CN101850425B - Rare earth alloy powders and manufacturing method thereof, compound for anisotropic bonded magnet and anisotropic bonded magnet - Google Patents
Rare earth alloy powders and manufacturing method thereof, compound for anisotropic bonded magnet and anisotropic bonded magnet Download PDFInfo
- Publication number
- CN101850425B CN101850425B CN 201010158490 CN201010158490A CN101850425B CN 101850425 B CN101850425 B CN 101850425B CN 201010158490 CN201010158490 CN 201010158490 CN 201010158490 A CN201010158490 A CN 201010158490A CN 101850425 B CN101850425 B CN 101850425B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- hydrogen
- earth alloy
- catabolite
- dehydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Powder Metallurgy (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention relates to rare earth alloy powders and a manufacturing method thereof, a compound for an anisotropic bonded magnet and the anisotropic bonded magnet. The manufacturing method for the rare earth alloy powders comprises following steps: a hydrogenolysis procedure (11) for hydrogenolyzing material alloy containing rho% by mass of rare earth elements at T1 so as to a decomposition product containing eta1% by mass of hydrogen; a first dehydrogenation recompounding procedure (IV) for releasing the hydrogen from the decomposition product at a predetermined speed at T2 higher than T1 until the hydrogen concentration eta1% by mass is reduced to eta2% by mass, satisfying a formula (1); and a second dehydrogenation recompounding procedure (V) for reducing the releasing speed of the hydrogen from the decomposition product and further reducing the hydrogen concentration of the decomposition product so as to obtain the rare earth alloy powders. 0.008Xrho<=eta2<=0.013Xrho (1).
Description
Technical field
The anisotropic bond magnet that the present invention relates to rare earth alloy powder and manufacturing approach thereof, contains this rare earth alloy powder is with compound and anisotropic bond magnet.
Background technology
As making the method for magnet with alloy powder, known have a HDDR method (dehydrogenation of suction hydrogen disproportionation is compound again).So-called HDDR method is to carry out the process of inhaling hydrogen (Hydrogenation), disproportionation (Disproportionation), dehydrogenation (Desorption) and compound again (Recombination) successively.
This HDDR method is because be the method that is attended by solid phase-gas-phase reaction, so its reaction mechanism is complicated, and can change according to the magnetic characteristic of the coercivity of the ferromagnetic powder that the difference of creating conditions obtained etc.For this reason, in the manufacture process of the ferromagnetic powder that uses the HDDR method, trial is created conditions through adjustment and is improved the magnetic characteristic of ferromagnetic powder.
For example, in patent documentation 1 (TOHKEMY 2001-115220 communique), proposed in the compound again processing of dehydrogenation, changed reaction speed through the control atmosphere, thereby improve the magnetic characteristic of ferromagnetic powder.
Yet,, also be difficult to obtain fully high coercivity even as above-mentioned patent documentation 1, control atmosphere.For this reason, seek to establish the method that use HDDR method is made the rare earth alloy powder with outstanding magnetic characteristic.
Summary of the invention
The present invention is In view of the foregoing and accomplishes, and its purpose is to provide a kind of manufacturing approach and the rare earth alloy powder with outstanding magnetic characteristic that is obtained by this manufacturing approach that can be made the rare earth alloy powder of the rare earth alloy powder with outstanding magnetic characteristic by the HDDR method.In addition, the present invention also aims to provide through containing anisotropic bond magnet and this anisotropic bond magnet that anisotropic above-mentioned rare earth alloy powder has outstanding magnetic characteristic and use compound.
In order to achieve the above object, the present invention provides a kind of rare earth alloy powder manufacturing approach, and the compound again rare earth alloy powder of making of hydrogen disproportionation dehydrogenation is inhaled in this method utilization, has: the hydrogenolysis operation, and in temperature T
1Down, making rare earth element content is the raw alloy hydrogenolysis of ρ (quality %), thereby the acquisition hydrogen concentration is η
1The catabolite of (quality %); The 1st dehydrogenation is compound working procedure again, than said temperature T
1High temperature T
2Down, hydrogen is discharged from said catabolite with the rate of release of regulation, until the hydrogen concentration of said catabolite from η
1(quality %) is reduced to the η that satisfies following formula (1)
2(quality %); And the 2nd dehydrogenation compound working procedure again, more said the 1st dehydrogenation compound working procedure again reduces the rate of release of hydrogen from said catabolite, further reduces the hydrogen concentration of said catabolite, thereby obtains rare earth alloy powder.
0.008×ρ≤η
2≤0.013×ρ (1)
According to the manufacturing approach of the invention described above, can utilize and inhale compound again the rare earth alloy powder of making of hydrogen disproportionation dehydrogenation with outstanding magnetic characteristic.As obtaining so principal element of rare earth alloy powder, think: the 1st dehydrogenation is the temperature T of the catabolite in the compound working procedure again
2Than the temperature T in the hydrogenolysis operation
1Increase, and in the compound again process of dehydrogenation, change temperature and hydrogen release speed.
In a word, in manufacturing approach of the present invention, through the 1st dehydrogenation temperature T of the catabolite in the compound working procedure again
2Temperature T than the catabolite in the hydrogenolysis operation
1Increase, thereby in the 1st dehydrogenation again in the compound working procedure, Hydrogen Energy is enough successfully to be got rid of from catabolite, thereby also just can increase the rate of release of hydrogen.Think thus: compare with existing manufacturing approach, at the compound again initial stage of dehydrogenation, the nuclear energy of the rare earth alloy in the catabolite is separated out enough more equably.
In addition; Think: dewater again in the compound working procedure the 2nd; Because hydrogen is slow than the 1st dewater the again rate of release of compound working procedure from the rate of release of catabolite; So that the nuclear of rare earth alloy grow up be carried out to gradually for maybe, and the intragranular that can be suppressed at the primary particle of the rare earth alloy powder that is finally obtained is separated out foreign matter.As previously discussed, the present invention is based on the inventor's particular views and accomplishes, and this opinion is in the mechanism that is conceived to karyogenesis and nuclear growth, finds to be suitable for creating conditions of this mechanism.Think thus: the foreign matter amount that fully reduces in the rare earth alloy powder becomes possibility, and makes the rare earth alloy powder with outstanding magnetic characteristic and also become possibility.
In addition; The present invention provides a kind of rare earth alloy; This rare earth alloy comprises a plurality of primary particles, said primary particle be through the raw alloy that contains rare earth element implement is inhaled the dehydrogenation of hydrogen disproportionation again Combined Processing obtain, said primary particle contains rare earth alloy as main component; And, 4/μ of the number per unit area average out to m of the segregation thing different on the said primary particle cross section with said rare earth alloy
2Below.
Rare earth alloy powder of the present invention, with existing through suction the dehydrogenation of hydrogen disproportionation again Combined Processing handle and the rare earth alloy powder that obtains is compared, reduced the number of segregation thing more fully, so have outstanding magnetic characteristic.
In addition, the invention provides a kind of anisotropic bond magnet and use compound, this anisotropic bond magnet contains anisotropic rare earth alloy powder and resin with compound.Anisotropic bond magnet of the present invention comprises the anisotropy rare earth alloy powder with outstanding magnetic characteristic with compound.For this reason, the anisotropic bond magnet of the application of the invention is used compound, thereby just can produce the anisotropic bond magnet with outstanding magnetic characteristic.
In addition, a kind of anisotropic bond magnet is provided in the present invention, this anisotropic bond magnet makes above-mentioned anisotropic bond magnet be shaped with compound in magnetic field and obtains.Because anisotropic bond magnet of the present invention comprises the anisotropy rare earth alloy powder with outstanding magnetic characteristic, and be in magnetic field, to be shaped and to obtain, therefore have outstanding magnetic characteristic.
According to the present invention, can provide to have the rare earth alloy powder manufacturing approach of the rare earth alloy powder of outstanding magnetic characteristic according to the HDDR manufactured, and the rare earth alloy powder with outstanding magnetic characteristic that obtains by this manufacturing approach.In addition, through containing anisotropic above-mentioned rare earth alloy powder, thereby just can provide anisotropic bond magnet and this anisotropic bond magnet to use compound with outstanding magnetic characteristic.
Description of drawings
Fig. 1 is the related time diagram preferred embodiment of rare earth alloy powder manufacturing approach of the present invention.
Fig. 2 is the pattern sectional view that amplifies expression rare earth alloy powder fine structure of the present invention.
Fig. 3 is the stereogram preferred embodiment of expression anisotropic bond magnet of the present invention.
The specific embodiment
The manufacturing approach of the rare earth alloy powder of this embodiment is to utilize so-called manufacturing approach of inhaling the rare earth alloy powder of hydrogen disproportionation dehydrogenation compound again (HDDR method).This manufacturing approach has: hydrogen occlusion operation, the content of preparing rare earth element is the raw alloy of ρ (quality %), and with this alloy in atmosphere of hydrogen, temperature T
0Under keep the stipulated time; The hydrogenolysis operation is than temperature T
0High temperature T
1Obtaining hydrogen concentration through hydrogenolysis down is η
1The catabolite of (quality %); Heating process is from temperature T
1Be warming up to and compare temperature T
1High temperature T
2The 1st dehydrogenation is compound working procedure again, in temperature T
2Speed with regulation discharges hydrogen from catabolite down, and the hydrogen concentration of said catabolite is from η
1(quality %) is reduced to the η that satisfies above-mentioned formula (1)
2(quality %); The 2nd dehydrogenation is compound working procedure again, than the 1st dehydrogenation again compound working procedure reduce the rate of release of hydrogen from catabolite, and further reduce the hydrogen concentration η of catabolite, thereby obtain not comprise basically the rare earth alloy powder of hydrogen; And refrigerating work procedure, rare earth alloy powder is cooled to room temperature.
Fig. 1 is the time diagram of the manufacturing approach of the related rare earth alloy powder of this embodiment.Fig. 1 (a) is the time diagram of temperature, and Fig. 1 (b) is the time diagram of the hydrogen concentration of raw alloy, catabolite and rare earth alloy powder.Below the manufacturing approach of this embodiment suitably is described with reference to Fig. 1.
Hydrogen occlusion operation (I among Fig. 1) be in atmosphere of hydrogen, temperature T
0Be the raw alloy maintenance stipulated time of ρ (quality %) with rare earth element content down, thereby make the operation of hydrogen occlusion in raw alloy.As raw alloy, can use R
2Fe
14The R-Fe-B class alloy of B etc.From obtaining to have the viewpoint of the rare earth alloy powder of magnetic characteristic more remarkably, the composition of R-Fe-B class alloy is preferably R:25～35 quality %; B:1～1.4 quality %; Fe:65.6～72 quality %.As R, can be a kind or the element more than 2 kinds that is selected among Y, La, Ce, Pr, Nd, Sm, Gd, Td, Dy, Ho, Er, Tm, the Lu.In addition, from the viewpoint of manufacturing cost and magnetic characteristic, preferred R contains Nd.
As the content ρ (quality %) of the R of the quality criteria in the rare earth metal kind according to employed rare earth metal, be preferably 25～35 quality %, be more preferably 27～33 quality %.
Above-mentioned raw alloy can for example thin strap continuous casting method (Strip-Casting Method), book mold (book mold) method or centre spinning be modulated according to common casting method.Also can impose the heat treatment that homogenizes to raw alloy.In addition, raw alloy also can contain the unavoidable impurities from feed metal or starting compound and manufacturing process.
The heat treatment that homogenizes is in the atmosphere of inert gases of vacuum or argon gas and nitrogen etc. and under 1000～1200 ℃ of temperature, raw alloy to be kept carrying out in 5～48 hours.Through carrying out the heat treatment that so homogenizes, thereby raw alloy is dissolved and raw alloy is homogenized.
The raw alloy that has been homogenized preferably sieves after the pulverizing means of using stamping mill or jaw crusher etc. are pulverized.Thus, just can modulate particle diameter is the dusty raw materials alloy below the 10mm.
In hydrogen occlusion operation, be in the atmosphere of hydrogen of 100～300kPa and in temperature T in the hydrogen dividing potential drop
0Following above-mentioned pulverous raw alloy is retained to time t
1Thus, just can make the hydrogen occlusion in the lattice of raw alloy, also can obtain hydrogen concentration is η
0The hydrogen occlusion alloy of (quality %).Hydrogen concentration η
0For example be set to the scope of following formula (2).Also have, raw alloy does not decompose in this stage.
0.013×ρ≤η
0≤0.019×ρ (2)
Temperature T in hydrogen occlusion operation
0Be preferably 100～200 ℃.In addition, the required time t of hydrogen occlusion operation
1Be preferably 0.5～2 hour.
In hydrogenolysis operation (II among Fig. 1), through in atmosphere of hydrogen and than temperature T
0High temperature T
1Under keep hydrogen occlusion alloy, thereby make the hydrogen occlusion alloy hydrogenolysis, the acquisition hydrogen concentration is η
1The catabolite of (quality %).
The hydrogen dividing potential drop of the atmosphere in the hydrogenolysis operation is preferably 10～100kPa, temperature T
1Be preferably 700～850 ℃.Through under this condition, carrying out the hydrogenolysis of hydrogen occlusion alloy, thereby just can obtain to have the rare earth alloy powder of magnetic anisotropy.If the hydrogen dividing potential drop, so just has the tendency that hydrogenolysis can not fully be carried out less than 10kPa, if surpassed 100kPa, then having becomes is difficult to obtain the tendency of anisotropic rare earth alloy powder.
If temperature T
1Less than 700 ℃, so just have the tendency that the hydrogenolysis of raw alloy can not fully be carried out.On the other hand, if temperature T
1Surpass 850 ℃, so just having becomes is difficult to obtain the tendency of desired catabolite (hydride).
The required time of the hydrogenolysis operation (t among Fig. 1
2-t
1) be preferably 0.5～600 hour.If should the time less than 0.5 hour, so just have the tendency that the hydrogenolysis of raw alloy can not fully be carried out, if surpass 600 hours, so just have the tendency that operation becomes long.
The catabolite that is obtained by the hydrogenolysis operation contains RH
xDeng hydride, α-Fe and Fe
2The iron compound of B etc.Catabolite in this stage has formed the trickle matrix (matrix) of 100nm level.
The hydrogen concentration η of above-mentioned catabolite
1The rare earth element that the upper limit of (quality %) is normally contained all becomes hydride (RH
x, x=2～3) concentration.Hydrogen concentration η
1(quality %) depends on the kind of rare earth element, for example satisfies the scope of following formula (3).
0.014×ρ≤η
1≤0.021×ρ (3)
In heating process (III among Fig. 1), with the temperature of catabolite from temperature T
1Be warming up to and compare temperature T
1High temperature T
2Temperature T
2Compare temperature T
1Height is preferably 720～950 ℃, is more preferably 750～950 ℃.Also have, for programming rate, have no particular limits.The required time of the heating process (t among Fig. 1
3-t
2) for example be 1～10 minute.
In the 1st dehydrogenation again in the compound working procedure (IV among Fig. 1), than temperature T
1High temperature T
2Rate of release with regulation discharges hydrogen from catabolite down, and the hydrogen concentration of catabolite is from η
1(quality %) is reduced to the η that satisfies above-mentioned formula (1)
2(quality %).Can think the nuclear that in the matrix of the catabolite that obtains by the hydrogenolysis operation, has generated rare earth alloy through this operation.
Hydrogen is η from hydrogen concentration
1The rate of release of the catabolite of (quality %) so that all quality of catabolite before the hydrogen release as benchmark, be preferably 0.4～13 quality %/minute.Thus, just can generate the nuclear of rare earth alloy more equably.In addition, the hydrogen concentration η of hydrogen release to catabolite is become satisfy following formula (4), preferably satisfy the hydrogen concentration η of following formula (5)
2The scope of (quality %).Thus, just can generate the nuclear of rare earth alloy more equably.Also has the hydrogen concentration η of catabolite
2(quality %) can obtain through the quality of measuring catabolite.
0.008×ρ≤η
2≤0.012×ρ (4)
0.0082×ρ≤η
2≤0.0115×ρ (5)
Hydrogen can be adjusted through the decrease speed of the hydrogen dividing potential drop the control atmosphere from the rate of release of catabolite.In a word, if increase the decrease speed of hydrogen dividing potential drop, so just can increase the rate of release of hydrogen from catabolite.The decrease speed of hydrogen dividing potential drop can be adjusted through for example importing argon gas or reducing pressure.The 1st dehydrogenation decrease speed of the hydrogen dividing potential drop in the compound working procedure again is preferably 2～10kPa/ branch.
The 1st dehydrogenation is the temperature T of the catabolite in the compound working procedure again
2Compare temperature T
1Height is preferably 750～950 ℃.Through temperature T with catabolite
2Be increased to and compare temperature T
1Height, thus hydrogen just becomes and from catabolite, breaks away from easily, thereby also just can generate the nuclear of rare earth alloy more equably.Temperature T
2With temperature T
1Temperature difference both can be more than 20 ℃, also can be more than 100 ℃.Through this temperature difference is adjusted to more than 100 ℃, thereby the uniformity of particle size can either be kept, the number of segregation thing can be further reduced again.
If temperature T
2Less than 750 ℃, so just can not fully increase the rate of release of hydrogen from catabolite, thereby with regard to the karyogenesis that the has rare earth alloy uneven tendency that becomes.On the other hand, if temperature T
2Surpass 950 ℃, so because hydrogen becomes excessive from the rate of release of catabolite, so the tendency of the hydrogen concentration η that is difficult to control catabolite will be arranged.
The 1st dehydrogenation is the time of the compound working procedure (t among Fig. 1 again
4-t
3) for example be 0.1～0.5 hour.Also have, this time exists with ... the rate of release of hydrogen from catabolite.
In the 2nd dehydrogenation again in the compound working procedure (V among Fig. 1); Hydrogen is reduced to from the rate of release of catabolite the rate of release of the hydrogen of compound working procedure is little again than the 1st dehydrogenation; Further reduce the hydrogen concentration of catabolite; And the hydrogen differential pressure drop in the atmosphere is low to moderate less than 1Pa, thereby obtains rare earth alloy.
The 2nd dehydrogenation temperature of compound working procedure again is preferably and adjusts to and the 1st dehydrogenation temperature T in the compound working procedure again
2Identical.Thus, just can successfully make the release of hydrogen from catabolite.
Hydrogen is η from hydrogen concentration
2The rate of release of the catabolite of (quality %), i.e. the decrease speed of the hydrogen concentration η of catabolite all quality of the catabolite of (the 1st dehydrogenation compound working procedure begins again before) is as benchmark so that before the hydrogen release, be preferably 0.01～0.4 quality %/minute.Thus, the growth of the nuclear of the rare earth alloy of in catabolite, separating out is slowly carried out, thereby also just can control the intragranular that the segregation thing residues in rare earth alloy.If the decrease speed of hydrogen concentration η surpassed 0.4 quality %/minute, can not carry out again compound and become residuing in the tendency of rare earth alloy intragranular easily with regard to having α-Fe and the rich iron phase that catabolite comprises so.In addition, if the decrease speed of hydrogen concentration η less than 0.01 quality %/minute, so have the rare earth alloy that the required time of operation becomes long and compound again the tendency that unusual grain is grown up take place easily.
As the segregation thing, can enumerate α-Fe, rich iron compound and from compound of the impurity such as Nb that raw alloy comprised etc.If so the segregation thing is present in the intragranular of the primary particle of rare earth alloy powder, will produces reverse domain so and become and be difficult to obtain high coercivity.
The 2nd dehydrogenation is the time of the compound working procedure (t among Fig. 1 again
5-t
4) for example can be set at 0.3～5 hour.This time exists with ... the rate of release of hydrogen from catabolite.Also have, the 2nd dehydrogenation decrease speed of the hydrogen dividing potential drop in the compound working procedure again is preferably 0.01～0.2kPa/ branch.
At last, will be cooled to room temperature (VI among Fig. 1) by the temperature of the 2nd dehydrogenation rare earth alloy powder that compound working procedure obtained again through refrigerating work procedure.Through above operation, thus the anisotropy rare earth alloy powder that the intragranular segregation thing that just can obtain primary particle has fully been reduced.This rare earth alloy powder has and the common identical composition of raw alloy.
In the manufacturing approach of the rare earth alloy powder of this embodiment; Through make the 1st dehydrogenation again the decrease speed of the hydrogen dividing potential drop in the compound working procedure decrease speed of the hydrogen dividing potential drop of compound working procedure is big again than the 2nd dehydrogenation, thereby make the 1st dehydrogenation again in the compound working procedure hydrogen from the rate of release of catabolite than the 2nd dehydrogenation again the compound working procedure rate of release of hydrogen big.In addition, because the 1st dehydrogenation temperature (T of compound working procedure again
2) than the temperature (T of hydrogenolysis operation
1) height, so just can be increased in the 1st dehydrogenation again in the compound working procedure hydrogen from the rate of release of catabolite.Think that thus the karyogenesis of rare earth alloy becomes more even than existing karyogenesis, in addition, when nuclear is grown up, can suppress the segregation thing and separate out at intragranular.
The rare earth alloy powder that is obtained by the manufacturing approach of the rare earth alloy powder of this embodiment is because the number of the intragranular segregation thing of rare earth alloy and amount fully reduced, so be suitably used as the alloy powder that rare earth element magnet is used.That is,, so just can make the superior magnet of performance aspect magnetic characteristic (particularly coercivity) if use the rare earth alloy powder that obtains by above-mentioned manufacturing approach to make magnet.
Then, just relevant rare earth alloy powder of the present invention preferred embodiment explains as follows.
Fig. 2 is the pattern sectional view that amplifies the rare earth alloy powder fine structure of this embodiment of expression.The cross section of this fine structure can be observed and confirms with transmission electron microscope.
The rare earth alloy powder of this embodiment is a plurality of primary particle 10 aggegations and constituting, and each primary particle 10 contains rare earth alloy as main component.Though primary particle 10 is made up of rare earth alloy basically; But the primary particle 10 of part also can have the segregation thing 20 different with rare earth alloy in inside, and this segregation thing 20 contains α-Fe and rich iron compound or from the compound of the impurity such as Nb that raw alloy comprised.
The rare earth alloy powder of this embodiment can make according to above-mentioned specific manufacturing approach.The rare earth alloy powder of this embodiment comprises the primary particle of rare earth alloy (R-Fe-B class alloy) as Main Ingredients and Appearance (more than the 99 for example whole quality %).This rare earth alloy powder is compared with existing rare earth alloy powder, as be present in primary particle inner and with the different material of main component, promptly the number of segregation thing is fully reduced.Particularly, 4/μ of the number per unit area average out to m of segregation thing on the cross section of primary particle 10
2Below.As previously discussed, because the number of segregation thing and amount have fully been reduced, thus generation that can reverse domain, and have outstanding coercivity.
From making the viewpoint of rare earth alloy powder, be preferably R:25～35 quality % as the composition of the R-Fe-B class alloy of the main component of rare earth alloy powder with more outstanding magnetic characteristic; B:1～1.4 quality %; Fe:65.6～72 quality %.As R, can be for being selected from a kind or the element more than 2 kinds among Y, La, Ce, Pr, Nd, Sm, Gd, Td, Dy, Ho, Er, Tm, the Lu.From the viewpoint of manufacturing cost and magnetic characteristic, R preferably contains Nd.
The mean value of the segregation thing number of the per unit area on the cross section of the primary particle of rare earth alloy powder can calculate according to following method.Rare earth alloy powder is embedded in the resin also with FIB (FIB) processing unit (plant) making thin slice sample, use transmission electron microscope (TEM, multiplying power: 50,000) observe this sample.Observe 10 visuals field; Each visual field is the zone of about 1.3 μ m * 1.3 μ m; Thereby carry out the composition analysis that relies on EDS for a plurality of primary particles 10, number goes out to have and segregation thing number as the rare earth alloy of the main component of primary particle 10 composition inequality.Then, calculate the mean number of the segregation thing that is detected, thus (the 1 μ m that also just can try to achieve per unit area
2) segregation thing number.Also have; Run into to count out segregation thing number in; Cause the zone that the possibility of segregation thing existence uprises for difference in TEM bright-field image,, segregation thing number thereby just can count effectively through carrying out the spot composition analysis that relies on EDS owing to contrast.
This rare earth alloy powder is preferably the ferromagnetic powder with magnetic anisotropy.Thus, can be suitable for the raw material of the anisotropic bond magnet that work does well aspect magnetic characteristic.
Then, just relevant anisotropic bond magnet of the present invention preferred embodiment explains as follows.
Fig. 3 is the stereogram of the anisotropic bond magnet of this embodiment of expression.The anisotropic magnetic iron powder that comprises resin and form by the represented anisotropic bond magnet 50 of Fig. 3 by this resin compounded.As the anisotropic magnetic iron powder, can use above-mentioned rare earth alloy powder.As resin, can enumerate the thermosetting resin of epoxy resin and phenolic resins etc.; Phenylethylene, olefines, polyurethanes, polyesters, polyamide-based elastomer; Ionomer; The thermoplastic resin of ethylene propylene copolymer (EPM) and ethylene-ethyl acrylate copolymer etc.Wherein preferred thermosetting resin is more preferably epoxy resin or phenolic resins.
The anisotropic bond magnet 50 of this embodiment is because the anisotropic magnetic iron powder is orientated on specific direction, so have outstanding magnetic characteristic.Ferromagnetic powder in the anisotropic bond magnet 50 and resin contain ratio, with respect to ferromagnetic powder 100 mass parts, preferably contain for example 0.5～20 mass parts of resin.With respect to ferromagnetic powder 100 mass parts,,, the tendency that is difficult to obtain fully superior magnetic characteristic will be arranged so if resin content surpasses 20 mass parts if the content of resin, so just has the ruined tendency of conformality less than 0.5 mass parts.
This anisotropic bond magnet can use usual way to make.An example of relevant manufacturing approach below is described.At first, come mixing resin binder and the ferromagnetic powder that contains above-mentioned resin, thereby the anisotropic bond magnet that modulation contains resin binder and ferromagnetic powder is with compound (composition) with pressurization mixing roll (pressurization kneader).With in the compound, can add coupling agent and other interpolation material at anisotropic bond magnet in case of necessity.
Modulated above-mentioned anisotropic bond magnet with compound after, carry out the forming process that in magnetic field, is shaped through compressing this compound, thereby just can obtain anisotropic bond magnet.Compression molding can use the compressing forming machine of mechanical press and hydraulic press etc. to carry out.So, just can obtain to contain the anisotropic magnetic iron powder that has been orientated and the anisotropic bond magnet of resin.Because this anisotropic bond magnet contains the segregation thing by the anisotropic magnetic iron powder that fully reduces, and this ferromagnetic powder is orientated on specific direction, therefore has outstanding magnetic characteristic.
Also have, the manufacturing approach of anisotropic bond magnet is not limited to rely on the method for above-mentioned compression molding, for example also can be shaped by injection moulding.In the case; Can anisotropic bond magnet be heated to the melt temperature of adhesive (thermoplastic resin) in case of necessity with compound; After becoming flow regime, this compound is expelled to has the regulation shape and be applied with in the mould in magnetic field, and carry out in the magnetic field and be shaped.Afterwards, cooling, and from mould, take out formed products (anisotropic bond magnet) with regulation shape.As stated, can produce anisotropic bond magnet.
Though more than just relevant preferred implementation of the present invention be described, but the present invention at all is not limited to above-mentioned embodiment.For example, anisotropic bond magnet is not limited to above-mentioned shape, and can be through changing the anisotropic bond magnet that mould has desirable shape (for example column, tabular or C type shape).
[embodiment]
Below come content of the present invention is elaborated, but the present invention is not limited to following embodiment with embodiment and comparative example.
(embodiment 1)
Has the following Nd that forms by the modulation of thin strap continuous casting method
2Fe
14The B raw alloy.
Nd:28.0 quality %
Fe:70.01 quality %
B:1.08 quality %
Ga:0.36 quality %
Nb:0.30 quality %
This raw alloy also contains the unavoidable impurities (accounting for 0.2～0.3 all quality % of raw alloy) of trace except containing above-mentioned element.In a vacuum, in 1000～1200 ℃ the temperature range this raw alloy is kept 24 hours (heat treatment step homogenizes).Pulverize the Nd after the heat treatment that homogenizes with stamping mill
2Fe
14B also carries out screening, thereby obtains that Powdered (particle diameter is 1～2mm) raw alloy.
This raw alloy is filled in the container of molybdenum system, fills in then in the tubulose heat-treatment furnace with infrared heating device, and implement according to the hydrogenolysis dehydrogenation processing of composite algorithm again (HDDR processing) with following condition.Also have, the time diagram of this processing is as shown in Figure 1.
At first, carry out hydrogen occlusion operation (I among Fig. 1), this operation is that hydrogen is imported in the tubulose heat-treatment furnace, and under the hydrogen gas atmosphere, the hydrogen dividing potential drop is 100kPa and temperature (T
0) be that 100 ℃ condition keeps raw material alloy powder 2 hours.Thus, make the hydrogen occlusion in raw alloy, thereby obtain hydrogen occlusion alloy.
Then, carry out hydrogenolysis operation (II among Fig. 1), this operation is to make with 10 ℃/minute in the hydrogen dividing potential drop in reducing stove that temperature heats up in the stove, thereby is 40kPa and temperature T in the hydrogen dividing potential drop
1Be under 800 ℃ the condition hydrogen occlusion alloy to be kept 1.5 hours.Make the hydrogen occlusion alloy hydrogenolysis thus and obtain catabolite.
Afterwards, make with 10 ℃/minute that temperature is warming up to temperature T in the stove
2=850 ℃ (heating process, the III among Fig. 1).Temperature is warming up to T in stove
2Afterwards, use vavuum pump to make the hydrogen exhaust, and reduce furnace pressure (hydrogen dividing potential drop), thereby begin to discharge the hydrogen (the 1st dehydrogenation is compound working procedure again, the IV among Fig. 1) that catabolite comprises through the speed of dividing with 4kPa/.
In the 1st dehydrogenation again in the compound working procedure, with making all quality of catabolite before the hydrogen release as benchmark, with 1.33 quality %/minute hydrogen release speed a hydrogen is discharged from catabolite, the hydrogen concentration in catabolite is reduced to the hydrogen concentration η of table 1
2
If the hydrogen concentration in the catabolite has dropped to the hydrogen concentration η of table 1
2, so just change exhaust velocity, thereby the decrease speed of furnace pressure (hydrogen dividing potential drop) adjusted to the 0.1kPa/ branch from the hydrogen in the stove.Thus, with making all quality of catabolite before the hydrogen release as benchmark, with hydrogen from the rate of release b of catabolite be adjusted to 0.35 quality %/minute.Afterwards, the pressure in stove (=hydrogen dividing potential drop) becomes less than 1Pa and passes through to continue release hydrogen, thereby from catabolite, removes dehydrogenation (the 2nd dehydrogenation is compound working procedure again, the V among Fig. 1) basically fully.Also have, the 1st dehydrogenation again in the compound working procedure the required time be approximately 10 minutes, the 2nd dehydrogenation again in the compound working procedure the required time be approximately 40～50 minutes.
Pressure in stove (hydrogen dividing potential drop) becomes less than stopping release hydrogen in the 1Pa.Afterwards, temperature in the stove is cooled to room temperature (about 20 ℃), thereby obtains anisotropy Nd through the HDDR processing
2Fe
14The B powder.
[evaluation of magnetic characteristic]
In atmosphere of inert gases, use mortar to pulverize the Nd that is obtained
2Fe
14The B powder, and sieve, thereby the Nd that particle diameter is 53～212 μ m processed
2Fe
14The B powder.This powder and paraffin are encased in the container, thereby and make the magnetic field that applies 1 tesla under the state of paraffin dissolving make the ferromagnetic powder orientation.On the direction that the differently-oriented directivity with ferromagnetic powder parallels, apply the pulsed magnetic field of 6 teslas, use vibrating example magnetometer (VSM) to measure magnetization-field curve, thus the magnetic characteristic of trying to achieve.The mensuration result of relict flux density (Br) and coercivity (Hcj) is shown in the table 1.
[evaluation of fine structure]
Calculate Nd by said method
2Fe
14Per unit area (μ m on the primary particle cross section of B powder
2) the mean number of segregation thing.Also have, run into to count out segregation thing number in, in TEM bright-field image because the difference of contrast causes the zone that possibility that the segregation thing exists uprises, the spot composition analysis of carrying out by means of EDS judges whether it is the segregation thing.Its evaluation result is shown in the table 1.
(embodiment 2～4, comparative example 1～5)
Except will from the 1st dehydrogenation again compound working procedure switch to the 2nd dehydrogenation hydrogen concentration (η of the catabolite compound working procedure (being altered to hydrogen release speed b) time again from hydrogen release speed a
2) change to by outside the represented value of table 1, all the other and embodiment 1 carry out Nd equally
2Fe
14The HDDR of B powder handles, thereby obtains anisotropy Nd
2Fe
14The B powder.Then, with embodiment 1 same Nd to being obtained
2Fe
14The B powder is carried out and is estimated.The HDDR treatment conditions and the evaluation result of embodiment 2～4 and comparative example 1～5 are shown in the table 1 together.Also have, from the 1st dehydrogenation again compound working procedure to the 2 dehydrogenations again the switching of compound working procedure be the switching degree through the adjustment air bleeding valve and change the exhaust velocity of carrying out the hydrogen of exhaust in the stove and carry out.
(embodiment 5)
Except with temperature T
1Adjust to 750 ℃ and with temperature T
2Adjust to outside 900 ℃, all the other are all carried out HDDR equally with embodiment 1 and handle, thereby obtain anisotropy Nd
2Fe
14The B powder.Then, with embodiment 1 same Nd to being obtained
2Fe
14The B powder is carried out and is estimated.HDDR treatment conditions and evaluation result are shown in the table 1.
(embodiment 6)
Except with temperature T
1Adjust to 830 ℃ and with temperature T
2Adjust to outside 850 ℃, all the other are all carried out HDDR equally with embodiment 1 and handle, thereby obtain anisotropy Nd
2Fe
14The B powder.Then, with embodiment 1 same Nd to being obtained
2Fe
14The B powder is carried out and is estimated.HDDR treatment conditions and evaluation result are shown in the table 1.
(embodiment 7)
Except with temperature T
1Adjust to 700 ℃ and with temperature T
2Adjust to outside 720 ℃, all the other are all carried out HDDR equally with embodiment 1 and handle, thereby obtain anisotropy Nd
2Fe
14The B powder.Then, with embodiment 1 same Nd to being obtained
2Fe
14The B powder is carried out and is estimated.HDDR treatment conditions and evaluation result are shown in the table 1.
(embodiment 8)
Except with the 1st dehydrogenation again the hydrogen release speed a in the compound working procedure adjust to 3.0 quality %/minute and with the 2nd dehydrogenation again the hydrogen release speed b in the compound working procedure adjust to 0.1 quality %/minute, all the other all obtain anisotropy Nd with embodiment 1 equally
2Fe
14The B powder.Hydrogen release speed a, b adjust through the decrease speed that changes furnace pressure.With embodiment 1 same Nd to being obtained
2Fe
14The B powder is carried out and is estimated.HDDR treatment conditions and evaluation result are shown in the table 1.
(embodiment 9)
Except with the 1st dehydrogenation again the hydrogen release speed a in the compound working procedure adjust to 0.8 quality %/minute and with the 2nd dehydrogenation again the hydrogen release speed b in the compound working procedure adjust to 0.4 quality %/minute, all the other all obtain anisotropy Nd with embodiment 1 equally
2Fe
14The B powder.Hydrogen release speed a, b adjust through the decrease speed that changes furnace pressure.With embodiment 1 same Nd to being obtained
2Fe
14The B powder is carried out and is estimated.HDDR treatment conditions and evaluation result are shown in the table 1.
[table 1]
| ? | Hydrogen concentration η 2Quality % | η 2/ρ | Hydrogen release speed a quality %/minute | Hydrogen release speed b quality %/minute | T 1 (℃) | T 2 (℃) | The number of intragranular segregation thing is (individual/μ m 2) | Relict flux density Br (kG) | Coercivity H j (kOe) |
| |
0.230 | 8.20×10 -3 | 1.33 | 0.35 | 800 | 850 | 3.3 | 13.06 | 15.14 |
| Embodiment 2 | 0.287 | 1.03×10 -2 | 1.33 | 0.35 | 800 | 850 | - | 12.89 | 15.39 |
| Embodiment 3 | 0.314 | 1.12×10 -2 | 1.33 | 0.35 | 800 | 850 | - | 13.05 | 15.12 |
| Embodiment 4 | 0.342 | 1.22×10 -2 | 1.33 | 0.35 | 800 | 850 | 2.8 | 13.13 | 15.07 |
| Comparative example 1 | 0.115 | 4.10×10 -3 | 1.33 | 0.35 | 800 | 850 | - | 12.20 | 13.67 |
| Comparative example 2 | 0.172 | 6.15×10 -3 | 1.33 | 0.35 | 800 | 850 | 4.6 | 12.97 | 14.37 |
| Comparative example 3 | 0.369 | 1.32×10 -2 | 1.33 | 0.35 | 800 | 850 | 5.0 | 12.93 | 12.74 |
| Comparative example 4 | 0.397 | 1.42×10 -2 | 1.33 | 0.35 | 800 | 850 | - | 13.08 | 11.11 |
| Comparative example 5 | 0.424 | 1.51×10 -2 | 1.33 | 0.35 | 800 | 850 | - | 13.41 | 10.95 |
| |
0.230 | 8.20×10 -3 | 1.33 | 0.35 | 750 | 900 | 2.3 | 11.87 | 15.78 |
| Embodiment 6 | 0.230 | 8.20×10 -3 | 1.33 | 0.35 | 830 | 850 | 4.0 | 12.88 | 14.53 |
| Embodiment 7 | 0.230 | 8.20×10 -3 | 1.33 | 0.35 | 700 | 720 | 3.6 | 13.54 | 14.82 |
| Embodiment 8 | 0.230 | 8.20×10 -3 | 3.0 | 0.1 | 800 | 850 | 2.1 | 12.78 | 15.97 |
| Embodiment 9 | 0.230 | 8.20×10 -3 | 0.8 | 0.4 | 800 | 850 | 3.3 | 13.12 | 14.97 |
Can confirm the Nd of embodiment 1～9 according to the result of table 1
2Fe
14The number of its intragranular segregation thing of B powder is fully reduced, thereby has outstanding magnetic characteristic (particularly coercivity).
Claims (4)
1. rare earth alloy powder is characterized in that:
Comprise a plurality of primary particles, said primary particle be through the raw alloy that contains rare earth element implement is inhaled the dehydrogenation of hydrogen disproportionation again Combined Processing obtain,
Said primary particle contains rare earth alloy as main component,
And, 4/μ of the number per unit area average out to m of the segregation thing different on the said primary particle cross section with said rare earth alloy
2Below.
2. an anisotropic bond magnet is used compound, it is characterized in that:
Contain described rare earth alloy powder of anisotropic claim 1 and resin.
3. anisotropic bond magnet is characterized in that:
The described anisotropic bond magnet of claim 2 is shaped with compound and obtains.
4. rare earth alloy powder as claimed in claim 1 is characterized in that:
Said rare earth alloy powder utilization suction hydrogen disproportionation dehydrogenation complex method is again made, and this method has:
The hydrogenolysis operation is in temperature T
1Down, making rare earth element content is the raw alloy hydrogenolysis of ρ (quality %), thereby the acquisition hydrogen concentration is η
1The catabolite of (quality %);
The 1st dehydrogenation is compound working procedure again, than said temperature T
1High temperature T
2Down, hydrogen is discharged from said catabolite with the rate of release of regulation, until the hydrogen concentration of said catabolite from η
1(quality %) is reduced to the η that satisfies following formula (1)
2(quality %); And
The 2nd dehydrogenation is compound working procedure again, and more said the 1st dehydrogenation compound working procedure again reduces the rate of release of hydrogen from said catabolite, further reduces the hydrogen concentration of said catabolite, thereby obtains rare earth alloy powder;
0.008×ρ≤η
2≤0.013×ρ (1)?。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-082845 | 2009-03-30 | ||
| JP2009082845 | 2009-03-30 | ||
| JP2010009065A JP2010255098A (en) | 2009-03-30 | 2010-01-19 | Rare earth alloy powder, method for producing the same, compound for anisotropic bond magnet, and anisotropic bond magnet |
| JP2010-009065 | 2010-01-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101850425A CN101850425A (en) | 2010-10-06 |
| CN101850425B true CN101850425B (en) | 2012-12-05 |
Family
ID=42802196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010158490 Active CN101850425B (en) | 2009-03-30 | 2010-03-30 | Rare earth alloy powders and manufacturing method thereof, compound for anisotropic bonded magnet and anisotropic bonded magnet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101850425B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011108173A1 (en) * | 2011-07-20 | 2013-01-24 | Aichi Steel Corporation | Magnetic material and process for its production |
| CN102768890B (en) * | 2012-08-10 | 2015-06-10 | 北矿磁材科技股份有限公司 | Preparation method of rare earth anisotropism magnetic powder, magnetic powder and magnetic body |
| CN104607645B (en) * | 2013-11-04 | 2017-12-01 | 三环瓦克华（北京）磁性器件有限公司 | The broken method of the continuous hydrogen of RE permanent magnetic alloy |
| CN104637667B (en) * | 2015-01-16 | 2018-02-09 | 浙江和也健康科技有限公司 | A kind of anti-oxidation flexible stickup NdFeB magnetic stripes and preparation method thereof |
| CN105839006B (en) * | 2015-01-29 | 2020-08-11 | 户田工业株式会社 | Method for producing R-T-B-based rare earth magnet powder, and bonded magnet |
| CN105957676A (en) * | 2015-10-19 | 2016-09-21 | 东莞市海天磁业股份有限公司 | Preparation method of anisotropic magnetic powder |
| CN108269667B (en) * | 2018-01-05 | 2020-07-03 | 北京科技大学 | Regulation and control method of rare earth-iron-boron as-cast uniform equiaxed crystal structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171313A (en) * | 1997-05-23 | 1998-01-28 | 冶金工业部钢铁研究总院 | Process for preparing permanent magnet powder |
| CN1483538A (en) * | 2003-08-12 | 2004-03-24 | 北京科技大学 | Method and apparatus for peparing hydrogen induced rareearth magnetic-like anisotropic magnetic powder |
| CN101393791A (en) * | 2007-09-21 | 2009-03-25 | 有研稀土新材料股份有限公司 | Anisotropic magnetic powder and manufacturing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4244089B2 (en) * | 1999-10-15 | 2009-03-25 | 日立金属株式会社 | Method for producing rare earth alloy powder for permanent magnet |
-
2010
- 2010-03-30 CN CN 201010158490 patent/CN101850425B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171313A (en) * | 1997-05-23 | 1998-01-28 | 冶金工业部钢铁研究总院 | Process for preparing permanent magnet powder |
| CN1483538A (en) * | 2003-08-12 | 2004-03-24 | 北京科技大学 | Method and apparatus for peparing hydrogen induced rareearth magnetic-like anisotropic magnetic powder |
| CN101393791A (en) * | 2007-09-21 | 2009-03-25 | 有研稀土新材料股份有限公司 | Anisotropic magnetic powder and manufacturing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2001-115220A 2001.04.24 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101850425A (en) | 2010-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101850425B (en) | Rare earth alloy powders and manufacturing method thereof, compound for anisotropic bonded magnet and anisotropic bonded magnet | |
| EP2722856B1 (en) | Making method for rare earth sintered magnet | |
| CN1333410C (en) | Process for producing anisotropic magnet powder | |
| CN101640087B (en) | Rare earth magnet and production process thereof | |
| CN101552060B (en) | Rare earth permanent magnet powder and preparation method thereof | |
| KR20020033504A (en) | Manufacturing method of an anisotropic magnet powder, precursory anisotropic magnet powder and bonded magnet | |
| CN102639266A (en) | Powder for magnet | |
| CN105190802A (en) | Method for producing RFeB sintered magnet and RFeB sintered magnet produced thereby | |
| CN103189943A (en) | Production method of rare earth magnet | |
| CN104051103A (en) | R-T-B-based rare earth magnet particles, process for producing the R-T-B-based rare earth magnet particles, and bonded magnet | |
| CN105448444B (en) | A kind of method and rare earth permanent-magnetic material of the rare earth permanent-magnetic material that processability improves | |
| CN104124017B (en) | R-T-B system permanent magnet | |
| CN103493159B (en) | The manufacture method of rare earth element magnet | |
| CN102199719A (en) | Alloy for rare-earth magnet and producing method of alloy for rare-eartch magnet | |
| US10026531B2 (en) | R-T-B based alloy powder, compound for anisotropic bonded magnet and anisotropic bonded magnet | |
| CN107464684B (en) | Method for treating sintered magnet | |
| CN103357882B (en) | R-T-B system rare earth magnet powder, the manufacture method of R-T-B system rare earth magnet powder and bonded permanent magnet | |
| JP2011190482A (en) | Method for producing powder of rare earth alloy, and permanent magnet | |
| JP4556236B2 (en) | Rare plate for sintering rare earth magnet and method for producing rare earth magnet using the same | |
| CN101423902B (en) | Processing method of R-T-B series alloy powder for radiation magnetic loop | |
| JP4702522B2 (en) | R-T-B system sintered magnet and manufacturing method thereof | |
| WO2012105346A1 (en) | Process for production of rare earth alloy powder, anisotropic bonded magnet, and sintered magnet | |
| JP6447804B2 (en) | Method for manufacturing magnet compact | |
| JPH10317003A (en) | Production of anisotropic rare earth alloy powder for permanent magnet | |
| JPH10189319A (en) | Manufacture of material powder for anisotropic permanent magnet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |