CN107739949B - Phase-rich alloy for recycling magnet waste and method for recycling waste magnet - Google Patents

Phase-rich alloy for recycling magnet waste and method for recycling waste magnet Download PDF

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CN107739949B
CN107739949B CN201710983104.2A CN201710983104A CN107739949B CN 107739949 B CN107739949 B CN 107739949B CN 201710983104 A CN201710983104 A CN 201710983104A CN 107739949 B CN107739949 B CN 107739949B
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magnet
alloy
waste
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hydrogen
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CN107739949A (en
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陈运鹏
毛华云
赖欣
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Jl Mag Rare Earth Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Hard Magnetic Materials (AREA)
  • Manufacturing Cores, Coils, And Magnets (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The invention provides a phase-rich alloy for recycling magnet waste, which has a general formula as shown in a formula I: REx‑My‑HzI; wherein x is more than or equal to 0.8 and less than or equal to 0.97, y is more than or equal to 0.02 and less than or equal to 0.2, z is more than or equal to 0.005 and less than or equal to 0.02, and x + y + z is equal to 1; RE is selected from one or more of La, Ce, Ho, Gd, Pr, Nd, Ho, Dy and Tb; m [ one or more selected from Al, Cu, Zn, Sn, Ga, Ge, Nb, V, W, Ti, Ni, Zr, Ta, Mn, Cd and Mo; h is hydrogen element. The invention provides a scheme for applying a phase-rich alloy to waste rare earth treatment, the alloy is obtained by combining rare earth, metal elements and hydrogen elements in a specific proportion, magnet wastes of different grades can be comprehensively utilized, and a magnet finished product of a specific grade or a new grade is produced by adjusting the proportion.

Description

Phase-rich alloy for recycling magnet waste and method for recycling waste magnet
Technical Field
The invention belongs to the technical field of magnet preparation, relates to a phase-rich alloy for recycling magnet waste and a preparation method of a magnet, and particularly relates to a phase-rich alloy for recycling neodymium iron boron magnet waste and a method for recycling waste sintered neodymium iron boron magnets.
Background
The permanent magnet is a hard magnet, can keep the magnetic magnet for a long time, is not easy to lose magnetism, and is not easy to magnetize. Thus, hard magnets are one of the most commonly used strong materials, both in industrial production and in daily life. The hard magnet can be divided into a natural magnet and an artificial magnet, and the artificial magnet can achieve the same effect as a natural magnet (magnet) by synthesizing alloys of different materials and can also improve the magnetic force. To date, the third generation of neodymium iron boron (NdFeB) permanent magnet material has been developed, which has produced values that greatly exceed those of the previous permanent magnet material, and has been developed into a large industry. At present, the industry often adopts a sintering method to manufacture the neodymium iron boron permanent magnet material, for example, the royal and the like, in the 'influence of key process parameters and alloy elements on the magnetic performance and the mechanical performance of sintered NdFeB' discloses a process flow for manufacturing the neodymium iron boron permanent magnet material by adopting the sintering method, and the process flow generally comprises the steps of material preparation, smelting, steel ingot crushing, powder preparation, hydrogen crushing, airflow grinding of ultrafine powder, powder orientation press forming, vacuum sintering, sorting, electroplating and the like. The Nd-Fe-B magnet has the advantages of high performance-price ratio and small volumeLight weight, good mechanical property and strong magnetism, etc., so the advantage of high energy density makes the Nd-Fe-B permanent magnetic material obtain wide application in modern industry and electronic technology, and is praised as magnetic king in the magnetic field, such as Nd2Fe14An R-Fe-B-based rare earth sintered magnet having a B-type compound as a main phase is a magnet having the highest performance among all magnetic materials, and is widely used for a Voice Coil Motor (VCM) for hard disk drive, a servo motor, a variable frequency air conditioner motor, a motor for mounting a hybrid vehicle, and the like.
However, with the continuous expansion and large-scale wide application of ndfeb magnets, especially the magnets contain rare earth materials and other non-renewable precious mineral resources, the recycling of rare earth is very important, which not only protects the environment, but also saves resources, so the recycling of waste ndfeb magnets has gradually become a focus of attention in the industry. The main rare earth elements comprise La, Ce, Ho, Gd, Pr, Nd, Dy and Tb, and the waste magnet can be leftover materials and performance scrap materials in the manufacturing process, or sintered neodymium-iron-boron magnets detached after scrapping waste motors and components, and the like.
In recent years, researchers and manufacturers gradually try to recycle waste magnets, and generally, the following treatment methods are mainly adopted: after the pretreatment such as cleaning, a small amount of waste magnets can be added as raw materials to the preparation process of the sintered magnet, and then a new magnet with performance meeting the design requirements is manufactured based on the original process, but still has many problems, such as part of burning loss and more slag formation in the smelting process affect the outturn percentage, and the adding amount is very limited; there are also some methods of electrowinning the waste magnets, but this method usually only refines rare earths and other elements are wasted.
Therefore, how to find a more reasonable method for utilizing the waste magnets, reduce the loss of the magnets, increase the treatment capacity of the waste magnets, and utilize more components in the waste magnets to achieve the purpose of multi-directional recycling has become one of the problems to be solved by many manufacturers and researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a phase-rich alloy and a neodymium iron boron magnet for recycling magnet waste, and in particular, a method for recycling waste sintered neodymium iron boron magnets.
The invention provides a phase-rich alloy for recycling magnet waste, which has a general formula as shown in a formula I:
REx-My-HzI；
wherein x is more than or equal to 0.8 and less than or equal to 0.97, y is more than or equal to 0.02 and less than or equal to 0.2, z is more than or equal to 0.005 and less than or equal to 0.02, and x + y + z = 1;
RE is selected from one or more of La, Ce, Ho, Gd, Pr, Nd, Ho, Dy and Tb;
m is selected from one or more of Al, Cu, Zn, Sn, Ga, Ge, Nb, V, W, Ti, Ni, Zr, Ta, Mn, Cd and Mo;
h is hydrogen element.
Preferably, the RE is selected from one or more of Pr, Nd, Dy, Tb, Ho and Gd;
the M is selected from one or more of Al, Cu, Ga, Nb, Ni, Ti and Zr;
the oxygen content of the phase-rich alloy is less than or equal to 1000 ppm.
The invention provides a method for preparing a magnet by adopting the phase-rich alloy in any one of the technical schemes, which is characterized by comprising the following steps:
1) crushing the magnet waste and hydrogen to obtain alloy A coarse powder;
smelting a phase-rich alloy raw material into a cast sheet or an ingot, and then crushing the cast sheet or the ingot by hydrogen to obtain B alloy coarse powder;
2) mixing the alloy A coarse powder and the alloy B coarse powder obtained in the step A, and grinding the mixture into powder to obtain mixed fine powder;
3) and (3) performing orientation molding and sintering on the mixed fine powder obtained in the step to obtain the magnet.
Preferably, the mass ratio of the alloy coarse powder A to the alloy coarse powder B is (90-99): (10-1);
the particle size after crushing is less than or equal to 30 mm;
the thickness of the cast piece after the cast piece is smelted is 0.1-0.6 mm; the single weight of the ingot after ingot smelting is 0.1-5 kg.
Preferably, the melting point of the B alloy is lower than that of the A alloy;
the magnet waste comprises magnet waste of the same grade or magnet waste of different grades;
the magnet waste is sintered magnet waste.
Preferably, in the hydrogen crushing process of the magnet waste, the hydrogen absorption time is 60-180 min, and the hydrogen absorption temperature is 20-300 ℃;
the dehydrogenation time is 3-7 h, and the dehydrogenation temperature is 550-600 ℃;
after the magnet waste is crushed by hydrogen, a water cooling step is also included;
the water cooling time is 0.5-2 h.
Preferably, the milling is carried out by adding a lubricant;
the lubricant accounts for 0.02-0.1% of the mixed fine powder by mass;
the particle size after milling is 2-5 μm.
Preferably, the orientation forming comprises orientation pressing and isostatic pressing;
the orientation forming specifically comprises the following steps: performing orientation molding under the condition of no oxygen or low oxygen;
the sintering temperature is 1030-1060 ℃; the sintering time is 6-10 h;
and the sintering process also comprises an aging treatment step.
Preferably, the aging treatment comprises a first aging treatment and a second aging treatment;
the temperature of the first time aging treatment is 700-950 ℃, and the time of the first time aging treatment is 2-15 hours;
the temperature of the second time aging treatment is 350-550 ℃, and the time of the second time aging treatment is 1-8 hours.
The invention also provides a method for preparing a magnet by using the phase-rich alloy in any one of the technical schemes, which is characterized by comprising the following steps:
a) crushing a magnet raw material and hydrogen crushing to obtain a coarse alloy powder a;
smelting a phase-rich alloy raw material into a cast sheet or an ingot, and then crushing the cast sheet or the ingot by hydrogen to obtain B alloy coarse powder;
b) mixing the alloy a coarse powder and the alloy B coarse powder obtained in the step a, and grinding the mixture into powder to obtain mixed fine powder;
c) and (3) performing orientation molding and sintering on the mixed fine powder obtained in the step to obtain the magnet.
The invention provides a phase-rich alloy for recycling magnet waste, which has a general formula as shown in a formula I: REx-My-HzI; wherein x is more than or equal to 0.8 and less than or equal to 0.97, y is more than or equal to 0.02 and less than or equal to 0.2, z is more than or equal to 0.005 and less than or equal to 0.02, and x + y + z = 1; RE is selected from one or more of La, Ce, Ho, Gd, Pr, Nd, Ho, Dy and Tb; m is selected from one or more of Al, Cu, Zn, Sn, Ga, Ge, Nb, V, W, Ti, Ni, Zr, Ta, Mn, Cd and Mo; h is hydrogen element. Also provides a method for recycling the waste sintered magnet. Compared with the prior art, the method provided by the invention aims at the defects of less additive amount, process loss and low comprehensive utilization rate of elements in the existing waste magnet recovery treatment mode. The invention provides a scheme of applying alloy to waste rare earth treatment, creatively obtains a phase-rich alloy for recycling magnet waste, and obtains the alloy by combining rare earth, metal elements and hydrogen elements according to a specific proportion. The invention also aims at the limitation problem that the existing waste magnet recovery processing mode can only utilize the waste magnets with the same grade, the phase-rich alloy can be adopted to comprehensively utilize the waste magnets with different grades, and the mixture ratio is adjusted to generate the waste magnetsThe method has the advantages that the finished product of the magnet with a specific mark or a new mark is produced, the utilization rate of waste recovery is effectively improved, and the problems that the addition amount of the waste magnet is limited, part of the waste magnet is burnt and the outturn rate is low in the smelting process, or other elements are wasted due to the adoption of the method of electrolyzing and refining rare earth are solved.
The invention uses the phase-rich alloy with the specific composition in the recycling process of the magnet waste, can obviously improve the magnetic properties such as coercive force and the like of the magnet waste, has large treatment capacity of the magnet waste, full recycling and recovery rate which can approach 100 percent, can produce neodymium iron boron magnets with different brands through different proportions, has high comprehensive utilization rate of resources, strong production flexibility, simple process, full utilization of the waste, resource saving and production cost reduction.
Experimental results show that when the magnet is prepared from the phase-rich alloy with the magnet waste recycled, the coercive force can be improved by 5KOE, and compared with a recycling method for refining the waste, the cost is reduced by about 50%.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts the conventional purity used in the field of industrial pure or neodymium iron boron magnet.
The invention provides a phase-rich alloy for recycling magnet waste, which has a general formula as shown in a formula I:
REx-My-HzI；
wherein x is more than or equal to 0.8 and less than or equal to 0.97, y is more than or equal to 0.02 and less than or equal to 0.2, z is more than or equal to 0.005 and less than or equal to 0.02, and x + y + z = 1;
RE is selected from one or more of La, Ce, Ho, Gd, Pr, Nd, Ho, Dy and Tb;
m is selected from one or more of Al, Cu, Zn, Sn, Ga, Ge, Nb, V, W, Ti, Ni, Zr, Ta, Mn, Cd and Mo;
h is hydrogen element.
The specific definition of the formula I in the present invention is not particularly limited, and may be expressed in such a manner as is well known to those skilled in the art, and may be understood as a mass ratio, a general formula, or other definitions of similar compositions.
In the general formula of formula I of the present invention, RE is preferably selected from one or more of La, Ce, Ho, Gd, Pr, Nd, Ho, Dy and Tb, more preferably two or more of La, Ce, Ho, Gd, Pr, Nd, Ho, Dy and Tb, more preferably one or more of Pr, Nd, Dy, Tb, Ho and Gd, and more preferably more of Pr, Nd, Dy, Tb, Ho and Gd, and can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements.
In the general formula of formula I of the present invention, M is preferably selected from one or more of Al, Cu, Zn, Sn, Ga, Ge, Nb, V, W, Ti, Ni, Zr, Ta, Mn, Cd and Mo, more preferably two or more of Al, Cu, Zn, Sn, Ga, Ge, Nb, V, W, Ti, Ni, Zr, Ta, Mn, Cd and Mo, more preferably one or more of Al, Cu, Ga, Nb, Ni, Ti and Zr, more preferably a plurality of Al, Cu, Ga, Nb, Ni, Ti and Zr, and can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements.
In the phase-rich alloy, x + y + z =1, namely the mass base number is 1 as a whole; the mass ratio of RE, namely x value, is 0.8-0.97, preferably 0.82-0.95, more preferably 0.85-0.93, and more preferably 0.87-0.9. The mass ratio of M, i.e. the y value, is 0.02 to 0.2, preferably 0.05 to 0.18, more preferably 0.08 to 0.15, and more preferably 0.1 to 0.13. The mass ratio of the hydrogen elements, namely the z value, is 0.005-0.02, preferably 0.007-0.018, more preferably 0.009-0.015, and more preferably 0.011-0.013.
The source of the H element in the phase-rich alloy is not particularly limited in the present invention, and the H element may be added to the alloy in a manner well known to those skilled in the art, and the present invention preferably introduces the H element by performing a hydrogen absorption reaction on the phase-rich alloy raw material during hydrogen fragmentation, and controls the content of the H element by the hydrogen absorption reaction process or the subsequent dehydrogenation reaction process, or may adopt a hydride form.
The other parameter properties of the phase-rich alloy are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to the actual production situation, product requirements and quality requirements, and the oxygen content of the phase-rich alloy of the present invention is preferably not more than 1000ppm, more preferably not more than 800ppm, and more preferably not more than 500 ppm.
The invention provides a method for preparing a magnet by adopting the phase-rich alloy in any one of the technical schemes, which comprises the following steps:
1) crushing the magnet waste and hydrogen to obtain alloy A coarse powder;
smelting a phase-rich alloy raw material into a cast sheet or an ingot, and then crushing the cast sheet or the ingot by hydrogen to obtain B alloy coarse powder;
2) mixing the alloy A coarse powder and the alloy B coarse powder obtained in the step A, and grinding the mixture into powder to obtain mixed fine powder;
3) and (3) performing orientation molding and sintering on the mixed fine powder obtained in the step to obtain the magnet.
In the above steps of the present invention, the selection principle and the preferred range of the phase-rich alloy raw material used correspond to the selection principle and the preferred range of the phase-rich alloy in the above steps, if not specifically noted, and are not described in detail herein. The proportion of the phase-rich alloy can be adjusted according to the specific components of the magnet waste, namely the alloy A, or the components of the magnet waste alloy and the grade of the final product.
Firstly, crushing magnet waste and hydrogen to obtain alloy A coarse powder; and smelting the phase-rich alloy raw material into a cast sheet or an ingot, and then crushing the cast sheet or the ingot by hydrogen to obtain B alloy coarse powder.
The magnet waste is not particularly limited by the present invention, and may be conventional magnet waste known to those skilled in the art, and those skilled in the art can select and adjust the magnet waste according to factors such as actual production conditions, product requirements, and quality control.
The specific composition of the magnet waste is not particularly limited, and the composition of the neodymium iron boron magnet known to those skilled in the art can be selected and adjusted according to factors such as actual production conditions, product requirements and quality control, and the like, and the components in the magnet waste of the invention preferably comprise the following components in percentage by mass: Pr-Nd: 28% -33%, Dy: 0-10%, Tb: 0-10%, Nb: 0-5%, B: 0.5% -2.0%, Al: 0-3.0%, Cu: 0-1%, Co: 0-3%, Ga: 0-2%, Gd: 0-2%, Ho: 0-2%, Zr: 0-2% and the balance Fe, more preferably comprising Pr-Nd: 28.40% -33.00%, Dy: 0.50% -6.0%, Tb: 0.50% -6.0%, B: 0.92% -0.98%, Al: 0.10% -3.0%, Cu: 0.10% -0.25%, Co: 0.10% -3.0%, Ga: 0.1% -0.3% and the balance of Fe.
The components in the magnet waste material comprise, by mass percentage, preferably one or more of other rare earth elements, more preferably one or more of Sc, Y, La, Ce, Pm, Sm, Eu, Er, Tm, Yb and Lu, and most preferably Sc and/or Y.
The invention has no special limitation on the specific grade of the magnet waste, and the magnet waste can be selected and adjusted according to the factors such as the practical application condition, the product requirement, the quality requirement and the like by using the conventional grade of the neodymium iron boron magnet known by the technical personnel in the field, and can be (low coercive force) N-type neodymium iron boron magnet, (medium coercive force) M-type neodymium iron boron magnet, (high coercive force) H-type neodymium iron boron magnet, the magnet scrap material can comprise magnet scrap materials of the same grade or magnet scrap materials of different grades, and the magnet scrap materials can be selected and adjusted by a person skilled in the art according to factors such as actual application conditions, product requirements, quality requirements and the like.
In order to ensure the utilization rate of the magnet waste and optimize and complete process route, the magnet waste is preferably pretreated magnet waste, and the pretreatment preferably comprises the steps of oil removal, cleaning and the like.
The crushing is preferably primary crushing, and the crushing is preferably mechanical crushing. The particle size after crushing is preferably 30mm or less, more preferably 20mm or less, and still more preferably 10mm or less. The particle size of the magnet waste after hydrogen crushing is preferably 200 mu m-2 mm, more preferably 500 mu m-1.5 mm, and more preferably 800 mu m-1.2 mm.
The method is not particularly limited in specific process and parameters of hydrogen crushing of the magnet waste, and can be realized by using the specific process and parameters of hydrogen crushing of the neodymium iron boron magnet, which are well known by the technicians in the field, and the technicians in the field can select and adjust the process according to factors such as actual application conditions, product requirements and quality requirements, in order to improve the utilization rate of the waste and ensure the magnetic performance of a final product, the hydrogen absorption time of the magnet waste in the hydrogen crushing process is preferably 60-180 min, more preferably 80-160 min, and more preferably 100-140 min; the hydrogen absorption temperature is preferably 20-300 ℃, more preferably 70-250 ℃, and more preferably 120-200 ℃; the dehydrogenation time is preferably 3-7 h, more preferably 3.5-6.5 h, and more preferably 4-5 h; the dehydrogenation temperature is preferably 550-600 ℃, more preferably 560-590 ℃, and more preferably 570-580 ℃.
After the magnet waste is subjected to hydrogen crushing, the method preferably further comprises a water cooling step. The water cooling time is preferably 0.5-2 h, more preferably 0.7-1.8 h, and more preferably 1-1.5 h.
The thickness of the phase-rich alloy raw material after smelting and casting is preferably 0.1-0.6 mm, more preferably 0.2-0.5 mm, and more preferably 0.3-0.4 mm. The equipment for smelting the casting pieces of the phase-rich alloy raw material is preferably an air induction smelting furnace. The invention has no particular limitation on the specific steps and parameters of the smelting and casting of the phase-rich alloy raw material, and the specific steps and parameters of the smelting and casting of the alloy material conventional known to those skilled in the art can be selected and adjusted according to factors such as actual production conditions, product requirements and quality requirements.
The single weight of the phase-rich alloy raw material after ingot casting is preferably 0.1-5 kg, more preferably 0.5-4.5 kg, more preferably 1.5-3.5 kg, and more preferably 2-3 kg. The invention has no particular limitation on the specific steps and parameters of the smelting ingot of the phase-rich alloy raw material, and the specific steps and parameters of the smelting ingot of the alloy material are known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to factors such as actual production conditions, product requirements and quality requirements.
The specific process and parameters of hydrogen crushing of the phase-rich alloy raw material are not particularly limited, and the specific process and parameters of hydrogen crushing of the alloy, which are well known to a person skilled in the art, can be selected and adjusted by the person skilled in the art according to factors such as actual application conditions, product requirements, quality requirements and the like, in order to improve the utilization rate of waste materials and ensure the magnetic performance of a final product, the hydrogen absorption temperature is preferably 20-300 ℃, more preferably 70-250 ℃, and more preferably 120-200 ℃ in the hydrogen crushing process of the phase-rich alloy raw material; the dehydrogenation time is preferably 3-7 h, more preferably 3.5-6.5 h, and more preferably 4-5 h; the dehydrogenation temperature is preferably 550-600 ℃, more preferably 560-590 ℃, and more preferably 570-580 ℃.
In order to improve the magnetic property of a final product and ensure the effect of waste recovery, the melting point of the B alloy is preferably lower than that of the A alloy.
After the phase-rich alloy raw material is subjected to hydrogen crushing, the method preferably further comprises a water cooling step. The water cooling time is preferably 0.5-2 h, more preferably 0.7-1.8 h, and more preferably 1-1.5 h.
The coarse powder of the alloy A and the coarse powder of the alloy B obtained in the step are mixed and ground to obtain mixed fine powder.
The mixing is preferably stirring mixing, and the mass ratio of the alloy A coarse powder to the alloy B coarse powder is preferably (90-99): (10-1), more preferably (92-97): (8-3), more preferably (94-95): (6-5).
The milling powder of the present invention is preferably a jet mill milling powder, and more preferably milling powder with the addition of a lubricant. The lubricant is not particularly limited in the present invention, and the lubricant may be ground with a magnet air stream well known to those skilled in the art. The mass ratio of the lubricant to the mixed fine powder is preferably 0.02-0.1%, more preferably 0.03-0.09%, and more preferably 0.05-0.07%.
The average particle size of the milled mixed fine powder, namely the average particle size of the mixed fine powder, is preferably 2 to 5 μm, more preferably 2.5 to 4.5 μm, and even more preferably 3 to 4 μm.
Finally, the mixed fine powder obtained in the step is subjected to orientation molding and sintering to obtain the magnet.
The specific steps and parameters of the orientation forming are not particularly limited by the present invention, and the specific steps and parameters of the orientation forming of the magnet, which are well known to those skilled in the art, can be selected and adjusted according to factors such as actual production conditions, product requirements, and quality requirements, and the like, and the orientation forming of the present invention preferably comprises the steps of orientation pressing and isostatic pressing, more preferably the magnetic field orientation forming is performed in a sealed glove box without oxygen or low oxygen, and ensures that the product is free of oxygen or low oxygen in the whole operation and isostatic pressing process.
The magnetic field intensity of the orientation pressing is preferably 1.5-2.0T, more preferably 1.6-1.9T, and more preferably 1.7-1.8T; the time for orientation pressing is preferably 2-10 s, more preferably 3-9 s, and more preferably 5-7 s; the pressure of the isostatic pressing is preferably 120-240 MPa, more preferably 150-210 MPa, and more preferably 160-200 MPa; the dwell time of the isostatic compaction is preferably 30-120 s, more preferably 50-100 s, and more preferably 70-80 s.
The invention has no special limitation on the specific steps and parameters of the sintering, and the specific steps and parameters of the magnet sintering known to those skilled in the art can be selected and adjusted according to factors such as actual production conditions, product requirements, quality requirements and the like, and the sintering in the invention is preferably vacuum sintering; the sintering process preferably further comprises an aging treatment step; the aging treatment more preferably includes a first aging treatment and a second aging treatment.
The sintering temperature is preferably 1030-1060 ℃, more preferably 1035-1055 ℃, and more preferably 1040-1050 ℃; the sintering time is preferably 6-10 h, more preferably 6.5-9.5 h, and more preferably 7-9 h.
The temperature of the first aging treatment is preferably 700-950 ℃, more preferably 750-900 ℃, and more preferably 800-850 ℃; the time of the first aging treatment is preferably 2 to 15 hours, more preferably 5 to 12 hours, and still more preferably 7 to 10 hours.
The temperature of the second aging treatment is preferably 350-550 ℃, more preferably 375-525 ℃, and more preferably 400-500 ℃; the time of the second aging treatment is preferably 1 to 8 hours, more preferably 2 to 7 hours, and still more preferably 4 to 5 hours.
The overall preparation process of the magnet is not particularly limited, and the sintered neodymium iron boron magnet well known to those skilled in the art can be prepared by a process of preparing the raw materials, namely, a blank is obtained by the steps of mixing, smelting and casting, crushing and crushing hydrogen, pulverizing into powder, orienting and pressing the powder, forming the powder, sintering the powder in vacuum and the like, and the blank is subjected to surface treatment and processing to obtain the finished product neodymium iron boron magnet.
The invention also provides a method for preparing a magnet by adopting the phase-rich alloy in any one of the technical schemes, which is characterized by comprising the following steps:
a) crushing a magnet raw material and hydrogen crushing to obtain a coarse alloy powder a;
smelting a phase-rich alloy raw material into a cast sheet or an ingot, and then crushing the cast sheet or the ingot by hydrogen to obtain B alloy coarse powder;
b) mixing the alloy a coarse powder and the alloy B coarse powder obtained in the step a, and grinding the mixture into powder to obtain mixed fine powder;
c) and (3) performing orientation molding and sintering on the mixed fine powder obtained in the step to obtain the magnet.
In the above steps of the present invention, the selection principle and the preferred range of the used materials, preparation processes and parameters, if not specifically noted, correspond to the selection principle and the preferred range of the materials, preparation processes and parameters in the foregoing preparation methods, and are not described in detail herein.
The magnet raw material is not particularly limited, and may be a conventional magnet raw material well known to those skilled in the art, and those skilled in the art may select and adjust the magnet raw material according to factors such as actual production conditions, product requirements, and quality control.
The specific composition of the raw material of the magnet is not particularly limited, and the composition of the neodymium iron boron magnet known to those skilled in the art can be selected and adjusted according to factors such as actual production conditions, product requirements and quality control, and the raw material of the magnet comprises the following components by mass percent, preferably: Pr-Nd: 28% -33%, Dy: 0-10%, Tb: 0-10%, Nb: 0-5%, B: 0.5% -2.0%, Al: 0-3.0%, Cu: 0-1%, Co: 0-3%, Ga: 0-2%, Gd: 0-2%, Ho: 0-2%, Zr: 0-2% and the balance Fe, more preferably comprising Pr-Nd: 28.40% -33.00%, Dy: 0.50% -6.0%, Tb: 0.50% -6.0%, B: 0.92% -0.98%, Al: 0.10% -3.0%, Cu: 0.10% -0.25%, Co: 0.10% -3.0%, Ga: 0.1% -0.3% and the balance of Fe.
The magnet raw material comprises the following components in percentage by mass, preferably further comprises one or more of other rare earth elements, more preferably further comprises one or more of Sc, Y, La, Ce, Pm, Sm, Eu, Er, Tm, Yb and Lu, and most preferably Sc and/or Y.
The specific grade of the magnet raw material is not particularly limited, and the conventional grade of the neodymium iron boron magnet known to those skilled in the art can be used, and those skilled in the art can select and adjust the specific grade according to the actual application condition, the product requirement, the quality requirement and other factors.
The phase-rich alloy provided by the invention can be used for recycling magnet waste materials and can also be used in the production process of conventional magnet raw materials to improve the magnetic properties of the magnet such as coercive force and the like.
The steps of the invention provide a method for recycling the rich-phase alloy and the waste sintered neodymium-iron-boron magnet used for recycling the neodymium-iron-boron magnet waste and a preparation method of the magnet. The invention provides a scheme of applying alloy to waste rare earth treatment, creatively obtains a phase-rich alloy for recycling magnet waste, and obtains the alloy by combining rare earth, metal elements and hydrogen elements according to a specific proportion. The invention adopts the phase-rich alloy to comprehensively utilize the magnet wastes of different grades, produces the magnet finished product of a specific grade or a new grade by adjusting the proportion, and obviously improves the magnetic properties such as coercive force and the like. The invention makes the waste magnet into an alloy, the proportion of the phase-rich alloy can be adjusted and designed according to the components of the alloy, and the magnet can be designed based on the components of the final magnet and finally made into the magnet meeting the performance requirements.
The invention uses the phase-rich alloy with the specific composition in the recycling process of the magnet waste or the preparation process of the conventional magnet, can obviously improve the magnetic properties of the magnet waste, such as coercive force and the like, has large treatment capacity of the magnet waste, full recycling and recovery rate of nearly 100 percent, can produce neodymium iron boron magnets with different brands through different proportions, has high comprehensive utilization rate of resources, strong production flexibility, simple process, full utilization of the waste, resource saving, no addition of waste in the smelting process, cost reduction and high flexibility, can produce magnets with different brands in batch and reduce production cost.
Experimental results show that when the magnet is prepared from the phase-rich alloy with the magnet waste recycled, the coercive force can be improved by 5KOE, and compared with a recycling method for refining the waste, the cost is reduced by about 50%.
For further illustration of the present invention, the following will describe in detail the phase-rich alloy for recycling magnet scraps and the method for preparing a magnet provided by the present invention with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given, only for further illustration of the features and advantages of the present invention, and not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
1. Preparation of alloy A
1.1 preprocessing the neodymium iron boron waste material such as oil removal and cleaning.
1.2 the initial crushing of the bulk raw material, the particle size after crushing being < 30mm, the invention is not particularly restricted to the crushing equipment and conditions.
1.3 Hydrogen crushing (HD) treatment alloy sheet production process, wherein the hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h, so as to obtain coarse powder (A alloy).
The alloy A prepared by the invention is subjected to component analysis, and specifically referred to in Table 1, wherein the Table 1 is the component composition of the scrap alloy A provided by the embodiment 1 of the invention.
TABLE 1
Effective element Nd Pr Dy Ho B Zr Cu Co Al Ga Fe
Element content 23.1 6.3 0.6 0.9 0.92 0.10 0.10 0.9 0.40 0.07 Balance of
2. Preparation of B alloy
2.1 designing phase-rich alloy component (r) Pr21 Nd70 Cu2 Al4Ga3 according to the alloy component
2.2, smelting, namely, preparing an alloy sheet by using a vacuum induction smelting furnace known in the field; the thickness of the cast sheet is 0.10-0.60 mm.
2.3, hydrogen crushing (HD) treatment of alloy sheets, wherein the hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder (B alloy).
3. Mixing the alloy A and the alloy B according to the ratio of A to B =98% and 2% to obtain alloy C powder; adding the alloy C powder into a lubricant, stirring and mixing.
4. The coarse powder was treated with an air jet mill to obtain a fine powder having an average particle size of 3.0. mu.m.
5. Magnetic field orientation profiling and isostatic pressing treatment; magnetic field orientation molding is performed in a sealed oxygen-free or low-oxygen glove box and ensures that the product is oxygen-free or low-oxygen throughout the running and isostatic pressing process.
6. And carrying out vacuum sintering and aging heat treatment to obtain the neodymium iron boron magnet. The sintering is carried out in a vacuum sintering furnace, and the sintering temperature is as follows: 1050 ℃, the sintering time is as follows: 6 h; aging is carried out for two times, the temperature of the first aging heat treatment is 920 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 550 ℃, and the time is 5 h.
The magnetic property of the ndfeb magnet prepared in example 1 of the present invention was measured.
Referring to table 2, table 2 shows the magnetic performance data of the ndfeb magnet prepared according to the example of the present invention.
TABLE 2
Figure DEST_PATH_IMAGE002
The neodymium iron boron magnet prepared in the embodiment 1 of the invention meets the performance requirement of a finished neodymium iron boron magnet with the grade of 42H.
Example 2
1. Preparation of alloy A
1.1 preprocessing the neodymium iron boron waste material such as oil removal and cleaning.
1.2 the large raw material is initially crushed, the granularity after crushing is less than 30mm, the crushing equipment and conditions are not particularly limited, and the technicians in the field can select different equipment according to the actual production conditions.
1.3 Hydrogen crushing (HD) treatment alloy sheet production process, wherein the hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h, so as to obtain coarse powder (A alloy).
The alloy A prepared in example 2 of the present invention was analyzed for composition, and the composition was the same as that of the scrap alloy A in example 1.
2. Preparation of B alloy
2.1 designing phase-rich alloy component (r) Pr16 Nd55 Dy20 Cu2 Al4Ga3 according to alloy component
2.2, smelting, namely, preparing an alloy sheet by using a vacuum induction smelting furnace known in the field; the thickness of the cast sheet is 0.10-0.60 mm.
2.3, hydrogen crushing (HD) treatment of alloy sheets, wherein the hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder (B alloy).
3. Mixing the alloy A and the alloy B according to the ratio of A to B =97.5% and 2.5% to obtain alloy C powder; adding the alloy C powder into a lubricant, stirring and mixing.
4. The coarse powder was treated with an air jet mill to obtain a fine powder having an average particle size of 3.0. mu.m.
5. Magnetic field orientation profiling and isostatic pressing treatment; magnetic field orientation molding is performed in a sealed oxygen-free or low-oxygen glove box and ensures that the product is oxygen-free or low-oxygen throughout the running and isostatic pressing process.
6. And carrying out vacuum sintering and aging heat treatment to obtain the neodymium iron boron magnet. The sintering is carried out in a vacuum sintering furnace, and the sintering temperature is as follows: 1050 ℃, the sintering time is as follows: 6 h; aging is carried out for two times, the temperature of the first aging heat treatment is 920 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 550 ℃, and the time is 5 h.
The magnetic property of the ndfeb magnet prepared in example 2 of the present invention was examined.
Referring to table 2, table 2 shows the magnetic performance data of the ndfeb magnet prepared according to the example of the present invention.
The neodymium iron boron magnet prepared in the embodiment 2 of the invention meets the performance requirement of a finished neodymium iron boron magnet with the grade of 42 SH.
Example 3
1. Preparation of alloy A
1.1 preprocessing the neodymium iron boron waste material such as oil removal and cleaning.
1.2 the large raw material is initially crushed, the granularity after crushing is less than 30mm, the crushing equipment and conditions are not particularly limited, and the technicians in the field can select different equipment according to the actual production conditions.
1.3 Hydrogen crushing (HD) treatment alloy sheet production process, wherein the hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h, so as to obtain coarse powder (A alloy).
The alloy A prepared in example 3 of the present invention was analyzed for composition, and the composition was the same as that of the scrap alloy A in example 1.
2. Preparation of B alloy
2.1 designing phase-rich alloy component (r) Pr16 Nd55 Dy10 Tb10 Cu2 Al4Ga3 according to alloy component
2.2, smelting, namely, preparing an alloy sheet by using a vacuum induction smelting furnace known in the field; the thickness of the cast sheet is 0.10-0.60 mm.
2.3, hydrogen crushing (HD) treatment of alloy sheets, wherein the hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder (B alloy).
3. Mixing the alloy A and the alloy B according to the ratio of A to B =97.5% and 2.5% to obtain alloy C powder; adding the alloy C powder into a lubricant, stirring and mixing.
4. The coarse powder was treated with an air jet mill to obtain a fine powder having an average particle size of 3.0. mu.m.
5. Magnetic field orientation profiling and isostatic pressing treatment; magnetic field orientation molding is performed in a sealed oxygen-free or low-oxygen glove box and ensures that the product is oxygen-free or low-oxygen throughout the running and isostatic pressing process.
6. And carrying out vacuum sintering and aging heat treatment to obtain the neodymium iron boron magnet. The sintering is carried out in a vacuum sintering furnace, and the sintering temperature is as follows: 1050 ℃, the sintering time is as follows: 6 h; aging is carried out for two times, the temperature of the first aging heat treatment is 920 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 550 ℃, and the time is 5 h.
The magnetic property of the ndfeb magnet prepared in example 3 of the present invention was examined.
Referring to table 2, table 2 shows the magnetic performance data of the ndfeb magnet prepared according to the example of the present invention.
The neodymium iron boron magnet prepared in the embodiment 3 of the invention meets the performance requirement of a finished product neodymium iron boron magnet with the grade of 42 SH.
The above detailed description of the present invention provides a method for recycling phase-rich alloy used for recycling waste ndfeb magnets, a method for recycling waste sintered ndfeb magnets, and a method for manufacturing magnets, and the principles and embodiments of the present invention are described herein with reference to specific examples, which are provided to assist understanding of the method and the core concept thereof, including the best mode, and to enable any person skilled in the art to practice the present invention, including making and using any devices or systems and performing any combination thereof. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. A phase-rich alloy for recycling magnet scrap, having the general formula of formula I:
REx-My-HzI；
wherein x is more than or equal to 0.8 and less than or equal to 0.97, y is more than or equal to 0.02 and less than or equal to 0.2, z is more than or equal to 0.005 and less than or equal to 0.02, and x + y + z = 1;
RE is selected from one or more of La, Ce, Ho, Gd, Pr, Nd, Ho, Dy and Tb;
m is selected from one or more of Al, Cu, Zn, Sn, Ga, Ge, Nb, V, W, Ti, Ni, Zr, Ta, Mn, Cd and Mo, wherein M is not independently selected from Al;
h is hydrogen element;
the phase-rich alloy for recycling the magnet waste can comprehensively utilize the magnet waste of different grades, and a magnet finished product of a specific grade or a new grade is produced by adjusting the proportion;
the magnet finished product is prepared from magnet waste and a phase-rich alloy.
2. The phase-rich alloy of claim 1, wherein the RE is selected from one or more of Pr, Nd, Dy, Tb, Ho, and Gd;
the M is selected from one or more of Al, Cu, Ga, Nb, Ni, Ti and Zr;
the oxygen content of the phase-rich alloy is less than or equal to 1000 ppm.
3. A method of producing a magnet using the phase rich alloy of claim 1 or 2, comprising the steps of:
1) crushing the magnet waste and hydrogen to obtain alloy A coarse powder;
smelting a phase-rich alloy raw material into a cast sheet or an ingot, and then crushing the cast sheet or the ingot by hydrogen to obtain B alloy coarse powder;
2) mixing the alloy A coarse powder and the alloy B coarse powder obtained in the step A, and grinding the mixture into powder to obtain mixed fine powder;
3) and (3) performing orientation molding and sintering on the mixed fine powder obtained in the step to obtain the magnet.
4. The method of claim 3, wherein the mass ratio of the A alloy coarse powder to the B alloy coarse powder is (90-99): (10-1);
the particle size after crushing is less than or equal to 30 mm;
the thickness of the cast piece after the cast piece is smelted is 0.1-0.6 mm; the single weight of the ingot after ingot smelting is 0.1-5 kg.
5. The method of claim 3, wherein the melting point of the B alloy is lower than the melting point of the A alloy;
the magnet waste comprises magnet waste of the same grade or magnet waste of different grades;
the magnet waste is sintered magnet waste.
6. The method according to claim 3, wherein in the hydrogen crushing process of the magnet waste, the hydrogen absorption time is 60-180 min, and the hydrogen absorption temperature is 20-300 ℃;
the dehydrogenation time is 3-7 h, and the dehydrogenation temperature is 550-600 ℃;
after the magnet waste is crushed by hydrogen, a water cooling step is also included;
the water cooling time is 0.5-2 h.
7. The method according to claim 3, characterized in that the milling is carried out with the addition of a lubricant;
the lubricant accounts for 0.02-0.1% of the mixed fine powder by mass;
the particle size after milling is 2-5 μm.
8. The method of claim 3, wherein the orientation forming comprises orientation pressing and isostatic pressing steps;
the orientation forming specifically comprises the following steps: performing orientation molding under the condition of no oxygen or low oxygen;
the sintering temperature is 1030-1060 ℃; the sintering time is 6-10 h;
and the sintering process also comprises an aging treatment step.
9. The method of claim 8, wherein the aging treatment comprises a first aging treatment and a second aging treatment;
the temperature of the first time aging treatment is 700-950 ℃, and the time of the first time aging treatment is 2-15 hours;
the temperature of the second time aging treatment is 350-550 ℃, and the time of the second time aging treatment is 1-8 hours.
10. A method of producing a magnet using the phase rich alloy of claim 1 or 2, comprising the steps of:
a) crushing a magnet raw material and hydrogen crushing to obtain a coarse alloy powder a;
smelting a phase-rich alloy raw material into a cast sheet or an ingot, and then crushing the cast sheet or the ingot by hydrogen to obtain B alloy coarse powder;
b) mixing the alloy a coarse powder and the alloy B coarse powder obtained in the step a, and grinding the mixture into powder to obtain mixed fine powder;
c) and (3) performing orientation molding and sintering on the mixed fine powder obtained in the step to obtain the magnet.
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CN113643872B (en) * 2021-07-30 2024-09-06 宁波中杭磁业有限公司 Cerium-containing neodymium-iron-boron magnetic steel and preparation method thereof
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