CN113774284A - Ultrathin nanocrystalline alloy strip, magnetic core and preparation method - Google Patents

Ultrathin nanocrystalline alloy strip, magnetic core and preparation method Download PDF

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CN113774284A
CN113774284A CN202111042659.XA CN202111042659A CN113774284A CN 113774284 A CN113774284 A CN 113774284A CN 202111042659 A CN202111042659 A CN 202111042659A CN 113774284 A CN113774284 A CN 113774284A
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strip
alloy strip
nanocrystalline alloy
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刘树海
刘红玉
刘昌伟
张世明
杨东
林福强
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Qingdao Yunlu Advanced Materials Technology Co ltd
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Qingdao Yunlu Advanced Materials Technology Co ltd
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    • 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
    • B22D11/0614—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 the casting wheel being immersed in a molten metal bath, and drawing out upwardly the casting strip
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    • 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
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    • 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
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    • C21D6/00—Heat treatment of ferrous alloys
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    • C21D6/00—Heat treatment of ferrous alloys
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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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • 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
    • H01F1/14766—Fe-Si based alloys
    • 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
    • H01F1/15308—Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
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    • C21—METALLURGY OF IRON
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    • C21D2201/00—Treatment for obtaining particular effects
    • C21D2201/03—Amorphous or microcrystalline structure
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C2200/02—Amorphous
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C2200/00—Crystalline structure
    • C22C2200/04—Nanocrystalline

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Abstract

The embodiment of the invention relates to the technical field of magnetic materials, in particular to an ultrathin nanocrystalline alloy strip, wherein the maximum thickness difference between three continuous test points of the nanocrystalline alloy strip in the width direction is less than 1 micrometer; and/or the maximum thickness difference between five continuous test points of the nanocrystalline alloy strip in the width direction is less than 2 microns; and/or the lamination coefficient fs of the nanocrystalline alloy strip is greater than or equal to 80%. The thickness of the nanocrystalline alloy strip is 8-16 microns, and the width of the nanocrystalline alloy strip is 60-200 millimeters. The nanocrystalline alloy strip has ultrathin thickness, larger width and higher uniformity, thereby having excellent magnetic performance and wide application prospect.

Description

Ultrathin nanocrystalline alloy strip, magnetic core and preparation method
Technical Field
The invention relates to the technical field of magnetic materials, in particular to an ultrathin nanocrystalline alloy strip, a magnetic core and a preparation method thereof.
Background
Magnetic materials are important functional materials that have the function of converting, transferring, storing, or changing the state of energy and information. Magnetic core materials are widely used in the fields of machinery, electronics, power, communication, and instrumentation. The soft magnetic material is a magnetic material with low coercive force and high magnetic permeability, and is a magnetic material widely used in industries such as power electronics, motors and the like. The iron-based nanocrystalline strip has the characteristics of high magnetic conductivity and low high-frequency loss, is mainly applied to the fields of mutual inductors, high-frequency transformers, common-mode inductors and the like, and is more suitable for the gradual development of electronic products in the high-frequency, small-sized, energy-saving and environment-friendly directions due to the excellent characteristics of the iron-based nanocrystalline strip.
The currently used iron-based nanocrystalline strip is mostly a FeSiBNbCu system, and is a nanocrystalline and amorphous two-phase structure formed after annealing of an amorphous strip prepared by rapid cooling. The saturation magnetic induction intensity of the current iron-based nanocrystalline strip is about 1.24T, and the thickness is more than 18 um.
As the thickness of the strip decreases, the permeability and high frequency loss of the iron-based nanocrystals are further optimized. Therefore, high-end applications and emerging fields are developing with the need for ultra-thinning of iron-based nanocrystalline ribbons.
Disclosure of Invention
The embodiment of the invention provides an ultrathin nanocrystalline alloy strip, a magnetic core and a preparation method thereof, wherein the iron-based amorphous nanocrystalline has ultrathin thickness, larger width and excellent magnetic performance; moreover, the preparation method can continuously cast the strip for a long time and can keep the quality of the strip stable.
In a first aspect, embodiments of the present invention provide an ultrathin nanocrystalline alloy strip having a maximum thickness difference between no more than 5 test points that are consecutive in a width direction of less than 2 um.
In one possible design, the maximum thickness difference between no more than 5 test points of the nanocrystalline alloy strip that are consecutive in the width direction is less than 2um, including: the maximum thickness difference between three continuous test points of the nanocrystalline alloy strip in the width direction is less than 1 micron; and/or the maximum thickness difference between five continuous test points of the nanocrystalline alloy strip in the width direction is less than 2 microns.
In one possible design, the lamination factor fs of the nanocrystalline alloy strip is greater than or equal to 80%; the thickness of the nanocrystalline alloy strip is 8-16 microns, and the width of the nanocrystalline alloy strip is 60-200 millimeters.
In one possible design, the rate of change of the nanocrystalline alloy strip in the width direction is less than 2.5%.
In one possible design, the nanocrystalline alloy strip is an ultra-thin nanocrystalline strip that is continuously cast in a single shot with a capacity of not less than 2 tons of molten steel in a smelting furnace.
In one possible design, the nanocrystalline alloy strip comprises an alloy having an atomic percentage as shown in formula (1);
Fe100-a-b-c-d-xMxSiaBbCuc(Nb1-yMoy)d (1)；
wherein M is one or two of Co and Ni, A is one or more of Si, P and C; x is more than or equal to 0 and less than or equal to 0.05, a is more than or equal to 12 and less than or equal to 16, b is more than or equal to 6.5 and less than or equal to 8.5, c is more than or equal to 0 and less than or equal to 1.5, d is more than or equal to 0.8 and less than or equal to 2.8, y is more than or equal to 0 and less than or equal to 0.45, and the total atomic content of (Fe + M) is more than or equal to 73.5 percent.
In a second aspect, embodiments of the present invention provide a continuous casting method for nanocrystalline alloy strip provided in the first aspect, including the following steps:
(1) the nanocrystalline alloy strip comprises an alloy with the atomic percentage as shown in the formula (1);
Fe100-a-b-c-d-xMxSiaBbCuc(Nb1-yMoy)d (1)；
wherein M is one or two of Co and Ni, A is one or more of Si, P and C;
x is more than or equal to 0 and less than or equal to 0.05, a is more than or equal to 12 and less than or equal to 16, b is more than or equal to 6.5 and less than or equal to 8.5, c is more than or equal to 0 and less than or equal to 1.5, d is more than or equal to 0.8 and less than or equal to 2.8, y is more than or equal to 0 and less than or equal to 0.45, and the total atomic content of (Fe + M) is more than or equal to 73.5 percent;
(2) in the preparation process of the nanocrystalline alloy strip, molten steel is rapidly cooled through a cooling roller; wherein the heat conductivity coefficient of the cooling roller is 130-250W/mK, and the hardness H is not lower than 180.
In one possible design, the mass fraction of Al in the molten steel is less than or equal to 0.002%, the mass fraction of Ti is less than or equal to 0.03%, and O is less than 10 ppm; the molten steel is poured onto a cooling roller through a nozzle, and in order to prevent the molten steel from being oxidized and control the temperature of the nozzle, gas protection is carried out at the nozzle, wherein the gas is reducing gas.
In a third aspect, embodiments of the present invention provide a magnetic core composed of the nanocrystalline alloy strip provided in the first aspect, and Ps of the magnetic core20k/0.5T≤10W/kg，μ20k＞50000，μ50kGreater than 40000.
In a fourth aspect, an embodiment of the present invention provides a method for preparing a magnetic core according to the third aspect, including:
winding the nanocrystalline alloy strip provided by the first aspect into a magnetic core, and performing heat treatment on the magnetic core; wherein the heat treatment process comprises: a heating section, a heat preservation section and a cooling section which are connected in sequence;
the temperature rise section comprises a plurality of sub-stages with different temperatures, the temperature difference between adjacent sub-stages in the sub-stages is greater than or equal to 10 ℃, and the heat preservation time of each sub-stage is 10-90 min;
the maximum temperature in the warming section is lower than the temperature of the holding section and is at least 30 ℃ lower than the temperature of the holding section;
the temperature of the heat preservation section is more than or equal to the first crystallization temperature Tx1And is less than or equal to (Tx)1The duration of the heat preservation section is 100 and 200min at +20 ℃;
the discharging temperature of the magnetic core of the cooling section is less than 100 ℃;
wherein a magnetic field is applied to the core during the soak period and during the cool-down period, wherein the magnetic field is in a direction along a height of the core and has a magnetic field strength of not less than 800 GS.
The embodiment of the invention provides an ultrathin iron-based nanocrystalline alloy strip, which is 8-16 microns thick, uniform in thickness, high in lamination coefficient and wide in application range prospect. The method for preparing the strip provided by the embodiment of the invention can continuously cast the iron-based nanocrystalline alloy strip with the thickness of 8-16 microns for a long time, and can keep the quality of the strip stable. In addition, the magnetic core formed by the strip material prepared by the embodiment of the invention has lower high-frequency loss and higher magnetic permeability.
Detailed Description
The technical solutions in the embodiments of the present invention are described below. It is to be understood that the embodiments described are only a few embodiments of the present disclosure, and not all embodiments.
In the examples of the present invention, "casting" and "preparation" have the same meaning and may be substituted for each other.
At present, the preparation process of the nanocrystalline strip is mainly divided into two types: pressure belt making and gravity belt making. The pressure strip making is mainly strip with the width of less than 60mm, the equipment cost of the pressure strip spraying is high, the single spraying yield is low, and the process is difficult to realize continuous casting.
The preparation process of the gravity spraying belt can prepare the belt material with the width of 200 mm. If a gravity strip spraying process which can realize continuous casting and has higher single-spraying yield is provided, the index cost of the nanocrystalline strip can be greatly reduced.
In the embodiment of the invention, the ultrathin nanocrystalline strip is prepared by adopting a gravity strip spraying process. In the test process, the iron-based nanocrystalline strip is found to have poor amorphous forming capability and flowability due to the component properties, and the preparation difficulty is far higher than that of the amorphous strip compared with the iron-based amorphous strip with simple components. Particularly, in the preparation process of the ultrathin nanocrystalline strip, the strip is difficult to be continuously prepared for a long time, and the strip is easy to break; besides the strip breakage, the deterioration of the strip quality also leads to a reduction in the casting time, and the deterioration of the strip during the production leads to a poor stability of the strip quality. The electronic device has less consumption of the strip material and large batch, so the requirement on the stability of the strip material quality is tighter. Therefore, the realization of stable and continuous preparation of high-quality ultrathin nanocrystals is a problem to be solved by the embodiments of the present invention.
The embodiment of the invention provides a preparation process of an ultrathin nanocrystalline alloy strip based on gravity strip spraying, which can realize continuous casting of the ultrathin iron-based nanocrystalline alloy strip for more than 3 hours without a more precise continuous casting technology. In addition, in the continuous casting process, the incidence rate of strip breakage and attenuation is low, and the ultrathin nanocrystalline alloy strip with stable quality can be efficiently and stably prepared. Specifically, the thickness of the prepared ultrathin nanocrystalline strip is 8-16um, and the width is as follows: 60-200mm, wherein the change rate of the strip width is less than 2.5% in the single-spraying strip making process; the 3-point range (V3) in the width direction of the strip is less than 1um, and the 5-point range (V5) is less than 2 um; the folding coefficient (fs) is more than or equal to 80 percent. The change rate of the strip width refers to a ratio obtained by comparing a width difference obtained by subtracting the minimum width from the maximum width of the strip with the maximum width. The 3-point pole difference refers to the maximum thickness difference between 3 continuous test points in the width direction, or the maximum thickness difference of 3 arbitrarily connected thickness test points. The 5-point pole difference refers to the maximum thickness difference between 5 continuous test points in the width direction, or the maximum thickness difference of any connected 5 thickness test points. The 3-point range and the 5-point range can be tested according to the first part of the national standard GB/T19345.1-2017 amorphous nanocrystalline alloy: the introduction of the Fe-based amorphous magnetically soft alloy strip is not repeated herein.
The inventors of the present invention found in the course of experiments that when iron-based nanocrystalline alloy strip having a thickness of less than 16um is continuously cast using gravity strip spraying, the problem of strip breakage is a more serious problem. The strip breakage refers to a phenomenon that a strip material is wound by a winding device in the strip manufacturing process, and the strip material is suddenly broken in the winding process. Generally, the breakage is mainly caused by the brittleness of the strip or the defect of the edge of the strip, and the fundamental reason is that the amorphous forming ability of the iron-based nanocrystalline strip is poor. And the thickness of the strip is less than 16um, so that the preparation of the strip can be realized by the current more precise continuous casting technology. The invention mainly solves the problems from two aspects, namely optimization of alloy components on one hand and optimization of cooling rolls on the other hand.
The first is the optimization of alloy composition.
In the invention, the chemical composition expression of the alloy is as follows according to atomic percentage: fe100-a-b-c-d- xMxSiaBbCuc(Nb1-yMoy) d, wherein M is one or two of Co and Ni, and the atomic ratio content of x, a, b, c, d and y is respectively as follows: x is more than or equal to 0 and less than or equal to 0.05, a is more than or equal to 12 and less than or equal to 16, b is more than or equal to 6.5 and less than or equal to 8.5, c is more than or equal to 0 and less than or equal to 1.5, d is more than or equal to 0.8 and less than or equal to 2.8, y is more than or equal to 0 and less than or equal to 0.45, and the balance is Fe. Wherein the total atomic content of Fe element and M element is more than or equal to 73.5 percent. Wherein the total atomic content of the Fe element and the M element is the sum of the atomic content of the Fe element and the atomic content of the M element. The composition used in the early experimental procedures was the conventional 1K107 composition, but this composition was in the continuous phaseIn the casting process, a thin strip is not easy to prepare, and the brittleness is high. Therefore, the invention adjusts the ratio of metalloid elements and Nb elements on the basis of 1K107 components, and improves the amorphous forming capability of the alloy. In addition, Mo is used to replace partial Nb, so that the complexity of the alloy system is increased, and the fluidity of the molten steel is improved.
The main element of the alloy component in the invention is iron element, the iron element is ferromagnetic element, and is the main source of the magnetism of the iron-based amorphous and nanocrystalline strip materials, and the high Fe content is an important guarantee that the strip material has proper saturation magnetic induction intensity value. In the embodiment of the invention, the main purpose is to obtain the components capable of realizing the ultrathin nanocrystalline strip and have excellent soft magnetic performance, so in the component optimization process, the level of Fe content must be ensured not to be lower than the existing components so as to ensure that the saturation magnetic induction intensity of the strip is not reduced. In addition, M is one or two of Co and Ni which are also ferromagnetic elements, and the addition of Co and Ni can increase the complexity of an alloy system, improve the fluidity of the alloy and promote the strip with better surface quality. In addition, Co and Ni elements can be preferentially combined with non-metal elements such as B, Si, C and the like, so that more amorphous phases are reserved in the treatment process, the growth of nano-crystalline grains with high iron content is inhibited, the average grain size of the nano-crystalline grains is reduced, and the Bs value and the soft magnetic property of an alloy system are improved. However, in terms of industrial applicability, the prices of Co and Ni are high, and the content of Co or Ni is controlled to 0-0.05%. In combination of the above two aspects, the total amount of Fe + M is not less than 73.5 atomic% for the ferromagnetic element.
B (boron) is an amorphous forming element, B is controlled to be more than or equal to 6.5 and less than or equal to 8.5, when the content of boron is less than 6.5, the amorphous forming capability is poor, the prepared strip is more prone to strip breakage, and under the condition of low content of B, the crystallization phenomenon can occur. When the boron content is more than 10, Bs of the alloy is caused to decrease.
Si element is also an amorphous forming element, so that the amorphous forming capability of the alloy is improved, and particularly, the Si element can reduce the melting point of the alloy and is a core element for improving the manufacturability of a nanocrystalline alloy system. The range is controlled as follows: a is more than or equal to 12.0 and less than or equal to 16.0.
The Cu element is a heterogeneous nucleation site of the alpha-Fe nanocrystal and is an essential element in a nanocrystal system. The element content is controlled to be 0-1.5, for the embodiment of the invention, when the Cu element exceeds 1.5, the total content of other elements is reduced, and further the allowance of increasing Bs is reduced, and when the Cu element is controlled to be 0-1.5, enough heterogeneous nucleation points can be formed for forming alpha-Fe nano-crystals.
The main functions of Nb and Mo are to prevent the crystal grain growth of the crystallized phase and to maintain the fineness of the nanocrystalline structure. In the conventional nanocrystalline alloy, most of Nb is used, and Mo is used to replace part of Nb in the invention, which can play two roles: firstly, the complexity of an alloy system is increased, the fluidity of molten steel is increased, and the Mo element is relatively Nb element, so that the raw material cost is low, and the components of the strip can be reduced to a certain extent. In the embodiment of the invention, the total atomic content of Nb and Mo is controlled to be 0.8-2.8%, and the atomic content of Mo element accounts for 0-0.45 of the total atomic ratio of Nb and Mo.
Second is chill roll optimization
The most important process part to achieve rapid solidification in the casting of strip is the chill roll. The invention solves the problem of strip breakage in the continuous casting process of the strip by optimizing the cooling roller. The main factors influencing the use effect of the cooling roller are cooling strength and cooling uniformity. The invention improves the use effect of the cooling roller and reduces the occurrence of broken belt by mainly controlling the heat conductivity coefficient and the hardness of the cooling roller. The inventor of the invention has found through a great deal of experiments that the occurrence rate of broken belt can be reduced when the thermal conductivity of the cooling roller is between 130-250W/mK and the Hardness (HB) is not lower than 180. The higher the thermal conductivity of the chill roll, the greater the cooling capacity of the chill roll, but the less the hardness of the corresponding chill roll. The hardness of the cooling roll directly affects the quality of the surface of the strip, defects can occur on the surface of the cooling roll under the impact of high-heat molten steel, the characteristics of the defects are left in the strip forming process, casting defects such as pinholes, bubbles, burrs and the like can occur on the surface of the strip, the surface defects can increase the frequency of strip breakage, and therefore the hardness of the cooling roll needs to be controlled within a certain range. For the invention, after multiple verification, the heat conductivity coefficient and the hardness of the cooling roller are balanced, and finally the heat conductivity coefficient of the cooling roller is confirmed to be 130-250W/mK, and the Hardness (HB) is not lower than 180.
The width of the ultrathin nanocrystalline alloy strip prepared by the invention is between 60 and 200 mm; in the single-spraying belt making process, the change rate of the belt width is less than 2.5 percent; the 3-point range (V3) in the width direction of the strip is less than 1um, and the 5-point range (V5) is less than 2 um; and fs of the strip is more than or equal to 80 percent. In the continuous casting process, if the width of the strip is greatly changed and the range fluctuation of the strip is too large or the fs coefficient is too low, it indicates that the quality of the strip is deteriorated and a fading condition occurs. The occurrence of a fade condition means the early end of continuous casting. In the evaluation of the attenuation, the rate of change of the strip width in the single-jet strip process means the rate of change of the maximum value and the minimum value of the width of all the seized rolls in the strip-jet process. The 3-point range (V3) of the strip in the width direction is the thickness difference of any connected 3 thickness test points. The 5-point range (V5) refers to the thickness difference of any connected 5 thickness test points, wherein the evaluation selected by the invention is that the single-spraying worst grabbing roll is taken as a test object.
The inventor of the present invention has found through a lot of experiments that the main influencing factors of the attenuation include: the fundamental cause of the degradation of the quality of molten steel at the front end and the temperature control and oxidation prevention of the strip at the rear end is the precipitation of inclusions.
First, the molten steel quality at the tip is described. For the preparation of amorphous and nanocrystalline strips, the control of the quality of molten steel is an important technical point, and the embodiment of the quality of the molten steel mainly refers to the purity of the molten steel. The better the purity of the molten steel, the better the quality of the produced strip, the less attenuation that occurs. In the present example, the purity of the molten steel mass is mainly represented by the contents (expressed by mass fraction) of three elements, i.e., Al, Ti, and O. Wherein the mass fraction of Al is less than or equal to 0.002%, the mass fraction of Ti is less than or equal to 0.03%, and O is less than 10 ppm. In the smelting process of iron-based amorphous and nanocrystalline alloy, the method for controlling the quality of molten steel is to controlThe amount of inclusions in the molten steel. The types of inclusions brought by different metal raw materials are different according to different alloy systems. For the present example, the main inclusion species is oxide inclusions. The oxide inclusions are mostly generated by the action of easily-oxidized elements and oxygen, and are brought in by a part of raw materials or brought by unclean falling of a furnace lining. Such as SiO2、TiO2、FeO、MnO、 Al2O3、Nb2O3And the like. There are also many complex oxides such as FeO. SiO2、MnO·SiO2、Al2O3·SiO2、MnO·Al2O3、 FeO·Al2O3And the like. In the test process of the invention, the content of the Al and Ti oxides is more, the content of the Al, Ti and O is controlled at a lower level, and the content of the inclusions in the molten steel can be greatly reduced. The quality of high-quality molten steel can obtain the iron-based nanocrystalline raw strip with excellent performance and surface quality.
The problems of temperature control and oxidation resistance of the belt at the rear end are solved. In the rapid quenching process, molten steel is poured onto a cooling roller through a nozzle to realize the preparation of a strip. The condition of the nozzles has a decisive influence on the quality of the strip. The attenuation problems are mainly the temperature control and oxidation resistance of the nozzle. The solution is as follows: a gas protection device is added on the structure of the original nozzle, the effects of heat preservation and molten steel oxidation resistance are achieved by burning reducing gas, and the used gas is characterized by the reducing gas. An air gap is added on the nozzle structure. The gas slit can spray reducing gas, and the reducing gas is combusted around the gas slit. Namely, the reducing gas is combusted around the jet slot through the gas slot, so that oxygen at the periphery of the jet slot can be combusted, the oxygen is prevented from entering molten steel in the process of producing the strip, the molten steel oxidation caused by the oxygen entering is avoided, and the generation of inclusions is reduced. In addition, the combustion gas can maintain the temperature of the nozzle in a proper range during the strip making process. The nozzle temperature is stabilized in a proper range, so that the molten steel solidification and inclusion generation caused by nozzle cooling can be effectively avoided, the attenuation in the strip manufacturing process is prevented, and the stable quality of the strip is effectively ensured.
The optimization scheme of the preparation process is introduced above. Next, in specific examples, the tape manufacturing process and the manufactured tape according to the examples of the present invention will be illustrated. It should be noted that, the following describes an improvement of the preparation process of the nanocrystalline alloy strip according to the embodiment of the present invention, and the specific process that is not described may refer to the description of the gravity strip spraying process in the prior art, and is not described herein again.
Example 1
This example corresponds to Fe100-a-b-c-dMxSiaBbCuc(Nb1-yMoy)dThe alloy composition is prepared, an intermediate frequency smelting furnace is used for remelting raw materials such as iron sources, metallic silicon, ferroboron, ferromolybdenum, electrolytic copper and the like in different proportions, after smelting is finished, tapping is carried out to an intermediate frequency bottom building furnace, after heating and heat preservation and sedation, the ultrathin iron-based nanocrystalline strip with the width of 102mm and the thickness of 8-16 mu m is prepared by a single-roller rapid quenching method.
According to the invention, in order to solve the problem of belt breakage in the preparation process, the process improvement mainly comprises component optimization and cooling roller optimization.
Table 1 shows the thickness, ductile-brittle band thickness, band breakage/hour (band breakage/h), grasping amount/hour (grasping amount/h) and other performance parameters of the ultrathin nanocrystalline strip with different alloy compositions. Among these parameters, the thickness of the ultra-thin nanocrystalline strip can reflect the amorphous forming ability of the alloy and the ability to prepare the ultra-thin strip. The tough and brittle band thickness refers to the band thickness at which a brittle point occurs in the case of a hand-torn band. The toughness and brittleness condition of the alloy is reflected by the thickness of the brittle belt, the toughness of the belt material is better, and the possibility of belt breakage is smaller. The belt breaking times and the grabbing amount reflect the effect of process optimization, wherein the belt breaking times and the grabbing amount are selected per hour to quantitatively explain the results of component optimization and process improvement.
TABLE 1 in the present example, the alloy compositions and strip thickness, ductile and brittle strip thickness, strip breakage/h, and pick-up/h
Figure BDA0003249945270000051
Figure BDA0003249945270000061
As can be seen from the data in Table 1, the original ribbon thickness of the ultra-thin nanocrystalline ribbon according to F1-F15 of the inventive example is between 8-16um, and the ribbon thickness of comparative example D1 is 18um, so that the soft magnetic performance, especially the high frequency performance, of the ultra-thin nanocrystalline is more excellent than the conventional ribbon thickness of 18um and the ribbon thickness of 8-16 um. For the optimization of the aspect of belt breakage, it can be seen that, under the same preparation process, the thickness of the ductile and brittle belt of the comparative example D1 is only 22um, the number of belt breakage per hour is more than 10, the gripping amount is only 500kg, a large amount of preparation time is used for adjustment during the belt breakage, the belt which cannot be gripped cannot be used, and the yield is very low. The alloy components optimized in the embodiment of the invention have the thickness of the ductile and brittle belt of 26-30um, which is 4-6um higher than that of the comparative example D1, the belt breakage frequency is obviously reduced compared with that of the comparative example D1, and the grabbing amount is obviously increased due to the reduction of the belt breakage frequency. As can be seen from the component optimization of F1-F15, the component optimization has obvious inhibition effect on the banding.
Table 2 shows the strip thickness, ductile to brittle strip thickness, number of breaks per hour, and pick-up per hour for F1, F3, and F13 of table 1 under four different chill roll settings.
TABLE 2 strip thickness, strip breakage/h, pick-up/h for different chill rolls
Figure BDA0003249945270000062
Figure BDA0003249945270000071
Table 2 is the result of the conditions for the three compositions F1, F3, F13 using 5 different sets of cooling rolls. From the results, the first three groups (i.e. experimental groups 1 to 3) of the 5 groups are cooling roll conditions meeting the test conditions of the embodiment of the invention, the thickness of the strip is 8 to 16um, the thickness of the ductile and brittle strip is better, and the strip breakage frequency and the grabbing amount are better. The 4 th experimental group belongs to the experimental conditions of high thermal conductivity and low hardness, and the result shows that the thickness of the strip and the thickness of the strip are consistent compared with the thickness of the strip in the invention group, but the strip breakage frequency is poorer, mainly because the hardness of the cooling roller is poorer, and the strip breakage frequency is increased due to various defects on the surface of the strip. The 5 th experiment group belongs to the test conditions of low thermal conductivity and high hardness, and as a result, the thickness of the strip is larger, the thickness of the tough and brittle strip is lower, the strip breaking frequency is higher, the grabbing amount is less, mainly because the thermal conductivity of the cooling roller is low, the cooling capacity is poor, and the strip may be partially crystallized under severe conditions. Therefore, for the embodiment of the present invention, the heat conduction times and hardness of the cooling roller are a set of balance parameters, the heat conduction coefficient should be controlled at 130-250W/mK, and the Brinell hardness should be above 180.
As described above, the 2 nd problem to be solved by the embodiment of the present invention is the problem of attenuation in the continuous strip production process, and the main process improvement point is the optimization of the purity of molten steel and the nozzle. As F3 in table 1: fe73.95Si14.5B7.8(Nb56Mo44)2.75Cu1Carrying out process test comparison for a target component: respectively, different Al, Ti and O components are controlled and optimized to be compared, wherein the optimization of the nozzle mainly means that the gas combustion protection function is realized by changing the structure of the nozzle, and in the test, the indexes for evaluating attenuation comprise: lamination factor (fs), rate of change of strip width in single-shot strip process, 3 point range (V3), 5 point range (V5) in strip width direction, wherein these indices are for evaluating strip quality and stability. The attenuation of the strip under the different test conditions is shown in table 3.
TABLE 3 attenuation of the strip under different test conditions
Figure BDA0003249945270000072
As can be seen from table 3: the different test conditions, each with a different attenuation effect on the strip. In the test groups from S1 to S5, the influence of different elemental contents of Al, Ti and O without atmosphere protection is mainly verified. From the results, the lamination factor, the width change rate, the V3, and the V5 values of the strip of S1 group were the best among the 5 groups of tests. In the group S2-S4, the content values of Al, Ti and O are higher in some aspect, especially in S5, which shows that the content of Al, Ti and O has a great influence on the attenuation of the strip, mainly the three elements of Al, Ti and O are directly coherent elements generated by inclusions in the smelting process, and the content of the elements is too high, so that the content of the inclusions in molten steel is increased, and the strip-making smoothness is affected, and in the strip-making process, the influence of the inclusions is cumulative and difficult to reverse, so that once the strip is attenuated, when the quality of the strip cannot meet the use requirement, the casting must be stopped, and the continuous casting of the ultra-thin strip cannot be realized. In the test group of S6-S10, gas protection measures are added in different tests of Al content, Ti content and O content, and the attenuation situation is improved in comparison with that of S1-S5 from the result, which shows that the generation of inclusions in the strip manufacturing process is slowed down in the gas protection process, the stability of the temperature of a nozzle is ensured on one hand, the entering of external oxygen is prevented on the other hand, the preparation of an ultra-thin strip is more smooth, and the quality of the strip is kept stable in the continuous casting process. Among 10 experiments, S6 has the best experimental effect, the lamination coefficient is more than 86%, the width change rate is less than 1%, V3 is less than 1um, V5 is less than 2um, and basically no attenuation occurs in the process of single-spraying belt manufacturing.
Example 2 magnetic core preparation
The embodiment provides an iron-based nanocrystalline magnetic core which is mainly used in the electronic field, in particular to an iron core of a high-power high-frequency transformer, such as an iron core in a main transformer of an inverter welding machine. The prepared iron-based nanocrystalline strip can be cut and wound into an annular magnetic core, and the magnetic core is subjected to nanocrystallization through heat treatment, so that the magnetic core has excellent high-frequency performance. Technical parameters of the transformer core after heat treatment are as follows: ps20k/0.5T≤10W/kg，μ20k＞50000，μ50kGreater than 40000.
The process of nano crystallization is to carry out heat treatment on the original nanocrystalline strip. The iron-based nanocrystalline strip and the iron-based amorphous strip are mainly distinguished by nanocrystallization, and the strip after nanocrystallization has excellent soft magnetic performance. The segmented magnetizing heat treatment process is adopted in this embodiment. The specific heat treatment process comprises the following steps: the device is divided into a temperature rising section T1, a heat preservation section T2 and a temperature reduction section T3.
Wherein, the temperature rising section T1 needs to be decomposed into 1-5 small sections according to actual conditions, and the temperatures are T11 and T12 … T15 respectively. Wherein the highest temperature of the temperature rising section T1 < (the temperature of the temperature rising section T2 is-30 ℃). The temperature setting intervals of T11, T12, T13 and T14 are not less than 10 degrees, and the heat preservation time of each small segment is as follows: 10-90 min.
The temperature of the soaking section T2 was set to: first crystallization temperature (Tx)1) To (Tx)1+20 ℃ C. Holding time of the holding section T2: 100 and 200 min.
The temperature of the cooling section T3 is the tapping temperature of the magnetic core and is less than 100 ℃.
Wherein, the magnetization is carried out during the heat preservation section T1 and the cooling section T2, the magnetization direction is vertical to the casting direction of the strip, the magnetic field intensity is not lower than 800GS, and the magnetization time is as follows: 150 ℃ and 300 min.
Next, in a specific example, a process of manufacturing the magnetic core and properties thereof are illustrated.
Using F3 in table 1: fe73.95Si14.5B7.8(Nb56Mo44)2.75Cu1、F13：Fe75.95Si13B8(Nb55Mo45)2Cu1.05And comparative example D1: fe73.5Si13.5B9Nb3Cu1The ultrathin iron-based nanocrystalline strip was prepared according to the process described in examples 1-4, and the obtained ultrathin iron-based nanocrystalline strip had a width of 142mm and thicknesses of 10um, 14um, and 18um, respectively.
The manufacturing of the magnetic core is carried out by using the ultrathin iron-based nanocrystalline strip, and the main process comprises the following steps:
cutting: a strip of 142mm width was slit into narrow strips of different widths.
Winding: selecting a shear band with the width of 25mm to be wound into an annular magnetic core, wherein the size of the magnetic core is as follows: 80 x 50 x 25 (outer diameter x inner diameter x width).
③ nanometer crystallization: annealing is carried out by adopting the heat treatment process listed in the table 4, so that the alloy strip is subjected to nano crystallization, and excellent high-frequency soft magnetic performance is obtained.
Performance evaluation: and (3) testing conditions are as follows: loss at 20k/0.5T and permeability ur at 20k/50 k.
Table 4 shows the heat treatment process and loss and permeability of F3 and F13 alloys
Figure BDA0003249945270000091
In Table 4, Tx1The first crystallization temperature of each alloy is set based on the temperature point, wherein: the temperature of the heat preservation section T2 is less than or equal to (Tx)1+20 ℃), and the heat preservation time is 200 min; the main function of the method is to enable the ultrathin nanocrystalline strip to generate uniform nanocrystalline grains in the heat treatment process. The temperature rise section T1 is mainly set for stable temperature rise, and a batch processing mode, in which a large number of cores are stacked together, and a multi-stage processing mode, in which the temperatures in the furnace and the cores are stable and uniform, are used in the heat treatment process. Wherein the highest temperature of the temperature rising section T1 is set to be < (the temperature of the heat preservation section T2 is-30 ℃), the temperature setting intervals of T11, T12 and T13 are not less than 10 ℃, and the heat preservation time is 10-90 min. The temperature of the cooling section T3 is the tapping temperature of the magnetic core and is less than 100 ℃.
On the basis of the above, the magnetization is performed during the heat-preserving section T2 and the cooling section T3, and the magnetization direction is perpendicular to the casting direction of the strip, or the direction of the magnetic field is along the height direction of the magnetic core. The magnetic field intensity is not lower than 800GS, and the magnetizing time is 150-300 min. The magnetic field is applied in the direction vertical to the casting direction of the strip, so that the high-frequency magnetic conductivity of the magnetic core can be effectively improved, the attenuation of the magnetic conductivity is slowed down under the frequency condition of 20kHz-50kHz, and the performance advantage of the ultrathin strip nanocrystalline magnetic core is improved.
As can be seen from Table 4, the magnetic cores corresponding to F3 and F13, after being nanocrystallized, have magnetic core losses Ps compared with the magnetic core corresponding to comparative example D120k/0.5T≤10W/kg，u20k＞50000，u50kThe performance of the F3 alloy with the thickness of 10um is better than that of the F13 alloy with the thickness of 14um, which shows that the excellent performance of the ultrathin nanocrystalline strip on the thickness can further improve the performance of the nanocrystalline magnetic core.
It is to be understood that the various numerical references referred to in the embodiments of the present specification are merely for descriptive convenience and are not intended to limit the scope of the embodiments of the present specification.

Claims (9)

1. An ultrathin nanocrystalline alloy strip characterized by: the maximum thickness difference between no more than 5 test points of the nanocrystalline alloy strip in the width direction is less than 2 um.
2. The nanocrystalline alloy strip according to claim 1, characterized in that: the maximum thickness difference between no more than 5 test points of the nanocrystalline alloy strip in the width direction is less than 2um, and the maximum thickness difference comprises the following steps:
the maximum thickness difference between three continuous test points of the nanocrystalline alloy strip in the width direction is less than 1 micron; and/or the presence of a gas in the gas,
the maximum thickness difference between five continuous test points of the nanocrystalline alloy strip in the width direction is less than 2 microns; and/or.
3. The nanocrystalline alloy strip according to claim 1, characterized in that:
the lamination coefficient fs of the nanocrystalline alloy strip is greater than or equal to 80%;
the thickness of the nanocrystalline alloy strip is 8-16 microns, and the width of the nanocrystalline alloy strip is 60-200 millimeters.
4. The nanocrystalline alloy strip according to claim 1, characterized in that:
the change rate of the width of the nanocrystalline alloy strip is less than 2.5%.
5. The nanocrystalline alloy strip according to any one of claims 1 to 4, characterized in that:
the nanocrystalline alloy strip comprises an alloy with the atomic percentage as shown in the formula (1);
Fe100-a-b-c-d-xMxSiaBbCuc(Nb1-yMoy)d (1)；
wherein M is one or two of Co and Ni, A is one or more of Si, P and C;
x is more than or equal to 0 and less than or equal to 0.05, a is more than or equal to 12 and less than or equal to 16, b is more than or equal to 6.5 and less than or equal to 8.5, c is more than or equal to 0 and less than or equal to 1.5, d is more than or equal to 0.8 and less than or equal to 2.8, y is more than or equal to 0 and less than or equal to 0.45, and the total atomic content of (Fe + M) is more than or equal to 73.5 percent.
6. A method of continuously casting nanocrystalline alloy strip according to any one of claims 1-5, characterized in that:
(1) the nanocrystalline alloy strip comprises an alloy with the atomic percentage as shown in the formula (1);
Fe100-a-b-c-d-xMxSiaBbCuc(Nb1-yMoy)d (1)；
wherein M is one or two of Co and Ni, A is one or more of Si, P and C;
x is more than or equal to 0 and less than or equal to 0.05, a is more than or equal to 12 and less than or equal to 16, b is more than or equal to 6.5 and less than or equal to 8.5, c is more than or equal to 0 and less than or equal to 1.5, d is more than or equal to 0.8 and less than or equal to 2.8, y is more than or equal to 0 and less than or equal to 0.45, and the total atomic content of (Fe + M) is more than or equal to 73.5 percent;
(2) in the preparation process of the nanocrystalline alloy strip, molten steel is rapidly cooled through a cooling roller; wherein the heat conductivity coefficient of the cooling roller is 130-250W/mK, and the hardness H is not lower than 180.
7. The method of claim 6, wherein:
the mass fraction of Al in the molten steel is less than or equal to 0.002%, the mass fraction of Ti is less than or equal to 0.03%, and O is less than 10 ppm;
the molten steel is poured onto a cooling roller through a nozzle, and in order to prevent the molten steel from being oxidized and control the temperature of the nozzle, gas protection is carried out at the nozzle, wherein the gas is reducing gas.
8. A magnetic core comprising the nanocrystalline alloy strip of any one of claims 1-5, having Ps20k/0.5T≤10W/kg，μ20k＞50000，μ50kGreater than 40000.
9. The method of manufacturing a magnetic core according to claim 8, comprising:
winding the nanocrystalline alloy strip according to any one of claims 1 to 5 into a magnetic core and heat treating the magnetic core; wherein the heat treatment process comprises: a heating section, a heat preservation section and a cooling section which are connected in sequence;
the temperature rise section comprises a plurality of sub-stages with different temperatures, the temperature difference between adjacent sub-stages in the sub-stages is greater than or equal to 10 ℃, and the heat preservation time of each sub-stage is 10-90 min;
the maximum temperature in the warming section is lower than the temperature of the holding section and is at least 30 ℃ lower than the temperature of the holding section;
the temperature of the heat preservation section is more than or equal to the first crystallization temperature Tx1And is less than or equal to (Tx)1+20 ℃); the duration of the heat preservation section is 100-200 min;
the discharging temperature of the magnetic core of the cooling section is less than 100 ℃;
wherein a transverse magnetic field is applied to the core during the soak period and during the cool down period, wherein the direction of the magnetic field is along the height direction of the core, and the magnetic field strength is not lower than 800 GS.
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CN112695261A (en) * 2020-12-07 2021-04-23 青岛云路先进材料技术股份有限公司 Iron-based amorphous alloy strip, preparation method thereof and single-roller rapid quenching device for iron-based amorphous alloy strip

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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
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