CN1860248A - Raw material alloy for r-t-b permanent magnet and r-t-b permanent magnet - Google Patents

Raw material alloy for r-t-b permanent magnet and r-t-b permanent magnet Download PDF

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Publication number
CN1860248A
CN1860248A CNA2004800285212A CN200480028521A CN1860248A CN 1860248 A CN1860248 A CN 1860248A CN A2004800285212 A CNA2004800285212 A CN A2004800285212A CN 200480028521 A CN200480028521 A CN 200480028521A CN 1860248 A CN1860248 A CN 1860248A
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alloy
rich
phase
permanent magnet
long
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国吉太
金子裕治
长谷川宽
佐佐木史郎
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Hitachi Metals Ltd
Resonac Holdings Corp
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Showa Denko KK
Neomax Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Hard Magnetic Materials (AREA)
  • Continuous Casting (AREA)
  • Powder Metallurgy (AREA)

Abstract

A raw material alloy for R-T-B permanent magnet of thin-sheet form comprising an R2T14B columnar crystal and an R enriched phase (R: at least one rare earth element including Y, T: Fe or Fe and at least one transition metal element other than Fe, and B: boron or boron and carbon), wherein in the alloy structure observed on any arbitrary section including the normal direction of the thin sheet, the aspect ratio is 10 or higher and the area ratio of R enriched phase whose longitudinal direction is 90+-30 DEG against the surface of the thin sheet is 30% or higher based on all the R enriched phases existing in the alloy.

Description

The R-T-B series permanent magnet is with raw alloy and R-T-B series permanent magnet
Technical field
The present invention relates to R-T-B series permanent magnet raw alloy, particularly utilize the R-T-B series permanent magnet raw alloy thin slice of thin strip casting manufactured.In addition, the present invention relates to by the R-T-B series permanent magnet of above-mentioned R-T-B series permanent magnet with the raw alloy making.
Background technology
In permanent magnet, has the R-T-B series permanent magnet of maximum magnetic energy product, owing to its high characteristic is used in HD (hard disk), MRI (MRI (magnetic resonance imaging) method), the various motors etc.In recent years, except its thermotolerance improved, market also improving, comprised that the ratio of the motor purposes of automobile rises to requirements of saving energy.
Here, " R " in " R-T-B series permanent magnet " mainly be meant with other rare earth element such as Pr, Dy and replace a part of Nd, is to comprise at least a among the rare earth element of Y." T " is meant with other transition metal such as Co, Ni and replaces a part of Fe." B " is boron, comprises with C or N replacing its part." R-T-B series permanent magnet ", its principal constituent are Nd, Fe, B, therefore are generically and collectively referred to as " Nd-Fe-B series magnet " or " R-Fe-B series magnet ".
" R-T-B series permanent magnet " in this specification sheets comprises a kind of magnet in the elements such as adding Cu, Al, Ti, V, Cr, Ga, Mn, Nb, Ta, Mo, W, Ca, Sn, Zr and/or Hf or makes up the magnet that adds above-mentioned multiple element.Known to adding such element, can realize the raising of all characteristics such as magnetic properties.
R-T-B is an alloy, is with the R as the ferromagnetism phase that helps magnetization 2T 14B is principal phase and alloy non magnetic, that the spissated low-melting rich R of rare earth element coexists mutually mutually.R-T-B is that alloy is active metal, therefore, normally fuses in vacuum or rare gas element and casts.In addition, be that alloy block is made sintered magnet in order to utilize powder metallurgic method from fluid origin R-T-B, alloy block is ground into about 3 μ m (FSSS: measure with Fischer particulate sieve apparatus), behind the formation powdered alloy, press forming in magnetic field.By the powder compact that press forming obtains, use sintering oven under about 1000～1100 ℃ high temperature, to carry out sintering.For the sintered compact of making like this, as required, normally implement thermal treatment, mechanical workout, also have in order to improve solidity to corrosion and implement to plate.
Rich R phase in the R-T-B based sintered magnet has vital role as follows.
1) fusing point of rich R phase is low, becomes liquid phase when sintering, helps the densification and the magnetized raising of magnet.
2) do not produce the concavo-convex of crystal boundary, the nucleation site of anti-magnetic region is reduced and the raising coercive force.
3) make the principal phase magnetic insulation and increase coercive force.
Therefore, if the dispersion state of the rich R phase in the magnet that has been shaped worsens, will cause that partial sintering is bad, the reduction of magnetic, therefore, rich R disperses just to become important mutually equably in the magnet that has been shaped.The distribution of the rich R phase in this R-T-B based sintered magnet is that alloy organizing produces influence greatly to the R-T-B as raw material.
R-T-B is the castmethod of alloy as casting, has developed thin strip casting method (being designated hereinafter simply as " SC method "), uses in the Shi Ji operation.In the SC method, by with alloy liquation curtain coating on the copper roller of inner water-cooled, make alloy liquation quench solidification, thus, casting thick is thin slice about 0.1～1mm.Utilize the SC method, because the crystal structure miniaturization of alloy is an alloy so can generate the R-T-B with the fine dispersed tissue of rich R phase.Like this, alloy with the casting of SC method, the inner mutually fine dispersion of rich R, thereby the dispersiveness of the rich R phase in the magnet after the pulverizing, sintering also becomes well, can realize the raising (spy opens flat 5-222488 communique and the flat 5-295490 communique of Te Kai) of the magnetic properties of magnet.
By the alloy sheet of SC method casting, the homogeneity of tissue is also excellent.The homogeneity of tissue can compare with the dispersion state of crystallization particle diameter or rich R phase.In the alloy sheet made from the SC method, chill thin crystalline substance (equiax crystal) takes place sometimes in the casting roll side of alloy sheet (after, as casting mold face side), but as all accessing appropriate fine, the uniform tissue that in quench solidification, causes.
As previously discussed, the R-T-B that casts with the SC method is an alloy, and rich R disperses mutually imperceptibly, and the homogeneity of tissue is also excellent, and therefore, under the situation of making sintered magnet, the homogeneity of the rich R phase in the final magnet also improves, and can improve magnetic properties.Like this, the R-T-B with the casting of SC method is that alloy block has the excellence tissue that is used to make sintered magnet.But,, more and more require the height control of the tissue of raw alloy, the particularly existence of rich R phase along with the characteristic of magnet improves.
Before, the inventor etc. have studied the relation that the R-T-B that is cast is the movement when broken of alloy organizing and hydrogen fragmentation or micro mist, found that, for the granularity of powdered alloy that sintered magnet is used is controlled to be evenly, the dispersion state of controlling rich R phase is important (spy opens the 2003-188006 communique).And find, the dispersion state of the rich R phase that the casting mold face adnation in alloy becomes, micronization takes place in thin terrifically zone (fine rich R region) easily, in the pulverizing stability that reduces alloy, make the size-grade distribution of powder roomy, recognize that in order to improve the magnet characteristic it is necessary reducing fine rich R region.
Utilization can improve and pulverize stability, magnetic properties at the few alloy in zone that the spy opens disclosed fine rich R phase in the 2003-188006 communique.But, fine rich R region is reduced, can not bring into play the original effect of above-mentioned rich R phase fully, wish to utilize the further high magnetization of the control permanent magnet that alloy structure produced.
Summary of the invention
The object of the present invention is to provide a kind of R-T-B series permanent magnet raw alloy of controlling existing rich R phase in the alloy, can bringing magnetic properties to improve with more small yardstick.
It is existing rich R phase in the alloy that the inventor etc. observe R-T-B with more small yardstick, found that there are big relation in the shape of rich R phase and magnetic properties.That is, the present invention is as described below.
(1) a kind of R-T-B series permanent magnet raw alloy, it is to contain R 2T 14(R is rare earth element at least a that comprises Y with raw alloy for B column crystallization and rich R laminal R-T-B series permanent magnet mutually, T is at least a of Fe or Fe and Fe transition metal in addition, B is boron or boron and carbon), it is characterized in that, in the observed alloy structure of the arbitrary section that comprises this thin plate normal direction, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 30% of existing whole rich R phases in the alloy with respect to thin sheet surface.
As above-mentioned (1) described R-T-B series permanent magnet raw alloy, it is characterized in that (2) long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 50% of existing whole rich R phases in the alloy with respect to thin sheet surface.
As above-mentioned (1) described R-T-B series permanent magnet raw alloy, it is characterized in that (3) long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 70% of existing whole rich R phases in the alloy with respect to thin sheet surface.
As above-mentioned (1)～(3) described R-T-B series permanent magnet raw alloy, it is characterized in that (4) long-width ratio is more than 20.
(5) a kind of R-T-B series permanent magnet raw alloy, it is to contain R 2T 14(R is rare earth element at least a that comprises Y with raw alloy for B column crystallization and rich R laminal R-T-B series permanent magnet mutually, T is at least a of Fe or Fe and Fe transition metal in addition, B is boron or boron and carbon), it is characterized in that, in the observed alloy structure of the arbitrary section that comprises this thin plate normal direction, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 50% of existing whole rich R phases in the alloy with respect to thin sheet surface.
(6) as above-mentioned (5) described R-T-B series permanent magnet raw alloy, it is characterized in that long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 30% of existing whole rich R phases in the alloy with respect to thin sheet surface.
(7) a kind of R-T-B series permanent magnet raw alloy, it is to contain R 2T 14(R is rare earth element at least a that comprises Y with raw alloy for B column crystallization and rich R laminal R-T-B series permanent magnet mutually, T is at least a of Fe or Fe and Fe transition metal in addition, B is boron or boron and carbon), it is characterized in that, in the observed alloy structure of the arbitrary section that comprises this thin plate normal direction, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 30% of existing whole rich R phases in the alloy with respect to thin sheet surface, and long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 50% of existing whole rich R phases in the alloy with respect to thin sheet surface.
(8) as above-mentioned (7) described R-T-B series permanent magnet raw alloy, it is characterized in that, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 50% of existing whole rich R phases in the alloy with respect to thin sheet surface, and long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 30% of existing whole rich R phases in the alloy with respect to thin sheet surface.
(9) as above-mentioned (1)～(8) described R-T-B series permanent magnet raw alloy, it is characterized in that, utilize the thin strip casting method to make.
As above-mentioned (9) described R-T-B series permanent magnet raw alloy, it is characterized in that (10) mean thickness is the above 0.50mm of 0.10mm.
(11) a kind of R-T-B series permanent magnet, it is that alloy is made by the described R-T-B in above-mentioned (1)～(10).
Description of drawings
Fig. 1 is the section tissue of alloy sheet is used in expression with the rare earth magnet of the rich R phase that contains cohesion of existing SC manufactured figure.
Fig. 2 is that expression exists the rare earth magnet of the rich R phase of the high order dendrite branch figure of the section tissue of alloy sheet with containing of existing SC manufactured.
Fig. 3 is the figure of expression rare earth magnet of the present invention with the section tissue of alloy sheet.
Fig. 4 is the synoptic diagram of the casting device of thin strip casting method.
Embodiment
Below, with reference to description of drawings R-T-B series permanent magnet of the present invention with raw alloy
Embodiment.
At first, see figures.1.and.2.These figure are the reflected electron images when to observe the Nd-Fe-B that casts with existing SC method be the section of alloy (Nd31.5 quality %) thin slice with SEM (scanning electronic microscope).Simultaneously, the left side of figure is the casting mold face side of alloy, and the right side is the free surface side of alloy.When the quench solidification of the alloy liquation that utilizes the SC method, the alloy liquation carries out crystallization from casting mold face side chilling.
White part among Fig. 1 is represented rich Nd phase (because R becomes Nd, so sometimes rich R is called mutually " rich Nd phase ").As being clear that from Fig. 1, rich Nd condenses on the shape ground that stretches mutually.On the other hand, in Fig. 2, very fine rich Nd exists with dendritic crystal state.
In order to be that alloy is made sintered magnet from R-T-B, need be that alloy is pulverized with R-T-B, suppress then and be made into body.As pulverizing R-T-B is the method for alloy, at first, preferably make R-T-B be alloy embrittlement by storage hydrogen after, carry out fine pulverizing.By the embrittlement that is caused by storage hydrogen, R-T-B is that alloy is by coarse reduction (fragmentation).At this R-T-B is that hydrogen is absorbed mutually by rich R in the hydrogen broken process of alloy, expands and becomes crisp hydride.Therefore, in the hydrogen fragmentation, in alloy, import along rich R phase or be the microcrack of starting point mutually with rich R.In the broken operation of micro mist after this, be the beginning with the microcrack of the volume that in the hydrogen fragmentation, generates, alloy destroys, thereby there is the tendency that influences the broken efficient of micro mist, micro mist shape in the dispersion state of rich R phase.Therefore, usefulness such as the inventor more fine-scale are observed rich R and are found mutually, the microcrack that forms in the shape of each rich R phase and hydrogen fragmentation, also have and have relation on the magnetic properties.
From the rich R of stretching shape shown in Figure 1 mutually as can be known, when gas is broken, form microcrack radially in, embrittlement also takes place in self.Therefore, then, when jet mill was pulverized, the rich R phase of the stretching shape of embrittlement most ofly was ground into very fine from the principal phase separation.Superfine micro mist by so rich R constitutes mutually separates and unrenewable ratio height with vortrap, therefore becomes the reason of the component fluctuation in the pulverizing.In addition, by the micro mist that rich R constitutes mutually, be very active, thereby become the reason that magnetic properties that the increase by oxygen concn causes reduces that the Security Countermeasures of operation are strengthened and also become necessary, cause making the reduction of efficient, the rising of cost.
On the other hand, the very tiny rich R phase that dendritic crystal state as shown in Figure 2 exists, its adjacent tiny dendritic rich R phase interval each other is also little than the grinding particle size that general sintered magnet is used.Therefore, the micro mist inside after jet mill is pulverized, the ratio that tiny dendritic rich R enters mutually uprises.Rich R becomes liquid phase mutually as mentioned above when sintering, help sintering.For this reason, there is rich R phase on the surface of each micro mist, need micro mist is wetting each other during sintering.But, for the rich R phase that enters in the powder, can not expect such effect, in addition,, can not bring effect of sufficient even ooze out on the surface, cause the reduction of the sintered density of magnet.
In addition, if the very tiny rich R that dendritic crystal state exists exists mutually in large quantities, there is the R that anisotropic orientation is different in large quantities in the branch part that just equals dendrite in powder inside 2T 14B uprises in the ratio of the inner coexistence of powder, and the orientation degree that therefore produces resulting permanent magnet reduces such problem.
Below, the Nd-Fe-B of the present invention that explanation utilizes the SC method to cast with reference to Fig. 3 is alloy (Nd31.5 quality %).Reflected electron image when Fig. 3 represents that to observe Nd-Fe-B of the present invention be the casting sheet section of alloy with SEM (scanning electronic microscope).
As being clear that from Fig. 3, appear on the cross sectional photograph rich Nd mutually among, be the status that accounts for governance in the ratio that makes thickness direction be in the rich Nd phase of the stratiform (laminar) of extending in the angular range that the center limits.The rich R phase that only has tension shape shown in Figure 1 or virguliform shown in Figure 2, but it exists ratio few.Alloy with such tissue, after inhaling the hydrogen fragmentation, if utilize jet mill to carry out powdered, then can solve the reduction of the magnetic that the increase by component fluctuation, oxygen, nitrogen concentration as the problem points in the alloy of tissue with Fig. 1 and Fig. 2 causes, the reduction of sintered density, the problems such as reduction of orientation degree.Consequently, can obtain as the R-T-B series permanent magnet that can bring into play the mutually original effect of rich R fully with and only raw alloy by using such raw alloy, can access the R-T-B series permanent magnet with high magnetic properties.
Existing R-T-B is in the alloy, all partly exists tissue as shown in Figure 3.In addition, record in the spy opens flat 09-170055 communique and the flat 10-36949 communique of Te Kai: R-T-B is the rich R dispersion state mutually in the alloy, and the control or the thermal treatment of the speed of cooling after the liquation in the time of can be by casting solidifies are controlled.But even be partly to have tissue as shown in figure 3 in the alloy at existing R-T-B, such as depicted in figs. 1 and 2 organizing also accounts for most, so can not bring into play the mutually original effect of rich R as described above fully.
Below, explain R-T-B series permanent magnet raw alloy of the present invention.
(1) thin strip casting method
At first, with reference to Fig. 4 the casting that utilize thin strip casting method of R-T-B series permanent magnet with raw alloy is described.Fig. 4 represents to be used for the schematic representation of apparatus of being cast by the thin strip casting method.
In general, R-T-B is an alloy, because its active character, so in vacuum or inert gas atmosphere, use 1 fusion of refractory body crucible.The liquation that fuses, 1300～1500 ℃ keep specific time after, as required, by rectification mechanism, be provided with the tundish 2 of the mechanism of removing slag, supply with and make casting that inside carries out water-cooled with rotation roller 3.
The rotating speed of the feed speed of liquation and rotation roller is controlled aptly according to the thickness of desired alloy.The rotation round speed of rotation roller is preferably set to about 0.5～3m/s.Casting obtains such reason well, easily from thermal conductivity and considers that copper or copper alloy are suitable with the material of rotation roller.Since rotate the material of roller or the condition of surface difference of roller, the casting easy adhesion metal in the surface of rotation roller, and therefore, as required, if clearing apparatus is set, the R-T-B that is cast is that the quality of alloy is just stablized.Be set in the alloy 4 of rotation on the roller, break away from from roller, reclaim with returnable 5 at the opposition side of tundish.Heating, cooling body are set in this returnable, just can control the structural state of rich R phase.
When making alloy of the present invention, need set cooling (being referred to as " once cooling ") and the cooling in returnable (being referred to as " secondary cooling ") on the casting roll aptly.
Once cooling specifically, is to make the alloy temperature when leaving casting roll reach 600～850 ℃.Need make alloy temperature when leaving casting roll than the fusing point height of rich R phase.Because form difference, the fusing point of rich R phase is higher or lower, but is more than 600 ℃.When the alloy temperature when leaving casting roll was lower than the fusing point of rich R phase, solidifying of rich R phase finished, and therefore formed tissue shown in Figure 2.On the other hand, when higher than 850 ℃, after breaking away from roller, rich R is condensed into the stretching shape mutually, forms tissue shown in Figure 1.The more preferably temperature range of the alloy when leaving casting roll is 600～800 ℃.Most preferred temperature range is 640～750 ℃.But because the alloy composition difference, preferred temperature range is higher or lower.
The dispersion state or the shape of rich R phase depend on TRE (total rare earth (TRE) class content) greatly.For example, in the mutually few alloy of the low and rich R of TRE, the collection less calories on the casting roll, so the alloy temperature of casting roll when breaking away from have the tendency that uprises, rich R condense mutually and to generate the tendency of stretching shape strong.On the other hand, high at TRE and in the alloy that rich R is many mutually, the collection heat on the casting roll is many, thereby it is strong to generate the tendency of the tissue with high order dendrite branch.Therefore, the alloy temperature when leaving casting roll in order to make reaches above-mentioned suitable temperature range, under the few situation of TRE, need make the thin thickness of alloy, under the many situations of TRE, need make the thickness of alloy thick.Specifically, be 30 weight % when following in the target of TRE, make a refrigerative degree big, thereby preferably make the mean thickness of alloy reach 0.10～0.30mm.0.15～0.27mm more preferably.Most preferably be 0.20～0.25mm.When the target of TRE was 30 weight % to 33 weight %, the preferred mean thickness of alloy was 0.25～0.35mm.0.26～0.32mm more preferably.In the target of TRE is 33 weight % when above, and the preferred mean thickness of alloy is 0.28～0.50mm.0.28～0.35mm more preferably.
In addition, select the surfaceness of casting roll aptly, the control casting roll also can be controlled the refrigerative degree one time from the collection heat of alloy.This method is below the 30 weight % as the target of TRE particularly or 33 weight % are effective when above.Surfaceness by making casting roll is big, can suppress necessary above collection heat.At TRE is 33 weight % when above, big by the surfaceness that makes casting roll, can moderately suppress the high thermal conduction to casting roll that is brought mutually by a large amount of rich R.The surfaceness of target in the case is more than 20 microns by 10 mean roughness Rz.About TRE is situation below the 30 weight %, on the contrary, in order not hinder the once cooling on the roller, below surfaceness is defined as about 20 microns, preferably prevents the transition cohesion of rich R phase.But surfaceness also is subjected to the influence of other factorses such as roller Facing material, thereby also is not limited to above-mentioned numerical value.
The casting roll surface temperature influences the wettability of alloy liquation and roller.If temperature is low excessively, the then wetting deterioration that becomes of alloy liquation and roller just has the tendency of the macrononuniformity of the contact that causes both.Consequently, in alloy, produce temperature distribution, become the variable of the alloy temperature when breaking away from, the difficulty that becomes of the generation with rich R phase of specified shape of the present invention from above-mentioned preferred casting roll.On the other hand, if temperature is too high, then the wettability of alloy liquation and roller becomes well, produces the hot sticky of part sometimes.Alloy is hot sticky to the roller surface, causes the thermal conduction of its part, the change of wettability, becomes the principal element of alloy structure change, thereby the difficulty that still just becomes of the generation with rich R phase of specified shape of the present invention.In addition, if hot sticky alloy amount becomes more, the stable operation difficulty that just becomes causes productivity to reduce.Therefore, it is suitable that the casting roll surface temperature is 50～400 ℃, and preferably 100～300 ℃ most preferably is 150～200 ℃.The temperature on the roller surface here is the temperature of the part of liquation touch roll, though it is difficult directly measuring, by under casting plane, immersion thermocouple or by contact tundish bottom etc. directly the measured value of the thermopair on the roller surface of the part of contact alloy or liquation can obtain.
On the other hand, secondary cooling for example, is provided with dividing plate in returnable, set the interval of this dividing plate aptly, and with the inside of cooled partitions such as rare gas element such as Ar or water, the speed of cooling of the alloy that control has been reclaimed is effective.When making alloy of the present invention, the alloy temperature when being recovered in the returnable is that the preferred speed of cooling that reaches 600 ℃ is 3～30 ℃/minute, preferably 3～20 ℃/minute under 650～700 ℃ the situation.Alloy temperature when being recovered in the returnable is that the preferred speed of cooling that reaches 600 ℃ is 10～40 ℃/minute, preferably 10～30 ℃/minute under 700～800 ℃ the situation.Alloy temperature when being recovered in the returnable is that the preferred speed of cooling that reaches 600 ℃ is 20～50 ℃/minute, preferably 30～50 ℃/minute under 800～850 ℃ the situation.In these temperature ranges,, just become tissue shown in Figure 2 easily if surpass the upper limit.If become in addition below the lower limit, just become tissue shown in Figure 1 easily.
Moreover alloy of the present invention is the alloy that tissue is stipulated, manufacture method is not limited to above-mentioned method.
The thickness of alloy sheet of the present invention is preferably below the above 0.5mm of 0.1mm.If the thickness of alloy sheet is thinner than 0.1mm, then setting rate increases with regard to transition ground, and the dispersion of rich R phase becomes meticulous.In addition, if the thickness of alloy sheet is thicker than 0.5mm, reduce and the problems such as reduction of the dispersiveness of the rich R phase that causes by setting rate with regard to causing.
(2) the rich R phase in the alloy
The present invention contains R 2T 14B column crystallization and rich R laminal R-T-B series permanent magnet mutually are with raw alloy (R is rare earth element at least a that comprises Y, and T is transition metal at least a beyond Fe or Fe and the Fe, and B is boron or boron and carbon).And in the alloy structure that the arbitrary section that comprises the thin plate normal direction is observed, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 30% of existing whole rich R phases in the alloy with respect to thin sheet surface.Consequently, component fluctuation was few when the micro mist in sintered magnet manufacturing process was broken, the not reduction of the magnetic properties that causes by the increase of oxygen and nitrogen concentration, do not have the reduction of sintered density and orientation degree, can obtain using and only raw alloy as the R-T-B series permanent magnet that can bring into play the mutually original effect of rich R fully.In addition, by using this raw alloy, can obtain having the R-T-B series permanent magnet of high magnetic properties.
The long-width ratio of the rich R phase in the alloy was less than 10 o'clock, and rich R is the stretching shape of cohesion mutually, if the ratio of so rich R phase increases, the component fluctuation that comes off, caused by the mistake pulverizing of the rich R phase when then pulverizing will increase.
Have, even long-width ratio is more than 10, long axis direction is beyond 90 ± 30 ° the scope with respect to thin sheet surface again, rich R more than necessary, its possibility that is spaced apart tiny virguliform is also high.The possibility height of individual's difference though on metallography high order dendrite can be described, in the alloy structure of reality, takes place in rich R phase like this in the identification of dendrite and the high order dendrite more than the secondary, defining geometrically, stipulates this scope.
Consequently, long-width ratio is more than 10 and its long axis direction is the area occupation ratio of 90 ± 30 ° rich R phase with respect to thin sheet surface, if become below 30% of existing whole rich R phases in the alloy, then the reduction of magnetic properties just becomes remarkable.
Preferably, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 50% of existing whole rich R phases in the alloy with respect to thin sheet surface.Most preferably, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 70% of existing whole rich R phases in the alloy with respect to thin sheet surface.
More preferably, in above-mentioned alloy, long-width ratio is for more than 20.More preferably, in above-mentioned alloy, long-width ratio is more than 30.
Perhaps, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 50% of existing whole rich R phases in the alloy with respect to thin sheet surface.Even long-width ratio is more than 10, long axis direction is a rich R phase below 30 ° or more than 150 ° with respect to thin sheet surface, is that the possibility of its high order dendrite branch that is spaced apart tiny virguliform is also high especially.
Preferably, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 30% of existing whole rich R phases in the alloy with respect to thin sheet surface.
Perhaps, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 30% of existing whole rich R phases in the alloy with respect to thin sheet surface, and long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 50% of existing whole rich R phases in the alloy with respect to thin sheet surface.
Preferably, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 50% of existing whole rich R phases in the alloy with respect to thin sheet surface, and long-width ratio is more than 10 and the relative metallic surface of its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 30% of existing whole rich R phases in the alloy.
Above-mentioned long-width ratio is more than 10 or long-width ratio is more than 20 or long-width ratio is a rich R phase more than 30, and its major axis dimension is more than 5% of sheet gauge size, and preferably having is length more than 10%.
The long-width ratio of the rich R phase in the alloy, long axis direction be with respect to the area occupation ratio of the angle of thin sheet surface and such rich R phase and since rich R on BEI than principal phase brightness height, so can use image analysis apparatus to resolve after mutually discerning principal phase and rich R.For example, the BEI of 10 alloy sheet sections will selecting at random with suitable multiplying power photographs, in 10 photos separately, to the total area of the rich R phase in its photo be that the long-width ratio of regulation and rich R total area mutually that its long axis direction is in the predetermined angular scope carry out image analysis respectively and handle, measure.Then, the aggregate value of obtaining the total area of the rich R phase of using 10 photos of being photographed is removed what obtained in photo separately be the aggregate value of total area of rich R phase of the long-width ratio of regulation and the angular range that its long axis direction is in regulation and the value that obtains, just can be used as the area occupation ratio of the rich R phase of regulation.
(3) R in the alloy 2T 14The B phase
Laminal RTB series permanent magnet raw alloy of the present invention is with the R as the ferromagnetism phase 2T 14B is principal phase mutually.R 2T 14B is column, preferably this R mutually 2T 14The B column crystallization is being to have major axis in 90 ± 30 ° the angle with respect to thin sheet surface.In addition, the length of major axis is more than 30% of sheet gauge size, preferably more than 50%.Above-mentioned preferred R is arranged again 2T 14The B column crystallization contains the R of thin plate in all 2T 14More than 30% of B column crystallization preferably contains more than 50%.
Moreover, so-called R in the case 2T 14The B column crystallization is meant the piece by the crystal orientation unanimity of the polarized light microscope observing that utilizes magnetic Kerr effect.
Below, embodiments of the invention and comparative example are described.
(embodiment 1)
In order to make alloy composition is that Nd:31.5 quality %, B:1.00 quality %, Co:1.0 quality %, Al:0.30 quality %, Cu:0.10 quality %, surplus are iron, the raw material of complexed metal neodymium, ferro-boron, cobalt, aluminium, copper, iron, fuse with the high-frequency melting stove, use the thin strip casting method that liquation is cast, make alloy sheet.
Casting is 300mm with the diameter of rotation roller, and material is the fine copper of wall thickness 50mm, and inner the circumferential speed of the roller during casting is 1.0m/s by water-cooled, generates the alloy sheet of mean thickness 0.27mm.At this moment, the mean roughness Rz on casting roll surface is 12 microns.During visual observation, alloy is positioned on the casting roll equably, does not see hot sticky to casting roll.
In addition, make the bottom on thermopair contact casting roll surface, measure the surface temperature of the casting roll in the casting.And, also measure casting roll with the temperature head of the water yield of water coolant and gangway, from the water temperature that casting roll is discharged, calculate from these measured values, be 170 ℃ in the surface temperature of the casting roll of the liquation of tundish and casting roll contact position.
In addition, measure to break away from the temperature of the alloy sheet of roller with infra-red thermometer, the result is 730 ℃.In the returnable of accommodating, be provided with and make the dividing plate of cooling with the Ar gas communication.Insert thermopair from the returnable side to inside, measure the temperature variation of alloy, the result is, top temperature is 720 ℃, to 600 ℃ average cooling rates be 22 ℃/minute.
Embed 10 resulting alloy sheets, after grinding, 100 times each alloy sheet is carried out reflection electronic imaging (BEI) with scanning electronic microscope (SEM) with multiplying power and photograph.The photo of photographing is placed on the image analysis apparatus measures, the result is, long-width ratio be more than 10 and its long axis direction with respect to the metallic surface be the area occupation ratio of 90 ± 30 ° rich R phase be in the alloy existing whole rich R phases 80%.In addition, long-width ratio is more than 20 and its long axis direction with respect to the metallic surface be the area occupation ratio of 90 ± 30 ° rich R phase be in the alloy existing whole rich R phases 65%.On the other hand, long-width ratio be more than 10 and the relative metallic surface of its long axis direction be the area occupation ratio of the rich R phase below 30 ° or more than 150 ° be in the alloy existing whole rich R phases 6%.
(comparative example 1)
Raw material is fitted in the composition identical with embodiment 1, fuse and implement to utilize the casting of SC method in the same manner with embodiment 1.Wherein, the wall thickness of casting roll is defined as 90mm, and the mean roughness Rz on casting roll surface is defined as 7 microns.In addition, the mean thickness of alloy sheet is defined as 0.35mm.When visual observation, the unusual high part of the alloy temperature on the casting roll takes place on a small quantity, sees hot sticky phenomenon in a part.
The surface temperature of casting roll that the liquation of the tundish of obtaining with the method identical with embodiment 1 is contacted with the position of casting roll is 400 ℃.
In addition, the temperature of measuring hot sticky the alloy sheet do not break away from roller with infra-red thermometer is 820 ℃.In addition, accommodate in the returnable of the alloy sheet that breaks away from roller, special cooling body is set.With the temperature variation of the thermocouple measurement alloy that inserts to inside from the returnable side, the result is, top temperature is 810 ℃, to 600 ℃ average cooling rates be 6 ℃/minute.
The resulting result who does not have hot sticky alloy sheet and embodiment 1 to estimate in the same manner is, many rich R cohesion take place mutually and form the stretching shape, thus long-width ratio be the area occupation ratio of the rich R phase more than 10 be in the alloy existing whole rich R phases 26%.
(comparative example 2)
Raw material is fitted in the composition identical with embodiment 1, fuse and implement to utilize the casting of SC method in the same manner with embodiment 1.Wherein, the wall thickness of casting roll is defined as 25mm, and the mean roughness Rz on casting roll surface is defined as 10 microns.In addition, the mean thickness of alloy sheet is defined as 0.22mm.When visual observation, produce the higher part of temperature in the part of the alloy on casting roll.
The surface temperature of casting roll that the alloy liquation of the tundish of obtaining with the method identical with embodiment 1 is contacted with the position of casting roll is 80 ℃.
In addition, the medial temperature that measure to break away from the alloy sheet of roller with infra-red thermometer is 670 ℃.In addition, in the returnable of accommodating the alloy sheet that breaks away from roller, the dividing plate that makes the water coolant circulation is set.With temperature variation from the returnable side to inside that insert the thermocouple measurement alloy from, the result is, top temperature is 660 ℃, to 600 ℃ average cooling rates be 35 ℃/minute.
The result that resulting alloy sheet and embodiment 1 are estimated in the same manner is, rich R contains the high order dendrite of a large amount of virguliforms mutually, long-width ratio be more than 10 and long axis direction with respect to the metallic surface be the area occupation ratio of 90 ± 30 ° rich R phase be in the alloy existing whole rich R phases 23%.On the other hand, long-width ratio be more than 10 and long axis direction with respect to the metallic surface be the area occupation ratio of the rich R phase below 30 ° or more than 150 ° be in the alloy existing whole rich R phases 54%.
Below, the embodiment of sintered magnet is described.
(embodiment 2)
Utilize known suction hydrogen break process that the alloy sheet that embodiment 1 obtains is carried out coarse reduction, in resulting coarse reduction powder, add the Zinic stearas powder of 0.07 quality %, after utilizing shaking mixer to mix in nitrogen atmosphere, it is broken to carry out micro mist with jet mill.Atmosphere when jet mill is pulverized is defined as the nitrogen atmosphere that has mixed 10000ppm oxygen.The oxygen concn of resulting powder is 5000ppm.Resulting powder is mixed, hardens, grinds with the cold resin of imbedding, the section of powder is carried out SEM-BEI observe, the dispersion state of the rich R phase in the investigation powder.Consequently, rich R is main mutually attached to the particulate surface that is made of principal phase.
Then, be in the magnetic field of 1.5T at alignment magnetic field, with pressure 1.0t/cm 2Resulting powder is carried out press forming, this molding is kept carrying out in 4 hours sintering at 1060 ℃.The sintered density of resulting sintered compact is 7.5g/cm 3More than, become the density of abundant size.Have again, this sintered compact is carried out thermal treatment in 1 hour in argon gas atmosphere, under 560 ℃ of temperature, make sintered magnet.
Measure the magnetic properties of this sintered magnet with the BH curvilinear recorder, show the result in the table 1.
(comparative example 3)
Use the method pulverizing comparative example 1 resulting alloy sheet identical, obtain micro mist with embodiment 2.At this moment, use the method identical to observe the powder section, can confirm that many rich R separate from principal phase, exist as the smaller particles that only constitutes mutually by rich R with embodiment 2.Via similarly to Example 2 shaping, agglomerating operation, make sintered magnet again.
Measure the magnetic properties of the sintered magnet that this comparative example 3 makes with the BH curvilinear recorder, show the result in the table 1.
(comparative example 4)
Use the method pulverizing comparative example 2 resulting alloy sheets identical, obtain micro mist with embodiment 2.At this moment, use the method identical with embodiment 2 to observe the powder section, can confirm, it also is about 7 times that the proportion of particles that exists rich R phase in inside is compared with embodiment 2.Via similarly to Example 2 shaping, agglomerating operation, make sintered magnet again.
Measure the magnetic properties of the sintered magnet that this comparative example 4 makes with the BH curvilinear recorder, show the result in the table 1.
Table 1
Density (g/cm 3) Br (T) iHc (kA·m) (BH) max (kJ/m 3) TRE amount (quality %) in the sintered magnet Oxygen amount (ppm) in the sintered magnet
Embodiment 2 7.55 1.39 1194 362 31.2 5500
Comparative example 3 7.48 1.37 1098 344 30.6 5400
Comparative example 4 7.52 1.37 1154 352 31.1 5500
As shown in table 1, comparative example 3 is compared with embodiment 2, and density is low, and aspect characteristic, magnetization, coercive force is low.Its reason deducibility is: the dispersion in the rich R phase in alloy stage worsens, thereby rich R is separated by the vortrap of pulverizer as active little powder body in pulverizing process, TRE reduces easily, the segregation of perhaps rich R phase reduces coking property, thereby does not bring into play function fully effectively when sintering.On the other hand, can be inferred as: though comparative example 4 is such not as comparative example 3, also demonstrate same movement, rich R helps the agglomerating effect insufficient mutually.
Utilizability on the industry
According to R-T-B series permanent magnet raw alloy of the present invention, can effectively apply flexibly to greatest extent the rich R phase in the alloy, therefore, by the sintered magnet that this alloy is made, compare with existing sintered magnet, show more excellent magnet characteristic. Namely, because rich R has brought into play original effect mutually fully, so in sintered magnet manufacturing process, component fluctuation during Crushing of Ultrafine is few, the reduction of the magnetic that is not caused by the increase of oxygen concentration, do not have the reduction of sintered density and the reduction of the degree of orientation etc., have the effect of the unavailable excellence of existing alloy. In addition, by using the above-mentioned raw materials alloy, just can access the R-T-B series permanent magnet with high magnetic characteristic.
The present invention can be fit to be applied in the various e-machines of the high performance sintered magnet of needs or electricapparatus etc.

Claims (11)

1. one kind contains R 2T 14B column crystallization and rich R laminal R-T-B series permanent magnet mutually is characterized in that with raw alloy (R is rare earth element at least a that comprises Y, and T is transition metal at least a beyond Fe or Fe and the Fe, and B is boron or boron and carbon):
In the alloy structure of observing on the arbitrary section that comprises described thin plate normal direction, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 30% of existing whole rich R phases in the alloy with respect to described thin sheet surface.
2. R-T-B series permanent magnet raw alloy according to claim 1 is characterized in that: long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 50% of existing whole rich R phases in the alloy with respect to thin sheet surface.
3. R-T-B series permanent magnet raw alloy according to claim 1 is characterized in that: long-width ratio is more than 10 and the relative thin sheet surface of its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 70% of existing whole rich R phases in the alloy.
4. according to each described R-T-B series permanent magnet raw alloy in the claim 1～3, it is characterized in that: long-width ratio is for more than 20.
5. one kind contains R 2T 14B column crystallization and rich R laminal R-T-B series permanent magnet mutually is characterized in that with raw alloy (R is rare earth element at least a that comprises Y, and T is transition metal at least a beyond Fe or Fe and the Fe, and B is boron or boron and carbon):
In the alloy structure of observing on the arbitrary section that comprises described thin plate normal direction, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 50% of existing whole rich R phases in the alloy with respect to thin sheet surface.
6. R-T-B series permanent magnet raw alloy according to claim 5 is characterized in that: long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 30% of existing whole rich R phases in the alloy with respect to thin sheet surface.
7. one kind contains R 2T 14B column crystallization and rich R laminal R-T-B series permanent magnet mutually is characterized in that with raw alloy (R is rare earth element at least a that comprises Y, and T is transition metal at least a beyond Fe or Fe and the Fe, and B is boron or boron and carbon):
In the alloy structure of on the arbitrary section that comprises described thin plate normal direction, observing, long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 30% of existing whole rich R phases in the alloy with respect to thin sheet surface, and long-width ratio is more than 10 and its long axis direction is that area occupation ratio for the rich R phase below 30 ° or more than 150 ° is below 50% of existing whole rich R phases in the alloy with respect to thin sheet surface.
8. R-T-B series permanent magnet raw alloy according to claim 7, it is characterized in that: long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of 90 ± 30 ° rich R phase is more than 50% of existing whole rich R phases in the alloy with respect to thin sheet surface, and long-width ratio is more than 10 and its long axis direction is that the area occupation ratio of the rich R phase below 30 ° or more than 150 ° is below 30% of existing whole rich R phases in the alloy with respect to thin sheet surface.
9. according to each described R-T-B series permanent magnet raw alloy in the claim 1～8, it is characterized in that: use the thin strip casting manufactured.
10. R-T-B series permanent magnet raw alloy according to claim 9 is characterized in that: mean thickness is below the above 0.50mm of 0.10mm.
11. R-T-B series permanent magnet of making of raw alloy by each described R-T-B series permanent magnet in the claim 1～10.
CNA2004800285212A 2003-09-30 2004-09-28 Raw material alloy for r-t-b permanent magnet and r-t-b permanent magnet Pending CN1860248A (en)

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