CN115637394A - 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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- 229910001004 magnetic alloy Inorganic materials 0.000 title claims abstract description 88
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 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 82
- 229910045601 alloy Inorganic materials 0.000 claims description 30
- 239000000956 alloy Substances 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 18
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 16
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000003723 Smelting Methods 0.000 claims description 11
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 7
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
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- 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
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 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
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- 238000010438 heat treatment Methods 0.000 abstract description 14
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- 230000000052 comparative effect Effects 0.000 description 22
- 229910002555 FeNi Inorganic materials 0.000 description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
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- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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Abstract
The application provides a cobalt-strengthened iron-nickel-based hard magnetic alloy and a preparation method thereof, wherein the cobalt-strengthened iron-nickel-based hard magnetic alloy consists of Fe, ni, co and P elements, and the composition component of the cobalt-strengthened iron-nickel-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 and d are atom percentage content respectively; 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, c is more than 0 and less than or equal to 14, and d is more than or equal to 14. According to the cobalt-strengthened iron-nickel-based hard magnetic alloy and the preparation method thereof, the heat treatment temperature of the cobalt-strengthened iron-nickel-based hard magnetic alloy is raised, and the cobalt-strengthened iron-nickel-based hard magnetic alloy is ensured to be in an ordered crystalline state at a higher temperature, so that the cobalt-strengthened iron-nickel-based hard magnetic alloy can be conveniently and manually prepared; in addition, cobalt strengthening can be improvedThe coercive force and the magnetic flux density of the iron-nickel-based hard magnetic alloy improve the magnetic performance of the cobalt-strengthened iron-nickel-based hard magnetic alloy.
Description
Technical Field
The application belongs to the technical field of magnetic materials, and particularly relates to a cobalt-strengthened iron-nickel-based hard magnetic alloy and a preparation method thereof.
Background
In recent years, with the popularization of concepts of green environmental protection and sustainable development, the development of new energy vehicles, wireless charging and other technologies is receiving wide social attention. Among them, a hard magnetic alloy, which is one of the key support materials of electronic components, has a wide application prospect because of having high saturation magnetization and high coercive force. At present, the comprehensive magnetic performance of the rare earth hard magnetic materials in the hard magnetic materials is higher than that of the other hard magnetic materials. However, since rare earth is one of strategic resources, it is not only expensive, but also not beneficial to environmental protection, which severely restricts the continuous development of hard magnetic materials.
In the related art, L1 in the iron-nickel based hard magnetic alloy 0 the-FeNi phase hard magnetic phase provides the alloy with hard magnetic performance, the theoretical magnetic energy product of the alloy is as high as 42MGOe, and the alloy can be compared with Nd-Fe-B.
However, in the preparation of L1 0 When the FeNi phase hard magnetic alloy is adopted, the transition temperature of the FeNi phase is lower, and the diffusion speed is lower; in addition, when FeNi is subjected to heat treatment at a high temperature, only a disordered A1-FeNi soft magnetic phase can be obtained, and the artificial preparation of the FeNi-based hard magnetic alloy is difficult to realize.
Disclosure of Invention
The application provides a cobalt-strengthened iron-nickel-based hard magnetic alloy and a preparation method thereof, which can improve the heat treatment temperature of the cobalt-strengthened iron-nickel-based hard magnetic alloy when preparing the cobalt-strengthened iron-nickel-based hard magnetic alloy, and ensure that the cobalt-strengthened iron-nickel-based hard magnetic alloy is in an ordered crystalline state at a higher temperature, thereby facilitating the manual preparation of the cobalt-strengthened 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 the embodiments of the present application, there is provided a cobalt-strengthened iron-nickel-based hard magnetic alloy, the cobalt-strengthened iron-nickel-based hard magnetic alloy being composed of Fe, ni, co and P elements, and the composition of the cobalt-strengthened 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 percentage content respectively; 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, c is more than 0 and less than or equal to 14, and d is more than or equal to 14.
In an alternative embodiment, fe a Ni b Co c P d The atomic percentage content of the Co in the alloy is that c is more than or equal to 2 and less than or equal to 8.
In an alternative design, the cobalt-strengthened Fe-Ni-based hard magnetic alloy has a composition 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 embodiments of the present application, there is provided a method for preparing a cobalt-strengthened iron-nickel-based hard magnetic alloy, the composition of which is expressed as Fe a Ni b Co c P d (ii) a Wherein a, b, c and d are atom percentage content respectively; 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, c is more than 0 and less than or equal to 14, and d is more than or equal to 14; the preparation method comprises the following steps:
mixing raw materials, namely weighing raw materials corresponding to elements according to the composition components of the cobalt-reinforced iron-nickel-based hard magnetic alloy and the atomic percentage content of each element, and mixing the raw materials to obtain a master alloy raw material;
smelting to obtain mother alloy with uniform components, remelting and rapidly quenching to obtain amorphous alloy; or, after the raw materials are fully mixed in the smelting stage, the raw materials are directly rapidly quenched to obtain amorphous alloy;
and annealing the amorphous alloy at 380-400 ℃ for 0.5-2h to obtain the cobalt-reinforced Fe-Ni-based hard magnetic alloy.
In an alternative embodiment, the melting process is carried out in any 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 any one of pure iron, iron phosphide or binary or ternary prealloy 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 mode, the cobalt element in the raw material is derived from pure cobalt, cobalt phosphide or binary or ternary prealloy of 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 is 0-14, and the atomic percentage of phosphorus is more than or equal to 14; therefore, in the process of manually preparing the cobalt-strengthened iron-nickel-based hard magnetic alloy, two elements of cobalt and phosphorus can influence the preparation process, the heat treatment temperature of the cobalt-strengthened iron-nickel-based hard magnetic alloy in the preparation process can be increased, the cobalt-strengthened iron-nickel-based hard magnetic alloy is ensured to be in an ordered crystalline state at a higher treatment temperature, and the manual preparation of the cobalt-strengthened iron-nickel-based hard magnetic alloy is facilitated. 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 in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a crystal phase structure diagram of a cobalt-strengthened Fe-Ni based hard magnetic alloy provided in an embodiment of the present application;
FIG. 2 is a graph of the amorphous state and post-annealing X-ray diffraction patterns of cobalt-strengthened Fe-Ni-based hard magnetic alloys provided in examples herein and cobalt-strengthened Fe-Ni-based hard magnetic alloys provided in comparative examples;
FIG. 3 is Fe provided in example 3 of the present application 38 Ni 38 Co 8 P 16 A transmission electron microscope atlas of the cobalt-reinforced iron-nickel-based hard magnetic alloy annealed strip;
fig. 4 is a flowchart of a process for preparing a cobalt-strengthened iron-nickel-based hard magnetic alloy according to an embodiment of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a cobalt-strengthened iron-nickel-based hard magnetic alloy, the cobalt-strengthened iron-nickel-based hard magnetic alloy consists of Fe, ni, co and P elements, and the composition component of the cobalt-strengthened iron-nickel-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 and d are atom percentage content respectively; 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, c is more than 0 and less than or equal to 14, and d is more than or equal to 14.
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 is 0-14, and the atomic percentage of phosphorus is greater than or equal to 14; therefore, in the process of manually preparing the cobalt-reinforced iron-nickel-based hard magnetic alloy, two elements of cobalt and phosphorus can influence the preparation process, the heat treatment temperature of the cobalt-reinforced iron-nickel-based hard magnetic alloy in the preparation process can be increased, the cobalt-reinforced iron-nickel-based hard magnetic alloy is ensured to be in an ordered crystalline state at a higher treatment temperature, and the manual preparation of the cobalt-reinforced iron-nickel-based hard magnetic alloy is facilitated. 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 chemically unnecessary soft FeNi (Co) phase obtained after heat treatment, and b in fig. 1 is an ordered hard FeNi (Co) phase. The addition of cobalt element can effectively improve the synthesis ratio of the ordered phase and improve the hard magnetic property (magnetocrystalline anisotropy energy) of the ordered phase. Thereby improving the hard magnetic performance of the material obtained by annealing, such as effectively improving the coercive force and residual magnetic coercive force of the annealed material.
In a specific implementation, the iron element in the cobalt-strengthened iron-nickel-based hard magnetic alloy provided by the embodiment of the present application may be derived from pure iron or iron phosphide, etc.
It should be noted that the pure iron referred to in the examples of the present application is generally a purity within the scope of those skilled in the art, for example, a raw material with an iron content of 99.9% and above. It will be appreciated that in some instances, such as in industrial production, relatively low iron content feedstocks may also be used in order to reduce costs. Additionally, in some examples, the iron element may also be derived from a binary prealloy of Fe, co, a binary prealloy of Fe, ni, or a ternary prealloy of Fe, co, ni, or the like.
It is understood that in the embodiment of the present application, the nickel element in the cobalt-strengthened iron-nickel-based hard magnetic alloy may be derived from pure nickel or nickel phosphide. 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 detailed description of the foregoing embodiments, it can be seen that, in the embodiments of the present application, the source of the Co element may be similar or similar to the iron element and the nickel element; for example, the Co element may be derived from a binary prealloy of pure cobalt, co, and Ni, or a binary prealloy of Fe and Co, or may be derived from a ternary prealloy of Fe, co, and Ni.
Wherein, the phosphorus element can be derived from raw materials such as pure phosphorus, iron phosphide or nickel phosphide and the like. Therefore, the occurrence of the condition of introducing impurities into the cobalt-strengthened iron-nickel-based hard magnetic alloy can be reduced, and the success rate of preparing the cobalt-strengthened iron-nickel-based hard magnetic alloy is ensured.
In an alternative example of the embodiments of the present application, fe a Ni b Co c P d Atomic percent of medium CoThe amount is more than 0 and less than or equal to 14.
As an alternative example of an embodiment of the present application, fe a Ni b Co c P d Wherein the atomic 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-strengthened iron-nickel based hard magnetic alloy is expressed as Fe 41 Ni 41 Co 2 P 16 . Through specific experimental detection, 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 the 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 . Through specific experimental detection, 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-strengthened iron-nickel-based hard magnetic alloy without adding cobalt element, the cobalt-strengthened 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 intensity is also obviously improved, the coercive force and the protective magnetization intensity of the cobalt-strengthened iron-nickel-based hard magnetic alloy are improved, and the magnetic performance of the cobalt-strengthened iron-nickel-based hard magnetic alloy is improved.
The embodiment of the application also provides a preparation method of the cobalt-strengthened iron-nickel-based hard magnetic alloy, and the composition component of the cobalt-strengthened iron-nickel-based hard magnetic alloy is expressed as Fe a Ni b Co c P d (ii) a Wherein a, b, c and d are atom percentage content respectively; 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, c is more than 0 and less than or equal to 14, and d is more than or equal to 14; the preparation method comprises the following steps:
Specifically, in the embodiment of the present application, the sources of the iron element, the nickel element, the cobalt element, and the phosphorus element in the cobalt-strengthened 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.
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 temperature of the melting, the shorter the time of melting, and thus the more uniformly dispersed master alloy.
It should be noted that the numerical values and numerical value ranges referred to in the present application are experimental values, and there may be a certain range of errors depending on the manufacturing process, and those skilled in the art may consider these errors to be negligible.
As a specific example of the embodiment of the present application, an alumina ceramic crucible may be used as the crucible, and specifically, a high-frequency induction melting furnace may be used to melt the mixed raw material. In the specific preparation process, the mixed raw materials can be put into an alumina crucible, a mechanical pump or a vacuum pump is utilized to carry out vacuum pumping in advance to ensure that the vacuum pressure is-0.1 Mpa, and then a molecular pump is utilized to carry out vacuum pumping to 1.0 multiplied by 10 -3 And (Pa (reading in vacuum complex) and then filling argon of 0.5atm as protective gas, smelting at 1100-1250 ℃ for 15-20min, stopping heating, and naturally cooling the alloy to 200 ℃ to obtain the master alloy with uniform components.
And 403, heating and melting the master alloy into a liquid state by adopting a melt rapid quenching system, and cooling by using the rapid quenching system to obtain the FeNi-based amorphous alloy.
In a specific example of the embodiment of the present application, a single-roll strip-spinning method may be adopted to make the master alloy ingot into an amorphous thin strip, wherein the diameter of the copper roll is 55mm, the rotation speed is 4000 rpm, and the experimental linear velocity is controlled to be above 45 meters per second.
Specifically, the uniformly mixed master alloy can be cut into small pieces with the particle size of less than 10mm, about 4g of the small pieces of the alloy are placed into a quartz tube with the inner diameter of 10mm and the bottom end of a sharp nozzle (the diameter of a round hole of the sharp nozzle is 0.5 mm), the small pieces of the alloy are sufficiently melted through induction heating, and melted liquid is sprayed onto the surface of a copper roller rotating at a high speed to obtain the strip-shaped iron-nickel-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 micrometers.
The following description will be made in detail with reference to two specific examples, in view of the method for preparing a cobalt-strengthened iron-nickel-based hard magnetic alloy provided in the embodiments of the present application.
Example 1
S1, weighing 11.28g of pure nickel, 0.67 g of pure cobalt and iron phosphide (Fe) 3 P) 15.33g, nickel phosphide (Ni) 3 P) 2.72g, 30g in total, for use:
s2, putting the raw materials weighed in the S1 into Al by adopting a high-frequency induction smelting furnace 2 O 3 The crucible is pre-pumped to-0.1 MPa by a mechanical pump and then pumped to 1.0 x 10 by a vacuum molecular pump -3 And (Pa (reading in vacuum complex) and then filling argon of 0.5atm as protective gas, smelting at 1100-1250 ℃ for 15-20min, stopping heating, and naturally cooling the alloy to 200 ℃ to obtain the master alloy with uniform components.
And S3, preparing the master alloy ingot into an amorphous thin strip by adopting a single-roller strip throwing method, wherein the diameter of a copper roller is 55mm, the rotating speed is 4000 revolutions per minute, and the wire speed in the experiment is controlled to be more than 45 meters per second. And (2) cutting the Fe-Ni-Co-P master alloy ingot obtained in the step (S2) into small blocks with the grain diameter of less than 10mm, putting about 4g of alloy fragments into a quartz tube with a tip nozzle (the diameter of a round hole of the tip nozzle is 0.5 mm) at the bottom end with the inner diameter of 10mm, fully melting the alloy fragments through induction heating, and spraying the molten liquid after melting 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.
And S4, placing the amorphous strip prepared in the S3 into a quartz test tube, vacuumizing by using a tube sealing system, introducing argon, and sealing the tube. Using muffle furnace to treat the aboveAnd annealing the crystal strip, wherein the heating rate is 10 ℃/min, the heat preservation temperature is 400 ℃, and the annealing is carried out for 1h. The annealing band is a polycrystalline alloy, and a specific XRD curve is shown in figure 2. Finally obtaining the amorphous alloy, namely the cobalt-strengthened iron-nickel-based hard magnetic alloy is Fe 41 Ni 41 Co 2 P 16 。
Example 2, example 3, example 4
The preparation steps of example 2, example 3 and example 4 differ from example 1 in that:
example 2
S1, weighing raw materials of 10.60g of pure nickel, 1.33 of pure cobalt and Fe (Fe) 3 P) 14.95g, nickel phosphide (Ni) 3 P) 3.12g, 30g in total, for use:
example 3
S1, weighing 9.27g of pure nickel, 2.66 g of pure cobalt and iron phosphide (Fe) 3 P) 14.18g, nickel phosphide (Ni) 3 P) 3.89g, 30g in total, for use:
the other preparation conditions were the same.
In order to prove the influence of adding cobalt element into the cobalt-strengthened iron-nickel-based hard magnetic alloy provided by the embodiment of the application on the magnetic performance of the material, two groups of comparative examples are also made in the embodiment of the application, specifically 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 contents and preparation conditions are the same, and the finally obtained cobalt-strengthened iron-nickel-based hard magnetic alloy can be represented as: fe 40 Ni 40 Si 4 P 16 。
Comparative example 2
Comparative example 2 is different from the foregoing example 2 in that the Co element is not added in comparative example 2, and the remaining content and the preparation conditions are the same, and the finally obtained cobalt-strengthened iron-nickel-based hard magnetic alloy can be expressed as: fe 42 Ni 42 P 16 。
In addition, in order to study the influence of heat treatment on the coercivity of the cobalt-strengthened iron-nickel-based hard magnetic alloy, comparative example 3 and comparative example 4 were also made in the examples of the present application.
Comparative example 3
The same as in example 1, except that the amorphous alloy Fe obtained in S3 41 Ni 41 Co 2 P 16 Fe-Ni-based amorphous material Fe is obtained without annealing treatment 41 Ni 41 Co 2 P 16 。
Comparative example 4
The same as example 2, except that the amorphous alloy Fe obtained in S3 40 Ni 40 Co 4 P 16 Fe-Ni based amorphous material Fe is obtained without annealing treatment 40 Ni 40 Co 4 P 16 。
Comparative example 5
Same as example 3, except that the amorphous alloy Fe obtained in S3 38 Ni 38 Co 8 P 16 Fe-Ni based amorphous material Fe is obtained without annealing treatment 38 Ni 38 Co 8 P 16 。
The magnetic properties of the products obtained by comparative example 1, example 2, example 3, comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5 are shown with reference to table 1, where table 1 is 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 And Fe 38 Ni 38 Co 8 P 16 The magnetic property table of (1).
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 coercive force can reach 898.1Oe, the saturation magnetization can reach 90.1emu/g, wherein the coercive force is shown in 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.
Compared with the example 1 and the example 2, the mass fraction of cobalt in the iron-nickel-based hard magnetic alloy is properly increased, and the performance of the prepared hard magnetic material is better. The addition of the strong magnetic Co in the iron-nickel-based hard magnetic alloy is beneficial to the improvement of the overall magnetic performance of the alloy on one hand, and on the other hand, the Co element can be partially dissolved in L1 in a gap solid solution in the annealing process 0 Within the FeNi lattice, thus L1 0 The disorder degree of FeNi is obviously improved, and the entropy difference between FeNi ordered and disordered phases is reduced, in other words, L1 0 FeNi needs to be converted to A1-FeNi at a higher temperature so that L1 is formed during low temperature annealing 0 The forming ability of-FeNi is improved compared with A1-FeNi. Compared with the example 1 and the comparative example 3, the example 2 and the comparative example 4, and the example 3 and the comparative example 5, the heat treatment has obvious effect on improving the coercive force of the strip, and the coercive force of the annealing strip is obviously higher than that of the amorphous strip because the hard magnetic phase L1 exists on the amorphous matrix in the annealing process of the amorphous strip 0 The precipitation of FeNi, and the existence of FeNi phase in the XRD pattern of the annealing band can be obviously observed.
FIG. 3 is Fe as provided in example 3 38 Ni 38 Co 8 P 16 And (3) a transmission electron microscope atlas of the cobalt-reinforced iron-nickel-based hard magnetic alloy annealing strip. Wherein, the picture a is electron microscope bright field image, the picture b is high resolution image and its selective area diffraction pattern of marked crystal grain in the upper left area circle frame in the picture a, the inner and outer layer dotted lines in the picture b respectively represent L1 0 -the positions of the FeNi (221) and (112) superlattices diffraction. Due to the fact that the diffraction of the superlattice in the system is L1 0 Characteristic diffraction signal of the FeNi phase, thus visually confirming Fe 38 Ni 38 Co 8 P 16 L1 in iron-nickel annealing strip 0 Existence of phase, further elucidating Fe 38 Ni 38 Co 8 P 16 The iron-nickel annealed strip is in a polycrystalline form.
The above description is only for the specific embodiments of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present application, and shall be covered by 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 (8)
1. The cobalt-strengthened iron-nickel-based hard magnetic alloy is characterized by consisting of Fe, ni, co and P elements, and the composition component of the cobalt-strengthened iron-nickel-based hard magnetic alloy is expressed as Fe a Ni b Co c P d Said Fe a Ni b Co c P d Is a nanocrystalline-amorphous composite structure; wherein a, b, c and d are atom percentage content respectively; 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, c is more than 0 and less than or equal to 14, and d is more than or equal to 14.
2. The cobalt-strengthened Fe-Ni-based hard magnetic alloy as claimed in claim 1, wherein Fe is Fe a Ni b Co c P d The atomic percentage content of the Co in the alloy is that c is more than or equal to 2 and less than or equal to 8.
3. The cobalt-strengthened Fe-Ni-based hard magnetic alloy as claimed in claim 1 or 2, wherein the composition of the Co-strengthened Fe-Ni-based hard magnetic alloy is 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 。
4. The preparation method of the cobalt-strengthened Fe-Ni-based hard magnetic alloy is characterized in that the composition component of the cobalt-strengthened Fe-Ni-based hard magnetic alloy is expressed as Fe a Ni b Co c P d (ii) a Wherein a, b, c and d are atom percentage content respectively; 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, c is more than or equal to 0 and less than or equal to 14, and d is more than or equal to 14; the preparation method comprises the following steps:
mixing raw materials, namely weighing raw materials corresponding to each element according to the composition of the cobalt-reinforced iron-nickel-based hard magnetic alloy and the atomic percentage content of each element, and mixing the raw materials to obtain a master alloy raw material;
smelting to obtain a mother alloy with uniform components, and then remelting and rapidly quenching to obtain an amorphous alloy; or, after the raw materials are fully mixed in the smelting stage, the raw materials are directly rapidly quenched 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.
5. The method of claim 4, wherein the melting process is performed in any one of an alumina crucible, a boron nitride crucible, or a graphite crucible.
6. The method of claim 4, wherein the iron element in the raw material is selected from pure iron, iron phosphide, or binary or ternary prealloy of Fe, co, and Ni.
7. The method of claim 4, wherein the nickel element in the raw material is derived from nickel, nickel phosphide or Fe, co, ni medium binary or ternary prealloy.
8. The method for preparing the cobalt-strengthened Fe-Ni-based hard magnetic alloy as claimed in claim 4, wherein the Co element in the raw material is derived from pure Co, cobalt phosphide or Fe, co, ni medium binary or ternary prealloy.
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