CN109295401A - A new type of iron-based amorphous nanocrystalline soft magnetic alloy and preparation method thereof - Google Patents
A new type of iron-based amorphous nanocrystalline soft magnetic alloy and preparation method thereof Download PDFInfo
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- CN109295401A CN109295401A CN201811512188.2A CN201811512188A CN109295401A CN 109295401 A CN109295401 A CN 109295401A CN 201811512188 A CN201811512188 A CN 201811512188A CN 109295401 A CN109295401 A CN 109295401A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 52
- 229910001004 magnetic alloy Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 90
- 239000000956 alloy Substances 0.000 claims abstract description 90
- 239000010949 copper Substances 0.000 claims abstract description 22
- 239000010955 niobium Substances 0.000 claims abstract description 21
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 238000002844 melting Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 25
- 238000000137 annealing Methods 0.000 claims description 12
- 229910000714 At alloy Inorganic materials 0.000 claims description 2
- 229910000521 B alloy Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 3
- 238000003723 Smelting Methods 0.000 abstract 1
- 230000006698 induction Effects 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 230000005415 magnetization Effects 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- -1 Si (99%) block Substances 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005492 condensed matter physics Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
-
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/001—Heat treatment of ferrous alloys containing Ni
-
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
-
- 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
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/153—Amorphous metallic alloys, e.g. glassy metals
- H01F1/15333—Amorphous metallic alloys, e.g. glassy metals containing nanocrystallites, e.g. obtained by annealing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/153—Amorphous metallic alloys, e.g. glassy metals
- H01F1/15341—Preparation processes therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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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
- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/03—Amorphous or microcrystalline structure
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/04—Nanocrystalline
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/02—Magnetic
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Abstract
本发明属于软磁合金技术领域，尤其涉及一种新型铁基非晶纳米晶软磁合金及其制备方法。本发明提供了一种新型铁基非晶纳米晶软磁合金，其化学式为Fe73.5‑xSi13.5B9Cu1Nb3Nix。本发明还提供了上述合金的制备方法，包括以下步骤：步骤1：将铁、硅、硼源、铜、铌和镍熔炼成合金锭；步骤2：将所述合金锭破碎得到破碎的合金锭、清洗；步骤3：将所述破碎的合金锭通过甩带法制得合金薄带；步骤4：将所述合金薄带进行热处理得到新型铁基非晶纳米晶软磁合金。本发明提供了一种新型铁基非晶纳米晶软磁合金及其制备方法，解决了现有技术中铁基非晶纳米晶合金的大规模应用受到严重限制的技术问题。
The invention belongs to the technical field of soft magnetic alloys, and in particular relates to a novel iron-based amorphous nanocrystalline soft magnetic alloy and a preparation method thereof. The invention provides a novel iron-based amorphous nanocrystalline soft magnetic alloy whose chemical formula is Fe 73.5-x Si 13.5 B 9 Cu 1 Nb 3 Ni x . The present invention also provides a method for preparing the above alloy, which includes the following steps: step 1: smelting iron, silicon, boron source, copper, niobium and nickel into alloy ingots; step 2: crushing the alloy ingots to obtain broken alloy ingots , cleaning; Step 3: The broken alloy ingot is obtained by the strip method to obtain an alloy thin strip; Step 4: The alloy thin strip is subjected to heat treatment to obtain a new type of iron-based amorphous nanocrystalline soft magnetic alloy. The invention provides a novel iron-based amorphous nanocrystalline soft magnetic alloy and a preparation method thereof, and solves the technical problem that the large-scale application of the iron-based amorphous nanocrystalline alloy in the prior art is severely limited.
Description
Technical field
The invention belongs to magnetically soft alloy technical field more particularly to a kind of new iron-based amorphous and nanocrystalline soft magnetic alloy and its
Preparation method.
Background technique
With being constantly progressive for society, due to computer network, high density recording technology, electric system and the micro- chinaware of high frequency
The development in the fields such as part and needs increasingly require various components used to have high-performance, high-quality, small-sized, light weight, this
Require that preparing the Metallic Functional Materials such as the magnetically soft alloy of these devices is continuously improved performance.Fe-based amorphous/nano-crystal soft-magnetic closes
Fitting has the features such as excellent soft magnet performance, such as high saturated magnetic induction, low-coercivity, high magnetic permeability, low-loss, many decades
Being the research hotspot in material and Condensed Matter Physics field always.In addition, the preparation work of Fe-based amorphous/nano-crystal soft magnetic alloy
Skill is simple, low in cost, is widely used in fields such as transformer, inductor, sensors.Structure and performance according to material
Feature is currently roughly divided into two major classes in the amorphous and nanocrystalline soft magnetic alloy studied or applied: i.e.: 1) having high saturation magnetic induction
The amorphous or nanometer crystal alloy of intensity are answered, mainly includes iron SiB system's amorphous alloy and iron SiBPCu system nano-crystal alloy.Iron SiB
It is amorphous alloy performance characteristics is that saturation induction density is higher, about 1.4-1.7T, other than Bs, performance is better than silicon steel.Closely
The iron SiBPCu nanometer crystal alloy of exploitation in several years, maximum feature are high Bs, generally about 1.8-1.9T, are much larger than iron SiB
Amorphous alloy.And high Bs can reduce the usage amount of material, reduce cost, reduce device volume.But high Fe content iron
The amorphous formation ability of SiBPCu nanometer crystal alloy is lower, it is difficult to prepare large-sized amorphous band.2) there is high initial magnetic
It is alloy, Nanoperm (iron MB, M=Zr, Hf, Nb that the nanometer crystal alloy of conductance, which mainly includes Finemet (iron SiBCuNb),
Deng) it is alloy and HITPERM (iron CoMB, M=Zr, Hf, Nb etc.) is alloy.Wherein, though Finemet alloy have it is excellent soft
Magnetic property, but because iron content is lower, typical composition iron73.5Si13.5B9Cu1Nb3Saturation induction density be only
1.25T limits the application in the power electronic devices to miniaturization to a certain extent.And Nanoperm system with
Hitperm system alloy is although saturation induction density with higher and magnetostriction coefficient level off to zero, a large amount of easy oxygen
Change noble metal Zr, the elements such as Hf exist, increase producting process difficulty, limit its application field to a certain extent.Therefore, existing
In some Fe-based amorphous nanocrystalline alloy systems, lower amorphous formation ability and low saturation induction density make Fe-based amorphous
The large-scale application of nanometer crystal alloy is seriously constrained to the technical problem urgently to be resolved for those skilled in the art.
Summary of the invention
In view of this, being solved the present invention provides a kind of new iron-based amorphous and nanocrystalline soft magnetic alloy and preparation method thereof
The technical issues of large-scale application of Fe-based amorphous nanocrystalline alloy receives serious limitation in the prior art.
The present invention provides a kind of new iron-based amorphous and nanocrystalline soft magnetic alloy, chemical formula Fe73.5- xSi13.5B9Cu1Nb3Nix；Wherein, 0≤x≤3.
The present invention also provides a kind of preparation methods of new iron-based amorphous and nanocrystalline soft magnetic alloy, comprising the following steps:
Step 1: will be by iron, silicon, boron source, copper, niobium and Ni-B alloy at alloy pig；
Step 2: the alloy pig being crushed and obtains broken alloy pig, cleaning；
Step 3: the broken alloy pig is obtained into alloy thin band by getting rid of band legal system；
Step 4: the alloy thin band being annealed to obtain new iron-based amorphous and nanocrystalline soft magnetic alloy.
Preferably, the width of the alloy thin band is 1~2mm；The alloy thin band with a thickness of
20~40 μm.
Preferably, the number of melting described in step 1 is 4~6 times.
Preferably, the temperature of the melting is 1100~1350 DEG C.
Preferably, the boron source includes boron and/or ferro-boron.
Preferably, the temperature of the annealing is 540~560 DEG C.
Preferably, the heating rate of the annealing is 20 DEG C/min.
Preferably, the time of the annealing is 60min.
Preferably, the chilling roller linear velocity got rid of with method is 45~55m/s.
Demand for development of the present invention for existing Fe-based amorphous nanocrystalline alloy system lightweight, miniaturization, design one
The novel iron-based amorphous and nanocrystalline soft magnetic alloy with low cost, high saturated magnetic induction and low-coercivity of kind, the present invention are real
New iron-based amorphous/the Nanoalloy for applying example preparation has strong amorphous formation ability, high saturated magnetic induction and low coercive
The excellent soft magnet performance such as power.By adding a small amount of Co, Ni, one of Al and Gd metallic element greatly optimize alloy
Amorphous formation ability, the shortcomings that improving the toughness and low saturation induction density of alloy strip steel rolled stock.Preparation of the embodiment of the present invention
New iron-based amorphous and nanocrystalline soft magnetic alloy is the structure of completely amorphous state by XRD analysis.Its saturation magnetization energy
Reach 1.58T, coercivity can be reduced to 3.6A/m, effectively optimize the soft magnet performance of FeSiBCuNb system amorphous alloy.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other attached drawings according to these attached drawings.
Fig. 1 is the process flow diagram of the new iron-based amorphous and nanocrystalline soft magnetic alloy of preparation of the embodiment of the present invention；
Fig. 2 is the X-ray diffractogram of amorphous thin ribbon prepared by the embodiment of the present invention 1~3；
Fig. 3 is the magnetization curve figure of new iron-based amorphous and nanocrystalline soft magnetic alloy prepared by the embodiment of the present invention 1~3；
Fig. 4 is that the coercivity of new iron-based amorphous and nanocrystalline soft magnetic alloy prepared by the embodiment of the present invention 1~3 changes song
Line.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of new iron-based amorphous and nanocrystalline soft magnetic alloys and preparation method thereof, solve the prior art
The technical issues of large-scale application of middle Fe-based amorphous nanocrystalline alloy receives serious limitation.Fig. 1 prepares iron-based non-for the present invention
The process flow diagram of brilliant nano-crystal soft magnetic alloy.
Embodiment 1
New iron-based amorphous and nanocrystalline soft magnetic alloy manufactured in the present embodiment is Fe72.5Si13.5B9Cu1Nb3Ni1。
(1) prepared by master alloy raw material: pressing Fe72.5Si13.5B9Cu1Nb3Ni1Atomic percent is converted to quality hundred by chemical formula
Divide ratio, weighs Fe (99.9%), FeB (17.51%) alloy, Si (99%) block, Cu (99.9%) block, Nb respectively in proportion
(99.9%) block and Ni (99.9%).
(2) foundry alloy melting: the raw material prepared is put into vacuum arc melting furnace, is evacuated to 5 × 10 to furnace body-3Afterwards
It is filled with argon gas/nitrogen atmosphere protection and closes charging valve when air pressure in furnace is higher than atmospheric pressure 0.01Mpa.It is former to heat melting
Material continues melting 3 minutes, is subsequently cooled to solidify, repeat melting 4 times, obtain after quickly being overturn after raw material is completely melt
To the uniform alloy pig of ingredient.
(3) alloy pig cleans: alloy pig being broken for fritter alloy, and is put into the beaker equipped with ethyl alcohol or acetone and carries out
Cleaning.
(4) prepared by amorphous thin ribbon: will be fitted into the quartz ampoule of lower ending opening after the cleaning of fritter alloy, is subsequently placed in and gets rid of band and set
In standby induction coil, it is evacuated to 5 × 10-3Being filled with purity afterwards is 99.99% high-purity argon gas as protective gas, adjusts electricity
Stream makes alloy melting, during which controls temperature at 1250 DEG C, controls the time 2 minutes, when alloy melting and when there is white light, utilizes gas
Alloy under molten condition is ejected into the copper roller surface that revolving speed is 50m/s by pressure difference, and obtained width is about 1mm, and thickness is about 20 μ
The amorphous ribbon strip of m.
(5) structure detection is carried out to alloy strip steel rolled stock with X-ray diffractometer, so that it is determined that the glass of alloy to form energy
Power.Referring to fig. 2, Fig. 2 is the X-ray diffractogram of the amorphous thin ribbon of preparation of the embodiment of the present invention.As shown in Figure 2, complete amorphous
State band about has the diffraction maximums of widthization disperse at 45 °, and in other ranges without obvious sharp crystallization peak.
(6) Crystallizing treatment: amorphous thin ribbon being put into heat-treatment furnace and is made annealing treatment, and is warming up to 440 DEG C with furnace, heat preservation
Strip is taken out after then cooling to room temperature with the furnace, is obtained Fe-based amorphous wherein being 20 DEG C/min with furnace heating rate by 10min
Nanometer crystal alloy.
The Fe-based amorphous nanocrystalline alloy prepared to the embodiment of the present invention 1 detects.
With magnetic detection equipment (vibrating specimen magnetometer VSM and soft magnetism DC test instrument) to the strip after annealing respectively into
Row saturation induction density (Ms) and coercivity (Hc) performance test.Gained performance parameter is as shown in the picture, wherein Bs=4 π ×
(ρ×Ms)×10-4(T)。
Referring to Fig. 3, Fig. 3 is the magnetization curve of the new iron-based amorphous and nanocrystalline soft magnetic alloy of preparation of the embodiment of the present invention
Figure.Referring to fig. 4, Fig. 4 is that the coercitive variation of the new iron-based amorphous and nanocrystalline soft magnetic alloy of preparation of the embodiment of the present invention is bent
Line.The result shows that iron-based amorphous and nanocrystalline soft magnetic alloy Fe prepared by the embodiment of the present invention 172.5Si13.5B9Cu1Nb3Ni1,
Saturation magnetization is 1.58T, coercivity 6.8A/m.
Embodiment 2
New iron-based amorphous and nanocrystalline soft magnetic alloy manufactured in the present embodiment is Fe71.5Si13.5B9Cu1Nb3Ni2,It is prepared
Step includes:
(1) prepared by master alloy raw material: pressing Fe71.5Si13.5B9Cu1Nb3Ni2Atomic percent is converted to quality hundred by chemical formula
Divide ratio, weighs Fe (99.9%), FeB (17.51%) alloy, Si (99%) block, Cu (99.9%) block, Nb respectively in proportion
(99.9%) block and Ni (99.9%).
(2) foundry alloy melting: the raw material prepared is put into vacuum arc melting furnace, is evacuated to 5 × 10 to furnace body-3Afterwards
It is filled with argon gas/nitrogen atmosphere protection and closes charging valve when air pressure in furnace is higher than atmospheric pressure 0.01Mpa.It is former to heat melting
Material continues melting 3 minutes, is subsequently cooled to solidify, repeat melting 4 times, obtain after quickly being overturn after raw material is completely melt
To the uniform alloy pig of ingredient.
(3) alloy pig cleans: alloy pig being broken for fritter alloy, and is put into the beaker equipped with ethyl alcohol or acetone and carries out
Cleaning.
(4) prepared by amorphous thin ribbon: will be fitted into the quartz ampoule of lower ending opening after the cleaning of fritter alloy, is subsequently placed in and gets rid of band and set
In standby induction coil, it is evacuated to 5 × 10-3Being filled with purity afterwards is 99.99% high-purity argon gas as protective gas, adjusts electricity
Stream makes alloy melting, during which controls temperature at 1250 DEG C, controls the time 2 minutes, when alloy melting and when there is white light, utilizes gas
Alloy under molten condition is ejected into the copper roller surface that revolving speed is 50m/s by pressure difference, and obtained width is about 1mm, and thickness is about 20 μ
The amorphous ribbon strip of m.
(5) structure detection is carried out to alloy strip steel rolled stock with X-ray diffractometer, so that it is determined that the glass of alloy to form energy
Power.Referring to fig. 2, Fig. 2 is the X-ray diffractogram of the amorphous thin ribbon of preparation of the embodiment of the present invention.As shown in Figure 2, complete amorphous
State band about has the diffraction maximums of widthization disperse at 45 °, and in other ranges without obvious sharp crystallization peak.
(6) Crystallizing treatment: amorphous thin ribbon being put into heat-treatment furnace and is made annealing treatment, and is warming up to 440 DEG C with furnace, heat preservation
Strip is taken out after then cooling to room temperature with the furnace, is obtained Fe-based amorphous wherein being 20 DEG C/min with furnace heating rate by 10min
Nanometer crystal alloy.
The Fe-based amorphous nanocrystalline alloy prepared to the embodiment of the present invention 2 detects.
With magnetic detection equipment (vibrating specimen magnetometer VSM and soft magnetism DC test instrument) to the strip after annealing respectively into
Row saturation induction density (Ms) and coercivity (Hc) performance test.Gained performance parameter is as shown in the picture, wherein Bs=4 π ×
(ρ×Ms)×10-4(T)。
Referring to the magnetization curve figure for the Fe-based amorphous nanocrystalline alloy that Fig. 3, Fig. 3 are preparation of the embodiment of the present invention.Referring to figure
The coercitive change curve of 4, Fig. 4 Fe-based amorphous nanocrystalline alloys prepared for the embodiment of the present invention.The result shows that the present invention
Iron-based amorphous and nanocrystalline soft magnetic alloy Fe prepared by embodiment 271.5Si13.5B9Cu1Nb3Ni2, saturation magnetization is
1.35T, coercivity 4.5A/m.
Embodiment 3
New iron-based amorphous and nanocrystalline soft magnetic alloy manufactured in the present embodiment is Fe70.5Si13.5B9Cu1Nb3Ni3, preparation
Step includes
(1) prepared by master alloy raw material: pressing Fe70.5Si13.5B9Cu1Nb3Ni3Atomic percent is converted to quality hundred by chemical formula
Divide ratio, weighs Fe (99.9%), FeB (17.51%) alloy, Si (99%) block, Cu (99.9%) block, Nb respectively in proportion
(99.9%) block and Ni (99.9%).
(2) foundry alloy melting: the raw material prepared is put into vacuum arc melting furnace, is evacuated to 5 × 10 to furnace body-3Afterwards
It is filled with argon gas/nitrogen atmosphere protection and closes charging valve when air pressure in furnace is higher than atmospheric pressure 0.01Mpa.It is former to heat melting
Material continues melting 3 minutes, is subsequently cooled to solidify, repeat melting 4 times, obtain after quickly being overturn after raw material is completely melt
To the uniform alloy pig of ingredient.
(3) alloy pig cleans: alloy pig being broken for fritter alloy, and is put into the beaker equipped with ethyl alcohol or acetone and carries out
Cleaning.
(4) prepared by amorphous thin ribbon: will be fitted into the quartz ampoule of lower ending opening after the cleaning of fritter alloy, is subsequently placed in and gets rid of band and set
In standby induction coil, it is evacuated to 5 × 10-3Being filled with purity afterwards is 99.99% high-purity argon gas as protective gas, adjusts electricity
Stream makes alloy melting, during which controls temperature at 1250 DEG C, controls the time 2 minutes, when alloy melting and when there is white light, utilizes gas
Alloy under molten condition is ejected into the copper roller surface that revolving speed is 50m/s by pressure difference, and obtained width is about 1mm, and thickness is about 20 μ
The amorphous ribbon strip of m.
(5) structure detection is carried out to alloy strip steel rolled stock with X-ray diffractometer, so that it is determined that the glass of alloy to form energy
Power.Referring to fig. 2, Fig. 2 is the X-ray diffractogram of the amorphous thin ribbon of preparation of the embodiment of the present invention.As shown in Figure 2, complete amorphous
State band about has the diffraction maximums of widthization disperse at 45 °, and in other ranges without obvious sharp crystallization peak.
(6) Crystallizing treatment: amorphous thin ribbon being put into heat-treatment furnace and is made annealing treatment, and is warming up to 440 DEG C with furnace, heat preservation
Strip is taken out after then cooling to room temperature with the furnace, is obtained Fe-based amorphous wherein being 20 DEG C/min with furnace heating rate by 10min
Nanometer crystal alloy.
The Fe-based amorphous nanocrystalline alloy prepared to the embodiment of the present invention 3 detects.
With magnetic detection equipment (vibrating specimen magnetometer VSM and soft magnetism DC test instrument) to the strip after annealing respectively into
Row saturation induction density (Ms) and coercivity (Hc) performance test.Gained performance parameter is as shown in the picture, wherein Bs=4 π ×
(ρ×Ms)×10-4(T)。
Referring to the magnetization curve figure for the Fe-based amorphous nanocrystalline alloy that Fig. 3, Fig. 3 are preparation of the embodiment of the present invention.Referring to figure
The coercitive change curve of 4, Fig. 4 Fe-based amorphous nanocrystalline alloys prepared for the embodiment of the present invention.The result shows that the present invention
Iron-based amorphous and nanocrystalline soft magnetic alloy Fe prepared by embodiment 370.5Si13.5B9Cu1Nb3Ni3, saturation magnetization is
1.32T, coercivity 3.6A/m.
The above is only a preferred embodiment of the present invention, it is noted that for making the professional technique of the art
Personnel are that by various modifications to these embodiments without departing from the technical principles of the invention, and these
Modification also should be regarded as the range that the present invention should protect.
Claims (10)
1. a kind of new iron-based amorphous and nanocrystalline soft magnetic alloy, which is characterized in that its chemical formula is Fe73.5- xSi13.5B9Cu1Nb3Nix；Wherein, 0≤x≤3.
2. a kind of preparation method of new iron-based amorphous and nanocrystalline soft magnetic alloy, which comprises the following steps:
Step 1: will be by iron, silicon, boron source, copper, niobium and Ni-B alloy at alloy pig；
Step 2: the alloy pig being crushed and obtains broken alloy pig, cleaning；
Step 3: the broken alloy pig is obtained into alloy thin band by getting rid of band legal system；
Step 4: the alloy thin band being annealed to obtain new iron-based amorphous and nanocrystalline soft magnetic alloy.
3. the preparation method of new iron-based amorphous and nanocrystalline soft magnetic alloy according to claim 2, which is characterized in that described
The width of alloy thin band is 1~2mm；The alloy thin band with a thickness of 20~40 μm.
4. the preparation method of new iron-based amorphous and nanocrystalline soft magnetic alloy according to claim 2, which is characterized in that step
The number of melting described in 1 is 4~6 times.
5. the preparation method of new iron-based amorphous and nanocrystalline soft magnetic alloy according to claim 2, which is characterized in that described
The temperature of melting is 1100~1350 DEG C.
6. the preparation method of new iron-based amorphous and nanocrystalline soft magnetic alloy according to claim 2, which is characterized in that described
Boron source includes boron and/or ferro-boron.
7. the preparation method of new iron-based amorphous and nanocrystalline soft magnetic alloy according to claim 2, which is characterized in that described
The temperature of annealing is 540~560 DEG C.
8. the preparation method of new iron-based amorphous and nanocrystalline soft magnetic alloy according to claim 2, which is characterized in that described
The heating rate of annealing is 20 DEG C/min.
9. the preparation method of new iron-based amorphous and nanocrystalline soft magnetic alloy according to claim 2, which is characterized in that described
The time of annealing is 60min.
10. the preparation method of new iron-based amorphous and nanocrystalline soft magnetic alloy according to claim 2~9 any one,
It is characterized in that, the chilling roller linear velocity got rid of with method is 45~55m/s.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112164541A (en) * | 2020-10-15 | 2021-01-01 | 太原理工大学 | Anti-direct-current iron-based nanocrystalline alloy and preparation method thereof |
| CN112877616A (en) * | 2021-01-11 | 2021-06-01 | 秦皇岛市燕秦纳米科技有限公司 | Preparation method of low-remanence amorphous nanocrystalline soft magnetic material |
| CN112877613A (en) * | 2020-12-28 | 2021-06-01 | 江苏三环奥纳科技有限公司 | Iron-based amorphous soft magnetic alloy and preparation method and application thereof |
| CN114694908A (en) * | 2022-05-30 | 2022-07-01 | 天津三环奥纳科技有限公司 | Low-temperature-resistant nanocrystalline magnetically soft alloy iron core, manufacturing method and application |
| WO2024130939A1 (en) * | 2022-12-19 | 2024-06-27 | 青岛云路先进材料技术股份有限公司 | Amorphous nanocrystalline soft magnetic alloy and preparation method therefor |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01247557A (en) * | 1988-03-30 | 1989-10-03 | Hitachi Metals Ltd | Manufacture of hyperfine-crystal soft-magnetic alloy |
| CN103060722A (en) * | 2011-10-21 | 2013-04-24 | 江苏奥玛德新材料科技有限公司 | Iron-based amorphous or nanocrystalline soft magnetic alloy and preparation method thereof |
| CN104561841A (en) * | 2013-10-25 | 2015-04-29 | 上海瀚涛纳米科技有限公司 | High-saturation-magnetization iron-base amorphous nanocrystal soft magnetic alloy and preparation method thereof |
| JP2015167183A (en) * | 2014-03-04 | 2015-09-24 | Ｎｅｃトーキン株式会社 | Nanocrystal soft magnetic alloy powder and powder-compact magnetic core arranged by use thereof |
| CN105074843A (en) * | 2013-02-15 | 2015-11-18 | 日立金属株式会社 | Annular magnetic core using Fe iron-based nanocrystalline soft-magnetic alloy and magnetic component using said annular magnetic core |
| CN106636981A (en) * | 2016-10-28 | 2017-05-10 | 上海理工大学 | Soft magnet-based amorphous alloy product |
| CN107365950A (en) * | 2017-07-24 | 2017-11-21 | 广东咏旺新材料科技有限公司 | Fe Si B Nb Cu are Fe-based amorphous/nanocrystalline magnetically soft alloy material and preparation and Technology for Heating Processing |
| CN107393673A (en) * | 2017-07-31 | 2017-11-24 | 东莞美壹磁电科技有限公司 | A kind of iron-based amorphous nanocrystalline soft magnetic alloy and preparation method thereof |
| CN109440021A (en) * | 2018-11-13 | 2019-03-08 | 广东工业大学 | A kind of iron-based amorphous and nanocrystalline soft magnetic alloy and its preparation method and application |
-
2018
- 2018-12-11 CN CN201811512188.2A patent/CN109295401A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01247557A (en) * | 1988-03-30 | 1989-10-03 | Hitachi Metals Ltd | Manufacture of hyperfine-crystal soft-magnetic alloy |
| CN103060722A (en) * | 2011-10-21 | 2013-04-24 | 江苏奥玛德新材料科技有限公司 | Iron-based amorphous or nanocrystalline soft magnetic alloy and preparation method thereof |
| CN105074843A (en) * | 2013-02-15 | 2015-11-18 | 日立金属株式会社 | Annular magnetic core using Fe iron-based nanocrystalline soft-magnetic alloy and magnetic component using said annular magnetic core |
| CN104561841A (en) * | 2013-10-25 | 2015-04-29 | 上海瀚涛纳米科技有限公司 | High-saturation-magnetization iron-base amorphous nanocrystal soft magnetic alloy and preparation method thereof |
| JP2015167183A (en) * | 2014-03-04 | 2015-09-24 | Ｎｅｃトーキン株式会社 | Nanocrystal soft magnetic alloy powder and powder-compact magnetic core arranged by use thereof |
| CN106636981A (en) * | 2016-10-28 | 2017-05-10 | 上海理工大学 | Soft magnet-based amorphous alloy product |
| CN107365950A (en) * | 2017-07-24 | 2017-11-21 | 广东咏旺新材料科技有限公司 | Fe Si B Nb Cu are Fe-based amorphous/nanocrystalline magnetically soft alloy material and preparation and Technology for Heating Processing |
| CN107393673A (en) * | 2017-07-31 | 2017-11-24 | 东莞美壹磁电科技有限公司 | A kind of iron-based amorphous nanocrystalline soft magnetic alloy and preparation method thereof |
| CN109440021A (en) * | 2018-11-13 | 2019-03-08 | 广东工业大学 | A kind of iron-based amorphous and nanocrystalline soft magnetic alloy and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 谢春晓等: "Co/Ni摩尔比对FeCoNiCrZr非晶合金晶化过程及磁性能的影响", 《中国有色金属学报》 * |
| 陈先朝等: "Ni/Co比例及微量Dy对FeCoNiBSiNb块体非晶合金玻璃形成能力和磁性能的影响", 《热加工工艺》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112164541A (en) * | 2020-10-15 | 2021-01-01 | 太原理工大学 | Anti-direct-current iron-based nanocrystalline alloy and preparation method thereof |
| CN112877613A (en) * | 2020-12-28 | 2021-06-01 | 江苏三环奥纳科技有限公司 | Iron-based amorphous soft magnetic alloy and preparation method and application thereof |
| CN112877616A (en) * | 2021-01-11 | 2021-06-01 | 秦皇岛市燕秦纳米科技有限公司 | Preparation method of low-remanence amorphous nanocrystalline soft magnetic material |
| CN112877616B (en) * | 2021-01-11 | 2022-06-24 | 秦皇岛市燕秦纳米科技有限公司 | Preparation method of low-remanence amorphous nanocrystalline soft magnetic material |
| CN114694908A (en) * | 2022-05-30 | 2022-07-01 | 天津三环奥纳科技有限公司 | Low-temperature-resistant nanocrystalline magnetically soft alloy iron core, manufacturing method and application |
| CN114694908B (en) * | 2022-05-30 | 2023-11-24 | 天津三环奥纳科技有限公司 | Low-temperature-resistant nanocrystalline magnetically soft alloy iron core, manufacturing method and application |
| WO2024130939A1 (en) * | 2022-12-19 | 2024-06-27 | 青岛云路先进材料技术股份有限公司 | Amorphous nanocrystalline soft magnetic alloy and preparation method therefor |
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