CN115732160A - All-metal iron-based nanocrystalline soft magnetic alloy, preparation method thereof and magnetic core - Google Patents
All-metal iron-based nanocrystalline soft magnetic alloy, preparation method thereof and magnetic core Download PDFInfo
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Abstract
The invention provides an all-metal iron-based nanocrystalline magnetically soft alloy, which is prepared by processing all-metal raw materials without adding non-metal elements; has a Fe-Co-M-N-Cu nano alloy system, wherein M = Zr, hf, nb; n = Li, be; in the Fe-M-N-Cu system, the content of Fe is 85-90%. By adopting the technical scheme of the invention, the provided all-metal iron-based nanocrystalline magnetically soft alloy material is an all-metal Fe-Co-M-N-Cu series nanocrystalline alloy material with high iron content, the structure of the alloy material comprises an amorphous matrix and nanocrystalline grains, and the average grain size of the nanocrystalline grain phase body-centered cubic alpha-Fe (Co) is less than 12nm; wherein the iron content can reach 90 percent at most, and simultaneously, the iron-containing composite material has high thermal stability and magnetic induction performance.
Description
Technical Field
The invention relates to the technical field of iron-based nanocrystalline magnetically soft alloy materials, in particular to an all-metal iron-based nanocrystalline magnetically soft alloy, a preparation method thereof and a magnetic core.
Background
With the development of high frequency and light weight of power systems and electronic communication devices, the soft magnetic performance index of the soft magnetic materials used therein is more and more required. The iron-based nanocrystalline alloy has the advantages of excellent soft magnetic properties such as high saturation induction density, high magnetic conductivity, low iron loss and low coercive force, low cost, good energy-saving effect and the like, is widely applied to power electronic devices such as high-frequency switching power transformers, high-medium-frequency high-power transformers, pulse transformers, electronic transformers, inverter type welding machine transformers and distribution transformers, and is beneficial to promoting the development of energy conservation, environmental protection, miniaturization and light weight of products.
The iron-based nanocrystalline alloy consists of an amorphous matrix and a nanocrystalline grain which are obtained by carrying out heat treatment on the amorphous alloy. Since 1988, yoshizawa et al, hitachi metal corporation, japan, discovered that a Fe-Si-B-Nb-Cu nanocrystal system is widely used due to its advantages of high magnetic permeability, low coercive force, and the like. Meanwhile, the research hot trend of the iron-based nanocrystalline magnetically soft alloy is also raised at home and abroad. After decades of research and exploration, the current nanocrystalline soft magnetic alloy mainly comprises four systems: feSiBMCu (M = Nb, ta, W, mo, etc.) Finemet alloys, feMB (Cu) Nanoperm alloys (M = Zr, hf, nb, etc.), (Fe, co) MBCu (M = Zr, hf, nb, etc.) Hitperm alloys, and FeSiBPCu Nanomet alloys. Among them, the Finemet alloy has excellent soft magnetic properties, but its typical component Fe is low because of the low Fe content 73.6 Nb 3 Si 13.5 B 9 Cu 1 The saturation magnetic induction of (2) is only 1.24, which limits the application of the power electronic device developing towards miniaturization to a certain extent; although the Nanoperm and Hitperm alloys have high saturation magnetic induction and magnetostriction coefficient close to zero, a large amount of elements such as easily-oxidized noble metals Zr and Hf exist, and the Hitperm alloys contain a large amount of Co elements, so that the production cost of the alloys is increased, and meanwhile, the preparation process is complex, so that the popularization and application are difficult. And the Fe-Si-B-P-Cu alloy system with high iron content has extremely high saturation magnetic induction intensity which can reach 1.9T, and has wide application prospect. However, the severe requirements of strip production and complex rapid thermal processing conditions limit the widespread use of this alloy system.
In addition, the iron-based nanocrystalline magnetically soft alloy is finally applied to power electronic devices in a mode that a strip is wound into a ring and an iron core is prepared through heat treatment. Therefore, in the actual production process, the problems of nonuniform heating, small and nonuniform precipitation amount of nano-crystalline grains can occur in the heat treatment process of large-batch nano-crystalline iron cores, so that the saturation magnetic induction intensity is low and the soft magnetic performance is poor, the quality stability of the produced nano-crystalline iron cores is poor, and the popularization and application of the iron-based nano-crystalline soft magnetic alloy, especially the production development of the soft magnetic alloy with high iron content is severely restricted. Therefore, research and development of the iron-based nanocrystalline soft magnetic alloy with excellent comprehensive soft magnetic performance, higher thermal stability, wider optimal heat treatment temperature and time interval become key research points and hot spots in the market and actual production.
The Chinese invention patent CN101796207A (Hitachi metals Co., ltd.) discloses an amorphous alloy thin strip, a nano-crystalline soft magnetic alloy and a magnetic core, which belong to a FeSiBMCu nano-crystalline alloy system, and the nano-crystalline alloy has high magnetic conductivity and low coercive force. However, the saturation induction of the alloy standard composition is only 1.6-1.65T, and needs to be further improved. In addition, the technical scheme of the invention improves the soft magnetic property of the nanocrystalline alloy to a certain extent through the adjustment of components and the optimization of a heat treatment process, but still has the defects of low saturation magnetic induction intensity, low magnetic permeability in a high application field, poor high-temperature thermal stability and the like. The Chinese invention patent CN112267057A discloses a soft magnetic high entropy alloy, which is prepared by adopting an all-metal system to prepare an all-metal alloy with soft magnetic performance, but the iron content of the all-metal alloy is 10-30%, a large proportion of Ni, co and Cu needs to be added, and the all-metal alloy is extremely difficult to popularize and apply on a large scale from the aspect of economic cost.
In conclusion, the development of the iron-based nanocrystalline magnetically soft alloy material with high saturation magnetic induction intensity, high-temperature thermal stability and high magnetic conductivity under high-field application has important significance for promoting the development of novel green energy-saving power electronic devices and the popularization and application of the iron-based nanocrystalline magnetically soft alloy.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides an all-metal iron-based nanocrystalline magnetically soft alloy, a preparation method thereof and a magnetic core.
In order to achieve the above object, the present invention provides an all-metal iron-based nanocrystalline magnetically soft alloy, which is characterized in that the material of the all-metal iron-based nanocrystalline magnetically soft alloy is processed by all-metal raw materials, and non-metal elements are not added; has a Fe-Co-M-N-Cu nano alloy system, wherein M = Zr, hf, nb; n = Li, be; wherein the content of Fe is 85-90%.
It is generally considered that Fe is a magnetic element and is a key for ensuring high saturation induction, but a higher Fe content can reduce amorphous forming ability, so the Fe content generally selected in the prior art is not higher than 85%. The invention provides the full-metal iron-based nanocrystalline soft magnetic alloy, which improves the Fe content as high as possible on the basis of ensuring the amorphous forming capability, and the Fe content can reach 90 percent at most and is far higher than the Fe content in the alloy in the prior art. Meanwhile, zr and Be are indispensable elements for improving the amorphous forming capability of the alloy, and Cu provides heterogeneous nucleation points for nanocrystalline nucleation and is an important element for improving the precipitation amount of the nanocrystalline. The addition of the Be element can obviously improve the bending toughness of the alloy strip, which has important significance for the subsequent winding and forming of the alloy strip. For the aspect of soft magnetic performance, the addition of the Be element can obviously reduce the magnetostriction coefficient of the alloy strip and optimize the soft magnetic performance of the alloy. As a better technical scheme, co is introduced into the alloy system and is used as an iron group transition element, so that the mixing enthalpy and the atomic mismatching ratio among alloy elements can be improved, the amorphous forming capacity can be improved, the growth of nano crystal grains can be inhibited, and the magnetic interaction coupling effect among FeCo elements can improve the saturation magnetic induction intensity of the alloy and improve the soft magnetic performance. Therefore, it is necessary to find a balance region in which the constituent alloy elements can simultaneously achieve the effects of increasing the amorphous forming ability and optimizing the soft magnetic properties and the heat treatment region and improving the high frequency characteristics. Based on the analysis of the theory, the invention further optimizes the components of the all-metal nanocrystalline soft magnetic alloy with high iron content.
As a preferred embodiment, the molecular formula of the all-metal iron-based nanocrystalline magnetically soft alloy is: fe a Zr b Be c Co d Cu e (ii) a Wherein a, b, c, d and e respectively represent the atomic percentage of each alloy element in the iron-based nanocrystalline magnetically soft alloy, and the following conditions are satisfied: a is more than or equal to 85 and less than or equal to 90;7b is less than or equal to 9;0c is less than or equal to 2;0d is less than or equal to 5; e is more than or equal to 0.7 and less than or equal to 2; a + b + c + d + e =100; more preferably, 0.7. Ltoreq. E.ltoreq.1.
In a preferred embodiment, the purity of the raw material of the all-metal iron-based nanocrystalline magnetically soft alloy is not less than 99.9%.
As a preferred embodiment, the all-metal iron-based nanocrystalline magnetically soft alloy has a body-centered Cubic (CA) -Fe (Co) nanocrystalline structure and is embedded in an amorphous substrate. More preferably, the average grain size of the alpha-Fe (Co) nanocrystals is 10 to 12nm.
In a preferred embodiment, the coercive force of the all-metal iron-based nanocrystalline soft magnetic composition is maintained at 10A/m after heat treatment at 580-620 ℃ for 30-60 minutes.
In a preferred embodiment, the nanocrystalline soft magnetic alloy after the crystallization heat treatment has a saturation induction density of 1.7 to 1.8T; the maximum magnetic permeability under the application field of 80A/m under 1kHz is more than or equal to 25000; the magnetic permeability under 10kHz is more than or equal to 25000.
In order to realize another purpose, the invention also provides a preparation method of the all-metal iron-based nanocrystalline magnetically soft alloy, which comprises the following steps:
(1) Weighing each alloy raw material for proportioning;
(2) Preparing a master alloy ingot: placing the alloy raw material in an electric arc melting device, and melting under the protection of inert atmosphere, wherein the melting temperature is 1300-1800 ℃; repeatedly smelting for 4-5 times to obtain the master alloy ingot;
(3) Preparing a quick quenching strip: crushing the master alloy ingot prepared in the step (2), putting the crushed master alloy ingot into a quartz tube with a nozzle at the bottom, and preparing a rapidly quenched ribbon of amorphous alloy by single-roller rapid cooling and strip throwing process treatment;
(4) Crystallization heat treatment: and (4) putting the amorphous alloy prepared in the step (3) into a heat treatment furnace, raising the temperature to 480-640 ℃ at a constant speed, preserving the heat for 10-60 min, taking out, quenching and cooling to room temperature to obtain the all-metal iron-based nanocrystalline magnetically soft alloy.
In a preferred embodiment, in the step (3), the rapidly quenched ribbon of amorphous alloy is in the form of a ribbon having a width of 1 to 2mm and a thickness of 20 to 25 μm. More preferably, the width of the rapid quenching strip is 1.5-2 mm, and the thickness is 23-25 μm.
In a preferred embodiment, in the step (3), the single-roll quenching melt-spinning process comprises melt-spinning at a speed of 30-40 m/s in an argon atmosphere.
In a preferred embodiment, in the step (4), the rate of the uniform temperature rise is 1 to 10 ℃/s.
Aiming at the technical problems in the prior art, the invention provides an all-metal iron-based nanocrystalline soft magnetic alloy without metalloids (Si, B, P and C) and with high Fe content, and the structural formula of the all-metal iron-based nanocrystalline soft magnetic alloy is Fe-Co-M-N-Cu (M = Zr, hf, nb and the like, N = Li, be and the like) series nanocrystalline alloy. The alloy system does not contain (Si, B, P and C) elements, and the content of Fe is obviously increased compared with the traditional alloy. Generally, a high-iron alloy is easy to deteriorate under a high-temperature condition, and the amorphous forming capability is reduced, so that the high-iron alloy does not have excellent soft magnetic performance.
Therefore, the saturation magnetization of the alloy is effectively improved, and the alloy has excellent high permeability and high frequency stability under a high application field, so that the development and research of the iron-based nanocrystalline structure alloy in the technical fields of energy-saving, environment-friendly, small-sized and light-weight accelerators, high-power-density ultrahigh-frequency high-precision power controllers, high-frequency transformers and the like are greatly promoted.
The all-metal iron-based nanocrystalline soft magnetic alloy provided by the above scheme is used for pulse power magnetic components used in various transformers, various reactors and choke coils, noise control components, laser power supplies, accelerators and the like, pulse transformers for communication, various motor cores, various generators, various magnetic sensors, antenna cores, various current sensors, magnetic shields and the like.
The technical scheme of the invention has the technical effects that:
1. by adopting the technical scheme of the invention, the provided all-metal iron-based nanocrystalline magnetically soft alloy material is an all-metal Fe-Co-M-N-Cu series nanocrystalline alloy material with high iron content, the structure of the alloy material comprises an amorphous matrix and nanocrystalline grains, and the average grain size of the nanocrystalline grain phase body-centered cubic alpha-Fe (Co) is less than 12nm; wherein the iron content can reach 90 percent at most, and simultaneously, the iron-containing composite material has high thermal stability and magnetic induction performance.
2. By adopting the technical scheme of the invention, after crystallization heat treatment, the obtained iron-based nanocrystalline magnetically soft alloy material has excellent soft magnetic performance, and simultaneously has the characteristics of high thermal stability, high power, high capacity, high frequency, high magnetic induction intensity and the like, wherein the saturation magnetic induction intensity is 1.70-1.80T, and the coercive force is-10A/m; meanwhile, the maximum magnetic permeability under the application field of 80A/m under 1kHz exceeds 25000 or more, the magnetic permeability under 10kHz exceeds 25000 or more, and the magnetic permeability has extremely high frequency stability.
3. The high-heat stability high-power high-capacity high-frequency high-magnetic-induction-strength novel all-metal iron-based nanocrystalline magnetically soft alloy material has the advantages of excellent comprehensive soft magnetic performance, high magnetic conductivity and high heat stability under high-field application and the like, has good application prospect, and is applied to the technical fields of high-power high-precision power controllers for accelerators, high-frequency transformers and the like.
4. By adopting the technical scheme of the invention, the soft magnetic alloy with high iron content is improved, the high-temperature stability and excellent soft magnetic performance are achieved, the raw material cost is reduced, the preparation process is simple, and the method has wide market application and popularization prospects.
Drawings
Fig. 1 is a flow chart of the preparation of the all-metal iron-based nanocrystalline alloy according to example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of quenched amorphous alloy ribbons of examples 1-2 of the present invention and comparative example 1.
FIG. 3 is a DSC curve of quenched amorphous alloy ribbons of examples 1-2 of the present invention and comparative example 1.
FIG. 4 is a graph showing the coercivity after heat treatment at 480-640 ℃ for 30min for the quenched amorphous alloys of examples 1-2 of the present invention and comparative example 1.
FIG. 5 is a graph showing the coercive force of the quenched amorphous alloys of examples 1 to 2 of the present invention and comparative example 1, which were heat-treated at 600 ℃ for various times.
FIG. 6a the hysteresis loop and saturation induction of nanocrystalline alloys obtained after crystallization heat treatment for inventive examples 1-2 and comparative example 1.
Fig. 6b is an enlarged view of fig. 6 a.
FIG. 7 is a graph showing permeability versus frequency at various field strengths after heat treatment at 520 ℃ for 30min according to comparative example 1 of the present invention.
FIG. 8 is a graph of permeability versus frequency at different field strengths after heat treatment at 600 ℃ for 30min according to example 1 of the present invention.
FIG. 9 is a graph of permeability versus frequency at different field strengths after heat treatment at 600 ℃ for 30min for example 2 of the present invention.
FIG. 10 is X-ray diffraction patterns of the amorphous alloys of examples 1-2 of the present invention and comparative example 1 after heat treatment at 600 ℃ for 30 min.
FIG. 11a is a TEM bright field image of the nanocrystalline alloy after heat treatment at 600 ℃ for 30min according to example 1 of the present invention.
FIG. 11b is a graph showing the distribution of the grain size of the nanocrystalline alloy after heat treatment at 600 ℃ for 30min according to example 1 of the present invention.
FIG. 12a is a TEM bright field image of the nanocrystalline alloy after heat treatment at 600 ℃ for 30min according to example 2 of the present invention.
FIG. 12b is a graph showing the distribution of the grain size of the nanocrystalline alloy after heat treatment at 600 ℃ for 30min according to example 2 of the present invention.
Detailed Description
The purpose, technical solutions and advantages of the embodiments of the present invention are made clearer, and the technical solutions in the embodiments of the present invention are clearly and completely described. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an all-metal iron-based nanocrystalline magnetically soft alloy, which is prepared by processing all-metal raw materials without adding non-metal elements; has an Fe-Co-M-N-Cu alloy system, wherein M = Zr, hf, nb; n = Li, be; the iron content is 85-90%.
In a preferred embodiment, the nanocrystalline soft magnetic alloy is provided with a formula: fe a Zr b Be c Co d Cu e (ii) a Wherein a, b, c, d and e respectively represent the atomic percentage content of each alloy element in the iron-based nanocrystalline magnetically soft alloy, and the following conditions are met: a is more than or equal to 85 and less than or equal to 90;7b is less than or equal to 9;0c is less than or equal to 2;0d is less than or equal to 5; e is more than or equal to 0.7 and less than or equal to 2; a + b + c + d + e =100; more preferably, 0.7. Ltoreq. E.ltoreq.1.
In a preferred embodiment, the purity of the raw material of the all-metal iron-based nanocrystalline magnetically soft alloy is not less than 99.9%.
In a preferred embodiment, the all-metal iron-based nanocrystalline magnetically soft alloy has a body-centered cubic (a — Fe) (Co) nanocrystalline structure embedded in an amorphous substrate. More preferably, the average grain size of the a-Fe (Co) nanocrystals is 10 to 12nm.
The invention provides a preparation method of the all-metal iron-based nanocrystalline magnetically soft alloy, which comprises the following specific steps:
(1) Weighing each alloy raw material for proportioning; specifically, according to the formula: the FeaZrbBecCodCue is weighed and mixed, subscripts a, b, c, d and e respectively represent the atom percentage content of each corresponding alloy element, and the following conditions are met: a is more than or equal to 85 and less than or equal to 90;7b is less than or equal to 9;0c is less than or equal to 2;0d is less than or equal to 5; e is more than or equal to 0.7 and less than or equal to 2.
(2) Preparing a master alloy ingot: placing the alloy raw material in the step (1) into an electric arc melting device, and melting under the protection of inert atmosphere, wherein the melting temperature is 1300-1800 ℃; repeatedly smelting for 4-5 times to obtain a master alloy ingot;
(3) Preparing a quick quenching strip: crushing the master alloy ingot prepared in the step (2), putting the crushed master alloy ingot into a quartz tube with a nozzle at the bottom, and preparing a rapidly quenched ribbon of amorphous alloy by single-roller rapid cooling and strip throwing process treatment;
(4) Crystallization heat treatment: and (4) putting the amorphous alloy prepared in the step (3) into a heat treatment furnace, uniformly heating to 480-640 ℃ at a heating rate of 1-10 ℃/s, keeping the temperature for 10-60 min, taking out, quenching and cooling to room temperature to obtain the all-metal iron-based nanocrystalline magnetically soft alloy.
The all-metal iron-based nanocrystalline magnetically soft alloy prepared by the scheme has the advantages of
The coercive force is kept at 10A/m after heat treatment for 30 to 60 minutes at 580 to 620 ℃; the saturation magnetic induction intensity of the nanocrystalline magnetically soft alloy obtained after crystallization heat treatment is more than or equal to 1.71T; the maximum magnetic permeability under the application field of 80A/m under 1kHz is more than or equal to 25000; the magnetic permeability under 10kHz is more than or equal to 25000.
The technical solution of the present invention will be described in further detail below with reference to specific examples.
Example 1
The molecular formula of the all-metal iron-based nanocrystalline magnetically soft alloy provided by the embodiment is Fe 90 Zr 7 Be 2 Cu 1 。
Referring to fig. 1, the specific manufacturing method is as follows:
step 1: raw materials of Fe, zr, be and Cu with the purity of more than 99.9 percent are mixed according to a composition relation formula Fe 90 Zr 7 Be 2 Cu 1 And (5) burdening.
Step 2: putting the proportioned raw materials into an electric arc melting furnace, vacuumizing to be lower than 2.0 multiplied by 10 -2 Pa, then filling argon to the pressure of-0.05-0.01 MPa, and smelting for 4-5 times on the front and back sides to obtain alloy ingots with uniform components.
And 3, step 3: and (3) crushing the alloy ingot obtained in the step (2), then loading the crushed alloy ingot into a quartz tube with a nozzle at the bottom, and spinning the alloy ingot at the speed of 30-40 m/s in an argon atmosphere by adopting a single-roller quenching and spinning process to obtain the amorphous alloy strip.
And 4, step 4: placing the amorphous alloy strip obtained in the step 3 in a quartz tube, and vacuumizing to 5.0 multiplied by 10 -3 And Pa, placing the quartz tube in a heat treatment furnace, raising the temperature to 600 ℃ at the heating rate of about 2 ℃/s, preserving the temperature for 30 minutes, then quickly taking out the quartz tube, placing the quartz tube in water, and quenching the quartz tube to room temperature to obtain the nanocrystalline alloy material.
The quenched alloy strip obtained in step 3 and the alloy strip after heat treatment in step 4 were characterized by their microstructures using a D8 advanced type polycrystalline X-ray diffractometer, and the results are shown in fig. 2 and 10.
Referring to the spectrum of example 1 in fig. 2, the alloy strip prepared in step 3 has a broadened dispersion diffraction peak, which indicates that the alloy strip has an amorphous structure.
Referring to the spectrum of example 1 in fig. 10, after the alloy strip is kept at 600 ℃ for 30min, a crystallization peak appears, and the crystallization phase is analyzed to be body-centered cubic structure Fe, namely alpha-Fe, and the grain size is estimated to be about 12nm by the Scherrer formula.
Further, fig. 11a and 11b show TEM bright field images and particle size distribution maps of the alloy strip after the heat treatment of step 4 under the optimal conditions, respectively; wherein the microstructure of the sample is measured using a transmission electron microscope of the Tecnai F20 type. It can be seen that the alloy strip structure after crystallization heat treatment consists of an amorphous phase and nano-crystalline grains distributed in an amorphous matrix, the size of the crystalline grains is about 10-12 nm, and the size is consistent with the result of X-ray diffraction analysis. The uniform distribution of the refined grains is an intrinsic factor that the alloy prepared in example 1 has excellent soft magnetic properties.
FIG. 3 shows the DSC curve of the alloy strip produced in step 3. Wherein, the DSC curve is measured by a NETZSCH DSC 404C differential scanning calorimeter, and the measured temperature rise rate is 0.67 ℃/s. It can be seen that the alloy strip has a significant enthalpy change of heat evolution, indicating that the alloy produced has the characteristics of an amorphous alloy.
Fig. 4 and 5 show the coercivity of the alloy strip after heat treatment in step 4 as a function of temperature and time. Wherein the coercive force is measured by a direct current B-H instrument (EXPH-100). It can be seen that the coercive force can be kept at about 10A/m within the range of 600-620 ℃ when the temperature is kept for 30min, and the coercive force can be kept at a relatively small value within the range of 20-40 min after the heat treatment at 600 ℃, so that the alloy has high-temperature thermal stability.
Fig. 6a and 6b show the magnetic hysteresis loop of the alloy strip after the heat treatment in step 4 under the optimal condition, wherein the magnetic hysteresis loop is measured by using a vibration sample magnetometer (VSM, lakeshore 7410) for testing the saturation magnetic induction intensity of the alloy, and it can be seen that the saturation magnetic induction intensity of the alloy is 1.71T, and the saturation magnetic induction intensity is significantly improved, which is beneficial to realizing energy conservation, environmental protection, miniaturization, light weight and the like of the product.
FIG. 8 shows the permeability of the alloy strip after heat treatment in step 4 at different field strengths under optimum conditions, as measured by an impedance analyzer (Agilent 4294A). It can be seen from the figure that the magnetic permeability shows a trend of increasing first and then decreasing with the increase of the applied field, the optimal magnetic permeability under the applied field of 50A/m and 1kHz can reach 33000, the magnetic permeability under the applied field of 80A/m and 1kHz can reach more than 26000, and meanwhile, the magnetic permeability under 10kHz does not generate attenuation phenomenon under the corresponding applied field, which shows that the alloy has higher frequency stability and ultrahigh magnetic permeability. The high magnetic conductivity and high frequency stability under high applied external field can be used in the technical fields of high-power density ultrahigh frequency high-precision power supply controllers for accelerators, high-frequency transformers and the like.
Example 2
In this example, the molecular formula of the novel all-metallic iron-based nanocrystalline magnetically soft alloy material is Fe 85 Zr 7 Be 2 Co 5 Cu 1 。
The specific preparation method of the iron-based nanocrystalline alloy comprises the following steps:
step 1: raw materials of Fe, zr, be, co and Cu with the purity of more than 99.9 percent are mixed according to a composition relation formula of Fe 85 Zr 7 Be 2 Co 5 Cu 1 And (5) burdening.
And 2, step: putting the proportioned raw materials into an electric arc melting furnace, and vacuumizing to be lower than 2.0 multiplied by 10 -2 Pa, then filling argon to the pressure of-0.05-0.01 MPa, and smelting the front and back surfaces for 4-5 times to obtain alloy ingots with uniform components.
And step 3: and (3) crushing the alloy ingot obtained in the step (2), then loading the crushed alloy ingot into a quartz tube with a nozzle at the bottom, and spinning the alloy ingot at the speed of 30-40 m/s in an argon atmosphere by adopting a single-roller quenching and spinning process to obtain the amorphous alloy strip.
And 4, step 4: placing the amorphous alloy strip obtained in the step 3 in a quartz tube, and vacuumizing to 5.0 multiplied by 10 -3 And Pa, placing the quartz tube in a heat treatment furnace, raising the temperature to 520-640 ℃ at the temperature rise rate of about 2 ℃/s, preserving the temperature for 10-60 minutes, then quickly taking out the quartz tube, placing the quartz tube in water, and quenching the quartz tube to room temperature to obtain the nanocrystalline alloy material.
The quenched alloy strip obtained in step 3 and the alloy strip after heat treatment in step 4 were characterized by their microstructures using a D8 advanced type polycrystalline X-ray diffractometer, and the results are shown in fig. 2 and 10. The alloy strip produced in step 3 is shown to have a broadened dispersion diffraction peak, indicating that the alloy strip has an amorphous structure. The alloy strip is kept at 600 ℃ for 30min, and then a crystallization peak appears, the crystallization phase is analyzed to be in a body-centered cubic structure, namely alpha-Fe (Co), and the grain size of the alloy strip is estimated to be about 11.5nm by a Scherrer formula.
FIG. 12a shows TEM bright field image of the alloy strip after heat treatment in step 4 under the optimal conditions; FIG. 12b is a graph showing the grain size distribution of the alloy strip after the heat treatment of step 4 under optimum conditions; wherein the microstructure of the sample is measured using a transmission electron microscope, type Tecnai F20. It can be seen that the alloy ribbon structure after crystallization heat treatment consists of an amorphous phase and nano-crystalline grains distributed in an amorphous matrix, and the size of the crystalline grains is about 10-12 nm and is consistent with the analysis result of X-ray diffraction. The addition of Co element to further refine crystal grains is an intrinsic factor of excellent soft magnetic performance of the alloy.
FIG. 3 shows the DSC curve of the alloy strip produced in step 3. Wherein, the DSC curve is measured by a NETZSCH DSC 404C differential scanning calorimeter, and the measured temperature rise rate is 0.67 ℃/s. It can be seen that the alloy strip has a significant enthalpy change of heat release, indicating that the alloy produced has the characteristics of an amorphous alloy.
Fig. 4 and 5 show the coercivity of the alloy strip after heat treatment in step 4 as a function of temperature and time. Wherein, the coercive force is measured by a direct current B-H instrument (EXPH-100). It can be seen that the coercive force can be kept at about 10A/m within the range of 580-620 ℃ when the temperature is kept for 30min, and the coercive force can be kept at a relatively small value within the range of 20-40 min after the heat treatment at 600 ℃, so that the alloy has high-temperature thermal stability.
Fig. 6 shows a magnetic hysteresis loop of the alloy strip after the heat treatment in step 4 under the optimal condition, wherein the magnetic hysteresis loop is measured by using a vibration sample magnetometer (VSM, lakeshore 7410) and used for testing the saturation magnetic induction of the alloy, and it can be seen that the saturation magnetic induction of the alloy is 1.78T, and the interactive coupling of Fe and Co elements significantly improves the saturation magnetic induction, which is more beneficial to realizing energy saving, environmental protection, miniaturization, light weight and the like of the product.
FIG. 9 shows the permeability of the alloy strip after heat treatment in step 4 at different field strengths under optimum conditions, as measured by an impedance analyzer (Agilent 4294A). It can be seen from the figure that the magnetic permeability shows a trend of increasing first and then decreasing with the increase of the applied field, the optimal magnetic permeability under the applied field of 80A/m and 1kHz can reach 27000, the magnetic permeability under the applied field of 100A/m and 1kHz can reach more than 25000, and meanwhile, the magnetic permeability under 10kHz does not generate the attenuation phenomenon under the corresponding applied field, which indicates that the alloy has higher frequency stability and ultrahigh magnetic permeability. The high magnetic conductivity and high frequency stability under high applied external field can be used in the technical fields of high-power large-capacity ultrahigh frequency high-precision power supply controllers for accelerators, high-frequency transformers and the like.
Comparative example 1
The comparison example takes Nanoperm alloy as comparison, and the molecular formula of the Nanoperm nanocrystalline magnetically soft alloy material is Fe 90 Zr 7 B 2 Cu 1 。
The specific preparation method of the iron-based nanocrystalline alloy of the comparative example comprises the following steps:
step 1: raw materials of Fe, zr, B and Cu with the purity of more than 99 percent are mixed according to a composition relation formula of Fe 90 Zr 7 B 2 Cu 1 And (5) burdening.
Step 2: putting the proportioned raw materials into an electric arc melting furnace, vacuumizing to be lower than 2.0 multiplied by 10 -2 Pa, then filling argon to the pressure of-0.05-0.01 MPa, and smelting for 4-5 times on the front and back sides to obtain alloy ingots with uniform components.
And 3, step 3: and (3) crushing the alloy ingot obtained in the step (2), then loading the crushed alloy ingot into a quartz tube with a nozzle at the bottom, and spinning the alloy ingot at the speed of 30-40 m/s in an argon atmosphere by adopting a single-roller quenching and spinning process to obtain the amorphous alloy strip.
And 4, step 4: placing the amorphous alloy strip obtained in the step 3 in a quartz tube, and vacuumizing to 5.0 multiplied by 10 -3 And Pa, placing the quartz tube in a heat treatment furnace, heating to 600 ℃ at the heating rate of 2 ℃/s, preserving the heat for 10-60 minutes, then quickly taking out the quartz tube, placing the quartz tube in water, and quenching to room temperature to obtain the nanocrystalline alloy material.
And (3) performance characterization:
XRD patterns of the quenched amorphous alloy strip prepared in the step 3 and the nanocrystalline alloy material after the heat treatment in the step 4 were respectively tested by a D8 advanced type polycrystalline X-ray diffractometer, and the results are shown in FIGS. 2 and 10.
Referring to fig. 2 and 10, the alloy ribbon prepared in step 3 is shown to have a broadened dispersion diffraction peak, indicating that the alloy ribbon has an amorphous structure. After the alloy strip is insulated for 30min at the temperature of 600 ℃, alpha-Fe and Fe appear in the alloy strip 3 Zr crystallization peak indicates that the alloy has poor high-temperature thermal stability.
The grain size was estimated to be around 18nm by the Scherrer equation.
FIG. 3 shows the DSC curve of the alloy strip produced in step 3. Wherein, the DSC curve is measured by a NETZSCH DSC 404C differential scanning calorimeter, and the measured temperature rise rate is 0.67 ℃/s. It can be seen that the alloy strip has a significant enthalpy change of heat release, indicating that the alloy produced has the characteristics of an amorphous alloy.
Fig. 4 and 5 show the coercive force of the alloy strip after heat treatment in step 4 as a function of temperature and time. Wherein, the coercive force is measured by a direct current B-H instrument (EXPH-100). It can be seen that the coercivity can be kept at about 10A/m within the range of 520-540 ℃ when the temperature is kept for 30min, and the coercivity is rapidly deteriorated when the temperature exceeds 540 ℃. The coercivity is only about 10A/m at 10min within 10min to 60min of heat treatment at 600 ℃, which indicates that the alloy has better high-temperature thermal stability in examples 1 and/or 2 than in examples 1 and/or 2.
Fig. 6a and 6b show the magnetic hysteresis loop and the enlarged view of the alloy strip after the heat treatment in step 4 under the optimal condition, wherein the magnetic hysteresis loop is measured by using a vibration sample magnetometer (VSM, lakeshore 7410) for testing the saturation induction of the alloy, and it can be seen that the saturation induction of the alloy is 1.61T.
FIG. 7 shows the permeability of the alloy strip after heat treatment in step 4 at different field strengths under optimum conditions, as measured by an impedance analyzer (Agilent 4294A). As can be seen from the graph, the magnetic permeability shows a trend of increasing and then decreasing with the increase of the applied field, the optimal magnetic permeability at 1kHz under the applied field of 50A/m is only 23000, and the optimal magnetic permeability at 10kHz is 22000, which shows that the alloy has relatively high frequency stability. However, the magnetic permeability under high applied external field is still relatively low and difficult to be used in the technical fields of high-power density ultrahigh frequency high-precision power supply controllers for accelerators, high-frequency transformers and the like.
According to the technical scheme and the performance detection results of the embodiment and the comparative example, the iron-based nanocrystalline soft magnetic alloy with all metal and high iron content provided by the embodiment is adopted, the iron content is controlled to be 85-90% under the condition that nonmetals such as Si, B, P, C and the like are not added, the saturation magnetization intensity of the soft magnetic alloy can be improved, and the soft magnetic alloy has excellent high permeability and high frequency stability under a high application field, so that the application of the soft magnetic alloy with all metal and high iron content in the technical fields of high-power-density ultrahigh-frequency high-precision power controllers for small-sized and light-weight accelerators, high-power-density ultrahigh-frequency high-precision power supplies, high-frequency transformers and the like is expanded.
The above is only a preferred embodiment of the present invention, which is not intended to limit the scope of the present invention, and various modifications and variations of the present invention are possible to those skilled in the art. Variations, modifications, substitutions, integrations and parameter changes of the embodiments may be made without departing from the principle and spirit of the invention, which may be within the spirit and principle of the invention, by conventional substitution or may realize the same function.
Claims (10)
1. The all-metal iron-based nanocrystalline magnetically soft alloy is characterized in that the all-metal iron-based nanocrystalline magnetically soft alloy is made of all-metal raw materials without adding non-metal elements; has a Fe-Co-M-N-Cu nano alloy system, wherein M = Zr, hf, nb; n = Li, be; in the Fe-Co-M-N-Cu system, the content of Fe is 85-90%.
2. The all-metallic iron-based nanocrystalline magnetically soft alloy according to claim 1, wherein the formula of the all-metallic iron-based nanocrystalline magnetically soft alloy is: fe a Zr b Be c Co d Cu e (ii) a Wherein a, b, c, d and e respectively represent the atomic percentage of each alloy element in the iron-based nanocrystalline magnetically soft alloy, and the following conditions are satisfied: a is more than or equal to 85 and less than or equal to 90;7b is less than or equal to 9;0c≤2；0d≤5；0.7≤e≤2；a+b+c+d+e＝100。
3. The all-metallic iron-based nanocrystalline magnetically soft alloy of claim 2, wherein the all-metallic iron-based nanocrystalline magnetically soft alloy has a-Fe (Co) nanocrystalline structure in a body-centered cubic structure embedded in an amorphous substrate.
4. The all-metallic iron-based nanocrystalline soft magnetic alloy according to claim 3, wherein the average grain size of the a-Fe (Co) nanocrystals is 10 to 12nm.
5. The all-metallic iron-based nanocrystalline magnetically soft alloy according to any one of claims 1 to 4, wherein the all-metallic iron-based nanocrystalline magnetically soft alloy is prepared by a smelting-single-roller quenching and melt spinning process-crystallization heat treatment process in sequence.
6. The all-metallic iron-based nanocrystalline magnetically soft alloy according to claim 5, wherein the coercive force remains at 10A/m after the all-metallic iron-based nanocrystalline magnetically soft alloy is subjected to heat treatment at 580-620 ℃ for 30-60 minutes;
the saturation magnetic induction intensity of the nanocrystalline magnetically soft alloy after crystallization heat treatment is 1.7-1.8T; the maximum magnetic permeability under the application field of 80A/m under 1kHz is more than or equal to 25000; the magnetic permeability under 10kHz is more than or equal to 25000.
7. The all-metallic iron-based nanocrystalline magnetically soft alloy according to any one of claims 1 to 4, wherein a purity of a raw material of the all-metallic iron-based nanocrystalline magnetically soft alloy is not less than 99.9%.
8. A method for preparing an all-metallic iron-based nanocrystalline magnetically soft alloy according to any one of claims 1 to 7, comprising the steps of:
(1) Weighing each alloy raw material for proportioning;
(2) Preparing a master alloy ingot: placing the alloy raw material in an electric arc melting device, and melting under the protection of inert atmosphere, wherein the melting temperature is 1300-1800 ℃; repeatedly smelting for 4-5 times to obtain the master alloy ingot;
(3) Preparing a quick quenching strip: crushing the master alloy ingot prepared in the step (2), putting the crushed master alloy ingot into a quartz tube with a nozzle at the bottom, and preparing a rapidly quenched ribbon of amorphous alloy by single-roller rapid quenching and strip-spinning process treatment;
(4) Crystallization heat treatment: and (4) putting the amorphous alloy prepared in the step (3) into a heat treatment furnace, raising the temperature to 480-640 ℃ at a constant speed, preserving the heat for 10-60 min, taking out, quenching and cooling to room temperature to obtain the all-metal iron-based nanocrystalline magnetically soft alloy.
9. The method for preparing an all-metallic iron-based nanocrystalline magnetically soft alloy according to claim 8, wherein in the step (3), the rapidly quenched ribbon is in a strip shape, has a width of 1 to 2mm and a thickness of 20 to 25 μm; the single-roller quenching melt-spinning process comprises melt-spinning at the speed of 30-40 m/s in an argon atmosphere;
and/or in the step (4), the rate of constant temperature rise is 1-10 ℃/s.
10. A magnetic core comprising the metallic iron-based nanocrystalline magnetically soft alloy according to any one of claims 2 to 7.
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