WO2022196672A1 - Procédé de production d'une bande mince d'alliage à solidification rapide à base de fe-si-b - Google Patents

Procédé de production d'une bande mince d'alliage à solidification rapide à base de fe-si-b Download PDF

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WO2022196672A1
WO2022196672A1 PCT/JP2022/011505 JP2022011505W WO2022196672A1 WO 2022196672 A1 WO2022196672 A1 WO 2022196672A1 JP 2022011505 W JP2022011505 W JP 2022011505W WO 2022196672 A1 WO2022196672 A1 WO 2022196672A1
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less
alloy
rapidly solidified
cooling
roll
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PCT/JP2022/011505
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English (en)
Japanese (ja)
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裕和 金清
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Ｈｉｌｌｔｏｐ株式会社
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    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing a rapidly solidified Fe-Si-B thick alloy ribbon.
  • Materials with low iron loss and high saturation magnetic flux density for various passive elements such as inductors and reactors used as electronic components, as well as transformers.
  • Materials with high magnetic permeability and low iron loss compared to electrical steel sheets include iron-based amorphous materials and iron-based nanocrystalline materials, which are soft magnetic materials made mainly of iron (Fe), boron (B), and silicon (Si). materials are known.
  • Fe-Si-B system rapidly solidified alloy ribbons with a thickness of about 17 ⁇ m to 25 ⁇ m, which are produced by the molten metal rapid solidification method using such soft magnetic materials, are used as wound cores for inductors, transformers, etc.
  • Demand is expanding year by year as a substitute for electrical steel sheets.
  • the iron-based amorphous alloy has excellent soft magnetic properties, with iron loss about 1/10 and magnetic permeability more than 3 times that of electromagnetic steel sheets (silicon steel sheets) used as laminated cores for motors. Therefore, in addition to the inductors and transformers described above, it is expected to contribute to the miniaturization and efficiency improvement of motors by using it as a wound iron core for motors.
  • iron-based amorphous alloys with a thickness of about 17 ⁇ m to 25 ⁇ m cannot be punched to form a laminated core, and the lamination factor decreases. It is only applied to motors with
  • Non-Patent Document 1 discloses that the rapid solidification rate is reduced by adding phosphorus (P), and an iron-based amorphous alloy ribbon having a thickness of about 50 ⁇ m can be obtained.
  • P phosphorus
  • the addition of phosphorus not only causes a decrease in the saturation magnetic flux density Bs, but also causes the phosphorus component to volatilize when the alloy is melted, resulting in significant contamination inside and outside the molten metal quenching device. Therefore, there are still few examples of application in the industrial field.
  • Patent document 1 and patent document 2 disclose a quenched alloy ribbon having a thickness (50 ⁇ m or more) that allows punching by a multiple slit method in which molten alloy is discharged from a plurality of slit nozzles onto a rotating cooling roll. is disclosed.
  • Patent Documents 1 and 2 disclose a manufacturing apparatus for mass-producing an iron-based amorphous alloy having such a plate thickness at a low cost while stably maintaining the homogeneity and uniform quality of the amorphous alloy. It does not disclose specifications or operating parameters.
  • Patent Documents 3 and 4 disclose a method of producing an iron-based amorphous alloy with a plate thickness of 30 ⁇ m or more by alternately tapping molten metal from multiple slit nozzles to two cooling rolls.
  • the production equipment used in this method requires two cooling rolls, which not only significantly increases production and running costs, but also greatly affects the plate thickness and quenching conditions of the iron-based amorphous alloy. and control of the gap on the surface of the cooling roll becomes extremely difficult compared to a conventional single roll molten metal quenching apparatus having only one cooling roll.
  • Patent Document 5 discloses a cooling roll used in a single-roll molten metal quenching apparatus for producing an iron-based amorphous alloy having a thickness of 30 ⁇ m or more. There is the problem of getting taller. Further, Patent Document 5 describes increasing the flow rate of cooling water as the thickness of the amorphous foil strip increases, but does not clarify the optimum roll cooling water flow rate. Furthermore, it is recommended that the diameter of the roll be different according to the thickness of the amorphous ribbon. Considering the production efficiency, it is difficult to apply it as a mass-production device.
  • Patent Document 6 discloses a method for producing a thin metal strip that uses a multi-hole nozzle to prevent the thickness of the thin metal strip from becoming non-uniform when producing a wide quenched thin strip.
  • the invention of Patent Document 6 is characterized by the shape of the nozzle opening, but there is a problem that the nozzle processing cost rises due to the difficulty of processing, and it is difficult to use at the mass production level.
  • Patent Document 7 discloses a method of producing a brazing ribbon with a thickness of 50 to 200 ⁇ m using a single-roll molten metal quenching apparatus, but the brazing ribbon obtained by this method is a crystalline Ni-based alloy. Therefore, it does not disclose a technique for producing a rapidly solidified alloy having an amorphous structure with a thickness of about 50 ⁇ m.
  • Patent Document 8 for the purpose of reducing hysteresis loss, which is the main factor of iron loss in a wide amorphous alloy ribbon, an Fe-based amorphous alloy ribbon having wavy unevenness formed on the free surface is produced by a single roll method. is disclosed.
  • Patent Document 8 describes the temperature distribution in the width direction of the molten metal nozzle and the roughness of the chill roll surface, it discloses a manufacturing technology for an iron-based rapidly solidified alloy having an amorphous structure that can be applied to a laminated core. not a thing
  • the Fe-Si-B-based amorphous material that is being applied to transformers, etc. has a thickness of around 20 ⁇ m, which is not at a level that can be used for laminated cores.
  • the prior art that makes it possible to increase the thickness of the Fe-Si-B system amorphous material either invites a decrease in soft magnetic properties or has problems in terms of productivity and cost. Therefore, there is a need for a method of mass-producing alloy ribbons made of Fe-Si-B based amorphous materials that are inexpensive and have high performance, and which can be made thicker from Fe-Si-B based amorphous materials regardless of the alloy composition. , is highly desired in the electronic component market.
  • the present invention provides an Fe-Si-B thick plate rapidly solidified alloy thin strip that can be easily mass-produced at low cost and is suitable for laminated cores of motors and the like.
  • the object is to provide a method for manufacturing an obi.
  • Fig. 6 is a schematic configuration diagram of an apparatus used in a conventional method for producing a rapidly solidified Fe-Si-B alloy ribbon.
  • the molten alloy supplied from the nozzle 52 of the molten metal container 51 to the surface of the cooling roll 54 is rapidly cooled on the cooling roll 54 and then peeled off from the cooling roll 54, resulting in Fe—Si A -B system melt-quenched alloy ribbon is obtained.
  • the molten alloy is rapidly cooled to obtain an amorphous structure so that the molten alloy is quickly passed between the melting point and the glass transition temperature of the alloy so that crystallization does not occur. Since the rapidly solidified alloy that has undergone primary cooling is in a supercooled state, it may recrystallize due to self-heating due to latent heat of solidification.
  • the molten metal is brought into contact with the cooling roll 54 about halfway around because if the rapidly solidified alloy ribbon 55 is separated from the cooling roll 54 immediately after being rapidly solidified, the rapidly solidified alloy ribbon is in a supercooled state. This is to prevent the solidification latent heat of 55 from being released and recrystallization.
  • the distance from the supply position of the molten metal on the surface of the cooling roll 54 to the separation position is increased in this way, the time until the molten metal is resupplied to the separation position by the rotation of the cooling roll 54 becomes shorter. If the molten metal supply rate per hit becomes high, the molten metal is repeatedly supplied to the chill roll 54 in a state where the surface temperature of the chill roll 54 is not sufficiently lowered. As a result, the surface temperature of the cooling roll 54 may rise excessively, making it impossible to continue rapid cooling of the molten metal.
  • the present invention has clarified through various tests the heat removal capacity required of the cooling roll in order to form a rapidly solidified alloy structure that does not recrystallize due to the release of solidification latent heat. That is, the present invention does not complicate the structure of the manufacturing apparatus by clarifying the preferable conditions of the surface speed, curvature, cooling water amount, and cooling water temperature of the cooling roll according to the size of the rapidly solidified alloy ribbon.
  • Fe--Si--B system molten metal quenching alloy ribbons that can be suitably used for laminated cores of motors, etc., can be easily mass-produced at low cost.
  • the object of the present invention is to eject a molten Fe-Si-B alloy essentially containing iron (Fe), boron (B) and silicon (Si) from a tapping nozzle onto the surface of a chill roll,
  • the cooling roll is passed through the cooling roll at a cooling water amount of 0.3 m 3 /min or more and less than 20 m 3 /min, so that the average thickness is 30 ⁇ m or more and less than 70 ⁇ m.
  • This is achieved by a method for producing a rapidly solidified Fe--Si--B thick plate alloy ribbon that has a width of 50 mm or more and less than 200 mm and contains an amorphous alloy structure of 90% by volume or more.
  • the slits of the tapping nozzle have the same length in the range of 45 mm or more and less than 200 mm, and the distance between them is 0.5 mm or more and 5.0 mm. mm, and the distance from the tip of the tapping nozzle to the surface of the cooling roll is preferably 0.15 mm or more and less than 30 mm.
  • the above object of the present invention is achieved by ejecting a molten Fe-Si-B alloy essentially containing iron (Fe), boron (B) and silicon (Si) from a tapping nozzle onto the surface of a chill roll, is rotated at a surface speed of 15 m/sec or more and 50 m/sec or less to quench the molten alloy on the surface of the cooling roll to produce an alloy ribbon, the tapping nozzle is formed with a single slit having a width of 0.5 mm or more and less than 1.5 mm, and the cooling roll has a curvature of 8 ⁇ 10 -4 or more and less than 4.0 ⁇ 10 -3 , and a cooling temperature of 5 ° C or more and less than 60 ° C.
  • the average thickness is 30 ⁇ m or more and less than 70 ⁇ m and the average width is 5 mm or more and less than 50 mm. It is achieved by a method for producing a rapidly solidified Fe--Si--B-based thick-plate, rapidly-solidified alloy ribbon containing at least vol %.
  • the length of the slit of the tapping nozzle is preferably 4 mm or more and less than 50 mm.
  • the distance to the surface is preferably 0.15 mm or more and less than 30 mm.
  • the cooling roll is made of a material containing any one of Cu, Mo or W as a main component, and has a surface arithmetic mean roughness Ra is 10 nm or more and less than 20 ⁇ m, the length is 50 mm or more and less than 400 mm longer than the length of the slit, and the thickness from the surface to the cooling water flow path is preferably 5 mm or more and less than 50 mm.
  • the pressure of the molten alloy ejected from the slit is preferably 2 kPa or more and less than 60 kPa.
  • the molten alloy has a composition formula of T loo-x-y-z-n Q x Si y M n
  • T is at least one element selected from the group consisting of Fe, Co and Ni, and Fe is A transition metal element that must be included
  • Q is one or more elements selected from the group consisting of B and C and must include B
  • M is P, Al, Ti, V, Cr, Mn, Nb, Cu, Zn, Ga, Mo , Ag, Hf, Zr, Ta, W, Pt, Au and Pb)
  • the composition ratio x, y and n are each 5 ⁇ x ⁇ 20 atomic % , 2 ⁇ y ⁇ 15 atomic %, 0 ⁇ n ⁇ 10 atomic %, and the composition ratio C/(B+C) of Q is 0 or more and less than 0.2.
  • amorphous structure with a thickness of 30 ⁇ m or more and less than 70 ⁇ m, which can be used as a laminated core that can be easily applied to motors, etc. It is possible to obtain a rapidly solidified Fe--Si--B-based thick plate alloy ribbon.
  • the above-mentioned Fe-Si-B thick plate rapidly solidified alloy ribbon is processed into a desired shape, and then the laminated iron core is laminated using a method such as resin bonding or caulking. can be obtained.
  • the produced laminated core can be further processed by wire cutting, laser cutting, or the like to obtain split cores that can be used for motors.
  • the rapidly solidified Fe-Si-B thick plate alloy ribbon suitable for laminated cores of motors and the like can be easily produced at low cost. Mass production is possible.
  • FIG. 1 is a schematic configuration diagram of an apparatus used in a method for producing a rapidly solidified Fe—Si—B thick alloy ribbon according to an embodiment of the present invention.
  • FIG. It is an enlarged drawing which shows the principal part of the apparatus shown in FIG. 1, (a) is sectional drawing, (b) is a bottom view.
  • FIG. 1 is a schematic diagram for explaining the details of a method for producing a rapidly solidified Fe—Si—B thick plate alloy ribbon according to an embodiment of the present invention.
  • 2 is an enlarged view showing another essential part of the device shown in FIG. 1, where (a) is a vertical cross-sectional view and (b) is a cross-sectional view taken along the line AA of (a).
  • FIG. 4 is an enlarged view of a main part of an apparatus used in a method for producing a rapidly solidified Fe—Si—B thick alloy ribbon according to another embodiment of the present invention, where (a) is a cross-sectional view and (b) is a bottom view; be.
  • 1 is a schematic configuration diagram of an apparatus used in a conventional method for producing a rapidly solidified Fe—Si—B alloy ribbon.
  • FIG. 1 is an X-ray diffraction pattern of a Fe--Si--B system rapidly solidified alloy ribbon obtained in an example of the present invention.
  • 4 is an X-ray diffraction pattern of a Fe--Si--B system rapidly solidified alloy ribbon obtained in another example of the present invention.
  • 4 is an X-ray diffraction pattern of a Fe--Si--B system rapidly solidified alloy ribbon obtained in still another example of the present invention.
  • 1 is an X-ray diffraction pattern of a Fe--Si--B system rapidly solidified alloy ribbon obtained in a comparative example of the present invention.
  • 4 is an X-ray diffraction pattern of a Fe--Si--B system rapidly solidified alloy ribbon obtained in another comparative example of the present invention.
  • 4 is an X-ray diffraction pattern of a Fe--Si--B system rapidly solidified alloy ribbon obtained in still another comparative example of the present invention.
  • composition formula of the molten alloy used in the method for producing the rapidly solidified Fe—Si—B thick plate alloy ribbon of the present embodiment is represented by T loo-x-y-z-n Q x Si y M n .
  • Q is one or more elements selected from the group consisting of B and C and necessarily containing B;
  • M is one selected from the group consisting of P, Al, Ti, V, Cr, Mn, Nb, Cu, Zn, Ga, Mo, Ag, Hf, Zr, Ta, W, Pt, Au and Pb.
  • composition ratios x, y and n are 5 ⁇ x ⁇ 20 atomic %, 2 ⁇ y ⁇ 15 atomic % and 0 ⁇ n ⁇ 10 atomic %, respectively. Also, the composition ratio C/(B+C) of Q is 0 or more and less than 0.2.
  • the transition metal T which contains Fe as an essential element, accounts for the remaining content of Q, Si, and M. Desired hard magnetic properties can be obtained by replacing part of Fe with one or both of Co and Ni, which are ferromagnetic elements like Fe. However, if the amount of replacement with respect to Fe exceeds 30%, the magnetic flux density will drop significantly, so the amount of replacement is limited to the range of 0% to 30%.
  • the composition ratio x is preferably 7 atomic % or more and less than 19 atomic %, more preferably 8 atomic % or more and less than 19 atomic %.
  • C/(B+C) is 0 or more and less than 0.2, preferably 0 or more and less than 0.15, and more preferably 0 or more and less than 0.1.
  • y should be less than 15 atomic %. Moreover, y is preferably 2 atomic % or more from the viewpoint of improving magnetic permeability. y is more preferably 2.5 atomic % or more and less than 12 atomic %.
  • n improves the productivity during rapid solidification by improving the ability to form amorphous material and refining the rapid solidification metal structure.
  • the composition ratio n of M exceeds 10 atomic %, the saturation magnetic flux density Bs is lowered, so n is limited to 0 atomic % or more and less than 10 atomic %.
  • n is preferably 0 atomic % or more and less than 7 atomic %, more preferably 0 atomic % or more and less than 5 atomic %.
  • FIG. 1 is a schematic configuration diagram of a single-roll molten-metal quenching apparatus used in a method for manufacturing a Fe--Si--B-based thick-plate, quench-solidified alloy ribbon according to one embodiment of the present invention.
  • the melting furnace 2 supplies the molten alloy 3 in which the raw materials are melted to the hot water storage container 5 by rotating the tilting shaft 4 .
  • the hot water storage container 5 is provided with a hot water nozzle 6 at the bottom, and the molten alloy 3 is jetted onto the surface (outer peripheral surface) of the cooling roll 8 from a slit 7 formed at the lower end of the hot water nozzle 6 .
  • the cooling roll 8 is supplied with cooling water to rapidly cool the molten alloy in contact with the surface thereof to form a rapidly solidified alloy ribbon 9 .
  • the slits 7 of the tapping nozzle 6 are multi-slits formed in two rows along the forming direction of the rapidly solidified alloy ribbon 9.
  • the single-roll molten metal quenching device 1 equipped with such a multi-slit is preferably used for producing a Fe-Si-B system thick plate rapidly solidified alloy ribbon having a thickness of 30 ⁇ m or more and less than 70 ⁇ m and a width of 50 mm or more and less than 200 mm. .
  • a rapidly solidified alloy ribbon having such a size is suitable for manufacturing laminated cores applied to, for example, motors for EVs, compressors, generators, and the like.
  • FIG. 2 is an enlarged view showing the tapping nozzle 6 of the device shown in FIG. 1, where (a) is a cross-sectional view and (b) is a bottom view.
  • the width W1 of the slit 7 shown in FIG. 2(a) is set to 0.2 mm or more and less than 1.2 mm. If the width is less than 0.2 mm, the flow of the molten metal passing through the slit 7 is obstructed, increasing the possibility of nozzle clogging. On the other hand, if the width is 1.2 mm or more, the molten metal tapping rate supplied to the cooling rolls becomes too high, and the cooling rolls cannot sufficiently cool the molten metal, so that the desired amorphous structure may not be obtained.
  • the width W1 of the slit 7 is more preferably 0.3 mm or more and less than 1.0 mm, and still more preferably 0.3 mm or more and less than 0.8 mm.
  • the widths W1 of the plurality of slits 7 may be the same or different.
  • the length L1 of the slit 7 shown in FIG. 2(b) is appropriately selected depending on the width of the cooling roll and the core size of the required motor, etc., and is not necessarily limited. While the application field is limited, if the length is 200 mm or more, the molten metal tapping rate supplied to the cooling roll 8 becomes too high, and the cooling roll 8 cannot sufficiently cool the molten metal, so that the desired amorphous structure cannot be obtained. There is a possibility that it will not.
  • the length L1 of the slit 7 is preferably 45 mm or more and less than 200 mm, more preferably 45 mm or more and less than 170 mm, more preferably 45 mm or more and less than 150 mm, in consideration of productivity including running costs and the cost of a single roll molten metal quenching device. preferable.
  • the lengths L1 of the plurality of slits 7 are preferably the same.
  • the depth D1 of the slit 7 shown in FIG. 2(a) is determined based on the thickness of the bottom of the molten metal tapping nozzle 6. If it is less than 2 mm, the strength of the bottom tends to be insufficient. The possibility of nozzle clogging increases due to the decrease in temperature. Therefore, the depth D1 of the slit 7 is preferably 2 mm or more and less than 15 mm, more preferably 3 mm or more and less than 12 mm, and even more preferably 3 mm or more and less than 10 mm in consideration of the stability (straightness) of tapping.
  • the slits 7 are arranged in two rows in the present embodiment, they may be arranged in three or four rows along the direction in which the rapidly solidified alloy ribbon 9 is formed. If the slits 7 are arranged in more than four rows, the total molten metal discharge rate obtained by summing the slits 7 is too large, and the molten metal cannot be sufficiently cooled by the cooling rolls, making it difficult to obtain an amorphous structure. Two or more rows and four rows or less are preferable. Considering the homogeneity of the rapidly solidified structure, the number of slits 7 is more preferably two or more and three or less. Considering the controllability of the molten metal rate and the production efficiency assuming continuous operation, it is more preferable to have two rows. preferable.
  • the interval S1 between the slits 7 shown in FIG. 2(b) is less than 0.5 mm, processing is difficult, while if it is 5 mm or more, it becomes difficult to obtain a rapidly solidified alloy ribbon having a desired thickness. Therefore, the interval S1 between the slits 7 is preferably 0.5 mm or more and less than 5.0 mm. Considering the possibility of the slits falling off when the molten metal is poured, it is preferably 1.0 mm or more and 5.0 mm or less. 1.0 mm or more and 3.0 mm or less is more preferable.
  • the molten metal supplied to the chill roll 8 from the tapping nozzle 6 forms a pool (puddle) on the surface of the chill roll 8, causing a rapid solidification reaction of the molten metal.
  • the distance d is preferably 0.15 mm or more and less than 30 mm.
  • the distance d is more preferably 0.3 mm or more and less than 30 mm, and considering the homogeneity of the rapidly solidified alloy structure, it is more preferably 0.3 mm or more and less than 20 mm.
  • the molten metal supplied to the surface of the cooling roll 8 is cooled by the rotation of the cooling roll 8 from the pouring position P directly below the slit 7 of the tapping nozzle 6 into a rapidly solidified alloy ribbon 9.
  • primary cooling to rapidly cool the molten alloy to a supercooled liquid state
  • secondary cooling to remove the solidification latent heat of the supercooled liquid and prevent recrystallization. is performed.
  • the distance ⁇ s from the pouring position P to the stripping position Q must be sufficient to complete the primary cooling and secondary cooling, but the stripping position Q rotates to the pouring position P again.
  • the rotation angle ⁇ of the cooling roll 8 from the pouring position P to the stripping position Q is a straight line from the pouring position P to the stripping position Q. It is preferable to be as small as possible.
  • ⁇ s can be obtained from the time required for the primary cooling and the secondary cooling.
  • a numerical range of 2R is determined.
  • a preferable value of ⁇ s depends on the size of the rapidly solidified alloy ribbon 9.
  • the cooling roll 8 When obtaining the rapidly solidified alloy ribbon 9 having an average thickness of 30 ⁇ m or more and less than 70 ⁇ m and an average width of 50 mm or more and less than 200 mm, the cooling roll 8
  • the diameter 2R is 1000 mm or more and less than 2500 mm, preferably 1500 mm or more and less than 2500 mm in consideration of the homogeneity of the rapidly solidified alloy structure, and 1500 mm in consideration of the restrictions on the processing equipment of the chill roll manufactured by forging and the manufacturing cost. It is more preferable to be at least 2300 mm or less.
  • the curvature ⁇ of the cooling roll 8 is the reciprocal of the radius R
  • the curvature ⁇ when obtaining the rapidly solidified alloy ribbon 9 having an average thickness of 30 ⁇ m or more and less than 70 ⁇ m and an average width of 50 mm or more and less than 200 mm is 8 ⁇ It is 10 ⁇ 4 or more and less than 2 ⁇ 10 ⁇ 3 , preferably 8 ⁇ 10 ⁇ 4 or more and less than 1.3 ⁇ 10 ⁇ 3 , more preferably 9 ⁇ 10 ⁇ 4 or more and less than 1.3 ⁇ 10 ⁇ 3 .
  • FIGS. 4A and 4B are schematic configuration diagrams showing an example of the cooling roll 8, where (a) is a vertical cross-sectional view and (b) is a cross-sectional view along AA.
  • the cooling water supplied from one end side (IN side) to the rotating shaft 81 of the cooling roll 8 spreads radially along the flow path 82 , cools the entire surface of the cooling roll 8 , and then joins the rotating shaft 81 . It is discharged from the other end side (OUT side).
  • the amount of cooling water is 0.3 m 3 /min or more and less than 20 m 3 /min, and in the single roll molten metal quenching device 1 that can be mass-produced assuming continuous operation, 0.5 m 3 /min or more and less than 20 m 3 /min is preferred, and 0.5 m 3 /min or more and less than 15 m 3 /min is more preferred.
  • the temperature of the cooling water of the cooling roll 8 affects the adhesion between the molten alloy and the cooling roll 8.
  • the temperature of the cooling water is 5° C. or more and less than 60° C., as it may cause failure of the pump that supplies the rolls 8 .
  • the lower limit of the cooling water temperature is particularly important, preferably 15°C or higher and lower than 60°C, more preferably 30°C or higher and lower than 60°C.
  • the adhesion between the molten alloy and the cooling roll 8 is also affected by the material of the cooling roll 8 .
  • the cooling roll 8 is preferably made of a material containing Cu, Mo or W as its main component. materials are preferred.
  • the term "Cu as the main component” includes not only alloys containing more than 50% by mass of Cu, but also pure copper (the same applies to materials containing Mo or W as the main component).
  • the arithmetic mean roughness Ra of the chill roll surface is 10 nm or more and less than 20 ⁇ m, which improves production efficiency and quality.
  • Ra is more preferably 50 nm or more and less than 10 ⁇ m, and still more preferably 100 nm or more and less than 10 ⁇ m.
  • the length L2 in the axial direction of the cooling roll 8 shown in FIG. 4(a) is preferably 50 mm or more and less than 400 mm longer than the length of the slit 7 shown in FIG. 2(b). Taking this into consideration, it is more preferably longer than the slit 7 by 100 mm or more and less than 300 mm, and more preferably 100 mm or more and less than 200 mm.
  • the ability of the cooling roll 8 to remove heat from the molten alloy is also affected by the thickness T2 from the surface of the cooling roll 8 to the flow path 82 shown in FIG. 4(a).
  • the thickness T2 is less than 5 mm, it becomes difficult to maintain the mechanical strength of the chill roll 8, while when the thickness T2 is 50 mm or more, the surface temperature of the chill roll 8 in contact with the molten alloy locally rises above the melting point. As a result, the rapidly solidified alloy may adhere to the surface of the chill roll 8, making it impossible to continue the rapid cooling of the molten metal. Therefore, the thickness T2 of the cooling roll 8 is preferably 5 mm or more and less than 50 mm.
  • the thickness T2 is more preferably 10 mm or more and less than 50 mm in consideration of wear due to roll grinding work after the molten metal quenching process, and more preferably 10 mm or more and less than 40 mm in consideration of operational stability in the molten metal quenching process.
  • the molten alloy ejected from the slit 7 of the tapping nozzle 6 is pressed against the surface of the cooling roll 8 to form a puddle as described above. Since it is difficult to form a desired puddle in the slit 7, the pressure of the molten alloy discharged from the slit 7 is preferably 2 kPa or more and less than 60 kPa. This tapping pressure is more preferably 10 kPa or more and less than 40 kPa, still more preferably 10 kPa or more and less than 30 kPa, in order to generate paddles more stably.
  • the hot water pressure can be adjusted by the head pressure and pressurization force in the hot water storage container 5 shown in FIG.
  • the above description shows preferred apparatus configurations and cooling conditions for producing a rapidly solidified Fe--Si--B thick plate alloy ribbon having an average thickness of 30 ⁇ m or more and less than 70 ⁇ m and an average width of 50 mm or more and less than 200 mm.
  • a rapidly solidified alloy ribbon containing 90% by volume or more of amorphous alloy structure can be obtained.
  • the single roll molten metal rapid cooling device 1 shown in FIG. A single slit nozzle having a single slit 7 is used as the tapping nozzle 6 in FIG.
  • preferable conditions in this case only points different from the above description will be described as follows.
  • the diameter 2R of the chill roll 8 is 500 mm or more and less than 2500 mm, preferably 570 mm or more and less than 2500 mm considering the homogeneity of the rapidly solidified alloy structure. Considering the manufacturing cost, it is more preferably 570 mm or more and less than 1500 mm. That is, the curvature ⁇ of the cooling roll 8 is 8 ⁇ 10 ⁇ 4 or more and less than 4 ⁇ 10 ⁇ 3 , preferably 8 ⁇ 10 ⁇ 4 or more and less than 3.5 ⁇ 10 ⁇ 3 , and 1.3 ⁇ 10 ⁇ 3 or more and 3.5 ⁇ 10 ⁇ Less than 3 is more preferred.
  • the cooling water flow rate is less than 0.05 m 3 /min, it becomes difficult to complete primary cooling and secondary cooling on the surface of the cooling roll 8.
  • the cooling water flow rate is 0.3 m 3 /min or more, 0.05 m 3 /min or more and less than 0.3 m 3 /min is preferable, and 0.05 m 3 /min or more and less than 0.2 m 3 /min is more preferable, because paddles generated during the period become unstable.
  • the width W2 of the slit 7 shown in FIG. 5(a) is set to 0.5 mm or more and less than 1.5 mm. If the width is less than 0.5 mm, the flow of molten metal passing through the slit 7 is obstructed, increasing the possibility of nozzle clogging. On the other hand, if the width is 1.5 mm or more, the molten metal tapping rate supplied to the cooling rolls becomes too high, and the cooling rolls cannot sufficiently cool the molten metal, so that the desired amorphous structure may not be obtained. Considering the workability and accuracy of the slit, the width W2 of the slit 7 is more preferably 0.5 mm or more and less than 1.2 mm, and still more preferably 0.6 mm or more and less than 1.0 mm.
  • the length L2 of the slit 7 shown in FIG. 5(b) is appropriately selected according to the width of the cooling roll and the core size of the required motor, etc., and is not necessarily limited. While the application field is limited, if the length is 50 mm or more, the molten metal tapping rate supplied to the cooling roll 8 becomes too high, and the cooling roll 8 cannot sufficiently cool the molten metal, so that the desired amorphous structure cannot be obtained. There is a possibility that it will not.
  • the length L2 of the slit 7 is preferably 4 mm or more and less than 50 mm, more preferably 7 mm or more and less than 50 mm, more preferably 10 mm or more and less than 50 mm, in consideration of productivity including running costs and the cost of a single roll molten metal quenching device. preferable.
  • the molten alloy in contact with the surface of the chill roll formed a puddle on the surface of the chill roll and was rapidly solidified at the interface between the paddle and the chill roll to obtain a ribbon-shaped rapidly solidified alloy.
  • Table 3 shows the average thickness and average width of this rapidly solidified alloy ribbon.
  • Example 2 is shown in FIG. 7
  • Example 5 is shown in FIG. 8
  • Example 10 is shown in FIG. .
  • Comparative Examples 13-21 as shown in Table 3, the volume ratio of the amorphous structure decreased compared to Examples 1-12 due to insufficient quenching ability.
  • Comparative Example 13 is shown in FIG. 10 and Comparative Example 17 is shown in FIG. 11, respectively.
  • Comparative Example 21 shown in FIG. 12 shows the X-ray diffraction pattern of a rapidly solidified alloy ribbon produced under the same conditions as in Example 10, except for the cooling water temperature of the chill roll.
  • the adhesion between the chill roll and the molten alloy is poor during rapid cooling of the molten metal, and the rapid cooling of the molten metal becomes uneven, resulting in a decrease in the overall molten metal quenching rate, and the ⁇ -Fe (200) on the free surface side exhibits very strong crystallinity. A peak is observed.
  • the rapidly solidified Fe-Si-B thick plate alloy ribbon obtained by the present invention can be suitably used as a low core loss laminated core that can be easily applied to reactors, various motors, generators, and the like.
  • Fe-Si-B amorphous alloys that can be used for laminated cores, which feature low iron loss and high magnetic permeability, at low cost on a mass production scale. can be offered to the market at

Abstract

L'invention concerne un procédé de production d'une bande mince d'alliage, dans lequel une matière fondue d'alliage à base de Fe-Si-B, qui contient essentiellement du fer (Fe), du bore (B) et du silicium (Si), est projetée à partir d'une buse de coulée sur la surface d'un rouleau de refroidissement et le rouleau de refroidissement est tourné de telle sorte que sa vitesse de surface est de 15 à 50 m/s, ce qui permet de refroidir rapidement la matière fondue d'alliage sur la surface du rouleau de refroidissement de façon à produire une bande mince d'alliage. En relation avec le procédé de production d'une bande mince d'alliage à solidification rapide selon la présente invention, la buse de coulée est pourvue de fentes qui sont agencées en deux à quatre rangées dans la direction de formation de la bande mince d'alliage, tout en ayant une largeur qui est supérieure ou égale à 0,2 mm mais inférieure à 1,2 mm ; le rouleau de refroidissement a une courbure qui est supérieure ou égale à 8 × 10-4 mais inférieure à 2 × 10-3 ; et une bande mince d'alliage à solidification rapide, qui a une épaisseur moyenne qui est supérieure ou égale à 30 µm mais inférieure à 70 µm et une largeur moyenne qui est supérieure ou égale à 50 mm mais inférieure à 200 mm, tout en contenant 90 % en volume ou plus d'une structure d'alliage amorphe, est produite par écoulement d'une eau de refroidissement qui est supérieure ou égale à 5 °C mais inférieure à 60 °C à travers le rouleau de refroidissement à un débit d'eau de refroidissement supérieur ou égal à 0,3 m3/min mais inférieur à 20 m3/min.
PCT/JP2022/011505 2021-03-17 2022-03-15 Procédé de production d'une bande mince d'alliage à solidification rapide à base de fe-si-b WO2022196672A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7429078B1 (ja) 2023-07-21 2024-02-07 Ｈｉｌｌｔｏｐ株式会社 鉄基結晶合金の製造方法

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JPS6368250A (ja) * 1986-09-06 1988-03-28 Kawasaki Steel Corp 急冷金属薄帯製造用の冷却ロ−ル
JPH07100599A (ja) * 1993-10-07 1995-04-18 Nippon Steel Corp 金属・合金薄帯の製造方法
JP2001001113A (ja) * 1999-04-15 2001-01-09 Hitachi Metals Ltd 合金薄帯並びにそれを用いた部材、及びその製造方法
JP2001269753A (ja) * 2000-03-29 2001-10-02 Nippon Steel Corp 急冷凝固薄帯鋳造用ノズルおよび急冷凝固薄帯の製造方法
WO2012102379A1 (fr) * 2011-01-28 2012-08-02 日立金属株式会社 Ruban en alliage magnétique doux à base de fe traité par trempe rapide, procédé de fabrication du ruban en alliage, et noyau de fer
WO2020235097A1 (fr) * 2019-05-23 2020-11-26 Okubo Yasuhiko Rouleau de refroidissement

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6368250A (ja) * 1986-09-06 1988-03-28 Kawasaki Steel Corp 急冷金属薄帯製造用の冷却ロ−ル
JPH07100599A (ja) * 1993-10-07 1995-04-18 Nippon Steel Corp 金属・合金薄帯の製造方法
JP2001001113A (ja) * 1999-04-15 2001-01-09 Hitachi Metals Ltd 合金薄帯並びにそれを用いた部材、及びその製造方法
JP2001269753A (ja) * 2000-03-29 2001-10-02 Nippon Steel Corp 急冷凝固薄帯鋳造用ノズルおよび急冷凝固薄帯の製造方法
WO2012102379A1 (fr) * 2011-01-28 2012-08-02 日立金属株式会社 Ruban en alliage magnétique doux à base de fe traité par trempe rapide, procédé de fabrication du ruban en alliage, et noyau de fer
WO2020235097A1 (fr) * 2019-05-23 2020-11-26 Okubo Yasuhiko Rouleau de refroidissement

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7429078B1 (ja) 2023-07-21 2024-02-07 Ｈｉｌｌｔｏｐ株式会社 鉄基結晶合金の製造方法

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