WO2014040525A1 - 稀土磁铁用合金粉末、稀土磁铁的制造方法及制粉装置 - Google Patents

稀土磁铁用合金粉末、稀土磁铁的制造方法及制粉装置 Download PDF

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WO2014040525A1
WO2014040525A1 PCT/CN2013/083238 CN2013083238W WO2014040525A1 WO 2014040525 A1 WO2014040525 A1 WO 2014040525A1 CN 2013083238 W CN2013083238 W CN 2013083238W WO 2014040525 A1 WO2014040525 A1 WO 2014040525A1
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Prior art keywords
powder
rare earth
earth magnet
alloy
pulverizing
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PCT/CN2013/083238
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English (en)
French (fr)
Inventor
永田浩
吴冲浒
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厦门钨业股份有限公司
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Priority claimed from CN201210339562.XA external-priority patent/CN102842419B/zh
Priority claimed from CN201210336861.8A external-priority patent/CN102842418B/zh
Application filed by 厦门钨业股份有限公司 filed Critical 厦门钨业股份有限公司
Priority to US14/427,159 priority Critical patent/US20150239048A1/en
Publication of WO2014040525A1 publication Critical patent/WO2014040525A1/zh
Priority to US15/937,795 priority patent/US10717131B2/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • H01F1/0536—Alloys characterised by their composition containing rare earth metals sintered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/044—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by jet milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/023—Hydrogen absorption
    • 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

Definitions

  • Alloy powder for rare earth magnet method for producing rare earth magnet, and powder making device
  • the present invention relates to the field of manufacturing technology of magnets, and more particularly to a method for producing an alloy powder for a rare earth magnet, a method for producing a rare earth magnet, and a pulverizing device for producing an alloy powder for a rare earth magnet.
  • the rare earth magnet is a magnet based on the intermetallic compound R 2 T 14 B, wherein R is a rare earth element, T is iron, or a transition metal element replacing a part of iron and iron, and B is boron, which is extremely high.
  • the magnetic properties known as magnetic kings, have a maximum magnetic energy product (BH) max higher than the maximum magnetic energy product of ferrite magnets (Ferrite) more than 10 times.
  • the rare earth magnets have excellent machinability and the highest operating temperature. 200 degrees Celsius, and its hard texture, stable performance, good cost performance, and extremely wide application.
  • the manufacturing process of the rare earth magnet has the following two types: one is a sintered rare earth magnet, and the other is a bonded rare earth magnet. Among them, the application of sintered rare earth magnets is more extensive.
  • the manufacturing process of the sintered rare earth magnet mainly includes the following processes: raw material preparation ⁇ melting ⁇ casting ⁇ hydrogen breaking pulverization ⁇ fine pulverization ⁇ magnetic field forming ⁇ sintering ⁇ heat treatment ⁇ magnetic property evaluation ⁇ oxygen content evaluation in the sintered body.
  • the powder milling process In the production process of the rare earth magnet, the powder milling process generally uses a jet milling method as a micro-crushing method of the rare earth magnet. It is generally known by those skilled in the art that the use of a jet mill to classify an ultrafine R-rich powder (below ⁇ ) with a throughput of 0.3% to 3% to remove oxidized ultrafine powder is generally considered. It is better. Such an R-rich ultrafine powder is extremely oxidized as compared with other powder particles having a relatively small content of the rare earth element R (having a relatively large particle diameter), if such an R-rich ultrafine powder is not removed from the powder. The sintered magnet is produced as it is, and the rare earth element undergoes significant oxidation in the manufacturing process up to the sintering process. As a result, the rare earth element R is consumed in the combination with oxygen, and the amount of formation of the R 2 T 14 B type crystal phase as the main phase is lowered.
  • FIG. 1 is a schematic view of a prior art apparatus for a powder milling process using a jet pulverization process.
  • the oxygen content in the atmosphere is about 10,000 ppm
  • the apparatus includes a pulverizing device, a classifying device 2', and a finished powder collection.
  • the device 3', the ultrafine powder recovery device 4' and the compressor 5' are equipped with a filter 1 in the pulverizing device, the filter 1 is connected to the air outlet of the pulverizing device, and the air inlet of the pulverizing device is connected to the compressor 5' through a pipe.
  • the classifying device 2' is connected by a pipe, and the classifying device 2' is connected to the finished powder collecting device 3' and the ultrafine powder collecting device 4', respectively.
  • the coarse powder also called raw material powder
  • the coarse powder is pulverized by the airflow pulverizing method in the pulverizing device, and filtered by the filter 1 Processing, the powder pulverized below the target particle size is sent to the classifying device 2' through the pipeline to perform the classification step, and the coarse powder that is not pulverized or not completely pulverized remains in the pulverizing device 1' to continue the jet pulverization;
  • the ultrafine powder enters the ultrafine powder recovery device 4' through the pipeline
  • the finished pulverized powder enters the finished powder collection device 3', and is supplied to the subsequent processing step; in the ultrafine powder recovery device 4 In the
  • the oxygen content in the magnet mainly depends on the jet milling process in which a large amount of gas is pulverized, and the jet milling is performed.
  • the oxygen content of the atmosphere is reduced to less than 1000 ppm, a high-performance sintered magnet having an oxygen content of 2500 ppm or less can be obtained.
  • the sintering process if the oxygen content is too small, over-sintering is likely to occur, and the problem of abnormal growth of crystal grains is liable to occur, and the problems of coercive force, squareness, and heat resistance are also more remarkable.
  • Ga, Zr, Mo, V, W, etc. are added in an amount of about 0.5% by weight to about 1% by weight in order to prevent abnormal growth of crystal grains, but these elements are mostly non-magnetic elements, and there are not only processes.
  • the drawbacks of increased complexity and production costs are also prone to low magnets Br and (BH) max.
  • An object of the present invention is to overcome the deficiencies of the prior art and to provide a method for producing an alloy powder for a rare earth magnet which is no longer pulverized from a low-oxygen content which is sent from a pulverizing apparatus having an atmospheric oxygen content of less than 1000 ppm during pulverization.
  • the ultrafine powder of ⁇ or less is separated in the middle, so that the subsequent sintering process of obtaining a low-oxygen sintered magnet is less likely to cause abnormal grain growth (AGG), and has the characteristics of simplifying the process and reducing the production cost.
  • a method for producing an alloy powder for a rare earth magnet wherein the rare earth magnet is a magnet containing a main phase of R 2 T 14 B, and the R is at least one selected from the group consisting of rare earth elements containing a ruthenium concept, and the T To include at least one of Fe and/or Co a transition metal element obtained by the step of finely pulverizing at least one alloy for rare earth magnet or at least one alloy coarse powder for rare earth magnet using an inert gas high-speed gas stream having an oxygen content of 1000 ppm or less
  • the powder having a particle diameter of 50 ⁇ m or less includes an ultrafine powder of ⁇ or less.
  • the invention no longer separates and discards ultrafine powder (particles with a particle size below ⁇ ) from the low-oxygen fine powder, and simultaneously adjusts the oxygen content of the inert gas high-speed gas stream, so that the overall oxygen content of the obtained powder is controlled at 1000 ⁇ 2000 ppm, so that the subsequent sintering process of the low-oxygen sintered magnet is less likely to cause abnormal grain growth (AGG), the coercive force is not lowered, and the most suitable sintering temperature range can be relaxed by about 40 ° C.
  • the coercive force can be increased by up to 12%, the squareness can be increased by up to 15%, and valuable rare earth can be saved, and the price can be made in terms of price. contribution.
  • non-separating ultrafine powder that is, the fact that all of the powder obtained by jet milling is used in the subsequent process.
  • all the powder is a small amount of residual powder remaining in the parts such as the inside of the pulverizer, in the sorting wheel, in the pipeline, in the compressor, in the pressure vessel, in the connection part of the valve, in the powder container, etc.
  • a nearly full-volume powder containing a superfine powder and being made into a magnet product by press molding and sample powder for QC storage, etc. it also refers to the effective use of the ultrafine powder which is separated and discarded in the prior art.
  • the particle size refers to the particle size of each powder. 50 ⁇ m below means that the particle diameter of each powder does not exceed 50 ⁇ m. That is, it refers to a group of crystal grains having a maximum particle diameter of not more than 50 ⁇ m (of course, this includes ultrafine powders of ⁇ or less).
  • the particle diameter of the powder is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less.
  • the ball equivalent diameter was measured by directly observing the powder under a microscope. This is because, in the measurement using the laser reflection method, in the process of performing statistics, there is a case where a small amount of the largest particle diameter is ignored and the maximum particle diameter cannot be detected. Further, when the measurement is performed by a gas permeation method such as FSSS, the average particle diameter estimated by the probability can be obtained. It is impossible to know the size of the largest crystal grain.
  • the rare earth magnet mentioned in the present invention may further comprise a doping element ⁇ of 0.01 at% to 10 at% in addition to the R, T and ⁇ elements which are indispensable for forming the main phase of R 2 T 14 B.
  • the crucible may be at least one selected from the group consisting of Al, Ga, Ca, Sr, Si, Sn, Ge, Ti, Bi, C, S or P.
  • the flow rate of the inert gas high-speed gas stream referred to in the present invention is 2 to 50 m/s.
  • the inert gas high-speed gas stream referred to in the present invention has a normal temperature dew point of -10 ° C or less at 0.1 MPa to 1.0 MPa.
  • the alloy for a rare earth magnet is an alloy of rare earth magnets having at least two kinds of rare earth components and/or different contents.
  • the alloy coarse powder is obtained by a coarse pulverization process of pulverizing the alloy by a hydrogen fragmentation method.
  • the alloy for a rare earth magnet is obtained by cooling a raw material alloy melt by a strip casting method at a cooling rate of 10 2 ° C / sec or more and 10 4 ° C / sec or less.
  • Another object of the present invention is to provide a method of producing a rare earth magnet.
  • a method for producing a rare earth magnet wherein the rare earth magnet is a magnet containing a main phase of R 2 T 14 B, and the R is at least one selected from the group consisting of rare earth elements containing a bismuth concept, and the T is including Fe And / or Co transition metal elements, including the following steps:
  • a powder having a particle diameter of 50 ⁇ m or less is obtained, including Ultrafine powder below ⁇ ;
  • the step of sintering the formed body to produce a rare earth magnet The step of sintering the formed body to produce a rare earth magnet.
  • Still another object of the present invention is to provide a pulverizing apparatus for producing the above alloy powder for a rare earth magnet.
  • a pulverizing apparatus for manufacturing an alloy powder for a rare earth magnet comprising a pulverizing device, a first collecting device, a material tank, and a compressor, wherein the pulverizing device is provided with a feed port, an air inlet at a lower portion, and an upper portion Air outlet, the crushing device a gas inlet is connected to the compressor, and a first filter for passing a powder having a particle diameter of 50 ⁇ m or less is disposed at an air outlet; the first collecting device is provided with an air inlet at an upper portion and an outlet at a top portion a gas port, the air inlet of which is connected to the gas outlet of the pulverizing device through a pipe, and the bottom of the first collecting device is connected to the material tank, wherein: the gas outlet of the first collecting device extends downward for one a second filter that is gas-solid separated and communicates with the compressor, the second filter being disposed corresponding to an intake port of the first collection device.
  • the pulverizing device is configured to add a filter for gas-solid separation in the first collecting device, so that the ultra-fine powder which is easily oxidized is not separated in the first collecting device, and is continuously mixed in the finished pulverized powder. Collected by the first collection device.
  • a pulverizing apparatus for manufacturing an alloy powder for a rare earth magnet comprising a pulverizing device, a first collecting device, a material tank, a second collecting device, and a compressor, wherein the pulverizing device is provided with a feed port and an intake air at a lower portion a port and an air outlet located at an upper portion, the air inlet of the pulverizing device is connected to the compressor, and a filter for passing a powder having a particle diameter of 50 ⁇ m or less is disposed at an air outlet of the pulverizing device; the first collecting device An intake port at the upper portion and an air outlet at the top, wherein the air inlet communicates with the air outlet of the pulverizing device through a duct, and the bottom of the first collecting device communicates with the tank; the second collection The device is an ultrafine powder collecting device, which is provided with an upper air inlet and an air outlet at the top, the air inlet communicates with the air outlet of the first collecting device through a pipeline, and the air outlet communicates with
  • the invention has the following characteristics:
  • the oxygen content in the high-speed gas stream of the inert gas in the JM pulverization is less than 1000 ppm, the rare earth element and the effective impurities in the ultrafine powder are hardly oxidized, and the ultrafine powder can be used as an effective sintering aid during sintering, and can also be used.
  • the subsequent sintering process is less prone to abnormal grain growth (AGG), improves coercivity and squareness, and has the characteristics of simplifying the process and reducing the manufacturing cost;
  • the ultrafine powder is relatively stable in oxygen, and since it contains more effective impurities such as Si, Cu, Cr, Mn, S, P, etc., the sintered body made of the fine powder containing the ultrafine powder has high corrosion resistance. Even if it is a magnet without Co, its corrosion resistance is also Will be dramatically improved, without the need to add expensive, precious Co;
  • FIG. 1 is a schematic view of a prior art airflow pulverizing apparatus
  • FIG. 2 is a schematic view of a jet mill apparatus used in Examples 1-3 and Comparative Examples 1-6 of the present invention
  • Fig. 3 is a schematic view showing the air flow pulverizing apparatus used in Examples 4 to 6 and Comparative Examples 7 to 12 of the present invention.
  • the invention takes the NdFeB rare earth alloy magnetic powder as an example to illustrate the preparation process and evaluation process of the rare earth magnetism.
  • the production process mainly includes the following processes: raw material preparation ⁇ melting ⁇ casting ⁇ hydrogen breaking pulverization ⁇ fine pulverization ⁇ magnetic field forming ⁇ sintering ⁇ heat treatment ⁇ magnetic property evaluation ⁇ oxygen content evaluation in the sintered body.
  • composition of the above 1 to 3 a total of 10 kg of raw materials were weighed and prepared.
  • the prepared raw materials were placed in a crucible made of alumina, and vacuum-melted to 1500 ° C in a vacuum of 10 - 2 Pa using an intermediate frequency vacuum induction melting furnace.
  • the casting process Ar gas was introduced into a melting furnace after vacuum melting to 10,000 Pa, and casting was performed by a centrifugal casting method at a cooling rate of 1000 ° C / sec to obtain a quenched alloy.
  • the hydrogen pulverization process the sealed pulverization chamber in which the quenched alloy is placed is evacuated at room temperature, and then the hydrogen gas having a purity of 99.5% is introduced into the pulverization chamber to a pressure of 0.1 MPa, and after standing for 2 hours, the vacuum is raised while heating. The vacuum was maintained at a temperature of 30 CTC for 2 hours. Thereafter, the mixture was cooled, and the sample after the hydrogen pulverization was taken out, and the average particle diameter thereof was 200 ⁇ m to 1000 ⁇ m.
  • the pulverization apparatus used in the fine pulverization process is as shown in FIG. 2, and includes a pulverization device 1, a first collection device 2, a material tank 3, and a compressor 4, and the pulverization device 1 is provided with a feed port 11
  • the air inlet 12 at the lower portion and the air outlet 13 at the upper portion, the air inlet 12 of the pulverizing device 1 is connected to the compressor 4, and the first filter 51 for passing the powder having a particle diameter of 50 ⁇ m or less is disposed at the air outlet 13
  • the first collecting device 2 is provided with an air inlet 21 at the upper portion and an air outlet 22 at the top, and the air inlet 21 is communicated with the air outlet 13 of the pulverizing device 1 through a pipe, and the bottom of the first collecting device 2 is connected to the tank 3.
  • a second filter 52 for gas-solid separation extends downwardly from the air outlet 22 of the first collecting device 2, and communicates with the compressor 4, and the second filter 52 corresponds to the intake of the first collecting device Port
  • the sample after hydrogen fragmentation is placed in the pulverizing apparatus 1 from the feed port 11, and the inert gas flow of the compressor 4 when the oxygen content is ⁇ 100 ppm, the dew point is -38 ° C (normal temperature, 0.4 MPa), and the flow rate is 5 m/s.
  • the circulation is performed, the gas flow enters the pulverizing device 1 from the inlet port 12, and the sample is subjected to jet milling under the condition that the pressure of the pulverizing chamber is 0.4 MPa, and the particles below 50 ⁇ m after the pulverization are driven by the air flow through the upper gas outlet.
  • the first filter 51 disposed at 13 enters the first collecting device 2, and the coarse powder that is not pulverized or not completely pulverized (that is, greater than a certain particle size requirement) continues to remain in the pulverizing device 1 to continue the airflow pulverization;
  • the gas stream of the pulverized powder enters the first collecting device 2, at which time, the powder of the larger particles falls to the bottom by the self-weight, and the powder of the ultrafine particles follows the gas flow to the gas outlet 22 of the first collecting device 2, but cannot pass
  • the second filter 52 which is also retained in the first collection device 2, is recovered into the tank 3 along with the larger particles of powder.
  • the air flow passing through the second filter 52 flows to the compressor 4 to effect circulation.
  • the first filter 51 and the second filter 52 are each mounted with a vibrating machine that applies vibration.
  • a commercially available forming aid used as a forming agent is added to the pulverized powder.
  • the forming aid is methyl octanoate in an amount of 0.2% by weight of the rare earth alloy magnetic powder, and then mixed with a V type. The feeder is fully mixed.
  • Forming process in a magnetic field Using a right-angle oriented magnetic field molding machine, in a 2.0 ⁇ orientation magnetic field, under a molding pressure of 0.8 ton / C m 2 under a relative humidity of 1 to 3%, the above is added.
  • the forming aid powder is formed into a side length
  • the 40 mm cube is demagnetized in a 0.2 T magnetic field after forming.
  • the oxygen content in the nitrogen atmosphere was fixed at less than 100 ppm during molding, and a humidifier and a cooling device were placed in the molding machine, and molding was carried out in an atmosphere at a temperature of 25 °C.
  • each of the molded bodies is conveyed to a sintering furnace for sintering, and sintered at a temperature of 20 CTC and 900 ° C for 2 hours under a vacuum of 10 ° C, and then sintered at a temperature of 105 CTC for 2 hours, and then introduced into Ar. After the gas reaches O.lMPa, it is cooled to room temperature.
  • the sintered body was heat-treated at a temperature of 580 ° C for 1 hour in a high-purity Ar gas, and then cooled to room temperature and taken out.
  • the sintered magnet was magnetically tested using the NIM-10000H bulk rare earth permanent magnet non-destructive testing system of China Metrology Institute, and the measurement temperature was 20 °C.
  • Oxygen content evaluation process in the sintered body The oxygen content in the sintered body is made by Japan HORIBA Co., Ltd.
  • the EMGA-620W oxygen and nitrogen analyzer was tested.
  • HAST Corrosion resistance test
  • Comparative Examples 1-6 differ from Examples 1-3 in that:
  • the pulverizing apparatus used in the fine pulverization process is as shown in Fig. 1, and includes a pulverizing apparatus 1', a grading apparatus 2', a finished powder collecting apparatus 3', an ultrafine powder collecting apparatus 4', and a compressor 5', which are pulverized.
  • the device ⁇ is provided with a filter 11' for passing a powder having a particle diameter of 50 ⁇ m or less, and the filter 1 is connected to an air outlet of the pulverizing device, and the air inlet of the pulverizing device 1' is connected to the compressor 5' through a pipe, and the pulverizing device 1'
  • the gas port is connected to the classifying device 2' by a pipe, and the classifying device 2' is connected to the finished powder collecting device 3' and the ultrafine powder collecting device 4', respectively.
  • coarse powder also called raw material powder
  • the air flow is circulated when the compressor 5' is in operation, and the airflow enters the pulverizing device 1' from the inlet of the pulverizing device.
  • the sample was subjected to jet milling at a pressure of 0.4 MPa at a pressure of 0.4 MPa using an inert gas flow having an oxygen content of ⁇ 10 ( ⁇ 1 ⁇ dew point of -38 ° C (normal temperature, 0.4 MPa) and a flow rate of 5 m/s,
  • the granules of less than 50 ⁇ m are driven by the airflow, pass through the first filter 11' provided at the outlet of the upper pulverizing device, enter the grading device 2' to perform the grading step, and the coarse powder which is not pulverized or not completely pulverized
  • the gas pulverization is continued in the pulverizing device; in the grading device 2', the ultrafine powder enters the ultrafine powder recovery device 4' through the pipeline through the grading treatment, and the finished pulverized powder enters the finished powder collecting device 3', Provided to the subsequent processing step; in the ultrafine powder recovery device 4', the airflow and the ultrafine powder
  • Ultrafine powder discard rate (%): Calculate the weight of the powder stored in the ultrafine powder recovery unit 4', divided by the weight of the raw material to be crushed, expressed as a percentage.
  • Table 3 is a comparison table of magnetic properties of the examples and comparative examples of the present invention.
  • the pulverizing apparatus used in the pulverizing process is as shown in Fig. 3, and includes a pulverizing device 1, a first collecting device 2, a tank 3, a second collecting device 4, and a compressor 5; the pulverizing device 1 is provided with a feed port 11.
  • the air inlet 12 at the lower portion and the air outlet 13 at the upper portion, the air inlet 12 of the pulverizing device is connected to the compressor 5, and the air outlet 13 of the pulverizing device is provided with a filter 14 for passing the powder having a particle diameter of 20 ⁇ m or less.
  • the first collecting device 2 is provided with an air inlet 21 at the upper portion and an air outlet 22 at the top, and the air inlet 21 communicates with the air outlet 13 of the pulverizing device through a pipe, and the bottom of the first collecting device 2 and the tank 3
  • the second collecting device 4 is an ultrafine powder collecting device, and is provided with an air inlet 41 at the upper portion and an air outlet 42 at the top, and the air inlet 41 communicates with the air outlet 22 of the first collecting device 2 through a pipe. , its air outlet
  • the 42-connected compressor 5 is further provided with a discharge port at the bottom of the second collecting device 4.
  • the discharge port 43 communicates with the bottom of the first collecting device 2 through a pipe 6 with a valve.
  • the sample after hydrogen fragmentation is placed in the pulverizing apparatus 1 from the feed port 11, and the gas stream is circulated while the compressor 5 is operating, and the gas stream enters the pulverizing apparatus 1 from the inlet port 12 at an oxygen content of 500 ppm to 1000 ppm and a dew point of -10. °C (normal temperature, 1.0MPa), an inert gas flow rate of 50m / s, the pressure of the crushing chamber is l.OMPa under pressure to grind the sample, after crushing
  • the powder below 20 ⁇ is passed through the filter 14 provided at the upper gas outlet 13 under the action of the gas stream, and enters the first collecting device 2, and the coarse powder which is not pulverized or not completely pulverized (that is, larger than a certain particle size requirement)
  • the airflow pulverization is continued; the airflow mixed with the pulverized powder enters the first collecting device 2, at which time, the powder of the larger particles falls to the bottom by the self-weight, and the powder of the ultrafine particles follows the flow of the airflow to the first collecting device 2
  • the ultrafine powder is collected and passed through the discharge port 43 into the bottom of the first collecting device 2, and the larger collected in the first collecting device 2
  • the powder of the granules is mixed and then introduced into the tank 3.
  • the air flow passing through the second collecting device 4 flows to the compressor 5 to effect circulation.
  • Comparative Example 7-12 differs from Comparative Example 1-6 in that:
  • the pulverizing apparatus used in the pulverizing process is as shown in Fig. 1, and includes a pulverizing device, a classifying device 2', a finished powder collecting device 3', an ultrafine powder collecting device 4', and a compressor 5', which are incorporated in the pulverizing device.
  • the classifying device 2' is connected to the finished powder collecting device 3' and the ultrafine powder collecting device 4', respectively.
  • the coarse powder also called the raw material powder
  • the air inlet enters the pulverizing device, and is tested under an inert gas flow atmosphere having an oxygen content of 500 ppm to 1000 ppm, a dew point of -10 ° C (normal temperature, 1.0 MPa), a flow rate of 5 m/s, and a pressure of the crushing chamber of 1.0 MPa.
  • the material is subjected to jet mill pulverization, and the pulverized particles less than 20 ⁇ m are driven by the airflow, passed through the first filter 1 disposed at the outlet of the upper pulverizing device, and enter the grading device 2' to perform the grading step without being pulverized or
  • the completely pulverized coarse powder continues to be left in the pulverizing device to continue the jet pulverization; in the grading device 2', the ultrafine powder enters the ultrafine powder recovery device 4' through the pipeline through the grading treatment, and the finished pulverized powder enters the finished powder.
  • the collecting device 3' is supplied to a subsequent processing step; in the ultrafine powder collecting device 4', the airflow and the ultrafine powder are separated, and the air outlet of the ultrafine powder recovery device 4' is connected to the compressor 5' through a pipe, The air flow is circulated through the compressor 5', and the ultrafine powder is left in the ultrafine powder recovery device 4'.
  • the ultrafine powder mentioned in the present invention is a particle having a particle diameter of less than ⁇ . The ultrafine powder collected by the ultrafine powder recovery device 4' is discarded.
  • Ultrafine powder discard rate (%): Calculate the weight of the powder stored in the ultrafine powder recovery unit 4', divided by the weight of the raw material to be crushed, expressed as a percentage.
  • Table 6 is a comparison table of magnetic properties of the examples and comparative examples of the present invention. Magnetic performance comparison table Ultrafine powder loss Br Hcj Hk/Hcj (BH) max HAST weight loss Sintered body oxygen
  • the present invention provides an alloy powder for a rare earth magnet, a method for producing a rare earth magnet, and a pulverizing device, which are no longer separated from a low-oxygen pulverized powder sent from a pulverizing device having an atmospheric oxygen content of less than 1000 ppm at the time of pulverization.
  • the ultrafine powder of ⁇ or less so that the subsequent sintering process of obtaining a low-oxygen sintered magnet is less likely to cause abnormal grain growth (AGG), and has a simplified process and a reduced production cost.

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Abstract

一种稀土磁铁用合金粉末、稀土磁铁的制造方法和制粉装置，它是在使用氧含量为1000ppm以下的惰性气体高速气流对至少一种的所述稀土磁铁用合金或至少一种的稀土磁铁用合金粗粉进行细破碎的工序中，获得粒径在50μm以下的全部粉末。其不再从粉碎时气氛氧含量降至1000ppm以下的粉碎装置中送过来的低氧含量粉碎粉中分出1μm以下的超细粉，从而使后续获得低氧含量烧结磁体的烧结工序不易发生晶粒异常长大（AGG），并具有简化工序和降低制作成本的特点。

Description

稀土磁铁用合金粉末、 稀土磁铁的制造方法及制粉装置 技术领域
本发明涉及磁铁的制造技术领域， 特别是涉及稀土磁铁用合金粉末的制造方法、 稀土 磁铁的制造方法及用于制造稀土磁铁用合金粉末的制粉装置。
背景技术
稀土磁铁是以金属间化合物 R2T14B为基础的磁铁， 这其中， R是稀土元素， T是铁， 或者是取代铁和铁的一部分的过渡金属元素， B是硼， 其拥有极高的磁性能， 被人们称为磁 王， 其最大磁能积 （BH) max高过铁氧体磁铁 （Ferrite) 最大磁能积 10倍以上， 另外， 稀 土磁铁的机械加工性能极佳， 工作温度最高可达 200摄氏度， 而且其质地坚硬， 性能稳定， 有很好的性价比， 应用极其广泛。
稀土磁铁的制作工艺有以下二种： 一种是烧结稀土磁铁， 另一种是粘结稀土磁铁。 这 其中， 又以烧结稀土磁铁的应用更为广泛。现有技术中， 烧结稀土磁铁的制作工艺主要包括 如下流程：原料配制→熔炼→铸造→氢破粉碎→微粉碎→磁场成形→烧结→热处理→磁性能 评价→烧结体中的氧含量评价等。
在稀土磁铁的制作工艺中， 其中的制粉工艺通常是采用气流粉碎法作为稀土磁铁的微 粉碎法。本技术领域的技术人员根据以往的常识普遍认为： 使用气流粉碎设备将相对于生产 量 0.3%〜3%的富 R超细粉（Ιμηι以下）进行分级以去除被氧化的超细粉这一做法是比较好 的。 这种富 R的超细粉， 与稀土元素 R的含量相对少的其他粉末粒子（具有相对大的粒径) 相比极容易被氧化， 如果不把这种富 R超细粉从粉末中除去， 而原封不动地制作烧结磁铁， 到烧结工序为止的制造工序中， 稀土元素会进行显著的氧化。 其结果是稀土元素 R消耗在 与氧的结合中， 导致作为主相的 R2T14B型结晶相的生成量降低。
图 1即为现有技术的采用气流粉碎法制粉工序的设备示意图， 在执行上述粉碎工序时， 气氛中的氧含量约为 1万 ppm，设备包括有粉碎装置 、分级装置 2'、成品粉收集装置 3 '、 超细粉回收装置 4' 和压缩机 5 '， 在粉碎装置 内装有过滤器 1 ， 过滤器 1 连通粉碎 装置 的出气口， 粉碎装置 的进气口通过管道连通压缩机 5 '， 粉碎装置 的出气口 通过管道连接分级装置 2 '，分级装置 2 '分别连接成品粉收集装置 3 '和超细粉回收装置 4 '。 在制粉过程中， 粗粉 （也称为原料粉） 从原料进口被送入粉碎装置 中， 在粉碎装置 内采用气流粉碎方式对粗粉 （原料粉） 进行粉碎处理， 经过过滤器 1 的过滤处理， 粉碎 至目标粒径以下的粉末通过管道被送入分级装置 2 ' 中执行分级步骤， 而未粉碎或未完全粉 碎的粗粉则继续留在粉碎装置 1 ' 内继续进行气流粉碎； 在分级装置 2 ' 中， 通过分级处理， 超细粉通过管道进入超细粉回收装置 4 '， 而成品粉碎粉则进入成品粉收集装置 3 '， 提供给 后继的加工工序； 在超细粉回收装置 4' 中， 对气流和超细粉进行分离， 超细粉回收装置 4' 的出气口通过管道连接至压缩机 5 '， 气流通过压缩机 5 ' 进行循环， 超细粉则留在超细粉回 收装置 4 ' 内， 这种制粉工序， 超细粉回收装置 4 ' 所收集的超细粉通常被丢弃。 以上述方 式获得的烧结体氧含量约为 2900ppm〜5300ppm。
另一方面， 随着制造方法整体的防氧化程度不断进步， 成形至烧结工序几乎不发生氧 化， 因此， 磁铁中的含氧量主要取决于在大量气流中进行粉碎的气流磨工序， 在气流粉碎时 气氛的氧含量降至 lOOOppm以下时， 可获得氧含量降至 2500ppm以下的高性能烧结磁铁。 然而， 在烧结过程中， 氧含量过少容易产生过烧结， 并易引起晶粒异常长大的问题， 且矫顽 力、 方形度、 耐热性的低下问题也更加显著。 作为众知的改良制法， 为防止晶粒异常长大通 常会添加 0.5重量％〜1重量％左右的 Ga、 Zr、 Mo、 V、 W等， 但是这些元素多为非磁性元 素， 不仅存在工序复杂和制作成本上升的弊端， 而且容易导致磁铁 Br、 (BH) max 的低下 问题。
发明内容
本发明的一个目的在于克服现有技术之不足， 提供一种稀土磁铁用合金粉末的制造方 法， 其不再从粉碎时气氛氧含量降至 lOOOppm以下的粉碎装置中送过来的低氧含量粉碎粉 中分出 Ιμιη以下的超细粉， 从而使后续获得低氧含量烧结磁体的烧结工序不易发生晶粒异 常长大 （AGG)， 并具有简化工序和降低制作成本的特点。
本发明采用的技术方案如下：
一种稀土磁铁用合金粉末的制造方法， 所述的稀土磁铁为含有 R2T14B主相的磁铁， 所 述的 R为选自包含钇概念的稀土元素中的至少一种， 所述 T为包括 Fe和 /或 Co的至少一种 过渡金属元素， 其特征在于： 在使用氧含量为 lOOOppm以下的惰性气体高速气流对至少一 种的所述稀土磁铁用合金或至少一种的稀土磁铁用合金粗粉进行细粉碎的工序中，获得粒径 在 50μηι以下的粉末， 包括 Ιμηι以下的超细粉。
本发明不再从低氧含量的细粉中分离和丢弃超细粉 （粒径在 Ιμηι以下的粉粒）， 同时 调节惰性气体高速气流的氧含量，使所得粉末的总体氧含量控制在 1000〜2000ppm，从而可 使后续获得低氧含量烧结磁体的烧结工序不易发生晶粒异常长大 （AGG)， 矫顽力不降低， 也可使最适合的烧结温度范围放宽 40°C左右， 性能方面： 与分离了超细粉的成品粉碎粉形 成的烧结磁体相比， 可使矫顽力最高提高 12%， 方形度最高提高 15%， 此外还可节约宝贵 的稀土， 在价格定价方面也能做出贡献。
本发明中涉及的 "不分离超细粉" ， 亦即， 在后续工艺中使用气流粉碎所得的事实上 的全部粉末。 事实上的全部粉末为除去一部分残余粉末 （如粉碎机内、 分选轮内、 管道内、 压缩机内、 压力容器内、 阀的连接部位、 粉末容器等部件中残留的少量残留粉末、 分析、 压 形试制和用于 QC保存等样品粉末等） 的、 含有超细粉被制成磁铁商品的几乎全量粉末。 当 然， 也是指有效利用在现有技术中被分离和丢弃的超细粉之事。
粒径指的是各个粉末的粒径。 50μιη以下指的是各个粉末的粒径全部没有超过 50μιη。 亦即， 指的是最大粒径不超过 50μιη的结晶粒群 （当然， 这其中包括 Ιμιη以下的超细粉）。
通过将含有不同结晶粒的合金用气流磨粉碎， 审慎制作含有超细粉的磁铁， 并进行无 数磁性能试验， 作为结果， 将粒径最大值定为 50μιη。 粉末粒径优选为 30μιη以下， 更优选 为 20μιη以下。
作为核发生型矫顽力发生机构， 烧结稀土磁铁中， 结晶粒径变大的话， 每个粒子的表 面缺陷的发生数变得非常高， 在我们的认识中， 这会使得烧结过程中通过富 R相修复表面 缺陷的机能不能有效发挥， 矫顽力及方形度急剧下降。 因此， 假如有超过 50μιη的大颗粒存 在， 会使得烧结磁铁中的矫顽力及方形度急剧下降。
粉末粒径的评价通过在显微镜下直接观察粉末， 测定球等价直径。 这是因为， 在使用 激光反射法进行测定时， 在进行统计的过程中， 存在少量最大粒径被无视， 无法检测出最大 粒径的情形。此外，使用 FSSS等的气体透过法进行测定之时， 能得到概率推算的平均粒径， 而无法知晓最大结晶粒的大小。
本发明所提及的稀土磁铁除形成 R2T14B主相必不可少的 R、 T、 Β元素之外， 还可以 包括占比为 0.01at%〜10 at%的掺杂元素 Μ， 所述 Μ可以为选自 Al、 Ga、 Ca、 Sr、 Si、 Sn、 Ge、 Ti、 Bi、 C、 S或 P中的至少一种。
本发明中所提及的所述惰性气体高速气流的流速为 2〜50m/s。
本发明中所提及的所述惰性气体高速气流在 0.1MPa〜1.0 MPa的常温露点为 -10°C以 下。
在推荐的实施例中， 所述稀土磁铁用合金为至少两种的稀土成分和 /或含量不同的稀土 磁铁用合金。
在推荐的实施例中， 所述合金粗粉通过用氢破碎法粉碎所述合金的粗粉碎工序获得。 在推荐的实施例中，所述稀土磁铁用合金是将原料合金熔融液用带材铸件法， 以 102°C/ 秒以上、 104°C/秒以下的冷却速度冷却得到的。
本发明的另一目的在于提供一种稀土磁铁的制造方法。
本发明提供的技术方案如下：
一种稀土磁铁的制造方法， 所述的稀土磁铁为含有 R2T14B主相的磁铁， 所述的 R为选 自包含钇概念的稀土元素中的至少一种， 所述 T为包括 Fe和 /或 Co的过渡金属元素， 包括 如下的步骤：
使用氧含量为 lOOOppm以下的惰性气体高速气流对至少一种的所述稀土磁铁用合金或 至少一种的稀土磁铁用合金粗粉进行细粉碎的工序中， 获得粒径在 50μιη以下的粉末， 包括 Ιμηι以下的超细粉； 以及
将所述粉末加工成形， 制作成形体的工序； 以及
将所述成形体进行烧结， 制作稀土磁铁的工序。
本发明的再一目的在于提供制造上述稀土磁铁用合金粉末的制粉装置。
本发明提供的一种技术方案如下：
一种用于制造稀土磁铁用合金粉末的制粉装置， 包括粉碎装置、 第一收集装置、 料罐 和压缩机， 所述粉碎装置设有进料口、位于下部的进气口和位于上部的出气口， 所述粉碎装 置的进气口连通所述压缩机， 其出气口处设置用以使粒径 50μηι以下粉末通过的第一过滤 器；所述第一收集装置设有位于上部的进气口和位于顶部的出气口，其进气口通过管道与所 述粉碎装置出气口相连通， 所述第一收集装置的底部连接所述料罐， 其特征在于： 第一收集 装置的出气口处向下延伸一用于气固分离的第二过滤器，并连通所述压缩机，所述第二过滤 器对应于所述第一收集装置的进气口设置。
该制粉装置通过在在第一收集装置内加装用于气固分离的过滤器， 从而使得易被氧化 的超细粉在第一收集装置内不被分离出来， 继续混合在成品粉碎粉中被第一收集装置所收 集。
本发明提供的另一种技术方案如下：
一种用于制造稀土磁铁用合金粉末的制粉装置， 包括粉碎装置、 第一收集装置、 料罐、 第二收集装置和压缩机，所述粉碎装置设有进料口、位于下部的进气口和位于上部的出气口， 所述粉碎装置的进气口连通所述压缩机，所述粉碎装置的出气口处设置用以使粒径 50μηι以 下粉末通过的过滤器； 所述第一收集装置设有位于上部的进气口和位于顶部的出气口，其进 气口通过管道与所述粉碎装置出气口相连通，第一收集装置的底部与所述料罐相连通； 所述 第二收集装置为超细粉收集装置，其设有位于上部的进气口和位于顶部的出气口，其进气口 通过管道连通第一收集装置的出气口， 其出气口连通压缩机， 其特征在于： 在第二收集装置 的底部还设有出料口， 该出料口通过一带有阀门的管道连通第一收集装置的底部。
与现有技术相比， 本发明具有如下的特点：
1 )通过混入以前废弃的包含丰富稀土的超细粉， 可达到节约宝贵稀土， 降低价格的效 果；
2) 由于 JM粉碎中的惰性气体高速气流中的氧含量为 lOOOppm以下， 超细粉中的稀土 元素及有效杂质几乎不发生氧化，超细粉可作为烧结时有效的烧结助剂，还可使后续的烧结 工序不易发生晶粒异常长大 （AGG)， 提高矫顽力和方形度， 并具有简化工序和降低制作成 本的特点；
3 ) 超细粉含氧而比较稳定， 且因为包含较多 Si、 Cu、 Cr、 Mn、 S、 P等有效杂质， 所 以包含该超细粉的细粉制成的烧结体耐腐蚀性较高， 就算是不含 Co的磁体， 其耐腐蚀性也 会戏剧性地变好， 无需添加昂贵、 宝贵的 Co;
4)无需使用以往必不可少的超细粉回收装置， 使设备变得精简， 且避免了以往的超细 粉回收装置在清扫设备时， 极易发生的超细粉燃烧、装置着火、操作人员烧伤等严重问题的 发生。
附图说明
图 1为现有技术的气流粉碎设备示意图；
图 2为本发明实施例 1-3、 比较例 1-6中使用的气流粉碎设备示意图；
图 3为本发明实施例 4-6、 比较例 7-12中使用的气流粉碎设备示意图。
具体实施方式
以下结合实施例对本发明作进一步详细说明， 但不构成对本发明保护范围的限制。 实施例 1-3
本发明以 NdFeB系稀土合金磁性粉末为例， 来说明稀土磁性的制作过程和评价过程。 其制作工艺主要包括如下流程： 原料配制→熔炼→铸造→氢破粉碎→微粉碎→磁场中 成形→烧结→热处理→磁性能评价→烧结体中的氧含量评价。
在原料配制工序： 准备纯度 99.5%的 Nd、 工业用 Fe-B和工业用纯 Fe， 各成分的重量 比符合表 1中所示：
表 1 各成分的重量配比
实验序号 Nd Fe B
实施例 1 28 71 1
实施例 2 30 69 1
实施例 3 33 66 1
根据上述 1至 3的配制组成， 分别称量、 配制了共计 10Kg的原料。
在熔炼工序:配制后的原料放入氧化铝制的坩埚中，使用中频真空感应熔炼炉，在 10—2Pa 真空中真空熔炼至 1500°C。
在铸造工序： 在真空熔炼后的熔炼炉中通入 Ar气至 1万 Pa后， 使用离心铸造法进行 铸造， 冷却速度为 1000°C/秒， 获得急冷合金。 在氢破粉碎工序： 在室温下将放置急冷合金的密封粉碎室抽真空， 而后向粉碎室内通 入纯度为 99.5%的氢气至压力为 0.1MPa， 放置 2小时后， 边升温边抽真空， 在 30CTC的温度 下保持真空状态 2小时； 之后进行冷却， 取出氢破粉碎后的试料， 其平均粒径为 200μηι〜 1000μιη。
在微粉碎工序： 微粉碎工序所使用的制粉装置如图 2中所示， 其包括粉碎装置 1、第一 收集装置 2、 料罐 3和压缩机 4， 粉碎装置 1设有进料口 11、 位于下部的进气口 12和位于 上部的出气口 13， 粉碎装置 1的进气口 12连通压缩机 4， 其出气口 13处设置用以使粒径 50μιη以下粉末通过的第一过滤器 51 ; 第一收集装置 2设有位于上部的进气口 21和位于顶 部的出气口 22， 其进气口 21通过管道与粉碎装置 1出气口 13相连通， 第一收集装置 2的 底部连接料罐 3，第一收集装置 2的出气口 22处向下延伸一用于气固分离的第二过滤器 52， 并连通压缩机 4， 第二过滤器 52对应于所述第一收集装置的进气口 21设置。
将氢破碎后的试料从进料口 11放入粉碎装置 1内， 压缩机 4工作时氧含量 <100ppm、 露点为 -38°C (常温， 0.4MPa)、 流速为 5m/s的惰性气流进行循环， 气流从进气口 12进入粉 碎装置 1， 在粉碎室压力为 0.4MPa的条件下对试料进行气流磨粉碎， 粉碎后 50μιη以下的 粉粒在气流的带动下， 通过上部的出气口 13处设置的第一过滤器 51， 进入第一收集装置 2 内， 而未粉碎或未完全粉碎的粗粉（即大于一定粒度要求）则继续留在粉碎装置 1内继续进 行气流粉碎； 混合有粉碎粉粒的气流进入第一收集装置 2， 此时， 较大颗粒的粉末依靠自重 掉向底部， 而超细颗粒的粉末跟随气流流向第一收集装置 2的出气口 22处， 但由于无法通 过第二过滤器 52， 同样被留在第一收集装置 2中， 并与较大颗粒的粉末一同回收到料罐 3 中。 经过第二过滤器 52的气流则流向压缩机 4， 实现循环。
为防止第一过滤器 51和第二过滤器 52发生堵塞， 第一过滤器 51和第二过滤器 52处 均安装有施加振动的振动机。
在粉碎后的粉末中添加作为成形剂使用的市面上销售的成形助剂， 本发明中， 成形助 剂为辛酸甲酯， 其添加量为稀土合金磁性粉末的重量 0.2%， 再用 V型混料机充分混合。
在磁场中成形工序： 使用直角取向型的磁场成型机， 在 2.0Τ的取向磁场中， 在 1〜3% 的相对湿度条件下， 在 0.8ton/Cm2的成型压力下， 将上述添加了成形助剂的粉末成形成边长 为 40mm的立方体， 成形后在 0.2T的磁场中退磁。
成形时氮气气氛中氧含量固定在 lOOOppm以下， 在成形机内设置加湿器和冷却设备， 在温度为 25 °C的气氛中进行成形。
在烧结工序： 各成形体搬运至烧结炉进行烧结， 烧结在 lO^Pa的真空下， 在 20CTC和 900 °C的温度下各保持 2小时后， 以 105CTC的温度烧结 2小时， 之后通入 Ar气体至 O.lMPa 后， 冷却至室温。
在热处理工序： 烧结体在高纯度 Ar气中， 以 580°C温度进行 1小时热处理后， 冷却至 室温后取出。
在磁性能评价工序： 烧结磁铁使用中国计量院的 NIM-10000H大块稀土永磁无损检测 系统进行磁性能检测， 测定温度为 20°C。
在烧结体中的氧含量评价工序： 烧结体中的氧含量使用日本 HORIBA公司的
EMGA-620W型氧氮分析仪进行检测。
耐腐蚀性试验 （HAST): 关于烧结体的耐腐蚀性试验， 使用精密电子天平评价 20天 HSAT (IEC68-2-66) 试验后的失重值 （mg)。
比较例 1-6
比较例 1-6与实施例 1-3的不同之处在于：
在原料配制工序：
准备纯度 99.5%的 Nd、 工业用 Fe-B、 工业用纯 Fe和纯度 99.9%的 Co， 各成分的重量 比符合表 2中所示：
表 2 各成分的重 t配比
实验序号 Nd Fe B Co
比较例 1 28 71 1 0
比较例 2 30 69 1 0
比较例 3 33 66 1 0
比较例 4 28 69 1 2
比较例 5 30 67 1 2 比较例 6 33 64 1 2
根据上述 1至 6的配制组成， 分别称量、 配制了共计 10Kg的原料。
在微粉碎工序：
微粉碎工序所使用的制粉装置如图 1中所示， 其包括粉碎装置 1'、 分级装置 2'、 成品 粉收集装置 3'、 超细粉回收装置 4' 和压缩机 5'， 在粉碎装置 Γ 内装有用以使粒径 50μιη 以下粉末通过的过滤器 11'， 过滤器 1 连通粉碎装置 的出气口， 粉碎装置 1' 的进气 口通过管道连通压缩机 5'， 粉碎装置 1' 的出气口通过管道连接分级装置 2'， 分级装置 2' 分别连接成品粉收集装置 3' 和超细粉回收装置 4'。 在制粉过程中， 粗粉 （也称为原料粉） 从原料进口被送入粉碎装置 1' 中， 压缩机 5' 工作时气流进行循环， 气流从粉碎装置 的进气口进入粉碎装置 1'， 用氧含量<10(^ 1^露点为 -38°C (常温， 0.4MPa)、流速为 5m/s 的惰性气流， 在粉碎室压力为 0.4MPa的压力下对试料进行气流磨粉碎， 粉碎后小于 50μιη 的粉粒在气流的带动下， 通过上部的粉碎装置出气口处设置的第一过滤器 11'， 进入分级装 置 2' 内执行分级步骤， 而未粉碎或未完全粉碎的粗粉则继续留在粉碎装置 内继续进行 气流粉碎； 在分级装置 2' 中， 通过分级处理， 超细粉通过管道进入超细粉回收装置 4'， 而 成品粉碎粉则进入成品粉收集装置 3'， 提供给后继的加工工序； 在超细粉回收装置 4' 中， 对气流和超细粉进行分离， 超细粉回收装置 4' 的出气口通过管道连接至压缩机 5'， 气流通 过压缩机 5' 进行循环， 超细粉则留在超细粉回收装置 4' 内， 需要说明的是， 本发明中提 及的超细粉为粒径在 Ιμιη以下的粉粒。 超细粉回收装置 4' 所收集的超细粉被丢弃。
超细粉丢弃率 （％)： 计算超细粉回收装置 4' 积存的粉末重量， 除以投入粉碎的原料 重量的数值， 用百分率表示。
表 3为本发明实施例和比较例的磁性能对照表。
磁性能对照表
超细粉丢 Br Hcj Hk/Hcj (BH)max HAST失重 烧结体中的 序号
弃率（％) (kGs) (kOe) (%) (MGOe) 值 (mg) 氧含量（ppm) 实施例 1 0 14.6 12.3 97.8 51.4 1.8 920 实施例 2 0 13.8 15.2 97.9 46.6 1.8 965 实施例 3 0 13.3 17.3 98.2 43.7 1.9 981 比较例 1 0.9 14.5 11.3 86.5 50.2 25.2 865 比较例 2 1.2 13.7 14.2 87.5 45.1 28.5 873 比较例 3 3.2 13.2 16.5 88.3 42.1 32.6 883 比较例 4 2.1 14.5 10.2 78.5 50.4 6.2 913 比较例 5 2.8 13.7 13.1 79.2 45.1 7.5 925 比较例 6 3.9 13.2 15.3 78.9 42.2 8.9 940 实施例 4-6 实施例 4-6与实施例 1-3的不同之处在于：
在原料配制工序： 准备纯度 99.5%的 Nd、 工业用 Fe-B和工业用纯 Fe， 各成分的重量 比符合表 4中所示:
表 4 各成分的重量配比
实验序号 Nd Fe B 实施例 4 28 71 1 实施例 5 30 69 1 实施例 6 33 66 1 根据上述 4至 6的配制组成， 分别称量、 配制了共计 10Kg的原料。
微粉碎工序所使用的制粉装置如图 3中所示， 其包括粉碎装置 1、 第一收集装置 2、 料 罐 3、 第二收集装置 4和压缩机 5 ; 粉碎装置 1设有进料口 11、 位于下部的进气口 12和位 于上部的出气口 13，粉碎装置的进气口 12连通压缩机 5，粉碎装置的出气口 13处设置用以 使粒径 20μιη以下粉末通过的过滤器 14; 第一收集装置 2设有位于上部的进气口 21和位于 顶部的出气口 22， 其进气口 21通过管道与粉碎装置出气口 13相连通， 第一收集装置 2的 底部与料罐 3相连通； 第二收集装置 4为超细粉收集装置， 其设有位于上部的进气口 41和 位于顶部的出气口 42， 其进气口 41通过管道连通第一收集装置 2的出气口 22， 其出气口
42连通压缩机 5， 在第二收集装置 4的底部还设有出料口 43， 该出料口 43通过一带有阀门 的管道 6连通第一收集装置 2的底部。
将氢破碎后的试料从进料口 11放入粉碎装置 1内， 压缩机 5工作时气流进行循环， 气 流从进气口 12进入粉碎装置 1，在氧含量 500ppm〜1000ppm、露点为 -10°C (常温， 1.0MPa)、 流速为 50m/s的惰性气流， 粉碎室压力为 l .OMPa的压力下对试料进行气流磨粉碎， 粉碎后
20μηι以下的粉粒在气流的带动下， 通过上部的出气口 13处设置的过滤器 14， 进入第一收 集装置 2内， 而未粉碎或未完全粉碎的粗粉 （即大于一定粒度要求）则继续留在粉碎装置 1 内继续进行气流粉碎； 混合有粉碎粉粒的气流进入第一收集装置 2， 此时， 较大颗粒的粉末 依靠自重掉向底部， 而超细颗粒的粉末跟随气流流向第一收集装置 2的出气口 22处， 进入 第二收集装置 4内， 在第二收集装置中， 超细粉被收集并通过出料口 43进入第一收集装置 2的底部， 与第一收集装置 2中收集的较大颗粒的粉末混合后进入料罐 3中。 经过第二收集 装置 4的气流则流向压缩机 5， 实现循环。
比较例 7-12
比较例 7-12与比较例 1-6的不同之处在于：
在原料配制工序：
准备纯度 99.5%的 Nd、 工业用 Fe-B、 工业用纯 Fe和纯度 99.9%的 Co， 各成分的重量 比符合表 5中所示：
表 5 各成分的重 t配比
实验序号 Nd Fe B Co
比较例 7 28 71 1 0
比较例 8 30 69 1 0
比较例 9 33 66 1 0
比较例 10 28 69 1 2
比较例 11 30 67 1 2
比较例 12 33 64 1 2
根据上述 7至 12的配制组成， 分别称量、 配制了共计 10Kg的原料。
在微粉碎工序：
微粉碎工序所使用的制粉装置如图 1中所示， 其包括粉碎装置 、 分级装置 2 '、 成品 粉收集装置 3 '、 超细粉回收装置 4' 和压缩机 5 '， 在粉碎装置 内装有用以使粒径 20μιη 以下粉末通过的过滤器 1 ， 过滤器 1 连通粉碎装置 的出气口， 粉碎装置 的进气 口通过管道连通压缩机 5 '， 粉碎装置 的出气口通过管道连接分级装置 2'， 分级装置 2' 分别连接成品粉收集装置 3 ' 和超细粉回收装置 4 '。 在制粉过程中， 粗粉 （也称为原料粉） 从原料进口被送入粉碎装置 1 ' 中， 压缩机 5 ' 工作时气流进行循环， 气流从粉碎装置 的进气口进入粉碎装置 ， 在氧含量 500ppm〜1000ppm、 露点为 -10°C (常温， 1.0MPa)、 流速为 5m/s的惰性气流气氛，粉碎室压力为 l.OMPa的压力下对试料进行气流磨粉碎，粉碎 后小于 20μηι的粉粒在气流的带动下，通过上部的粉碎装置出气口处设置的第一过滤器 1 ， 进入分级装置 2 ' 内执行分级步骤， 而未粉碎或未完全粉碎的粗粉则继续留在粉碎装置 内继续进行气流粉碎； 在分级装置 2 ' 中， 通过分级处理， 超细粉通过管道进入超细粉回收 装置 4 '， 而成品粉碎粉则进入成品粉收集装置 3 '， 提供给后继的加工工序； 在超细粉回收 装置 4 ' 中， 对气流和超细粉进行分离， 超细粉回收装置 4 ' 的出气口通过管道连接至压缩 机 5 '， 气流通过压缩机 5 ' 进行循环， 超细粉则留在超细粉回收装置 4 ' 内， 需要说明的是， 本发明中提及的超细粉为粒径在 Ιμηι以下的粉粒。 超细粉回收装置 4 ' 所收集的超细粉被 丢弃。
超细粉丢弃率 （％)： 计算超细粉回收装置 4 ' 积存的粉末重量， 除以投入粉碎的原料 重量的数值， 用百分率表示。
表 6为本发明实施例和比较例的磁性能对照表。 磁性能对照表 超细粉丢 Br Hcj Hk/Hcj (BH) max HAST失重 烧结体中氧 序号
弃率（％) ( kGs) (kOe ) (%) (MGOe) 值 (mg ) 含量 ( pm) 实施例 4 0 14. 5 12. 1 98. 2 50. 8 1. 7 925 实施例 5 0 13. 7 15. 3 98. 1 46. 0 1. 6 940 实施例 6 0 13. 4 17. 4 97. 9 44. 4 1. 7 970 比较例 7 0. 8 14. 4 11. 2 85. 5 49. 4 30. 2 898 比较例 8 1. 3 13. 6 14. 1 83. 2 44. 5 32. 6 923 比较例 9 3. 1 13. 0 15. 9 83. 9 40. 8 36. 3 940 比较例 10 2. 0 14. 4 9. 9 74. 3 49. 4 7. 4 933 比较例 11 2. 7 13. 7 12. 8 76. 8 45. 0 6. 9 942 比较例 12 4. 2 13. 1 14. 9 72. 3 41. 6 7. 3 935 上述实施例仅用来进一步说明本发明的几种具体实施例， 但本发明并不局限于实施例， 凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均落入本 发明技术方案的保护范围内。
工业实用性
本发明提供了一种稀土磁铁用合金粉末、 稀土磁铁的制造方法和制粉装置， 其不再从 粉碎时气氛氧含量降至 lOOOppm以下的粉碎装置中送过来的低氧含量粉碎粉中分出 Ιμηι以 下的超细粉，从而使后续获得低氧含量烧结磁体的烧结工序不易发生晶粒异常长大（AGG)， 并具有简化工序和降低制作成本。

Claims

2014/040525 权 禾 ij 要 求 书 PCT/CN2013/083238
1. 一种稀土磁铁用合金粉末的制造方法， 所述的稀土磁铁为含有 R2T14B主相的磁 铁， 所述的 R为选自包含钇概念的稀土元素中的至少一种， 所述 T为包括 Fe和 / 或 Co的至少一种过渡金属元素， 其特征在于： 在使用氧含量为 lOOOppm以下的 惰性气体高速气流对至少一种的所述稀土磁铁用合金或至少一种的稀土磁铁用合 金粗粉进行细粉碎的工序中， 获得粒径在 50μιη以下的粉末， 包括 Ιμιη以下的超 细粉。
2. 根据权利要求 1中所述的一种稀土磁铁用合金粉末的制造方法， 其特征在于： 所 述稀土磁铁用合金为至少两种的稀土成分和 /或含量不同的稀土磁铁用合金。
3. 根据权利要求 1中所述的一种稀土磁铁用合金粉末的制造方法， 其特征在于： 所 述合金粗粉通过用氢破碎法粉碎所述合金的粗粉碎工序获得。
4. 根据权利要求 3中所述的一种稀土磁铁用合金粉末的制造方法， 其特征在于： 所 述稀土磁铁用合金是将原料合金熔融液用带材铸件法， 以 102°C/秒以上、 104°C/ 秒以下的冷却速度冷却得到的。
5. 根据权利要求 1中所述的一种稀土磁铁用合金粉末的制造方法， 其特征在于： 所 述惰性气体高速气流的流速为 2〜50m/s。
6. 根据权利要求 5中所述的一种稀土磁铁用合金粉末的制造方法， 其特征在于： 所 述惰性气体高速气流在 0.1MPa〜1.0 MPa的常温露点为 -10°C以下。
7. 一种稀土磁铁的制造方法， 所述的稀土磁铁为含有 R2T14B主相的磁铁， 所述的 R 为选自包含钇概念的稀土元素中的至少一种， 所述 T为包括 Fe和 /或 Co的至少 一种过渡金属元素， 其特征在于， 包括如下的步骤：
使用氧含量为 lOOOppm以下的惰性气体的高速气流对至少一种的所述稀土 磁铁用合金或至少一种的稀土磁铁用合金粗粉进行细粉碎的工序中，获得粒径在 50μηι以下的粉末， 包括 Ιμηι以下的超细粉； 以及
将所述粉末加工成形， 制作成形体的工序；
以及将所述成形体进行烧结， 制作稀土磁铁的工序。
8. 一种用于制造稀土磁铁用合金粉末的制粉装置， 包括粉碎装置、 第一收集装置、 料罐和压缩机， 所述粉碎装置设有进料口、 位于下部的进气口和位于上部的出气 口， 所述粉碎装置的进气口连通所述压缩机， 其出气口处设置用以使粒径 50μηι 以下粉末通过的第一过滤器； 所述第一收集装置设有位于上部的进气口和位于顶 部的出气口， 其进气口通过管道与所述粉碎装置出气口相连通， 所述第一收集装 置的底部连接所述料罐， 其特征在于： 第一收集装置的出气口处向下延伸一用于 气固分离的第二过滤器， 并连通所述压缩机， 所述第二过滤器对应于所述第一收 集装置的进气口设置。
9. 一种用于制造稀土磁铁用合金粉末的制粉装置， 包括粉碎装置、 第一收集装置、 料罐、 第二收集装置和压缩机， 所述粉碎装置设有进料口、 位于下部的进气口和 位于上部的出气口， 所述粉碎装置的进气口连通所述压缩机， 所述粉碎装置的出 气口处设置用以使粒径 50μιη以下粉末通过的过滤器； 所述第一收集装置设有位 于上部的进气口和位于顶部的出气口， 其进气口通过管道与所述粉碎装置出气口 相连通， 第一收集装置的底部与所述料罐相连通； 所述第二收集装置为超细粉收 集装置， 其设有位于上部的进气口和位于顶部的出气口， 其进气口通过管道连通 第一收集装置的出气口， 其出气口连通压缩机， 所述的超细粉为粒径 Ιμηι以下的 粉末， 其特征在于： 在第二收集装置的底部还设有出料口， 该出料口通过一带有 阀门的管道连通第一收集装置的底部。
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