CN117577407A - Double-amorphous core-shell structure soft magnetic composite material and preparation method thereof - Google Patents

Double-amorphous core-shell structure soft magnetic composite material and preparation method thereof Download PDF

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CN117577407A
CN117577407A CN202311559302.8A CN202311559302A CN117577407A CN 117577407 A CN117577407 A CN 117577407A CN 202311559302 A CN202311559302 A CN 202311559302A CN 117577407 A CN117577407 A CN 117577407A
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amorphous alloy
core
amorphous
shell
soft magnetic
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龚攀
胡飞
丁华平
王新云
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Huazhong University of Science and Technology
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Abstract

The invention belongs to the technical field of amorphous alloy composite materials, and particularly relates to a soft magnetic composite material with a double amorphous core-shell structure and a preparation method thereof. The matching degree of the mechanical property and the soft magnetic property of the coating layer and the core amorphous alloy material is fully considered, and the oxide of the other magnetic amorphous alloy is selected as a shell layer material to be coated on the surface of the amorphous soft magnetic material. The amorphous structure and the configuration entropy are regulated and controlled to cooperatively improve the mechanical strength and the comprehensive soft magnetic performance of the core amorphous alloy, so that the problems of mechanical strength reduction, magnetic conductivity reduction, coercivity increase and the like caused by the fact that the non-magnetic/crystalline oxide shell layer is difficultly matched with the mechanical and soft magnetic performance of the core amorphous alloy in the prior art are solved.

Description

Double-amorphous core-shell structure soft magnetic composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of amorphous alloy composite materials, and particularly relates to a soft magnetic composite material with a double amorphous core-shell structure and a preparation method thereof.
Background
The soft magnetic material is a kind of magnetic material which is easy to magnetize and demagnetize, generally has the characteristics of low coercive force, high magnetic permeability and the like, is an important functional material for magneto-electric conversion and transmission, and is widely applied to industries such as automobiles, electric power, energy sources and the like. In order to improve the resistivity and reduce the eddy current loss under the high-frequency working condition, the insulated coated magnetic powder is usually prepared into a soft magnetic composite material by powder metallurgy pressing and heat treatment. The conventional soft magnetic composite material comprises an Fe powder core, an Fe-Si powder core, an Fe-Ni powder core, an amorphous alloy powder core and the like. With technological advancement and social development, electronic power equipment such as inductors and transformers are miniaturized and have high frequency, and new soft magnetic materials with high strength, high saturation magnetization, low coercivity and low loss are more urgent.
In the soft magnetic composite material, the amorphous alloy powder core has no dislocation due to the amorphous alloy material,Defects such as grain boundaries and the like, so that the alloy has excellent mechanical properties such as ultrahigh mechanical strength, high elastic limit and the like; in addition, the amorphous alloy has no crystal defect to block domain wall motion and shows magnetic isotropy, so that the amorphous alloy has good comprehensive soft magnetic performance. The surface of amorphous alloy is usually coated with SiO by researchers 2 、Al 2 O 3 And nonmagnetic/crystalline insulating layers to improve the resistivity of the material and reduce eddy current loss at high frequencies, but this technique also causes problems such as reduced strength of the material, reduced permeability, increased coercivity, etc. Meanwhile, the traditional soft magnetic composite material molding process mainly adopts a mode of compression molding and heat treatment, and has the problems of high residual stress, crystallization and the like. In summary, the existing cladding technology has various problems and the traditional powder metallurgy technology has adverse effects on the performance of the amorphous alloy, so that the preparation of the novel soft magnetic composite material with high mechanical strength, high magnetic permeability and low coercivity and the powder metallurgy technology suitable for the characteristics of the amorphous alloy have important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a soft magnetic composite material with a double amorphous core-shell structure and a preparation method thereof, so as to solve the technical problems that the mechanical property and the soft magnetic property of a non-magnetic/crystalline oxide shell layer are difficult to match with those of a core amorphous alloy, the mechanical strength is reduced, the magnetic permeability is reduced, the coercive force is increased after insulating coating, the residual stress of the traditional powder pressing and heat treatment molding process is large, the crystallization is easy and the like in the prior art.
In order to achieve the above purpose, the invention provides a soft magnetic composite material with a double amorphous core-shell structure, which comprises a core part and a shell layer, wherein the core part is made of a first amorphous alloy, and the shell layer is made of an amorphous oxide of a second amorphous alloy; the first amorphous alloy of the core part and the second amorphous alloy of the shell layer have soft magnetic properties; and the saturation magnetization intensity of the first amorphous alloy of the core is larger than that of the second amorphous alloy of the shell, and the coercive force of the first amorphous alloy of the core is smaller than that of the second amorphous alloy of the shell.
Preferably, the core first amorphous alloy composition has a saturation magnetization of greater than or equal to 1T and a coercivity of less than or equal to 3A/m;
the saturation magnetization intensity of the shell layer second amorphous alloy component is larger than or equal to 0.5T, the coercive force is smaller than or equal to 10A/m, and the breaking strength is larger than or equal to 3GPa; the amorphous oxide of the second amorphous alloy has a resistivity greater than or equal to 1 mu Ω -m.
Preferably, the selection criteria for the core amorphous alloy composition are: the amorphous alloy comprises iron-based, cobalt-based, iron-cobalt-based, nickel-based or iron-nickel-based amorphous alloy, wherein the critical forming size of the amorphous alloy is more than or equal to 0.1mm, and the difference between the upper limit and the lower limit of the temperature of the supercooling liquid phase region is more than 20K;
the shell amorphous alloy comprises the following components in percentage by weight: the amorphous alloy component is iron-based, cobalt-based, iron-cobalt-based, nickel-based or iron-nickel-based amorphous alloy, the critical forming size of the amorphous alloy component is more than or equal to 0.1mm, and the difference between the upper limit and the lower limit of the temperature of the supercooling liquid phase region is more than 20K.
Preferably, the core first amorphous alloy and the shell second amorphous alloy are both amorphous alloys having a high mixed entropy, which has a configurational entropy Δs in a random mutual dissolution state conf ≥1R。
According to another aspect of the present invention, there is provided a method for preparing the double amorphous core-shell structure soft magnetic composite material, comprising the steps of:
(1) Respectively selecting a first amorphous alloy component of the core and a second amorphous alloy component of the shell, and respectively preparing a powdery first amorphous alloy of the core and a powdery second amorphous alloy of the shell according to the component proportion of the selected amorphous alloy; the core first amorphous alloy and the shell second amorphous alloy both have soft magnetic properties;
(2) Preparing an amorphous oxide coating layer on the surface of the core part first amorphous alloy to obtain the core part first amorphous alloy with the surface coated with the amorphous oxide; wherein the amorphous oxide coating is an amorphous oxide of the shell layer second amorphous alloy;
(3) And (3) performing high-temperature presintering on the first amorphous alloy of the core part of which the surface is coated with the amorphous oxide in the step (2) to bond and compound powder, and then performing low-temperature final sintering to optimize internal stress and microstructure of the material, so that hysteresis loss caused by internal stress is reduced, and comprehensive soft magnetic performance is improved.
Preferably, in the step (1), a powder-shaped first amorphous alloy core and a powder-shaped second amorphous alloy shell are prepared according to the component proportion of the selected amorphous alloy by adopting an air atomization method, a water atomization method, a mechanical ball milling method, a plasma ball milling method or a plasma rotating electrode method.
Preferably, the powder particle size of the powdery core first amorphous alloy is in the range of 1 μm to 50 μm, and the powder particle size of the shell second amorphous alloy is in the range of 1nm to 500 nm.
Preferably, step (2) prepares an amorphous oxide coating layer on the surface of the core first amorphous alloy by a physical vapor deposition method under an oxygen-containing atmosphere.
Preferably, the physical vapor deposition method is an electron beam evaporation technology, a radio frequency sputtering technology, a magnetron sputtering technology or an ion plating technology, and the free oxygen content in the oxygen-containing atmosphere is 5% -20%.
Preferably, the temperature of the pre-sintering in the step (3) is located in a supercooled liquid phase region of the first amorphous alloy component of the core and the second amorphous alloy component of the shell, the sintering pressure of the pre-sintering is 100-600 MPa, and the sintering time is 5-30 min;
the final sintering temperature is set at the glass transition temperature T of the first amorphous alloy component of the core and the second amorphous alloy component of the shell g The final sintering is carried out under the conditions of 10-200K, the sintering pressure of 10-100 MPa, the sintering time of 10-60 min and the temperature rise and drop rate of 20-200K/min.
In general, the above technical solutions conceived by the present invention have the following compared with the prior art
The beneficial effects are that:
(1) The invention provides a soft magnetic composite material with a double amorphous core-shell structure, which fully considers the matching degree of the mechanical property and the soft magnetic property of a cladding layer and a core amorphous alloy material, and selects the oxide of another magnetic amorphous alloy as a shell layer material to be clad on the surface of the amorphous soft magnetic material. Compared with crystalline materials, amorphous materials have no defects such as dislocation and grain boundary, so that the amorphous materials generally have excellent mechanical properties such as ultrahigh mechanical strength and high elastic modulus. Therefore, the mechanical property of the soft magnetic composite material can be effectively improved by selecting the amorphous alloy as the coating layer.
(2) The core and shell amorphous alloy components of the double amorphous core-shell structure soft magnetic composite material provided by the invention can be amorphous alloys with high mixing entropy such as iron base, cobalt base, iron cobalt base, nickel base, iron nickel base and the like, and generally have high magnetic permeability and low coercive force, and have magnetic isotropy due to no ordered structure of crystals; in addition, the ferromagnetic coupling formed by the amorphous alloy core and the shell layer can further improve the ferromagnetism at the interface of the core-shell structure and the resistivity.
(3) The core amorphous alloy and the shell amorphous alloy components are selected according to the characteristics of the core and the shell, and the core amorphous alloy is a main component of the soft magnetic composite material and plays a leading role in the mechanical property and the comprehensive soft magnetic property of the composite material, so that the amorphous alloy components with high mechanical strength, high saturation magnetization and low coercivity are required to be selected; for shell amorphous alloy, the shell amorphous alloy has good mechanical strength and soft magnetic property, and meanwhile, has high resistivity, so that eddy current loss under a high-frequency working condition is reduced. By reasonably selecting two amorphous alloy components of the core and the shell, the mechanical and magnetic properties of the soft magnetic material can be synchronously improved.
(4) Compared with the common amorphous alloy composition, the invention selects the amorphous alloy with high mixing entropy. An amorphous alloy with high mixed entropy means that the mixed entropy is high due to its many components. The high configuration entropy can influence the difference between the components and the atomic configuration in the core-shell structure, and the structural heterogeneity is enhanced, so that the expansion of a shear band is limited, and the mechanical property of the material is improved; the high-configuration entropy can induce the reduction of the spatial heterogeneity of the atomic structure, shows more uniform element distribution and lattice distortion, compensates the magnetic performance reduction caused by the introduction of non-magnetic elements, and can realize the cooperative enhancement of mechanical and magnetic performances through entropy regulation.
(5) The traditional soft magnetic composite material molding process mainly comprises the steps of carrying out compression molding on mixed powder and then carrying out annealing treatment, wherein the main compression molding methods at present comprise cold compression molding, warm compression molding, hot compression sintering molding and the like, and the amorphous alloy soft magnetic composite material mainly adopts hot compression sintering molding such as vacuum hot compression sintering and hot isostatic pressing sintering, but the two methods have the problems of low heating rate, long sintering time, large residual stress and the like, the heating rate is low, the powder is heated unevenly inside and outside to be crystallized easily, and meanwhile, the residual stress can cause the deterioration of structural sensitivity such as coercive force, magnetic permeability and the like of the soft magnetic material, and the hysteresis loss is increased. The invention firstly selects proper core amorphous alloy components and shell amorphous alloy components, then prepares an amorphous oxide coating layer of shell magnetic amorphous alloy on the surface of the core amorphous alloy, and prepares the composite material with a double amorphous core-shell structure by utilizing a two-step spark plasma sintering process. The invention adopts spark plasma sintering to prepare the double amorphous core-shell structure composite material, which is a rapid sintering technology for realizing densification by applying pulse current to powder and under the assistance of pressure, has the characteristics of high sintering speed, low sintering temperature, small required pressure and the like, and solves the problems of high residual stress, easy crystallization and the like caused by the application of the traditional soft magnetic composite material molding process to the amorphous alloy composite material.
(6) The preparation method of the double amorphous core-shell structure soft magnetic composite material provided by the invention utilizes a two-step spark plasma sintering technology comprising high-temperature short-time presintering and low-temperature long-time final sintering to prepare the double amorphous mixed powder into the double amorphous core-shell structure composite material, and can realize the integration of preparation and heat treatment. The high-temperature presintering can obtain a high-densification composite material to form a larger number of powder blanks with larger contact radius, and the densification is promoted and the structure regulation effect of pulse current is fully exerted at the same time, so that the room-temperature fracture strength of the sintered amorphous alloy is improved; by low-temperature final sintering, the internal stress state and microstructure of the composite material can be further optimized, hysteresis loss caused by internal stress is reduced, and comprehensive soft magnetic performance is improved.
Drawings
FIG. 1 is a flow chart of a soft magnetic composite material with a double amorphous core-shell structure and a preparation method thereof.
Fig. 2 is a schematic diagram of a method for preparing a powder with a double amorphous core-shell structure constructed according to example 1 of the present invention.
Fig. 3 is a schematic diagram of a dual amorphous core-shell structured soft magnetic composite and a spark plasma sintering mold according to an embodiment of the present invention.
Fig. 4 is a process curve of a two-step spark plasma sintering according to an embodiment of the present invention.
The same reference numbers are used throughout the drawings to reference like elements or structures, wherein:
1-upper pressure head, 2-double amorphous core-shell structure soft magnetic composite material, 3-lower pressure head, 4-upper electrode, 5-female die and 6-lower electrode.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Aiming at the problem that the mechanical property and the soft magnetic property of the soft magnetic composite material are mutually restricted to limit the wide application of the soft magnetic composite material, the invention provides the soft magnetic composite material with the double amorphous core-shell structure and the preparation method thereof, and the method can realize the synchronous improvement of the mechanical property and the soft magnetic property of the soft magnetic composite material. Specifically, the invention provides a soft magnetic composite material with a double amorphous core-shell structure, which comprises a core part and a shell layer, wherein the core part is made of a first amorphous alloy, and the shell layer is made of an amorphous oxide of a second amorphous alloy; the first amorphous alloy of the core part and the second amorphous alloy of the shell layer have soft magnetic properties; and the saturation magnetization intensity of the first amorphous alloy of the core is larger than that of the second amorphous alloy of the shell, and the coercive force of the first amorphous alloy of the core is smaller than that of the second amorphous alloy of the shell.
In some embodiments, the first amorphous alloy composition of the core has a saturation magnetization greater than or equal to 1T and a coercivity less than or equal to 3A/m; the saturation magnetization intensity of the second amorphous alloy component of the shell layer is more than or equal to 0.5T, and the coercive force is less than or equal to 10A/m; the breaking strength is 3GPa or more, and the resistivity of the amorphous oxide coating layer of the shell amorphous alloy is 1 mu omega-m or more, preferably 1.2-2 mu omega-m.
In a preferred embodiment, the amorphous alloy composition of the core is selected from the group consisting of: the amorphous alloy components are iron-based, cobalt-based, iron-cobalt-based, nickel-based, iron-nickel-based and other amorphous alloys, the critical forming size of the amorphous alloy components is more than or equal to 0.1mm, and the difference between the upper limit and the lower limit of the temperature of the supercooling liquid phase region is more than 20K; supercooling liquid region DeltaT x ＝T x -T g I.e. DeltaT x Greater than 20K; t (T) x For crystallization temperature, T g Is the glass transition temperature of the amorphous alloy material to provide a sufficient spark plasma sintering process window. The selection criteria of the amorphous alloy composition of the shell layer are as follows: the amorphous alloy components are iron-based, cobalt-based, iron-cobalt-based, nickel-based, iron-nickel-based and other amorphous alloys, the critical forming size of the amorphous alloy components is larger than or equal to 0.1mm, and the upper and lower temperature limit difference value of the supercooled liquid phase region is larger than 20K.
In some embodiments, the first amorphous alloy of the core and the second amorphous alloy of the shell are both amorphous alloys with high mixed entropy, which have a configurational entropy Δs in a random, miscible state conf And the gas constant is equal to or more than 1R, and the value of R is 8.314J/(mol.K).
In a preferred embodiment, the first amorphous alloy of the core is an amorphous alloy composition such as Fe-Ni-P-B, fe-Si-Nb-B-Cu, co-Fe-P-B, fe-Co-Nb-B-Si, and the second amorphous alloy of the shell is an amorphous alloy composition such as Co-Fe-Ni-P-B, co-Fe-Nb-B-Si, co-Ni-P-B, co-Fe-Mo-Y-B.
The invention also provides a preparation method of the double amorphous core-shell structure soft magnetic composite material, as shown in figure 1, comprising the following steps:
(1) Respectively selecting a first amorphous alloy component of the core and a second amorphous alloy component of the shell, and respectively preparing a powdery first amorphous alloy of the core and a powdery second amorphous alloy of the shell according to the component proportion of the selected amorphous alloy; the core first amorphous alloy and the shell second amorphous alloy both have soft magnetic properties;
(2) Preparing an amorphous oxide coating layer on the surface of the core part first amorphous alloy to obtain the core part first amorphous alloy with the surface coated with the amorphous oxide; wherein the amorphous oxide coating is an amorphous oxide of the shell layer second amorphous alloy;
(3) And (3) performing high-temperature presintering on the first amorphous alloy of the core part of which the surface is coated with the amorphous oxide in the step (2) to bond and compound powder, and then performing low-temperature final sintering to optimize internal stress and microstructure of the material, so that hysteresis loss caused by internal stress is reduced, and comprehensive soft magnetic performance is improved.
The step (1) of the invention can adopt powder preparation technology to obtain micron-sized amorphous alloy powder with core and shell layers. In some embodiments, step (1) adopts an air atomization method, a water atomization method, a mechanical ball milling method, a plasma ball milling method or a plasma rotating electrode method to respectively prepare a powdery core first amorphous alloy and a shell second amorphous alloy according to the component proportion of the selected amorphous alloy. The particle size of the powder of the powdery core first amorphous alloy is in the range of 1-50 mu m, and the particle size of the powder of the shell second amorphous alloy is in the range of 1-500 nm.
The step (2) can adopt various methods for coating the powder surface to prepare an amorphous oxide coating layer on the surface of the core amorphous alloy. In some embodiments, step (2) prepares an amorphous oxide coating layer on the core first amorphous alloy surface by physical vapor deposition in an oxygen-containing atmosphere. The physical vapor deposition includes, but is not limited to, electron beam evaporation technology, radio frequency sputtering technology, magnetron sputtering technology, ion plating technology and the like, wherein the free oxygen content in the oxygen-containing atmosphere is 5-20%, and other gases are inert gases such as argon. The oxidation degree of the shell amorphous alloy can be controlled by regulating and controlling the oxygen content in the oxidation process, so that the amorphous alloy has good resistivity and certain mechanical strength.
Different deposition methods can regulate and control technological parameters according to requirements to prepare an amorphous oxide coating layer of the shell amorphous alloy on the surface of the core amorphous alloy. For example, in some embodiments, an amorphous oxide coating layer of a shell amorphous alloy is prepared on the surface of a core amorphous alloy by adopting an electron beam evaporation technology, the distance between target amorphous alloy powder (shell amorphous alloy) and matrix amorphous alloy powder (core amorphous alloy) is 100-200 mm, the deposition power of an electron gun is 10-100 KW, the deposition time is 1-20 min, the current of an electron beam is 20-200 mA, in the process of electron beam evaporation, high-energy electrons emitted by the electron gun are collected into high-energy high-speed electron beams under the action of an accelerating electric field, and the high-energy high-speed electron beams are rotated for 270 degrees under the action of a magnetic field to act on a target, so that target molecules escape from the surface of the target to form vapor flow, and finally, the vapor flow is deposited on the matrix powder to form a solid oxide coating layer of 10-60 mu m. In other embodiments, the amorphous oxide coating of the shell amorphous alloy is prepared on the surface of the core amorphous alloy by a magnetron sputtering method, the distance between the target amorphous alloy powder (shell amorphous alloy) and the matrix amorphous alloy powder (core amorphous alloy) is 50-120 mm, the matrix heating temperature is room temperature-300 ℃ (room temperature is 20-30 ℃), the radio frequency power is 100-1000W, the movement track of electrons is bent under the action of an electric field and a magnetic field, the electrons collide with gas atoms in the process of flying to the matrix, so that the gas molecules ionize cations and electrons, the electrons fly to an anode, the cations can accelerate to fly to the target under the action of the electric field, the target surface is bombarded by high energy, and the target is sputtered to enable the target molecules to escape from the target surface to form a vapor stream and finally deposit on the matrix powder to form a solid oxide coating of 10-60 mu m.
In some embodiments, in order to obtain the soft magnetic composite material with the double amorphous core-shell structure with high density and good mechanical properties, the pre-sintering temperature in the step (3) is located in a supercooled liquid phase region of the first amorphous alloy component of the core and the second amorphous alloy component of the shell, the sintering pressure of the pre-sintering is 100-600 MPa, and the sintering time is 5-30 min; the final sintering temperature is set at the glass transition temperature T of the first amorphous alloy component of the core and the second amorphous alloy component of the shell g The sintering pressure is 10-100 MPa, the sintering time is 10-60 min, and the temperature rising and falling rates are 20-200K/min.
Example 1
In one embodiment, [ (Fe) with better soft magnetic property and mechanical property is preferred in the developed component library of the amorphous alloy with high mixing entropy such as iron base, cobalt base, iron-cobalt base, nickel base, iron-nickel base and the like 0.9 Co 0.1 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 (T g For 820K, T x 880K; configuration entropy delta S in random mutual dissolution state conf =1.06R) and (Co 0.7 Fe 0.3 ) 68 B 21.9 Si 5.1 Nb 5 (T g Is 815K, T x 870K; configuration entropy delta S in random mutual dissolution state conf =1.31r), and the critical forming size of the amorphous alloy component is not less than 0.1mm. With better soft magnetic property [ (Fe) 0.9 Co 0.1 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 As the core, a core having higher breaking strength and resistivity (Co 0.7 Fe 0.3 ) 68 B 21.9 Si 5.1 Nb 5 As a shell amorphous alloy, the amorphous oxide is coated with [ (Fe) 0.9 Co 0.1 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 A surface.
Weighing high-purity metal raw materials according to nominal components, and carrying out arc melting on high-purity elements for six times in an argon atmosphere by adopting a Ti getter to obtain [ (Fe) 0.9 Co 0.1 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 And (Co) 0.7 Fe 0.3 ) 68 B 21.9 Si 5.1 Nb 5 The high-purity nitrogen atomization method is adopted to prepare two amorphous alloy powders, the high-purity nitrogen atomization pressure is 20MPa, the diameter of a diversion hole is 2mm, and the iron-based amorphous alloy powder with the particle size of 1-50 μm and the cobalt-based amorphous alloy powder with the particle size of 1-500 nm are screened.
TABLE 1 Forming ability, magnetic and mechanical Properties of two amorphous alloy compositions
In [ (Fe) by electron beam evaporation technique 0.9 Co 0.1 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 Deposition on aerosolized powder (Co 0.7 Fe 0.3 ) 68 B 21.9 Si 5.1 Nb 5 Oxide coating, controlling vacuum degree in cavity to be 1×10 -3 Pa, introducing a mixed atmosphere of argon and oxygen to-0.5 atm, wherein the oxygen content in the atmosphere is 10%, and mixing (Co 0.7 Fe 0.3 ) 68 B 21.9 Si 5.1 Nb 5 Placing the powder into a crucible to serve as a target material, wherein the target material and [ (Fe) 0.9 Co 0.1 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 The distance of the matrix is 150mm, the deposition power of the electron gun is 50KW, the deposition time is 15min, the current of the electron beam is 140mA, in the process of electron beam evaporation, high-energy electrons emitted by the electron gun are collected into high-energy high-speed electron beams under the action of an accelerating electric field, and the high-energy high-speed electron beams are rotated 270 degrees to act on a target under the action of a magnetic field, so that target molecules escape from the surface of the target to form steam flow, and the steam flow is finally deposited to [ (Fe after oxidation 0.9 Co 0.1 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 A50 μm solid oxide coating layer was formed on the base powder, as shown in FIG. 2, to obtain iron/cobalt-based amorphous alloy composite particles of core-shell structure, and the solid oxide film had a resistivity of 1.8. Mu.Ω. M. In the schematic diagram of the spark plasma sintering mold shown in fig. 3 ((1-upper pressure head, 2-core-shell structured iron-based/cobalt-based amorphous alloy composite particles, 3-lower pressure head, 4-upper electrode, 5-female die, 6-lower electrode in the figure)), the dual amorphous core-shell structured composite material is prepared by a two-step spark plasma sintering technology, and the technological parameters adopted by spark plasma sintering are as follows: the sintering temperature of high temperature pre-sintering is 820K, the sintering pressure is 300MPa, the sintering time is 15min, the temperature of low temperature final sintering is 650K, the sintering pressure is 100MPa, the sintering time is 30min, the temperature rising and falling rate is 50K/min, and the sintering processThe process curve is shown in fig. 4.
Example 2
In another embodiment, [ (Fe) with better soft magnetic property and mechanical property is preferred in the developed component library of the amorphous alloy with high mixing entropy such as iron base, cobalt base, iron-cobalt base, nickel base, iron-nickel base and the like 0.8 Ni 0.2 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 (T g For 814K, T x 866K; configuration entropy delta S in random mutual dissolution state conf =1.19R) and Co 52 Fe 20 Zr 8 B 20 (T g Is 844K, T x 887K; configuration entropy delta S in random mutual dissolution state conf =1.04R) and the critical forming size of the amorphous alloy component is not less than 0.1mm. With better soft magnetic property [ (Fe) 0.8 Ni 0.2 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 Co with higher breaking strength and resistivity as core 52 Fe 20 Zr 8 B 20 As a shell amorphous alloy, the amorphous oxide is coated with [ (Fe) 0.8 Ni 0.2 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 A surface.
Weighing high-purity metal raw materials according to nominal components, and carrying out arc melting on high-purity elements in argon atmosphere by adopting a Ti getter for seven times to obtain [ (Fe) 0.8 Ni 0.2 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 And Co 52 Fe 20 Zr 8 B 20 The mother alloy ingot of the alloy is prepared into two amorphous alloy powders by adopting a high-nitrogen atomization method, the high-purity nitrogen atomization pressure is 20MPa, the diameter of a diversion hole is 2mm, and the iron-nickel-based amorphous alloy powder with the particle size of 1-50 mu m and the cobalt-based amorphous alloy powder with the particle size of 1-500 nm are screened.
TABLE 2 Forming ability, magnetic and mechanical Properties of two amorphous alloy Components in example 2
The magnetic control sputtering technology is adopted in [ (Fe) 0.8 Ni 0.2 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 Deposition on aerosolized powder (Co 0.7 Fe 0.3 ) 68 B 21.9 Si 5.1 Nb 5 Oxide coating, controlling vacuum degree in cavity to be 1×10 -3 Pa, introducing oxygen and argon into the mixed atmosphere to-0.5 atm, wherein the oxygen content in the atmosphere is 10%, and mixing (Co 0.7 Fe 0.3 ) 68 B 21.9 Si 5.1 Nb 5 Placing the powder into a crucible to serve as a target material, wherein the target material and [ (Fe) 0.8 Ni 0.2 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 The distance of the matrix is 100mm, the heating temperature of the matrix is 200 ℃, the radio frequency power is 300W, the movement track of electrons is bent under the action of an electric field and a magnetic field, the electrons collide with gas atoms in the process of flying to the matrix, so that gas molecules ionize to generate cations and electrons, the electrons fly to an anode, the cations can accelerate to fly to a target under the action of the electric field, the target surface is bombarded with high energy, and the target is sputtered to enable the target molecules to escape from the target surface to form steam flow and be oxidized and finally deposited to [ (Fe) 0.8 Ni 0.2 ) 0.75 B 0.2 Si 0.05 ] 96 Nb 4 And forming a solid oxide coating layer with the thickness of 50 mu m on the matrix powder, wherein the resistivity of a film of the solid oxide coating layer is 1.9 mu omega-m, so as to obtain the iron-nickel-base/cobalt-base amorphous alloy composite particles with the core-shell structure. In the schematic diagram of a spark plasma sintering mold shown in fig. 3 (in the figure, a 1-upper pressure head, a 2-core-shell structure iron-nickel-base/cobalt-base amorphous alloy composite particle, a 3-lower pressure head, a 4-upper electrode, a 5-female die and a 6-lower electrode), a dual amorphous core-shell structure composite material is prepared by a two-step spark plasma sintering technology, and the technological parameters adopted by spark plasma sintering are as follows: the sintering temperature of high-temperature pre-sintering is 860K, the sintering pressure is 300MPa, the sintering time is 15min, the low-temperature final sintering temperature is 700K, the sintering pressure is 100MPa, the sintering time is 30min, and the temperature rising and falling rate is 50K/min.
According to the embodiment of the invention, two amorphous alloys with strong amorphous forming capability, good mechanical property and comprehensive soft magnetic property and high mixing entropy are respectively used as a core and a shell of the soft magnetic composite material, the powdery core amorphous alloy and the shell amorphous alloy are respectively prepared according to the respective atomic ratio of the two amorphous alloys, then an amorphous oxide coating layer of the shell amorphous alloy is prepared on the surface of the core amorphous alloy by adopting physical vapor deposition methods such as electron beam evaporation, magnetron sputtering and the like on the surface of the original core amorphous alloy powder, and the double amorphous core-shell structure soft magnetic composite material is prepared by adopting a two-step discharge plasma sintering process of high-temperature short-time presintering and low-temperature long-time final sintering.
According to the embodiment of the invention, amorphous or high-entropy amorphous oxide is used as a shell layer, and the mechanical strength and the comprehensive soft magnetic performance of the core amorphous alloy are synergistically improved through the regulation and control of the amorphous structure and the configuration entropy, so that the problems of mechanical strength reduction, magnetic conductivity reduction, coercivity increase and the like caused by the fact that the mechanical property and the soft magnetic performance of the core amorphous alloy are difficult to match due to the fact that the amorphous/crystalline oxide shell layer is adopted in the prior art, and the core amorphous alloy is coated are solved. Meanwhile, the two-step spark plasma sintering process can realize the integration of preparation and heat treatment of the soft magnetic composite material, reduce the complexity and cost of the preparation process and improve the production efficiency.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. The soft magnetic composite material with the double amorphous core-shell structure is characterized by comprising a core part and a shell layer, wherein the core part is made of a first amorphous alloy, and the shell layer is made of an amorphous oxide of a second amorphous alloy; the first amorphous alloy of the core part and the second amorphous alloy of the shell layer have soft magnetic properties; and the saturation magnetization intensity of the first amorphous alloy of the core is larger than that of the second amorphous alloy of the shell, and the coercive force of the first amorphous alloy of the core is smaller than that of the second amorphous alloy of the shell.
2. The soft magnetic composite of claim 1, wherein the core first amorphous alloy composition has a saturation magnetization greater than or equal to 1T and a coercivity less than or equal to 3A/m;
the saturation magnetization intensity of the shell layer second amorphous alloy component is larger than or equal to 0.5T, the coercive force is smaller than or equal to 10A/m, and the breaking strength is larger than or equal to 3GPa; the amorphous oxide of the second amorphous alloy has a resistivity greater than or equal to 1 mu Ω -m.
3. A soft magnetic composite material as claimed in claim 1, wherein the core amorphous alloy composition has a selection criteria of: the amorphous alloy comprises iron-based, cobalt-based, iron-cobalt-based, nickel-based or iron-nickel-based amorphous alloy, wherein the critical forming size of the amorphous alloy is more than or equal to 0.1mm, and the difference between the upper limit and the lower limit of the temperature of the supercooling liquid phase region is more than 20K;
the shell amorphous alloy comprises the following components in percentage by weight: the amorphous alloy component is iron-based, cobalt-based, iron-cobalt-based, nickel-based or iron-nickel-based amorphous alloy, the critical forming size of the amorphous alloy component is more than or equal to 0.1mm, and the difference between the upper limit and the lower limit of the temperature of the supercooling liquid phase region is more than 20K.
4. The soft magnetic composite of claim 1, wherein the core first amorphous alloy and the shell second amorphous alloy are both amorphous alloys having a high mixed entropy with a configuration entropy Δs in a random mutual solution state conf ≥1R。
5. The method for preparing a soft magnetic composite material with a double amorphous core-shell structure according to any one of claims 1 to 4, comprising the steps of:
(1) Respectively selecting a first amorphous alloy component of the core and a second amorphous alloy component of the shell, and respectively preparing a powdery first amorphous alloy of the core and a powdery second amorphous alloy of the shell according to the component proportion of the selected amorphous alloy; the core first amorphous alloy and the shell second amorphous alloy both have soft magnetic properties;
(2) Preparing an amorphous oxide coating layer on the surface of the core part first amorphous alloy to obtain the core part first amorphous alloy with the surface coated with the amorphous oxide; wherein the amorphous oxide coating is an amorphous oxide of the shell layer second amorphous alloy;
(3) And (3) performing high-temperature presintering on the first amorphous alloy of the core part of which the surface is coated with the amorphous oxide in the step (2) to bond and compound powder, and performing low-temperature final sintering to optimize internal stress and microstructure of the material and reduce internal stress.
6. The method according to claim 5, wherein the step (1) comprises preparing the core first amorphous alloy and the shell second amorphous alloy in powder form according to the component ratio of the selected amorphous alloy by gas atomization, water atomization, mechanical ball milling, plasma ball milling or plasma rotary electrode method.
7. The method according to claim 5, wherein the powder particle size of the powdery core first amorphous alloy is in the range of 1 μm to 50 μm and the powder particle size of the shell second amorphous alloy is in the range of 1nm to 500 nm.
8. The method of claim 5, wherein step (2) comprises preparing an amorphous oxide coating layer on the surface of the core first amorphous alloy by physical vapor deposition under an oxygen-containing atmosphere.
9. The method of claim 8, wherein the physical vapor deposition method is electron beam evaporation, radio frequency sputtering, magnetron sputtering or ion plating, and the free oxygen content in the oxygen-containing atmosphere is 5% -20%.
10. The method according to claim 5, wherein the pre-sintering temperature in step (3) is located in the supercooled liquid phase region of the core first amorphous alloy component and the shell second amorphous alloy component, the sintering pressure of the pre-sintering is 100 to 600MPa, and the sintering time is 5 to 30min;
the final sintering temperature is set at the glass transition temperature T of the first amorphous alloy component of the core and the second amorphous alloy component of the shell g The final sintering is carried out under the conditions of 10-200K, the sintering pressure of 10-100 MPa, the sintering time of 10-60 min and the temperature rise and drop rate of 20-200K/min.
CN202311559302.8A 2023-11-03 2023-11-20 Double-amorphous core-shell structure soft magnetic composite material and preparation method thereof Pending CN117577407A (en)

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