CN112342347A - Hydrogenation heat treatment process for amorphous nano alloy - Google Patents
Hydrogenation heat treatment process for amorphous nano alloy Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 92
- 239000000956 alloy Substances 0.000 title claims abstract description 68
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000003723 Smelting Methods 0.000 claims abstract description 29
- 239000012298 atmosphere Substances 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 238000004804 winding Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 37
- 229910052786 argon Inorganic materials 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 230000001681 protective effect Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 12
- 238000009792 diffusion process Methods 0.000 claims description 10
- 230000006698 induction Effects 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- 230000005415 magnetization Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 description 12
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 7
- 230000005389 magnetism Effects 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 229910052582 BN Inorganic materials 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910002546 FeCo Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention relates to the technical field of metal materials, in particular to a hydrogenation heat treatment process of amorphous nano alloy, which comprises the following steps: smelting a master alloy; strip preparation: placing the master alloy ingot in a smelting furnace for melting, after full melting, spraying the master alloy ingot to a copper roller through a nozzle, and cooling the surface of the copper roller to obtain a strip; preparing an iron core: winding the strip to obtain a coiled strip, and preparing the coiled strip into an amorphous iron core in an iron core winding machine; heat treatment; according to the hydrogenation heat treatment process of the amorphous nano alloy, high-purity hydrogen is introduced for protecting atmosphere during annealing heat treatment, so that the amorphous matrix is induced to be nano-crystallized, and the internal stress of the alloy is reduced. The nanocrystalline alloy prepared by the novel heat treatment process ensures the saturation magnetization intensity, improves the inductance and the magnetic conductivity, greatly reduces the alternating current coercive force and the iron loss, and obviously improves the soft magnetic performance.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a hydrogenation heat treatment process of amorphous nano alloy.
Background
The atomic arrangement in the amorphous alloy presents the characteristics of short-range order and long-range disorder, and two-dimensional and three-dimensional defects such as crystal grains, crystal boundaries, dislocation, stacking faults and the like do not exist in the amorphous alloy. The special atomic structure enables the amorphous alloy to show excellent mechanical, magnetic and corrosion resistance properties, and has great application prospect in the fields of soft magnetic functional materials, electronic devices, corrosion resistant coatings, structural materials and the like. In the recently emerging field of wireless charging, the finnment nanocrystalline alloy becomes a key material for improving wireless charging power because of its higher saturation magnetization, lower loss and controllable magnetic permeability.
The Finemet amorphous alloy is prepared into an amorphous alloy thin strip by adopting a single-roller rapid quenching method, and then crystallization annealing heat treatment is carried out at a temperature slightly higher than the crystallization temperature of the amorphous alloy thin strip, so that the amorphous alloy is crystallized to form an alpha-Fe (Si) single solid solution phase with the grain size of about 10-20 nm. The small-sized nanocrystalline structure enables the Finemet alloy to have a very low effective magnetocrystalline anisotropy constant (K) and a saturation magnetostriction coefficient (ground) close to zero, and ensures that the Finemet alloy obtains excellent soft magnetic properties. In order to further improve the soft magnetic property of the Finment alloy, one method is to change the alloy components, for example, part of Fe in the Co alloy is used to form FeCo crystallized phase with higher Curie point, so as to improve the high temperature magnetic property and the high frequency magnetic property, but the method greatly improves the production cost.
Disclosure of Invention
The purpose of the invention is: the heat treatment process is characterized in that high-purity hydrogen protective atmosphere is introduced during annealing heat treatment to induce the amorphous matrix to be nano-crystallized and reduce the internal stress of the alloy.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a hydrogenation heat treatment process of amorphous nano alloy is characterized in that: the method comprises the following steps:
smelting a master alloy: according to the expression FeaSibBcCudNbeBatching, wherein a, b, c, d and e respectively represent the atomic percentage content of each corresponding component, and a + b + c + d + e is 100, and repeatedly smelting the batching in a smelting furnace under the atmosphere of inert protective gas to form a master alloy ingot with uniform components;
strip preparation: placing the master alloy ingot in a smelting furnace for melting, after full melting, spraying the master alloy ingot to a copper roller through a nozzle, and cooling the surface of the copper roller to obtain a strip;
preparing an iron core: winding the strip to obtain a coiled strip, and preparing the coiled strip into an amorphous iron core in an iron core winding machine;
and (3) heat treatment: the amorphous iron core is placed on a heat treatment tray and is placed in a positive pressure annealing furnace, after vacuumizing, protective gas and high-purity hydrogen are introduced for heat treatment, and the protective gas in the invention is selected from nitrogen, argon, helium and the like.
Further, the expression FeaSibBcCudNbeWhere a is 73.5, b is 13.5, c is 9, d is 3, and e is 1.
Further, the strip preparation is carried out in a medium-frequency induction smelting furnace, and the alloy is melted through eddy current heating generated by an induction coil.
Further, the alloy solution is sprayed by the nozzle in the strip preparation process under the protection of argon.
Further, the coiled material strip is 45-60mm in thickness and 10mm in width.
Further, the amorphous iron core has an inner diameter of 20mm, an outer diameter of 30mm, a height of 10mm, and a weight of 20 +/-0.5 g.
Further, before the amorphous iron core is placed in the positive pressure annealing furnace, the air tightness of each component of the vacuum furnace is checked, the components comprise each valve, a furnace door sealing rubber ring, an air cylinder sealing rod, the air tightness of an external air source and a pressure reducing valve, circulating water is opened, and the water temperature is kept at room temperature, namely 25 ℃.
Further, the vacuumizing operation comprises the steps of opening a mechanical pump, opening a main path valve and a bypass valve, closing an air door and vacuumizing to 500 Pa; starting diffusion pump, preheating to 180 deg.C, starting Roots pump, and vacuumizing to 1 × 10-1Pa; closing the bypass valve and raising the vacuum to 7-8 x 10-3Pa。
Further, the heat treatment temperature is 550 ℃, the heat preservation time is 60min, and the heating rate is 10K/min.
Further, the pressure of the protective gas and the high-purity hydrogen is more than 0.5atm and less than 10atm, wherein the volume ratio of the protective gas to the high-purity hydrogen is arbitrary, and is preferably 96: 4. The volume fraction of the hydrogen is controlled to be 4% or below 4%, so that the operation is safer.
The technical scheme adopted by the invention has the beneficial effects that:
according to the hydrogenation heat treatment process of the amorphous nano alloy, high-purity hydrogen is introduced for protecting atmosphere during annealing heat treatment, so that the amorphous matrix is induced to be nano-crystallized, and the internal stress of the alloy is reduced. The nanocrystalline alloy prepared by the novel heat treatment process ensures the saturation magnetization intensity, improves the inductance and the magnetic conductivity, greatly reduces the alternating current coercive force and the iron loss, and obviously improves the soft magnetic performance. The method provided by the invention can be used for rapidly preparing the high-performance nanocrystalline alloy in a large scale, has low additional cost and greatly improved performance, and can better meet the requirements of the energy and communication fields on the amorphous nanocrystalline alloy material.
Drawings
Fig. 1 and 2 show the core inductance and quality factor measured using an impedance analyzer.
Fig. 3 and 4 show the coercive force and the remanence ratio of the iron core measured by an alternating-current magnetic core magnetism measuring instrument.
Fig. 5 shows the core loss at different frequencies measured by the ac core magnetism measuring instrument.
Fig. 6 shows the effective permeability of the core at different frequencies measured by an ac core magnetic measuring instrument.
Detailed Description
The invention will now be described in further detail with reference to specific embodiments and the accompanying drawings. The following examples are intended to provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the scope of the present invention. Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
Smelting of S1 master alloy: according to the following expression FeaSibBcCudNbeAnd (2) preparing materials, wherein a, b, c, d and e respectively represent the atomic percentage content (namely the molar ratio) of each corresponding component, a is 73.5, b is 13.5, c is 9, d is 3, e is 1, and a + b + c + d + e is 100, and repeatedly smelting the materials into master alloy ingots with uniform components by using a high-vacuum large-scale electric arc smelting furnace in an inert protective gas nitrogen atmosphere.
S2 tape preparation: the method is characterized in that a single-roller rotary quenching melt spinning machine is adopted for preparation, a mother alloy ingot smelted in the step 1 is placed in a medium-frequency induction smelting furnace, the alloy is melted through eddy current heating generated by an inductance coil, after the alloy is completely melted, an injection key is pressed, alloy melt is sprayed to a copper roller right below from a boron nitride nozzle in an argon protection atmosphere under the action of pressure difference between the upper part and the bottom part of the nozzle, the melt is rapidly cooled on the surface of the copper roller, continuous strip materials are obtained, and 200 kg-2 tons of strip materials can be produced at one time.
Preparing an S3 iron core: and (3) utilizing the strip produced in the step two, obtaining a coiled strip of 45mm by using a coil separator, then preparing a coiled strip of 10mm in width by using a roller shear, and then operating an iron core coiling machine to prepare an amorphous iron core with 20mm of inner diameter, 30mm of outer diameter, 10mm of height and 20 +/-0.5 g of weight.
S4 heat treatment: and (4) placing the iron core prepared in the third step on a heat treatment tray and placing the tray into a positive pressure annealing furnace. Checking the air tightness of each part of the vacuum furnace, wherein each part comprises each valve (an inflation valve, an air release valve, a main path valve and a bypass valve), a furnace door sealing rubber ring, a cylinder sealing rod and the like. And checking the pressure of an external air source and the air tightness of the pressure reducing valve to ensure that the pressure of the air source is enough. And (3) opening circulating water, and keeping the water temperature at room temperature, namely 25 ℃, so as to ensure that the circulating water continuously works in the heat treatment process to cool the furnace body. The furnace door and the locking ring are closed to prevent the furnace door from popping out in the heat treatment process. Opening the mechanical pump, opening the main path valve and the bypass valve, closing the air door, and vacuumizing to 500 Pa; starting diffusion pump, preheating to 180 deg.C, starting Roots pump, and vacuumizing to 1 × 10-1Pa; closing the bypass valve and raising the vacuum to 7-8 x 10-3Pa; closing a diffusion pump, closing valves at all stages, and introducing protective atmosphere and high-purity hydrogen (96% argon +4% hydrogen) to a certain pressure (1 atm); setting a temperature control program: heating rate at 550 deg.C for 10K/min, air cooling, starting heating control program, and opening heating kettle; and opening the air door after the heat treatment program is operated, opening the cooling fan, cooling to room temperature, then discharging air, opening the locking ring and the furnace door, and taking out the product.
Example 2
Smelting of S1 master alloy: according to the following expression FeaSibBcCudNbeAnd (2) preparing materials, wherein a, b, c, d and e respectively represent the atomic percentage content (namely the molar ratio) of each corresponding component, a is 73.5, b is 13.5, c is 9, d is 3, e is 1, and a + b + c + d + e is 100, and repeatedly smelting the materials into master alloy ingots with uniform components by using a high-vacuum large-scale electric arc smelting furnace in an inert protective gas helium atmosphere.
S2 tape preparation: the method is characterized in that a single-roller rotary quenching melt spinning machine is adopted for preparation, a mother alloy ingot smelted in the step 1 is placed in a medium-frequency induction smelting furnace, the alloy is melted through eddy current heating generated by an inductance coil, after the alloy is completely melted, an injection key is pressed, alloy melt is sprayed to a copper roller right below from a boron nitride nozzle in an argon protection atmosphere under the action of pressure difference between the upper part and the bottom part of the nozzle, the melt is rapidly cooled on the surface of the copper roller, continuous strip materials are obtained, and 200 kg-2 tons of strip materials can be produced at one time.
Preparing an S3 iron core: and (3) utilizing the strip produced in the step two, obtaining a coiled strip of 60mm by using a coil separator, then obtaining a coiled strip of 10mm in width by using a roller shear, and then operating an iron core coiling machine to prepare an amorphous iron core with 20mm of inner diameter, 30mm of outer diameter, 10mm of height and 20 +/-0.5 g of weight.
S4 heat treatment: and (4) placing the iron core prepared in the third step on a heat treatment tray and placing the tray into a positive pressure annealing furnace. Checking the air tightness of each part of the vacuum furnace, wherein each part comprises each valve (an inflation valve, an air release valve, a main path valve and a bypass valve), a furnace door sealing rubber ring, a cylinder sealing rod and the like. And checking the pressure of an external air source and the air tightness of the pressure reducing valve to ensure that the pressure of the air source is enough. And (3) opening circulating water, and keeping the water temperature at room temperature, namely 25 ℃, so as to ensure that the circulating water continuously works in the heat treatment process to cool the furnace body. The furnace door and the locking ring are closed to prevent the furnace door from popping out in the heat treatment process. Opening the mechanical pump, opening the main path valve and the bypass valve, closing the air door, and vacuumizing to 500 Pa; starting diffusion pump, preheating to 180 deg.C, starting Roots pump, and vacuumizing to 1 × 10-1Pa; closing the bypass valve and raising the vacuum to 7-8 x 10-3Pa; closing a diffusion pump, closing valves at each stage, and introducing protective atmosphere and high-purity hydrogen (such as 96% argon +4% hydrogen) to a certain pressure (such as atmospheric pressure 1 atm); setting a temperature control program: heating rate is 10K/min, heat treatment temperature is 550 ℃, heat preservation time is 30min, wind is used for starting a heating control program, and a heating kettle is opened; and opening the air door after the heat treatment program is operated, opening the cooling fan, cooling to room temperature, then discharging air, opening the locking ring and the furnace door, and taking out the product.
Example 3
Smelting of S1 master alloy: according to the following expression FeaSibBcCudNbePreparing materials, wherein a, b, c, d and e respectively represent the atom percentage content (i.e. molar ratio) of each corresponding component, a is 73.5, b is 13.5, c is 9, d is 3, e is 1, and a + b + c + d + e is 100, smelting the materials by using a high-vacuum large-scale electric arc smelting furnace under the atmosphere of inert protective gas argon, and repeatedly smelting the materials into the mixtureA master alloy ingot with uniform composition.
S2 tape preparation: the method is characterized in that a single-roller rotary quenching melt spinning machine is adopted for preparation, a mother alloy ingot smelted in the step 1 is placed in a medium-frequency induction smelting furnace, the alloy is melted through eddy current heating generated by an inductance coil, after the alloy is completely melted, an injection key is pressed, alloy melt is sprayed to a copper roller right below from a boron nitride nozzle in an argon protection atmosphere under the action of pressure difference between the upper part and the bottom part of the nozzle, the melt is rapidly cooled on the surface of the copper roller, continuous strip materials are obtained, and 200 kg-2 tons of strip materials can be produced at one time.
Preparing an S3 iron core: and (3) utilizing the strip produced in the step two, obtaining a coiled strip of 65mm by using a coil separator, then obtaining a coiled strip of 10mm in width by using a roller shear, and then operating an iron core coiling machine to prepare an amorphous iron core with 20mm of inner diameter, 30mm of outer diameter, 10mm of height and 20 +/-0.5 g of weight.
S4 heat treatment: and (4) placing the iron core prepared in the third step on a heat treatment tray and placing the tray into a positive pressure annealing furnace. Checking the air tightness of each part of the vacuum furnace, wherein each part comprises each valve (an inflation valve, an air release valve, a main path valve and a bypass valve), a furnace door sealing rubber ring, a cylinder sealing rod and the like. And checking the pressure of an external air source and the air tightness of the pressure reducing valve to ensure that the pressure of the air source is enough. And (3) opening circulating water, and keeping the water temperature at room temperature, namely 25 ℃, so as to ensure that the circulating water continuously works in the heat treatment process to cool the furnace body. The furnace door and the locking ring are closed to prevent the furnace door from popping out in the heat treatment process. Opening the mechanical pump, opening the main path valve and the bypass valve, closing the air door, and vacuumizing to 500 Pa; starting diffusion pump, preheating to 180 deg.C, starting Roots pump, and vacuumizing to 1 × 10-1Pa; closing the bypass valve and raising the vacuum to 7-8 x 10-3Pa; closing a diffusion pump, closing valves at each stage, and introducing protective atmosphere and high-purity hydrogen (such as 96% argon +4% hydrogen) to a certain pressure (such as atmospheric pressure 1 atm); setting a temperature control program: for example, the heating rate is 10K/min, the heat treatment temperature is 550 ℃, the heat preservation time is 60min, air cooling is carried out, a heating control program is started, and a heating kettle is opened; and opening the air door after the heat treatment program is operated, opening the cooling fan, cooling to room temperature, then discharging air, opening the locking ring and the furnace door, and taking out the product.
Example 3
Smelting of S1 master alloy: according to the following expression FeaSibBcCudNbeAnd (2) preparing materials, wherein a, b, c, d and e respectively represent the atomic percentage content (namely the molar ratio) of each corresponding component, a is 73.5, b is 13.5, c is 9, d is 3, e is 1, and a + b + c + d + e is 100, and repeatedly smelting the materials into master alloy ingots with uniform components by using a high-vacuum large-scale electric arc smelting furnace in an inert protective gas nitrogen atmosphere.
S2 tape preparation: the method is characterized in that a single-roller rotary quenching melt spinning machine is adopted for preparation, a mother alloy ingot smelted in the step 1 is placed in a medium-frequency induction smelting furnace, the alloy is melted through eddy current heating generated by an inductance coil, after the alloy is completely melted, an injection key is pressed, alloy melt is sprayed to a copper roller right below from a boron nitride nozzle in an argon protection atmosphere under the action of pressure difference between the upper part and the bottom part of the nozzle, the melt is rapidly cooled on the surface of the copper roller, continuous strip materials are obtained, and 200 kg-2 tons of strip materials can be produced at one time.
Preparing an S3 iron core: and (3) utilizing the strip produced in the step two, obtaining a coiled strip of 65mm by using a coil separator, then obtaining a coiled strip of 10mm in width by using a roller shear, and then operating an iron core coiling machine to prepare an amorphous iron core with 20mm of inner diameter, 30mm of outer diameter, 10mm of height and 20 +/-0.5 g of weight.
S4 heat treatment: and (4) placing the iron core prepared in the third step on a heat treatment tray and placing the tray into a positive pressure annealing furnace. Checking the air tightness of each part of the vacuum furnace, wherein each part comprises each valve (an inflation valve, an air release valve, a main path valve and a bypass valve), a furnace door sealing rubber ring, a cylinder sealing rod and the like. And checking the pressure of an external air source and the air tightness of the pressure reducing valve to ensure that the pressure of the air source is enough. And (3) opening circulating water, and keeping the water temperature at room temperature, namely 25 ℃, so as to ensure that the circulating water continuously works in the heat treatment process to cool the furnace body. The furnace door and the locking ring are closed to prevent the furnace door from popping out in the heat treatment process. Opening the mechanical pump, opening the main path valve and the bypass valve, closing the air door, and vacuumizing to 500 Pa; starting diffusion pump, preheating to 180 deg.C, starting Roots pump, and vacuumizing to 1 × 10-1Pa; closing the bypass valve and raising the vacuum to 7-8 x 10-3Pa; shut-down diffusion pumpClosing valves at each stage, and introducing protective atmosphere and high-purity hydrogen (such as 96% argon and 4% hydrogen) to a certain pressure (such as atmospheric pressure 1 atm); setting a temperature control program: for example, the heating rate is 10K/min, the heat treatment temperature is 550 ℃, the heat preservation time is 120min, air cooling is carried out, a heating control program is started, and a heating kettle is opened; and opening the air door after the heat treatment program is operated, opening the cooling fan, cooling to room temperature, then discharging air, opening the locking ring and the furnace door, and taking out the product.
For the iron cores prepared in examples 1 to 4, the inductance, impedance and quality factor (e.g., voltage 1V, frequency 100 kHz) of the iron core at different frequencies were measured using an impedance analyzer. Placing the iron core into a plastic ring with a proper specification, winding a copper coil with a certain number of turns outside, and calculating a correlation coefficient (effective cross-sectional area Ae =0.3989 cm)2Effective magnetic path length Le =7.74cm, effective volume Ve =3.089cm3Schmidt constant = 2.5), measuring iron loss, magnetic permeability, remanence ratio and coercive force under different frequencies by using an alternating current magnetic measuring instrument, and taking the average value of multiple groups of measured results.
Specifically, detection: the soft magnetic performance of the commercial 1K107B iron core under different heat treatment conditions (vacuum heat treatment and hydrogen argon mixed atmosphere heat treatment) under different use working conditions. The heat treatment temperature is 550 ℃, the heating rate is 10K/min, the heat preservation time is from 10min to 120min, and the cooling mode is furnace cooling. Compared with vacuum heat treatment in a hydrogen-argon mixed atmosphere, the heat treatment method has the advantages that the iron core inductance can be improved, the magnetic permeability can be improved, the coercive force can be reduced, the iron loss can be reduced, and the soft magnetic performance of the commercial 1K107B iron core is greatly improved. The specific experimental results are shown in fig. 1 and fig. 2.
Fig. 1 and 2 show the core inductance and quality factor measured using an impedance analyzer. Inductance represents the ability of the core to induce a magnetic field, and the quality factor represents the ratio of the voltage developed across the core to the voltage of the applied power supply. When the voltage and the frequency of an externally-applied power supply are fixed, the higher the inductance is, the stronger the magnetic field generated by the iron core is, and the higher the magnetic permeability is generally; the larger the Q value, the higher the voltage generated across the core.
As shown in fig. 1 and 2, compared with the vacuum heat treatment, the heat treatment in the hydrogen-argon gas mixed atmosphere can greatly improve the inductance value of the iron core, and the inductance value is improved from 10.4 muh to 14 muh when the holding time is 60min, and the improvement ratio is 34.6%. Meanwhile, the quality factor of the iron core subjected to heat treatment under the hydrogen-argon mixed atmosphere has large fluctuation when the heat preservation time is 30-60 min, and the highest magnetic permeability of the iron core with the heat preservation time of 30min is found subsequently.
Fig. 3 and 4 show the coercive force and residual magnetism ratio of the iron core measured by an ac magnetic core magnetism measuring instrument, the actual operating condition of the 1K107 nanocrystalline strip material when the mobile phone is wirelessly charged is selected as the test condition, and the specific parameters are current frequency 25kHz and external magnetic field 50 mT. Coercivity and remanence are important magnetic performance parameters representing the ability of a magnetic material to resist demagnetization, and good soft magnetic materials require low coercivity and low remanence. When the heat preservation time is 60min, the remanence ratio of the iron core obtained by vacuum heat treatment is 0.734, and the coercive force is 12.5A/m; the remanence ratio of the iron core obtained by the heat treatment in the atmosphere of hydrogen and argon is 0.64, the coercive force is 9.6, and the remanence ratio is reduced by 12.8 percent and 23.2 percent respectively. It can be seen that the remanence and the coercive force of the iron core can be greatly reduced by heat treatment under the hydrogen-argon mixed atmosphere, and the soft magnetic property of the iron core is improved.
Fig. 5 shows that the iron core iron loss of the iron core under different frequencies is measured by using an alternating current magnetic core magnetism measuring instrument, and the 1K107 nanocrystalline strip is mostly applied with high-frequency alternating current such as wireless charging, mutual inductors and the like, so that the current frequencies of 100kHz, 50kHz and 25kHz are selected as the test conditions. The iron loss is an important magnetic performance parameter, and refers to the sum of hysteresis loss and eddy current loss (the residual loss is negligible) of a magnetic material in an alternating magnetic field and a pulsating magnetic field per unit mass or unit volume, and the lower the iron loss, the smaller the loss in practical use.
As shown in FIG. 5, the heat preservation time is 60min, when the test frequencies are 100kHz, 50kHz and 25kHz respectively, the iron core iron losses obtained by vacuum heat treatment are 3.25W/kg, 0.945W/kg and 0.281W/kg respectively, and the iron core iron losses obtained by heat treatment in the mixed atmosphere of hydrogen and argon are 2.301W/kg, 0.616W/kg and 0.163W/kg respectively, which are reduced by 29.3%, 34.8% and 42%. The data show that the iron core loss can be greatly reduced by heat treatment under the hydrogen-argon mixed atmosphere, and the energy loss in the use process of the iron core is effectively reduced.
Fig. 6 shows the effective permeability of the core at different frequencies measured by an ac core magnetic measuring instrument.
The heat preservation time is 30min, when the test frequencies are 100kHz, 50kHz and 25kHz respectively, the effective magnetic permeability of the iron core obtained by vacuum heat treatment is 18396.5, 24464.9 and 30271.3 respectively, the effective magnetic permeability of the iron core obtained by hydrogen-argon mixed atmosphere heat treatment is 28615.8, 41116.3 and 51326.1 respectively, and 55.6%, 68.1% and 69.6% are respectively improved.
The heat preservation time is 60min, when the test frequencies are 100kHz, 50kHz and 25kHz respectively, the effective magnetic permeability of the iron core obtained by vacuum heat treatment is 19544.6, 25926.2 and 31341.4 respectively, the effective magnetic permeability of the iron core obtained by hydrogen-argon mixed atmosphere heat treatment is 24563.8, 31671.5 and 37983.5 respectively, and the effective magnetic permeability is improved by 25.7%, 22.2% and 21.2% respectively.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A hydrogenation heat treatment process of amorphous nano alloy is characterized in that: the method comprises the following steps:
smelting a master alloy: according to the expression FeaSibBcCudNbeBatching, wherein a, b, c, d and e respectively represent the atomic percentage content of each corresponding component, and a + b + c + d + e is 100, and repeatedly smelting the batching in a smelting furnace under the atmosphere of inert protective gas to form a master alloy ingot with uniform components;
strip preparation: placing the master alloy ingot in a smelting furnace for melting, after full melting, spraying the master alloy ingot to a copper roller through a nozzle, and cooling the surface of the copper roller to obtain a strip;
preparing an iron core: winding the strip to obtain a coiled strip, and preparing the coiled strip into an amorphous iron core in an iron core winding machine;
and (3) heat treatment: and placing the amorphous iron core on a heat treatment tray, placing the tray into a positive pressure annealing furnace, vacuumizing, introducing protective gas and high-purity hydrogen, and carrying out heat treatment.
2. The hydrogenation heat treatment process of amorphous nano alloy according to claim 1, characterized in that: the expression FeaSibBcCudNbeWhere a is 73.5, b is 13.5, c is 9, d is 3, and e is 1.
3. The hydrogenation heat treatment process of amorphous nano alloy according to claim 1, characterized in that: the strip is prepared in a medium-frequency induction smelting furnace, and the alloy is melted by heating through eddy current generated by an induction coil.
4. The hydrogenation heat treatment process of amorphous nano alloy according to claim 1, characterized in that: and in the strip preparation process, the alloy solution is sprayed by a nozzle under the protection of argon.
5. The hydrogenation heat treatment process of amorphous nano alloy according to claim 1, characterized in that: the coiled material strip is 45-60mm in thickness and 10mm in width.
6. The hydrogenation heat treatment process of amorphous nano alloy according to claim 1, characterized in that: the amorphous iron core has the inner diameter of 20mm, the outer diameter of 30mm, the height of 10mm and the weight of 20 +/-0.5 g.
7. The hydrogenation heat treatment process of amorphous nano alloy according to claim 1, characterized in that: before the amorphous iron core is placed in a positive pressure annealing furnace, the air tightness of each component of the vacuum furnace is checked, the components comprise valves, a furnace door sealing rubber ring, an air cylinder sealing rod, the pressure of an external air source and the air tightness of a pressure reducing valve, circulating water is opened, and the water temperature is kept at room temperature, namely 25 ℃.
8. The hydrogenation heat treatment process of amorphous nano alloy according to claim 1, characterized in that: the vacuumizing operation comprises the steps of opening a mechanical pump, opening a main path valve and a bypass valve, closing an air door and vacuumizing to 500 Pa; starting diffusion pump, preheating to 180 deg.C, starting Roots pump, and vacuumizing to 1 × 10-1Pa; closing the bypass valve and raising the vacuum to 7-8 x 10-3Pa。
9. The hydrogenation heat treatment process of amorphous nano alloy according to claim 1, characterized in that: the heat treatment temperature is 550 ℃, the heat preservation time is 60min, and the heating rate is 10K/min.
10. The hydrogenation heat treatment process of amorphous nano alloy according to claim 1, characterized in that: the pressure of the protective gas and the high-purity hydrogen is more than 0.5atm and less than 10atm, wherein the volume ratio of the protective gas to the high-purity hydrogen is arbitrary.
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