 to 92.The magnet of Comparative Examples 4 also obtains by repeating above-mentioned operation, does not just use diffusion-alloyed powder.
Table 17 has gathered the temperature and time of compound, DIFFUSION TREATMENT between the composition, the major metal in the diffusion alloy of female sintered body of embodiment 85 to 92 and Comparative Examples 4 and diffusion alloy.Table 18 shows the magnetic property of the magnet of described embodiment 85 to 92 and Comparative Examples 4.As can be seen, the coercive force of the magnet of embodiment 85 to 92 is significantly greater than the coercive force of Comparative Examples 4, and remanent magnetism descends and only is about 10mT.
Table 17
Table 18
| Br(T) | Hcj(kAm -1) | (BH) max(kJ/m 3) | |
| Embodiment 85 | 1.411 | 1720 | 386 |
| Embodiment 86 | 1.409 | 1740 | 384 |
| Embodiment 87 | 1.412 | 1880 | 388 |
| Embodiment 88 | 1.410 | 1890 | 385 |
| Embodiment 89 | 1.414 | 1570 | 387 |
| Embodiment 90 | 1.413 | 1580 | 386 |
| Embodiment 91 | 1.409 | 1640 | 384 |
| Embodiment 92 | 1.408 | 1660 | 382 |
| Comparative Examples 4 | 1.422 | 890 | 377 |
Claims (15)
1. method for preparing rare-earth permanent magnet may further comprise the steps:
Consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of R
1 i-M
1 jAnd the intermetallic compound phase that comprises at least 70 volume %, wherein R
1Be at least a element that is selected from the rare earth element that comprises Y and Sc, M
1It is at least a element that is selected among Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, " i " and " j " expression atomic percentage and scope are: 15＜j≤99, the i of surplus and
The sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is heat-treated, so that make the R in the powder
1And M
1In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside.
2. method according to claim 1, wherein said deposition step comprises: grind and consist of R
1 i-M
1 jAnd the alloy that comprises at least 70 volume % intermetallic compound phases, wherein R
1, M
1, i and j definition as above, grind to form the average particle size particle size powder of 500 μ m at the most, described powder is dispersed in organic solvent or the water, the slurry that obtains is applied in the surface of sintered body, and dry.
3. method according to claim 1, wherein said heat treatment step are included in 200 ℃ and carry out 1 minute to 30 hours heat treatment between (Ts-10) ℃, and wherein Ts represents the sintering temperature of sintered body.
4. method according to claim 1, the shape of wherein said sintered body comprise having the least part that size is equal to or less than 20mm.
5. method for preparing rare-earth permanent magnet may further comprise the steps:
Consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of R
1 xT
2 yM
1 zAnd the intermetallic compound phase that comprises at least 70 volume %, wherein R
1Be at least a element that is selected from the rare earth element that comprises Y and Sc, T
2Be at least a element that is selected among Fe and the Co, M
1It is at least a element that is selected among Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, x, y and z represent that atomic percentage and scope are: 5≤x≤85,15＜z≤95, surplus be y and greater than 0 and
The sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is heat-treated, so that make the R in the powder
1And M
1In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside.
6. method according to claim 5, wherein said deposition step comprises: grind and consist of R
1 xT
2 yM
1 zAnd the alloy that comprises at least 70 volume % intermetallic compound phases, wherein R
1, T
2, M
1, x, y and z definition as above, grind to form the average particle size particle size powder of 500 μ m at the most, described powder is dispersed in organic solvent or the water, the slurry that obtains is applied in the surface of sintered body, and dry.
7. method according to claim 5, wherein said heat treatment step are included in 200 ℃ and heat-treat to the temperature of (Ts-10) ℃ and continue 1 minute to 30 hours, and wherein Ts represents the sintering temperature of sintered body.
8. method according to claim 5, the shape of wherein said sintered body comprise having the least part that size is equal to or less than 20mm.
9. rare-earth permanent magnet, it is to adopt following method preparation: consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of R
1 i-M
1 jAnd the intermetallic compound phase that comprises at least 70 volume %, wherein R
1Be at least a element that is selected from the rare earth element that comprises Y and Sc, M
1It is at least a element that is selected among Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, " i " and " j " expression atomic percentage and scope are: 15＜j≤99, the i of surplus, the sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is then heat-treated, wherein
R in the powder
1And M
1In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside, thereby the coercive force of described magnet brought up to the magnetic that is higher than former sintered body.
10. rare-earth permanent magnet, it is to adopt following method preparation: consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of R
1 xT
2 yM
1 zAnd the intermetallic compound phase that comprises at least 70 volume %, wherein R
1Be at least a element that is selected from the rare earth element that comprises Y and Sc, T
2Be at least a element that is selected among Fe and the Co, M
1It is at least a element that is selected among Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, x, y and z represent that atomic percentage and scope are: 5≤x≤85,15＜z≤95, surplus is y and greater than 0, the sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is then heat-treated, wherein
R in the powder
1And M
1In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside, thereby the coercive force of described magnet brought up to the magnetic that is higher than former sintered body.
11. a method for preparing rare-earth permanent magnet may further comprise the steps:
Consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of M
1 d-M
2 eAnd the intermetallic compound phase that comprises at least 70 volume %, wherein M
1And M
2Each is selected from least a element among Al, Si, C, P, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, M naturally
1With M
2Difference, " d " and " e " expression atomic percentage and scope are: 0.1≤e≤99.9, the d of surplus and
The sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is heat-treated, so that make the M in the powder
1And M
2In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside.
12. method according to claim 11, wherein said deposition step comprises: grind and consist of M
1 d-M
2 eAnd the alloy that comprises at least 70 volume % intermetallic compound phases, wherein M
1, M
2, d and e definition as above, grind to form the average particle size particle size powder of 500 μ m at the most, in organic solvent or water, disperse described powder, the slurry that obtains is applied in the surface of sintered body, and dry.
13. method according to claim 11, wherein said heat treatment step are included in 200 ℃ and heat-treat to the temperature of (Ts-10) ℃ and continue 1 minute to 30 hours, wherein Ts represents the sintering temperature of sintered body.
14. comprising, method according to claim 11, the shape of wherein said sintered body have the least part that size is equal to or less than 20mm.
15. a rare-earth permanent magnet, it is to adopt following method preparation: consisting of R
a-T
1 b-B
cThe sintered body surface on arrange alloy powder, wherein R is at least a element that is selected from the rare earth element that comprises Y and Sc, T
1Be at least a element that is selected among Fe and the Co, B is a boron, and " a ", " b " and " c " expression atomic percentage and scope are: 12≤a≤20,4.0≤c≤7.0, the b of surplus, described alloy powder consist of M
1 d-M
2 eAnd the intermetallic compound phase that comprises at least 70 volume %, wherein M
1And M
2Each is selected from least a element among Al, Si, C, P, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb and the Bi, M naturally
1With M
2Different, ＂ d ＂ and ＂ e ＂ represent that atomic percentage and scope are: 0.1≤e≤99.9, the d of surplus, the sintered body that is furnished with described powder in vacuum or inert gas on being equal to or less than under the temperature of sintered body sintering temperature the surface is then heat-treated, wherein
M in the powder
1And M
2In at least a Elements Diffusion near the crystal boundary and/or the intragranular crystal boundary of sintered body primary phase of sintered body inside, thereby the coercive force of described magnet brought up to the magnetic that is higher than former sintered body.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007068803 | 2007-03-16 | ||
| JP2007068823 | 2007-03-16 | ||
| JP2007068823A JP4482769B2 (en) | 2007-03-16 | 2007-03-16 | Rare earth permanent magnet and manufacturing method thereof |
| JP2007068803 | 2007-03-16 | ||
| JP2007-068803 | 2007-03-16 | ||
| JP2007-068823 | 2007-03-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101521068A true CN101521068A (en) | 2009-09-02 |
| CN101521068B CN101521068B (en) | 2012-07-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101799497A Active CN101521068B (en) | 2007-03-16 | 2008-03-14 | Rare earth permanent magnet and method of manufacturing the same |
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| Country | Link |
|---|---|
| JP (1) | JP5093485B2 (en) |
| CN (1) | CN101521068B (en) |
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| JP5093485B2 (en) | 2012-12-12 |
| JP2008263179A (en) | 2008-10-30 |
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