CN114360884A - High-magnetic-induction low-loss gradient nanocrystalline magnetic powder core suitable for high-frequency inductance element and preparation method and application thereof - Google Patents
High-magnetic-induction low-loss gradient nanocrystalline magnetic powder core suitable for high-frequency inductance element and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core suitable for a high-frequency inductance element, and a preparation method and application thereof. The method comprises the steps of carrying out discharge plasma treatment on Fe-based amorphous alloy powder to enable the surface layer of the amorphous powder to be subjected to nano crystallization, then carrying out compression molding after adding a coating agent and a lubricating agent, and finally carrying out sintering treatment at the temperature higher than the crystallization temperature of the Fe-based amorphous alloy powder, wherein the nano crystals on the surface of the powder continue to grow and the amorphous nano crystals in the powder are subjected to nano crystallization to form the gradient difference of the sizes of the grains, so that the high-magnetic-induction low-loss gradient nano-crystalline magnetic powder core with large grains at the outer layer and small grains at the inner layer is obtained. The method provided by the invention is simple, environment-friendly and low in cost, effectively improves the saturation magnetic induction strength, the magnetic conductivity and the resistivity of the Fe-based magnetic powder core, greatly reduces the magnetic loss, and can be widely applied to medium-high frequency electronic devices in various fields.
Description
Technical Field
The invention belongs to the technical field of soft magnetic material forming, and particularly relates to a high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core suitable for a high-frequency inductance element, and a preparation method and application thereof.
Background
With the continuous update and update of modern technologies, electrification is more and more widely used in many industries, and the miniaturization of electronic devices gradually becomes a trend, for example, in the fields of 3C products, communication electronics, medical instruments, new energy vehicles, aerospace and the like, and target devices of specific applications thereof are, for example, in 5G communication devices, 5G communication base stations, inductors, execution components, generators, intelligent temperature control devices, transformers, motors, transformers, chokes, complex dampers and the like. Therefore, higher magnetic performance and higher efficiency of the inductance element are required to meet the trend of miniaturization of power devices. In particular, these devices are required to operate at high frequencies above a few hundred megahertz (MHz), with powers of up to several kilowatts, and therefore have high magnetic induction (B)s) And low magnetic loss (W)m) The soft magnetic alloy can meet the requirements of modularization and high-efficiency integration of electronic devices, so that the soft magnetic material can be a key material for high-efficiency operation of next-generation electronic power equipment and electronic devices thereof.
Magnetic powder core soft magnetic composite materials are the focus of research in the field of magnetic materials in recent years. Generally, the preparation of a magnetic powder core soft magnetic composite material comprises the following steps: (1) preparing soft magnetic alloy powder by using methods such as gas atomization or water atomization, wherein the soft magnetic material is generally an iron-based pre-alloy component containing silicon, nickel, aluminum or cobalt; (2) coating an insulating layer on the surface of the soft magnetic alloy powder; (3) mixing the insulation-coated soft magnetic powder with a lubricant; (4) pressing and forming the mixed powder obtained in the step (3) to prepare a green body; (5) sintering at 350-900 deg.c to obtain the magnetically soft composite magnetic powder core material. The magnetic powder core soft magnetic composite material insulation coating layer is characterized in that: each powder particle coated with an insulating layer has a very small eddy current path inside it and has a high specific resistance, so that eddy current loss generated during operation of the soft magnetic composite material can be greatly reduced. Thus, the individual soft magnetic powder particles and their insulating coating layers may be referred to as "functional elements", and the soft magnetic composite material is formed by combining a plurality of functional elements.
On the other hand, the nanocrystalline soft magnetic composite material has higher magnetic induction strength and magnetic permeability. The unique structure length of the nanocrystalline soft magnetic alloy is far lower than the ferromagnetic exchange length, so that the magnetic anisotropy constant is reduced, and the nanocrystalline soft magnetic alloy has excellent soft magnetic performance and can be applied to various occasions. According to the definition, the nanocrystalline functional element is internally composed of a soft magnetic amorphous matrix and randomly nucleated nanocrystals, and the outside is a coated insulating layer. The internal structure is generally obtained by a two-stage route: firstly, an amorphous structure is obtained through rapid solidification, and then a nanocrystalline is formed through modification treatment and crystallization.
The Yoshizawa et al have demonstrated that superior soft magnetic properties can be obtained by sintering Fe-Si-B with small additions of Cu and Nb (Fe-Si-B-Nb-Cu is also known as Finemet alloy) at 500 to 600 c for 1 hour. This is because the introduction of Cu increases the number of nucleation sites, while Nb prevents grain growth while inhibiting the formation of boride phases, so the developed microstructure consists of an amorphous matrix and α -Fe + FeSi nanocrystals (about 10 nm). B of Finemet alloy, howeversThe value is not yet sufficient for some of the required high BsThe need for an inductive device of (1). To develop high BsSoft magnetic alloys, Suzuki et al, a manufacturing base based on Finemet alloys, developed Fe-Zr-B based alloys known as Nanoperm alloys. Also, Makino et al developed Nanomet alloys containing the non-metals Fe-Si-B-P-Cu.
Although the Nanoperm alloy and the Nanomet alloy improved the saturation induction strength BsValue, but its magnetic loss W at high frequency operationmStill higher, can not satisfy the demand of low loss of future increasingly miniaturized electronic devices. On the other hand, for nanocrystalline soft magnetic alloys, although the regulation and control of the material composition thereof have been studied and reported, the regulation and control of the gradient size difference of the nanocrystals have not been reported. Therefore, it is necessary to find a high magnetic induction and low loss nano gradient magnetic material to expand the industrial application field.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims at providing a preparation method of a high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core, which comprises the steps of carrying out discharge plasma treatment on Fe-based amorphous alloy powder to crystallize the surface layer of the powder, then adding a coating agent and a lubricating agent to carry out pressing, and finally carrying out sintering treatment at a temperature higher than the crystallization temperature to continuously grow the nanocrystalline grains on the surface of the powder and crystallize the amorphous grains in the powder to form the gradient difference of the grain sizes, thereby obtaining the high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core with large grains at the outer layer and small grains at the inner layer.
The method can improve the magnetic conductivity U of the original Fe-based micron-sized magnetic powder coreiAnd the magnetic loss during the operation of medium and high frequency is reduced, and the manufacturing process flow is simple, and the method can be manufactured in a personalized way and can also be produced in batch, and is particularly suitable for the application of medium and high frequency electronic devices.
The invention also aims to provide the nanocrystalline magnetic powder core with high magnetic induction and low loss gradient, which is prepared by the method.
The invention further aims to provide the application of the high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core in electronic devices in the medium-high frequency field.
The high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core can be applied to the fields of 3C products, communication electronics, medical instruments, new energy automobiles, aerospace and the like, and target devices of the high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core can be specifically applied to 5G communication devices, 5G communication base stations, choke coils, inductors, executive components, generators, intelligent temperature control devices, transformers, motors, mutual inductors, dampers and the like.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core comprises the following steps:
(1) carrying out discharge plasma treatment on Fe-based amorphous alloy powder under the following treatment conditions: the voltage is 130-150V, the current is 1.6-2.2A, the rotating speed is 1000-1500 r/min, the time of each discharge treatment is 2-4 h, the next discharge treatment is carried out every 10-30 minutes after each discharge treatment is finished until the number of discharge treatment times reaches 5-10 times, and the Fe-based alloy powder with the nano-crystallized surface is obtained;
(2) mixing, coating and drying the Fe-based alloy powder subjected to surface nanocrystallization in the step (1) and a coating agent, then uniformly mixing the Fe-based alloy powder and the coating agent with a lubricant, and performing compression molding to obtain a high-density magnetic powder core pressed compact;
(3) and (3) sintering and forming the high-density magnetic powder core pressed compact in the step (2) in an inert gas atmosphere, wherein the nanocrystalline on the surface of the Fe-based alloy powder grows into large-size nanocrystalline, and the nanocrystalline inside the Fe-based alloy powder is crystallized into small-size nanocrystalline, so that the high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core is obtained.
Preferably, the discharge plasma treatment conditions in step (1) are as follows: the voltage is 135V, the current is 2-2.3A, the rotating speed is 1100-1200 r/min, the time of each discharge treatment is 2.3-3 h, and the next discharge treatment is carried out after 10-30 minutes after each discharge treatment until the number of discharge treatment times reaches 5-10.
Preferably, the Fe-based amorphous alloy powder in the step (1) has an element content of Fe 70-90 at.%, and the balance is composed of two or more elements selected from the following components: si, Co, B, C, P, Cu, Ni, Mo, Al, Ta, Nb and Sn elements; the particle size of the Fe-based amorphous alloy powder is 20-110 mu m.
More preferably, the Fe-based amorphous alloy powder of step (1) is Fe83Si5B8Cu4、Fe80Si10B6Nb4And Fe82Si7B6P3Cu2At least one of (1).
Preferably, the Fe-based amorphous alloy powder in the step (1) is prepared by raw material batching, rod making, alloy powder preparation by a rotary electrode atomization method and screening.
Preferably, the discharge Plasma treatment equipment in the step (1) is a Plasma-BM-S type discharge Plasma machine.
Preferably, the discharge plasma treatment in step (1) is performed in a stainless steel ball mill pot, and before the discharge plasma treatment, the atmosphere is purged with a high-purity inert gas and then an inert gas is introduced.
Preferably, a layer of nano-crystal film with the thickness of 50-500nm is obtained on the surface of the Fe-based alloy powder subjected to surface nano-crystallization in the step (1).
Preferably, the coating agent in the step (2) is organic silicon resin, and the coating agent and an organic solvent are mixed according to a volume ratio of 75-85: 25-15, and mixing with surface nano-crystallized Fe-based alloy powder, wherein the mass ratio of the surface nano-crystallized Fe-based alloy powder to the coating agent solution is 10: 1; the organic solvent is a ketone organic solvent, and more preferably at least one of butanone and acetone.
Preferably, the mixing and coating time of the Fe-based alloy powder subjected to surface nano crystallization in the step (2) and a coating agent is 25-55 min; the drying temperature is 50-80 ℃, and the drying time is 20-40 min.
Preferably, the lubricant in the step (2) is zinc stearate, and the lubricant accounts for 0.1-0.5% of the total mass of the Fe-based alloy powder with the nano-crystallized surface and the coating agent.
Preferably, the mixing time with the lubricant in the step (2) is 10-30 min.
Preferably, the pressure of the compression molding in the step (2) is 1.5-3 GPa, and the compression time is 5-60 s.
Preferably, the sintering temperature in the step (3) is higher than the crystallization temperature of the Fe-based amorphous alloy powder, and the time is 10 min-1 h; more preferably 30 to 35 min.
Preferably, the nanocrystalline magnetic powder core with high magnetic induction and low loss gradient obtained in the step (3) can be further subjected to paint spraying, the paint spraying material is epoxy resin or polyester mixture, and the spraying thickness is 80-260 mu m; more preferably 80 to 150 μm.
The paint spraying treatment of the obtained high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core is to prevent the magnetic powder core from being oxidized and corroded by oxygen, water and the like to cause the deterioration of the soft magnetic performance of the magnetic powder core.
The method can prepare the high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core.
The high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core is applied to electronic devices in the field of medium and high frequency (more than 30 MHz).
Preferably, the medium-high frequency (greater than 30MHz) fields are the fields of 3C products, communication electronics, medical instruments, new energy automobiles and aerospace; more preferred electronic devices are 5G communication devices, 5G communication base stations, chokes, inductors, actuators, generators, intelligent temperature control devices, transformers, motors, transformers and dampers.
In the discharge treatment process of the discharge plasma in the step (1), high-frequency alternating current can generate high voltage between an iron core electrode bar and a stainless steel grinding groove, and the high voltage can break down gas in a discharge chamber (between a discharge barrier and the grinding groove) so as to generate cold discharge plasma; in the discharge process, the instantaneous high temperature enables the surface of the Fe-based amorphous powder to generate a layer of nano-crystal film with the thickness of about 50-500nm, thereby obtaining the soft magnetic gradient alloy powder with the nano-surface and the amorphous structure inside. Meanwhile, in the plasma treatment process, partial closed pores in the Fe-based amorphous powder can be opened and most of satellite powder stuck to the surface of the powder can be removed, so that the compactness of the pressed powder is improved. And (3) crystallizing the Fe-based amorphous powder in the sintering process in the step (3), wherein the surface of the powder is crystallized due to the plasma treatment in the step (1), so that the surface crystal grains of the powder continue to grow up in the sintering process, the powder starts to crystallize inside, and the gradient difference of the crystal grain sizes is formed, specifically, the surface nano-crystal grows to be close to 100nm, the internal amorphous phase is crystallized to be about 10nm, and thus, the high-magnetic-induction low-loss gradient nano-crystal magnetic powder core with large outer-layer crystal grains and small inner-layer crystal grains is obtained.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the unique gradient nanostructure of the high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core prepared by the method of the invention improves the magnetic performance of the Fe-based magnetic powder core. Compared with the Fe-based magnetic powder core without the nano crystallization treatment on the powder surface in the step (1), the magnetic conductivity and the saturation magnetic induction of the magnetic powder core are improved, the improvement range is 8-15%, and in addition, the magnetic loss of the magnetic powder core can be reduced by 6-10%. The plasma discharge surface crystallization treatment process is simple, environment-friendly and low in cost, and can improve the comprehensive performance of the composite magnetic powder core.
Drawings
FIG. 1 is a schematic cross-sectional view of an amorphous alloy powder obtained in step (2) of the present application.
FIG. 2 is a schematic diagram of gradient nanocrystals generated by the sintering process in step (4) of the present application.
FIG. 3 is a schematic diagram of the gradient nanocrystal obtained in step (4) of the embodiment of the present application.
FIG. 4 shows the permeability of gradient nanocrystalline magnetic powder core with high magnetic induction and low loss in step (5) of example 1.
FIG. 5 shows the saturation induction strength of gradient nanocrystalline magnetic powder core with high induction and low loss in step (5) of the paint spraying treatment of example 1.
FIG. 6 shows the magnetic loss of the gradient nanocrystalline magnetic powder core with high magnetic induction and low loss in step (5) of the paint spraying treatment of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
(1) Milling: fe of pure iron, pure silicon, pure boron and pure copper according to design83Si5B8Cu4Preparing materials in atomic percentage, preparing a rod, preparing alloy powder by a rotary electrode gas atomization method, and screening the powder to obtain Fe with the particle size of 20-110 mu m83Si5B8Cu4Spherical amorphous powder.
(2) Powder surface crystallization: fe obtained in the step (1)83Si5B8Cu4Placing the spherical amorphous powder into a stainless steel ball-milling tank under a pressure of 2 × 105And purifying the atmosphere in the grinding groove for 3 times by using high-purity argon of Pa, and then introducing argon. Treating the powder with Plasma-BM-S type discharge Plasma machine with voltage of 135V, current of 2A, motor speed of 1100r/min, and discharge treatment time per timeThe time is 2.5 h. After each discharge treatment, the next time was performed 10 minutes apart until the number of discharge treatments reached 8. In the discharge treatment process, high-frequency alternating current can generate high voltage between the iron core electrode bar and the stainless steel grinding groove, and the high voltage can break down gas in a discharge chamber (between the discharge barrier and the grinding groove) so as to generate cold discharge plasma. So that during the discharge process, the instantaneous high temperature makes Fe83Si5B8Cu4A layer of nano crystal film is generated on the surface of the spherical amorphous powder, and the thickness is about 150 nm. Meanwhile, Fe can be added in the plasma treatment process83Si5B8Cu4And opening and removing most of satellite powder adhered to the surface of the powder body by using part of closed-pore hollow powder in the spherical amorphous powder so as to improve the compactness of the pressed powder.
(3) Powder coating and compression molding: mixing organic silicon resin (MQ silicon resin) and acetone according to a mass ratio of 85: 15 evenly mixing to obtain organic silicon resin acetone mixed solution, and then adding the Fe subjected to the plasma surface crystallization treatment in the step (2)83Si5B8Cu4And stirring the spherical amorphous powder for 30min to finish coating, wherein the mass ratio of the amorphous powder to the organic silicon resin acetone mixed solution is 10: 1. And (3) putting the coated powder into a drying box at 65 ℃ for drying treatment for 30 min. And then uniformly mixing the dried coating powder with zinc stearate, wherein the zinc stearate accounts for 0.4 percent of the total mass of the amorphous powder and the organic silicon resin. Finally, cold pressing is carried out, the forming pressure is 2GPa, the pressing time is 20s, and Fe is formed83Si5B8Cu4Magnetic powder core.
(4) Sintering to generate gradient nano-crystals: fe obtained in the step (3)83Si5B8Cu4And sintering the magnetic powder core in an argon atmosphere. Fe83Si5B8Cu4The crystallization temperature of the alloy components is 490 ℃, so the sintering temperature is 490 ℃, and the sintering time is 30 min. Fe in sintering process83Si5B8Cu4The amorphous powder starts to crystallize, and since the plasma treatment in step 2 has caused the powder surface to crystallize, during sintering,the crystal grains on the surface of the powder begin to grow up first, and the inside of the powder begins to crystallize, so that the difference of the sizes of the crystal grains is formed, and the gradient nano magnetic powder core with high magnetic induction and low loss is obtained.
(5) And (3) spray painting treatment: in order to prevent the magnetic powder core from being oxidized and corroded by oxygen, water and the like to cause the deterioration of the soft magnetic performance, the gradient nano magnetic powder core with high magnetic induction and low loss obtained in the step (4) needs to be subjected to paint spraying treatment, epoxy resin E-44 is selected as a paint spraying material, and the spraying thickness is about 110 mu m.
High-magnetic-induction low-loss nano gradient Fe prepared by adopting method83Si5B8Cu4Magnetic powder core, unique gradient nanostructure makes Fe83Si5B8Cu4The nano magnetic property of the magnetic powder core is improved. And Fe which is not subjected to surface crystallization treatment of the powder in the step (2)83Si5B8Cu4Compared with the magnetic powder core (only the steps (1), (3) and (5)), the magnetic powder core has the advantages that the magnetic permeability is improved from 210H/m to 230H/m (shown in figure 4), the magnetic permeability is improved by 9 percent, the saturation magnetic induction intensity is improved from 166emu/g to 186emu/g, the saturation magnetic induction intensity is improved by 11 percent (shown in figure 5), and the magnetic loss is reduced by 6.1 percent (shown in figure 6). Therefore, the comprehensive demand characteristics of the composite magnetic powder core obtained by plasma discharge surface crystallization treatment are improved.
Example 2
(1) Milling: mixing pure iron, pure silicon, pure boron and pure niobium into Fe80Si10B6Nb4The designed atomic percentage is used for preparing materials and rods, alloy powder is prepared by a rotary electrode gas atomization method, and the powder is screened to obtain Fe with the particle size of 20-110 mu m80Si10B6Nb4Spherical amorphous powder.
(2) Powder surface crystallization: fe obtained in the step (1)80Si10B6Nb4Placing the spherical amorphous powder into a stainless steel ball-milling tank under a pressure of 2 × 105And purifying the atmosphere in the grinding groove for 3 times by using high-purity argon of Pa, and then introducing argon. Treating the powder with Plasma-BM-S type discharge Plasma machine with voltage of 135V, current of 2.1A, motor speed of 1200r/min, and discharge each timeThe treatment time was 3 h. After each discharge treatment, the next time was performed 10 minutes apart until the number of discharge treatments reached 7. In the discharge treatment process, high-frequency alternating current can generate high voltage between the iron core electrode bar and the stainless steel grinding groove, and the high voltage can break down gas in a discharge chamber (between the discharge barrier and the grinding groove) so as to generate cold discharge plasma. So that during the discharge process, the instantaneous high temperature makes Fe80Si10B6Nb4A layer of nano crystal film is generated on the surface of the spherical amorphous powder, and the thickness is about 150 nm. Meanwhile, Fe can be added in the plasma treatment process80Si10B6Nb4And opening and removing most of satellite powder adhered to the surface of the powder body by using part of closed-pore hollow powder in the spherical amorphous powder so as to improve the compactness of the pressed powder.
(3) Powder coating and compression molding: mixing organic silicon resin (MQ silicon resin) and butanone according to a mass ratio of 80: 20 to obtain organic silicon resin acetone mixed solution, and then adding the Fe subjected to the plasma surface crystallization treatment in the step (2)83Si5B8Cu4And stirring the spherical amorphous powder for 35min to finish coating, wherein the mass ratio of the amorphous powder to the organic silicon resin acetone mixed solution is 10: 1. And (3) putting the coated powder into a drying box at 65 ℃ for drying treatment for 35 min. And then uniformly mixing the dried coating powder with zinc stearate, wherein the zinc stearate accounts for 0.5 percent of the total mass of the amorphous powder and the organic silicon resin. Finally, cold pressing is carried out, the forming pressure is 2.2GPa, the pressing time is 25s, and Fe is formed80Si10B6Nb4Magnetic powder core.
(4) Sintering to generate gradient nano-crystals: fe obtained in the step (3)80Si10B6Nb4And sintering the magnetic powder core in an argon atmosphere. Fe80Si10B6Nb4The crystallization temperature of the alloy components is 440 ℃, so that the sintering temperature is 440 ℃, and the sintering time is 35 min. Fe in sintering process80Si10B6Nb4The amorphous powder starts to crystallize, since the plasma treatment in step 2 has caused the powder surface to crystallize, and therefore,during the sintering process, the crystal grains on the surface of the powder begin to grow up first, and the inside of the powder begins to crystallize, so that the difference of the sizes of the crystal grains is formed, and the gradient nano magnetic powder core with high magnetic induction and low loss is obtained.
(5) And (3) spray painting treatment: in order to prevent the magnetic powder core from being oxidized and corroded by oxygen, water and the like to cause the deterioration of the soft magnetic performance, the gradient nano magnetic powder core with high magnetic induction and low loss obtained in the step (4) needs to be subjected to paint spraying treatment, the paint spraying material is epoxy resin type E-44, and the spraying thickness is about 130 mu m.
High-magnetic-induction low-loss nano gradient Fe prepared by adopting the scheme80Si10B6Nb4Magnetic powder core, unique gradient nanostructure makes Fe80Si10B6Nb4The nano magnetic property of the magnetic powder core is improved. And Fe which is not subjected to surface crystallization treatment of the powder in the step (2)80Si10B6Nb4Compared with the magnetic powder core (only the steps (1), (3) and (5)), the magnetic powder core has the magnetic permeability increased from 215H/m to 240H/m and increased by 11 percent, the saturation magnetic induction intensity increased from 160emu/g to 179emu/g and increased by 10 percent, and the magnetic loss reduced by 7.2 percent. Therefore, the comprehensive demand characteristics of the composite magnetic powder core obtained by plasma discharge surface crystallization treatment are improved.
Example 3
(1) Milling: pure iron, pure silicon, pure boron, pure copper, iron-phosphorus alloy are mixed according to Fe82Si7B6P3Cu2The designed atomic percentage is used for preparing materials and rods, alloy powder is prepared by a rotary electrode gas atomization method, and the powder is screened to obtain Fe with the particle size of 20-110 mu m82Si7B6P3Cu2Spherical amorphous powder.
(2) Powder surface crystallization: fe obtained in the step (1)82Si7B6P3Cu2Placing the spherical amorphous powder into a stainless steel ball-milling tank under a pressure of 2 × 105And purifying the atmosphere in the grinding groove for 3 times by using high-purity argon of Pa, and then introducing argon. Treating the powder with Plasma-BM-S type discharge Plasma machine with voltage of 135V, current of 2.3A, and motor speed1000r/min, and each discharge treatment time is 2.3 h. After each discharge treatment, the next time was performed 10 minutes apart until the number of discharge treatments reached 9. In the discharge treatment process, high-frequency alternating current can generate high voltage between the iron core electrode bar and the stainless steel grinding groove, and the high voltage can break down gas in a discharge chamber (between the discharge barrier and the grinding groove) so as to generate cold discharge plasma. So that during the discharge process, the instantaneous high temperature makes Fe82Si7B6P3Cu2A layer of nano crystal film is generated on the surface of the spherical amorphous powder, and the thickness is about 180 nm. Meanwhile, Fe can be added in the plasma treatment process82Si7B6P3Cu2And opening and removing most of satellite powder adhered to the surface of the powder body by using part of closed-pore hollow powder in the spherical amorphous powder so as to improve the compactness of the pressed powder.
(3) Powder coating and compression molding: mixing organic silicon resin (MQ silicon resin) and acetone according to a mass ratio of 82: 18 to obtain organic silicon resin acetone mixed solution, and then adding the Fe subjected to the plasma surface crystallization treatment in the step (2)83Si5B8Cu4And stirring the spherical amorphous powder for 28min to finish coating, wherein the mass ratio of the amorphous powder to the organic silicon resin acetone mixed solution is 10: 1. And (3) putting the coated powder into a drying oven at 60 ℃ for drying treatment for 40 min. And then uniformly mixing the dried coating powder with zinc stearate, wherein the zinc stearate accounts for 0.4 percent of the total mass of the amorphous powder and the organic silicon resin. Finally, cold pressing is carried out, the forming pressure is 2.3GPa, the pressing time is 15s, and Fe is formed82Si7B6P3Cu2Magnetic powder core.
(4) Sintering to generate gradient nano-crystals: fe obtained in the step (3)82Si7B6P3Cu2And sintering the magnetic powder core in an argon atmosphere. Fe82Si7B6P3Cu2The crystallization temperature of the alloy components is 452 ℃, so the sintering temperature is 452 ℃, and the sintering time is 40 min. Fe in sintering process82Si7B6P3Cu2Amorphous formAnd (3) starting crystallization of the powder, wherein the surface of the powder is crystallized by the plasma treatment in the step (2), so that the crystal grains on the surface of the powder begin to grow up firstly in the sintering process, and the inside of the powder begins to crystallize to form the difference of the crystal grain sizes, thereby obtaining the gradient nano magnetic powder core with high magnetic induction and low loss.
(5) And (3) spray painting treatment: in order to prevent the magnetic powder core from being oxidized and corroded by oxygen, water and the like to cause the deterioration of the soft magnetic performance, the gradient nano magnetic powder core with high magnetic induction and low loss obtained in the step (4) needs to be subjected to paint spraying treatment, epoxy resin E-44 is selected as a paint spraying material, and the spraying thickness is about 115 mu m.
High-magnetic-induction low-loss nano gradient Fe prepared by adopting the scheme82Si7B6P3Cu2Magnetic powder core, unique gradient nanostructure makes Fe82Si7B6P3Cu2The nano magnetic property of the magnetic powder core is improved. And Fe which is not subjected to surface crystallization treatment of the powder in the step (2)82Si7B6P3Cu2Compared with the magnetic powder core (only the steps (1), (3) and (5)), the magnetic powder core has the advantages that the magnetic permeability is improved from 224H/m to 245H/m and is improved by 9 percent, the saturation magnetic induction intensity is improved from 157emu/g to 179emu/g and is improved by 12 percent, and the magnetic loss is reduced by 8.1 percent. Therefore, the comprehensive demand characteristics of the composite magnetic powder core obtained by plasma discharge surface crystallization treatment are improved.
Comparative example 1
This comparative example changed only the plasma ball milling treatment parameters of the step (2) to Fe83Si5B8Cu4The amorphous alloy powder surface could not be crystallized, and the composition and other experimental parameter steps were consistent with those of example 1.
(1) Milling: fe of pure iron, pure silicon, pure boron and pure copper according to design83Si5B8Cu4Preparing materials in atomic percentage, preparing a rod, preparing alloy powder by a rotary electrode gas atomization method, and screening the powder to obtain Fe with the particle size of 20-110 mu m83Si5B8Cu4Spherical amorphous powder.
(2) Powder surface crystallization: fe obtained in the step (1)82Si7B6P3Cu2Placing the spherical amorphous powder into a stainless steel ball-milling tank under a pressure of 2 × 105And purifying the atmosphere in the grinding groove for 3 times by using high-purity argon of Pa, and then introducing argon. The powder is treated by using a Plasma-BM-S type discharge Plasma machine, the voltage is set to be 130V, the current is controlled to be 1.7A, the rotating speed of a motor is 1000r/min, and the treatment time of each discharge is 2 h. After each discharge treatment, the next time was performed 10 minutes apart until the number of discharge treatments reached 9.
(3) Powder coating and compression molding: mixing organic silicon resin (MQ silicon resin) and acetone according to a mass ratio of 85: 15 evenly mixing to obtain organic silicon resin acetone mixed solution, and then adding the Fe subjected to the plasma surface crystallization treatment in the step (2)83Si5B8Cu4And stirring the spherical amorphous powder for 30min to finish coating, wherein the mass ratio of the amorphous powder to the organic silicon resin acetone mixed solution is 10: 1. And (3) putting the coated powder into a drying box at 65 ℃ for drying treatment for 30 min. And then uniformly mixing the dried coating powder with zinc stearate, wherein the zinc stearate accounts for 0.4 percent of the total mass of the amorphous powder and the organic silicon resin. Finally, cold pressing is carried out, the forming pressure is 2GPa, the pressing time is 20s, and Fe is formed83Si5B8Cu4Magnetic powder core.
(4) And (3) sintering to generate nano-crystals: fe obtained in the step (3)83Si5B8Cu4And sintering the magnetic powder core in an argon atmosphere. Fe83Si5B8Cu4The crystallization temperature of the alloy components is 490 ℃, so the sintering temperature is 490 ℃, and the sintering time is 30 min. Fe in sintering process83Si5B8Cu4The amorphous powder generates nanocrystals.
(5) And (3) spray painting treatment: in order to prevent the magnetic powder core from being oxidized and corroded by oxygen, water and the like to cause the deterioration of the soft magnetic performance, the gradient nano magnetic powder core with high magnetic induction and low loss obtained in the step (4) needs to be subjected to paint spraying treatment, epoxy resin E-44 is selected as a paint spraying material, and the spraying thickness is about 110 mu m.
Fe prepared by the above method83Si5B8Cu4Magnetic powder core with 214H/m magnetic permeability and 169emu/g saturation magnetic induction strength, compared with nanometer gradient Fe of example 183Si5B8Cu4The magnetic powder core has 7% lower magnetic permeability, 9.2% lower saturation induction and 6.2% higher magnetic loss. It can be seen that the prepared Fe is caused by the difference of the grain structure83Si5B8Cu4The magnetic performance of the magnetic powder core is reduced.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a high magnetic induction low loss gradient nanocrystalline magnetic powder core is characterized by comprising the following steps:
(1) carrying out discharge plasma treatment on Fe-based amorphous alloy powder under the following treatment conditions: the voltage is 130-150V, the current is 1.6-2.2A, the rotating speed is 1000-1500 r/min, the time of each discharge treatment is 2-4 h, the next discharge treatment is carried out every 10-30 minutes after each discharge treatment is finished until the number of discharge treatment times reaches 5-10 times, and the Fe-based alloy powder with the nano-crystallized surface is obtained;
(2) uniformly mixing the Fe-based alloy powder subjected to surface nanocrystallization in the step (1) with a coating agent, coating and drying, uniformly mixing with a lubricant, and performing compression molding to obtain a high-density magnetic powder core pressed compact;
(3) and (3) sintering the high-density magnetic powder core pressed compact in the step (2) in an inert gas atmosphere for forming, wherein the nanocrystalline on the surface of the Fe-based alloy powder grows into large-size nanocrystalline, and the nanocrystalline inside the Fe-based alloy powder is crystallized into small-size nanocrystalline, so that the gradient nanocrystalline magnetic powder core with high magnetic induction and low loss is obtained.
2. The method for preparing a high magnetic induction low loss gradient nanocrystalline magnetic powder core according to claim 1, characterized in that, in step (1), the Fe-based amorphous alloy powder has an elemental content of Fe 70-90 at.%, and the balance is composed of two or more elements of the following components: si, Co, B, C, P, Cu, Ni, Mo, Al, Ta, Nb and Sn elements; the particle size of the Fe-based amorphous alloy powder is 20-110 mu m;
the sintering treatment temperature in the step (3) is higher than the crystallization temperature of the Fe-based amorphous alloy powder, and the time is 10 min-1 h.
3. The method for preparing the nanocrystalline magnetic powder core with high magnetic induction and low loss gradient according to claim 1, wherein the discharge plasma treatment conditions in the step (1) are as follows: the voltage is 135V, the current is 2-2.3A, the rotating speed is 1100-1200 r/min, the time of each discharge treatment is 2.3-3 h, and the next discharge treatment is carried out after 10-30 minutes after each discharge treatment until the number of discharge treatment times reaches 5-10 times;
the Fe-based amorphous alloy powder in the step (1) is Fe83Si5B8Cu4、Fe80Si10B6Nb4And Fe82Si7B6P3Cu2At least one of;
and (4) the time of the sintering treatment in the step (3) is 30-35 min.
4. The method for preparing a high magnetic induction low loss gradient nanocrystalline magnetic powder core according to claim 1, characterized in that the surface nanocrystalline Fe-based alloy powder in the step (1) has a surface crystal film thickness of 50-500 nm.
5. The method for preparing the nanocrystalline magnetic powder core with high magnetic induction and low loss gradient according to claim 1, wherein the discharge plasma treatment in the step (1) is carried out in a stainless steel ball milling tank, and before the discharge plasma treatment, high-purity inert gas is used for purifying the atmosphere, and then inert gas is introduced;
the coating agent in the step (2) is organic silicon resin, and the coating agent and an organic solvent are mixed according to a volume ratio of 75-85: 25-15, and mixing with surface nano-crystallized Fe-based alloy powder, wherein the mass ratio of the surface nano-crystallized Fe-based alloy powder to the coating agent solution is 10: 1;
the lubricant in the step (2) is zinc stearate, and accounts for 0.1-0.5% of the total mass of the Fe-based alloy powder and the coating agent with the nano-crystallized surfaces;
and (3) the pressure of the compression molding in the step (2) is 1.5-3 GPa.
6. The method for preparing the high magnetic induction low loss gradient nanocrystalline magnetic powder core according to claim 1, characterized in that the high magnetic induction low loss gradient nanocrystalline magnetic powder core obtained in step (3) can be further subjected to paint spraying, the paint spraying material is epoxy resin or polyester mixture, and the spraying thickness is 80-260 μm.
7. A high magnetic induction low loss gradient nanocrystalline magnetic powder core prepared by the method of any one of claims 1 to 6.
8. The use of the nanocrystalline magnetic powder core of claim 7 with high magnetic induction and low loss gradient in electronic devices in medium and high frequency fields.
9. The application of the high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core according to claim 8 in electronic devices in medium-high frequency fields, wherein the medium-high frequency fields are 3C product fields, communication electronics fields, medical apparatus fields, new energy automobile fields and aerospace fields.
10. The application of the high-magnetic-induction low-loss gradient nanocrystalline magnetic powder core in the middle-high frequency field electronic device according to claim 9, characterized in that the middle-high frequency field electronic device is a 5G communication base station, a 5G communication device, an inductor, an execution component, a generator, an intelligent temperature control device, a transformer, a motor, a mutual inductor, a choke coil and a damper.
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