WO2016015662A1 - 稀土磁铁用急冷合金和稀土磁铁的制备方法 - Google Patents

稀土磁铁用急冷合金和稀土磁铁的制备方法 Download PDF

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WO2016015662A1
WO2016015662A1 PCT/CN2015/085555 CN2015085555W WO2016015662A1 WO 2016015662 A1 WO2016015662 A1 WO 2016015662A1 CN 2015085555 W CN2015085555 W CN 2015085555W WO 2016015662 A1 WO2016015662 A1 WO 2016015662A1
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rare earth
alloy
earth magnet
magnet
quenched alloy
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永田浩
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Xiamen Tungsten Co Ltd
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Xiamen Tungsten Co Ltd
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Priority to ES15826755T priority Critical patent/ES2879807T3/es
Priority to US15/328,258 priority patent/US10096413B2/en
Priority to DK15826755.9T priority patent/DK3176794T3/da
Priority to EP15826755.9A priority patent/EP3176794B1/en
Priority to JP2017505079A priority patent/JP6411630B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • 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
    • H01F41/0273—Imparting anisotropy
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic
    • 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

  • the invention relates to the technical field of manufacturing magnets, in particular to a method for preparing a quenched alloy for a rare earth magnet and a rare earth magnet.
  • Japanese Laid-Open Patent Publication No. 2013-70062 discloses a low B rare earth magnet including R (R is an element selected from at least one of rare earth elements containing Y, Nd is an essential component), B, Al, The composition of Cu, Zr, Co, O, C and Fe as main components, the content of each element is R: 25 to 34% by weight, B: 0.87 to 0.94% by weight, Al: 0.03 to 0.3% by weight, Cu: 0.03 to 0.11% by weight, Zr: 0.03 to 0.25% by weight, Co: 3% by weight or less (and not including 0), O: 0.03 to 0.1% by weight, C: 0.03 to 0.15% by weight, and residual Fe.
  • R is an element selected from at least one of rare earth elements containing Y, Nd is an essential component
  • B Al
  • the composition of Cu, Zr, Co, O, C and Fe as main components, the content of each element is R: 25 to 34% by weight, B: 0.87 to 0.94% by weight, Al: 0.
  • the invention reduces the content of the B-rich phase by lowering the content of B, thereby increasing the volume ratio of the main phase, and finally obtaining a magnet having a high Br.
  • a soft magnetic R 2 T 17 phase (generally R 2 Fe 17 phase) is formed, which tends to cause a decrease in coercive force (Hcj), and the present invention adds a trace amount of Cu, The precipitation of the R 2 T 17 phase is suppressed, and the R 2 T 14 C phase (generally R 2 Fe 14 C phase) which enhances Hcj and Br is formed.
  • the low boron high copper magnet or the low boron high copper aluminum magnet also has a low SQ, resulting in a problem that the minimum saturated magnetic field is extremely high and the magnetization is not easy.
  • the magnetization of the magnet can be minimized by the magnetization process.
  • the magnetization field strength value is used to characterize. Generally, when the magnetization field intensity is increased by 50% from a certain value, the increase of Br and Hcj of the sample does not exceed 1%, and the magnetic field value is considered to be the permanent magnet material.
  • the lowest saturation magnetization field strength value for the convenience of characterization, the magnetization curve of the magnet in the open state is generally used to describe the magnetization of the magnet, and the shape of the magnetization curve is affected by the magnet composition and its microstructure. In the open state, the magnetization process of the magnet is closely related to its shape and size. For magnets of the same shape and size, the smaller the minimum saturation magnetization field, the easier the magnet is magnetized.
  • high-performance NdFeB magnets usually require 2.0T or more.
  • the magnet can be magnetized to a saturated state, in particular, the smaller the ratio of the aspect ratio (the ratio of the length of the magnet orientation direction to the maximum diameter of the magnet perpendicular to the plane of the magnetization direction), the magnet required to magnetize to the saturation magnetization state in the open state. The larger the magnetic field.
  • the high-performance sintered NdFeB magnet cannot usually be saturated magnetized.
  • the object of the present invention is to overcome the deficiencies of the prior art and provide a quenching alloy for a rare earth magnet.
  • the fine powder obtained by the above alloy the number of magnetic domains in a single crystal grain is reduced, and it is easier to orient along an applied magnetic field. High-performance magnet that is easy to magnetize.
  • a quenched alloy for a rare earth magnet containing R 2 Fe 14 B main phase crystal wherein R is a rare earth element including Nd, wherein the main phase crystal has an average particle diameter of 10 to 15 ⁇ m in the short axis direction,
  • the average interval of the Nd-rich phase is 1.0 to 3.5 ⁇ m.
  • the average phase diameter of the main phase crystal of the ordinary quenched alloy sheet in the short axis direction is 20 to 30 ⁇ m, and the average interval of the Nd-rich phase is 4 to 10 ⁇ m), therefore, a refined alloy powder can be obtained after hydrogen crushing and jet milling.
  • the number of magnetic domains in a single crystal grain is reduced, and it is easier to orient along an applied magnetic field to obtain a high-performance magnet which is easy to magnetize.
  • the squareness and coercivity of the magnet Both force and heat resistance are significantly improved.
  • the rare earth elements mentioned in the present invention include lanthanum elements.
  • the primary phase crystal grain size is defined as the Nd 2 Fe 14 B crystal in the short axis direction judged by the kerr imaging (Kerr imaging) in the approximate middle position in the thickness direction of the quenched alloy sheet. The average of the particle size.
  • the rare earth magnet is a Nd-Fe-B based magnet.
  • the quench alloy has an average thickness of from 0.2 to 0.4 mm.
  • 95% or more of the quenched alloy has a thickness of 0.1 to 0.7 mm by weight.
  • the present invention improves the microstructure of the crystal by controlling the thickness of the quenched alloy.
  • the quenched alloy having a sheet thickness of less than 0.1 mm contains a large amount of amorphous phase and equiaxed crystals, which causes the crystal grain size of the main phase to become small, the average interval of adjacent Nd-rich phases to be shortened, and the magnetic domains in the crystal grains.
  • the nucleation growth resistance increases and the magnetization performance deteriorates.
  • the quenched alloy having a sheet thickness of more than 0.7 mm a large amount of ⁇ -Fe and R 2 Fe 17 phases are formed, and a large Nd-rich phase is formed, which in turn causes an average interval of adjacent Nd-rich phases to be shortened.
  • the magnetic domains in the particles increase the nucleation growth resistance during the orientation process, and the magnetization performance deteriorates.
  • the quenched 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, and the use thereof includes Made from the following ingredients:
  • T 0 at% to 2.0 at%, T is selected from the group consisting of Ti, Zr, V, Mo, Co, Zn, Ga, Nb, Sn, Sb, Hf, Bi, Ni, Si, Cr, Mn, S or P At least one element,
  • the content of Cu is controlled to 0.1 at% to 0.8 at%
  • the content of Al is controlled to 0.1 at% to 2.0 at%
  • the content of B is controlled at 5.2 at% to 5.8 at%
  • the content of W is controlled at After 0.0005at% ⁇ 0.03at%
  • Cu does not enter the main phase of Nd 2 Fe 14 B, mainly distributed in the grain-rich Nd phase, and W in the cooling process of the melt, along with the main phase of R 2 Fe 14 B Precipitation, concentration to the crystal grain boundary, and precipitation in a small and uniform manner, the main phase grains become smaller, part of Al occupies the 8j2 crystal position of the main phase, and forms an ⁇ -Fe layer with the adjacent Fe inside the main phase.
  • the main phase crystal grain size is controlled, and the addition of Al makes the grain refinement of the alloy, and the blockiness of the Nd-rich phase and the B-rich phase become smaller, and part of the Al enters the Nd-rich phase and interacts with Cu to improve the Nd-rich phase.
  • the wetting angle between the main phase and the main phase is such that the Nd-rich phase is uniformly distributed along the boundary.
  • the low-B magnet realizes the main phase crystal grain size of 10-15 ⁇ m, and the Nd-rich phase
  • the average interval is 1.0 to 3.5 ⁇ m. Therefore, in the fine powder obtained by the alloy of the above components, the magnetic domains in the crystal grains become smaller during the orientation process, and the domain walls can move rapidly, so that all the magnetic domains are rotated to the same direction of the magnetic field. , magnetization saturation.
  • the unavoidable impurities may be selected from at least one of elements such as O, C, and N.
  • W may also be an impurity of a raw material (such as pure iron, rare earth metal, B, etc.), and the raw material used in the present invention is selected according to the content of impurities in the raw material; of course, the W content may also be selected.
  • Raw materials such as pure iron, rare earth metals, B, etc.
  • having the detection limit of the equipment which may be regarded as not containing W
  • W W
  • Table 1 shows the W element content of metal Nd in different workshops in different places.
  • a graphite crucible electrolytic cell a barrel-shaped graphite crucible is used as an anode, a tungsten (W) rod is arranged on the crucible axis as a cathode, and a rare earth is used to collect rare earth at the bottom.
  • a rare earth element such as Nd
  • a small amount of W is inevitably mixed therein.
  • other high-melting-point metals such as molybdenum (Mo) may be used as the cathode, and the rare earth metal may be obtained by using molybdenum rhenium to collect the rare earth metal.
  • the content of Cu is preferably from 0.3 at% to 0.7 at%.
  • the squareness exceeds 99%, and a magnet having good heat resistance and good magnetization performance can be produced.
  • the content of Cu is outside the range of 0.3 at% to 0.7 at%, the squareness is gradually lowered, and once the squareness is deteriorated, the thermal magnetic detection of the magnet is deteriorated, and the heat resistance is also deteriorated.
  • the alloy for a rare earth magnet is kept at a temperature of 500 to 700 ° C for 0.5 to 5 hours in a receiving tank after rapid cooling to 500 to 750 ° C.
  • the narrow Nd-rich phase of the main phase crystallizes to the central region, the Nd-rich phase becomes compact and concentrated, and the average interval of the Nd-rich phase is better controlled.
  • the content range of R: 13.5 at% to 15.5 at% is a conventional choice in the industry, and therefore, in the examples, the range of the content of R was not tested and verified.
  • Another object of the present invention is to provide a method of preparing a rare earth magnet.
  • a method for preparing a rare earth magnet comprising the steps of:
  • the present invention has the following characteristics:
  • the rare earth magnet quenched alloy has a primary phase crystal grain size average particle diameter (short axis direction) of 10 to 15 ⁇ m, and an average interval of the Nd-rich phase of 1.0 to 3.5 ⁇ m, and a single crystal of the fine powder obtained by the above alloy The number of magnetic domains in the granules is reduced, and it is easier to orient along the applied magnetic field to obtain a high-performance magnet that is easy to magnetize.
  • the present invention has an optimum content distribution of Al in both the main phase and the grain boundary phase by controlling the Al content, thereby Al is divided into the main phase to control the crystal grain size of the main phase, and part of Al acts with Cu to improve the wetting angle between the Nd-rich phase and the main phase, so that the Nd-rich phase is uniformly distributed along the boundary to realize main phase crystallization.
  • the average particle diameter (short axis direction) is 10 to 15 ⁇ m, and the average interval of the Nd-rich phase is 1.0 to 3.5 ⁇ m.
  • the present invention controls the thickness of the quenched alloy of 95% by weight or more to 0.1 to 0.7 mm, and controls the thickness of the quenched alloy to improve the microstructure of the crystal, thereby making the average crystal grain size of the main phase and the distribution of the Nd-rich phase more. To be even.
  • Example 1 is a schematic view showing the main phase crystal of the SC piece of Example 2 in Example 1 magnified 200 times under a Kerrkin microscope;
  • Example 2 is a schematic view showing the interval of the ⁇ -rich phase of the SC sheet of Example 2 in Example 1 under a 3D color scanning laser microscope.
  • Nd having a purity of 99.5%, Dy having a purity of 99.8%, Fe-B having an industrial purity, pure Fe for industrial use, Cu, Al having a purity of 99.5%, and W having a purity of 99.999% are prepared at an atomic percentage at%.
  • Each serial number group was prepared according to the elemental composition in Table 1, and 10 Kg of raw materials were weighed and prepared separately.
  • Smelting process 1 part of the prepared raw material is placed in a crucible made of alumina, and vacuum-melted at a temperature of 1500 ° C or lower in a vacuum of 10 ⁇ 2 Pa in a high-frequency vacuum induction melting furnace.
  • Casting process Ar gas is introduced into the melting furnace after vacuum melting to bring the gas pressure to 50,000 Pa, and then cast by a single roll quenching method to obtain a quenched alloy at a cooling rate of 10 2 ° C / sec to 10 4 ° C / sec.
  • the quenched alloy has an average thickness of 0.3 mm, and more than 95% of the quenched alloy has a thickness of 0.1 to 0.7 mm.
  • the quenched alloy is subjected to heat treatment at 500 ° C for 5 hours, and then cooled to room temperature.
  • Hydrogen breaking pulverization process a hydrogen-breaking furnace in which a quenching alloy is placed is evacuated at room temperature, and then a hydrogen gas having a purity of 99.5% is introduced into a hydrogen-breaking furnace to a pressure of 0.1 MPa, and after standing for 2 hours, the temperature is raised while evacuating. The vacuum was evacuated at a temperature of 500 ° C for 2 hours, and then cooled, and the hydrogen-crushed powder was taken out.
  • the sample after the hydrogen pulverization is subjected to jet milling and pulverization under a pressure of a pulverization chamber pressure of 0.4 MPa in an atmosphere having an oxidizing gas content of 100 ppm or less to obtain a fine powder, and the average particle size of the fine powder is 3.4 ⁇ m.
  • Oxidizing gas refers to oxygen or moisture.
  • the finely pulverized fine powder (30% by weight based on the total weight of the fine powder) was sieved to remove the particles having a particle diameter of 1.0 ⁇ m or less, and the fine powder after the sieving was mixed with the remaining unsifted fine powder.
  • the volume of the powder having a particle diameter of 1.0 ⁇ m or less is reduced to 10% or less of the entire volume of the powder.
  • Methyl octanoate was added to the powder after the jet mill pulverization, and the methyl octanoate was added in an amount of 0.15% by weight of the mixed powder, followed by thorough mixing with a V-type mixer.
  • Magnetic field forming process Using a right-angle oriented magnetic field forming machine, the above-mentioned methyl octanoate-added powder was once formed into a cube having a side length of 25 mm in a 1.8 T orientation magnetic field at a molding pressure of 0.2 ton/cm 2 . After one forming, it demagnetizes in a magnetic field of 0.2T.
  • each formed body is moved to a sintering furnace for sintering, and the sintering is maintained at a temperature of 200 ° C and 850 ° C for 1.5 hours under a vacuum of 10 -3 Pa, and then sintered at a temperature of 1080 ° C for 2 hours, and then passed through. After the Ar gas was introduced to bring the gas pressure to 0.1 MPa, it was cooled to room temperature.
  • Heat treatment process The sintered body is heat-treated in a high-purity Ar gas at a temperature of 600 ° C for 1 hour, and then cooled to a chamber. Remove after warming.
  • Magnetic performance evaluation process The sintered magnet was magnetically tested using the NIM ⁇ 10000H BH bulk rare earth permanent magnet non-destructive measurement system of China Metrology Institute.
  • Minimum saturation magnetization field strength When the magnetization voltage continues to increase and the magnetization field strength is increased by 50% from a certain value, the increase of (BH)max or Hcb of the sample is not more than 1%, and the magnetic field value is considered Is the lowest saturation magnetization field strength.
  • the main phase crystal average particle size test SC sheet (quenching alloy sheet) was placed under a Kerr phase microscope to magnify 200 times for shooting, and the roll surface was parallel to the lower side of the field of view. In the measurement, a straight line having a length of 445 ⁇ m is drawn at the center of the field of view, and the average crystal grain size of the main phase is calculated by counting the number of crystals of the main phase passing through the straight line.
  • the test results are shown in Figure 1.
  • the lowest magnetization saturation voltage value in the table represents the voltage value required for the sample to be magnetized to saturation at the lowest saturation magnetization field strength.
  • magnetization is performed using the same magnetization apparatus, and therefore, a magnetization voltage can be selected to characterize the magnetization magnetic field strength.
  • the content of Cu exceeds 0.8 at%, the content of Cu in the crystal is excessive, and the average grain size of the crystal grains of the main phase becomes small, and the average interval of the Nd-rich phase also becomes small, and the magnetic domains in the crystal grains are small.
  • the nucleation growth resistance increases, and the minimum saturation magnetization field increases, which is not suitable for use in an open circuit magnetic field.
  • the content of Cu is from 0.1 at% to 0.8 at%, the squareness of the magnet exceeds 95%, and the magnetization performance is good.
  • the squareness of the magnet When the content of Cu is from 0.3 at% to 0.7 at%, the squareness of the magnet further exceeds 99%, and the squareness is excellent, and a magnet having good heat resistance can be produced.
  • the 5% thermal demagnetization (heat resistance) temperatures of Comparative Examples 1 and 2 were 60 ° C and 80 ° C, respectively, while the 5% thermal demagnetization (heat resistance) temperatures of Examples 1 to 6 were 110 ° C and 125 ° C, respectively. 125 ° C, 125 ° C, 125 ° C and 120 ° C.
  • Each serial number group was prepared according to the elemental composition in Table 3, and 10 Kg of raw materials were weighed and prepared separately.
  • Casting process Ar gas is introduced into the melting furnace after vacuum melting to bring the gas pressure to 50,000 Pa, and then cast by a single roll quenching method to obtain a quenched alloy at a cooling rate of 10 2 ° C / sec to 10 4 ° C / sec.
  • the quenched alloy has an average thickness of 0.25 mm, and more than 95% of the quenched alloy has a thickness of 0.1 to 0.7 mm.
  • the quenched alloy is subjected to heat treatment at 700 ° C for 0.5 hour, and then cooled to room temperature.
  • Hydrogen breaking and pulverizing process a hydrogen breaking furnace in which a quenching alloy is placed is evacuated at room temperature, and then a hydrogen gas having a purity of 99.5% is introduced into a hydrogen breaking furnace to a pressure of 0.08 MPa, and after standing for 2 hours, the temperature is raised while evacuating. The mixture was evacuated at a temperature of 480 ° C for 1.5 hours, and then cooled, and hydrogen was taken out to break the pulverized powder.
  • the sample after the hydrogen pulverization is subjected to jet milling at a pressure of 0.45 MPa in an atmosphere having an oxidizing gas content of 100 ppm or less to obtain a fine powder, and the average particle size of the fine powder is 3.6 ⁇ m.
  • Oxidizing gas refers to oxygen or moisture.
  • Methyl octanoate was added to the powder after the jet mill pulverization, and the methyl octanoate was added in an amount of 0.2% by weight of the sieved powder, and then thoroughly mixed by a V-type mixer.
  • Magnetic field forming process Using a right-angle oriented magnetic field forming machine, the above-mentioned methyl octanoate-added powder was once formed into a cube having a side length of 25 mm in a 1.8 T orientation magnetic field at a molding pressure of 0.2 ton/cm 2 . After one molding, the magnetic field was demagnetized in a magnetic field of 0.2 T, the molded body was taken out from the space, and another magnetic field was applied to the molded body, and the magnetic powder adhering to the surface of the molded body was subjected to a second demagnetization treatment.
  • each formed body is moved to a sintering furnace for sintering, and the sintering is maintained at a temperature of 200 ° C and 900 ° C for 2 hours under a vacuum of 10 -3 Pa, and then sintered at a temperature of 1020 ° C for 2 hours, and then passed through.
  • the Ar gas was introduced to bring the gas pressure to 0.1 MPa, it was cooled to room temperature.
  • Heat treatment process The sintered body was heat-treated at a temperature of 620 ° C for 1 hour in high-purity Ar gas, and then cooled to room temperature and taken out.
  • Magnetic performance evaluation process The sintered magnet was magnetically tested using the NIM ⁇ 10000H BH bulk rare earth permanent magnet non-destructive measurement system of China Metrology Institute.
  • Minimum saturation magnetization field strength When the magnetization voltage continues to increase and the magnetization field strength is increased by 50% from a certain value, the increase of (BH)max or Hcb of the sample is not more than 1%, and the magnetic field value is considered Is the lowest saturation magnetization field strength.
  • SC sheet quenched alloy sheet
  • SC sheet quenched alloy sheet
  • the surface of the roller is parallel to the lower side of the field of view.
  • a straight line having a length of 445 ⁇ m is drawn at the center of the field of view, and the average crystal grain size of the main phase is calculated by counting the number of crystals of the main phase passing through the straight line.
  • the test results are shown in Figure 1.
  • the lowest magnetization saturation voltage value in the table represents the voltage value required for the sample to be magnetized to saturation at the lowest saturation magnetization field strength.
  • magnetization is performed using the same magnetization apparatus, and therefore, a magnetization voltage can be selected to characterize the magnetization magnetic field strength.
  • the content of Al exceeds 2.0 at%, the content of Al in the crystal is excessive, and the average grain size of the crystal grains of the main phase becomes small, and the average interval of the Nd-rich phase also becomes small, and the magnetic domains in the crystal grains are small.
  • the nucleation growth resistance increases, and the minimum saturation magnetization field increases, which is not suitable for use in an open circuit magnetic field.
  • Each serial number group was prepared according to the elemental composition in Table 5, and 10 kg of raw materials were weighed and prepared.
  • Casting process Ar gas is introduced into the melting furnace after vacuum melting to bring the gas pressure to 60,000 Pa, and then cast by a single roll quenching method to obtain a quenched alloy at a cooling rate of 10 2 ° C / sec to 10 4 ° C / sec.
  • the quenched alloy has an average thickness of 0.38 mm, and more than 95% of the quenched alloy has a thickness of 0.1 to 0.7 mm.
  • the quenched alloy is subjected to heat treatment at 600 ° C for 3 hours, and then cooled to room temperature.
  • Hydrogen breaking and pulverizing process the hydrogen quenching furnace in which the quenching alloy is placed is evacuated at room temperature, and then hydrogen gas having a purity of 99.5% is introduced into the hydrogen breaking furnace to a pressure of 0.09 MPa, and after standing for 2 hours, the temperature is raised while vacuuming. The vacuum was evacuated at a temperature of 520 ° C for 2 hours, and then cooled, and the hydrogen-crushed powder was taken out.
  • the sample after the hydrogen pulverization is subjected to jet milling at a pressure of a pulverization chamber pressure of 0.5 MPa in an atmosphere having an oxidizing gas content of 100 ppm or less to obtain a fine powder, and the average particle size of the fine powder is 3.6 ⁇ m.
  • Oxidizing gas refers to oxygen or moisture.
  • Methyl octanoate was added to the powder after pulverization by a jet mill, and the amount of methyl octanoate added was 0.2% by weight of the powder after sieving. Mix thoroughly with a V-blender.
  • Magnetic field forming process Using a right-angle oriented magnetic field forming machine, the above-mentioned methyl octanoate-added powder was once formed into a cube having a side length of 25 mm in a 1.8 T orientation magnetic field at a molding pressure of 0.2 ton/cm 2 . After one molding, the magnetic field was demagnetized in a magnetic field of 0.2 T, the molded body was taken out from the space, and another magnetic field was applied to the molded body, and the magnetic powder adhering to the surface of the molded body was subjected to a second demagnetization treatment.
  • Sintering process Each formed body is moved to a sintering furnace for sintering, and the sintering is maintained at a temperature of 200 ° C and 800 ° C for 2 hours under a vacuum of 10 -3 Pa, and then sintered at a temperature of 1030 ° C for 2 hours, and then passed through. After the Ar gas was introduced to bring the gas pressure to 0.1 MPa, it was cooled to room temperature.
  • Heat treatment process The sintered body was heat-treated at a temperature of 580 ° C for 1 hour in high-purity Ar gas, and then cooled to room temperature and taken out.
  • Magnetic performance evaluation process The sintered magnet was magnetically tested using the NIM ⁇ 10000H BH bulk rare earth permanent magnet non-destructive measurement system of China Metrology Institute.
  • Minimum saturation magnetization field strength When the magnetization voltage continues to increase and the magnetization field strength is increased by 50% from a certain value, the increase of (BH)max or Hcb of the sample is not more than 1%, and the magnetic field value is considered Is the lowest saturation magnetization field strength.
  • the main phase crystal average particle size test SC sheet (quenching alloy sheet) was placed under a Kerr phase microscope to magnify 200 times for shooting, and the roll surface was parallel to the lower side of the field of view. In the measurement, a straight line having a length of 445 ⁇ m is drawn at the center of the field of view, and the average crystal grain size of the main phase is calculated by counting the number of crystals of the main phase passing through the straight line.
  • the test results are shown in Figure 1.
  • the lowest magnetization saturation voltage value in the table represents the voltage value required for the sample to be magnetized to saturation at the lowest saturation magnetization field strength.
  • magnetization is performed using the same magnetization apparatus, and therefore, a magnetization voltage can be selected to characterize the magnetization magnetic field strength.
  • Nd with a purity of 99.5%, Fe-B for industrial use, pure Fe for industrial use, and Al, Cu, Zr, Co with a purity of 99.5% and W with a purity of 99.999% are prepared at atomic percentage at%.
  • none of the selected Nd, Fe, B, Al, Cu, Zn, and Co contains W, and the source of W is all W metal.
  • Each serial number group was prepared according to the elemental composition in Table 7, and 100 kg of raw materials were weighed and prepared.
  • Casting process Ar gas is introduced into the melting furnace after vacuum melting to bring the gas pressure to 45,000 Pa, and then casting is performed by a single roll quenching method, and a quenched alloy is obtained at a cooling rate of 10 2 ° C / sec to 10 4 ° C / sec.
  • the quenched alloy has an average thickness of 0.21 mm, and more than 95% of the quenched alloy has a thickness of 0.1 to 0.7 mm.
  • the quenched alloy is subjected to heat treatment at 560 ° C for 1 hour, and then cooled to room temperature.
  • Hydrogen breaking pulverization process vacuuming the hydrogen quenching furnace in which the quenching alloy is placed at room temperature, and then introducing a purity of 99.5% of hydrogen into the hydrogen breaking furnace to a pressure of 0.085 MPa, leaving it for 2 hours, and then heating up while vacuuming The vacuum was evacuated at a temperature of 540 ° C for 2 hours, and then cooled, and hydrogen was taken out to break the pulverized powder.
  • the sample after the hydrogen pulverization is subjected to jet milling at a pressure of a pulverization chamber pressure of 0.55 MPa in an atmosphere having an oxidizing gas content of 100 ppm or less to obtain a fine powder, and the average particle size of the fine powder is 3.6 ⁇ m.
  • Oxidizing gas refers to oxygen or moisture.
  • Magnetic field forming process Using a right-angle oriented magnetic field forming machine, the above-mentioned methyl octanoate-added powder was once formed into a cube having a side length of 25 mm in a 1.8 T orientation magnetic field at a molding pressure of 0.2 ton/cm 2 . After one molding, the magnetic field was demagnetized in a magnetic field of 0.2 T, the molded body was taken out from the space, and another magnetic field was applied to the molded body, and the magnetic powder adhering to the surface of the molded body was subjected to a second demagnetization treatment.
  • each formed body is moved to a sintering furnace for sintering, and the sintering is maintained at a temperature of 200 ° C and 700 ° C for 2 hours under a vacuum of 10 -3 Pa, and then sintered at a temperature of 1050 ° C for 2 hours, followed by After the Ar gas was introduced to bring the gas pressure to 0.1 MPa, it was cooled to room temperature.
  • Heat treatment process The sintered body is heat treated at 620 ° C for 1 hour in high purity Ar gas, and then cooled to the chamber. Remove after warming.
  • Magnetic performance evaluation process The sintered magnet was magnetically tested using the NIM ⁇ 10000H BH bulk rare earth permanent magnet non-destructive measurement system of China Metrology Institute.
  • Minimum saturation magnetization field strength When the magnetization voltage continues to increase and the magnetization field strength is increased by 50% from a certain value, the increase of (BH)max or Hcb of the sample is not more than 1%, and the magnetic field value is considered Is the lowest saturation magnetization field strength.
  • the main phase crystal average particle size test SC sheet (quenching alloy sheet) was placed under a Kerr phase microscope to magnify 200 times for shooting, and the roll surface was parallel to the lower side of the field of view. In the measurement, a straight line having a length of 445 ⁇ m is drawn at the center of the field of view, and the average crystal grain size of the main phase is calculated by counting the number of crystals of the main phase passing through the straight line.
  • the test results are shown in Figure 1.
  • the lowest magnetization saturation voltage value in the table represents the voltage value required for the sample to be magnetized to saturation at the lowest saturation magnetization field strength.
  • magnetization is performed using the same magnetization apparatus, and therefore, a magnetization voltage can be selected to characterize the magnetization magnetic field strength.
  • the present invention provides a quenched alloy for a rare earth magnet.
  • the number of magnetic domains in a single crystal grain is reduced, and it is easier to orient along an applied magnetic field to obtain a high-performance magnet which is easy to magnetize.

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Abstract

本发明公开了一种稀土磁铁用急冷合金和稀土磁铁的制备方法，其含有R2Fe14B主相，所述的R为包括Nd的稀土元素，其特征在于，所述合金的主相结晶在短轴方向的平均粒径为10～15μm，富Nd相的平均间隔为1.0～3.5μm。如此，上述合金所制得的细粉中，单个晶粒内的磁畴数量减少，更容易沿外加磁场取向，获得易磁化的磁体，且磁铁的方形度、矫顽力和耐热性均有明显的改善。

Description

稀土磁铁用急冷合金和稀土磁铁的制备方法 技术领域
本发明涉及磁铁的制造技术领域，特别是涉及一种稀土磁铁用急冷合金和稀土磁铁的制备方法。
背景技术
对于各种高性能电机、发电机中使用的(BH)max超过40MGOe的高性能磁铁而言，为得到高磁化的磁铁，减少非磁性元素B的使用量的“低B组份磁铁”的开发就变得非常有必要。
现在，“低B组份磁铁”的开发采用了各种各样的方式，然而，截止目前，还未能开发出市场化的产品。“低B组份磁铁”的最大的缺点在于退磁曲线的方形度(亦称为Hk或者SQ)比较差，导致磁铁的充磁性能变差，其形成原因比较复杂，主要是由于R2Fe17相的出现和富B相(R1T4B4相)的缺乏导致晶界处出现局部B不足。
日本专利特开2013‐70062中公开了一种低B的稀土磁铁，其包括R(R为包含Y的稀土元素中选择的至少一种的元素，Nd为必有组分)、B、Al、Cu、Zr、Co、O、C及Fe作为主成分的组成，各元素的含量为R：25～34重量％，B：0.87～0.94重量％、Al：0.03～0.3重量％、Cu：0.03～0.11重量％、Zr：0.03～0.25重量％、Co：3重量％以下(且不包含0)、O：0.03～0.1重量％、C：0.03～0.15重量％、以及残余为Fe。该发明通过降低B的含量，使得富B相的含量降低，进而使得主相含有的体积比例增加，并最终获得高Br的磁铁。通常，在B含量减少的情况下，会形成软磁性的R2T17相(一般为R2Fe17相)，极易使得矫顽力(Hcj)降低，而本发明通过添加微量的Cu，使得R2T17相的析出被抑制，更形成了使Hcj和Br提高的R2T14C相(一般为R2Fe14C相)。然而，上述的低硼高铜磁铁、或低硼高铜中铝磁铁同样存在SQ低，导致最低饱和充磁场极高、不易充磁的问题，磁体的易磁化强度可以用磁化过程中的最低饱和磁化场强度值来表征，一般来说，当磁化场强度由某一值增加50％时，试样的Br和Hcj增加均不超过1％，该磁场值就被认为是这种永磁材料的最低饱和磁化场强度值， 为方便表征，通常使用同一形状尺寸的磁体在开路状态下的磁化曲线来描述磁体的易磁化强度，而磁化曲线的形状受磁体成分及其显微结构的影响。在开路状态下，磁体的磁化过程与其形状、尺寸密切相关，具有相同形状和尺寸的磁体，其最低饱和磁化场越小，磁体越容易磁化。
另一方面，为了达到便于装配、减少杂质吸附及降低管理成本的目的，一些高端产品需采用先安装再充磁的方法，而在开路状态下，高性能NdFeB磁体通常需要2.0T以上的充磁场才能使其充磁到饱和状态，特别是长径比(磁体取向方向的长度和磁体垂直于充磁方向平面的最大直径之比)越小的磁体，开路状态下磁化到饱和磁化状态所需的磁场越大。然而，由于用户的充磁装置所能提供的磁场受到成本、空间的限制，通常不能使高性能烧结NdFeB磁体达到饱和磁化，因此，为了获得足够大的磁通，往往需要更高磁能积的磁体，如本来可以使用磁能积为35MGOe磁体，被迫使用38MGOe以上的磁体，增加了使用成本。因此，如何改善Nd‐Fe‐B系磁铁的SQ和充磁特性，从而使磁体更加容易充磁到饱和磁化状态，是目前的技术难题。高SQ、高充磁性能的磁铁开发变得尤为重要。
发明内容
本发明的目的在于克服现有技术之不足，提供一种稀土磁铁用急冷合金，在上述合金所制得的细粉中，单个晶粒内的磁畴数量减少，更容易沿外加磁场取向，获得易磁化的高性能磁体。
本发明提供的技术方式如下：
稀土磁铁用急冷合金，其含有R2Fe14B主相结晶，所述的R为包括Nd的稀土元素，其特征在于，所述主相结晶在短轴方向的平均粒径为10～15μm，富Nd相的平均间隔为1.0～3.5μm。
由于合金主相结晶的粒径变小(与本发明的急冷合金不同，普通的急冷合金片的主相结晶在短轴方向的平均粒径为20～30μm，富Nd相的平均间隔为4～10μm)，因此，可以在氢破碎和气流磨之后获得细化的合金粉末。上述合金所制得的细粉中，单个晶粒内的磁畴数量减少，更容易沿外加磁场取向，获得易磁化的高性能磁体。同时，磁铁的方形度、矫顽 力和耐热性均有明显改善。
本发明中提及的稀土元素包括钇元素在内。
通常来讲，在一个结晶粒的中间具有复数的薄层状富Nd相，文献中非常常见的错误观点是以薄层状富Nd相作为间隔来判断主相结晶粒粒径，而本发明采用正确的方法来判断主相结晶粒的粒径。本发明中，主相结晶粒径的定义为在急冷合金片厚度方向的大约中间位置，用kerr成像(克尔成像)的浓淡结果来判断的、在短轴方向的Nd2Fe14B系结晶粒粒径的平均值。
在推荐的实施方式中，所述的稀土磁铁为Nd‐Fe‐B系磁铁。
在推荐的实施方式中，所述急冷合金的平均厚度为0.2～0.4mm。
在推荐的实施方式中，按重量比计，95％以上的急冷合金的厚度为0.1～0.7mm。
本发明通过控制急冷合金的厚度来改善结晶的微观结构。具体地，片厚小于0.1mm的急冷合金中包含较多的非晶相及等轴晶，会导致主相结晶粒径变小，相邻富Nd相的平均间隔缩短，晶粒内的磁畴在取向过程中形核长大阻力增加，磁化性能变差。与此相对地，片厚超过0.7mm的急冷合金中包含较多的α‐Fe及R2Fe17相，形成较大的富Nd相，进而同样导致相邻富Nd相的平均间隔缩短，晶粒内的磁畴在取向过程中形核长大阻力增加，磁化性能变差。
在推荐的实施方式中，所述稀土磁铁用急冷合金是将原料合金熔融液用带材铸件法，以102℃/秒以上、104℃/秒以下的冷却速度冷却得到的，其使用包括如下成分的原料制成：
R：13.5at％～15.5at％，
B：5.2at％～5.8at％，
Cu：0.1at％～0.8at％，
Al：0.1at％～2.0at％，
W：0.0005at％～0.03at％，
T：0at％～2.0at％，T为选自Ti、Zr、V、Mo、Co、Zn、Ga、Nb、Sn、Sb、Hf、Bi、Ni、Si、Cr、Mn、S或P中的至少一种元素，
以及余量为Fe和不可避免的杂质。
本发明中，在将Cu的含量控制到0.1at％～0.8at％、Al的含量控制到0.1at％～2.0at％，B的含量控制在5.2at％～5.8at％，W的含量控制在0.0005at％～0.03at％之后，Cu不进入Nd2Fe14B主相内，主要分布在晶界富Nd相内，W则在熔融液的冷却过程中，随着R2Fe14B主相的析出，向结晶晶界浓缩，并以微小并且均一的方式实现析出，使主相晶粒变小，部分Al占据主相的8j2晶位，在主相内部与邻近的Fe形成α‐Fe层，控制主相结晶粒径，而Al的添加使合金晶粒细化，同时使富Nd相和富B相的块度变小，部分Al则进入富Nd相与Cu共同作用，改善富Nd相与主相之间的浸润角，使富Nd相极为均匀地沿边界分布，在Cu、Al和W的共同作用下，使低B磁铁实现主相结晶平均粒径为10～15μm，富Nd相的平均间隔为1.0～3.5μm。由此，上述成分的合金所制得的细粉中，晶粒内的磁畴在取向过程中形核长大阻力变小，畴壁可以迅速移动，使所有的磁畴都转动至磁场相同方向，充磁饱和。
所述不可避免的杂质可选自O、C、N等元素的至少一种。
在本发明中，W也可以是原料(如纯铁、稀土金属、B等)等的杂质，其根据原料中杂质的含量选定本发明所使用的原料；当然，也可以选择W含量在现有设备的检测限以下(可视为不含有W)的原料(如纯铁、稀土金属、B等)，采用加入本发明所描述含量的W金属原料的方式。简而言之，只要原料中含有必要量的W即可，不管W的来源为何。表1中举例显示了不同产地不同工场的金属Nd的W元素含量。
表1 不同产地不同工场的金属Nd的W元素含量
Figure PCTCN2015085555-appb-000001
表1中的2N5所代表的含义为99.5％。
需要说明的是，在目前较多采用的稀土制备方法中，有采用石墨坩埚电解槽，圆桶形石墨坩埚作阳极，坩埚轴线上配置钨(W)棒做阴极，且底部用钨坩埚收集稀土金属的方式。在上述制备稀土元素(如Nd)的过程中，不可避免有少量W混入其中。当然，也可以使用钼(Mo)等其他高熔点金属做阴极，同时使用钼坩埚收集稀土金属的方式，获得完全不含W的稀土元素。
在推荐的实施方式中，Cu的含量优选为0.3at％～0.7at％。在Cu的含量为0.3at％～0.7at％之时，方形度超过99％，可制造出耐热性能好、充磁性能佳的磁铁。而在Cu的含量在0.3at％～0.7at％之外时，方形度徐徐下降，一旦方形度变差，磁铁的热检磁变差，耐热性能也变差。
在推荐的实施方式中，所述稀土磁铁用合金在急速冷却至500～750℃之后，在收料桶中以500～700℃的温度保温0.5～5小时。在经过保温工序之后，主相结晶的狭长富Nd相向中心区域缩短，富Nd相变得紧凑、集中，富Nd相的平均间隔得到更好地控制。
需要说明的是，本发明中，R：13.5at％～15.5at％的含量范围为本行业的常规选择，因此，在实施例中，没有对R的含量范围加以试验和验证。
本发明的另一目的在于提供稀土磁铁的制备方法。
稀土磁铁的制备方法，其特征在于，包括如下的步骤：
1)将上述稀土磁铁用急冷合金粗粉碎后再通过微粉碎制成细粉的工序；
2)将所述细粉放入磁场进行预取向，后经磁场成形法获得成形体的工序；
3)以及在真空或惰性气体中以900℃～1100℃的温度对所述成形体进行烧结的工序。
与现有技术相比，本发明具有如下的特点：
1)该稀土磁铁急冷合金的主相结晶粒径平均粒径(短轴方向)为10～15μm，富Nd相的平均间隔为1.0～3.5μm，上述合金所制得的细粉中，单个晶粒内的磁畴数量减少，更容易沿外加磁场取向，获得易磁化的高性能磁体。
2)在不影响磁铁剩磁的情况下，本发明合金所制得的细粉中，晶粒内的磁畴在取向过程中形核长大阻力变小，畴壁可以迅速移动，获得易磁化的磁体。
3)本发明通过控制Al含量，使Al在主相和晶界相中均有最适的含量分布，由此，部 分Al进入主相内部，控制主相结晶粒径，部分Al则与Cu共同作用，改善富Nd相与主相之间的浸润角，使富Nd相极为均匀地沿边界分布，实现主相结晶平均粒径(短轴方向)为10～15μm，富Nd相的平均间隔为1.0～3.5μm。
4)本发明将95重量％以上的急冷合金的厚度控制为0.1～0.7mm，通过控制急冷合金的厚度，以此改善结晶的微观结构，使主相结晶平均粒径和富Nd相的分布更为均匀。
5)通过在原料中加入W，W以微小并且均一的方式实现析出，因此，添加适量的W可以控制急冷合金的主相结晶粒径，使主相结晶粒径变小。
附图说明
图1为实施例一中实施例2的SC片放在克尔金相显微镜下放大200倍的主相晶示意图；
图2为实施例一中实施例2的SC片放在3D彩色扫描激光显微镜下放大1000倍的富钕相间隔示意图。
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。
实施例一
在原料配制过程：准备纯度99.5％的Nd、纯度99.8％的Dy、工业用Fe‐B、工业用纯Fe、纯度99.5％的Cu、Al和纯度99.999％的W，以原子百分比at％配制。
各元素的含量如表1所示：
表1 各元素的配比(at％)
Figure PCTCN2015085555-appb-000002
各序号组按照表1中元素组成进行配制，分别称量、配制了10Kg的原料。
熔炼过程：每次取1份配制好的原料放入氧化铝制的坩埚中，在高频真空感应熔炼炉 中在10‐2Pa的真空中以1500℃以下的温度进行真空熔炼。
铸造过程：在真空熔炼后的熔炼炉中通入Ar气体使气压达到5万Pa后，使用单辊急冷法进行铸造，以102℃/秒～104℃/秒的冷却速度获得急冷合金，急冷合金的平均厚度为0.3mm，95％以上的急冷合金的厚度为0.1～0.7mm，将急冷合金在500℃进行5小时的保温热处理，然后冷却到室温。
氢破粉碎过程：在室温下将放置急冷合金的氢破用炉抽真空，而后向氢破用炉内通入纯度为99.5％的氢气至压力0.1MPa，放置2小时后，边抽真空边升温，在500℃的温度下抽真空2小时，之后进行冷却，取出氢破粉碎后的粉末。
在微粉碎工序：在氧化气体含量100ppm以下的气氛下，在粉碎室压力为0.4MPa的压力下对氢破粉碎后的试料进行气流磨粉碎，得到细粉，细粉的平均粒度为3.4μm。氧化气体指的是氧或水分。
对部分微粉碎后的细粉(占细粉总重量30％)过筛，除去粒径1.0μm以下的粉粒，再将过筛后的细粉与剩余未过筛的细粉混合。混合后的细粉中，粒径1.0μm以下的粉末体积减少至全体粉末体积的10％以下。
在气流磨粉碎后的粉末中添加辛酸甲酯，辛酸甲酯的添加量为混合后粉末重量的0.15％，再用V型混料机充分混合。
磁场成形过程：使用直角取向型的磁场成型机，在1.8T的取向磁场中，在0.2ton/cm2的成型压力下，将上述添加了辛酸甲酯的粉末一次成形成边长为25mm的立方体，一次成形后在0.2T的磁场中退磁。
为使一次成形后的成形体不接触到空气，将其进行密封，再使用二次成形机(等静压成形机)在1.4ton/cm2的压力下进行二次成形。
烧结过程：将各成形体搬至烧结炉进行烧结，烧结在10‐3Pa的真空下，在200℃和850℃的温度下各保持1.5小时后，以1080℃的温度烧结2小时，之后通入Ar气体使气压达到0.1MPa后，冷却至室温。
热处理过程：烧结体在高纯度Ar气中，以600℃温度进行1小时热处理后，冷却至室 温后取出。
磁性能评价过程：烧结磁铁使用中国计量院的NIM‐10000H型BH大块稀土永磁无损测量系统进行磁性能检测。
最低饱和磁化场强度：当充磁电压继续增加，使磁化场强度由某一值增加50％时，测得试样的(BH)max或Hcb增加量不超过1％，此磁场值就被认为是最低饱和磁化场强度。
主相结晶平均粒径测试：SC片(急冷合金片)放在克尔金相显微镜下放大200倍进行拍摄，拍摄时贴辊面与视场下边平行。测量时，在视场中心位置画一长度为445μm的直线，通过数出通过直线的主相结晶个数，计算主相结晶平均粒径。检测结果参见图1。
富钕相间隔测试：用稀FeCl2溶液(FeCl2+HCl+酒精)腐蚀过的SC片放在3D彩色扫描激光显微镜下放大1000倍进行拍摄，拍摄时贴辊面与视场下边平行。测量时，在视场中心位置画一长度为283μm的直线，通过数出通过直线的二次晶个数，计算富钕相间隔。检测结果参见图2。
实施例和比较例的磁铁的评价结果如表2中所示：
表2 实施例和比较例的磁性能评价情况
Figure PCTCN2015085555-appb-000003
表中的最低充磁饱和电压值代表样品在最低饱和磁化场强度下被磁化到饱和时所需的电压值。本发明中，使用同一充磁设备进行充磁，因此，可选用充磁电压来表征充磁磁场强度。
从表2可以看到，在磁铁的Cu含量小于0.1at％之时，Cu在晶界富Nd相内的分布不足，难以与Al在晶界中形成复合相，进而导致主相结晶平均粒径变大，富Nd相的平均间隔也过 大，晶粒内的磁畴在取向过程中形核长大阻力增加，剩磁、BH(max)下降，磁铁性能降低。
在Cu的含量超过0.8at％之时，则会导致晶体内部Cu的含量过量，进而主相结晶晶粒的平均粒径变小，富Nd相的平均间隔也变小，晶粒内的磁畴在取向过程中形核长大阻力增加，最低饱和磁化场强度增加，而不适合在开路状态的磁场中使用。
在Cu的含量为0.1at％～0.8at％之时，磁铁的方形度超过95％，充磁性能好。
在Cu的含量为0.3at％～0.7at％之时，磁铁的方形度进一步超过99％，具有非常好的方形度，可生产出耐热性能良好的磁铁。
对比例1、2的5％热减磁(耐热)温度依次为60℃和80℃，而实施例1～实施例6的5％热减磁(耐热)温度依次为110℃、125℃、125℃、125℃、125℃和120℃。
实施例2
在原料配制过程：准备纯度99.5％的Nd、纯度99.8％的Ho、工业用Fe‐B、工业用纯Fe和纯度99.5％的Cu、Al和纯度99.999％的W，以原子百分比at％来配制。
各元素的含量如表3所示：
表3 各元素的配比(at％)
Figure PCTCN2015085555-appb-000004
各序号组按照表3中元素组成进行配制，分别称量、配制了10Kg的原料。
熔炼过程：每次取1份配制好的原料放入氧化铝制的坩埚中，在高频真空感应熔炼炉中在10‐2Pa的真空中以1500℃以下的温度进行真空熔炼。
铸造过程：在真空熔炼后的熔炼炉中通入Ar气体使气压达到5万Pa后，使用单辊急冷法进行铸造，以102℃/秒～104℃/秒的冷却速度获得急冷合金，急冷合金的平均厚度为0.25mm，95％以上的急冷合金的厚度为0.1～0.7mm，将急冷合金在700℃进行0.5小时的保 温热处理，然后冷却到室温。
氢破粉碎过程：在室温下将放置急冷合金的氢破用炉抽真空，而后向氢破用炉内通入纯度为99.5％的氢气至压力0.08MPa，放置2小时后，边抽真空边升温，在480℃的温度下抽真空1.5小时，之后进行冷却，取出氢破粉碎后的粉末。
在微粉碎工序：在氧化气体含量100ppm以下的气氛下，在粉碎室压力为0.45MPa的压力下对氢破粉碎后的试料进行气流磨粉碎，得到细粉，细粉的平均粒度为3.6μm。氧化气体指的是氧或水分。
在气流磨粉碎后的粉末中添加辛酸甲酯，辛酸甲酯的添加量为过筛后粉末重量的0.2％，再用V型混料机充分混合。
磁场成形过程：使用直角取向型的磁场成型机，在1.8T的取向磁场中，在0.2ton/cm2的成型压力下，将上述添加了辛酸甲酯的粉末一次成形成边长为25mm的立方体，一次成形后在0.2T的磁场中退磁，将成形体从空间取出，再向成形体施加另一磁场，对附着在成形体表面的磁粉进行第二次退磁处理。
为使一次成形后的成形体不接触到空气，将其进行密封，再使用二次成形机(等静压成形机)在1.4ton/cm2的压力下进行二次成形。
烧结过程：将各成形体搬至烧结炉进行烧结，烧结在10‐3Pa的真空下，在200℃和900℃的温度下各保持2小时后，以1020℃的温度烧结2小时，之后通入Ar气体使气压达到0.1MPa后，冷却至室温。
热处理过程：烧结体在高纯度Ar气中，以620℃温度进行1小时热处理后，冷却至室温后取出。
磁性能评价过程：烧结磁铁使用中国计量院的NIM‐10000H型BH大块稀土永磁无损测量系统进行磁性能检测。
最低饱和磁化场强度：当充磁电压继续增加，使磁化场强度由某一值增加50％时，测得试样的(BH)max或Hcb增加量不超过1％，此磁场值就被认为是最低饱和磁化场强度。
主相结晶平均粒径测试：SC片(急冷合金片)放在克尔金相显微镜下放大200倍进行 拍摄，拍摄时贴辊面与视场下边平行。测量时，在视场中心位置画一长度为445μm的直线，通过数出通过直线的主相结晶个数，计算主相结晶平均粒径。检测结果参见图1。
富钕相间隔测试：用稀FeCl2溶液(FeCl2+HCl+酒精)腐蚀过的SC片放在3D彩色扫描激光显微镜下放大1000倍进行拍摄，拍摄时贴辊面与视场下边平行。测量时，在视场中心位置画一长度为283μm的直线，通过数出通过直线的二次晶个数，计算富钕相间隔。检测结果参见图2。
实施例和比较例的磁铁的评价结果如表4中所示：
表4 实施例和比较例的磁性能评价情况
Figure PCTCN2015085555-appb-000005
表中的最低充磁饱和电压值代表样品在最低饱和磁化场强度下被磁化到饱和时所需的电压值。本发明中，使用同一充磁设备进行充磁，因此，可选用充磁电压来表征充磁磁场强度。
实施例1～6的SQ全部达到99％以上，而对比例1～2的SQ在85％以下。
从表4可以看到，在磁铁的Al含量小于0.1at％之时，Al在晶界富Nd相和主相内的分布均不足，难以与Cu在晶界中形成复合相，进而导致主相结晶平均粒径变大，富Nd相的平均间隔也过大，晶粒内的磁畴在取向过程中形核长大阻力增加，剩磁、BH(max)下降，磁铁性能降低。
在Al的含量超过2.0at％之时，则会导致晶体内部Al的含量过量，进而主相结晶晶粒的平均粒径变小，富Nd相的平均间隔也变小，晶粒内的磁畴在取向过程中形核长大阻力增加，最低饱和磁化场强度增加，而不适合在开路状态的磁场中使用。
实施例3
在原料配制过程：准备纯度99.5％的Nd、纯度99.5％的Ho、工业用Fe‐B、工业用纯Fe、和纯度99.5％的Al、Cu、Zr、Co和纯度为99.999％的W，以原子百分比at％来配制。
各元素的含量如表5所示：
表5 各元素的配比(at％)
Figure PCTCN2015085555-appb-000006
各序号组按照表5中元素组成进行配制，分别称量、配制了10Kg的原料。
熔炼过程：每次取1份配制好的原料放入氧化铝制的坩埚中，在高频真空感应熔炼炉中在10‐2Pa的真空中以1500℃以下的温度进行真空熔炼。
铸造过程：在真空熔炼后的熔炼炉中通入Ar气体使气压达到6万Pa后，使用单辊急冷法进行铸造，以102℃/秒～104℃/秒的冷却速度获得急冷合金，急冷合金的平均厚度为0.38mm，95％以上的急冷合金的厚度为0.1～0.7mm，将急冷合金在600℃进行3小时的保温热处理，然后冷却到室温。
氢破粉碎过程：在室温下将放置急冷合金的氢破用炉抽真空，而后向氢破用炉内通入纯度为99.5％的氢气至压力0.09MPa，放置2小时后，边抽真空边升温，在520℃的温度下抽真空2小时，之后进行冷却，取出氢破粉碎后的粉末。
在微粉碎工序：在氧化气体含量100ppm以下的气氛下，在粉碎室压力为0.5MPa的压力下对氢破粉碎后的试料进行气流磨粉碎，得到细粉，细粉的平均粒度为3.6μm。氧化气体指的是氧或水分。
在气流磨粉碎后的粉末中添加辛酸甲酯，辛酸甲酯的添加量为过筛后粉末重量的0.2％， 再用V型混料机充分混合。
磁场成形过程：使用直角取向型的磁场成型机，在1.8T的取向磁场中，在0.2ton/cm2的成型压力下，将上述添加了辛酸甲酯的粉末一次成形成边长为25mm的立方体，一次成形后在0.2T的磁场中退磁，将成形体从空间取出，再向成形体施加另一磁场，对附着在成形体表面的磁粉进行第二次退磁处理。
为使一次成形后的成形体不接触到空气，将其进行密封，再使用二次成形机(等静压成形机)在1.4ton/cm2的压力下进行二次成形。
烧结过程：将各成形体搬至烧结炉进行烧结，烧结在10‐3Pa的真空下，在200℃和800℃的温度下各保持2小时后，以1030℃的温度烧结2小时，之后通入Ar气体使气压达到0.1MPa后，冷却至室温。
热处理过程：烧结体在高纯度Ar气中，以580℃温度进行1小时热处理后，冷却至室温后取出。
磁性能评价过程：烧结磁铁使用中国计量院的NIM‐10000H型BH大块稀土永磁无损测量系统进行磁性能检测。
最低饱和磁化场强度：当充磁电压继续增加，使磁化场强度由某一值增加50％时，测得试样的(BH)max或Hcb增加量不超过1％，此磁场值就被认为是最低饱和磁化场强度。
主相结晶平均粒径测试：SC片(急冷合金片)放在克尔金相显微镜下放大200倍进行拍摄，拍摄时贴辊面与视场下边平行。测量时，在视场中心位置画一长度为445μm的直线，通过数出通过直线的主相结晶个数，计算主相结晶平均粒径。检测结果参见图1。
富钕相间隔测试：用稀FeCl2溶液(FeCl2+HCl+酒精)腐蚀过的SC片放在3D彩色扫描激光显微镜下放大1000倍进行拍摄，拍摄时贴辊面与视场下边平行。测量时，在视场中心位置画一长度为283μm的直线，通过数出通过直线的二次晶个数，计算富钕相间隔。检测结果参见图2。
实施例和比较例的磁铁的评价结果如表6中所示：
表6 实施例和比较例的磁性能评价情况
Figure PCTCN2015085555-appb-000007
表中的最低充磁饱和电压值代表样品在最低饱和磁化场强度下被磁化到饱和时所需的电压值。本发明中，使用同一充磁设备进行充磁，因此，可选用充磁电压来表征充磁磁场强度。
实施例1～7的SQ全部达到99％以上，而对比例1～3的SQ在85％以下。
从表6可以看到，在磁铁的B含量小于5.2at％之时，由于B在晶界富Nd相和主相内的分布均不足，进而导致主相结晶平均粒径变大，富Nd相的平均间隔也过大，晶粒内的磁畴在取向过程中形核长大阻力增加，剩磁、BH(max)下降，磁铁性能降低。
而在B的含量超过5.8at％之时，磁铁的剩磁、BH(max)有所下降，难以获得高性能的磁铁。
实施例4
在原料配制过程：准备纯度99.5％的Nd、工业用Fe‐B、工业用纯Fe、和纯度99.5％的Al、Cu、Zr、Co和纯度99.999％的W，以原子百分比at％来配制。
为准确控制W的使用配比，该实施例中，所选用的Nd、Fe、B、Al、Cu、Zn和Co中均不含有W，W的来源全部W金属。
各元素的含量如表7所示：
表7 各元素的配比(at％)
Figure PCTCN2015085555-appb-000008
Figure PCTCN2015085555-appb-000009
各序号组按照表7中元素组成进行配制，分别称量、配制了100Kg的原料。
熔炼过程：每次取1份配制好的原料放入氧化铝制的坩埚中，在高频真空感应熔炼炉中在10‐2Pa的真空中以1500℃以下的温度进行真空熔炼。
铸造过程：在真空熔炼后的熔炼炉中通入Ar气体使气压达到4.5万Pa后，使用单辊急冷法进行铸造，以102℃/秒～104℃/秒的冷却速度获得急冷合金，急冷合金的平均厚度为0.21mm，95％以上的急冷合金的厚度为0.1～0.7mm，将急冷合金在560℃进行1小时的保温热处理，然后冷却到室温。
氢破粉碎过程：在室温下将放置急冷合金的氢破用炉抽真空，而后向氢破用炉内通入纯度为99.5％的氢气至压力0.085MPa，放置2小时后，边抽真空边升温，在540℃的温度下抽真空2小时，之后进行冷却，取出氢破粉碎后的粉末。
在微粉碎工序：在氧化气体含量100ppm以下的气氛下，在粉碎室压力为0.55MPa的压力下对氢破粉碎后的试料进行气流磨粉碎，得到细粉，细粉的平均粒度为3.6μm。氧化气体指的是氧或水分。
磁场成形过程：使用直角取向型的磁场成型机，在1.8T的取向磁场中，在0.2ton/cm2的成型压力下，将上述添加了辛酸甲酯的粉末一次成形成边长为25mm的立方体，一次成形后在0.2T的磁场中退磁，将成形体从空间取出，再向成形体施加另一磁场，对附着在成形体表面的磁粉进行第二次退磁处理。
为使一次成形后的成形体不接触到空气，将其进行密封，再使用二次成形机(等静压成形机)在1.4ton/cm2的压力下进行二次成形。
烧结过程：将各成形体搬至烧结炉进行烧结，烧结在10‐3Pa的真空下，在200℃和700℃的温度下各保持2小时后，以1050℃的温度烧结2小时，之后通入Ar气体使气压达到0.1MPa后，冷却至室温。
热处理过程：烧结体在高纯度Ar气中，以620℃温度进行1小时热处理后，冷却至室 温后取出。
磁性能评价过程：烧结磁铁使用中国计量院的NIM‐10000H型BH大块稀土永磁无损测量系统进行磁性能检测。
最低饱和磁化场强度：当充磁电压继续增加，使磁化场强度由某一值增加50％时，测得试样的(BH)max或Hcb增加量不超过1％，此磁场值就被认为是最低饱和磁化场强度。
主相结晶平均粒径测试：SC片(急冷合金片)放在克尔金相显微镜下放大200倍进行拍摄，拍摄时贴辊面与视场下边平行。测量时，在视场中心位置画一长度为445μm的直线，通过数出通过直线的主相结晶个数，计算主相结晶平均粒径。检测结果参见图1。
富钕相间隔测试：用稀FeCl2溶液(FeCl2+HCl+酒精)腐蚀过的SC片放在3D彩色扫描激光显微镜下放大1000倍进行拍摄，拍摄时贴辊面与视场下边平行。测量时，在视场中心位置画一长度为283μm的直线，通过数出通过直线的二次晶个数，计算富钕相间隔。检测结果参见图2。
实施例和比较例的磁铁的评价结果如表8中所示：
表8 实施例和比较例的磁性能评价情况
Figure PCTCN2015085555-appb-000010
表中的最低充磁饱和电压值代表样品在最低饱和磁化场强度下被磁化到饱和时所需的电压值。本发明中，使用同一充磁设备进行充磁，因此，可选用充磁电压来表征充磁磁场强度。
实施例1～4的SQ全部达到99％以上，而对比例1～2的SQ在90％以下。
从表8可以看到，由于W与主要构成元素的稀土元素、铁、硼的离子半径及电子构造不同，所以，R2Fe14B主相中几乎不存在W，微量的W在熔融液的冷却过程中，随着R2Fe14B 主相的析出，向结晶晶界浓缩，W以微小并且均一的方式实现析出，因此，添加适量的W可以控制合金的主相结晶粒径，并提高磁铁的取向度。
上述实施例仅用来进一步说明本发明的几种具体的实施方式，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
本发明提供一种稀土磁铁用急冷合金，在上述合金所制得的细粉中，单个晶粒内的磁畴数量减少，更容易沿外加磁场取向，获得易磁化的高性能磁体。

Claims (7)

  1. 稀土磁铁用急冷合金，其含有R2Fe14B主相结晶，所述的R为包括Nd的稀土元素，其特征在于，所述主相结晶在短轴方向的平均粒径为10～15μm，富Nd相的平均间隔为1.0～3.5μm。
  2. 根据权利要求1所述的稀土磁铁用急冷合金，其特征在于：所述急冷合金的平均厚度为0.2～0.4mm。
  3. 根据权利要求2所述的稀土磁铁用急冷合金，其特征在于：按重量比计，95％以上的急冷合金的厚度为0.1～0.7mm。
  4. 根据权利要求3中所述的稀土磁铁用急冷合金，其特征在于，由包括如下成分的原料制成：
    R：13.5at％～15.5at％，
    B：5.2at％～5.8at％，
    Cu：0.1at％～0.8at％，
    Al：0.1at％～2.0at％，
    W的含量在0.0005at％以上、0.03at％以下，
    T：0at％～2.0at％，T为选自Ti、Zr、V、Mo、Co、Zn、Ga、Nb、Sn、Sb、Hf、Bi、Ni、Si、Cr、Mn、S或P中的至少一种元素，
    以及余量为Fe和不可避免的杂质，
    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℃/秒以上、104℃/秒以下的冷却速度冷却得到的。
  5. 根据权利要求4所述的稀土磁铁用急冷合金，其特征在于：Cu的含量优选为0.3at％～0.7at％。
  6. 根据权利要求4所述的稀土磁铁用急冷合金，其特征在于：所述稀土磁铁用合金在急速冷却至500～750℃之后，在收料桶中以500～700℃的温度保温0.5～5小时。
  7. 稀土磁铁的制备方法，其特征在于，包括如下的步骤：
    1)将权利要求1、2、3、4、5或6的稀土磁铁用急冷合金粗粉碎后再通过微粉碎制成细粉的工序；
    2)将细粉放入磁场进行预取向，后经磁场成形法获得成形体的工序；
    3)以及在真空或惰性气体中以900℃～1100℃的温度对所述成形体进行烧结的工序。
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