CN117884622A - Soft magnetic high-entropy amorphous nanocrystalline powder and preparation method thereof - Google Patents
Soft magnetic high-entropy amorphous nanocrystalline powder and preparation method thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 74
- 239000010935 stainless steel Substances 0.000 claims description 56
- 229910001220 stainless steel Inorganic materials 0.000 claims description 56
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 239000010949 copper Substances 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 28
- 230000008018 melting Effects 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 229910000831 Steel Inorganic materials 0.000 claims description 21
- 239000010959 steel Substances 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
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- 229910000592 Ferroniobium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- ZFGFKQDDQUAJQP-UHFFFAOYSA-N iron niobium Chemical compound [Fe].[Fe].[Nb] ZFGFKQDDQUAJQP-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010703 silicon Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
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- MTRJKZUDDJZTLA-UHFFFAOYSA-N iron yttrium Chemical compound [Fe].[Y] MTRJKZUDDJZTLA-UHFFFAOYSA-N 0.000 claims description 2
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 2
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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
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Abstract
The invention belongs to the technical field of magnetic materials, and discloses soft magnetic high-entropy amorphous nanocrystalline powder and a preparation method thereof, wherein the chemical expression is Fe 100‑a‑b‑c‑x‑y‑zBaNbbPcSixYyGdz, a is more than or equal to 7 and less than or equal to 9, b is more than or equal to 4 and less than or equal to 6, c is more than or equal to 3 and less than or equal to 5, x is more than or equal to 1 and less than or equal to 3,0.4, y is more than or equal to 0.6,0.4 and z is more than or equal to 0.6. The invention takes the traditional FePBNb amorphous alloy as the basis, improves the amorphous forming capability and soft magnetism of the design alloy by adding Si element and rare earth element Y, gd, prepares the design alloy into alloy strips by using a melt rapid quenching method, and prepares the alloy strips into the amorphous nanocrystalline powder by using a dry grinding and wet grinding two-step ball milling method.
Description
Technical Field
The invention belongs to the technical field of magnetic materials, and particularly relates to soft magnetic high-entropy amorphous nanocrystalline powder and a preparation method thereof.
Background
In recent years, there has been an increasing demand for inductors used in internet of things devices and automobiles. In particular, the inductor needs to exhibit excellent dc bias characteristics corresponding to high-current high-power integrated circuits. Furthermore, metallic magnetic materials have long been used to prepare inductors in place of oxide-based magnetic materials, such as ferrite.
At present, iron-based soft magnetic materials are widely used as magnetic core materials in inductors, and iron-based magnetic materials as inductive magnetic cores are classified into crystal structures and unbalanced structures according to their respective microstructures. Representative metallic soft magnetic materials having a crystal structure are Fe-Si, fe-Ni and Fe-Si-Al alloys. On the other hand, feSiB type amorphous alloy, fePBNb type amorphous metal alloy, feNbB type nanocrystalline alloy and FeSiBPCu type nanocrystalline alloy are metal soft magnetic materials with unbalanced structures. In summary, in the iron-based soft magnetic material, the iron-based nanocrystalline alloy with high boron and low carbon is promising. However, since most iron-based nanocrystalline alloys have low amorphous forming ability, it is difficult to powder the iron-based amorphous nanocrystalline alloys having an iron content of 75% or more. Therefore, only a few iron-based amorphous nanocrystalline powders, such as Fe 73.5Si13.5B9Nb3Cu1 iron-based amorphous nanocrystalline powder with B s (magnetic induction) of 1.22T, are commercialized in the market at present.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides soft magnetic high-entropy amorphous nanocrystalline powder and a preparation method thereof, so as to fill the blank of single type of iron-based amorphous nanocrystalline powder with high iron content in the current market. The invention is based on the traditional FePBNb amorphous alloy, improves the amorphous forming capability and soft magnetism of the design alloy by adding Si element and rare earth element Y, gd, prepares the design alloy into an alloy strip by using a melt rapid quenching method, and prepares the alloy strip into the amorphous nanocrystalline powder by using a dry grinding and wet grinding two-step ball milling method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides soft magnetic high-entropy amorphous nanocrystalline powder, wherein the chemical expression of the amorphous nanocrystalline powder is Fe 100-a-b-c-x-y-zBaNbbPcSixYyGdz, a, b, c, x, y, z respectively represents the atomic mass percentage content of corresponding components, wherein a is more than or equal to 7 and less than or equal to 9, b is more than or equal to 4 and less than or equal to 6, c is more than or equal to 3 and less than or equal to 5, x is more than or equal to 1 and less than or equal to 3,0.4, y is more than or equal to 0.6,0.4 and z is less than or equal to 0.6.
Preferably, the raw materials of the amorphous nanocrystalline powder comprise pure iron, pure silicon, ferroboron, ferroniobium, ferric phosphide, yttrium iron and gadolinium iron, wherein Fe in the pure iron is more than 99.9%, si in the pure silicon is more than 99.9%, nb in the ferroniobium is 64.8%, si 1.9%, nb+Si+Fe is more than 99.5%, B17.73%, B+Fe is more than 99.5%, Y64.15%, Y+Fe is more than 99.8%, gd 73% and Gd+Fe is more than 99.9%.
Preferably, the preparation method of the soft magnetic high-entropy amorphous nanocrystalline powder specifically comprises the following steps:
s1, uniformly smelting raw materials forming amorphous nanocrystalline powder by using a vacuum arc smelting furnace, and cooling to obtain a design alloy;
S2, crushing the design alloy obtained in the step S1 into small alloy blocks, and rapidly cooling the small alloy blocks after melting by using a single-roller melt-spinning method to obtain alloy strips;
S3, placing the alloy strips obtained in the step S2 into a stainless steel ball ink tank containing a large stainless steel ball and a small stainless steel ball, carrying out dry grinding under the protection of argon, adding isopropanol to carry out wet grinding when the mutual adhesion phenomenon occurs between the alloy strips, taking out and drying to obtain amorphous nanocrystalline powder.
Preferably, in step S1, the method specifically includes the following steps:
S1.1, placing 16-18 g raw materials into a copper crucible in a vacuum arc melting furnace;
s1.2, vacuumizing a vacuum arc melting furnace to 1.5 Pa by using a mechanical pump, and vacuumizing the vacuum arc melting furnace to 6 x 10 -3 Pa by using a diffusion pump;
s1.3, electrifying and feeding a current of 6A, continuously smelting for 20S after the raw materials in the copper crucible are completely melted, and then powering off and cooling;
S1.4, repeating the process of the step S1.3 for 4 times to ensure that the raw materials are uniformly smelted, and cooling to obtain the designed alloy.
Preferably, in step S2, the single-roll melt-spinning method uses a single-roll melt-spinning machine, where the single-roll melt-spinning machine is composed of an induction coil, a quartz tube and a copper roll, the induction coil is connected with the quartz tube, and the quartz tube is connected with the copper roll.
Preferably, in step S2, the method specifically includes the following steps:
S2.1, taking design alloy 13-15 g, crushing the design alloy into small alloy blocks of 2-3 g, and putting the small alloy blocks into a quartz tube;
s2.2, vacuumizing and heating until small alloy blocks in the quartz tube are completely melted into molten steel, and continuously refining 5-7 min of molten steel in the quartz tube;
S2.3, injecting argon into the quartz tube, leaking molten steel from the bottom of the quartz tube, and rapidly cooling after contacting a copper roller with the rotation linear speed of 28-30 m/S to obtain an alloy strip.
Preferably, in step S3, the rotational speed of the stainless steel ball ink tank is 400 rpm, the ball milling time is 30-40 h, the ball milling time interval is 10 h, the diameter of the large stainless steel ball is 12 mm, the diameter of the small stainless steel ball is 8 mm, and the number ratio of the large stainless steel ball to the small stainless steel ball is 2:3.
Preferably, in step S3, the amount of isopropyl alcohol added is 50 ml and the wet milling time is 5 h.
The beneficial effects obtained by the invention are as follows: the chemical expression of the amorphous nanocrystalline powder is Fe 100-a-b-c-x-y-zBaNbbPcSixYyGdz, wherein a is more than or equal to 7 and less than or equal to 9, b is more than or equal to 4 and less than or equal to 6, c is more than or equal to 3 and less than or equal to 5, x is more than or equal to 1 and less than or equal to 3,0.4, y is more than or equal to 0.6,0.4 and z is more than or equal to 0.6, and the amorphous nanocrystalline powder is prepared by grinding a brand new design alloy.
The alloy is designed by adding Si element and rare earth element Y, gd on the basis of the traditional FePBNb type amorphous alloy. Due to the addition of Si element, compared with the traditional FePBNb type amorphous alloy (-54 kJ/mol Nb-B, -89.5 kJ/mol Nb-P), the alloy (-54 kJ/mol Nb-B, -89.5 kJ/mol Nb-P, -56 kJ/mol Nb-Si) of the invention shows strong interatomic network, and the amorphous forming capability of the alloy is greatly improved as an iron-based nanocrystalline alloy with high iron content. As the rare earth element Y, gd is added, the mismatching degree between Nb-Y and Nb-Gd atoms in the designed alloy is enhanced, so that the precipitation of amorphous phase in the designed alloy is promoted. In addition, the affinity of Y and Gd to O is far higher than that of iron and other elements, and the Y and Gd elements are added in the process of smelting the design alloy and react with O preferentially to take away impurities, inhibit the adverse effect of O, reduce heterogeneous nuclei and facilitate the improvement of the amorphous forming capacity of the design alloy and form stable amorphous states. Therefore, the amorphous forming capability of the iron-based nanocrystalline alloy with high iron content under the combined action of Si element and rare earth element Y, gd is greatly improved, the difficult problem of powdering the iron-based nanocrystalline alloy with high iron content is overcome, and the prepared amorphous nanocrystalline powder fills the blank of single type of the iron-based amorphous nanocrystalline powder with high iron content in the current market.
The invention uses a two-step ball milling method of melt rapid quenching and dry milling and wet milling to grind the design alloy into amorphous nanocrystalline powder. Because the amorphous forming capability is an important factor for determining the strength of soft magnetism, the amorphous nanocrystalline powder prepared from the alloy designed by the invention has excellent soft magnetism, and is particularly characterized in that the lowest coercive force H c can be kept between 0.33 and 0.35A/m, the highest magnetic induction intensity B s can reach between 1.45 and 1.47T, and the maximum magnetic conductivity um can reach between 850 and 870 k.
Drawings
FIG. 1 is an SEM image of amorphous nanocrystalline powder of example 1 (left) and comparative example 1 (right) of the present invention;
FIG. 2 is an XRD pattern of amorphous nanocrystalline powders according to examples 1 to 3 and comparative example 1 of the present invention;
FIG. 3 is a bar graph of the lowest coercivity H c of the amorphous nanocrystalline powders of examples 1-3 and comparative example 2 of the present invention;
FIG. 4 is a bar graph of the highest magnetic induction B s of the amorphous nanocrystalline powders of examples 1-3 and comparative example 2 of the present invention;
fig. 5 is a bar graph of maximum permeability um of amorphous nanocrystalline powders of examples 1-3 and comparative example 2 of the present invention.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the experimental materials used in the examples described below, unless otherwise specified, were purchased from commercial sources.
Example 1: the invention is based on the traditional FePBNb amorphous alloy, improves the amorphous forming capability and the soft magnetism of the design alloy by adding Si element and rare earth element Y, gd, prepares the design alloy into an alloy strip by using a melt rapid quenching method, and prepares the alloy strip into the amorphous nanocrystalline powder of the example 1 by using a dry grinding and wet grinding two-step ball milling method, wherein the chemical expression is Fe 84.2B7Nb4P3Si1Y0.4Gd0.4, and the specific steps are as follows:
S1, placing 16 g raw materials into a copper crucible in a vacuum arc melting furnace, vacuumizing the vacuum arc melting furnace to 1.5 Pa by using a mechanical pump, vacuumizing the vacuum arc melting furnace to 6 x 10 -3 Pa by using a diffusion pump, electrifying 6A current after vacuumizing is finished until the raw materials in the copper crucible are completely melted, continuously electrifying and melting 20S, powering off and cooling, and repeating the power transmission and power outage processes for 4 times to obtain the designed alloy;
S2, taking a design alloy 13 g, putting the design alloy 13 into a quartz tube, crushing the design alloy into small alloy blocks of 2 g, vacuumizing and heating until the small alloy blocks in the quartz tube are completely melted into molten steel, continuously refining molten steel 5min in the quartz tube, then injecting argon into the quartz tube, and enabling the molten steel to leak out from the bottom of the quartz tube, contact with a copper roller with the rotating speed of 28 m/S and be cooled to obtain an alloy strip;
S3, placing the alloy strip into a stainless steel ball ink tank containing a large stainless steel ball and a small stainless steel ball, wherein the rotating speed of the stainless steel ball ink tank is 400 rpm, the ball milling time is 30 h, the ball milling time interval is 10 h, the diameter of the large stainless steel ball is 12 mm, the diameter of the small stainless steel ball is 8 mm, and the number ratio of the large stainless steel ball to the small stainless steel ball is 2: and 3, carrying out dry grinding on the alloy strips under the protection of argon after the parameters are set, immediately adding 50 ml isopropanol when the mutual adhesion phenomenon occurs between the alloy strips in the dry grinding process, carrying out wet grinding 5h, and taking out and drying after the completion of the wet grinding to obtain the amorphous nanocrystalline powder in the embodiment 1.
Example 2: the invention is based on the traditional FePBNb amorphous alloy, improves the amorphous forming capability and the soft magnetism of the design alloy by adding Si element and rare earth element Y, gd, prepares the design alloy into an alloy strip by using a melt rapid quenching method, and prepares the alloy strip into the amorphous nanocrystalline powder of the example 2 by using a dry grinding and wet grinding two-step ball milling method, wherein the chemical expression is Fe 80B8Nb5P4Si2Y0.5Gd0.5, and the specific steps are as follows:
s1, placing 17 g raw materials into a copper crucible in a vacuum arc melting furnace, vacuumizing the vacuum arc melting furnace to 1.5 Pa by using a mechanical pump, vacuumizing the vacuum arc melting furnace to 6 x 10 -3 Pa by using a diffusion pump, electrifying 6A current after vacuumizing is finished until the raw materials in the copper crucible are completely melted, continuously electrifying and melting 20S, powering off and cooling, and repeating the power transmission and power outage processes for 4 times to obtain a designed alloy;
s2, taking a design alloy 14 g, crushing the design alloy 14 g into small alloy blocks of 2 g, putting the small alloy blocks into a quartz tube, vacuumizing and heating until the small alloy blocks in the quartz tube are completely melted into molten steel, continuously refining molten steel 6 min in the quartz tube, then injecting argon into the quartz tube, and enabling the molten steel to leak out from the bottom of the quartz tube, contact with a copper roller with the rotating speed of 29 m/S and be cooled to obtain an alloy strip;
s3, placing the alloy strip into a stainless steel ball ink tank containing a large stainless steel ball and a small stainless steel ball, wherein the rotating speed of the stainless steel ball ink tank is 400 rpm, the ball milling time is 35 h, the ball milling time interval is 10 h, the diameter of the large stainless steel ball is 12 mm, the diameter of the small stainless steel ball is 8 mm, and the number ratio of the large stainless steel ball to the small stainless steel ball is 2: and 3, carrying out dry grinding on the alloy strips under the protection of argon after the parameters are set, immediately adding 50 ml isopropanol when the mutual adhesion phenomenon occurs between the alloy strips in the dry grinding process, carrying out wet grinding 5h, and taking out and drying after the completion of the wet grinding to obtain the amorphous nanocrystalline powder in the embodiment 2.
Example 3: the invention is based on the traditional FePBNb amorphous alloy, improves the amorphous forming capability and the soft magnetism of the design alloy by adding Si element and rare earth element Y, gd, prepares the design alloy into an alloy strip by using a melt rapid quenching method, and prepares the alloy strip into the amorphous nanocrystalline powder of the example 3 by using a dry grinding and wet grinding two-step ball milling method, wherein the chemical expression is Fe 75.8B9Nb6P5Si3Y0.6Gd0.6, and the specific steps are as follows:
S1, placing 18 g raw materials into a copper crucible in a vacuum arc melting furnace, vacuumizing the vacuum arc melting furnace to 1.5 Pa by using a mechanical pump, vacuumizing the vacuum arc melting furnace to 6 x 10 -3 Pa by using a diffusion pump, electrifying 6A current after vacuumizing is finished until the raw materials in the copper crucible are completely melted, continuously electrifying and melting 20S, powering off and cooling, and repeating the power transmission and power outage processes for 4 times to obtain a designed alloy;
s2, taking a design alloy 15 g, crushing the design alloy 15 into small alloy blocks of 3 g, putting the small alloy blocks into a quartz tube, vacuumizing and heating until the small alloy blocks in the quartz tube are completely melted into molten steel, continuously refining molten steel 7 min in the quartz tube, then injecting argon into the quartz tube, and enabling the molten steel to leak out from the bottom of the quartz tube, contact with a copper roller with the rotating speed of 30 m/S and be cooled to obtain an alloy strip;
S3, placing the alloy strip into a stainless steel ball ink tank containing a large stainless steel ball and a small stainless steel ball, wherein the rotating speed of the stainless steel ball ink tank is 400 rpm, the ball milling time is 40 h, the ball milling time interval is 10 h, the diameter of the large stainless steel ball is 12 mm, the diameter of the small stainless steel ball is 8 mm, and the number ratio of the large stainless steel ball to the small stainless steel ball is 2: and 3, carrying out dry grinding on the alloy strips under the protection of argon after the parameters are set, immediately adding 50 ml isopropanol when the mutual adhesion phenomenon occurs between the alloy strips in the dry grinding process, carrying out wet grinding 5h, and taking out and drying after the completion of the wet grinding to obtain the amorphous nanocrystalline powder in the embodiment 3.
Comparative example 1: the difference between the comparative example and the examples 1-3 is that Si element and rare earth element Y, gd are not added in the designed alloy, and the designed alloy is ground into amorphous nanocrystalline powder of the comparative example 1 by using a melt rapid quenching and dry grinding and wet grinding two-step ball milling method on the basis, wherein the chemical expression is Fe 78P8B10Nb4, and the specific steps are as follows:
S1, placing 16 g raw materials into a copper crucible in a vacuum arc melting furnace, vacuumizing the vacuum arc melting furnace to 1.5 Pa by using a mechanical pump, vacuumizing the vacuum arc melting furnace to 6 x 10 -3 Pa by using a diffusion pump, electrifying 6A current after vacuumizing is finished until the raw materials in the copper crucible are completely melted, continuously electrifying and melting 20S, powering off and cooling, and repeating the power transmission and power outage processes for 4 times to obtain the designed alloy;
S2, taking a design alloy 13 g, putting the design alloy 13 into a quartz tube, crushing the design alloy into small alloy blocks of 2 g, vacuumizing and heating until the small alloy blocks in the quartz tube are completely melted into molten steel, continuously refining molten steel 5min in the quartz tube, then injecting argon into the quartz tube, and enabling the molten steel to leak out from the bottom of the quartz tube, contact with a copper roller with the rotating speed of 28 m/S and be cooled to obtain an alloy strip;
S3, placing the alloy strip into a stainless steel ball ink tank containing a large stainless steel ball and a small stainless steel ball, wherein the rotating speed of the stainless steel ball ink tank is 400 rpm, the ball milling time is 30 h, the ball milling time interval is 10 h, the diameter of the large stainless steel ball is 12 mm, the diameter of the small stainless steel ball is 8 mm, and the number ratio of the large stainless steel ball to the small stainless steel ball is 2: and 3, carrying out dry grinding on the alloy strips under the protection of argon after the parameters are set, immediately adding 50 ml isopropanol when the mutual adhesion phenomenon occurs between the alloy strips in the dry grinding process, carrying out wet grinding 5h, and taking out and drying after finishing to obtain the amorphous nanocrystalline powder in the comparative example 1.
Comparative example 2: the amorphous nanocrystalline powder of the comparative example is amorphous nanocrystalline powder Fe 73.5Si13.5B9Nb3Cu1 with high iron content in the current market, and differs from examples 1-3 in that no rare earth element Y, gd is added, and the specific steps are as follows:
s1, placing 17 g raw materials into a copper crucible in a vacuum arc melting furnace, vacuumizing the vacuum arc melting furnace to 1.5 Pa by using a mechanical pump, vacuumizing the vacuum arc melting furnace to 6 x 10 -3 Pa by using a diffusion pump, electrifying 6A current after vacuumizing is finished until the raw materials in the copper crucible are completely melted, continuously electrifying and melting 20S, powering off and cooling, and repeating the power transmission and power outage processes for 4 times to obtain a designed alloy;
s2, taking a design alloy 14 g, crushing the design alloy 14 g into small alloy blocks of 2 g, putting the small alloy blocks into a quartz tube, vacuumizing and heating until the small alloy blocks in the quartz tube are completely melted into molten steel, continuously refining molten steel 6 min in the quartz tube, then injecting argon into the quartz tube, and enabling the molten steel to leak out from the bottom of the quartz tube, contact with a copper roller with the rotating speed of 29 m/S and be cooled to obtain an alloy strip;
s3, placing the alloy strip into a stainless steel ball ink tank containing a large stainless steel ball and a small stainless steel ball, wherein the rotating speed of the stainless steel ball ink tank is 400 rpm, the ball milling time is 35 h, the ball milling time interval is 10 h, the diameter of the large stainless steel ball is 12 mm, the diameter of the small stainless steel ball is 8 mm, and the number ratio of the large stainless steel ball to the small stainless steel ball is 2: and 3, carrying out dry grinding on the alloy strips under the protection of argon after the parameters are set, immediately adding 50 ml isopropanol when the mutual adhesion phenomenon occurs between the alloy strips in the dry grinding process, carrying out wet grinding 5h, and taking out and drying after finishing to obtain the amorphous nanocrystalline powder in the comparative example 2.
Experimental example
1. In the invention, a Japanese JEOL-JSM-IT800 field emission scanning electron microscope is used for microscopic structure observation of amorphous nanocrystalline powder in the embodiment 1 and the comparative example 1, a small amount of powder is required to be mixed with phenolic resin before observation, the mixture is pressed into a cylindrical sample, and the end face is subjected to grinding and mechanical polishing and then is corroded by 4 wt percent of nitrate alcohol for 5min to be sent for detection.
2. According to the invention, the amorphous nanocrystalline powder is subjected to powder phase analysis by using a German Bruker D8 Discover type X-ray diffractometer in examples 1-3 and comparative example 1, a small amount of powder is required to be mixed with phenolic resin before analysis, the mixture is pressed into a cylindrical sample, the end face of the sample is subjected to grinding and mechanical polishing, then the sample can be sent for detection, the equipment working voltage is 400 kV, the scanning range is 10-110 degrees, and the test step length is 0.05/s.
3. The static soft magnetic properties of inventive examples 1-3 and comparative example 2 were tested using a hysteresis loop instrument to obtain H cBs and um values. Test conditions: hi=0.08A/m, hj=0.8A/m, hs=40A/m, turns ratio 5:2.
Analysis of results
Fig. 1 is an SEM image of amorphous nanocrystalline powder of example 1 (left) and comparative example 1 (right) according to the present invention, and it can be observed that amorphous nanocrystalline powder of comparative example 1 has low amorphous forming ability, and that the crystallization of -Fe phase can be clearly observed on the SEM image, whereas the SEM image of comparative example 1 shows a single amorphous phase without abnormal growth of -Fe phase, which means that amorphous nanocrystalline powder of example 1 has a great improvement in amorphous forming ability compared with conventional FePBNb type amorphous alloy, i.e., si element content is optimal between 1 and 3%.
Fig. 2 shows XRD patterns of amorphous nanocrystalline powders of examples 1 to 3 and comparative example 1 according to the present invention, it can be observed that the amorphous nanocrystalline powder of comparative example 1 exhibits a significant alpha-Fe phase crystallization peak around 45 , and when Si element and rare earth element Y, gd are added, the alpha-Fe phase crystallization peak in the amorphous nanocrystalline powders of examples 1 to 3 has a significant tendency to decrease, i.e., crystallization of the alpha-Fe phase is suppressed, indicating that the amorphous nanocrystalline powders of examples 1 to 3 have a significant improvement in amorphous forming ability, i.e., si element content is optimal between 1 and 3%, as compared with the conventional FePBNb type amorphous alloy.
FIG. 3 is a bar graph of the lowest coercivity H c of the amorphous nanocrystalline powders of examples 1-3 and comparative example 2 of the present invention, and it can be observed that the amorphous nanocrystalline powders of examples 1-3 with rare earth element Y, gd added have a lowest coercivity far lower than that of the amorphous nanocrystalline powder of Fe 73.5Si13.5B9Nb3Cu1, and excellent soft magnetic properties, i.e., the Y, gd element content is optimal between 0.4 and 0.6%.
Fig. 4 is a bar graph of the highest magnetic induction intensity B s of the amorphous nanocrystalline powders of examples 1 to 3 and comparative example 2 according to the present invention, and it can be observed that the amorphous nanocrystalline powders of examples 1 to 3, to which the rare earth element Y, gd is added, have higher highest magnetic induction intensity than the amorphous nanocrystalline powders of Fe 73.5Si13.5B9Nb3Cu1, and excellent soft magnetic properties, that is, the content of Y, gd element is optimal between 0.4 and 0.6%.
Fig. 5 is a bar graph of maximum magnetic permeability um of the amorphous nanocrystalline powders of examples 1 to 3 and comparative example 2 according to the present invention, and it can be observed that the amorphous nanocrystalline powders of examples 1 to 3 added with the rare earth element Y, gd have a higher maximum magnetic permeability than the amorphous nanocrystalline powder of Fe 73.5Si13.5B9Nb3Cu1, and have excellent soft magnetic properties, i.e., the content of Y, gd element is optimal between 0.4 and 0.6%.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (8)
1. A soft magnetic high-entropy amorphous nanocrystalline powder is characterized in that: the chemical expression of the amorphous nanocrystalline powder is Fe 100-a-b-c-x-y-zBaNbbPcSixYyGdz, a, b, c, x, y, z respectively represents the atomic mass percentage content of the corresponding components, wherein a is more than or equal to 7 and less than or equal to 9, b is more than or equal to 4 and less than or equal to 6, c is more than or equal to 3 and less than or equal to 5, x is more than or equal to 1 and less than or equal to 3,0.4, y is more than or equal to 0.6,0.4 and z is more than or equal to 0.6.
2. The method for preparing the soft magnetic high-entropy amorphous nanocrystalline powder according to claim 1, which is characterized in that: the amorphous nanocrystalline powder comprises pure iron, pure silicon, ferroboron, ferroniobium, ferric phosphide, yttrium iron and gadolinium iron, wherein Fe in the pure iron is more than 99.9%, si in the pure silicon is more than 99.9%, nb in the ferroniobium is 64.8%, si 1.9%, nb+Si+Fe is more than 99.5%, B17.73%, B+Fe is more than 99.5%, Y64.15%, Y+Fe is more than 99.8%, gd 73% and Gd+Fe is more than 99.9%.
3. A method for preparing the soft magnetic high-entropy amorphous nanocrystalline powder according to any one of claims 1 to 2, characterized in that: the method specifically comprises the following steps:
s1, uniformly smelting raw materials forming amorphous nanocrystalline powder by using a vacuum arc smelting furnace, and cooling to obtain a design alloy;
S2, crushing the design alloy obtained in the step S1 into small alloy blocks, and rapidly cooling the small alloy blocks after melting by using a single-roller melt-spinning method to obtain alloy strips;
S3, placing the alloy strips obtained in the step S2 into a stainless steel ball ink tank containing a large stainless steel ball and a small stainless steel ball, carrying out dry grinding under the protection of argon, adding isopropanol to carry out wet grinding when the mutual adhesion phenomenon occurs between the alloy strips, taking out and drying to obtain amorphous nanocrystalline powder.
4. The method for preparing soft magnetic high-entropy amorphous nanocrystalline powder according to claim 3, wherein: in step S1, the method specifically includes the following steps:
S1.1, placing 16-18 g raw materials into a copper crucible in a vacuum arc melting furnace;
S1.2, vacuumizing a vacuum arc melting furnace to 1.5 Pa by using a mechanical pump, and vacuumizing the vacuum arc melting furnace to 6 x 10 -3 Pa by using a diffusion pump;
s1.3, electrifying and feeding a current of 6A, continuously smelting for 20S after the raw materials in the copper crucible are completely melted, and then powering off and cooling;
S1.4, repeating the process of the step S1.3 for 4 times to ensure that the raw materials are uniformly smelted, and cooling to obtain the designed alloy.
5. The method for preparing soft magnetic high-entropy amorphous nanocrystalline powder according to claim 3, wherein: in step S2, the single-roller melt-spinning method uses a single-roller melt-spinning machine, wherein the single-roller melt-spinning machine consists of an induction coil, a quartz tube and a copper roller, the induction coil is connected with the quartz tube, and the quartz tube is connected with the copper roller.
6. The method for preparing soft magnetic high-entropy amorphous nanocrystalline powder according to claim 3, wherein: in step S2, the method specifically includes the following steps:
S2.1, taking design alloy 13-15 g, crushing the design alloy into small alloy blocks of 2-3 g, and putting the small alloy blocks into a quartz tube;
s2.2, vacuumizing and heating until small alloy blocks in the quartz tube are completely melted into molten steel, and continuously refining 5-7 min of molten steel in the quartz tube;
S2.3, injecting argon into the quartz tube, leaking molten steel from the bottom of the quartz tube, and rapidly cooling after contacting a copper roller with the rotation linear speed of 28-30 m/S to obtain an alloy strip.
7. The method for preparing soft magnetic high-entropy amorphous nanocrystalline powder according to claim 3, wherein: in the step S3, the rotating speed of the stainless steel ball ink tank is 400 rpm, the ball milling time is 30-40 h, the ball milling time interval is 10 h, the diameter of the large stainless steel ball is 12 mm, the diameter of the small stainless steel ball is 8mm, and the number ratio of the large stainless steel ball to the small stainless steel ball is 2:3.
8. The method for preparing soft magnetic high-entropy amorphous nanocrystalline powder according to claim 3, wherein: in step S3, the addition amount of isopropyl alcohol was 50 ml and the wet milling time was 5 h.
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