CN114582581A - Amorphous nanocrystalline alloy strip and manufacturing method thereof - Google Patents

Amorphous nanocrystalline alloy strip and manufacturing method thereof Download PDF

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Publication number
CN114582581A
CN114582581A CN202011389601.8A CN202011389601A CN114582581A CN 114582581 A CN114582581 A CN 114582581A CN 202011389601 A CN202011389601 A CN 202011389601A CN 114582581 A CN114582581 A CN 114582581A
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strip
amorphous nanocrystalline
nanocrystalline alloy
temperature
amorphous
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史杨
李百松
李昭
刘国栋
李志刚
陈文智
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Antai Amorphous Technology Co ltd
Advanced Technology and Materials Co Ltd
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Antai Amorphous Technology Co ltd
Advanced Technology and Materials Co Ltd
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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
    • H01F1/15333—Amorphous metallic alloys, e.g. glassy metals containing nanocrystallites, e.g. obtained by annealing
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/003—Making ferrous alloys making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/008—Amorphous alloys with Fe, Co or Ni as the major constituent
    • 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
    • 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
    • H01F1/15391—Elongated structures, e.g. wires
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/24—Magnetic cores
    • H01F27/25—Magnetic cores made from strips or ribbons
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F3/00—Cores, Yokes, or armatures
    • H01F3/04—Cores, Yokes, or armatures made from strips or ribbons

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Continuous Casting (AREA)

Abstract

The invention provides an amorphous nanocrystalline alloy strip and a manufacturing method thereof. The preparation method reduces the variation amplitude of the thermal stress of the roll surface and effectively reduces the thermal fatigue degree by controlling the roll surface temperature and the strip stripping temperature, thereby reducing the generation and the expansion of cracks, reducing the material stripping of the roll surface, finally reducing the pockmarks of the strip adhered to the roll surface and leading the strip to be attached to the roll surfaceThe density of pits with length of more than 100 μm on the surface of the pasting roller is reduced to 100cm2Not more than 10, thereby improving the surface quality of the strip.

Description

Amorphous nanocrystalline alloy strip and manufacturing method thereof
Technical Field
The invention relates to the field of soft magnetic material research in the field of magnetic functional materials, in particular to an amorphous nanocrystalline alloy strip with good surface quality and a manufacturing method thereof.
Background
The amorphous nanocrystalline alloy is a soft magnetic material which is rapidly developed in recent years, has higher magnetic conductivity and lower alternating current loss compared with the traditional soft magnetic materials such as electrical steel, ferrite and the like, and is widely applied to iron cores in magnetic components such as transformers, inductors, mutual inductors, motor stators and the like. When the amorphous nanocrystalline alloy strip is used for a transformer, an inductor, a mutual inductor, a motor stator and the like, the amorphous nanocrystalline alloy strip with the thickness of about 0.025mm is generally wound or stacked into an iron core. For a strip having a width of 50mm or more, it is often first slit into narrow strips, and then subjected to core winding or the like.
The amorphous nanocrystalline strip is generally manufactured by adopting a planar flow technology, and the method comprises the following steps: melting raw materials in a certain ratio into alloy liquid by using a smelting furnace; then, pouring the alloy liquid into a nozzle ladle with a slit nozzle at the bottom; the alloy liquid in the nozzle package flows out of the nozzle, spreads on the outer circumferential surface of a copper alloy cooling roller rotating at high speed below the nozzle, forms a molten pool of alloy liquid with certain size between the surface of the cooling roller and the bottom surface of the nozzle, is rapidly extracted and rapidly cooled, and meanwhile, the alloy liquid in the nozzle gap is continuously replenished into the molten pool, so that a continuous thin strip with an amorphous or nanocrystalline structure is formed. The thin strip clings to the outer surface of the cooling roller to rotate at high speed along with the cooling roller, is peeled off by high-pressure gas or a mechanical device at a proper position of the outer surface of the cooling roller, and finally is wound into a coil by a winding device.
For the amorphous nanocrystalline alloy strip manufactured by the plane flow technology, the roll surface of the amorphous nanocrystalline alloy strip sometimes has pockmark defects, namely: in a partial area of the strip, some macroscopic point defects exist, for example, fig. 1, and fig. 1 shows a pockmark schematic diagram of the roll surface of the strip when the amorphous nanocrystalline alloy strip is manufactured by using a planar flow technology in the prior art. The defects can be observed in various shapes such as long strips, polygons and other irregular shapes under a microscope, most of the defects are approximately L-shaped with long tails, and the length of the tail can reach about 50-500 mu m, as shown in figure 2, and figure 2 shows a schematic view of the micro-morphology of pockmarks on the surface of a strip attached to a roller when an amorphous nanocrystalline alloy strip is manufactured by using a planar flow technology in the prior art. The pits may be either above or below the surface of the strip. If the pits are higher than the surface of the strip, the lamination coefficient of an iron core processed subsequently is obviously reduced; if the pits are below the surface of the strip, the local cooling will be insufficient due to failure to adhere to the roll, resulting in local brittle spots that can be a source of breakage during processing of the strip. In addition, the pockmarks of the strip material can easily cause the strip material to be interrupted in the production process of the strip material, the coiling of the strip material is interrupted, and the production efficiency is seriously reduced.
Chinese patent CN103155054B discloses a ferromagnetic amorphous alloy strip, which has protrusions with a height of more than 3 μm on the surface of a pasting roller, and reduces the number of surface protrusions by adjusting the surface tension of alloy liquid. However, the surface tension of the alloy liquid can only be adjusted by means of the components of the alloy liquid, the temperature, the ambient atmosphere and the like, and the method is too complicated; moreover, this method does not completely eliminate the roll surface defect, which is the cause of the formation of the surface projections of the strip, from the root.
Chinese patent CN1116137C discloses a cooling roll cover material for producing amorphous microcrystalline alloy strip, which is made of copper alloy, has average crystal grain size less than 200 μm, no crystal grains with size more than 500 μm, and compact gaussian distribution of crystal grain size, and aims to reduce the generation of roll surface defects by improving the microstructure and mechanical properties of the roll cover material. However, the patent does not provide any improvement on how to reduce the defects of the roll surface in the production process of the amorphous alloy strip.
In a word, the roll surface pocking mark defect of the amorphous nanocrystalline strip has obvious adverse effect on the quality and the toughness of the strip, but the prior art mainly takes measures in the aspects of improving the quality of a roll sleeve material and the characteristics of alloy liquid, and no better solution is provided in the aspect of the production process of the amorphous alloy strip.
Disclosure of Invention
In order to solve the problems, the invention provides an amorphous nanocrystalline alloy strip, which comprises the following steps:
melting raw materials in a certain ratio into alloy liquid by using a smelting furnace;
pouring alloy liquid into a nozzle ladle with a nozzle at the bottom;
the alloy liquid flows out of the nozzle, spreads on the outer circumferential surface of the cooling roller rotating at a high speed below the nozzle, and the temperature of the outer circumferential surface of the cooling roller before entering the weld puddle is controlled to be 70-150 ℃;
and rapidly cooling to form a continuous thin belt with an amorphous or nanocrystalline structure, wherein the stripping temperature range of the strip is controlled to be 120-200 ℃ when the strip is stripped from the outer circumferential surface of the cooling roller.
Further, the temperature of the outer circumferential surface of the cooling roller before entering the weld puddle is controlled to be 90-120 ℃.
Further, the stripping temperature of the strip is controlled to be 140-180 ℃ when the strip is stripped from the outer circumferential surface of the cooling roller.
Further, the outer circumferential surface of the cooling roller is polished by a sand paper wheel, an abrasive cloth wheel, a metal brush wheel or a resin brush wheel containing abrasive particles, and the roughness Ra of the outer circumferential surface of the cooling roller is not more than 0.5 mu m.
The invention also provides an amorphous nanocrystalline alloy strip, and the density of pits with the length of more than 100 mu m on the roller-attached surface of the strip is not more than 100cm2Ten.
Further, it is characterized byThe density of pits with length of more than 100 μm on the surface of the strip close to the roller is not more than 100cm2Two of them.
Further, the main components of the amorphous nanocrystalline alloy strip have the following general expression:
XaYbZc
x is a metal element, and the total content a is 65-85 at%; y is a transition metal element, and the total content b is 0-10 at%; z is an amorphous element, the total content c is 15-30 at%, and the alloy also contains impurity elements with the total content not more than 0.5 at%.
Further, X is a ferromagnetic metal element.
Further, X includes at least one of Fe, Co, Ni.
Further, Y includes at least one of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Cu, Ag, Au, Zn, and Al, Sn.
Further, Z comprises at least one of Si, B, P and C.
Further, the width of the strip is 50-300 mm, and the thickness of the strip is 10-50 microns.
The invention also provides an iron core comprising the strip material of the invention.
The present invention also provides a magnetic component including the iron core, the magnetic component including: transformer, inductor, mutual-inductor and motor stator.
According to the invention, by controlling the temperature range of the roller surface and the strip stripping temperature range, the variation range of thermal stress is reduced, and the thermal fatigue degree is effectively reduced, so that the generation and the expansion of cracks are reduced, the contraction stress of the strip is reduced, the material peeling of the roller surface is reduced, and finally the pockmarks of the strip adhered to the roller surface are reduced.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is a schematic diagram showing the pocking mark of a roll surface of a strip material when an amorphous nanocrystalline alloy strip material is manufactured by a planar flow technology in the prior art;
FIG. 2 is a schematic diagram showing the micro-topography of pits on the surface of a strip close to a roller when an amorphous nanocrystalline alloy strip is manufactured by a planar flow technology in the prior art.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
When amorphous nanocrystalline alloy ribbon is manufactured by the planar flow technology, pockmarks sometimes exist on the roll surface of the manufactured ribbon, namely: in the partial area of the strip, some macroscopic point defects (pockmarks for short) are present. The pockmark defect is irregular under a microscope, has the size of about 50-500 mu m, and can be higher than the surface of the strip or lower than the surface of the strip. If the pits are higher than the surface of the strip, the lamination coefficient of an iron core processed subsequently can be obviously reduced; if the pockmarks are lower than the surface of the strip, the local cooling is insufficient due to failure of the roll, and local brittle spots are generated, which become a fracture source of the strip.
Through the research of the inventor, the pockmarks of the surface of the strip close to the roller are caused by the surface defects of the cooling roller.
On the other hand, in the process of producing an amorphous nanocrystalline strip, when an alloy liquid at about 1300 ℃ contacts only one point on the surface of a cooling roll at about 100 ℃, the temperature of the point rises rapidly. Then, the point moves out of the weld puddle along with the rotation of the cooling roller, and the point is rapidly cooled and cooled as the heat carried by the alloy liquid, namely the strip, is rapidly conducted to the inside of the cooling roller. After the cooling roller rotates for a circle, the point is contacted with the alloy liquid again, and the process of rapid temperature rise-rapid temperature reduction is carried out again. Thus, the roll face material is subjected to periodic thermal and cold cycling. Due to the expansion and contraction characteristics of the roller sleeve material, the interior of the outer layer material of the roller sleeve can be subjected to periodic 'compressive stress-tensile stress' cyclic alternating action.
On the other hand, although the surface of the cooling roller is subjected to pre-grinding and is continuously ground in the strip preparation process, the surface of the cooling roller always has some grinding lines. These lines are in fact longitudinal (strip length direction) or diagonal grooves with a certain depth. Under the periodic cyclic alternating action of compressive stress and tensile stress, the grooves generate tiny cracks due to the stress concentration effect and continuously propagate. This process is called thermal fatigue.
With the continuous continuation of thermal fatigue, fatigue cracks continuously expand, surface roll sleeve materials near the cracks loosen, and under the adhesion action of the strip, the roll sleeve materials at the positions near the fatigue cracks are peeled off from the roll surface along with the strip after loosening, so that pits are formed on the roll surface. When the pit part on the roller surface contacts the alloy liquid again, if the alloy liquid enters the pit, convex pits are generated on the corresponding part of the strip. If gas or other contaminants remain in the pits, depressed pits may form in the corresponding portion of the strip and the cooling rate of the strip in that portion may be severely reduced, resulting in localized brittleness and even localized crystallization. In summary, the cause of the strip pitting on the roll surface is: the roller surface layer generates cracks due to thermal fatigue, and then local material loosening and local peeling are generated to form roller surface pits, so that the defects higher than or lower than the surface of the strip are generated at the corresponding position of the strip.
Therefore, in order to reduce the generation of pockmarks, besides the improvement measures in the prior art from the aspect of the quality of the sleeve material, the matching measures in the strip production process are required to reduce the peeling of the sleeve material caused by the thermal fatigue of the roll surface. The invention reduces the surface thermal stress of the roller sleeve and the strip shrinkage by controlling the roller surface temperature and the strip peeling temperature in the production process of the amorphous nanocrystalline strip, thereby reducing the generation of roller surface defects and strip pits.
Specifically, on one hand, the temperature of the surface of the roller is controlled, so that the temperature of the outer surface of the cooling roller before entering the weld puddle is controlled to be 70-150 ℃; preferably, the surface temperature of the cooling roller is controlled to be between 90 and 120 ℃. The adjustment of the roll surface temperature can be realized by changing the temperature and/or the flow rate of cooling water inside the cooling roll, the thermal conductivity of the material of the cooling roll sleeve, the thickness of the cooling roll sleeve and the like.
On the other hand, the temperature (stripping temperature) of the strip when the strip is stripped from the surface of the cooling roller is controlled to be 120-200 ℃; preferably, the stripping temperature of the strip is controlled between 140 and 180 ℃. The regulation of the stripping temperature is realized by changing the position of the strip stripping point (namely the contact length of the strip and the roller surface), the thermal conductivity of the material of the cooling roller sleeve, the thickness of the cooling roller sleeve and the like.
The invention reduces the variation range of the thermal stress of the roller surface and effectively reduces the thermal fatigue degree by controlling the roller surface temperature and the strip stripping temperature, thereby reducing the generation and the expansion of cracks, reducing the peeling of the roller surface material and finally reducing the pockmarks on the roller surface of the strip, and aims to provide the amorphous nanocrystalline alloy strip with good surface quality and the manufacturing method thereof, which reduce the density of the pockmarks with the length of more than 100 mu m on the roller surface of the strip to every 100cm2Not more than 10, thereby improving the surface quality of the strip.
The invention also provides a manufacturing method of the amorphous nanocrystalline alloy strip, and the amorphous nanocrystalline alloy strip is manufactured by adopting a plane flow rapid solidification process.
The raw materials adopted by the invention are all industrial grade pure simple substances or alloys.
Firstly, raw materials with a certain proportion are melted into alloy liquid by a smelting furnace.
Specifically, the main components of the amorphous nanocrystalline alloy strip of the invention have the following general expression:
XaYbZc
the method comprises the following steps of (1) obtaining a ferromagnetic metal element, wherein X is a metal element, the total content a is 65-85 at%, specifically, X is a ferromagnetic metal element and comprises at least one of Fe, Co and Ni, the embodiment of the invention is only exemplified by Fe, Co and Ni, the actual operation process is not limited to the elements, and other metal elements are within the protection range of the invention;
y is a transition metal element, the total content b is 0-10 at%, concretely, Y comprises at least one of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Cu, Ag, Au, Zn and Al and Sn, the embodiment of the invention is only exemplified by Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Cu, Ag, Au, Zn, Al and Sn, the actual operation process is not limited to the elements, and other transition metal elements are within the protection range of the invention;
z is an amorphous forming element, the total content C is 15-30 at%, specifically, Z comprises at least one of Si, B, P and C, the embodiment of the invention is only illustrated by Si, B, P and C, the actual operation process is not limited to the elements, and other amorphous forming elements are within the protection scope of the invention.
In addition, the alloy may further contain impurity elements in a total amount of not more than 0.5 at%.
The smelted alloy liquid can be poured into a tundish for temperature regulation and production rhythm buffering. The tundish can also be omitted when the strip is prepared on a small scale or in a laboratory.
Then, the alloy liquid is poured into a nozzle ladle with a slit nozzle at the bottom. The alloy liquid in the nozzle pack flows out from the nozzle, spreads over the outer circumferential surface of the copper alloy cooling roll rotating at high speed below the nozzle, and is rapidly cooled to form a continuous thin strip having an amorphous or nanocrystalline structure.
The temperature of the alloy liquid in the nozzle pack is 1250-1450 ℃; more preferably, the temperature is between 1300 ℃ and 1420 ℃.
The bottom of the nozzle bag is provided with a slit nozzle, and the width of the slit nozzle is 0.2-0.5 mm.
The static pressure of the alloy liquid at the nozzle is 20-50 kPa; more preferably, between 25 and 40 kPa.
A cooling roller which rotates at a high speed and is provided with a copper alloy outer circumferential surface is arranged below the nozzle, and the surface linear velocity of the cooling roller is 15-30 m/s. The interior of the chill roll may be cooled with a flowing liquid, such as water.
The distance between the bottom edge of the nozzle and the surface of the cooling roller (the distance between the roller nozzles) is 0.1-0.7 mm.
The outer circumferential surface of the cooling roll is previously processed so that the surface roughness Ra thereof is not more than 0.5 μm.
Ar, N for space between nozzle and cooling roller surface2CO or CO2And the like or the mixed gas thereof, so as to prevent the alloy liquid from oxidizing, reduce air entrainment, adjust the temperature of the alloy liquid in the weld puddle and the like.
The surface of the chill roll is continuously dressed with a sandpaper (cloth) wheel, a metal brush wheel or a resin brush wheel containing abrasive grains to remove the residues accumulated on the surface and to make the surface roughness Ra not more than 0.5 μm.
The temperature of the outer surface of the cooling roller before entering the weld puddle is controlled to be 70-150 ℃. Preferably, the surface temperature of the cooling roller is controlled to be between 90 and 120 ℃. If the temperature of the roll surface is too low, on one hand, the fluctuation range of the thermal fatigue stress of the surface layer of the roll sleeve is increased, and the generation and the expansion of the micro-cracks of the roll surface are aggravated; on the other hand, the shrinkage stress of the strip in the cooling process is too large, so that large shrinkage is easy to occur, and the local loose material on the roller surface, which is generated due to thermal fatigue, is torn off from the roller surface to form roller surface defects. However, if the roll surface temperature is too high, the cooling rate of the strip is seriously affected, the strip is embrittled, and even the strip is crystallized. The adjustment of the roll surface temperature can be realized by changing the temperature and/or the flow rate of cooling water inside the cooling roll, the thermal conductivity of the material of the cooling roll sleeve, the thickness of the cooling roll sleeve and the like.
The temperature (stripping temperature) of the strip when the strip is stripped from the surface of the cooling roller is controlled to be 120-200 ℃. Preferably, the stripping temperature of the strip is controlled between 140 and 180 ℃. If the strip peeling temperature is too low, the shrinkage stress of the strip in the cooling process is too large, large shrinkage is easy to occur, and the local loose material on the roller surface generated by thermal fatigue is torn off from the roller surface to form roller surface defects. However, if the stripping temperature is too high, the strip will be brittle and even crystallized after being wound into a coil. The regulation of the stripping temperature is realized by changing the position of the strip stripping point (namely the contact length of the strip and the roller surface), the thermal conductivity of the material of the cooling roller sleeve, the thickness of the cooling roller sleeve and the like.
The amorphous nanocrystalline strip produced by the method has good surface quality, and the density of pits with the length of more than 100 mu m on the surface of the roller is not more than 100cm2Ten. Preferably, the density of pits with a length of more than 100 μm on the surface of the roller is not more than 100cm2And the width of the manufactured amorphous nanocrystalline alloy strip is 50-300 mm, and the thickness of the manufactured amorphous nanocrystalline alloy strip is 10-50 mu m.
Specifically, the amorphous nanocrystalline alloy strip with the high lamination coefficient can be applied to various power or electronic transformer magnetic components. For example: transformer, inductor, mutual inductor, motor stator, etc.
In order to further illustrate that the amorphous nanocrystalline strip prepared by the preparation method of the invention has good surface quality, a plurality of examples and comparative examples are further provided in the examples of the invention for illustration.
Smelting mother alloy liquid with different components by using industrial pure raw materials. The plane flow technology is used for manufacturing the iron-based amorphous alloy and nanocrystalline alloy strips with different widths and thicknesses. Table 1 shows the process parameters used for the manufacture of the strip, in which the alloy liquid temperature is measured continuously by means of a thermocouple; the pressure of the alloy liquid at the nozzle is converted by the liquid level height of the alloy liquid in the nozzle bag; the roll surface temperature and the strip stripping temperature are continuously measured by an infrared thermometer or a thermal imager, wherein the roll surface temperature measuring points are four opposite directions of strip castingThe strip making middle position of the roller surface at one-half circumference, and the strip stripping temperature measuring point is the width middle position of the strip separating point from the roller surface; roughness R of roll surfaceaMeasured with a roughness tester. In order to obtain the desired strip of the present invention, parameters such as the roll surface temperature and the strip peeling temperature are set. For comparison, process parameters not in accordance with the scope of the present invention were also set as comparative examples, respectively.
TABLE 1
Figure BDA0002810843430000091
Figure BDA0002810843430000101
The lengths and densities of pits on the surfaces of the belt attaching rollers of the examples and the comparative examples were observed and measured by a metallographic microscope. The measured data are shown in Table 2. It can be seen that the density of the pockmarks on the face of the strip facing the roll achieves the object of the invention when the solution specified in the invention is used.
TABLE 2
Figure BDA0002810843430000102
In comparative example 1 and comparative example 1, the surface roughness R of the cooling roll was satisfied at the same time when the smelting composition of the raw material of the alloy liquid was the same, the temperature of the alloy liquid in the nozzle, the pressure of the alloy liquid at the nozzle, and the linear velocity of the surface of the cooling roll were all the sameaNot more than 0.5 μm, in example 1, the temperature of the outer circumferential surface of the cooling roll before entering the weld puddle is controlled to be 90-120 ℃, specifically 95 ℃, the peeling temperature of the strip when peeling off the outer circumferential surface of the cooling roll is controlled to be 140-180 ℃, specifically 155 ℃, in comparative example 1, the temperature of the outer circumferential surface of the cooling roll before entering the weld puddle is controlled to be 90-120 ℃, specifically 97 ℃, the peeling temperature of the strip when peeling off the outer circumferential surface of the cooling roll is controlled to be 132 ℃, which is not in the range of the embodiment of the invention, and the band junction is manufacturedAfter that, the width of the tapes of example 1 and comparative example 1 was maintained at 143mm, the thickness of the tape of example 1 was 24 μm, and the thickness of the tape of comparative example was 25 μm, and the tapes prepared in example 1 and comparative example 1 were observed for each 100cm2The number of pocks in the area, per 100cm in example 12The number of pockmarks having a length of more than 100 μm in area is 1, while in comparative example 1, the number of pockmarks per 100cm is2The number of pockmarks in the area with a length of more than 100 μm is 25. In conclusion, when the temperature of the outer circumferential surface of the cooling roll before entering the weld puddle is within the temperature range of the embodiment of the invention, and the stripping temperature of the strip when stripping the outer circumferential surface of the cooling roll is out of the temperature range of the embodiment of the invention, the strip with good surface quality and toughness cannot be obtained.
In comparative example 3 and comparative example 2, the surface roughness R of the cooling roll was satisfied under the condition that the smelting components of the raw materials of the alloy liquid were the same, the temperature of the alloy liquid in the nozzle, the pressure of the alloy liquid at the nozzle and the linear velocity of the surface of the cooling roll were all the sameaNot more than 0.5 μm, in example 3, the temperature of the outer circumferential surface of the cooling roll before entering the weld puddle was controlled to 90-120 ℃, specifically 101 ℃, the peeling temperature of the strip when peeling off the outer circumferential surface of the cooling roll was controlled to 140-180 ℃, specifically 171 ℃, in comparative example 2, the temperature of the outer circumferential surface of the cooling roll before entering the weld puddle was controlled to 65 ℃, which is not within the range of the examples of the present invention, the peeling temperature of the strip when peeling off the outer circumferential surface of the cooling roll was controlled to 140-180 ℃, specifically 164 ℃, after the end of strip production, the width and the thickness of the strip of example 3 and comparative example 2 were maintained at 213mm, 29 μm, and the strip produced in example 3 and comparative example 2 was observed to be per 100cm2The number of pocks in the area, per 100cm in example 32The number of pockmarks having a length of more than 100 μm in area was 2, while in comparative example 2, the pockmarks were present per 100cm2The number of pockmarks in the area with a length of more than 100 μm is 18. In sum, it is full ofThe strip prepared by the preparation method of the embodiment 3 of the invention reduces the variation amplitude of thermal stress and effectively lightens the thermal fatigue degree, thereby lightening the generation and the expansion of cracks, reducing the contraction stress of the strip, reducing the peeling of roll surface materials and finally reducing pockmarks of the strip adhered to the roll surface.
In comparative example 4 and comparative example 3, the surface roughness R of the cooling roll was satisfied under the condition that the smelting components of the raw materials of the alloy liquid were the same, the temperature of the alloy liquid in the nozzle, the pressure of the alloy liquid at the nozzle and the linear velocity of the surface of the cooling roll were all the sameaNot more than 0.5 μm, in example 4, the temperature of the outer circumferential surface of the chill roll before entering the weld puddle was controlled to 90 to 120 ℃, specifically 99 ℃, the peeling temperature of the strip when peeling off the outer circumferential surface of the chill roll was controlled to 140 to 180 ℃, specifically 168 ℃, in comparative example 3, the temperature of the outer circumferential surface of the chill roll before entering the weld puddle was controlled to 59 ℃, which is not within the range of the examples of the present invention, the peeling temperature of the strip when peeling off the outer circumferential surface of the chill roll was controlled to 127 ℃, which is not within the range of the examples of the present invention, after the end of the strip production, the widths of the strips of example 4 and comparative example 3 were all maintained at 120mm, the thicknesses of the strips of example 4 and comparative example 3 were all 18 μm, and each 100cm of the strips prepared in example 4 and comparative example 3 were observed, respectively, and2the number of pocks in the area, per 100cm in example 42The number of pits with a length of more than 100 μm in the area is 0, while the number of pits with a length of more than 100 μm per 100cm2 in comparative example 3 is 22. In conclusion, the strip material prepared by the preparation method of the embodiment 4 of the invention has the advantages that the strip temperature of the strip material when the strip material is stripped from the outer circumferential surface of the cooling roller is 140-180 ℃ in the embodiment of the invention, the temperature of the outer circumferential surface of the cooling roller before entering the weld puddle is 90-120 ℃ in the embodiment of the invention, and the strip material with good surface quality and toughness can not be obtainedAnd the degree of the cracking is reduced, the shrinkage stress of the strip is reduced, the material peeling of the roll surface is reduced, and finally pockmarks of the strip adhered to the roll surface are reduced.
In example 2, even though the alloy liquid raw material smelting composition of the strip is different from that of examples 1, 3 and 4, the surface roughness R of the chill roll was satisfied in example 2 simultaneously with that of examples 1, 3 and 4aThe thickness is not more than 0.5 mu m, the temperature of the outer circumferential surface of the cooling roller before entering the weld puddle is controlled between 90 and 120 ℃, and the stripping temperature of the strip when the outer circumferential surface of the cooling roller is stripped is controlled between 140 and 180 ℃, so that the strip with good surface quality can be obtained.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (14)

1. A preparation method of an amorphous nanocrystalline alloy strip is characterized by comprising the following steps:
melting raw materials in a certain ratio into alloy liquid by using a smelting furnace;
pouring alloy liquid into a nozzle ladle with a nozzle at the bottom;
the alloy liquid flows out of the nozzle, spreads on the outer circumferential surface of the cooling roller rotating at a high speed below the nozzle, and the temperature of the outer circumferential surface of the cooling roller before entering the weld puddle is controlled to be 70-150 ℃;
and rapidly cooling to form a continuous thin belt with an amorphous or nanocrystalline structure, wherein the stripping temperature range of the strip is controlled to be 120-200 ℃ when the strip is stripped from the outer circumferential surface of the cooling roller.
2. The method for preparing the amorphous nanocrystalline alloy strip according to claim 1, wherein the temperature of the outer circumferential surface of the cooling roller before entering the weld puddle is controlled to be 90-120 ℃.
3. The method for preparing the amorphous nanocrystalline alloy strip according to claim 1, wherein a peeling temperature of the strip when peeling off the outer circumferential surface of the cooling roller is controlled to be 140-180 ℃.
4. The method of preparing an amorphous nanocrystalline alloy ribbon according to claim 1,
the outer circumferential surface of the cooling roller is polished by abrasive paper wheels, abrasive cloth wheels, metal brush wheels or resin brush wheels containing abrasive particles, and the roughness R of the outer circumferential surface of the cooling roller is ensuredaNot more than 0.5 μm.
5. An amorphous nanocrystalline alloy strip produced by the production method according to any one of claims 1 to 4, wherein the density of pits with a length of more than 100 μm on the roll-attaching surface of the strip is not more than 100cm per square meter2Ten.
6. An amorphous nanocrystalline alloy ribbon according to claim 5, wherein the density of pits with a length of more than 100 μm on the roll facing side of the ribbon is not more than 100cm per side2Two of them.
7. The amorphous nanocrystalline alloy ribbon according to claim 5, wherein the amorphous nanocrystalline alloy ribbon has a general expression for the main component:
XaYbZc
x is a metal element, and the total content a is 65-85 at%; y is a transition metal element, and the total content b is 0-10 at%; z is an amorphous element, the total content c is 15 to 30 at%, and the alloy further contains impurity elements in a total amount of not more than 0.5 at%.
8. The amorphous nanocrystalline alloy ribbon of claim 7, wherein X is a ferromagnetic metal element.
9. The amorphous nanocrystalline alloy ribbon of claim 8, wherein X comprises at least one of Fe, Co, Ni.
10. The amorphous nanocrystalline alloy ribbon of claim 7, wherein Y comprises at least one of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Cu, Ag, Au, Zn, and Al, Sn.
11. The amorphous nanocrystalline alloy ribbon of claim 7, wherein Z comprises at least one of Si, B, P, C.
12. An amorphous nanocrystalline alloy ribbon according to claim 5, wherein the ribbon has a width of 50 to 300mm and a thickness of 10 to 50 μm.
13. A core comprising a strip according to any one of claims 1 to 4.
14. A magnetic component, characterized in that the magnetic component comprises the iron core of claim 13, the magnetic component comprising: transformer, inductor, mutual-inductor and motor stator.
CN202011389601.8A 2020-12-01 2020-12-01 Amorphous nanocrystalline alloy strip and manufacturing method thereof Pending CN114582581A (en)

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