CN1572006A - R-T-B based rare earth element permanent magnet - Google Patents

R-T-B based rare earth element permanent magnet Download PDF

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CN1572006A
CN1572006A CNA038013142A CN03801314A CN1572006A CN 1572006 A CN1572006 A CN 1572006A CN A038013142 A CNA038013142 A CN A038013142A CN 03801314 A CN03801314 A CN 03801314A CN 1572006 A CN1572006 A CN 1572006A
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rare earth
permanent magnet
alloy
earth element
product
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CN1295713C (en
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石坂力
西泽刚一
日高徹也
福野亮
内田信也
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TDK Corp
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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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    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0228—Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • H01F1/0555—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

An R-T-B system rare earth permanent magnet, which is a sintered body comprising: a main phase consisting of an R2T14B phase (wherein R represents one or more rare earth elements (providing that the rare earth elements include Y), and T represents one or more transition metal elements essentially containing Fe, or Fe and Co); and a grain boundary phase containing a higher amount of R than the above main phase, wherein a product that is rich in Zr exists in the above R2T14B phase. The product that is rich in Zr has a platy or acicular form. The R-T-B system rare earth permanent magnet containing the product enables to inhibit the grain growth, while keeping a decrease in magnetic properties to a minimum, and to obtain a wide suitable sintering temperature range.

Description

The 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 (T be essential transition metal at least a kind or more with Fe or with Fe and Co) and B (boron) be 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 desired 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 make the oxygen content in the alloy to reduce.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 the M-B compound being disperseed and separating out.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 further improving the R-T-B based rare earth element permanent magnet of the sintering temperature width of cloth of crystal grain.
The present inventor finds, constitutes the R of the principal phase of 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 controlled at Min. and suppress growing up and improving the sintering temperature width of cloth of crystal grain.Promptly the invention provides a kind of R-T-B based rare earth element permanent magnet, it is by containing by R 2T 14The B phase (R be among the rare earth element more than a kind or 2 kinds, wherein rare earth element is that the notion, the T that contain Y is the transition metal more than at least a kind based on Fe or Fe and Co) principal phase formed and contain than principal phase and more to many sintered body of crystal boundary phase of R and constitute, wherein at R 2T 14There is the product of enrichment Zr in mutually in B.
For R-T-B based rare earth element permanent magnet of the present invention, the oxygen amount that contains in the sintered body is comparatively desirable below 2000ppm.This is that reason is in R 2T 14The effect that there be growing up of inhibition crystal grain that the product of enrichment Zr causes in mutually in B and enlarge the sintering temperature width of cloth is the tangible cause of occasion of the low oxygen content below the 2000ppm in the oxygen amount.
For R-T-B based rare earth element permanent magnet of the present invention, preferably consist of: R:28～33 weight %, B:0.5～1.5 weight %, Al:0.03～0.3 weight %, Cu:0.3 weight % following (not comprising 0), Zr:0.05～0.2 weight %, Co:4 weight % following (not comprising 0) and remainder are essentially Fe and constitute.
Again, for R-T-B based rare earth element permanent magnet of the present invention, it is even more ideal to make its scope at 0.1～0.15 weight % contain Zr.
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 composition 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 Energy Dispersive X-ray FluorescenceSpectroscopy: distribution map energy dispersion type x-ray analysis equipment optical spectroscopy) of the middle product that exists of sample (the Zr amount is the sample of 0.10 weight %) 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 (mapping) 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 R at least 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) is formed and than principal phase contain more many R crystal boundary mutually.Feature of the present invention is, at R 2T 14There is the product of enrichment Zr in mutually in B.The R-T-B based rare earth element permanent magnet that has this product can be controlled at the reduction of magnetic characteristic growing up of Min. and inhibition crystal grain and also 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 the R-T-B based rare earth element permanent magnet, as at 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 necessary condition of B is 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.Mixing method is typically 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 is contained Zr by making in low R alloy and high R alloy any, 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 also that on the other hand contain Zr and the occasion of making permanent magnet in making high R alloy, the product of enrichment Zr is not present in R 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 14When B was interior mutually, the product of enrichment Zr was present in the enrichment R phase (crystal boundary phase) of the triple point that is in the sintering structure behind sintering, and did 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 raw alloy stage 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 Strip casting method (stripcasting).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 present 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 by (greatly about more than 700 ℃) in the temperature province of hanging down the R alloy organizing in change, then at the R that hangs down the R alloy 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.
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, in order to make R 2T 14B 1The anisotropy field of phase increases, makes coercive force to improve, and Dy is effective.Therefore, select Nd and Dy as R, Nd and Dy to be aggregated in 25～33 weight % comparatively desirable.And in this scope, the amount of Dy is comparatively desirable at 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 in the low occasion of oxygen content, and its effect is remarkable.The preferred content of Zr is 0.05～0.2 weight %, and preferred content is 0.1～0.15 weight %.
R-T-B based rare earth element permanent magnet of the present invention, its oxygen content 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 determines the oxygen amount that contains in the sintered body below 2000ppm, is preferably below the 1500ppm, more preferably below the 1000ppm.But, oxygen content is reduced, can reduce oxide phase with inhibition 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, the suitable manufacture method with regard to R-T-B based rare earth element permanent magnet of the present invention describes.
In this example, just use with R 2T 14B contains for the alloy of main body (low R alloy) and than low R alloy mutually and more manys the method for alloy (high R alloy) manufacturing R-T-B based rare earth element permanent magnet of the present invention of R, is explained.
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 low R alloy strip steel rolled stock is necessary to consider at R 2T 14B does not generate the product of enrichment Zr in mutually.Particularly, make the scope of the peripheral speed of chill roll at 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 because pass through at R 2T 14B mutually in the low R alloy of product of no enrichment Zr interpolation Zr 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 and B, also can make it contain Cu and Al again.
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.Its weight ratio of blending ratio of low R alloy powder and high R alloy powder gets final product about 80: 20～97: 3.Equally, the blending ratio of the occasion that low R alloy powder is pulverized with high R alloy powder also is that its weight ratio gets final product about 80: 20～97: 3.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 gas shielding atmosphere.Sintering temperature is necessary according to not equal all condition adjustment of composition, breaking method, granularity and particle size distribution, gets final product in 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 important on 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 coercive force has very big increase during near the heat treatment 600 ℃, 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 1 the composition 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.But for the low R alloy of comparative example among Fig. 13, the peripheral speed of chill roll is decided to be 0.6m/s.The thickness of alloy is the average thickness value of measuring 50 linecasting sheets (band).Again, for the low R alloy among 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 test 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 zinc stearate that adds 0.05 weight % before of fine powder, will hang down the R alloy with the combination of embodiment shown in Figure 11, comparative example 1～comparative example 3 and in Nautamixer (Nauta mixer), 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, carefully be crushed to average particulate diameter 4.8～5.1 μ m with aeropulverizer till.
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
With this formed body in a vacuum in 1070 ℃ of sintering chilling 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 in the 2nd quadrant of magnetic hysteresis loop becomes residual magnetic flux density again.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.The chemical composition of resulting sintered body is shown in Fig. 1's the hurdle of " sintered body composition ".Again, confirm not mutually in the comparative example 3 in product, but crystal boundary mutually in affirmation 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) of product in confirming have 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, residual magnetic flux density (Br) reduces significantly.Again, R-T-B based rare earth element permanent magnet (comparative example 2, comparative example 3) for product in confirming do not have 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 has substantial degradation (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 14B is the 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, its as a result this product no longer be included in R 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.
For according to the R-T-B based rare earth element permanent magnet of the Zr of embodiment 1 amount, with the above-mentioned the same tem observation that carries out at 0.10 weight %.Observed result is shown in Fig. 6～Fig. 8.Again, Fig. 6 be Zr amount at 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 be 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, for 20 whole crystal grain (R 2T 14The B phase), product in all not observing mutually.
The hypomere of Figure 11 (a) is expressed the Zr amount of embodiment 1 at the EPMA of the sample of 0.10 weight % (Electron Probe Micro Analyzer: Zr mapping result electron probe microanalyzer).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 in the Zr of the EPMA of the sample of 0.10 weight % mapping result.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, with the embodiment 1 the same magnetic characteristic of measuring, 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, the curve that the magnetic characteristic under each sintering temperature is mapped with respect to residual magnetic flux density (Br) with squareness ratio (Hk/HcJ) is shown in Figure 16.
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.Specifically, 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.As adding element M when adding Ti, residual magnetic flux density (Br) reduces (comparative example 4), and in not existing mutually the occasion of product, its 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 its 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 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 17 being combined in the Nautamixer.Be broken into average particulate diameter 4.1 μ m by the aeropulverizer fine powder then.With the fine powder that obtains with after being shaped in magnetic field with the same condition of the 1st embodiment at 1010～1090 ℃ of sintering that carry out 4 hours.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 ℃ sintering 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, the occasion of product in existing mutually can obtain high magnetic characteristic with the wide sintering 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, will hang down the R alloy and high R alloy mixed 30 minutes in Nautamixer according to combination shown in Figure 19.Be broken into average particulate diameter 4.0 μ m by the aeropulverizer fine powder then.After the powder that obtains is shaped in magnetic field with similarly to Example 1 condition 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.Again 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, by making the R of the principal phase that constitutes the R-T-B based rare earth element permanent magnet 2T 14There is the product of enrichment Zr in mutually in B, the reduction of magnetic characteristic can be controlled at Min., can suppress growing up of crystal grain simultaneously.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 heating-up temperature fluctuation, 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 (5)

1. R-T-B based rare earth element permanent magnet, it is by containing by R 2T 14(R is more than a kind or 2 kinds of rare earth element to the B phase, wherein rare earth element is that the notion, the T that contain Y is to be the essential transiens metallic element more than a kind or 2 kinds with Fe or with Fe and Co) principal phase formed and contain than above-mentioned principal phase and more to many crystal boundary sintered body mutually of R and constitute, wherein at above-mentioned R 2T 14There is the product of enrichment Zr in mutually in B.
2. 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 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.
4. the R-T-B based rare earth element permanent magnet of putting down in writing according to claim 1, it is characterized in that the consisting of of described sintered body: R:28～33 weight %, B:0.5～1.5 weight %, Al:0.03～0.3 weight %, Cu:0.3 weight % following but do not comprise 0, Zr:0.05～0.2 weight %, Co:4 weight % be following but do not comprise that O and remainder are essentially Fe.
5. the R-T-B based rare earth element permanent magnet of putting down in writing according to claim 4 is characterized in that, the content of Zr is 0.1～0.15 weight % in the described sintered body.
CNB038013142A 2002-09-30 2003-09-30 R-T-B based rare earth element permanent magnet Expired - Lifetime CN1295713C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107358998A (en) * 2017-07-20 2017-11-17 杭州乐荣电线电器有限公司 Flat anti-interference foldable soft data line

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7199690B2 (en) * 2003-03-27 2007-04-03 Tdk Corporation R-T-B system rare earth permanent magnet
EP1749599B1 (en) * 2004-04-30 2015-09-09 Hitachi Metals, Ltd. Methods for producing raw material alloy for rare earth magnet, powder and sintered magnet
JP4618437B2 (en) * 2006-03-30 2011-01-26 Ｔｄｋ株式会社 Method for producing rare earth permanent magnet and raw material alloy thereof
CN101471165B (en) * 2007-12-26 2012-09-19 北京中科三环高技术股份有限公司 NbFeB sintered rare earth permanent magnet alloy and method for producing the same
CN101819841A (en) * 2010-05-17 2010-09-01 上海交通大学 Neodymium iron boron magnetic material and preparation method thereof
JP6156375B2 (en) * 2012-06-22 2017-07-05 Tdk株式会社 Sintered magnet
JP6314380B2 (en) * 2013-07-23 2018-04-25 Tdk株式会社 Rare earth magnet, electric motor, and device including electric motor
CN106782971A (en) * 2016-12-05 2017-05-31 湖南航天磁电有限责任公司 A kind of NdFeB material and preparation method thereof
JP6849806B2 (en) * 2016-12-29 2021-03-31 北京中科三環高技術股▲ふん▼有限公司Ｂｅｉｊｉｎｇ Ｚｈｏｎｇ Ｋｅ Ｓａｎ Ｈｕａｎ Ｈｉ−Ｔｅｃｈ Ｃｏ．，Ｌｔｄ． Fine-grained rare earth alloy slabs, their manufacturing methods, and rotary cooling roll equipment

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242187B1 (en) * 1986-04-15 1992-06-03 TDK Corporation Permanent magnet and method of producing same
JPH01103805A (en) * 1987-07-30 1989-04-20 Tdk Corp Permanent magnet
JPH01196104A (en) * 1988-02-01 1989-08-07 Tdk Corp Manufacture of rare earth alloy magnet
US4895607A (en) * 1988-07-25 1990-01-23 Kubota, Ltd. Iron-neodymium-boron permanent magnet alloys prepared by consolidation of amorphous powders
JP3367726B2 (en) * 1993-11-08 2003-01-20 ティーディーケイ株式会社 Manufacturing method of permanent magnet
JP3724513B2 (en) * 1993-11-02 2005-12-07 Ｔｄｋ株式会社 Method for manufacturing permanent magnet
US5858123A (en) * 1995-07-12 1999-01-12 Hitachi Metals, Ltd. Rare earth permanent magnet and method for producing the same
JP3237053B2 (en) * 1996-07-25 2001-12-10 三菱マテリアル株式会社 Rare earth magnet material powder having excellent magnetic properties and method for producing the same
JP2891215B2 (en) * 1996-12-17 1999-05-17 三菱マテリアル株式会社 Method for producing rare earth-B-Fe based sintered magnet excellent in corrosion resistance and magnetic properties
JPH10259459A (en) * 1997-01-14 1998-09-29 Mitsubishi Materials Corp Raw material alloy for producing rare earth magnet powder and production of rare earth magnet powder using this raw material alloy
JPH1064712A (en) * 1997-07-18 1998-03-06 Hitachi Metals Ltd R-fe-b rare earth sintered magnet
ATE241710T1 (en) * 1998-08-28 2003-06-15 Showa Denko Kk ALLOY FOR USE IN PRODUCING R-T-B BASED SINTERED MAGNETS AND METHOD FOR PRODUCING R-T-B BASED SINTERED MAGNETS
EP0994493B1 (en) * 1998-10-14 2003-09-10 Hitachi Metals, Ltd. R-T-B sintered permanent magnet
EP1014392B9 (en) * 1998-12-15 2004-11-24 Shin-Etsu Chemical Co., Ltd. Rare earth/iron/boron-based permanent magnet alloy composition
JP3951099B2 (en) * 2000-06-13 2007-08-01 信越化学工業株式会社 R-Fe-B rare earth permanent magnet material
EP1164599B1 (en) * 2000-06-13 2007-12-05 Shin-Etsu Chemical Co., Ltd. R-Fe-B base permanent magnet materials
JP2002164239A (en) * 2000-09-14 2002-06-07 Hitachi Metals Ltd Manufacturing method of rare earth sintered magnet, ring magnet, and arc segment magnet
JP3452254B2 (en) * 2000-09-20 2003-09-29 愛知製鋼株式会社 Method for producing anisotropic magnet powder, raw material powder for anisotropic magnet powder, and bonded magnet

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107358998A (en) * 2017-07-20 2017-11-17 杭州乐荣电线电器有限公司 Flat anti-interference foldable soft data line

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CX01 Expiry of patent term