CN100334662C - Method for producing r-t-b based rare earth element permanent magnet - Google Patents

Method for producing r-t-b based rare earth element permanent magnet Download PDF

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CN100334662C
CN100334662C CNB038013134A CN03801313A CN100334662C CN 100334662 C CN100334662 C CN 100334662C CN B038013134 A CNB038013134 A CN B038013134A CN 03801313 A CN03801313 A CN 03801313A CN 100334662 C CN100334662 C CN 100334662C
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alloy
rare earth
earth element
permanent magnet
product
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CN1572005A (en
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石坂力
西泽刚一
日高徹也
福野
内田信也
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TDK Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C33/02—Making ferrous alloys by powder metallurgy
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

A method for producing an R-T-B based rare earth element permanent magnet which is composed of a sintered product having a main phase comprising an R2T14B phase, where R represents one or more rare elements including Y and T represents one or more transition metal elements comprising Fe or Fe and Co, and a grain boundary phase containing R in a content more than that in the main phase, wherein a product being rich in Zr is present in the R2T14B phase, characterized in that it comprises a step of preparing an R-T-B alloy which contains an R2T14B phase as a main phase, contains Zr, and does not contain a product being rich in Zr in the R2T14B phase, and an R-T alloy containing R and T as main components and containing R in a content more than that in the R-T-B alloy, a step of preparing a mixture of a powder comprising the R-T-B alloy with a powder comprising the R-T alloy, a step of manufacturing a formed article comprising the mixture and having a predetermined shape, and a step of sintering the formed article, and in that the product being rich in Zr is formed inside the R2T14B phase in the step of sintering.

Description

The manufacture method of R-T-B based rare earth element permanent magnet
Technical field
The present invention relates to R (R be among the rare earth element more than a kind or 2 kinds, but rare earth element is the notion that contains Y), T (be essential transition metal at least a kind or more with Fe or with Fe and Co) and B (boron) be the manufacture method of the R-T-B based rare earth element permanent magnet of principal component.
Background technology
In rare earth element permanent magnet, owing to R-T-B based rare earth element permanent magnet magnetic characteristic excellence, principal component Nd aboundresources and more cheap, so demand increases year by year.
For the research and development of the magnetic characteristic that improves the R-T-B based rare earth element permanent magnet are carried out energetically.For example, open in the flat 1-219143 communique the spy and report: can improve magnetic characteristic by the Cu that adds 0.02～0.5 atom % in the R-T-B based rare earth element permanent magnet, heat-treat condition also can be improved.But the spy opens the method for being put down in writing in the flat 1-219143 communique, requires such high magnetic characteristic, is inadequate for obtaining than higher coercive force (HcJ) and residual magnetic flux density (Br) particularly for obtaining high-performance magnet.
At this, the magnetic characteristic of the R-T-B based rare earth element permanent magnet that is obtained by sintering exists with ... sintering temperature sometimes.On the other hand, for commercial production scale, it evenly is difficult that the whole zone in sintering furnace makes heating-up temperature.Therefore, for the R-T-B based rare earth element permanent magnet, even the sintering temperature fluctuation still requires to obtain desirable magnetic characteristic.Here, to access the sintering range of desirable magnetic characteristic be the sintering temperature width of cloth to title.
For the R-T-B based rare earth element permanent magnet is made more high performance permanent magnet, be necessary to reduce the oxygen content in the alloy.But, when oxygen content in making alloy reduces, causing easily that in sintering circuit abnormal grain grows up, squareness ratio (being also referred to as square ratio) reduces.This is because the formed oxide of the oxygen in the alloy suppresses growing up of crystal grain.
At this,, discussed the method for in containing the R-T-B based rare earth element permanent magnet of Cu, adding new element as the means that improve magnetic characteristic.Open in the 2000-234151 communique the spy and to report,, add Zr and/or Cr in order to obtain high coercive force and residual magnetic flux density.
Equally, open in the 2002-75717 communique the spy and to report, by ZrB compound fine in the R-T-B based rare earth element permanent magnet that contains Co, Al, Cu and contain Zr, Nb or Hf, NbB compound or HfB compound (to call the M-B compound in the following text) are evenly separated out dispersedly, suppress the grain growth of sintering process, improve the magnetic characteristic and the sintering temperature width of cloth.
Open the 2002-75717 communique according to the spy,, can enlarge the sintering temperature width of cloth by disperseing and separating out the M-B compound.But, to open among 2002-75717 communique the disclosed embodiments 3-1 the spy, the sintering temperature width of cloth is about narrower 20 ℃.Therefore, for the sintering furnace of producing in batches etc.,, wish further to enlarge the sintering temperature width of cloth in order to improve magnetic characteristic.Again, in order to obtain the fully wide sintering temperature width of cloth, the addition that increases Zr is effective.But, follow increasing of Zr addition, residual magnetic flux density reduces, and can not obtain the high characteristic as original purpose.
Summary of the invention
Therefore, the objective of the invention is to: provide the reduction of magnetic characteristic to be controlled to Min. and suppress growing up and can improving the manufacture method of the R-T-B based rare earth element permanent magnet of the sintering temperature width of cloth once again of crystal grain.
The present inventor finds, to containing with specific form in the R-T-B based rare earth element permanent magnet of Zr, more particularly at the R of the principal phase that constitutes the R-T-B based rare earth element permanent magnet 2T 14There is the occasion of the product of enrichment Zr in mutually in B, the reduction of magnetic characteristic can be suppressed at Min. and suppress growing up and improving the sintering temperature width of cloth of crystal grain.And, comprise in the manufacture method of R-T-B based rare earth element permanent magnet of following operation: with R 2T 14The B phase (R be among the rare earth element more than a kind or 2 kinds (but rare earth element is the notion that contains Y), T is to be the essential transition metal more than a kind or 2 kinds based on Fe or Fe and Co) the R-T-B alloy that contains Zr, and contain than the R-T-B alloy and more to many manufacturing process of R based on the R-T alloy of R and T, obtain the operation of the powder that constitutes by described R-T-B alloy and the mixture of the powder that constitutes by described R-T alloy, making is made of the operation of the formed body of reservation shape this mixture, and in the operation of sintered shaped body; This R-T-B based rare earth element permanent magnet is that sintering circuit makes R 2T 14The interior mutually product that generates enrichment Zr of B is important.This interior mutually product has the form of sheet (tabular) or needle-like.
Sintered body of the present invention preferably has following composition: R:25～35 weight %, B:0.5～4.5 weight %, Al and Cu a kind or 2 kinds: 0.02～0.6 weight %, Zr:0.03～0.25 weight %, Co:4 weight % following (not comprising 0), and remainder is essentially the Fe formation, more preferably have following composition: R:28～33 weight %, B:0.5～1.5 weight %, Al:0.03～0.3 weight %, Cu:0.03～0.15 weight %, Zr:0.05～0.2 weight %, Co:0.1～below the 2.0 weight %, and remainder is essentially Fe and constitutes, and wherein Zr is preferably established at 0.1～0.15 weight % especially.
Description of drawings
Fig. 1 is illustrated in the combination of low R alloy that the 1st embodiment uses and high R alloy and the chart of the permanent magnet that obtains.
Fig. 2 is the chart that is illustrated in the magnetic characteristic of the permanent magnet that the 1st embodiment obtains.
Fig. 3 is the relation curve that is illustrated in interpolation element M (Zr or Ti) amount with the residual magnetic flux density (Br) of the permanent magnet that the 1st embodiment obtains.
Fig. 4 is illustrated in interpolation element M (Zr or the Ti) amount of the permanent magnet that the 1st embodiment obtains and the relation curve of coercive force (HcJ).
Fig. 5 is the relation curve that is illustrated in interpolation element M (Zr or Ti) amount with the squareness ratio (Hk/HcJ) of the permanent magnet that the 1st embodiment obtains.
Fig. 6 is TEM (the Transmission Electron Microscope: photo transmission electron microscope) of the sample (the Zr amount is the sample of 0.10 weight %) of expression the 1st embodiment.
Fig. 7 (a) is EDS (the EnergyDispersive X-ray Fluorescence Spectroscopy: distribution map energy dispersion type x-ray analysis equipment optical spectroscopy) of the product that exists in the sample of expression the 1st embodiment.
Fig. 7 (b) is the R of the sample (Zr content is the sample of 0.10 weight %) of expression the 1st embodiment 2T 14The EDS distribution map of B phase.
Fig. 8 is the TEM high resolution picture of the sample (Zr content is the sample of 0.10 weight %) of expression the 1st embodiment.
Fig. 9 is the TEM photo of the sample (Zr content is the sample of 0.10 weight %) of expression the 1st embodiment.
Figure 10 is the TEM photo of the sample (Zr content is the sample of 0.10 weight %) of expression the 1st embodiment.
Figure 11 (a) is that (Electron Probe Micro Analyzer: Zr electron probe microanalyzer) surveys and draws result's photo (hypomere) and surveys and draws the photo (epimere) of result at the composition picture of same visual field with Zr the EPMA that represents the sample (Zr content is the sample of 0.10 weight %) of the 1st embodiment.
Figure 11 (b) be expression comparative example 2 sample (Zr content is the sample of 0.10 weight %) EPMA Zr mapping result photo (hypomere) and with the photo (epimere) of Zr mapping result at the composition picture of same visual field.
Figure 12 is the chart that is illustrated in the magnetic characteristic of the permanent magnet that the 2nd embodiment obtains.
Figure 13 is the sintering temperature of expression the 2nd embodiment and the relation curve of residual magnetic flux density (Br).
Figure 14 is the sintering temperature of expression the 2nd embodiment and the relation curve of coercive force (HcJ).
Figure 15 is the sintering temperature of expression the 2nd embodiment and the relation curve of squareness ratio (Hk/HcJ).
Figure 16 is illustrated in the residual magnetic flux density (Br) and the corresponding relation curve of squareness ratio (Hk/HcJ) that makes each sintering temperature among the 2nd embodiment.
Figure 17 is that low R alloy that expression the 3rd embodiment uses makes up with high R alloy phase and the chart of the composition of the permanent magnet that obtains.
Figure 18 is the chart of the magnetic characteristic of the permanent magnet that obtains of expression the 3rd embodiment.
Figure 19 is illustrated in the combination of the low R alloy that uses among the 4th embodiment and high R alloy and the chart of the composition of the permanent magnet that obtains.
Figure 20 is the chart that is illustrated in the magnetic characteristic of the permanent magnet that obtains among the 4th embodiment.
Embodiment
Below, describe with regard to the form of enforcement of the present invention.
＜tissue 〉
As everybody knows, the permanent magnet that obtains according to the present invention contains at least by R 2T 14The principal phase that B phase (R is that (but rare earth element is the notion that contains Y), the T more than a kind or 2 kinds among the rare earth element is to be essential more than a kind or 2 kinds of transition metal with Fe or with Fe and Co) constitutes and than principal phase contain more many R crystal boundary mutually.Feature of the present invention is to make R 2T 14There is the product of enrichment Zr in mutually in B.Exist the R-T-B based rare earth element permanent magnet of this product the reduction of magnetic characteristic can be suppressed in the Min. and suppress the growing up of crystal grain, and can access the sintering temperature width of cloth of broad.This product is present in R 2T 14B is necessary in mutually, but and does not require and all be present in R 2T 14B mutually in.Again, to be present in crystal boundary also passable in mutually for this product.But, only there is the occasion of the product of enrichment Zr in mutually at crystal boundary, can not enjoy effect of the present invention.
For this R-T-B based rare earth element permanent magnet, as R 2T 14The interior mutually interpolation element that forms product of B, the past is Ti (for example J.Appl.Phys.69 (1991) 6055) as everybody knows.The present inventor finds, by adding Zr and Ti at R 2T 14When B forms product in mutually, obtain enlarging the sintering temperature width of cloth effective.Here, adding the occasion of Zr,, causing the reduction of magnetic characteristic hardly, specifically causing the reduction of residual magnetic flux density (Br) hardly even when adding the amount of the effect that can fully enlarge the sintering temperature width of cloth.Know that on the other hand in the occasion of adding Ti, when adding the amount of the effect that can fully enlarge the sintering temperature width of cloth, residual magnetic flux density (Br) reduces significantly, and is unsatisfactory on the implementation.As above, be defined as the composition of enrichment Zr by the composition that makes product, the permanent magnet of high characteristic is made on the temperature web stabilization ground of broad becomes possibility.
The present inventor confirms, for the product that makes enrichment Zr is present in R 2T 14B mutually in, the main points of several respects are arranged on method for making.A series of operation according to the manufacture method of permanent magnet of the present invention will be narrated afterwards, just be present in R for the product of enrichment Zr at this 2T 14The interior mutually main points of B are illustrated.
As the manufacture method of R-T-B based rare earth element permanent magnet, there are two kinds of methods: promptly being the method (to call " mixing method " in the following text) of initial feed with the corresponding to single alloy of the desired composition method (to call " simplex method " in the following text) that is initial feed and with multiple alloy with different compositions.Mix rule with R 2T 14B contains and more manys the alloy (high R alloy) of R as initial feed for the alloy of main body (low R alloy) and than hanging down the R alloy mutually.
The present inventor makes among low R alloy and high R alloy arbitrary contains Zr, obtains the R-T-B based rare earth element permanent magnet.Results verification contains Zr and the occasion of making permanent magnet, at R in making low R alloy 2T 14There is the product of enrichment Zr in mutually in B.Confirm on the other hand, in making high R alloy, contain Zr and the occasion of making permanent magnet, be not present in R at the product of enrichment Zr 2T 14B mutually in.
Even if in making low R alloy, contain the occasion of Zr, be present in R at the product of the stage enrichment Zr of low R alloy again, 2T 14The B phase time, the product of enrichment Zr is present in the enrichment R phase (crystal boundary phase) of the triple point that is in the sintering structure behind sintering, does not confirm at R 2T 14There is the product of enrichment Zr in mutually in B.Therefore, in order to make the R of R-T-B based rare earth element permanent magnet 2T 14There is the product of enrichment Zr in mutually in B, makes R in the stage of raw alloy 2T 14It is important that there is not the product of enrichment Zr in B in mutually.
For this reason, be necessary to consider the manufacture method of raw alloy.In the occasion of making low R alloy, be necessary to control the peripheral speed of chill roll with the Strip casting method.In the slower occasion of the peripheral speed of chill roll, when causing the separating out of α-Fe, in the R of low R alloy 2T 14The interior mutually product that generates enrichment Zr of B.Through inventor's research, the peripheral speed of chill roll can access R in the scope of 1.0～1.8m/s 2T 14There is not the low R alloy of the product of enrichment Zr in mutually in B.And, can access the permanent magnet of high magnetic characteristic by using this low R alloy.
Again, even obtain R 2T 14There is not the low R alloy of the product of enrichment Zr in mutually in B, to its impose heat treatment again with it as raw alloy, also be unfavorable for the present invention.This is because impose heat treatment then at the R that hangs down the R alloy by (greatly about more than 700 ℃) in the humidity province of hanging down the R alloy organizing in change 2T 14The interior mutually cause that can generate the product of enrichment Zr of B.
＜chemical composition 〉
Secondly, the desirable chemical composition with regard to R-T-B based rare earth element permanent magnet of the present invention describes.Here said chemical composition is meant the chemical composition behind the sintering.
R-T-B based rare earth element permanent magnet of the present invention contains the R of 25～35 weight %.
Here, R be among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu and Y, select more than a kind or 2 kinds.When R contains quantity not sufficient 25 weight %, become the R of the principal phase of rare earth element permanent magnet 2T 14B 1The generation of phase is insufficient.Therefore, α-Fe with soft magnetism etc. separates out, and coercive force significantly descends; On the other hand, when R content surpasses 35 weight %, as the R of principal phase 2T 14B 1The volume ratio of phase descends, and residual magnetic flux density reduces.Again, when R content surpassed 35 weight %, R and oxygen reaction increased the oxygen amount that contains, and reduced mutually the effective R enrichment of coercive force takes place thereupon, caused coercitive reduction.Therefore, the R amount is determined at 25～35 weight %.Preferred R amount is 28～33 weight %, and preferred R amount is 29～32 weight %.
The aboundresources of Nd, relatively more cheap, therefore select Nd comparatively desirable as the principal component of R.Again, containing Dy anisotropy field is increased, is effective to coercive force is improved therefore.Therefore, R selects Nd and Dy, and the total of Nd and Dy is preferably 25～33 weight %.And in this scope, the amount of Dy is preferably 0.1～8 weight %.According to paying attention to residual magnetic flux density and coercitive degree separately, Dy definite its amount in above-mentioned scope is advisable.That is, in the occasion of wishing to get high residual magnetic flux density, the Dy amount is preferably 0.1～3.5 weight %, is wishing to get the occasion of high-coercive force, and the Dy amount is preferably 3.5～8 weight %.
Again, rare earth element permanent magnet boracic of the present invention (B) 0.5～4.5 weight %.In the occasion of B less than 0.5 weight %, can not obtain high coercive force; But cross the occasion of 4.5 weight % at B ultrasonic, the tendency that exists residual magnetic flux density to reduce.Therefore, be defined as 4.5 weight % on.Preferred B content is 0.5～1.5 weight %, and preferred B content is 0.8～1.2 weight %.
R-T-B based rare earth element permanent magnet of the present invention can contain Al and Cu a kind or 2 kinds in the scope of 0.02～0.6 weight %.By making it contain Al and Cu a kind or 2 kinds in this scope, the improvement of the high-coercive forceization of resulting permanent magnet, high corrosion-resistantization and temperature characterisitic becomes possibility.In the occasion of adding Al, preferred Al amount is 0.03～0.3 weight %, and preferred Al amount is 0.05～0.25 weight %.Again, in the occasion of adding Cu, the Cu amount (does not comprise 0) below 0.3 weight %, and preferred Cu amount (does not comprise 0) below 0.15 weight %, and preferred Cu amount is 0.03～0.08 weight %.
R-T-B based rare earth element permanent magnet of the present invention is in order to make R 2T 14B generates the product of enrichment Zr in mutually, preferably contains the Zr of 0.03～0.25 weight %.For the magnetic characteristic of making every effort to the R-T-B based rare earth element permanent magnet improves, the Zr performance suppresses the effect that the crystal grain of sintering process is grown up unusually when reducing oxygen content, makes the even tissue of sintered body and tiny.Therefore, Zr is remarkable in low its effect of occasion of oxygen content.The preferred content of Zr is 0.05～0.2 weight %, and preferred content is 0.1～0.15 weight %.
The oxygen content of R-T-B based rare earth element permanent magnet of the present invention is below 2000ppm.In oxygen content for a long time, increase mutually, magnetic characteristic is reduced as the oxide of non magnetic composition.At this, the present invention is defined as the oxygen amount that contains in the sintered body below the 2000ppm, is preferably below the 1500ppm, more preferably below the 1000ppm.But, the oxygen content reduction can be reduced have the oxide phase that suppresses the grain growth effect, when sintering, in the process that obtains abundant density rising, cause grain growth easily.At this, the present invention makes in the R-T-B based rare earth element permanent magnet to contain can bring into play in the sintering process with scheduled volume and suppresses grow up the unusually Zr of effect of crystal grain.
R-T-B based rare earth element permanent magnet of the present invention contains Co and (do not comprise 0) below 4 weight %, is preferably 0.1～2.0 weight %, more preferably 0.3～1.0 weight %.It is mutually same with Fe that Co forms, and corrosion proof raising mutually produces effect with crystal boundary to the raising of Curie temperature.
＜manufacture method 〉
Secondly, just describe according to the ideal form of the manufacture method of R-T-B based rare earth element permanent magnet of the present invention.
The present invention uses with R 2T 14B contains for the alloy of main body (low R alloy) and than low R alloy mutually and more manys alloy (high R alloy) the manufacturing R-T-B based rare earth element permanent magnet of R.
At first, by feed metal in a vacuum or in the inert gas, is preferably carried out Strip casting in the Ar protective atmosphere, obtain low R alloy and high R alloy.At this, such as described above, for the band that obtains, especially the low-alloy band is necessary to consider at R 2-T 14-B does not generate the product of enrichment Zr in mutually.Particularly, the peripheral speed of chill roll is set in the scope of 1.0～1.8m/s.The peripheral speed of desirable chill roll is 1.2～1.5m/s.
Has the R that does not have enrichment Zr product 2T 14After the low R alloy of B phase is obtained, before sintering circuit described later, do not make it at R 2T 14Interior mutually this product that generates of B is even it keeps this R 2T 14The form of B phase is important for the present invention.For example, before pulverizing the pulverizing process of beginning, avoid comparatively desirable in the heat treatment of carrying out heat tracing more than 700 ℃ to low R alloy from hydrogen.For this point, in the 1st embodiment described later, also to introduce.
In the form of this enforcement, the item of feature is to add the Zr this point at low R alloy.As＜tissue〉the hurdle in illustrate like that, this is in order to pass through at R 2T 14B adds Zr in the low R alloy of product of no enrichment Zr in mutually, can make the R of R-T-B based rare earth element permanent magnet 2T 14There is the product of enrichment Zr in mutually in B.In low R alloy, except rare earth element, Fe, Co and B, can make it contain Cu and Al.In high R alloy, except rare earth element, Fe, Co, can make it contain Cu and Al again.Also can make in the high R alloy and contain B.
After low R alloy and high R alloy were made, their raw alloy can be pulverized respectively or together.Pulverizing process has coarse crushing operation and the broken operation of fine powder.At first, the coarse crushing of raw alloy difference is arrived about the hundreds of μ m of particle diameter.Coarse crushing is advisable in inert protective gas with bruisher, jaw crusher, Blang's pulverizer (Block ラ ウ Application ミ Le) etc.For the meal fragility is improved, make it inhale that to carry out coarse crushing behind hydrogen comparatively effective.Again, hydrogen is emitted after inhaling hydrogen, carry out coarse crushing again.
The coarse crushing operation moves to the broken operation of fine powder after finishing.The broken main use aeropulverizer of fine powder, the corase meal about the hundreds of μ m of particle diameter is crushed to average particulate diameter 3～5 μ m.Aeropulverizer is to make it high speed airflow take place and quicken the coarse crushing powder by this high speed airflow to make it that method of colliding and pulverizing with the collision of target or chamber wall mutually between the coarse crushing powder take place from narrow nozzle ejection the inert gas of high pressure (for example nitrogen).
In the broken operation of fine powder,, will in blanket of nitrogen, mix through fine powder broken low R alloy powder and high R alloy powder in the occasion of the pulverizing of hanging down R alloy and high R alloy respectively.The blending ratio of low R alloy powder and high R alloy powder gets final product about 80: 20～97: 3 in weight ratio.In like manner, the blending ratio when low R alloy powder is pulverized with high R alloy powder also is to get final product about 80: 20～97: 3 in weight ratio.When fine powder is broken,, can access the higher fine powder of orientation when moulding by adding the additives such as zinc stearate about 0.01～0.3 weight %.
Then, the mixed-powder that low R alloy powder and high R alloy powder are constituted be filled to by electromagnet embrace round mould in, apply magnetic field and make crystal axis become state of orientation in magnetic field, to be shaped.Be shaped in this magnetic field, in the magnetic field of 12.0～17.0kOe with 0.7～1.5t/cm 2About pressure get final product.
After in magnetic field, being shaped, its formed body sintering in a vacuum or in the inert protective gas.Sintering temperature is necessary according to not equal all condition adjustment of composition, breaking method, granularity and particle size distribution, gets final product about 1～5 hour at 1000～1100 ℃ of sintering.In the present invention, make the product of enrichment Zr at R in this sintering circuit 2T 14B is interior mutually to be generated.Although the mechanism that generates behind sintering at the product of low R alloy stage and non-existent enrichment Zr it be unclear that, in low R alloy stage solid solution in R 2T 14The possibility that the interior mutually Zr of B separates out in sintering circuit exists.
Behind the sintering, can impose Ageing Treatment to the sintered body that obtains.Ageing Treatment is being important aspect the control coercive force.Dividing 2 sections occasions of carrying out Ageing Treatment, near 800 ℃ and to carry out the insulation of the scheduled time near 600 ℃ be effective.Coercive force increases when carrying out near the heat treatment 800 ℃ behind sintering, so mixing method is especially effective.Again, because near the heat treatment 600 ℃ makes coercive force that very big increase be arranged, therefore with 1 section occasion of carrying out Ageing Treatment, near the Ageing Treatment that imposes 600 ℃ gets final product.
(embodiment)
＜the 1 embodiment 〉
Make the R-T-B based rare earth element permanent magnet according to following manufacturing process.
1) raw alloy
Make by the Strip casting method and to have shown in Figure 11 form and the raw alloy (band) of thickness.The peripheral speed of chill roll: for low R alloy is 1.5m/s; For high R alloy is 0.6m/s.The thickness of alloy is the average thickness value of measuring 50 linecasting sheets (band).But for the low R alloy of Fig. 1 comparative example 3, the peripheral speed of chill roll is decided to be 0.6m/s.Again, for the low R alloy of the embodiment 1 of Fig. 1, in R 2T 14B does not find the product (with product in calling in the following text mutually) of enrichment Zr in mutually, in contrast to this, confirms at R in the low R alloy of comparative example 3 2T 14There is the product of enrichment Zr in mutually in B.
2) hydrogen pulverizing process
In the Ar protective atmosphere, carry out 600 ℃ * 1 hour dehydrogenation after at room temperature making it inhale hydrogen, implement the hydrogen pulverization process.
In order to obtain high magnetic characteristic, in this experiment with the Control for Oxygen Content of sintered body below 2000ppm, therefore pulverize (recovery after the pulverization process) is controlled at not enough 100ppm to the protective atmosphere of each operation of sintering (input sintering furnace) oxygen concentration from hydrogen.
3) mixing-pulverizing process
Usually carry out 2 sections broken pulverizing of coarse crushing and fine powder, but omit the coarse crushing operation in the present embodiment.
Carry out the broken additive package before of fine powder.The kind of additive is restriction especially not, as long as the additive of the raising of orientation when selecting aptly to help smashing raising and shaping, add the zinc stearate of 0.05 weight % in the present embodiment, will hang down the R alloy with the combination of embodiment shown in Figure 11, comparative example 1～comparative example 3 and in Nautamixer, mix 30 minutes with high R alloy.Again, among embodiment 1, comparative example 1～comparative example 3 arbitrary, the blending ratio of its low R alloy and high R alloy is 90: 10.
Then, it is broken to carry out fine powder with aeropulverizer, till the alloy powder average diameter becomes 4.8～5.1 μ m.
4) forming process
With the fine powder that obtains in the magnetic field of 15.0kOe with 1.2t/cm 2Pressure forming, obtain formed body.
5) sintering, timeliness operation
This formed body is carried out quenching in 1070 ℃ of sintering in a vacuum after 4 hours.Then, the sintered body that obtains is imposed 800 ℃ * 1 hour 2 sections Ageing Treatment with 550 ℃ * 2.5 hours (all in the Ar protective atmosphere).
For the permanent magnet that obtains, measure magnetic characteristic by the B-H plotter, it the results are shown in Fig. 2～Fig. 5.Again, in Fig. 2～Fig. 5, Br represents that residual magnetic flux density, HcJ represent that coercive force, " Hk/HcJ " represent squareness ratio.Again, squareness ratio (Hk/HcJ) is the index of magnetic property, the rectangle stretching degree in the 2nd quadrant of expression magnetic hysteresis loop.Hk is 90% o'clock the external magnetic field strength that magnetic flux density becomes residual magnetic flux density in the 2nd quadrant of magnetic hysteresis loop.In Fig. 2～Fig. 5, interior mutually product is identified usefulness " zero " symbolic representation of existence, and interior mutually product is identified non-existent usefulness " * " symbolic representation.The affirmation of mutually interior product is based on (the Transmission Electron Microscope: observation transmission electron microscope (the system TEM-3010 of Jeol Ltd.)) according to TEM.Observe sample and make, observe R of the ion milling method 2T 14The C face of B phase.Do not have the existence of product in confirming mutually in the comparative example 3, but crystal boundary mutually in affirmation the existence of the product of enrichment Zr is arranged.
From Fig. 2 and Fig. 5 as can be known, for the R-T-B based rare earth element permanent magnet (embodiment 1, comparative example 1) that product is arranged in confirming mutually, abnormal grain is grown up and is suppressed, and by a small amount of interpolation M (Zr or Ti), squareness ratio (Hk/HcJ) is enhanced.But, as shown in Figure 3, select the occasion of Ti as adding element M, the reduction of residual magnetic flux density (Br) is remarkable.Again, for the R-T-B based rare earth element permanent magnet (comparative example 2, comparative example 3) that does not have product in confirming mutually, the Zr of the volume by adding 0.2 weight %, squareness ratio (Hk/HcJ) improves (with reference to figure 5), but residual magnetic flux density (Br) still reduces (with reference to figure 3).Such as shown above, confirm to have the R-T-B based rare earth element permanent magnet of interior product mutually, when suppressing residual magnetic flux density (Br) reduction, can access high squareness ratio (Hk/HcJ).
Again, for confirming at low R alloy stage R 2T 14The comparative example 3 of product in B has in mutually mutually, the reason of product was not done following supposition in its R-T-B based rare earth element permanent magnet did not exist mutually: low its R of R alloy stage 2T 14The B product of the interior enrichment Zr that generates (product mutually) mutually looks very thick.Therefore do not cause volumetric expansion even can infer this product through the hydrogen pulverization process yet, can be interpreted as, when hydrogen is pulverized in R 2T 14B cracks with the interface of this product.When under this state, supplying with pulverizing process, this product and R 2T 14B is separated, and this product no longer is included in R as a result 2T 14B mutually in, with R 2T 14B has an independent existence mutually.Therefore can think, even also just just there is the product of enrichment Zr in mutually through sintering process according to the R-T-B based rare earth element permanent magnet of comparative example 3 at crystal boundary.
Zr amount for embodiment 1 is the R-T-B based rare earth element permanent magnet of 0.10 weight %, with the above-mentioned the same tem observation that carries out.Observed result is shown in Fig. 6～Fig. 8.Again, Fig. 6 is that Zr amount is that TEM photo, Fig. 7 of the sample of 0.10 weight % is the product that exists in this sample and the R of this sample 2T 14The EDS of B phase (Energy Dispersive X-ray FluorescenceSpectroscopy: distribution map energy dispersion type x-ray analysis equipment optical spectroscopy); Fig. 8 is the TEM high resolution picture of this sample.
As shown in Figure 6, at R 2T 14B can confirm in mutually to have axial ratio bigger mutually in product.This product has the form of sheet (promptly tabular) or needle-like.Again, Fig. 6 is a photo of observing the section of sample, judges that therefore its interior mutually product is that sheet or needle-like are difficult.When considering the observed result of other sample and Fig. 8, mutually in product have the length of several 100 μ m and the width of number nm～15nm.This mutually in the detailed chemical composition of product it be unclear that, but can confirm from Fig. 7 (a), this mutually in product enrichment Zr at least.Again, the observed result of other sample, except axial ratio big mutually in the product, as Fig. 9 and as shown in Figure 10, also observe unsetting and circular interior mutually product.In embodiment 1, observe 20 crystal grain (R again, 2T 14The B phase) result wherein has 6 crystal grain to observe interior mutually product.In contrast to this, in comparative example 2,20 whole crystal grain (R 2T 14The B phase) in, do not observe interior mutually product.
The Zr amount that the hypomere of Figure 11 (a) is expressed embodiment 1 is EPMA (the Electron Probe Micro Analyzer: Zr mapping result electron probe microanalyzer) of the sample of 0.10 weight %.The epimere of Figure 11 (a) is represented the composition picture of the Zr mapping result shown in the hypomere with Figure 11 (a) in same visual field.Again, the hypomere of Figure 11 (b) represents that the Zr amount of comparative example 2 is the Zr mapping result of EPMA of the sample of 0.10 weight %.The epimere of Figure 11 (b) is represented the composition picture of the Zr mapping result shown in the hypomere with Figure 11 (b) in same visual field.
The same with the observed result of TEM, from Figure 11 (a) as can be known, there is the R of enrichment Zr in embodiment 1 2T 14B phase and also have mutually Zr at crystal boundary.In contrast to this, fail to confirm to have the R of enrichment Zr at comparative example 2 from Figure 11 (b) 2T 14The B phase, Zr only be present in crystal boundary mutually in.
＜the 2 embodiment 〉
Interpolation element M (Zr or the Ti) amount of forming for sintered body be the sample of 0.10 weight % in 1010～1090 ℃ temperature range sintering 4 hours respectively, obtain the R-T-B based rare earth element permanent magnet with embodiment 1 in addition the samely.To the R-T-B based rare earth element permanent magnet that obtains, measure magnetic characteristic with embodiment 1 the samely.It the results are shown in Figure 12.Magnetic characteristic is shown in Figure 13～Figure 15 with the variation of sintering temperature again.Again, with the magnetic characteristic under each sintering temperature with squareness ratio (Hk/HcJ) Figure 16 that the results are shown in respect to residual magnetic flux density (Br) mapping.
As Figure 12～as shown in Figure 16 as can be known, the occasion of product in obtaining mutually can stably obtain high magnetic characteristic in the sintering range of broad as adding element M interpolation Zr.Particularly, according to embodiments of the invention 2, can access the residual magnetic flux density (Br) more than the 13.9kG, coercive force (HcJ) and the squareness ratio more than 95% (Hk/HcJ) more than the 13.0kOe 1030～1090 ℃ sintering ranges.When adding Ti as the interpolation element M, residual magnetic flux density (Br) reduces (comparative example 4), the occasion of product in not existing mutually, and squareness ratio (Hk/HcJ) is not good, the sintering temperature width of cloth yet narrow (comparative example 5).
＜the 3 embodiment 〉
With the peripheral speed of chill roll is that the Strip casting method of 0.6～1.8m/s is made and had 4 kinds low R alloys of composition shown in Figure 17 and thickness, 2 kinds high R alloys.Then, obtain 4 kinds of R-T-B based rare earth element permanent magnets according to combination shown in Figure 17.Again, any to Sample A～D, the blending ratio of low R alloy and high R alloy all is 90: 10.Low R alloy shown in Figure 17 is carried out hydrogen with high R alloy with embodiment 1 the samely to be pulverized.Add the butyl oleate of 0.05 weight % after the hydrogen pulverization process, low R alloy and high R alloy were mixed 30 minutes according to shown in Figure 17 being combined in the Nautamixer.Be broken to average particulate diameter 4.1 μ m by the aeropulverizer fine powder then.Carry out 4 hours sintering after the powder that obtains is shaped in magnetic field with similarly to Example 1 condition 1010～1090 ℃ temperature.Then, carry out 2 sections Ageing Treatment of 800 ℃ * 1 hour and 550 ℃ * 2.5 hours.Composition, oxygen content and the nitrogen content of the sintered body that obtains are shown in Figure 17, magnetic characteristic is shown in Figure 18.
As shown in Figure 18, can access the residual magnetic flux density (Br) more than the 14.0kG, coercive force (HcJ) and the squareness ratio more than 95% (Hk/HcJ) more than the 13.0kOe for Sample A in 1030～1070 ℃ sintering range.
Compare with Sample A, for Nd content lower sample B and sample C, can access the residual magnetic flux density (Br) more than the 14.0kG, coercive force (HcJ) and the squareness ratio more than 95% (Hk/HcJ) more than the 13.5kOe in 1030～1070 ℃ sintering ranges.
Compare with Sample A,, can access the residual magnetic flux density (Br) more than the 13.5kG, coercive force (HcJ) and the squareness ratio more than 95% (Hk/HcJ) more than the 15.5kOe in 1030～1070 ℃ temperature ranges for the higher sample D of Dy content.
Again, to the result of the sample tem observation of 1050 ℃ of sintering, product in all samples are all observed mutually.
By above result as can be known, the occasion of product in existing mutually can obtain high magnetic characteristic on the wide temperature web stabilization ground more than 40 ℃.
＜the 4 embodiment 〉
Make 2 kinds low R alloys and 2 kinds high R alloys with the Strip casting legal system, obtain 2 kinds of R-T-B based rare earth element permanent magnets according to combination shown in Figure 19.Again, for sample E, the blending ratio of low R alloy and high R alloy is 90: 10; On the other hand, for sample F, the blending ratio of low R alloy and high R alloy is 80: 20.Low R alloy shown in Figure 19 is carried out hydrogen with high R alloy with the 1st embodiment the samely to be pulverized.Add the butyl oleate of 0.05 weight % after the hydrogen pulverization process, low R alloy and high R alloy were mixed 30 minutes according to shown in Figure 19 being combined in the Nautamixer.Be broken to average particulate diameter 4.0 μ m by the aeropulverizer fine powder then.After the powder that obtains is shaped in magnetic field with the condition of the 1st embodiment respectively to sample E in 1070 ℃ of sintering 4 hours, to sample F 1020 ℃ of sintering 4 hours.Then, sample E and F are carried out 2 sections Ageing Treatment of 800 ℃ * 1 hour and 550 ℃ * 2.5 hours respectively.Composition, oxygen content and the nitrogen content of the sintered body that obtains are shown in Figure 19, magnetic characteristic is shown in Figure 20.For the ease of relatively, the magnetic characteristic of Sample A～D that the 3rd embodiment is made also is shown in Figure 20 in the lump.
As Sample A～F,, still can access the above residual magnetic flux density (Br) of 13.8kG, above coercive force (HcJ) and the 95% above squareness ratio (Hk/HcJ) of 13.0kOe even if make when constituting element variation.
Such as described in detail above, be present in R in sintering circuit by the product that makes enrichment Zr 2T 14B mutually in, the reduction of magnetic characteristic can be suppressed at Min., simultaneously can suppress growing up of crystal grain.Again,, can guarantee the sintering temperature width of cloth more than 40 ℃, even therefore be easy to generate the occasion of the large-scale sintering furnace of temperature inequality, the R-T-B based rare earth element permanent magnet that still can easily obtain having stable high magnetic characteristic in use according to the present invention.

Claims (4)

1. the manufacture method of a R-T-B based rare earth element permanent magnet, this R-T-B based rare earth element permanent magnet is by containing by R 2T 14The principal phase that B constitutes mutually and contain than above-mentioned principal phase and more to many sintered body of crystal boundary phase of R and constitute, wherein, R be among the rare earth element more than a kind or 2 kinds, described rare earth element is the notion that contains Y, T is to be the essential transition metal more than a kind or 2 kinds with Fe or with Fe and Co, and at above-mentioned R 2T 14There is the product of enrichment Zr in mutually in B, and this manufacture method comprises following operation:
Making is with R 2T 14B contains for the R-T-B alloy that contains Zr of main body and than above-mentioned R-T-B alloy mutually and more manys the operation based on the R-T alloy of R and T of R, obtain the operation of the powder that constitutes by above-mentioned R-T-B alloy and the mixture of the powder that constitutes by above-mentioned R-T alloy, the operation of the formed body of the reservation shape that making is made of described mixture, and the operation of the above-mentioned formed body of sintering; And
With the peripheral speed of chill roll is that the Strip casting method of the condition of 1.0～1.8m/s is made described R-T-B alloy; And
Make above-mentioned product at above-mentioned R in above-mentioned sintering circuit 2T 14B is interior mutually to be generated; Wherein
Described sintered body has following composition: R:25～35 weight %, and R is more than a kind or 2 kinds of rare earth element that contains Y here; B:0.5～4.5 weight %; Al and Cu a kind or 2 kinds: 0.02～0.6% weight %; Zr:0.03～0.25 weight %; Co:4 weight % is following but do not comprise 0; And remainder is Fe.
2. the manufacture method of the R-T-B based rare earth element permanent magnet of putting down in writing according to claim 1 is characterized in that described product is sheet or needle-like.
3. the manufacture method of the R-T-B based rare earth element permanent magnet of putting down in writing according to claim 1, it is characterized in that, make the described R-T-B alloy that does not contain described product, avoid the generation of the described product that produces by heat tracing then, implement the operation till the operation of the described formed body of sintering.
4. the manufacture method of the R-T-B based rare earth element permanent magnet of putting down in writing according to claim 1 is characterized in that the oxygen amount that contains in the described sintered body is below the 2000ppm.
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