WO2017101577A1 - 一种耐腐蚀的富镧铈烧结钕铁硼磁体及制造方法 - Google Patents

一种耐腐蚀的富镧铈烧结钕铁硼磁体及制造方法 Download PDF

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WO2017101577A1
WO2017101577A1 PCT/CN2016/101950 CN2016101950W WO2017101577A1 WO 2017101577 A1 WO2017101577 A1 WO 2017101577A1 CN 2016101950 W CN2016101950 W CN 2016101950W WO 2017101577 A1 WO2017101577 A1 WO 2017101577A1
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rich
rare earth
corrosion
permanent magnet
alloy
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PCT/CN2016/101950
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French (fr)
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李润锋
陈巧玲
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浙江东阳东磁稀土有限公司
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Priority to EP16874635.2A priority Critical patent/EP3355319B1/en
Publication of WO2017101577A1 publication Critical patent/WO2017101577A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • 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
    • 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
    • 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

Definitions

  • the invention relates to the technical field of neodymium iron boron magnets, in particular to a corrosion-resistant bismuth-rich sintered neodymium iron boron magnet and a manufacturing method thereof.
  • the rare earth permanent magnet material of NdFeB is the third generation rare earth permanent magnet functional material invented in the early 1980s, and its excellent magnetic properties of high remanence, high coercivity and high magnetic energy product are widely used.
  • Automation technology, communication and transportation technology, information technology, aerospace technology and other sectors of the national economy have become one of the important basic materials supporting the contemporary electronic information industry. By this year, the usage has reached 100,000 tons, becoming a modern science and technology and people's life. An important material basis.
  • rare earth materials used as the main raw material for material manufacturing is also constantly increasing. More importantly, the application of rare earth materials as modern industrial "vitamins" is not limited to the manufacture of rare earth permanent magnet materials.
  • manufacturers of sintered NdFeB permanent magnet materials have used relatively low-cost rare earth lanthanum elements to partially replace the higher-priced rare earth lanthanum elements to produce low-cost sintered NdFeB magnets, but Important applications are in the field of magnetic refrigeration materials and optical information storage. Therefore, in a strict sense, it is a waste to use tantalum instead of tantalum to manufacture low-cost sintered NdFeB permanent magnets. Once you find that you have a more important use, you will find it is an irreparable loss. It is also the same effect and problem to replace ⁇ with ⁇ .
  • rare earth elements of Pr and Nd are the main raw materials for producing rare earth permanent magnet materials of sintered NdFeB, and the average amount in the material is about 19% by weight to 33% by weight, in order to obtain some high coercive force.
  • the magnet material also needs to add a small amount of Dy, Tb heavy rare earth elements, and other non-rare earth metals such as Nb, Cu, Al, Ga, Ti, V, Mn, Zn, Zr, W, Si, Sn, Cr, Mo, etc. To form the ratio of the entire material.
  • the rare earth element can be partially replaced by the rare earth element to make the NdFeB rare earth permanent magnet material, the cost of the material can be reduced and the resource utilization can be balanced.
  • the lanthanum element is more easily oxidized than lanthanum, the corrosion resistance of the sintered NdFeB permanent magnet material to which the yttrium element is added is deteriorated, even if the magnet plated with some metal plating is placed in the air, half a year later. It is severely corroded and has little practical use value.
  • the main reason for the corrosion of NdFeB magnets lies in the electrode potential difference between the main phase and the yttrium-rich phase.
  • the electrode potential of the main phase is higher than the electrode potential of the yttrium-rich phase, so that the ⁇ -rich phase is in the “primary cell reaction.
  • the corrosion of the enthalpy-rich phase is accelerated, so that the crystal grains in the magnet are continuously etched along the crystal, and the main phase is detached and powdered due to the loss of the grain boundary phase, thereby completing the macroscopic oxidation of the permanent magnet. Therefore, how to reduce the two-phase potential difference in the sintered NdFeB magnet is the key to improve the corrosion resistance of the magnet.
  • the corrosion resistance of the sintered NdFeB material is improved by adding the elements Co and Cu to the material, wherein the addition of Cu as a small metal is not excessive (0.05 wt% to 0.25). Wt%), the second Cu element forms a mass at the grain boundary of the magnet, and generally does not participate in the replacement of the main phase element, so it has little effect on the magnetic properties.
  • the Co element in addition to being distributed at the grain boundary of the magnet, the Co element also replaces the Fe element to form the Nd 2 Co 14 B phase, which lowers the magnetic properties of the material.
  • the present invention is to overcome the above-mentioned deficiencies in the prior art, and to provide a corrosion-resistant bismuth-rich sintered NdFeB magnet and a manufacturing method thereof for improving the corrosion resistance of a magnet based on the magnetic properties of the magnet.
  • a corrosion-resistant bismuth-rich sintered neodymium iron boron magnet comprising a lanthanum-rich element neodymium-iron-boron rare earth permanent magnet material and a Co-rich alloy material for improving corrosion resistance of a material, said yttrium-rich element NdFeB
  • the rare earth permanent magnet material component is Re ⁇ Fe 100- ⁇ - ⁇ - ⁇ B ⁇ M ⁇ , wherein: Re is a rare earth element, including two or more elements of La, Ce, and Nd elements and necessarily contains Nd.
  • M is an additive element, and includes one selected from the group consisting of Ti, V, Cr, Ni, Zn, Ga, Ge, Al, Zr, Nb, Co, Cu, Ag, Sn, W, Pb, Bi, Pd or More than one element;
  • Fe is Fe and unavoidable impurities; ⁇ , ⁇ , ⁇ are atomic percentages of each element, wherein: 12 ⁇ ⁇ ⁇ 17, 5.1 ⁇ ⁇ ⁇ 6.8, 0.1 ⁇ ⁇ ⁇ 7.8.
  • the invention applies a cobalt-rich alloy material for improving the corrosion resistance of a material to the doping and modification of the rare earth element-rich NdFeB rare earth permanent magnet material, so that more Co element energy can be obtained in the sintered NdFeB magnet. It is distributed at the grain boundary instead of forming the Nd 2 Co 14 B phase which affects the magnetic properties of the magnet, which is beneficial to the preservation of the magnetic properties of the material and the corrosion resistance of the grain boundary of the magnet.
  • the La and Ce elements in the rare earth element Re account for 15 wt% to 45 wt% of the total amount of rare earth in the rare earth-rich neodymium-iron-boron rare earth permanent magnet material.
  • the use of lanthanum and lanthanum light rare earth elements instead of lanthanum and cerium rare earth elements will slow down the exploitation of rare earth resources and reduce the formation of rare earth waste ore with high peaks, thus reducing environmental pollution.
  • the rare earth element Re further includes one or more elements selected from the group consisting of Pr, Pm, Sm, Eu, Gd, Ho, Er, Tm, Yb, Lu, Y, and Sc.
  • the Co-rich alloy material composition is: Co x A 100-xy N y , wherein: A is a rare earth element, including one or more selected from the group consisting of Pr, Nd, Dy, Tb, Gd, and Ho. N is an additive element, including one or more selected from the group consisting of Ti, V, Zn, Ga, Al, Zr, Nb, Cu, Cr; x, y is the atomic percentage content of each element, wherein: 10 ⁇ x ⁇ 75,0 ⁇ y ⁇ 20, the element-rich Fe is inevitably not contained in the Co-rich alloy material. Used to improve the corrosion resistance of the grain boundary of the magnet.
  • the invention also provides a method for manufacturing a corrosion-resistant bismuth-rich sintered NdFeB magnet, and the specific operation steps are as follows:
  • the Co-rich alloy material obtained in the step (2) is added to the cerium-rich element NdFeB rare earth permanent magnet material alloy powder by a certain mass percentage, wherein the Co-rich alloy material passes through the milling and mixing materials.
  • the process allows the Co-rich alloy material to be uniformly mixed into the cerium-rich element NdFeB rare earth permanent magnet material alloy powder;
  • the formed blank is placed in a high-vacuum sintering furnace for high-temperature sintering, and a two-stage tempering process is performed to obtain a corrosion-resistant cerium-rich sintered NdFeB magnet.
  • the corrosion-resistant cerium-rich sintered NdFeB magnet will be composed of a Nd-rich phase, a main phase (Nd 2 Fe 14 B), a Co-rich alloy powder, and a very small amount of B-rich phase (Nd).
  • Nd Nd 2 Fe 14 B
  • Co-rich alloy powder exists between the gaps of the main phase particles, improves the corrosion resistance of the magnet on the basis of ensuring the magnetic properties of the magnet, and makes the sintered NdFeB permanent magnet rich in antimony element
  • ordinary sintered NdFeB permanent magnets it has good corrosion resistance and has become a rare earth permanent magnet material with practical application value.
  • the preparation process employed in the step (1) and the step (2) is a casting process or a rapid setting sheet process; in the step (3), the crushing mode employed is a mechanical crushing or a hydrogen breaking plus a jet milling method.
  • the preparation process employed in the steps (1) and (2) is a rapid setting sheet process.
  • the roll speed of the cooled copper roll used in the quick-setting sheet process of the step (2) is 5 to 15 times the roll speed of the cooled copper roll used in the quick-setting sheet process of the step (1). Wherein: 5 to 15 times the roll speed is preferred, but step (2) can also be prepared by the same roll speed as step (1).
  • the Co-rich alloy material accounts for 1% to 5% by mass of the antimony-rich NdFeB rare earth permanent magnet material alloy.
  • the sintering temperature is 1030 ° C ⁇ 1090 ° C
  • the sintering time is 2.0 ⁇ 8.0 hours
  • the second stage tempering process is: tempering at 890 ° C ⁇ 920 ° C, constant temperature time is 1.5 ⁇ 3 hours; secondary tempering at 480 ° C ⁇ 520 ° C, constant temperature for 2 to 6 hours. Since the melting point of the main phase is about 1185 ° C, and the Co-rich alloy powder generally begins to melt at 600 ° C to 750 ° C, the NdFeB alloy is composed of a solid main phase and a molten Nd-rich phase at the sintering temperature.
  • the B-rich phase and the Co-rich alloy phase composition, and the molten phases penetrate into the voids between the solid main phase powder particles by liquid phase flow and molecular thermal motion, thereby allowing the Co-rich alloy phase to penetrate better.
  • the invention has the beneficial effects that: through the innovation of the manufacturing method, the Co element in the magnet is more distributed at the grain boundary of the magnet, and the corrosion resistance of the magnet is improved on the basis of ensuring the magnetic properties of the magnet, and the bismuth-rich element is sintered.
  • the NdFeB magnet has the same good corrosion resistance as the ordinary sintered NdFeB permanent magnet, and has become a rare earth permanent magnet material with practical application value.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • a Co-rich alloy material having a composition of Nd 21.72 Pr 7.41 Co 70.87 (at%) is obtained by a rapid condensing sheet process;
  • the Co-rich alloy material is added to the cerium-rich element lanthanum-boron rare earth permanent magnet material alloy in a ratio of 1 wt% for hydrogen breaking, and a mixed alloy powder having an average particle diameter of 3.5 ⁇ m is obtained by a jet milling process;
  • the mixed alloy powder is press-formed into a 52 ⁇ 52 ⁇ 29 (mm) square blank in an orientation magnetic field of ⁇ 1.5T;
  • the formed blank is placed in a high-vacuum sintering furnace, sintered at 1035 ° C for 6.0 hours, tempered at 920 ° C for 2 hours and 500 ° C for 3-5 hours to obtain corrosion-resistant bismuth-rich elements.
  • the two kinds of magnets were machined to obtain a standard of ⁇ 10 ⁇ 10 (mm), and then the HAST test (131 ° C, 96% RH, 2.6 bar, 96H) was used to test the corrosion resistance of the material.
  • the properties are shown in Table 1.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the cerium-rich element NdFeB rare earth permanent magnet material having the composition of Pr 3.06 Nd 8.96 Ce 3.31 Fe remaining B 5.88 M 2.25 (at%) is obtained by the rapid condensation sheet process according to the technical scheme of the present invention. Elemental neodymium iron boron rare earth permanent magnet material alloy;
  • a Co-rich alloy material having a composition of Nd 23.41 Pr 10.97 Dy 3 Co 61.24 Zr 1.38 (at%) is obtained by a rapid setting sheet process;
  • cerium-rich element lanthanum-boron rare earth permanent magnet material alloy and the Co-rich alloy material are respectively subjected to hydrogen breaking, and any one of the smelting element-based NdFeB rare earth permanent magnet material alloy is subjected to a gas flow milling process.
  • the Co-rich alloy material is added in a ratio of 2 wt% during the period, and the mixed alloy powder having an average particle diameter of 2.8-3.0 ⁇ m is obtained by powdering, and the mixed alloy powder is uniformly mixed by a mixer;
  • the uniformly mixed powder is pressed into a 52 ⁇ 52 ⁇ 29 (mm) square blank in an orientation magnetic field of ⁇ 1.8T;
  • the two kinds of magnets were machined to obtain a standard of ⁇ 10 ⁇ 10 (mm), and then the HAST test (131 ° C, 96% RH, 2.6 bar, 96H) was used to test the corrosion resistance of the material.
  • the properties are shown in Table 2.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the rare earth permanent magnet material containing Pr 2.11 Nd 6.18 Ce 4.71 Gd 0.84 Ho 0.6 Fe remaining B 5.87 M 1.08 (at%), which is made by quick-setting sheeting according to the technical scheme of the present invention.
  • a rich rare earth element rare earth permanent magnet material alloy
  • a Co-rich alloy material having a composition of Nd 36.98 Pr 12.62 Ho 1 Gd 5 Co 28.47 Cr 1.95 Cu 3.20 Zn 1.55 Al 3.76 Nb 5.47 (at%) is obtained by a rapid setting sheet process;
  • the above-mentioned lanthanum-rich NdFeB rare earth permanent magnet material alloy and Co-rich alloy material are respectively subjected to hydrogen breaking, and the cerium-rich element NdFeB rare earth permanent magnet material alloy is subjected to jet milling to obtain an average particle.
  • the powder is added to the cerium-rich element NdFeB rare earth permanent magnet material alloy powder, and the two alloy powders are uniformly mixed by the mixing;
  • the uniformly mixed powder is pressed into a 52 ⁇ 52 ⁇ 29 (mm) square blank in an orientation magnetic field of ⁇ 2.2T;
  • the blank was placed in a high-vacuum sintering furnace, sintered at 1060 ° C for 8.0 hours, tempered at 910 ° C for 3.0 hours, and tempered at 480 ° C for 2.0 hours to obtain a yttrium-rich sintered NdFeB magnet.
  • the two kinds of magnets were machined to obtain a standard of ⁇ 10 ⁇ 10 (mm), and then the HAST test (131 ° C, 96% RH, 2.6 bar, 96H) was used to test the corrosion resistance of the material.
  • the properties are shown in Table 3.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • a Co-rich alloy material having a composition of Nd 77.91 Pr 10.71 Co 10 Ti 0.38 V 1 (at%) is obtained by a rapid setting sheet process;
  • the above-mentioned lanthanum-rich NdFeB rare earth permanent magnet material alloy and Co-rich alloy material are respectively subjected to hydrogen breaking, and the cerium-rich element NdFeB rare earth permanent magnet material alloy is subjected to airflow milling to obtain an average particle.
  • the cerium-rich elemental NdFeB rare earth permanent magnet material alloy powder with a diameter of 3.4-3.6 ⁇ m is added to the airflow mill at a ratio of 4 wt% after the cerium-rich NdFeB rare earth permanent magnet material alloy is powdered.
  • Continuous powdering is carried out to obtain a Co-rich alloy material powder having an average particle diameter of 2.5-2.7 ⁇ m, which is contained in a drum together with a rare earth-rich NdFeB rare earth permanent magnet material alloy powder, and two kinds of three-dimensional mixer are used.
  • the alloy powder is evenly mixed;
  • the uniformly mixed powder is pressed into a 52 ⁇ 52 ⁇ 29 (mm) square blank in an orientation magnetic field of ⁇ 1.5T;
  • the blank was placed in a high-vacuum sintering furnace, sintered at 1060 ° C for 3.5 hours, tempered at 900 ° C for 2.0 hours, and tempered at 510 ° C for 3.5 hours to obtain a yttrium-rich sintered NdFeB magnet.
  • the two kinds of magnets were machined to obtain a standard of ⁇ 10 ⁇ 10 (mm), and then the HAST test (131 ° C, 96% RH, 2.6 bar, 96H) was used to test the corrosion resistance of the material.
  • the properties are shown in Table 4.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • a Co-rich alloy material having a composition of Nd 24.37 Pr 8.31 Co 60.02 Ga 2.54 Nb 4.76 (at%) is obtained by a rapid setting sheet process;
  • the above-mentioned lanthanum-rich NdFeB rare earth permanent magnet material alloy and Co-rich alloy material are separately broken by hydrogen, and respectively subjected to gas flow milling to obtain lanthanum-rich element having an average particle diameter of 3.8-4.0 ⁇ m.
  • Iron-boron rare earth permanent magnet material alloy powder and Co-rich alloy powder with an average particle diameter of 2.8-3.0 ⁇ m, the Co-rich alloy powder is added to the cerium-rich element NdFeB rare earth permanent magnet material alloy powder at a ratio of 5 wt% Mixing the two alloy powders uniformly by mixing;
  • the uniformly mixed powder is pressed into a 52 ⁇ 52 ⁇ 29 (mm) square blank in an orientation magnetic field of ⁇ 1.6T;
  • the blank was placed in a high-vacuum sintering furnace, sintered at 1090 ° C for 2.0 hours, tempered at 900 ° C for 2.5 hours, and tempered at 490 ° C for 4.0 hours to obtain a yttrium-rich sintered NdFeB magnet.
  • the two kinds of magnets were machined to obtain a standard of ⁇ 10 ⁇ 10 (mm), and then the HAST test (131 ° C, 96% RH, 2.6 bar, 96H) was used to test the corrosion resistance of the material.
  • the properties are shown in Table 5.

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Abstract

一种耐腐蚀的富镧铈烧结钕铁硼磁体及制造方法，该方法具体操作步骤如下：制得富镧铈元素钕铁硼稀土永磁材料合金；制得富Co合金材料；对富镧铈元素钕铁硼稀土永磁材料合金进行破碎；将制得的富Co合金材料按一定的质量百分含量均匀混合到富镧铈元素钕铁硼稀土永磁材料合金粉末内；混合后的合金粉末于氮气气氛保护下，在≥1.5T的取向磁场中压制成型毛坯；将成型好的毛坯放入高真空烧结炉内进行高温烧结，并执行二段回火工艺后，制得耐腐蚀的富镧铈元素烧结钕铁硼磁体。通过将磁体中的Co元素更多的分布在磁体晶界处，在保证磁体磁性能的基础上提高磁体的耐腐蚀性能。

Description

一种耐腐蚀的富镧铈烧结钕铁硼磁体及制造方法 技术领域
本发明涉及钕铁硼磁体相关技术领域，尤其是指一种耐腐蚀的富镧铈烧结钕铁硼磁体及制造方法。
背景技术
钕铁硼基的稀土永磁材料是二十世纪八十年代初发明的第三代稀土永磁功能材料，其高剩磁、高矫顽力和高磁能积的优异磁特性被广泛的应用于自动化技术、通讯与交通技术、信息技术、航空航天技术等国民经济各部门并成为支撑当代电子信息产业的重要基础材料之一，至今年使用量已达到10万吨，成为现代科学技术和人民生活的重要物质基础。
随着材料使用量的提升，作为材料制造的主要原材料的稀土材料用量也在不断的提高，更重要的是作为现代工业“维生素”的稀土材料的应用领域并不仅局限在稀土永磁材料的制造方面，如：近年来烧结钕铁硼永磁材料的制造厂家就用相对低价的稀土钆元素来部分代替价格更高的稀土镨钕元素来制造低成本的烧结钕铁硼磁体，但钆的重要应用领域是在磁制冷材料和光信息储存部门，因此，从严格的意义上来说，用钆取代钕来制造低成本的烧结钕铁硼永磁体是一种浪费。一旦发现钆有更重要的用途，就会发现这是一种无可挽回的损失。用钬部分取代钕也有同样的效果与问题。
在现有技术中，Pr、Nd二种稀土元素是生产烧结钕铁硼稀土永磁材料的主要原材料，在材料中平均用量大约在19wt％～33wt％左右，而为获得某些高矫顽力磁体材料也需要适量添加少量的Dy、Tb重稀土元素，及其它非稀土金属Nb、Cu、Al、Ga、Ti、V、Mn、Zn、Zr、W、Si、Sn、Cr、Mo等元素 来组成整个材料的配比。以当前国内烧结钕铁硼永磁材料的制造技术水平而言，批量生产Hcj≤17kOe的中低牌号产品已经不需要再添加Dy、Tb之类的重稀土元素，但对Pr、Nd二种轻稀土元素的依赖则日显突出，而在稀土矿物中Pr、Nd二种元素仅占6～7wt％的含量，为满足烧结钕铁硼永磁材料的生产，势必会加快稀土资源的开采同时造成更多富含镧铈高峰度稀土废矿的生成，从而加重环境的污染。
因此，如果能用镧铈稀土元素来部分替代镨钕材料进行钕铁硼稀土永磁材料的制造，即能降低材料的成本又能起到平衡利用资源的作用。但由于镧铈元素比镨钕更容易氧化而使添加了镧铈元素的烧结钕铁硼永磁材料耐腐蚀性能变差，哪怕是电镀了某些金属镀层的磁体放置在空气中，半年后就被严重腐蚀，几乎不具备实际的使用价值。
基于以上的原因，提高富镧铈烧结钕铁硼材料本身的耐腐蚀能力，就成为了该材料具有实用价值的基础。而钕铁硼磁体的主要腐蚀原因是在于主相与富钕相之间的电极电位差，这其中主相的电极电位要高于富钕相的电极电位，使富钕相在“原电池反应”中成为阳极加速富钕相的腐蚀，从而出现磁体中各晶粒不断的沿晶腐蚀，主相因失去晶界相的包裹而脱落粉化，完成对永磁体的宏观氧化作用。因此如何使得烧结钕铁硼磁体中二相电位差减少是提高磁体耐腐蚀能力的关键。
为了抵抗这种机理，人们通过在材料中添加元素Co和Cu来提高烧结钕铁硼材料的耐腐蚀能力，其中Cu元素作为小金属的添加，一则量不会过多(0.05wt％～0.25wt％)，二则Cu元素是在磁体的晶界处形成弥撒相，一般不参与主相元素的置换，所以对磁性能的影响不大。但Co元素除会分布在磁体 晶界处外，还会替换Fe元素形成Nd2Co14B相，降低材料的磁性能。
发明内容
本发明是为了克服现有技术中存在上述的不足，提供了一种保证磁体磁性能基础上提高磁体抗腐蚀能力的耐腐蚀的富镧铈烧结钕铁硼磁体及制造方法。
为了实现上述目的，本发明采用以下技术方案：
一种耐腐蚀的富镧铈烧结钕铁硼磁体，包括富镧铈元素钕铁硼稀土永磁材料和用于提高材料耐腐蚀能力的富Co合金材料，所述的富镧铈元素钕铁硼稀土永磁材料成分为ReαFe100-α-β-γBβMγ，其中：Re为稀土元素，包括La、Ce、Nd三种元素中的两种或两种以上元素且必然含有Nd元素；M为添加元素，包括选自Ti、V、Cr、Ni、Zn、Ga、Ge、Al、Zr、Nb、Co、Cu、Ag、Sn、W、Pb、Bi、Pd中的一种或一种以上的元素；Fe为Fe和不可避免的杂质；α、β、γ为各元素的原子百分比含量，其中：12≤α≤17，5.1≤β≤6.8，0.1≤γ≤7.8。
本发明将一种用于提高材料耐腐蚀能力的富钴合金材料应用于富镧铈元素钕铁硼稀土永磁材料的掺杂和改性，使得在烧结钕铁硼磁体中更多Co元素能分布在晶界处而不是形成影响磁体磁性能的Nd2Co14B相，这样即有利于材料磁性能的保全，又能提高磁体晶界的抗腐蚀能力。
作为优选，所述稀土元素Re中的La、Ce元素占所述富镧铈元素钕铁硼稀土永磁材料中稀土总用量的15wt％～45wt％。使用镧、铈轻稀土元素来代替镨、钕稀土元素，会减缓稀土资源的开采同时减少富含镧铈高峰度稀土废矿的生成，从而减轻环境的污染。
作为优选，所述稀土元素Re中还包括选自Pr、Pm、Sm、Eu、Gd、Ho、Er、Tm、Yb、Lu、Y、Sc中的一种或一种以上的元素。
作为优选，所述的富Co合金材料成分为：CoxA100-x-yNy，其中：A为稀土元素，包括选自Pr、Nd、Dy、Tb、Gd、Ho中的一种或多种；N为添加元素，包括选自Ti、V、Zn、Ga、Al、Zr、Nb、Cu、Cr中的一种或多种；x、y为各元素的原子百分比含量，其中：10≤x≤75，0≤y≤20，所述的富Co合金材料中必然不包含元素Fe。用于提高磁体晶界的抗腐蚀能力。
本发明还提供了一种耐腐蚀的富镧铈烧结钕铁硼磁体的制造方法，具体操作步骤如下：
(1)按照富镧铈元素钕铁硼稀土永磁材料成分制得富镧铈元素钕铁硼稀土永磁材料合金；
(2)按照富Co合金材料成分制得富Co合金材料；
(3)对富镧铈元素钕铁硼稀土永磁材料合金进行破碎，制得平均粒径在2.5～4.5μm的富镧铈元素钕铁硼稀土永磁材料合金粉末；
(4)将步骤(2)制得的富Co合金材料按一定的质量百分含量加入到富镧铈元素钕铁硼稀土永磁材料合金粉末内，其中富Co合金材料通过制粉和混料的过程使得富Co合金材料均匀的混入到富镧铈元素钕铁硼稀土永磁材料合金粉末内；
(5)混合后的合金粉末于氮气气氛保护下，在≥1.5T的取向磁场中压制成型毛坯；
(6)将成型好的毛坯放入高真空烧结炉内进行高温烧结，并执行二段回火工艺后，制得耐腐蚀的富镧铈元素烧结钕铁硼磁体。
在经过上述工艺后，所制得耐腐蚀的富镧铈元素烧结钕铁硼磁体将由富Nd相、主相(Nd2Fe14B)、富Co合金材料粉末和极少量的富B相(Nd1.1Fe4B4)组成，富Co合金材料粉末存在于主相颗粒的间隙之间，在保证磁体磁性能的基础上提高磁体的耐腐蚀性能，使富镧铈元素的烧结钕铁硼永磁体与普通的烧结钕铁硼永磁体一样具有很好的耐腐蚀性能，成为有实际应用价值的稀土永磁材料。
作为优选，在步骤(1)和步骤(2)中采用的制备工艺为铸造工艺或速凝薄片工艺；在步骤(3)中，采用的破碎方式为机械破碎或氢破加气流磨方式。
作为优选，在步骤(1)和步骤(2)中采用的制备工艺为速凝薄片工艺。
作为优选，步骤(2)的速凝薄片工艺中所采用冷却铜辊的辊速为步骤(1)的速凝薄片工艺中所采用冷却铜辊的辊速的5～15倍。其中：5～15倍的辊速作为优选方案，但步骤(2)同样可以用与步骤(1)相同的辊速进行制备
作为优选，在步骤(4)中，富Co合金材料占富镧铈元素钕铁硼稀土永磁材料合金的质量百分含量为1％～5％。
作为优选，在步骤(6)中，烧结温度为1030℃～1090℃，烧结时间为2.0～8.0小时，二段回火工艺为：在890℃～920℃一级回火，恒温时间为1.5～3小时；在480℃～520℃二级回火，恒温时间为2～6小时。由于主相的熔点约为1185℃，而富Co合金材料粉末一般在600℃～750℃时就开始溶化，因此在烧结温度状态下钕铁硼合金系由固态的主相、熔化的富Nd相、富B相和富Co合金相组成，并且熔化的各相通过液相流动、分子热运动的方式渗透到固态的主相粉末颗粒间的空隙处，从而使富Co合金相更好的渗透到主相之间的晶界处。
本发明的有益效果是：通过制造方法的创新，将磁体中的Co元素更多的分布在磁体晶界处，在保证磁体磁性能的基础上提高磁体的耐腐蚀性能，使富镧铈元素烧结钕铁硼磁体与普通的烧结钕铁硼永磁体一样具有很好的耐腐蚀性能，成为有实际应用价值的稀土永磁材料。
具体实施方式
下面结合具体实施方式对本发明做进一步的描述。
实施例一：
1、将成分为Nd12.3Ce2.4Fe余B6.0M1.7(at％)的富镧铈元素钕硼铁稀土永磁材料，按本发明的技术方案以速凝薄片工艺制得富镧铈元素钕铁硼稀土永磁材料合金；
2、通过速凝薄片工艺制得成分为Nd21.72Pr7.41Co70.87(at％)的富Co合金材料；
3、将富Co合金材料按1wt％的比例加入富镧铈元素钕铁硼稀土永磁材料合金中一起进行氢破，用气流磨工艺获得平均粒径在3.5μm的混合合金粉末；
4、混合后的合金粉末在≥1.5T的取向磁场中压制成型52×52×29(mm)的方块毛坯；
5、将成型好的毛坯放入高真空烧结炉内，在1035℃烧结6.0小时，在920℃一级回火2小时和500℃二级回火3.5小时，制得耐腐蚀的富镧铈元素烧结钕铁硼磁体。
6、直接用得到的Nd12.3Ce2.4Fe余B6.0M1.7(at％)的富镧铈元素钕铁硼稀土永磁材料合金，不加入富Co合金材料，采用相同的制造工艺制备成富镧铈元 素烧结钕铁硼磁体。
将二种磁体通过机加工制得Φ10×10(mm)的标样，再进行HAST实验(131℃，96％RH，2.6bar，96H)来测试材料的耐腐蚀性，其性能如表1。
表1 耐腐蚀性试验结果
Figure PCTCN2016101950-appb-000001
实施例二：
1、将成分为Pr3.06Nd8.96Ce3.31Fe余B5.88M2.25(at％)的富镧铈元素钕铁硼稀土永磁材料，按本发明的技术方案以速凝薄片工艺制得富镧铈元素钕铁硼稀土永磁材料合金；
2、通过速凝薄片工艺制得成分为Nd23.41Pr10.97Dy3Co61.24Zr1.38(at％)的富Co合金材料；
3、将上述的富镧铈元素钕铁硼稀土永磁材料合金与富Co合金材料分别进行氢破，在富镧铈元素钕铁硼稀土永磁材料合金进行气流磨制粉过程的其中任何一个时段按2wt％的比例加入富Co合金材料，制粉获得平均粒径在2.8-3.0μm的混合合金粉末，通过混料机将混合合金粉末混合均匀；
4、混合均匀的粉末在≥1.8T的取向磁场中压制成型52×52×29(mm)的方块毛坯；
5、将毛坯放入高真空烧结炉内，在1075℃烧结4.0小时，在890℃一级 回火1.5小时和510℃二级回火6.0小时，制得富镧铈元素烧结钕铁硼磁体。
6、直接用得到的Pr3.06Nd8.96Ce3.31Fe余B5.88M2.25(at％)的富镧铈元素钕铁硼稀土永磁材料合金，不加入富Co合金材料，采用相同的制造工艺制备成富镧铈元素烧结钕铁硼磁体。
将二种磁体通过机加工制得Φ10×10(mm)的标样，再进行HAST实验(131℃，96％RH，2.6bar，96H)来测试材料的耐腐蚀性，其性能如表2。
表2 耐腐蚀性试验结果
Figure PCTCN2016101950-appb-000002
实施例三：
1、将成分为Pr2.11Nd6.18Ce4.71Gd0.84Ho0.6Fe余B5.87M1.08(at％)的富镧铈元素钕铁硼稀土永磁材料，按本发明的技术方案以速凝薄片工艺制得富镧铈元素钕铁硼稀土永磁材料合金；
2、通过速凝薄片工艺制得成分为Nd36.98Pr12.62Ho1Gd5Co28.47Cr1.95Cu3.20Zn1.55Al3.76Nb5.47(at％)的富Co合金材料；
3、将上述的富镧铈元素钕铁硼稀土永磁材料合金与富Co合金材料分别进行氢破，并对富镧铈元素钕铁硼稀土永磁材料合金进行气流磨制粉，获得平均粒径在3.0-3.2μm的永磁合金粉末；对富Co合金材料进行球磨制粉，获得平均粒径在4.2-4.5μm的富Co合金粉末，按3wt％的比例将富Co合金 粉末加入到富镧铈元素钕铁硼稀土永磁材料合金粉末中，通过混料将二种合金粉末混合均匀；
4、混合均匀的粉末在≥2.2T的取向磁场中压制成型52×52×29(mm)的方块毛坯；
5、将毛坯放入高真空烧结炉内，在1060℃烧结8.0小时，在910℃一级回火3.0小时和480℃二级回火2.0小时，制得富镧铈元素烧结钕铁硼磁体。
6、直接用得到的Pr2.11Nd6.18Ce4.71Gd0.84Ho0.6Fe余B5.87M1.08(at％)的富镧铈元素钕铁硼稀土永磁材料合金，不加入富Co合金材料，采用相同的制造工艺制备成富镧铈元素烧结钕铁硼磁体。
将二种磁体通过机加工制得Φ10×10(mm)的标样，再进行HAST实验(131℃，96％RH，2.6bar，96H)来测试材料的耐腐蚀性，其性能如表3。
表3 耐腐蚀性试验结果
Figure PCTCN2016101950-appb-000003
实施例四：
1、将成分为Nd7.34Ce5.53Gd0.41Fe余B5.91M3.32(at％)的富镧铈元素钕铁硼稀土永磁材料，按本发明的技术方案以速凝薄片工艺制得富镧铈元素钕铁硼稀土永磁材料合金；
2、通过速凝薄片工艺制得成分为Nd77.91Pr10.71Co10Ti0.38V1(at％)的富Co 合金材料；
3、将上述的富镧铈元素钕铁硼稀土永磁材料合金与富Co合金材料分别进行氢破，并将富镧铈元素钕铁硼稀土永磁材料合金进行气流磨制粉，获得平均粒径在3.4-3.6μm的富镧铈元素钕铁硼稀土永磁材料合金粉末，在富镧铈元素钕铁硼稀土永磁材料合金制粉后按4wt％的比例将富Co合金材料加入气流磨进行连续制粉，获得平均粒径在2.5-2.7μm的富Co合金材料粉末，与富镧铈元素钕铁硼稀土永磁材料合金粉末一起盛在料桶中，通过三维混料机将两种合金粉末混合均匀；
4、混合均匀的粉末在≥1.5T的取向磁场中压制成型52×52×29(mm)的方块毛坯；
5、将毛坯放入高真空烧结炉内，在1060℃烧结3.5小时，在900℃一级回火2.0小时和510℃二级回火3.5小时，制得富镧铈元素烧结钕铁硼磁体。
6、直接用得到的Nd7.34Ce5.53Gd0.41Fe余B5.91M3.32(at％)的富镧铈元素钕铁硼稀土永磁材料合金，不加入富Co合金材料，采用相同的制造工艺制备成富镧铈元素烧结钕铁硼磁体。
将二种磁体通过机加工制得Φ10×10(mm)的标样，再进行HAST实验(131℃，96％RH，2.6bar，96H)来测试材料的耐腐蚀性，其性能如表4。
表4 耐腐蚀性试验结果
Figure PCTCN2016101950-appb-000004
实施例五：
1、将成分为Pr2.01Nd5.88Ce7.21Ho0.4Fe余B6.21M0.98(at％)的富镧铈元素钕铁硼稀土永磁材料，按本发明的技术方案以速凝薄片工艺制得富镧铈元素钕铁硼稀土永磁材料合金；
2、通过速凝薄片工艺制得成分为Nd24.37Pr8.31Co60.02Ga2.54Nb4.76(at％)的富Co合金材料；
3、将上述的富镧铈元素钕铁硼稀土永磁材料合金与富Co合金材料分别进行氢破，并分别进行气流磨制粉，获得平均粒径在3.8-4.0μm的富镧铈元素钕铁硼稀土永磁材料合金粉末和平均粒径在2.8-3.0μm的富Co合金材料粉末，按5wt％的比例将富Co合金材料粉末加入到富镧铈元素钕铁硼稀土永磁材料合金粉末中，通过混料将二种合金粉末混合均匀；
4、混合均匀的粉末在≥1.6T的取向磁场中压制成型52×52×29(mm)的方块毛坯；
5、将毛坯放入高真空烧结炉内，在1090℃烧结2.0小时，在900℃一级回火2.5小时和490℃二级回火4.0小时，制得富镧铈元素烧结钕铁硼磁体。
6、直接用得到的Pr2.01Nd5.88Ce7.21Ho0.4Fe余B6.21M0.98(at％)的富镧铈元素 钕铁硼稀土永磁材料合金，不加入富Co合金材料，采用相同的制造工艺制备成富镧铈元素烧结钕铁硼磁体。
将二种磁体通过机加工制得Φ10×10(mm)的标样，再进行HAST实验(131℃，96％RH，2.6bar，96H)来测试材料的耐腐蚀性，其性能如表5。
表5 耐腐蚀性试验结果
Figure PCTCN2016101950-appb-000005

Claims (10)

  1. 一种耐腐蚀的富镧铈烧结钕铁硼磁体，其特征是，包括富镧铈元素钕铁硼稀土永磁材料和用于提高材料耐腐蚀能力的富Co合金材料，所述的富镧铈元素钕铁硼稀土永磁材料成分为ReαFe100-α-β-γBβMγ，其中：Re为稀土元素，包括La、Ce、Nd三种元素中的两种或两种以上元素且必然含有Nd元素；M为添加元素，包括选自Ti、V、Cr、Ni、Zn、Ga、Ge、Al、Zr、Nb、Co、Cu、Ag、Sn、W、Pb、Bi、Pd中的一种或一种以上的元素；Fe为Fe和不可避免的杂质；α、β、γ为各元素的原子百分比含量，其中：12≤α≤17，5.1≤β≤6.8，0.1≤γ≤7.8。
  2. 根据权利要求1所述的一种耐腐蚀的富镧铈烧结钕铁硼磁体，其特征是，所述稀土元素Re中的La、Ce元素占所述富镧铈元素钕铁硼稀土永磁材料中稀土总用量的15wt％～45wt％。
  3. 根据权利要求1所述的一种耐腐蚀的富镧铈烧结钕铁硼磁体，其特征是，所述稀土元素Re中还包括选自Pr、Pm、Sm、Eu、Gd、Ho、Er、Tm、Yb、Lu、Y、Sc中的一种或一种以上的元素。
  4. 根据权利要求1所述的一种耐腐蚀的富镧铈烧结钕铁硼磁体，其特征是，所述的富Co合金材料成分为：CoxA100-x-yNy，其中：A为稀土元素，包括选自Pr、Nd、Dy、Tb、Gd、Ho中的一种或多种；N为添加元素，包括选自Ti、V、Zn、Ga、Al、Zr、Nb、Cu、Cr中的一种或多种；x、y为各元素的原子百分比含量，其中：10≤x≤75，0≤y≤20，所述的富Co合金材料中必然不包含元素Fe。
  5. 一种耐腐蚀的富镧铈烧结钕铁硼磁体的制造方法，其特征是，具体操作步骤如下：
    (1)按照富镧铈元素钕铁硼稀土永磁材料成分制得富镧铈元素钕铁硼稀土永磁材料合金；
    (2)按照富Co合金材料成分制得富Co合金材料；
    (3)对富镧铈元素钕铁硼稀土永磁材料合金进行破碎，制得平均粒径在2.5～4.5μm的富镧铈元素钕铁硼稀土永磁材料合金粉末；
    (4)将步骤(2)制得的富Co合金材料按一定的质量百分含量加入到富镧铈元素钕铁硼稀土永磁材料合金粉末内，其中富Co合金材料通过制粉和混料的过程使得富Co合金材料均匀的混入到富镧铈元素钕铁硼稀土永磁材料合金粉末内；
    (5)混合后的合金粉末于氮气气氛保护下，在≥1.5T的取向磁场中压制成型毛坯；
    (6)将成型好的毛坯放入高真空烧结炉内进行高温烧结，并执行二段回火工艺后，制得耐腐蚀的富镧铈元素烧结钕铁硼磁体。
  6. 根据权利要求5所述的一种耐腐蚀的富镧铈烧结钕铁硼磁体的制造方法，其特征是，在步骤(1)和步骤(2)中采用的制备工艺为铸造工艺或速凝薄片工艺；在步骤(3)中，采用的破碎方式为机械破碎或氢破加气流磨方式。
  7. 根据权利要求6所述的一种耐腐蚀的富镧铈烧结钕铁硼磁体的制造方法，其特征是，在步骤(1)和步骤(2)中采用的制备工艺为速凝薄片工艺。
  8. 根据权利要求7所述的一种耐腐蚀的富镧铈烧结钕铁硼磁体的制造方法，其特征是，步骤(2)的速凝薄片工艺中所采用冷却铜辊的辊速为步骤(1)的速凝薄片工艺中所采用冷却铜辊的辊速的5～15倍。
  9. 根据权利要求5所述的一种耐腐蚀的富镧铈烧结钕铁硼磁体的制造方法，其 特征是，在步骤(4)中，富Co合金材料占富镧铈元素钕铁硼稀土永磁材料合金的质量百分含量为1％～5％。
  10. 根据权利要求5所述的一种耐腐蚀的富镧铈烧结钕铁硼磁体的制造方法，其特征是，在步骤(6)中，烧结温度为1030℃～1090℃，烧结时间为2.0～8.0小时，二段回火工艺为：在890℃～920℃一级回火，恒温时间为1.5～3小时；在480℃～520℃二级回火，恒温时间为2～6小时。
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