CN115637394B - Cobalt-reinforced iron-nickel-based hard magnetic alloy and preparation method thereof - Google Patents
Cobalt-reinforced iron-nickel-based hard magnetic alloy and preparation method thereof Download PDFInfo
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- CN115637394B CN115637394B CN202211290986.1A CN202211290986A CN115637394B CN 115637394 B CN115637394 B CN 115637394B CN 202211290986 A CN202211290986 A CN 202211290986A CN 115637394 B CN115637394 B CN 115637394B
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- 229910001004 magnetic alloy Inorganic materials 0.000 title claims abstract description 93
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 80
- 229910045601 alloy Inorganic materials 0.000 claims description 42
- 239000000956 alloy Substances 0.000 claims description 42
- 239000002994 raw material Substances 0.000 claims description 32
- 239000010941 cobalt Substances 0.000 claims description 22
- 229910017052 cobalt Inorganic materials 0.000 claims description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 17
- 238000003723 Smelting Methods 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims description 7
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910017061 Fe Co Inorganic materials 0.000 claims 5
- 229910020630 Co Ni Inorganic materials 0.000 claims 2
- 230000005291 magnetic effect Effects 0.000 abstract description 23
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 230000004907 flux Effects 0.000 abstract description 4
- 229910002555 FeNi Inorganic materials 0.000 description 19
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000005415 magnetization Effects 0.000 description 7
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- 238000013461 design Methods 0.000 description 6
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- 239000012634 fragment Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
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- 238000002074 melt spinning Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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Abstract
The application provides a cobalt-reinforced Fe-Ni-based hard magnetic alloy and a preparation method thereof, wherein the cobalt-reinforced Fe-Ni-based hard magnetic alloy consists of Fe, ni, co and P elements, and the composition of the cobalt-reinforced Fe-Ni-based hard magnetic alloy is expressed as Fe a Ni b Co c P d ，Fe a Ni b Co c P d Is a nanocrystalline-amorphous composite structure; wherein a, b, c, d is atom percent; a is more than or equal to 36 and less than or equal to 42, b is more than or equal to 36 and less than or equal to 42,0, c is more than or equal to 14, and d is more than or equal to 14. According to the cobalt-reinforced iron-nickel-based hard magnetic alloy and the preparation method thereof, the heat treatment temperature of the cobalt-reinforced iron-nickel-based hard magnetic alloy is increased, and the cobalt-reinforced iron-nickel-based hard magnetic alloy is ensured to be in an ordered crystalline state at a higher temperature, so that the cobalt-reinforced iron-nickel-based hard magnetic alloy is convenient to manually prepare; in addition, the coercive force and the magnetic flux density of the cobalt-reinforced iron-nickel-based hard magnetic alloy can be improved, and the magnetic performance of the cobalt-reinforced iron-nickel-based hard magnetic alloy is improved.
Description
Technical Field
The application belongs to the technical field of magnetic materials, and particularly relates to a cobalt-reinforced iron-nickel-based hard magnetic alloy and a preparation method thereof.
Background
In recent years, with the popularization of the concepts of green environmental protection and sustainable development, the development of new energy automobiles, wireless charging and other technologies has received extensive attention from society. Among them, a hard magnetic alloy, which is one of the key pillar materials of electronic components, has a wide application prospect due to its high saturation magnetization and high coercivity. At present, the comprehensive magnetic properties of rare earth hard magnetic materials in hard magnetic materials are higher than those of other hard magnetic materials. However, since rare earth is one of strategic resources, it is not only expensive but also disadvantageous for environmental protection, which severely restricts the sustainable development of hard magnetic materials.
In the related art, L1 in the Fe-Ni based hard magnetic alloy 0 The FeNi phase hard magnetic phase provides the alloy with hard magnetic properties, and the theoretical magnetic energy product is as high as 42MGOe, which is comparable with Nd-Fe-B.
However, in the preparation of L1 0 When the FeNi phase is hard-magnetic alloy, the transition temperature of the FeNi phase is lower, and the diffusion speed is highThe degree is low; in addition, the thermal treatment of FeNi in the high-temperature thermal treatment can only obtain disordered A1-FeNi soft magnetic phase, and the artificial preparation of FeNi-based hard magnetic alloy is difficult to realize.
Disclosure of Invention
The application provides a cobalt-reinforced iron-nickel-based hard magnetic alloy and a preparation method thereof, which can raise the heat treatment temperature of the cobalt-reinforced iron-nickel-based hard magnetic alloy and ensure that the cobalt-reinforced iron-nickel-based hard magnetic alloy is in an ordered crystalline state at a higher temperature when preparing the cobalt-reinforced iron-nickel-based hard magnetic alloy, thereby being convenient for the manual preparation of the cobalt-reinforced iron-nickel-based hard magnetic alloy; in addition, the coercive force and the magnetic flux density of the cobalt-reinforced iron-nickel-based hard magnetic alloy can be improved, and the magnetic performance of the cobalt-reinforced iron-nickel-based hard magnetic alloy is improved.
According to a first aspect of an embodiment of the present application, there is provided a cobalt-reinforced iron-nickel-based hard magnetic alloy composed of Fe, ni, co and P elements, the composition of the cobalt-reinforced iron-nickel-based hard magnetic alloy being expressed as Fe a Ni b Co c P d ，Fe a Ni b Co c P d Is a nanocrystalline-amorphous composite structure; wherein a, b, c, d is atom percent; a is more than or equal to 36 and less than or equal to 42, b is more than or equal to 36 and less than or equal to 42,0, c is more than or equal to 14, and d is more than or equal to 14.
In an alternative design, fe a Ni b Co c P d The atom percentage of Co is more than or equal to 2 and less than or equal to 8.
In an alternative design, the composition of the cobalt-strengthened iron-nickel-based hard magnetic alloy is expressed as Fe 41 Ni 41 Co 2 P 16 、Fe 40 Ni 40 Co 4 P 16 Or Fe 38 Ni 38 Co 8 P 16 。
According to a second aspect of the embodiment of the application, there is provided a method for preparing a cobalt-reinforced iron-nickel-based hard magnetic alloy, the composition of the cobalt-reinforced iron-nickel-based hard magnetic alloy being expressed as Fe a Ni b Co c P d The method comprises the steps of carrying out a first treatment on the surface of the Wherein a, b, c, d is atom percent; a is more than or equal to 36 and less than or equal to 42, b is more than or equal to 36 and less than or equal to 42,0, c is more than or equal to 14, and d is more than or equal to 14; the preparation method comprises the following stepsThe steps are as follows:
raw materials are mixed, and raw materials corresponding to all elements are weighed and mixed according to the composition components of the cobalt-reinforced iron-nickel-based hard magnetic alloy and the atomic percentage content of all elements, so as to obtain master alloy raw materials;
melting to obtain mother alloy with uniform components, remelting and quick quenching to obtain amorphous alloy; or, after fully mixing in the raw material smelting stage, directly and quickly quenching to obtain amorphous alloy;
annealing the amorphous alloy at 380-400 ℃ for 0.5-2h to obtain the cobalt-reinforced iron-nickel-based hard magnetic alloy.
In an alternative design, the smelting process is performed in any one of an alumina crucible, a boron nitride crucible, or a graphite crucible.
In an alternative design, the iron element in the raw material is derived from pure iron, iron phosphide or any one of binary or ternary prefabricated alloys of Fe, co and Ni.
In an alternative design, the nickel element in the raw material is derived from nickel, nickel phosphide or binary or ternary prealloy of Fe, co and Ni.
In an alternative design, the cobalt element in the raw material is derived from pure cobalt, cobalt phosphide or binary or ternary prealloy in Fe, co and Ni.
In the embodiment of the application, two elements of cobalt and phosphorus are added in the preparation process of the cobalt-reinforced iron-nickel-based hard magnetic alloy, the atomic percentage of iron is set to be 36-42, the atomic percentage of nickel is set to be 36-42, the sum of the atomic percentages of cobalt elements is 0-14, and the atomic percentage of phosphorus is more than or equal to 14; in this way, in the process of artificially preparing the cobalt-reinforced iron-nickel-based hard magnetic alloy, two elements of cobalt and phosphorus can influence the preparation process, so that the heat treatment temperature of the cobalt-reinforced iron-nickel-based hard magnetic alloy in the preparation process can be increased, and the cobalt-reinforced iron-nickel-based hard magnetic alloy is ensured to be in an ordered crystalline state at a higher treatment temperature, thereby being convenient for the artificial preparation of the cobalt-reinforced iron-nickel-based hard magnetic alloy. In addition, the coercive force and the magnetic flux density of the cobalt-reinforced iron-nickel-based hard magnetic alloy can be improved, and the magnetic performance of the cobalt-reinforced iron-nickel-based hard magnetic alloy is improved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a diagram of the structure of a crystalline phase of a cobalt-strengthened iron-nickel-based hard magnetic alloy provided by an embodiment of the present application;
FIG. 2 is an X-ray diffraction chart of an amorphous state and an annealed cobalt-fortified Fe-Ni-based hard magnetic alloy according to an embodiment of the present application and a cobalt-fortified Fe-Ni-based hard magnetic alloy according to a comparative example;
FIG. 3 is a diagram of Fe provided in example 3 of the present application 38 Ni 38 Co 8 P 16 A transmission electron microscope spectrum of the cobalt-reinforced iron-nickel-based hard magnetic alloy annealing strip;
fig. 4 is a flow chart of a preparation process of the cobalt-reinforced iron-nickel-based hard magnetic alloy provided by the embodiment of the application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The embodiment of the application provides a cobalt-reinforced iron-nickel-based hard magnetic alloy, which consists of Fe, ni, co and P elements, wherein the composition components of the cobalt-reinforced iron-nickel-based hard magnetic alloy are expressed as Fe a Ni b Co c P d ，Fe a Ni b Co c P d Is a nanocrystalline-amorphous composite structure; wherein a, b, c, d is respectively atomic percent；36≤a≤42，36≤b≤42，0＜c≤14，14≤d。
In the embodiment of the application, two elements of cobalt and phosphorus are added in the preparation process of the cobalt-reinforced iron-nickel-based hard magnetic alloy, the atomic percentage of iron is set to be 36-42, the atomic percentage of nickel is set to be 36-42, the atomic percentage of cobalt element is 0-14, and the atomic percentage of phosphorus element is more than or equal to 14; in this way, in the process of artificially preparing the cobalt-reinforced iron-nickel-based hard magnetic alloy, two elements of cobalt and phosphorus can influence the preparation process, so that the heat treatment temperature of the cobalt-reinforced iron-nickel-based hard magnetic alloy in the preparation process can be increased, and the cobalt-reinforced iron-nickel-based hard magnetic alloy is ensured to be in an ordered crystalline state at a higher treatment temperature, thereby being convenient for the artificial preparation of the cobalt-reinforced iron-nickel-based hard magnetic alloy. In addition, the coercive force and the magnetic flux density of the cobalt-reinforced iron-nickel-based hard magnetic alloy can be improved, and the magnetic performance of the cobalt-reinforced iron-nickel-based hard magnetic alloy is improved.
Specifically, referring to fig. 1, a in fig. 1 is a soft magnetic FeNi (Co) phase of chemical non-needed after heat treatment, and b in fig. 1 is an ordered hard magnetic FeNi (Co) phase. The addition of cobalt element can effectively promote the synthesis proportion of ordered phases and improve the hard magnetic performance (magnetocrystalline anisotropy energy) of ordered phases. Thereby improving the overall hard magnetic performance of the annealed material, for example, effectively improving the coercive force and remanence coercive force of the annealed material.
In specific implementation, the iron element in the cobalt-reinforced iron-nickel-based hard magnetic alloy provided by the embodiment of the application can be derived from pure iron or iron phosphide and the like.
It should be noted that the pure iron referred to in the examples of the present application is generally a raw material having a purity within the range understood by those skilled in the art, for example, having an iron content of 99.9% and above. It will be appreciated that in some examples, such as in industrial production, raw materials having relatively low iron content may also be used in order to reduce costs. In addition, in some examples, the elemental iron may also be derived from a binary pre-alloyed of Fe, co, a binary pre-alloyed of Fe, ni, or a ternary pre-alloyed of Fe, co, ni, or the like.
It will be appreciated that in embodiments of the present application, the nickel element in the cobalt-reinforced iron-nickel-based hard magnetic alloy may be derived from pure nickel or nickel phosphide, and the like. In some possible examples, the nickel element may also be derived from a binary threshold alloy of Fe, ni or a binary pre-alloy of Co, ni; in other possible examples, the nickel element may also be derived from a ternary prealloy of Fe, co, ni.
From the foregoing detailed description of embodiments, it can be seen that in embodiments of the present application, the source of Co element may be similar or approximate to that of iron and nickel; for example, the Co element may be derived from binary pre-alloys of pure cobalt, co and Ni, or binary pre-alloys of Fe and Co, but may also be derived from ternary pre-alloys of Fe, co and Ni.
Wherein the phosphorus element can be derived from raw materials such as pure phosphorus, iron phosphide or nickel phosphide. Therefore, the occurrence of the condition of introducing impurities into the cobalt-reinforced iron-nickel-based hard magnetic alloy can be reduced or reduced, and the preparation success rate of the cobalt-reinforced iron-nickel-based hard magnetic alloy is ensured.
In an alternative example of embodiment of the present application, fe a Ni b Co c P d The atom percentage content of Co is more than 0 and less than or equal to 14.
As an alternative example of the embodiment of the present application, fe a Ni b Co c P d The atom percentage of Co is more than or equal to 2 and less than or equal to 8.
In a specific example of an embodiment of the present application, the composition of the cobalt-reinforced iron-nickel-based hard magnetic alloy is expressed as Fe 41 Ni 41 Co 2 P 16 . Specific experiments prove that in the embodiment of the application, the coercive force of the cobalt-reinforced iron-nickel-based hard magnetic alloy is 898.1Oe, and the saturation magnetization is 90.1emu/g.
In another specific example of an embodiment of the present application, the composition of the cobalt-strengthened iron-nickel-based hard magnetic alloy is expressed as Fe 40 Ni 40 Co 4 P 16 . Specific experiments prove that in the embodiment of the application, the coercive force of the cobalt-reinforced iron-nickel-based hard magnetic alloy is 1089.8Oe, and the saturation magnetization is 102.8emu/g.
Compared with cobalt-reinforced iron-nickel-based hard magnetic alloy without adding cobalt, the cobalt-reinforced iron-nickel-based hard magnetic alloy provided by the embodiment of the application has the advantages that the coercive force is obviously improved, the saturation magnetization is also obviously improved, the coercive force and the protection magnetization of the cobalt-reinforced iron-nickel-based hard magnetic alloy are improved, and the magnetic performance of the cobalt-reinforced iron-nickel-based hard magnetic alloy is improved.
The embodiment of the application also provides a preparation method of the cobalt-reinforced iron-nickel-based hard magnetic alloy, wherein the composition components of the cobalt-reinforced iron-nickel-based hard magnetic alloy are expressed as Fe a Ni b Co c P d The method comprises the steps of carrying out a first treatment on the surface of the Wherein a, b, c, d is atom percent; a is more than or equal to 36 and less than or equal to 42, b is more than or equal to 36 and less than or equal to 42,0, c is more than or equal to 14, and d is more than or equal to 14; the preparation method comprises the following steps:
step 401, mixing raw materials, and weighing and mixing raw materials corresponding to each element according to the composition components of the cobalt-reinforced iron-nickel-based hard magnetic alloy and the atomic percentage content of each element to obtain a master alloy raw material.
Specifically, in the embodiment of the present application, sources of the iron element, the nickel element, the cobalt element and the phosphorus element in the cobalt-reinforced iron-nickel-based hard magnetic alloy may refer to the detailed description of the foregoing embodiment, which is not repeated in the embodiment of the present application.
Step 402, smelting, namely placing a master alloy raw material into a crucible, and smelting for 15-20min at 1100-1250 ℃ under the protection of inert gas to obtain a master alloy with uniform dispersion.
The inert gas may be any one of argon, xenon or helium. In the embodiment of the application, the smelting temperature can be 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ or the like. The smelting time can be 15min, 17min or 20min respectively. As an alternative example, it may be that the higher the smelting temperature, the shorter the smelting time is relatively, and thus, or the more dispersed master alloy.
It should be noted that the numerical values and numerical ranges related to the present application are experimental values, and may have a certain range of errors under the influence of the manufacturing process, and those errors may be considered to be negligible by those skilled in the art.
As a specific example of an embodiment of the present application, wherein,the crucible can be an alumina ceramic crucible, and specifically, a high-frequency induction smelting furnace can be adopted to smelt the mixed raw materials. In the specific preparation process, the mixed raw materials can be placed into an alumina crucible, and vacuum is pumped by a mechanical pump or a vacuum pump in advance to ensure that the vacuum pressure is minus 0.1Mpa, and then the mixed raw materials are pumped by a vacuum molecular pump to 1.0X10 -3 Pa (vacuum compounding total reading) is filled with argon of 0.5atm as shielding gas, smelting is carried out for 15-20min at 1100-1250 ℃, heating is stopped, and when the alloy is naturally cooled to 200 ℃, master alloy with uniform composition is obtained.
And step 403, heating and melting the master alloy into a liquid state by adopting a melt rapid quenching system, and cooling by adopting the rapid quenching system to obtain the FeNi-based amorphous alloy.
In a specific example of the embodiment of the application, a single-roll melt-spinning method can be adopted to prepare the master alloy ingot into an amorphous thin strip, wherein the diameter of a copper roll is 55mm, the rotating speed is 4000 rpm, and the linear speed in the experiment is controlled to be more than 45 m/s.
Specifically, the master alloy which is uniformly mixed can be sheared into small blocks with the particle size smaller than 10mm, about 4g of alloy fragments are taken and put into a quartz tube with the inner diameter of a tip mouth at the bottom end of 10mm (the diameter of a round hole of the tip mouth is 0.5 mm), the alloy fragments are fully melted through induction heating, molten liquid after melting is sprayed onto the surface of a copper roller which rotates at a high speed, and the strip-shaped iron-nickel-based amorphous alloy is obtained, wherein the melting temperature is 1150 ℃, the spraying pressure is 0.07MPa, and the thickness of the obtained strip is about 10-20 mu m.
And 404, annealing the amorphous alloy at 380-400 ℃ for 0.5-2 hours to obtain the cobalt-reinforced iron-nickel-based hard magnetic alloy.
The preparation method of the cobalt-reinforced iron-nickel-based hard magnetic alloy provided by the embodiment of the application is described in detail below with reference to two specific embodiments.
Example 1
S1, weighing 11.28g of raw material pure nickel, 0.67 g of pure cobalt and 0.67 g of iron phosphide (Fe 3 P) 15.33g, nickel phosphide (Ni 3 P) 2.72g, 30g total, ready for use:
s2, adopting a high-frequency induction smelting furnace, and putting the raw materials weighed in the S1 into Al 2 O 3 The crucible is evacuated to-0.1 MPa by a mechanical pump in advance, and then evacuated to 1.0X10 by a vacuum molecular pump -3 Pa (vacuum compounding total reading) is filled with argon of 0.5atm as shielding gas, smelting is carried out for 15-20min at 1100-1250 ℃, heating is stopped, and when the alloy is naturally cooled to 200 ℃, master alloy with uniform composition is obtained.
S3, preparing the master alloy ingot into an amorphous ribbon by adopting a single-roller melt-spinning method, wherein the diameter of a copper roller is 55mm, the rotating speed is 4000 rpm, and the linear speed in the experiment is controlled to be more than 45 m/S. Cutting the Fe-Ni-Co-P master alloy ingot obtained in the step S2 into small blocks with the particle size smaller than 10mm, taking about 4g of alloy fragments, putting the alloy fragments into a quartz tube with the inner diameter of a 10mm bottom tip (the diameter of a tip round hole is 0.5 mm), fully melting the alloy fragments through induction heating, and spraying melted solution onto the surface of a copper roller rotating at a high speed to obtain the strip-shaped Fe-Ni-based amorphous alloy, wherein the melting temperature is 1150 ℃, the spraying pressure is 0.07MPa, and the thickness of the obtained strip is about 10-20 mu m.
S4, placing the amorphous strip prepared in the step S3 into a quartz test tube, vacuumizing by adopting a tube sealing system, and introducing argon gas to perform tube sealing treatment. And (3) annealing the amorphous strip by utilizing a muffle furnace, wherein the heating speed is 10 ℃/min, the heat preservation temperature is 400 ℃, and the annealing is carried out for 1h. The annealed strips were polycrystalline alloys and the specific XRD patterns are shown in figure 2. Finally obtaining amorphous alloy, namely the cobalt-reinforced Fe-Ni-based hard magnetic alloy is Fe 41 Ni 41 Co 2 P 16 。
Example 2, example 3, example 4
The procedure for the preparation of example 2, example 3 and example 4 differs from that of example 1 in that:
example 2
S1, weighing 10.60g of raw material pure nickel, 1.33 g of pure cobalt and 1.33 g of iron phosphide (Fe 3 P) 14.95g, nickel phosphide (Ni 3 P) 3.12g, 30g total, for standby:
example 3
S1, weighing 9.27g of raw material pure nickel, 2.66 of pure cobalt and 2.66 of iron phosphide (Fe 3 P) 14.18g, nickel phosphide (Ni 3 P) 3.89g, 30g total, ready for use:
the other preparation conditions were the same.
To prove the influence of cobalt element added into the cobalt-reinforced iron-nickel-based hard magnetic alloy provided by the embodiment of the application on the magnetic performance of the iron-nickel gene material, two groups of comparative examples are also provided in the embodiment of the application, and the specific steps are as follows:
comparative example 1
Comparative example 1 is different from the foregoing example 2 in that the element added in comparative example 1 is Si element, and the remaining content and preparation conditions are the same, and the finally obtained cobalt-reinforced iron-nickel-based hard magnetic alloy can be expressed as: fe (Fe) 40 Ni 40 Si 4 P 16 。
Comparative example 2
Comparative example 2 is different from the foregoing example 2 in that no Co element is added in comparative example 2, and the remaining content and preparation conditions are the same, and the finally obtained cobalt-reinforced iron-nickel-based hard magnetic alloy can be expressed as: fe (Fe) 42 Ni 42 P 16 。
In addition, in order to study the influence of heat treatment on the coercive force of cobalt-reinforced iron-nickel-based hard magnetic alloy, comparative example 3 and comparative example 4 were also made in examples of the present application.
Comparative example 3
The same as in example 1, except that the amorphous alloy Fe obtained in S3 was 41 Ni 41 Co 2 P 16 Obtaining Fe of Fe-Ni based amorphous material without annealing treatment 41 Ni 41 Co 2 P 16 。
Comparative example 4
The same as in example 2, except that the amorphous alloy Fe obtained via S3 40 Ni 40 Co 4 P 16 Obtaining Fe of Fe-Ni based amorphous material without annealing treatment 40 Ni 40 Co 4 P 16 。
Comparative example 5
The same as in example 3, except that the amorphous alloy Fe obtained via S3 38 Ni 38 Co 8 P 16 Obtaining Fe of Fe-Ni based amorphous material without annealing treatment 38 Ni 38 Co 8 P 16 。
The magnetic properties of the products obtained by comparative examples 1, 2, 3, 4 and 5 are shown in Table 1 with reference to Table 1, table 1 being Fe 41 Ni 41 Co 2 P 16 、Fe 40 Ni 40 Co 4 P 16 、Fe 38 Ni 38 Co 8 P 16 、Fe 40 Ni 40 Si 4 P 16 、Fe 42 Ni 42 P 16 Fe 41 Ni 41 Co 2 P 16 、Fe 40 Ni 40 Co 4 P 16 Fe (b) 38 Ni 38 Co 8 P 16 Magnetic properties of (a) are provided.
TABLE 1
As can be seen from Table 1, in the examples of the present application, example 1 (Fe 41 Ni 41 Co 2 P 16 ) The coercivity can reach 898.1Oe and the saturation magnetization can reach 90.1emu/g, example 2 (Fe 40 Ni 40 Co 4 P 16 ) The coercive force can reach 1089.8Oe, and the saturation magnetization can reach 102.8emu/g.
The comparison of the example 1 and the example 2 can be used for properly improving the mass fraction of cobalt in the iron-nickel-based hard magnetic alloy, and the prepared hard magnetic material has better performance. The addition of ferromagnetic Co in Fe-Ni based hard magnetic alloy is favorable for improving the overall magnetic performance of the alloy, and on the other hand, co element can be partially in clearance solution in L1 in the annealing process 0 Within the FeNi lattice, thus L1 0 The degree of disorder of the FeNi will be significantly increased, the entropy difference between the ordered disordered phases of FeNi will also be reduced, in other words L1 0 FeNi needs to be converted to A1-FeNi at a higher temperature to enable L1 during low temperature annealing 0 The formation capacity of FeNi is improved compared with A1-FeNi. From example 1 and comparative example 3, example 2 and comparative example 4, example 3 and comparative example 5 are comparableThe heat treatment has obvious effect on improving the coercivity of the strip, and the coercivity of the annealed strip is obviously higher than that of the amorphous strip, because the amorphous matrix is provided with a hard magnetic phase L1 in the annealing process of the amorphous strip 0 The precipitation of FeNi is also evident in the XRD pattern of the annealed strip.
FIG. 3 is a diagram of Fe provided in example 3 38 Ni 38 Co 8 P 16 Transmission electron microscope spectrum of cobalt reinforced iron-nickel base hard magnetic alloy annealing band. Wherein, figure a is an electron microscope bright field image, figure b is a high resolution image of the marked crystal grain in the upper left region circular frame in figure a and a selected area diffraction pattern thereof, and inner and outer layer broken lines in the illustration of figure b respectively represent L1 0 The locations of the superlattice diffractions of FeNi (221) and (112). Due to superlattice diffraction to L1 in the system 0 The characteristic diffraction signal of the FeNi phase thus intuitively confirms Fe 38 Ni 38 Co 8 P 16 L1 in iron-nickel annealed strip 0 The presence of phases further illustrates Fe 38 Ni 38 Co 8 P 16 The iron-nickel annealed strip is in a polycrystalline form.
The foregoing is merely illustrative of the present application, and the present application is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (7)
1. A cobalt-reinforced Fe-Ni-based hard magnetic alloy is characterized in that the cobalt-reinforced Fe-Ni-based hard magnetic alloy consists of Fe, ni, co and P elements, and the composition of the cobalt-reinforced Fe-Ni-based hard magnetic alloy is expressed as Fe a Ni b Co c P d The Fe is a Ni b Co c P d Is a nanocrystalline-amorphous composite structure; wherein a, b, c, d is atom percent; a is more than or equal to 36 and less than or equal to 42, b is more than or equal to 36 and less than or equal to 42,2, c is more than or equal to 8, and d is more than or equal to 14; the preparation method of the cobalt-reinforced iron-nickel-based hard magnetic alloy comprises the following steps:
raw material mixing, namely weighing raw materials corresponding to each element according to the composition components of the cobalt-reinforced iron-nickel-based hard magnetic alloy and the atomic percentage content of each element, and carrying out batch mixing to obtain master alloy raw materials;
melting to obtain mother alloy with uniform components, remelting and quick quenching to obtain amorphous alloy; or, after fully mixing in the raw material smelting stage, directly and quickly quenching to obtain amorphous alloy;
and annealing the amorphous alloy at 380-400 ℃ for 0.5-2h to obtain the cobalt-reinforced iron-nickel-based hard magnetic alloy.
2. The cobalt-strengthened iron-nickel-based hard magnetic alloy according to claim 1, wherein the composition of the cobalt-strengthened iron-nickel-based hard magnetic alloy is expressed as Fe 41 Ni 41 Co 2 P 16 、Fe 40 Ni 40 Co 4 P 16 Or Fe 38 Ni 38 Co 8 P 16 。
3. A preparation method of cobalt-reinforced iron-nickel-based hard magnetic alloy is characterized in that the composition components of the cobalt-reinforced iron-nickel-based hard magnetic alloy are expressed as Fe a Ni b Co c P d The method comprises the steps of carrying out a first treatment on the surface of the Wherein a, b, c, d is atom percent; a is more than or equal to 36 and less than or equal to 42, b is more than or equal to 36 and less than or equal to 42,2, c is more than or equal to 8, and d is more than or equal to 14; the preparation method comprises the following steps:
raw material mixing, namely weighing raw materials corresponding to each element according to the composition components of the cobalt-reinforced iron-nickel-based hard magnetic alloy and the atomic percentage content of each element, and carrying out batch mixing to obtain master alloy raw materials;
melting to obtain mother alloy with uniform components, remelting and quick quenching to obtain amorphous alloy; or, after fully mixing in the raw material smelting stage, directly and quickly quenching to obtain amorphous alloy;
and annealing the amorphous alloy at 380-400 ℃ for 0.5-2h to obtain the cobalt-reinforced iron-nickel-based hard magnetic alloy.
4. The method for producing a cobalt-reinforced iron-nickel-based hard magnetic alloy according to claim 3, wherein the melting treatment is performed in any one of an alumina crucible, a boron nitride crucible, and a graphite crucible.
5. The method for producing a cobalt-reinforced iron-nickel-based hard magnetic alloy according to claim 3, wherein the iron element in the raw material is derived from any one of pure iron, iron phosphide, a binary pre-alloy of Fe Co, a binary pre-alloy of Fe Ni, or a ternary pre-alloy of Fe Co Ni.
6. The method for producing a cobalt-reinforced iron-nickel-based hard magnetic alloy according to claim 3, wherein the nickel element in the raw material is derived from any one of nickel, nickel phosphide, a binary pre-alloy of Fe Ni, a binary pre-alloy of Co Ni, or a ternary pre-alloy of Fe Co Ni.
7. The method for producing a cobalt-reinforced iron-nickel-based hard magnetic alloy according to claim 3, wherein the cobalt element in the raw material is derived from any one of pure cobalt, cobalt phosphide, a binary pre-alloy of Fe Co, a binary pre-alloy of Co Ni, or a ternary pre-alloy of Fe Co Ni.
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| CN101692364A (en) * | 2009-10-12 | 2010-04-07 | 钢铁研究总院 | One-dimensional permanent magnetic nano-material, in which hard magnetic tubes are coated with soft magnetic wires and preparation method thereof |
| CN102280113A (en) * | 2011-05-11 | 2011-12-14 | 复旦大学 | Exchange coupling medium L10-FePt/[Co/Ni]N and preparation method thereof |
| CN107614715A (en) * | 2015-04-23 | 2018-01-19 | 国立大学法人东北大学 | Contain L10The iron-nickel alloy constituent of sections nickel rule phase, contain L10The manufacture method of the iron-nickel alloy constituent of sections nickel rule phase, the iron-nickel alloy constituent using amorphous as principal phase, the foundry alloy of amorphous material, amorphous material, the manufacture method of magnetic material and magnetic material |
| CN113025912A (en) * | 2021-03-01 | 2021-06-25 | 西北工业大学重庆科创中心 | Iron-nickel-based hard magnetic material and preparation method thereof |
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| CN101692364A (en) * | 2009-10-12 | 2010-04-07 | 钢铁研究总院 | One-dimensional permanent magnetic nano-material, in which hard magnetic tubes are coated with soft magnetic wires and preparation method thereof |
| CN102280113A (en) * | 2011-05-11 | 2011-12-14 | 复旦大学 | Exchange coupling medium L10-FePt/[Co/Ni]N and preparation method thereof |
| CN107614715A (en) * | 2015-04-23 | 2018-01-19 | 国立大学法人东北大学 | Contain L10The iron-nickel alloy constituent of sections nickel rule phase, contain L10The manufacture method of the iron-nickel alloy constituent of sections nickel rule phase, the iron-nickel alloy constituent using amorphous as principal phase, the foundry alloy of amorphous material, amorphous material, the manufacture method of magnetic material and magnetic material |
| CN113025912A (en) * | 2021-03-01 | 2021-06-25 | 西北工业大学重庆科创中心 | Iron-nickel-based hard magnetic material and preparation method thereof |
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