CN116313356A - Iron-based amorphous-nanocrystalline magnetically soft alloy, strip and preparation method thereof - Google Patents

Iron-based amorphous-nanocrystalline magnetically soft alloy, strip and preparation method thereof Download PDF

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CN116313356A
CN116313356A CN202310572678.6A CN202310572678A CN116313356A CN 116313356 A CN116313356 A CN 116313356A CN 202310572678 A CN202310572678 A CN 202310572678A CN 116313356 A CN116313356 A CN 116313356A
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iron
based amorphous
alloy
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nanocrystalline magnetically
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张广强
周少雄
李宗臻
张迁
宋苏
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Changzhou Chuangming Magnetic Material Technology Co ltd
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Abstract

The invention discloses an iron-based amorphous-nanocrystalline magnetically soft alloy, a strip and a preparation method thereof, wherein the atomic percentage of Fe in the iron-based amorphous-nanocrystalline magnetically soft alloy is 75-80, and the iron-based amorphous-nanocrystalline magnetically soft alloy consists of (Fe a Co b Si c B d P e C fg Cu h And unavoidable impurities, wherein a, b, c, d, e, f, g and h represent the atomic percentage of each corresponding constituent element, a+b+c+d+e+f=100, g+h=100, respectively. The alloy provided by the invention has the advantages of high saturation magnetic induction and other magnetic properties on the premise of meeting the strong amorphous forming capability required by single-roller rapid quenching for preparing wide strips. In addition, the alloy only contains a small amount of magnetic metal elements, is suitable for production by using industrial purity raw materials, has a simple preparation method, and has the advantage of low production cost.

Description

Iron-based amorphous-nanocrystalline magnetically soft alloy, strip and preparation method thereof
Technical Field
The invention belongs to the field of amorphous-nanocrystalline magnetically soft alloy in functional materials, and particularly relates to an iron-based amorphous-nanocrystalline magnetically soft alloy material with high saturation induction intensity.
Background
The Fe-based soft magnetic amorphous alloy gradually replaces the traditional soft magnetic silicon steel to be a novel transformer iron core material due to the excellent soft magnetic performance and energy-saving property of the Fe-based soft magnetic amorphous alloy, and also becomes an amorphous alloy material with the widest application range and highest value in the current amorphous alloy field. The iron-based amorphous alloy ribbon plays an important functional role in the amorphous iron core transformer, and greatly influences power transmission. The 21 st century is entered, the popularization and application of the high-efficiency energy-saving transformer are quickened, the energy resource utilization efficiency is improved, and the promotion of green low-carbon high-quality development is a long-term target and key challenge of device development, so that the soft magnetic performance of the magnetic material is required to be continuously improved.
The traditional commercial Fe-Si-B amorphous soft magnetic alloy has good comprehensive properties, including higher saturation magnetization (1.5-1.6T) and lower coercivity (< 10A/m). However, the lower iron content in the Fe-Si-B amorphous soft magnetic alloy makes the saturation magnetization of the Fe-Si-B amorphous soft magnetic alloy have a gap from that of the traditional silicon steel, and the improvement of the Fe content is difficult and limited due to the insufficient amorphous forming capability. The ideal Fe-based soft magnetic amorphous alloy has the following characteristics: the cost is low, and noble metal elements are not contained; higher amorphous forming ability; high saturation magnetization; a low coercivity; excellent mechanical properties including high tensile strength, fracture toughness, and the like; high resistivity; good corrosion resistance. However, due to the limitations of the current amorphous alloy preparation technology and Fe-based amorphous alloy composition, it is very difficult to develop Fe-based amorphous alloys having all of the above characteristics. On the one hand, increasing the saturation magnetization of Fe-based amorphous alloys generally requires increasing the iron content to ensure, but at the same time means that a decrease in the amorphous forming element content is often accompanied by a decrease in the amorphous forming ability; on the other hand, the coercivity of the soft magnetic amorphous alloy with specific components is reduced, the alloy is usually required to be subjected to relaxation or heat treatment, but the room-temperature brittleness of the alloy can be obviously increased along with the reduction of the free volume in an amorphous structure in the heat treatment process, and the normal service of the amorphous soft magnetic material can be influenced due to the excessively high brittleness.
Amorphous alloy is widely applied to the field of power electronics due to excellent soft magnetic performance, however, amorphous alloy is in a thermodynamically unstable state, has poor thermal stability, can be crystallized when used at a higher temperature, and is separated out to be large in size>20 nm) grains, resulting in an increase in coercivity. And the performance of the amorphous alloy may deteriorate with an increase in the frequency of use, which limits the range of application of the amorphous alloy. In 1988, yoshizaw et al developed Fe on the basis of FeSiB amorphous alloys 73.5 Si 13.5 B 9 Nb 3 Cu 1 Nanocrystalline alloys, known as FINEMET alloys. By first preparing amorphous Fe 73.5 Si 13.5 B 9 Nb 3 Cu 1 The alloy is annealed to precipitate dispersed 10-15nm alpha-Fe (Si) grains on the amorphous matrixCoercivity of alloy with crystal/nanocrystalline dual-phase structureH c As low as 0.53A/m, saturation magnetizationB s =1.24t, permeabilityμ e (1kHz)=1.0×10 5 The saturation magnetization is improved, the stress sensitivity is reduced, and excellent high-frequency soft magnetic properties are exhibited as compared with amorphous materials. Such an alloy having a two-phase structure of amorphous and nanoscale crystalline phases is called a nanocrystalline alloy.
The work done in 1988 developed FINEMET nanocrystalline alloys, which received attention from a vast array of researchers, howeverB s Only 1.24T, far lower than conventional silicon steel, researchers expect to develop nanocrystalline alloys with better properties. In 1998, suzuki et al developed a high Fe content by increasing the Fe content and adding a transition metal element>86 at.%) and FeMBCu (m=zr, hf, nb, ta) nanocrystalline alloy systems, and are registered as Nanoperm alloys. Which is a kind ofB s Can reach 1.7T (the component is Fe 91 Zr 7 B 2 ) And the coercive force is only 7.2A/m,B s significantly improved, while also having a magnetostriction coefficient close to 0, and a very good amorphous forming ability. However, because of containing Zr, nb and other easily oxidized elements, the catalyst cannot be directly prepared in air, and atmosphere protection is required, so that the industrialization difficulty and the cost are increased. In addition, willard et al developed FeCoMBCu (M=Zr, hf, nb) Hitperm nanocrystalline alloys by substituting Co element for Fe in the Nanoperm alloy system, and typically contained Fe 44 Co 44 Zr 7 B 4 Cu 1 Which is provided withB s About 1.61T. The series of nanocrystalline alloy has high Curie temperature and good thermal stability, can work in high-temperature environment (up to 600 ℃), and FINEMET and Nanoperm can only work below 200 ℃. However, the cost is increased due to the large addition of Co element, and the addition of Co causes the coercive force to be increased (Fe 44 Co 44 Zr 7 B 4 Cu 1 A kind of electronic deviceH c 10.0A/m). In 2009, makino et al developed a super-high power deviceB s The Fe-Si-B-P-Cu nanocrystalline alloy of (2) is named NANOMET, whichB s Up to 189-1.94T, which is close to oriented silicon steel, and the coercivity is only 7-10A/m, but the amorphous forming capability of the alloy is low, the nano crystallization process is strictly required, and the commercialization is difficult.
How to improve the amorphous forming ability of iron-based amorphous-nanocrystalline alloys to meet production requirements and maintain excellent soft magnetic properties is an important issue in their development.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the iron-based amorphous-nanocrystalline magnetically soft alloy which has reasonable component design, high saturation magnetic induction intensity, low production cost and excellent comprehensive magnetic property, and the amorphous forming capability meets the production requirement.
In order to achieve the aim of the invention, the invention is realized by the following technical scheme:
in a first aspect, the present invention provides an iron-based amorphous-nanocrystalline magnetically soft alloy consisting of (Fe a Co b Si c B d P e C fg Cu h And unavoidable impurities, wherein a, b, c, d, e, f, g and h represent the atomic percentage of each corresponding component, respectively, 75.ltoreq.a.ltoreq.80, a+b+c+d+e+f=100, g+h=100.
Further, the saturation magnetic induction intensity of the iron-based amorphous-nanocrystalline magnetically soft alloy is more than or equal to 1.670T, and/or the coercive force is less than or equal to 10A/m. The saturated magnetic induction intensity of the iron-based amorphous-nanocrystalline magnetically soft alloy can be specifically 1.670T, 1.680T, 1.690T, 1.70T, 1.710T, 1.730T and the like, and the coercive force can be specifically 10A/m, 9.8A/m, 9.5A/m, 9.3A/m, 9.1A/m, 8.8A/m, 8.5A/m, 7A/m and the like.
Further, wherein 3.ltoreq.b.ltoreq.5, 1.ltoreq.c.ltoreq.7, 7.ltoreq.d.ltoreq.13, e.ltoreq.1, f.ltoreq.3, g.ltoreq.100, h.ltoreq.0.
Further, wherein b is 3-5, c is 1-7, d is 7-13, e is 1, f is 3, g is 99-99.5,0.5 h is 1.
In the iron-based amorphous-nanocrystalline magnetically soft alloy, fe is a magnetic element, and in order to obtain high saturation induction intensity, the alloy must be ensured to contain higher Fe content. However, too high a Fe content results in a significant decrease in amorphous forming ability, so considering the content of Fe in combination, a may be preferably 75 to 80, and particularly preferably 75, 76, 77, 78, 79, 80. In addition, in the nanocrystalline, co can form an alpha-Fe (Co) phase of a bcc structure after replacing Fe, and the structure has large magnetic moment and high Curie temperature, so that the heat stability and high-temperature magnetic property of the nanocrystalline can be improved. However, co addition increases the magnetic anisotropy of the alloy and increases the coercivity. Therefore, considering the Co content in total, b may be preferably 3 to 5, and particularly may be preferably 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5.
The addition of Si and B can effectively improve the amorphous forming capability, however, the B element can reduce the difference between the first crystallization peak and the second crystallization peak of the amorphous/nanocrystalline, reduce the thermal stability of the nanocrystalline and reduce the thermal interval, and the Fe-B hard magnetic phase is easier to separate out in the heat treatment process, so that the magnetic performance is deteriorated, and therefore, the B content should not be too high. The addition of Si can also improve the stability of amorphous phase, in addition, si element can be dissolved into alpha-Fe crystal lattice to form alpha-Fe (Si) phase, magnetostriction can be reduced, and magnetic permeability of alloy can be improved. P is often used to replace B to reduce cost. Meanwhile, the melting point of the P element is low, so that the energy loss in the alloy smelting process can be reduced. The grain size of the alloy can be improved after P is added into the nanocrystalline, and the P element is not dissolved in the grain but is enriched in the residual amorphous during the crystallization of alpha-Fe, so that the residual amorphous phase is stabilized and the grain size is refined. Therefore, considering the contents of Si, B, and P in combination, c in Si may be preferably 1 to 7, and particularly may be preferably 1, 1.2, 1.5, 1.8, 2, 3, 4, 5, 6, 6.5, 6.8, and 7; d in B may preferably be 7 to 13, and particularly may preferably be 7, 7.2, 7.5, 7.8, 8, 9, 10, 11, 12, 12.5, 12.8, 13; e in P may preferably be 1.
The C element can increase the radius difference of alloy atoms, and because the mixing enthalpy of Fe and the C element is negative, fe is preferentially formed 3 The C phase, the competition between phases causes mutual inhibition to improve amorphous forming ability and thermal stability. Thus, considering the C content in combination, f may preferably be 3.
Cu isThe nano crystal forming element has small solubility in Fe or is insoluble in Fe, can be separated out in the crystallization process to form clusters, can be used as nucleation points of alpha-Fe crystals, improves nucleation rate, refines grain size, promotes uniform distribution of grains to form nano crystals, and has higher nano crystals than amorphous nano crystalsB s . However, cu is a large atom, and too high a content lowers the alloyB s . Therefore, h may be preferably 0, 0.5 to 1, and particularly preferably 0, 0.5, 0.6, 0.7, 0.8, 0.9, 1, considering the Cu content in total.
Further, the iron-based amorphous-nanocrystalline magnetically soft alloy consists of (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And unavoidable impurities, and the saturated magnetic induction intensity of the iron-based amorphous-nanocrystalline magnetically soft alloy is 1.720T.
Further, the iron-based amorphous-nanocrystalline magnetically soft alloy consists of (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 And unavoidable impurities, and the saturation induction intensity of the iron-based amorphous-nanocrystalline magnetically soft alloy is 1.70T.
Further, the iron-based amorphous-nanocrystalline magnetically soft alloy consists of (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 And unavoidable impurities, and the saturation induction intensity of the iron-based amorphous-nanocrystalline magnetically soft alloy is 1.710T.
The invention adds certain Si and B element content and Cu element at the same time, so that the alloy has high saturation magnetic induction intensity and meets the amorphous forming capability required by production, (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 The saturation induction of the two component points is as high as 1.720T (tesla) and 1.710T (tesla), respectively.
In a second aspect, the present invention provides the use of the above iron-based amorphous-nanocrystalline magnetically soft alloy for the preparation of an amorphous iron core or an iron-based amorphous-nanocrystalline magnetically soft alloy ribbon.
Further, the amorphous iron core is applied to an amorphous motor or an amorphous transformer. The iron-based amorphous-nanocrystalline magnetically soft alloy is used for preparing an amorphous iron core, so that the iron loss of the iron core is lower, the iron core can be applied to scenes with high power and high energy density, and the noise is low. The amorphous iron core can be formed by rolling a strip made of the iron-based amorphous-nanocrystalline magnetically soft alloy, and can also be formed by rolling the iron-based amorphous-nanocrystalline magnetically soft alloy.
Further, the iron-based amorphous-nanocrystalline magnetically soft alloy ribbon is a fully amorphous alloy ribbon formed by a single roll rapid quenching method of the iron-based amorphous-nanocrystalline magnetically soft alloy.
Further, the critical thickness of the iron-based amorphous-nanocrystalline magnetically soft alloy strip is more than or equal to 30 mu m.
In a third aspect, the present invention provides a method for preparing the above iron-based amorphous-nanocrystalline soft magnetic alloy ribbon, comprising the steps of:
preparing a master alloy: according to atomic percent (Fe a Co b Si c B d P e C fg Cu h (a+b+c+d+e+f=100, g+h=75.ltoreq.a.ltoreq.80, 3.ltoreq.b.ltoreq.5, 1.ltoreq.c.ltoreq.7, 7.ltoreq.d.ltoreq.13, e=1, f=3, g=100, h=0) or (Fe a Co b Si c B d P e C fg Cu h Mixing raw materials in a proportion of (a+b+c+d+e+f=100, g+h=100, a is 75-80, b is 3-5, c is 1-7, d is 7-13, e=1, f=3, g is 99-99.5,0.5-h is 1), placing the mixed raw materials in a boron nitride crucible, placing the boron nitride crucible in an induction melting furnace, and melting to obtain master alloy;
and (3) strip casting: crushing the smelted master alloy by a mechanical crushing method, and then placing the crushed master alloy in a belt spraying device; and then melting the crushed master alloy through induction melting, spraying the master alloy onto a copper roller rotating at a high speed by using a spraying device, and preparing the iron-based amorphous-nanocrystalline magnetically soft alloy belt through quenching.
Further, in the master alloy preparation, the raw materials include: fe with purity of 99.99%, co with purity of 99.99%, cu with purity of 99.99%, elemental silicon, ferroboron with B content of 20%, ferrophosphorus with P content of 25.23% and carbon iron with C content of 5%.
Further, in the preparation of the master alloy, the induction smelting furnace is vacuumized and then filled with argon. Argon is introduced to protect the master alloy from oxidation at high temperatures.
Further, the vacuum degree of the vacuum is 5.0X10 -3 Pa。
Still further, the argon gas had a purity of 99.99%.
Further, in the preparation of the master alloy, the smelting is repeated for 2 times to ensure the uniformity of the master alloy.
Further, in the melt-spun, the melted master alloy is crushed by a mechanical crushing method and then is placed in a belt spraying device, when the vacuum degree reaches 5.0 multiplied by 10 -3 And during Pa, introducing argon with the purity of 99.99 percent, and the pressure of-0.03 MPa, then melting the broken master alloy through induction melting, spraying the broken master alloy onto a copper roller rotating at a high speed by using a spraying device, and preparing the iron-based amorphous-nanocrystalline magnetically soft alloy belt through quenching.
Further, the preparation method further comprises a heat treatment step, wherein the iron-based amorphous-nanocrystalline magnetically soft alloy strip obtained by melt spinning is placed into a tubular heat treatment furnace, vacuumized, then subjected to heat treatment, and cooled with air, so that the annealed iron-based amorphous-nanocrystalline magnetically soft alloy strip is obtained.
Further, in the heat treatment step, a vacuum is drawn to 1Pa or less.
Further, the annealing temperature of the heat treatment is 340-420 ℃, preferably 360-400 ℃, and the annealing time is 10min. Specifically, the annealing temperature may be 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃. The annealing temperature cannot be too low or too high, resulting in an increase in the coercivity of the alloy.
Further, the coercivity of the annealed iron-based amorphous-nanocrystalline magnetically soft alloy ribbon is less than or equal to 10A/m.
When the preparation method is used for melt-spinning, the speed of spraying the master alloy melted by induction smelting on the surface of the copper roller is determined according to actual design requirements, preferably the rotating speed of the copper roller is 30m/s, the width of a nozzle gap is 0.3mm, the distance between the nozzle and the surface of the copper roller is determined according to actual design requirements, and the preferred distance is 0.15-0.25 mm; the pressure of the master alloy after induction melting and melting sprayed on the surface of the copper roller is determined according to actual design requirements, and the pressure difference is preferably 0.045MPa.
Compared with the prior art, the invention has the beneficial effects that:
1. the saturation magnetic induction intensity of the iron-based amorphous-nanocrystalline magnetically soft alloy is more than or equal to 1.670T, and/or the coercive force is less than or equal to 10A/m. The component design is reasonable, the saturation magnetic induction intensity is high, the amorphous forming capability meets the production requirement (complete amorphous can be prepared), the production cost is low, and the comprehensive magnetic property is excellent.
2. The iron-based amorphous-nanocrystalline magnetically soft alloy provided by the invention has the advantages of high saturation magnetic induction and other magnetic properties on the premise of meeting the strong amorphous forming capability required by single-roller rapid quenching for preparing wide strips, and the coercivity of the annealed iron-based amorphous-nanocrystalline magnetically soft alloy strip is less than or equal to 10A/m.
3. The iron-based amorphous-nanocrystalline magnetically soft alloy provided by the invention only contains a small amount of magnetic metal elements, is suitable for production by using industrial purity raw materials, and has the advantages of simple preparation method and low production cost.
4. The iron-based amorphous-nanocrystalline magnetically soft alloy or the iron-based amorphous-nanocrystalline magnetically soft alloy ribbon can be used for preparing an amorphous iron core, can enable the iron loss of the iron core to be lower, can be applied to scenes of high power and high energy density, can be particularly applied to an amorphous motor or an amorphous transformer, and is low in noise.
Drawings
FIG. 1 shows Fe obtained in example 1 78 Co 3 Si 5 B 10 P 1 C 3 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and Fe obtained in example 7 76 Co 3 Si 7 B 10 P 1 C 3 DSC curve of iron-based amorphous-nanocrystalline magnetically soft alloy ribbon;
FIG. 2 shows the composition obtained in example 13 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon, obtained in example 19 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and (Fe) obtained in example 25 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 DSC curve of iron-based amorphous-nanocrystalline magnetically soft alloy ribbon;
FIG. 3 shows the Fe obtained in example 1 78 Co 3 Si 5 B 10 P 1 C 3 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and Fe obtained in example 7 76 Co 3 Si 7 B 10 P 1 C 3 XRD curve of iron-based amorphous-nanocrystalline magnetically soft alloy ribbon;
FIG. 4 shows the composition obtained in example 13 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon, obtained in example 19 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and (Fe) obtained in example 25 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 XRD curve of iron-based amorphous-nanocrystalline magnetically soft alloy ribbon;
FIG. 5 shows Fe obtained in example 3 78 Co 3 Si 5 B 10 P 1 C 3 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and Fe obtained in example 9 76 Co 3 Si 7 B 10 P 1 C 3 VSM curve of iron-based amorphous-nanocrystalline magnetically soft alloy ribbon;
FIG. 6 shows the composition obtained in example 15 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon, obtained in example 21 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and (Fe) obtained in example 27 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 VSM curve of iron-based amorphous-nanocrystalline soft magnetic alloy ribbon.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention will be further described in detail below in connection with the embodiments of the invention. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope 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.
The examples of the present invention are implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, in which the process parameters of specific conditions are not noted, and generally according to conventional conditions.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention.
In the present invention, unless otherwise specified and/or indicated, all numbers referring to amounts of components are "atomic percent" throughout. The process parameters for the specific conditions not noted in the examples below are generally as usual.
The invention is further illustrated below in conjunction with specific examples.
Examples 1 to 12Fe 78 Co 3 Si 5 B 10 P 1 C 3 And Fe (Fe) 76 Co 3 Si 7 B 10 P 1 C 3 Iron-based amorphous-nanocrystalline magnetically soft alloy and preparation of strip thereof
Preparing a master alloy: fe is added to 78 Co 3 Si 5 B 10 P 1 C 3 And Fe (Fe) 76 Co 3 Si 7 B 10 P 1 C 3 The raw materials are respectively mixed according to atomic percent, then the mixed raw materials are respectively placed in boron nitride crucibles, the boron nitride crucibles are placed in an induction smelting furnace, and the induction smelting furnace is vacuumized to a vacuum degree of 5.0 multiplied by 10 -3 And (3) filling high-purity argon in Pa, wherein the purity of the filled argon is 99.99%, and the filled argon has the function of protecting the master alloy from oxidation at high temperature. Then smelting is carried out respectively, the master alloy is repeatedly smelted for 2 times in the smelting process to ensure the uniformity of the master alloy, and finally Fe is obtained respectively 78 Co 3 Si 5 B 10 P 1 C 3 And Fe (Fe) 76 Co 3 Si 7 B 10 P 1 C 3 Master alloy. Wherein the raw materials comprise: fe with the purity of 99.99 percent, co with the purity of 99.99 percent, simple substance silicon, ferroboron with the content of 20 percent, ferrophosphorus with the content of 25.23 percent and carbon iron with the content of 5 percent.
And (3) strip casting: smelting Fe 78 Co 3 Si 5 B 10 P 1 C 3 And Fe (Fe) 76 Co 3 Si 7 B 10 P 1 C 3 And the master alloy is crushed by a mechanical crushing method and then is placed in a belt spraying device. Vacuumizing until the vacuum degree reaches 5.0X10 -3 During Pa, high-purity argon (purity 99.99%) is introduced to a pressure of-0.03 MPa to obtain Fe 78 Co 3 Si 5 B 10 P 1 C 3 And Fe (Fe) 76 Co 3 Si 7 B 10 P 1 C 3 The master alloy is respectively melted by induction melting and is sprayed to high-speed rotation by a spraying deviceOn the rotating copper roller, the rotating speed of the copper roller is 30m/s, the width of a nozzle gap is 0.3mm, and the distance between the nozzle and the surface of the copper roller is 0.2mm; the pressure difference of the alloy melt sprayed to the surface of the copper roller is 0.045MPa, and Fe is prepared by quenching 78 Co 3 Si 5 B 10 P 1 C 3 And Fe (Fe) 76 Co 3 Si 7 B 10 P 1 C 3 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon.
Wherein Fe of example 1 78 Co 3 Si 5 B 10 P 1 C 3 And Fe of example 7 76 Co 3 Si 7 B 10 P 1 C 3 The iron-based amorphous-nanocrystalline soft magnetic alloy ribbon of (1) is an alloy ribbon without annealing treatment, fe of examples 2 to 6 78 Co 3 Si 5 B 10 P 1 C 3 And Fe of examples 8-12 76 Co 3 Si 7 B 10 P 1 C 3 The iron-based amorphous-nanocrystalline magnetically soft alloy ribbon is an annealed alloy ribbon, and the annealing process is as follows:
fe obtained by melt spinning 78 Co 3 Si 5 B 10 P 1 C 3 And Fe (Fe) 76 Co 3 Si 7 B 10 P 1 C 3 The iron-based amorphous-nanocrystalline magnetically soft alloy strips are respectively placed into a tubular heat treatment furnace, vacuumized to below 1Pa, then heat treated, annealed at 340-420 ℃ for 10min, and cooled with air to obtain annealed Fe, wherein the specific temperature is shown in Table 1 78 Co 3 Si 5 B 10 P 1 C 3 And Fe (Fe) 76 Co 3 Si 7 B 10 P 1 C 3 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon.
TABLE 1
Figure SMS_1
Examples 13 to 30 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 、(Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 Iron-based amorphous-nanocrystalline magnetically soft alloy of (2) and strip preparation thereof
Preparing a master alloy: will (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 、(Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 The raw materials of (1) are respectively mixed according to atomic percent, then the mixed raw materials are respectively placed in a boron nitride crucible, the boron nitride crucible is placed in an induction smelting furnace, and the induction smelting furnace is pumped with high vacuum until the vacuum degree is 5.0 multiplied by 10 -3 And (3) filling high-purity argon in Pa, wherein the purity of the filled argon is 99.99%, and the filled argon has the function of protecting the master alloy from oxidation at high temperature. Then smelting respectively, wherein the master alloy is repeatedly smelted for 2 times in the smelting process to ensure the uniformity of the master alloy, and finally (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 、(Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 Master alloy. Wherein the raw materials comprise: fe with purity of 99.99%, co with purity of 99.99%, cu with purity of 99.99%, elemental silicon, ferroboron with B content of 20%, ferrophosphorus with P content of 25.23% and carbon iron with C content of 5%.
And (3) strip casting: the melted (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 、(Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 And the master alloy is crushed by a mechanical crushing method and then is placed in a belt spraying device. Vacuumizing until the vacuum degree reaches 5.0X10 -3 During Pa, high-purity argon (purity 99.99%) is introduced to a pressure of-0.03 MPa, and (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 、(Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 The master alloy is respectively melted by induction melting and is sprayed onto a copper roller rotating at a high speed by a spraying device, the rotating speed of the copper roller is 30m/s, the width of a nozzle gap is 0.3mm, and the distance between a nozzle and the surface of the copper roller is 0.15mm; the pressure difference of the alloy melt sprayed onto the surface of the copper roller was 0.045MP, and was prepared separately by quenching (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 、(Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon.
Wherein (Fe) of example 13 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 (Fe of example 19 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) of example 25 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 The iron-based amorphous-nanocrystalline soft magnetic alloy ribbon of examples 14 to 18 was an alloy ribbon without annealing treatment (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 (Fe of examples 20 to 24 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) of examples 26 to 30 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 The iron-based amorphous-nanocrystalline magnetically soft alloy ribbon is an annealed alloy ribbon, and the annealing process is as follows:
the melt-spun product (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 、(Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 The iron-based amorphous-nanocrystalline magnetically soft alloy strips are respectively placed into a tubular heat treatment furnace, vacuumized to below 1Pa, then heat treated, annealed at 340-420 ℃ for 10min, and cooled with air to obtain annealed (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 、(Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And (Fe) 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon.
TABLE 2
Figure SMS_2
Figure SMS_3
Comparative examples 1 to 6Fe 82 Si 2.5 B 13 C 2.5 (HB 1) iron-based amorphous-nanocrystalline magnetically soft alloy and strip preparation thereof
Preparing a master alloy: fe is added to 82 Si 2.5 B 13 C 2.5 The raw materials are mixed according to the atomic percentage, and then the mixed raw materials are placed in a boron nitride crucible to lead nitrogenThe boron carbide crucible is placed in an induction smelting furnace, and the induction smelting furnace is vacuumized to a vacuum degree of 5.0 multiplied by 10 -3 And (3) filling high-purity argon in Pa, wherein the purity of the filled argon is 99.99%, and the filled argon has the function of protecting the master alloy from oxidation at high temperature. And then smelting, wherein the master alloy is repeatedly smelted for 2 times in the smelting process so as to ensure the uniformity of the master alloy, and finally obtaining the HB1 master alloy.
And (3) strip casting: and crushing the smelted HB1 master alloy by a mechanical crushing method, and then placing the crushed HB1 master alloy in a belt spraying device. Vacuumizing until the vacuum degree reaches 5.0X10 -3 During Pa, high-purity argon (purity 99.99%) is introduced, the pressure is reduced to-0.03 MPa, HB1 master alloy is melted through induction melting, the high-speed copper roller is sprayed onto the high-speed copper roller by utilizing a spraying device, the rotating speed of the copper roller is 30m/s, the width of a nozzle gap is 0.3mm, the distance between the nozzle and the surface of the copper roller is 0.15mm, the pressure difference of the alloy melt sprayed onto the surface of the copper roller is 0.045MPa, and the HB1 iron-based amorphous-nanocrystalline soft magnetic alloy belt is prepared through quenching.
Wherein the HB1 iron-based amorphous-nanocrystalline magnetically soft alloy ribbon of comparative example 1 is an alloy ribbon which has not undergone annealing treatment, the HB1 iron-based amorphous-nanocrystalline magnetically soft alloy ribbon of comparative examples 2 to 6 is an alloy ribbon which has undergone annealing treatment, and the annealing treatment process is as follows:
placing the HB1 iron-based amorphous-nanocrystalline magnetically soft alloy belt obtained by melt spinning into a tubular heat treatment furnace, vacuumizing to below 1Pa, then performing heat treatment, wherein the annealing temperature is 340-420 ℃, the annealing time is 10min, and the annealed HB1 iron-based amorphous-nanocrystalline magnetically soft alloy belt is obtained after cooling along with air.
TABLE 3 Table 3
Figure SMS_4
Comparative examples 7 to 12Fe 78 B 13 Si 9 (1K101) Iron-based amorphous-nanocrystalline magnetically soft alloy and preparation of strip thereof
Preparing a master alloy: fe is added to 78 B 13 Si 9 Raw materials are mixed according to atomic percent, and then the mixed raw materials are placed in a boron nitride cruciblePlacing boron nitride crucible in induction smelting furnace, and vacuum-pumping induction smelting furnace to vacuum degree of 5.0X10 -3 And (3) filling high-purity argon in Pa, wherein the purity of the filled argon is 99.99%, and the filled argon has the function of protecting the master alloy from oxidation at high temperature. And then smelting, wherein the master alloy is repeatedly smelted for 2 times in the smelting process so as to ensure the uniformity of the master alloy, and finally obtaining the 1K101 master alloy.
And (3) strip casting: and crushing the smelted 1K101 master alloy by a mechanical crushing method, and then placing the crushed master alloy in a belt spraying device. Vacuumizing until the vacuum degree reaches 5.0X10 -3 And during Pa, high-purity argon (purity is 99.99%), pressure is reduced to-0.03 MPa, 1K101 master alloy is melted through induction melting, the master alloy is sprayed onto a copper roller rotating at a high speed by using a spraying device, the rotating speed of the copper roller is 30m/s, the width of a nozzle gap is 0.3mm, the distance between the nozzle and the surface of the copper roller is 0.15mm, the pressure difference of alloy melt sprayed onto the surface of the copper roller is 0.045MPa, and the 1K101 iron-based amorphous-nanocrystalline soft magnetic alloy strip is prepared through quenching.
Wherein the 1K101 iron-based amorphous-nanocrystalline magnetically soft alloy ribbon of comparative example 7 is an alloy ribbon which has not undergone annealing treatment, and the 1K101 iron-based amorphous-nanocrystalline magnetically soft alloy ribbon of comparative examples 8 to 12 is an alloy ribbon which has undergone annealing treatment, the annealing treatment process is as follows:
and (3) placing the 1K101 iron-based amorphous-nanocrystalline magnetically soft alloy strip obtained by melt spinning into a tubular heat treatment furnace, vacuumizing to below 1Pa, then performing heat treatment, wherein the annealing temperature is 340-420 ℃, the annealing time is 10min, and cooling with air to obtain the annealed 1K101 iron-based amorphous-nanocrystalline magnetically soft alloy strip.
Testing
(1) Crystallization temperature test
And measuring crystallization temperature of the iron-based amorphous-nanocrystalline magnetically soft alloy strips with different components obtained by the melt spinning by utilizing a differential scanning calorimetry. The temperature rising rate is 40 ℃/min when the differential scanning calorimetry is used for measurement, and the temperature rising range is as follows: room temperature to 800 ℃.
Wherein Fe obtained in example 1 78 Co 3 Si 5 B 10 P 1 C 3 Iron-based amorphous-nanocrystallineSoft magnetic alloy strip and Fe obtained in example 7 76 Co 3 Si 7 B 10 P 1 C 3 DSC curves of the iron-based amorphous-nanocrystalline magnetically soft alloy belts at 300-700 ℃ are shown in figure 1.
The product of example 13 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon, obtained in example 19 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and (Fe) obtained in example 25 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 DSC curves of the iron-based amorphous-nanocrystalline magnetically soft alloy belts at 300-700 ℃ are shown in figure 2.
(2) XRD testing
XRD test is carried out on the iron-based amorphous-nanocrystalline magnetically soft alloy strips with different components obtained by the melt spinning.
Wherein Fe obtained in example 1 78 Co 3 Si 5 B 10 P 1 C 3 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and Fe obtained in example 7 76 Co 3 Si 7 B 10 P 1 C 3 XRD graphs of the iron-based amorphous-nanocrystalline magnetically soft alloy ribbons, as shown in FIG. 3, are all completely amorphous structures.
The product of example 13 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon, obtained in example 19 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and (Fe) obtained in example 25 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 XRD graphs of the iron-based amorphous-nanocrystalline magnetically soft alloy ribbons, as shown in FIG. 4, are all completely amorphous structures.
(3) Saturation magnetic induction intensityB s And coercivity (coercive force)H c Testing
The iron-based amorphous-nanocrystalline magnetically soft alloy belts obtained in examples 1 to 30 and those obtained in comparative examples 1 to 12 were each examined for saturation induction by using a 7410-type Vibration Sample Magnetometer (VSM) manufactured by Lake Shore Co., ltdB s The method comprises the steps of carrying out a first treatment on the surface of the The model MATS-2010SD soft magnetic direct current testing device manufactured by Hunan Union is used for detecting coercive forceH c See table 4 for specific test results.
TABLE 4 Table 4
Figure SMS_5
In addition, fe obtained in example 3 78 Co 3 Si 5 B 10 P 1 C 3 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and Fe obtained in example 9 76 Co 3 Si 7 B 10 P 1 C 3 VSM plot of iron-based amorphous-nanocrystalline soft magnetic alloy ribbon, as shown in fig. 5.
The product of example 15 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon, obtained in example 21 (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 Iron-based amorphous-nanocrystalline magnetically soft alloy ribbon and (Fe) obtained in example 27 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 VSM plot of iron-based amorphous-nanocrystalline soft magnetic alloy ribbon, as shown in fig. 6.
(4) Critical thickness test
The thickness of the strip thrown out in examples 3, 9, 15, 21 and 27 was measured by using a micrometer manufactured by general-purpose Hasho company, and the maximum thickness of the completely amorphous strip was obtained as a critical thickness, and the results are shown in Table 5. Of these, example 9 had the greatest critical thickness, indicating that it had the best amorphous forming ability.
TABLE 5
Figure SMS_6
The foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be apparent that the invention is not limited thereto, and that any modifications, additions, or equivalent substitutions made within the principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. An iron-based amorphous-nanocrystalline magnetically soft alloy characterized in that the iron-based amorphous-nanocrystalline magnetically soft alloy consists of (Fe a Co b Si c B d P e C fg Cu h And unavoidable impurities, wherein a, b, c, d, e, f, g and h represent the atomic percentage of each corresponding component, respectively, 75.ltoreq.a.ltoreq.80, a+b+c+d+e+f=100, g+h=100.
2. The iron-based amorphous-nanocrystalline magnetically soft alloy according to claim 1, wherein the saturation induction of the iron-based amorphous-nanocrystalline magnetically soft alloy is not less than 1.670T;
and/or: the coercive force of the iron-based amorphous-nanocrystalline magnetically soft alloy is less than or equal to 10A/m.
3. The iron-based amorphous-nanocrystalline magnetically soft alloy according to claim 1 or 2, wherein 3.ltoreq.b.ltoreq.5, 1.ltoreq.c.ltoreq.7, 7.ltoreq.d.ltoreq.13, e.ltoreq.1, f.=3, g.ltoreq.100, h.ltoreq.0;
and/or: wherein b is more than or equal to 3 and less than or equal to 5, c is more than or equal to 1 and less than or equal to 7, d is more than or equal to 7 and less than or equal to 13, e is more than or equal to 1, f is more than or equal to 3, g is more than or equal to 99 and less than or equal to 99.5,0.5, h is more than or equal to 1.
4. The iron-based amorphous-nanocrystalline magnetically soft alloy according to claim 3, wherein the iron-based amorphous-nanocrystalline magnetically soft alloy consists of (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.2 Cu 0.8 And unavoidable impurities, the saturated magnetic induction intensity of the iron-based amorphous-nanocrystalline magnetically soft alloy is 1.720T;
and/or: the iron-based amorphous-nanocrystalline magnetically soft alloy consists of (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99.4 Cu 0.6 And unavoidable impurities, the saturation induction intensity of the iron-based amorphous-nanocrystalline magnetically soft alloy is 1.70T;
and/or: the iron-based amorphous-nanocrystalline magnetically soft alloy consists of (Fe 78 Co 3 Si 5 B 10 P 1 C 3 ) 99 Cu 1 And unavoidable impurities, and the saturation induction intensity of the iron-based amorphous-nanocrystalline magnetically soft alloy is 1.710T.
5. An amorphous core comprising the iron-based amorphous-nanocrystalline soft magnetic alloy according to any one of claims 1 to 4.
6. Use of an amorphous core according to claim 5 in an amorphous motor or an amorphous transformer.
7. An iron-based amorphous-nanocrystalline magnetically soft alloy ribbon, characterized in that it is obtained by using the iron-based amorphous-nanocrystalline magnetically soft alloy according to any one of claims 1 to 4.
8. The iron-based amorphous-nanocrystalline magnetically soft alloy ribbon of claim 7, wherein the iron-based amorphous-nanocrystalline magnetically soft alloy ribbon is a fully amorphous alloy ribbon of the iron-based amorphous-nanocrystalline magnetically soft alloy formed by a single roll rapid quenching process;
and/or: the critical thickness of the iron-based amorphous-nanocrystalline magnetically soft alloy belt is more than or equal to 30 mu m.
9. A method for producing the iron-based amorphous-nanocrystalline magnetically soft alloy ribbon according to claim 7 or 8, comprising the steps of:
preparing a master alloy: mixing the raw materials according to the atomic percentage, and then placing the mixture into a smelting furnace for smelting to obtain a master alloy;
and (3) strip casting: crushing the smelted master alloy by a mechanical crushing method, and then placing the crushed master alloy in a belt spraying device; and then melting the crushed master alloy through induction melting, spraying the master alloy onto a copper roller rotating at a high speed by using a spraying device, and preparing the iron-based amorphous-nanocrystalline magnetically soft alloy belt through quenching.
10. The method of claim 9, wherein in the master alloy preparation, the raw materials include: fe with the purity of 99.99 percent, co with the purity of 99.99 percent, cu with the purity of 99.99 percent, elemental silicon, ferroboron with the content of 20 percent, ferrophosphorus with the content of 25.23 percent and carbon iron with the content of 5 percent;
and/or: in the preparation of the master alloy, the smelting furnace is vacuumized and then filled with argon; the vacuum degree of the vacuum is 5.0X10 -3 Pa; the purity of the argon is 99.99 percent;
and/or: in the preparation of the master alloy, the smelting is repeated for 2 times;
and/or: in the melt-spun, the melted master alloy is crushed by a mechanical crushing method and then is placed in a belt spraying device when the vacuum degree reaches 5.0 multiplied by 10 -3 Introducing argon with the purity of 99.99 percent to the pressure of-0.03 MPa, then carrying out induction melting on the crushed master alloy, spraying the master alloy onto a copper roller rotating at a high speed by using a spraying device, and preparing the iron-based amorphous-nanocrystalline magnetically soft alloy belt through quenching;
and/or: in the melt-spun, when the master alloy after induction melting is sprayed to the surface of a copper roller, the rotating speed of the copper roller is 30m/s, the width of a nozzle gap is 0.3mm, and the distance between a nozzle and the surface of the copper roller is 0.15-0.25 mm; the pressure difference of the master alloy sprayed to the surface of the copper roller after induction melting is 0.045MPa;
and/or: the preparation method further comprises a heat treatment step, wherein the iron-based amorphous-nanocrystalline magnetically soft alloy strip obtained by melt spinning is placed into a tubular heat treatment furnace, vacuumized to be below 1Pa, then subjected to heat treatment, and the annealing temperature is 340-420 ℃ and the annealing time is 10min, and the annealed iron-based amorphous-nanocrystalline magnetically soft alloy strip is obtained after cooling along with air;
the coercivity of the annealed iron-based amorphous-nanocrystalline magnetically soft alloy strip is less than or equal to 10A/m.
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CN109778083A (en) * 2019-02-02 2019-05-21 清华大学 High saturated magnetic induction Fe-based amorphous alloy and preparation method thereof
CN110379581A (en) * 2019-07-22 2019-10-25 广东工业大学 High saturated magnetic induction and high-plasticity iron-base soft magnetic alloy and preparation method thereof
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