CN113658767A - Method for improving grain refinement and uniformity of alloy surface layer - Google Patents

Method for improving grain refinement and uniformity of alloy surface layer Download PDF

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CN113658767A
CN113658767A CN202110818841.3A CN202110818841A CN113658767A CN 113658767 A CN113658767 A CN 113658767A CN 202110818841 A CN202110818841 A CN 202110818841A CN 113658767 A CN113658767 A CN 113658767A
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surface layer
alloy
alloy surface
magnetic field
uniformity
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贺爱娜
董亚强
黎嘉威
夏卫星
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention discloses a method for improving grain refinement and uniformity of an alloy surface layer, which comprises the following steps: preparing materials according to alloy components and proportion thereof, and smelting to prepare a master alloy; preparing an alloy surface layer with a disordered matrix and heterogeneous grains coexisting from the master alloy by a single-roller rapid quenching method; and putting the alloy surface layer into a magnetic field for annealing to obtain the final alloy surface layer. The method can prepare the alloy surface layer with refined and uniform crystal grains under lower magnetic field intensity. The invention also discloses an alloy surface layer prepared by the method, and the alloy surface layer has the advantages of grain refinement, uniform distribution, lower loss and lower dynamic coercive force.

Description

Method for improving grain refinement and uniformity of alloy surface layer
Technical Field
The invention relates to the technical field of magnetic materials, in particular to a method for improving grain refinement and uniformity of an alloy surface layer.
Background
The iron-based amorphous soft magnetic material and the iron-based nanocrystalline soft magnetic material have excellent performances such as higher saturation magnetic induction intensity, low coercive force, low loss and high magnetic conductivity, and can be widely applied to power electronic devices such as transformers, sensors, mutual inductors, common mode inductors, wireless charging and the like. With the development of 5G + technology and science and technology, new requirements are put forward on soft magnetic materials, higher saturation magnetic induction and more excellent soft magnetic performance are pursued, and the development trend of high power, high frequency and low power consumption is met.
The iron-based amorphous soft magnetic material is obtained from amorphous stress relief annealing. The iron-based nanocrystalline soft magnetic material is a nanocrystalline material which is obtained after amorphous state annealing crystallization, and has the grain size smaller than 20nm and uniform distribution. However, high saturation magnetic sensor strength iron-based amorphous materials and iron-based nanocrystalline materials require high iron content, which reduces the amorphous forming ability of the materials, and large grains are likely to appear on the surface layer of the materials, which deteriorates the soft magnetic performance. The Journal of Magnetic Materials 62(1986)143-151 discloses that the strip surface has a distinct micro-dendritic grain of about 200nm and that the rapid quenching induces micro-dendrites to point to the amorphous mass in the iron-rich amorphous alloy. During annealing, the micro-dendrites grow up to micron-size along the rapid quenching induction direction. The Acta mater.49(2001) 4069-4077 document discloses that in the iron-rich nanocrystalline alloy, the loss of the material containing coarse grains in the surface layer was found to be 0.36W/kg at 1.4T and 50Hz, while the loss thereof at 1.4T and 50Hz was reduced to 0.24W/kg after the removal of the coarse grains in the surface layer.
The Acta Materialia 53(2005)4155-4161 discloses that it was found in NdPrDyFeMoB permanent magnetic materials that the nanosized soft magnetic phase could be refined by high magnetic field heat treatment, the grain size of the a-Fe phase after no magnetic field treatment was 20nm, and the grain size of the a-Fe phase after 19T high magnetic field treatment was reduced to 17 nm.
The Journal of Magnetic and Magnetic Materials 518(2021)167434 discloses that the average grain size can be reduced from-25 nm to-20 nm in the quenched state after 1T high-intensity Magnetic field heat treatment in (Nd0.8Pr0.2)2.2Fe12Co2B permanent magnet material.
The magnetic field heat treatment mentioned above can refine the grains, but the required magnetic field strength is very high, and needs more than 1T, even 19T, which is difficult to achieve by the conventional magnetic field heat treatment furnace. The iron-based amorphous soft magnetic material and the iron-based nanocrystalline soft magnetic material generally need to be subjected to heat treatment in a vacuum environment or a protective atmosphere, and a large magnetic field cannot be met according to the magnetic circuit design of the existing electromagnet. Meanwhile, in order to meet the industrial application, a large heat treatment area is required and a certain magnetic field is ensured. Therefore, it is urgently needed to develop a method for refining surface layer grains and improving grain uniformity under a weak magnetic field so as to improve the soft magnetic performance of the material.
Disclosure of Invention
The invention provides a method for refining surface layer grains and improving uniformity, and an alloy surface layer of iron-rich amorphous nanocrystalline with high soft magnetic performance can be prepared under the condition of a weak magnetic field by using the method.
A method for improving grain refinement and uniformity of an alloy surface layer, comprising:
preparing materials according to alloy components and proportion thereof, and smelting to prepare a master alloy;
preparing an alloy surface layer with a disordered matrix and heterogeneous grains coexisting from the master alloy by a single-roller rapid quenching method;
and putting the alloy surface layer into a magnetic field for annealing to obtain the final alloy surface layer.
Aiming at the problems that the iron-rich amorphous material and the iron-rich nanocrystalline material are easy to separate out crystal grains on the surface layer in the rapid quenching process in the prior art, and the crystal grains are thick after subsequent heat treatment to deteriorate the soft magnetism, the interaction between the ferromagnetic phase and the weak magnetic field enables the ferromagnetic phase which is not enough for nucleation to satisfy the nucleation barrier nucleation and growth by the energy supplement from the external magnetic field, thereby obtaining a large amount of nucleation crystal grains to reduce the nucleation radius, achieving the purposes of refining the crystal grains on the surface layer and improving the uniformity of the crystal grains, and further improving the soft magnetism performance of the iron-rich amorphous material and the iron-rich nanocrystalline material. The preparation method provided by the invention can achieve the purpose of grain refinement only by providing a weak magnetic field.
The magnetic field intensity of the weak magnetic field is not higher than 110 mT.
The alloy component is FeCuSiBNbM or FeSiBM, wherein M is any one or more of Mo, Al, Cr, Co, Ni, Mn, Ga, Mg, C, P and O.
The heterogeneous crystal grains account for 45-75% of the surface layer.
The alloy is an iron-based alloy with high saturation magnetic induction intensity, wherein the atomic percentage of iron is more than or equal to 75 percent. An appropriate amount of iron provides more alpha-Fe phase, more core, and more grains.
The thickness of the surface layer is 500-800 nm.
The annealing process comprises the following steps: heating to the crystallization temperature of heterogeneous crystal grains at the temperature of 1-60 ℃ per hour, preserving the heat for 1-5 hours, and then cooling to the room temperature.
Through a slow temperature rise process, enough heterogeneous crystal grains have enough time, energy from a magnetic field and external temperature rise is obtained, nucleation grows to form a large number of crystal grains, a pinning effect is achieved on crystal boundaries, and the crystal grain boundaries are mutually inhibited from expanding to form a small and uniform surface layer.
The crystallization temperature of the disordered matrix is 500-580 ℃. The proper heat preservation temperature not only enables the surface layer to have smaller and uniform crystal grains, but also enables the matrix to form proper crystal grains, thereby improving the soft magnetic performance, and the overhigh heat preservation temperature enables alloy elements to be separated out, thereby reducing the soft magnetic performance.
The heterogeneous grains have a preferred orientation and are perpendicular to the surface layer.
The magnetic field direction of the weak magnetic field is vertical to the preferred orientation of the heterogeneous crystal grains.
The surface layer crystal grains grow along the surface vertical direction (the preferred orientation of heterogeneous crystal grains), and when the magnetic field direction is vertical to the preferred orientation of the heterogeneous crystal grains in annealing, namely the magnetic field direction is parallel to the surface, the crystal grains can be prevented from growing along the outside of the surface, the crystal grains are oriented along the plane, and the magnetic conductivity is favorably improved.
Further, the magnetic field intensity is 80-100mT, and the annealing process comprises the following steps: heating to 520-560 ℃ at the temperature of 1-30 ℃ per hour, and then preserving the heat for 1-2 hours.
In the alloy surface layer where the disordered matrix and the heterogeneous grains coexist, compositional heterogeneity exists in the disordered matrix due to the heterogeneous grains, and the Fe element is relatively enriched but does not reach the critical nucleation radius. When a magnetic field (80-100mT) is applied in annealing, the application of the magnetic field can introduce static magnetic energy; meanwhile, the slow temperature rise rate (1-30 ℃ per hour) is favorable for the diffusion of the Fe element to the enrichment region; heating to 520 ℃ and 560 ℃ to facilitate the formation of uniform crystal grains on the surface layer and the formation of fine nano crystal grains on the block part; the heat preservation for 1-2h can help the ordered pair arrangement of elements.
The alloy surface layer is prepared according to the method for improving the grain refinement and uniformity of the alloy surface layer, and the grain size of the alloy surface layer is 280-310 nm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method provided by the invention can effectively refine surface layer grains, improve the uniformity of grain distribution and reduce domain wall energy.
(2) The method provided by the invention ensures that the loss value under 1.0T and 10kHz is 18-19.5W/kg, the dynamic coercive force under 1.0T and 10kHz is 3-4A/m, and the loss factor under 1MHz is 1.4-1.6.
Drawings
FIG. 1 is an XRD pattern of a surface layer of the quenched alloy strip of example 1 with a thickness of 1 micron removed from the surface layer, wherein A is the XRD pattern of the surface layer and B is the XRD pattern with a thickness of 1 mm removed from the surface inward;
FIG. 2 is a TEM image of the surface layer of the quenched alloy strip of example 1 and the 1 micron thickness removed from the surface layer, wherein A is a TEM image of the surface layer and B is a TEM image of the 1 mm thickness removed from the surface inwards;
FIG. 3 is a TEM image of the surface layer and the cross section of the alloy strip after the low-intensity magnetic field annealing in example 1, wherein A is the TEM image of the surface layer, and B is the TEM image of the cross section;
fig. 4 is a TEM image of the surface layer of the strip after nonmagnetic annealing in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
Example 1
The alloy of the embodiment comprises the following components in percentage by atom: 76 at% Fe, 1 at% Cu, 14 at% Si, 6 at% B and 3 at% Nb, which is prepared by the following steps:
mixing industrial-grade iron raw materials, copper raw materials, silicon raw materials, ferroboron pre-alloy ingot raw materials and ferroniobium pre-alloy ingot raw materials according to the proportion, obtaining master alloy through a vacuum induction melting furnace, then putting the master alloy into a rapid quenching furnace, spraying high-temperature molten liquid onto a rotary copper roller through a touch nozzle, and obtaining a quenched alloy belt with a surface layer containing crystal grains.
Placing the quenched alloy strip in a heat treatment furnace, slowly raising the temperature to 520 ℃ at a temperature raising rate of 5 ℃ per hour under a weak magnetic field of 100mT, and preserving the temperature for 1 hour; then cooled to room temperature.
The quenched alloy of this example was examined for phase structure and microstructure using a polycrystalline X-ray diffractometer (XRD) of the D8 Advance type, as shown in FIG. 1. A is the XRD pattern of the surface layer and B is the XRD pattern with a thickness of 1 micron removed from the surface layer. The XRD results showed that the alloy surface layer of this example had a sharp crystallization peak near 65 °, which disappeared after removal of 1 micron thickness from the surface layer, leaving only the steamed bun peak near 45 °. The results of the measurement are shown in FIG. 2 by the observation with a Talos Transmission Electron Microscope (TEM), where A is a TEM image of the surface layer and B is a TEM image of the surface layer with a thickness of 1 μm removed therefrom. TEM results show that the surface layer of this example is heterogeneous grains coexisting with a disordered matrix, with a grain size of about 185 nm; the proportion of heterogeneous crystal grains in the surface layer is 45 percent; the heterogeneous grains disappeared after removal of 1 micron thickness from the surface layer.
The microstructure of the alloy after the low-field annealing in this example was observed by Talos-TEM, and as a result, a is a TEM image of the surface layer and B is a TEM image of the cross section, as shown in fig. 3. According to a TEM image, the microstructure of the alloy surface layer after the low-intensity magnetic field annealing is that the grains are uniformly distributed, and the grain size is about 290 mm. As can be seen from the cross-sectional TEM image, the surface layer has a thickness of about 500nm, and the alloy matrix has a fine and uniform nanocrystalline structure.
The loss factor of the alloy after annealing in the weak magnetic field is tested by an Aglient4924 impedance analyzer in the United states, and the loss factor is 1.6 under 1 MHz. The loss and the dynamic coercive force of the alloy after the annealing in the weak magnetic field are tested by an alternating current B-H tester under the test conditions of 1.0T and 10kHz, the loss value is 19.8W/kg, and the dynamic coercive force value is 4A/m.
Example 2
The alloy of the embodiment comprises the following components in percentage by atom: 75 at% Fe, 1 at% Cu, 13 at% Si, 8 at% B, 2 at% Nb, and 1 at% Mn; the preparation method comprises the following steps:
mixing industrial-grade iron raw materials, copper raw materials, silicon raw materials, ferroboron pre-alloy ingot raw materials, ferromanganese pre-alloy ingot raw materials and ferroniobium pre-alloy ingot raw materials according to the proportion, obtaining master alloy through a vacuum induction melting furnace, then putting the master alloy into a rapid quenching furnace, spraying high-temperature molten liquid onto a rotary copper roller through a touch nozzle to obtain a quenched alloy strip with a surface layer containing crystal grains.
Placing the quenched alloy strip in a heat treatment furnace, slowly raising the temperature to 540 ℃ at a temperature rise rate of 1 ℃ per hour under a weak magnetic field of 110mT, and preserving the temperature for 2 hours; then cooled to room temperature.
The microstructure of the surface layer of the quenched alloy and the removal of 1 micron from the surface layer in this example was examined by polycrystalline X-ray diffractometer (XRD) of the D8 Advance type, and the structure showed that the surface layer of the alloy of this example had a sharp crystallization peak near 65 °, and that the crystallization peak disappeared after the removal of 1 micron from the surface layer, and only the peak of the steamed bread near 45 ° remained. The surface layer of the example was observed by Talos Transmission Electron Microscope (TEM) to be heterogeneous grains coexisting with a disordered matrix, wherein the grain size was about 190 nm; the proportion of heterogeneous crystal grains in the surface layer is 75 percent; the heterogeneous grains disappeared after removal of 1 micron thickness from the surface layer.
The microstructure of the alloy after the low-intensity magnetic field annealing in the embodiment is observed by Talos-TEM, and the microstructure of the alloy surface layer after the low-intensity magnetic field annealing is that the grains are uniformly distributed, and the grain size is about 300 nm. As can be seen from the cross-sectional TEM image, the thickness of the surface layer is about 600nm, and the alloy matrix is partially in a fine and uniform nanocrystalline structure.
The loss factor of the alloy after annealing in the weak magnetic field is tested by an Aglient4924 impedance analyzer in the United states, and the loss factor is 1.5 under 1 MHz. The loss and the dynamic coercive force of the alloy after the annealing in the weak magnetic field are tested by an alternating current B-H tester under the test conditions of 1.0T and 10kHz, the loss value is 18.5W/kg, and the dynamic coercive force value is 3.6A/m.
Comparative example 1
According to the process of example 1, the weak magnetic field of 100mT is not increased only during the preparation process.
As shown in FIG. 4, the microstructure of the alloy after nonmagnetic annealing in this example was observed by Talos-TEM, and the microstructure of the alloy surface layer after nonmagnetic annealing was coarse grains and contained a part of fine nano-grains, the size of the coarse grains was about 550nm, and the size of the fine nano-grains was about 14 nm.
The loss factor of the alloy after annealing in the weak magnetic field is tested by an Aglient4924 impedance analyzer in the United states, and the loss factor is 2.7 under 1 MHz. The loss and the dynamic coercive force of the alloy after the annealing in the weak magnetic field are tested by an alternating current B-H tester under the test conditions of 1.0T and 10kHz, the loss value is 30.9W/kg, and the dynamic coercive force value is 6.5A/m.
Comparative example 2
According to the process of example 2, the weak magnetic field of 110mT is not increased only during the preparation process.
As can be seen by observing the microstructure of the alloy after nonmagnetic annealing in the example by Talos-TEM, the microstructure of the alloy surface layer after nonmagnetic annealing is coarse grains and contains part of fine nano grains, the size of the coarse grains is about 570nm, and the size of the fine nano grains is about 16 nm.
The loss factor of the alloy after annealing in the weak magnetic field is tested by an Aglient4924 impedance analyzer in the United states, and the loss factor is 2.9 under 1 MHz. The loss and the dynamic coercive force of the alloy after the annealing in the weak magnetic field are tested by an alternating current B-H tester under the test conditions of 1.0T and 10kHz, the loss value is 41W/kg, and the dynamic coercive force value is 6.8A/m.

Claims (10)

1. A method for improving grain refinement and uniformity of an alloy surface layer is characterized by comprising the following steps:
preparing materials according to alloy components and proportion thereof, and smelting to prepare a master alloy;
preparing an alloy surface layer with a disordered matrix and heterogeneous grains coexisting from the master alloy by a single-roller rapid quenching method;
and putting the alloy surface layer into a magnetic field for annealing to obtain the final alloy surface layer.
2. The method of claim 1, wherein the magnetic field has a magnetic field strength of not more than 110 mT.
3. The method for improving grain refinement and uniformity of an alloy surface layer according to claim 1, wherein the annealing process comprises: heating to the crystallization temperature of heterogeneous crystal grains at the temperature of 1-60 ℃ per hour, preserving the heat for 1-5 hours, and then cooling to the room temperature.
4. The method of claim 1, wherein the alloy component is FeCuSiBNbM or FeSiBM, wherein M is one or more of Mo, Al, Cr, Co, Ni, Mn, Ga, Mg, C, P, and O.
5. A method for improving the grain refinement and uniformity of an alloy surface layer as claimed in any one of claims 1 to 4, wherein said heterogeneous grains account for 45 to 75% of the surface layer.
6. The method for improving the grain refinement and uniformity of the alloy surface layer according to any one of claims 1 to 4, wherein the alloy is a high saturation induction iron-based alloy, and the atomic percent of iron is greater than or equal to 75%.
7. The method as claimed in any one of claims 1 to 4, wherein the thickness of the final alloy surface layer is 500-800 nm.
8. A method for improving the grain refinement and uniformity of an alloy surface layer as claimed in any one of claims 1 to 4 wherein said heterogeneous grains have a preferred orientation and are perpendicular to the final alloy surface layer.
9. The method of claim 8, wherein the magnetic field is directed perpendicular to the preferred orientation of the heterogeneous grains.
10. The alloy surface layer prepared by the method for improving the grain refinement and uniformity of the alloy surface layer according to any one of claims 1 to 9, wherein the grain size in the alloy surface layer is 280-310 nm.
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Publication number Priority date Publication date Assignee Title
CN102304679A (en) * 2011-09-28 2012-01-04 宋玉军 Amorphous nanocrystal gradient functional material and preparation method thereof
CN107267838A (en) * 2017-05-11 2017-10-20 东北大学 It is a kind of to prepare the method with high tough fine grain high-entropy alloy using pyromagnetic coupling
CN108109803A (en) * 2017-12-19 2018-06-01 青岛云路先进材料技术有限公司 Distribution amorphous transformer
CN108856662A (en) * 2018-06-21 2018-11-23 中国科学院宁波材料技术与工程研究所 A kind of preparation method of applied static magnetic field device and Fe Based Nanocrystalline Alloys band
CN109604606A (en) * 2018-11-30 2019-04-12 东莞理工学院 A kind of longitudinally magnetic heat treatment method of iron-based non-crystalline soft magnetic-powder core

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102304679A (en) * 2011-09-28 2012-01-04 宋玉军 Amorphous nanocrystal gradient functional material and preparation method thereof
CN107267838A (en) * 2017-05-11 2017-10-20 东北大学 It is a kind of to prepare the method with high tough fine grain high-entropy alloy using pyromagnetic coupling
CN108109803A (en) * 2017-12-19 2018-06-01 青岛云路先进材料技术有限公司 Distribution amorphous transformer
CN108856662A (en) * 2018-06-21 2018-11-23 中国科学院宁波材料技术与工程研究所 A kind of preparation method of applied static magnetic field device and Fe Based Nanocrystalline Alloys band
CN109604606A (en) * 2018-11-30 2019-04-12 东莞理工学院 A kind of longitudinally magnetic heat treatment method of iron-based non-crystalline soft magnetic-powder core

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