US20190176224A1 - Apparatus for producing thin metal strip and method for producing thin metal strip using the same - Google Patents
Apparatus for producing thin metal strip and method for producing thin metal strip using the same Download PDFInfo
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- US20190176224A1 US20190176224A1 US15/779,741 US201615779741A US2019176224A1 US 20190176224 A1 US20190176224 A1 US 20190176224A1 US 201615779741 A US201615779741 A US 201615779741A US 2019176224 A1 US2019176224 A1 US 2019176224A1
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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
- 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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- 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
- B22D11/0637—Accessories therefor
- B22D11/064—Accessories therefor for supplying molten metal
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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
- B22D11/0634—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 casting wheel and a co-operating shoe
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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
- B22D11/0637—Accessories therefor
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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
- B22D11/10—Supplying or treating molten metal
- B22D11/103—Distributing the molten metal, e.g. using runners, floats, distributors
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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
- B22D11/10—Supplying or treating molten metal
- B22D11/11—Treating the molten metal
- B22D11/112—Treating the molten metal by accelerated cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/003—Apparatus, e.g. furnaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/048—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by pulverising a quenched ribbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
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- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/18—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on silicides
Definitions
- the present invention relates to an apparatus for producing a thin metal strip and a method for producing a thin metal strip using the apparatus.
- rapid solidification process can provide metal materials with various properties.
- the rapid solidification process refers to a process for solidifying molten metal at a certain cooling rate or higher.
- the rapid solidification process enables, for example, refining crystal structures of a metal material, homogenizing a solute distribution, increasing a solid-solubility limit, producing amorphous layers (amorphous), and producing thermodynamic non-equilibrium phases.
- known methods for producing a cast piece by the rapid solidification process include the strip casting process, the melt spinning process, the atomization process, the melt spinning process, and the like.
- the melt spinning process is a method in which molten metal is jetted and rapidly cooled on a roll rotating at high speed to produce a ribbon-shaped thin metal strip in a flying manner.
- a jet of a small amount of molten metal is supplied onto the roll. Therefore, the cooling rate is high.
- the melt spinning process enables the production of a thin metal strip including fine grains.
- a small amount of the molten metal is supplied onto the roll. Therefore, the melt spinning process has its limitation in production capability and has a difficulty of producing a thin metal strip in volume.
- a method capable of producing a thin metal strip in volume is, for example, a single roll strip casting process.
- the single roll strip casting process is a method for producing a thin metal strip by continuously supplying molten metal onto a rotating roll to rapidly cool the molten metal.
- Methods for producing a cast piece using the strip casting process are, for example, described in Japanese Patent Application Publication No. 2011-206835 (Patent Literature 3) and Japanese Patent Application Publication No. 2001-291514 (Patent Literature 4).
- the producing apparatus described in Japanese Patent Application Publication No. 2011-206835 is a producing apparatus for an aluminum clad plate.
- This producing apparatus includes a first roll with a cooling capability and a first pool for storing first molten alloy.
- the first pool is surrounded by a surface of the first roll, a first front plate, a rear member, and both-side members.
- the first front plate lies forward of the first roll in a rotation direction.
- the rear member lies rearward of the first roll in the rotation direction.
- the first front plate includes a front edge portion and is movably provided such that the distance between the front edge portion and the surface of the first roll can vary.
- the first roll cools the first molten alloy in the first pool to form a first metallic layer in a semi-solidified state or a solidified state on the surface of the first roll and rotates with the first metallic layer.
- the first front plate is urged so that the front edge portion of the first front plate always abuts against a semi-solidified surface of the first metallic layer moving with the rotation of the first roll, at given force.
- the strip casting process In the strip casting process, the amount of molten metal supplied onto a roll is large as compared with the melt spinning process. Therefore, the strip casting process enables the production of a thin metal strip in large volume. However, in the strip casting process, the cooling rate of the molten metal is low as compared with the melt spinning process. Therefore, the strip casting process has a difficulty of refining grains. For that reason, the strip casting process is requested to provide more refined grains.
- Patent Literature 1 International Application Publication No. WO2012/099056
- Patent Literature 2 Japanese Patent Application Publication No. 2013-161785
- Patent Literature 4 Japanese Patent Application Publication No. 2001-291514
- An objective of the present invention is to provide an apparatus for producing a thin metal strip that is capable of efficiently producing a thin metal strip including fine grains.
- a producing apparatus is an apparatus for producing a thin metal strip by a single roll strip casting process.
- the producing apparatus includes a cooling roll, a tundish, and a molten metal remover.
- the cooling roll includes an outer peripheral surface and is configured to cool and solidify molten metal on the outer peripheral surface while rotating.
- the tundish can accommodate the molten metal and is configured to supply the molten metal onto the outer peripheral surface of the cooling roll.
- the molten metal remover is disposed downstream of the tundish in the rotating direction of the cooling roll with a gap provided between the molten metal remover and the outer peripheral surface of the cooling roll.
- the molten metal remover is configured to remove a portion of a thickness of the molten metal on the outer peripheral surface of the cooling roll that is larger than the width of the gap described above. As a result, the thickness of the molten metal on the outer peripheral surface of the cooling roll is cut down to the width of the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- a method for producing a thin metal strip according to the present embodiment is a method for producing a thin metal strip by a single roll strip casting process using the producing apparatus described above.
- the producing method includes a supplying step, a rapid cooling step, and a thickness adjustment step.
- the supplying step the molten metal in the tundish is supplied onto the outer peripheral surface of the cooling roll.
- the rapid cooling step the molten metal on the outer peripheral surface is rapidly cooled with the cooling roll to be formed into the thin metal strip.
- the thickness adjustment step a portion of a thickness of the molten metal on the outer peripheral surface of the cooling roll that is larger than the width of the gap described above is removed by the molten metal remover. As a result, the thickness of the molten metal on the outer peripheral surface is cut down to the width of the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- Using the apparatus for producing a thin metal strip according to the present embodiment enables a thin metal strip including fine grains to be produced efficiently.
- FIG. 1 is a cross-sectional view of an apparatus for producing a thin metal strip according to the present embodiment.
- FIG. 2 is a cross-sectional view of the vicinity of a front edge of a molten metal remover of the producing apparatus in an enlarging manner.
- FIG. 3 is a diagram illustrating an attachment angle of the molten metal remover.
- FIG. 6 is a diagram illustrating the cross sectional shape of a molten metal remover.
- FIG. 7 is a diagram illustrating the cross sectional shape of a molten metal remover different from that illustrated in FIG. 6 .
- FIG. 8 is a diagram illustrating the cross sectional shape of a molten metal remover different from those illustrated in FIG. 6 and FIG. 7 .
- FIG. 9 is a picture of a cross section of a thin metal strip produced by a production method according to the present embodiment, taken under an electron microscope (SEM).
- FIG. 10 is a picture of a cross section of a thin metal strip produced without using the molten metal remover, taken under the electron microscope (SEM).
- a producing apparatus is an apparatus for producing a thin metal strip by a single roll strip casting process.
- the producing apparatus includes a cooling roll, a tundish, and a molten metal remover.
- the cooling roll includes an outer peripheral surface and is configured to cool and solidify molten metal on the outer peripheral surface while rotating.
- the tundish can accommodate the molten metal and is configured to supply the molten metal onto the outer peripheral surface of the cooling roll.
- the molten metal remover is disposed downstream of the tundish in the rotating direction of the cooling roll with a gap provided between the molten metal remover and the outer peripheral surface of the cooling roll.
- the molten metal remover is configured to remove a portion of a thickness of the molten metal that is larger than the width of the gap described above (hereafter, also referred to as a surface portion). As a result, the thickness of the molten metal on the outer peripheral surface of the cooling roll is cut down to the width of the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- the producing apparatus includes a molten metal remover.
- the molten metal remover is configured to be in contact with the molten metal when a free surface of the molten metal (a surface of the molten metal on a side on which the molten metal is not in contact with the cooling roll) in a liquid state or a semi-solidified state.
- the molten metal remover is configured to remove the surface portion of the molten metal on the outer peripheral surface.
- the thickness of the molten metal on the outer peripheral surface of the cooling roll is cut down to the width of the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- the molten metal on the outer peripheral surface of the cooling roll becomes thin.
- the cooling rate of the molten metal increases.
- grains in the thin metal strip become small.
- by using the strip casting it is possible to efficiently produce a thin metal strip including fine grains.
- by cutting down the width of the thickness of the molten metal to the width of the gap as described above it is possible to perform rapid solidification without being affected not much by viscosity of the molten metal, wettability to the roll material, supply amount of the molten metal, and the like.
- the width of a gap between the outer peripheral surface of the cooling roll and the molten metal remover is smaller than the thickness of the molten metal on the outer peripheral surface of the cooling roll on an upstream side of the molten metal remover in the rotating direction of the cooling roll.
- the molten metal on the outer peripheral surface of the cooling roll becomes thinner. Therefore, the cooling rate of the molten metal becomes higher. As a result, the grains in the thin metal strip are more refined.
- the tundish is disposed in the vicinity of the outer peripheral surface of the cooling roll and includes a supply end configured to guide the molten metal onto the outer peripheral surface of the cooling roll.
- the molten metal remover is disposed above the supply end of the tundish.
- the molten metal is cooled while being wound up by the cooling roll. Therefore, the time for which the molten metal is in contact with the outer peripheral surface of the cooling roll is long, and the cooling time of the molten metal is long. As a result, the grains in the thin metal strip are more refined.
- molten metal remover is disposed opposite to the outer peripheral surface of the cooling roll and includes a heat dissipation surface configured to be in contact with the molten metal passing through the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- the molten metal is subjected to heat dissipation from a surface in contact with the molten metal remover, as well as a surface in contact with the cooling roll (hereafter, also referred to as a solidified portion). Therefore, the cooling rate of the molten metal becomes high. As a result, the grains in the thin metal strip are more refined.
- a method for producing a thin metal strip according to the present embodiment is a method for producing a thin metal strip by a single roll strip casting process using the producing apparatus described above.
- the producing method includes a supplying step, a rapid cooling step, and a thickness adjustment step.
- the supplying step the molten metal in the tundish is supplied onto the outer peripheral surface of the cooling roll.
- the rapid cooling step the molten metal on the outer peripheral surface is rapidly cooled with the cooling roll to be formed into the thin metal strip.
- the thickness adjustment step a portion of a thickness of the molten metal on the outer peripheral surface of the cooling roll that is larger than the width of the gap described above is removed by the molten metal remover. As a result, the thickness of the molten metal on the outer peripheral surface is cut down to the width of the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- the producing method according to the present embodiment includes the thickness adjustment step.
- the thickness adjustment step Through the thickness adjustment step, the molten metal on the outer peripheral surface of the cooling roll becomes thin. Therefore, the cooling rate of the molten metal becomes high. As a result, the grains in the thin metal strip are refined. In other words, by using the strip casting process, it is possible to efficiently produce a thin metal strip including fine grains.
- the thin metal strip produced by the above production method of a thin metal strip may contain a chemical composition that includes Cu and Sn, and may contain a phase having D0 3 structure in the Strukturbericht notation.
- the powder obtained by pulverizing this thin metal strip can be used as a negative electrode active material for a nonaqueous electrolyte secondary battery, such as a lithium ion secondary battery.
- This negative electrode active material has excellent charge-discharge capacity and capacity retention characteristics.
- a chemical composition of the above thin metal strip consists of, for example, 10 to 20 at % or 21 to 27 at % of Sn, with the balance being Cu and impurities.
- the chemical composition of the above thin metal strip may further contain one or more selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Al, Si, B, and C in place of a part of Cu.
- the ratio of the phase having D0 3 structure (hereinafter referred to as D0 3 phase) can be increased. Therefore, battery characteristics (capacity retention rate etc.) are increased.
- FIG. 1 is a cross-sectional view of an example of an apparatus for producing a thin metal strip according to the present embodiment.
- a producing apparatus 1 includes a cooling roll 2 , a tundish 4 , and a molten metal remover 5 .
- the cooling roll 2 has an outer peripheral surface and is configured to cool and solidify molten metal 3 on the outer peripheral surface while rotating.
- the cooling roll 2 includes a column-shaped barrel portion and a shaft portion not illustrated.
- the barrel portion includes the outer peripheral surface described above.
- the shaft portion is disposed at a central axis position of the barrel portion and attached to a driving source not illustrated.
- the cooling roll 2 is configured to be rotated about a central axis 9 of the cooling roll 2 by the driving source.
- the starting material of the cooling roll 2 is preferably a material having a high hardness and a high thermal conductivity.
- the starting material of the cooling roll 2 is, for example, one selected from the group consisting of copper and copper alloys.
- the starting material of the cooling roll 2 is preferably copper.
- the cooling roll 2 may further include a coating on its surface. This inclusion of the coating increases the hardness of the cooling roll 2 . Therefore, it is advantageous, particularly in mass production.
- the coating is, for example, one or two selected from the group consisting of plating coating and cermet coating.
- the plating coating is, for example, one or two selected from the group consisting of chromium plating and nickel plating.
- the cermet coating contains, for example, one, or two or more selected from the group consisting of tungsten (W), cobalt (Co), titanium (Ti), chromium (Cr), nickel (Ni), silicon (Si), aluminum (Al), boron (B), and carbides, nitrides, and carbo-nitrides of these elements. It is preferable that the outer layer of the cooling roll 2 is made of copper, and the cooling roll 2 further includes a chromium plating coating on its surface.
- Reference character X illustrated in FIG. 1 denotes the rotating direction of the cooling roll 2 .
- the cooling roll 2 rotates in a given direction X.
- the molten metal 3 coming into contact with the cooling roll 2 is partially solidified on the outer peripheral surface of the cooling roll 2 and moves with the rotation of the cooling roll 2 .
- the cooling roll 2 includes a cooling zone that lies downstream of the tundish 4 to be described later in the rotating direction of the cooling roll 2 but does not reach the molten metal remover 5 to be described later.
- the molten metal 3 supplied onto the outer peripheral surface of the cooling roll 2 has a free surface. Therefore, rapid cooling is enabled. If the molten metal 3 has no free surface, that is, if a solidified portion of the molten metal 3 is covered with another portion of molten metal 3 , the solidified portion cannot be subjected to sufficient heat dissipation. This is because heat is continuously added to the solidified portion from the molten metal 3 lying on the solidified portion.
- the molten metal 3 is made to have the free surface by being supplied onto the outer peripheral surface of the cooling roll 2 . Therefore, the solidified portion can be subjected to sufficient heat dissipation, which enables the rapid cooling. As a result, it is possible to obtain the thin metal strip 6 including more refined grains.
- the roll peripheral speed of the cooling roll 2 is set as appropriate in consideration of the cooling rate and the efficiency of manufacturing of the molten metal 3 .
- the upper limit of the roll peripheral speed is not particularly limited but, for example, 500 m/min in consideration of a plant capacity.
- the roll peripheral speed can be determined from the diameter and the number of revolutions of the roll.
- the inside of the cooling roll 2 may be filled with solvent for the heat dissipation. It is thereby possible to subject the molten metal 3 to the heat dissipation efficiently.
- the solvent is, for example, one, or two or more selected from the group consisting of water, organic solvent, and oil.
- the solvent may stay inside the cooling roll 2 or may be circulated through the outside.
- the tundish 4 can accommodate the molten metal 3 and is configured to supply the molten metal 3 onto the outer peripheral surface of the cooling roll 2 .
- the tundish 4 may always be heated. In this case, the melted state of the molten metal 3 having a high fusing point can be maintained. As a result, the molten metal 3 can be removed remaining in the melted state, with the molten metal remover 5 to be described later.
- a heating temperature is not particularly limited as long as the heating temperature is equal to or higher than the liquidus temperature of a raw material. In a case of producing a Si alloy, the heating temperature is, for example, 1200° C. or more, and a more preferable heating temperature is 1500° C. or more. In a case of producing an alloy material for a magnet, the heating temperature is, for example, 1000° C. or more.
- the shape of the tundish 4 is not particularly limited as long as the molten metal 3 can be supplied onto the outer peripheral surface of the cooling roll 2 . As shown in FIG. 1 , the shape of the tundish 4 may be a box-like shape with an open top, or may be other shapes.
- the tundish 4 includes a supply end 7 for guiding the molten metal 3 on the outer peripheral surface of the cooling roll 2 .
- the molten metal 3 is supplied from a crucible (not shown) to the tundish 4 , and then supplied to the outer peripheral surface of the cooling roll 2 through the supply end 7 .
- the shape of the supply end 7 is not particularly limited.
- the cross section of the supply end 7 may be rectangular as shown in FIG. 1 or it may be inclined. Alternatively, the supply end 7 may be in the form of a nozzle.
- the tundish 4 is disposed in the vicinity of the outer peripheral surface of the cooling roll 2 .
- the molten metal 3 can be stably supplied onto the outer peripheral surface of the cooling roll 2 .
- the gap between the tundish 4 and the cooling roll 2 is appropriately set within a range where the molten metal 3 does not leak.
- the material of the tundish 4 is preferably refractory.
- the tundish 4 is made of, for example, one or more selected from the group consisting of aluminum oxide (Al 2 O 3 ), silicon monoxide (SiO), silicon dioxide (SiO 2 ), chromium oxide (Cr 2 O 3 ), magnesium oxide (MgO), titanium oxide (TiO 2 ), aluminum titanate (Al 2 TiO 5 ), And zirconium oxide (ZrO 2 ).
- the molten metal remover 5 is a member that extends along the shaft direction of the cooling roll 2 .
- An example of the molten metal remover 5 is a plate-shaped member that is disposed in parallel to the shaft direction of the cooling roll 2 , as illustrated in FIG. 1 .
- the molten metal remover 5 is disposed downstream of the tundish 4 in the rotating direction of the cooling roll 2 with a gap provided between the molten metal remover 5 and the outer peripheral surface of the cooling roll 2 .
- the molten metal remover 5 consists a main body 51 and a front edge portion 50 that is disposed opposite to the outer peripheral surface of the cooling roll 2 .
- the shape of the front edge portion 50 is not particularly limited.
- FIG. 2 is a cross-sectional view illustrating the vicinity of the front edge portion 50 of the molten metal remover 5 included in the producing apparatus 1 (a region surrounded by a broken line in FIG. 1 ) in an enlarging manner.
- the molten metal remover 5 is disposed with a gap A between the molten metal remover 5 and the outer peripheral surface of the cooling roll 2 .
- the molten metal remover 5 is configured to cut down the thickness of the molten metal 3 on the outer peripheral surface of the cooling roll 2 to the width of the gap A between the outer peripheral surface of the cooling roll 2 and the molten metal remover 5 .
- the molten metal 3 lying upstream of the molten metal remover 5 in the rotating direction of the cooling roll 2 has a large thickness as compared with the width of the gap A.
- an amount of molten metal 3 corresponding to a thickness by which the thickness of the molten metal 3 is more than the width of the gap A is removed by the molten metal remover 5 .
- the thickness of the molten metal 3 is reduced to the width of the gap A.
- the reduced thickness of the molten metal 3 makes the cooling rate of the molten metal 3 higher. As a result, the grains in the thin metal strip 6 are refined.
- the width of the gap A is preferably smaller than a thickness B of the molten metal 3 on the outer peripheral surface on an upstream side of the molten metal remover 5 in the rotating direction of the cooling roll 2 .
- the molten metal 3 on the outer peripheral surface of the cooling roll 2 becomes thinner. Therefore, the cooling rate of the molten metal 3 becomes higher. As a result, the grains in the thin metal strip 6 are more refined.
- the width of the gap A between the outer peripheral surface of the cooling roll 2 and the molten metal remover 5 is a shortest distance between the molten metal remover 5 and the outer peripheral surface of the cooling roll 2 .
- the width of the gap A is set as appropriate in accordance with a target cooling rate and a target efficiency of manufacturing. The smaller the width of the gap A, the thinner the molten metal 3 subjected to thickness adjustment. Therefore, the cooling rate of the molten metal 3 becomes higher. As a result, the grains in the thin metal strip 6 are more easily refined. Consequently, the upper limit of the gap A is preferably 400 more preferably 250 ⁇ m, still more preferably 100 ⁇ m, even still more preferably 50 ⁇ m, even still more preferably 30 ⁇ m.
- the cooling rate is slow as compared with a case where the surface of the cooling roll 2 is made of copper. Therefore, in this case, the gap A is preferably narrowed.
- the lower limit of the gap A is not particularly limited but, for example to, 10 ⁇ m.
- the distance between a location where the molten metal 3 is supplied from the tundish 4 and a location where the molten metal remover 5 is disposed is set as appropriate.
- the molten metal remover 5 may be disposed in a region where the free surface of the molten metal 3 (a surface of the molten metal 3 on a side on which the molten metal 3 is not in contact with the cooling roll 2 ) is in contact with the molten metal remover 5 in the liquid state or the semi-solidified state.
- FIG. 3 is a diagram illustrating an attachment angle of the molten metal remover 5 .
- the molten metal remover 5 is disposed such that an angle ⁇ formed by a plane PL 1 including the central axis 9 of the cooling roll 2 and a supply end 7 , and a plane PL 2 including the central axis 9 of the cooling roll 2 and the front edge portion 50 of the molten metal remover 5 is constant (Hereafter, this angle ⁇ will be referred to as an attachment angle ⁇ .).
- the attachment angle ⁇ can be set as appropriate.
- the upper limit of the attachment angle ⁇ is, for example, 45°.
- the upper limit of the attachment angle ⁇ is preferably 30°.
- the lower limit of the attachment angle ⁇ is not particularly limited but is preferably within such a range that does not cause the molten metal remover 5 not to directly come into contact with the molten metal 3 on the tundish 4 .
- the molten metal remover 5 includes a heat dissipation surface 8 .
- the heat dissipation surface 8 is disposed opposite to the outer peripheral surface of the cooling roll 2 .
- the heat dissipation surface 8 is configured to come into contact with the molten metal 3 passing through a gap between the outer peripheral surface of the cooling roll 2 and the molten metal remover 5 .
- the starting material of the molten metal remover 5 is preferably a refractory material.
- the molten metal remover 5 contains, for example, one, or two or more selected from the group consisting of aluminum oxide (Al 2 O 3 ), silicon monoxide (SiO), silicon dioxide (SiO 2 ), chromium oxide (Cr 2 O 3 ), magnesium oxide (MgO), titanium oxide (TiO 2 ), aluminum titanate (Al 2 TiO 5 ), and zirconium oxide (ZrO 2 ).
- the molten metal remover 5 contains one, or two or more selected from the group consisting of aluminum oxide (Al 2 O 3 ), silicon dioxide (SiO 2 ), aluminum titanate (Al 2 TiO 5 ), and magnesium oxide (MgO).
- the molten metal remover 5 removes a surface portion of the molten metal 3 on the outer peripheral surface of the cooling roll 2 .
- the surface portion of the molten metal 3 means a portion of a thickness of the molten metal 3 on the outer peripheral surface of the cooling roll 2 that is larger than the width of the gap A between the outer peripheral surface of the cooling roll 2 and the molten metal remover 5 .
- the molten metal 3 on the outer peripheral surface of the cooling roll 2 becomes thin.
- the reduction of the molten metal 3 in thickness makes the cooling rate of the molten metal 3 higher. Therefore, by producing a thin metal strip using the producing apparatus 1 , it is possible to obtain the thin metal strip 6 including more refined grains.
- the apparatus for producing a thin metal strip according to the present embodiment is not limited to the producing apparatus 1 described above.
- the molten metal 3 is supplied from a lateral side of the cooling roll 2 .
- the molten metal 3 can be supplied above the cooling roll 2 .
- FIG. 4 is a cross-sectional view of a producing apparatus 10 according to another embodiment, which is different from that illustrated in FIG. 1 to FIG. 3 .
- the tundish 4 and the supply end 7 are disposed above the cooling roll 2 .
- the molten metal remover 5 is disposed below the supply end 7 .
- the rest of the configuration of the producing apparatus 10 is the same as that of the producing apparatus 1 .
- the molten metal 3 is supplied from above the cooling roll 2 onto the outer peripheral surface of the cooling roll 2 .
- the thickness of the molten metal 3 supplied onto the outer peripheral surface of the cooling roll 2 is cut down by the molten metal remover 5 as with the producing apparatus 1 .
- the thickness of the molten metal 3 on the outer peripheral surface of the cooling roll 2 is reduced to the width of the gap A between the outer peripheral surface of the cooling roll 2 and the molten metal remover 5 .
- the molten metal 3 is cooled while descending from the top of the cooling roll 2 along the outer peripheral surface of the cooling roll 2 .
- the molten metal 3 is supplied from a lateral side of the cooling roll 2 in the same direction as the rotating direction of the cooling roll 2 .
- the molten metal 3 is wound up by the cooling roll 2 to reach the top of the cooling roll 2 and then descends on the outer peripheral surface of the cooling roll 2 to be cooled. For that reason, in a case of using the producing apparatus 1 , the time for which the molten metal 3 is in contact with the outer peripheral surface of the cooling roll 2 is long as compared with the producing apparatus 10 .
- the cooling time of the molten metal 3 is long.
- the grains in the thin metal strip 6 are more refined. Consequently, the producing apparatus 1 illustrated in FIG. 1 , that is, disposing the molten metal remover 5 above the supply end 7 of the tundish 4 is preferable.
- the number of molten metal removers 5 to be disposed may be one as illustrated in FIG. 1 to FIG. 4 , or a plurality of molten metal removers 5 may be disposed continuously in the rotating direction of the cooling roll 2 .
- the molten metal remover(s) 5 disposed on a downstream side in the rotating direction of the cooling roll 2 are disposed to be closer to the cooling roll 2 than the molten metal remover(s) 5 disposed on an upstream side in the rotating direction of the cooling roll 2 .
- a molten metal remover 5 at a most downstream position in the rotating direction of the cooling roll 2 is disposed such that a gap A between the molten metal remover 5 and the outer peripheral surface of the cooling roll 2 becomes the narrowest. Disposing a plurality of molten metal removers 5 enables stepwise removal of the molten metal 3 . In this case, a load applied to one molten metal remover 5 is lower. In this case, moreover, precise control of the thickness of the molten metal 3 is facilitated.
- the molten metal remover 5 may be disposed in a direction along a normal line of the cooling roll 2 as illustrated in FIG. 1 to FIG. 4 or may be disposed in a direction different from a normal line of the cooling roll 2 as illustrated in FIG. 5 .
- the molten metal remover 5 is disposed such as to incline from a normal direction of the cooling roll 2 toward the rotating direction of the cooling roll 2 .
- it is easy to remove a portion of the molten metal 3 on the outer peripheral surface of the cooling roll 2 that is higher than the width of the gap A.
- FIG. 5 the molten metal remover 5 is disposed such as to incline from a normal direction of the cooling roll 2 toward the rotating direction of the cooling roll 2 .
- the molten metal remover 5 is configured to have a cross sectional shape different from that illustrated in FIG. 1 to FIG. 4 , which will be described later. In this case, the removal of the molten metal 3 can be performed even more efficiently.
- the direction of the molten metal remover 5 is set as appropriate such that the cut-down of the thickness of the molten metal 3 is easy.
- the cross sectional shape of the front edge portion 50 of the molten metal remover 5 (an edge of the molten metal remover 5 to be in contact with the molten metal 3 ) in a cross section perpendicular to the shaft of the roll may be a rectangle as illustrated in FIG. 1 to FIG. 4 or may be in another shape. Another shape may be, for example, a triangle as illustrated in FIG. 6 . Alternatively, as illustrated in FIG. 5 and FIG.
- the front edge portion 50 of the molten metal remover 5 may be in a shape in which the width of a gap between the front edge portion 50 of the molten metal remover 5 on an entrance side for the molten metal 3 and the outer peripheral surface of the cooling roll 2 is different from the width of a gap between the front edge portion 50 of the molten metal remover 5 on an exit side for the molten metal 3 and the outer peripheral surface of the cooling roll 2 .
- the cross sectional shape of the front edge portion 50 of the molten metal remover 5 is set as appropriate such that the thickness of the molten metal 3 is easily cut down.
- a method for producing the thin metal strip 6 according to the present embodiment is a producing method using the producing apparatus 1 or 10 described above.
- the producing method includes a supplying step, a rapid cooling step, and a thickness adjustment step.
- the molten metal 3 is prepared.
- the composition of the molten metal 3 is set as appropriate in accordance with an intended composition of the thin metal strip 6 .
- the molten metal 3 contains, for example, one, or two or more selected from the group consisting of silicon (Si), titanium (Ti), chromium (Cr), vanadium (vanadium), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), copper (Cu), and tin (Sn), with the balance being impurities.
- the molten metal 3 In the case of producing a metal ribbon for a negative electrode active material used in a lithium secondary battery or the like, it is preferable to produce the molten metal 3 so as to obtain a metal ribbon having the chemical composition described below.
- the molten metal 3 consists, for example, neodymium (Nd), boron (B), and iron (Fe), with the balance being impurities.
- the molten metal 3 is produced by heating a raw material having the chemical composition described above to the fusing point of the raw material or higher.
- the molten metal 3 is produced.
- the method of the heating include high-frequency induction heating, arc heating, plasma arc heating, electric resistance heating, and electron beam heating.
- a heating temperature is not particularly limited as long as the heating temperature is equal to or higher than the liquidus temperature of the raw material.
- the heating temperature is, for example, 1200° C. or more, more preferably 1500° C. or more.
- the heating temperature is, for example, 1000° C. or more.
- the molten metal 3 in the tundish 4 is supplied onto the outer peripheral surface of the cooling roll 2 .
- the molten metal 3 is supplied from the crucible to the tundish 4 .
- the supply of the molten metal 3 from the crucible to the tundish 4 may be made by tilting the crucible to pour the molten metal 3 directly.
- a nozzle or the like may be used to supply the molten metal 3 from the crucible to the tundish 4 .
- the molten metal 3 is supplied onto the outer peripheral surface of the cooling roll 2 .
- the cooling roll 2 rotates, as described above, about the central axis 9 of the cooling roll 2 at a given speed.
- the molten metal 3 supplied from the tundish 4 comes into contact with the outer peripheral surface of the cooling roll 2 , the molten metal 3 is partially solidified to be transferred to the cooling roll 2 .
- the molten metal 3 moves with the rotation of the cooling roll 2 .
- a surface of the molten metal 3 not in contact with the outer peripheral surface of the cooling roll 2 (free surface) is in a liquid state or a semi-solidified state.
- the tundish 4 may always be heated. In this case, the melted state of the molten metal 3 having a high fusing point can be maintained. Therefore, the molten metal 3 can be removed by the molten metal remover 5 while being in the melted state.
- a heating temperature is not particularly limited as long as the heating temperature is equal to or higher than the liquidus temperature of the raw material. In a case of producing a Si alloy, the heating temperature is, for example, 1200° C. or more, and a more preferable heating temperature is 1500° C. or more. In a case of producing an alloy material for a magnet, the heating temperature is, for example, 1000° C. or more.
- the molten metal 3 on the outer peripheral surface is rapidly cooled with the cooling roll 2 to be formed into the thin metal strip 6 .
- the rapid cooling step is started when the molten metal 3 is supplied onto the outer peripheral surface of the cooling roll 2 in the supplying step described above. In the rapid cooling process, the molten metal 3 is cooled from a solidified portion.
- the cooling roll 2 includes a cooling zone that lies downstream of the tundish 4 in the rotating direction of the cooling roll 2 but does not reach the molten metal remover 5 .
- the molten metal 3 supplied onto the outer peripheral surface of the cooling roll 2 includes a free surface. Therefore, rapid cooling is enabled. If the molten metal 3 has no free surface, that is, if the solidified portion is covered with another portion of molten metal 3 , the solidified portion cannot be subjected to sufficient heat dissipation. This is because heat is continuously added to the solidified portion from the molten metal 3 lying on the solidified portion.
- the molten metal 3 is made to have the free surface by being supplied onto the outer peripheral surface of the cooling roll 2 . Therefore, the solidified portion can be subjected to sufficient heat dissipation, which enables the rapid cooling. As a result, the thin metal strip 6 including more refined grains can be produced.
- the thickness of the molten metal 3 on the outer peripheral surface of the cooling roll 2 is cut down by the molten metal remover 5 , in the middle of the rapid cooling step, to the width of the gap A between the outer peripheral surface of the cooling roll 2 and the molten metal remover 5 .
- the molten metal 3 is not solidified as a whole but gradually solidified from a solidified portion.
- the free surface of the molten metal 3 comes into contact with the molten metal remover 5 , in a liquid state or a semi-solidified state.
- the hardness of the molten metal 3 in the liquid state or the semi-solidified state is low.
- the thickness of the molten metal 3 is larger than the width of the gap A, the free surface of the molten metal 3 in the liquid state or the semi-solidified state is blocked or removed.
- the molten metal 3 thereby becomes thin.
- the cooling rate of the molten metal 3 increases.
- the thin metal strip 6 including more refined grains can be produced.
- the disposition of the heat dissipation surface 8 enables the molten metal 3 to be subjected to heat dissipation from the heat dissipation surface 8 as well as the solidified portion. In this case, the cooling rate of the molten metal 3 becomes high.
- the area and shape of the heat dissipation surface 8 are set as appropriate. For example, as illustrated in FIG. 8 , by forming the front edge portion 50 of the molten metal remover 5 into an L shape, the area of the heat dissipation surface 8 can be increased. In this case, the cooling rate of the molten metal 3 can be made higher.
- the molten metal 3 reduced in thickness through the thickness adjustment step is subsequently cooled on the cooling roll 2 .
- the molten metal 3 is thin. Therefore, the cooling rate is remarkably high. As a result, grains in the thin metal strip 6 are fine.
- the entire molten metal 3 is solidified into the thin metal strip 6 .
- the thin metal strip 6 is separated from the outer peripheral surface of the cooling roll 2 and collected.
- the ratio of a phase having D0 3 structure in Strukturbericht notation (hereinafter also referred to as D0 3 phase) is large.
- the D0 3 phase acts as a host for occlusion and release a lithium. Therefore, the greater the ratio of D0 3 phase in the metal strip is, the better the electric capacity and the cycle life of a battery are.
- a preferable chemical composition of the thin metal strip as a negative electrode active material is Sn, with the balance being Cu and impurities. More preferably, the chemical composition of the thin metal strip contains 10 to 20 at % or 21 to 27 at % of Sn, with the balance being Cu and impurities. In the chemical composition of the thin metal strip, the more preferable Sn content is 13 to 16 at %, 18.5 to 20 at %, or 21 to 27 at %.
- the chemical composition may contain 10 to 20 at % or 21 to 27 at % of Sn, and one or more selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Al, Si, B, and C, with the balance being Cu and impurities.
- the above chemical composition may contain: Sn: 10 to 20 at % or 21 to 27 at % of Sn, and one or more selected from the group consisting of Ti: 9.0 at % or less, V: 49.0 at % or less, Cr: 49.0 at % or less, Mn: 9.0 at % or less, Fe: 49.0 at % or less, Co: 49.0 at % or less, Ni: 9.0 at % or less, Zn: 29.0 at % or less, Al: 49.0 at % or less, Si: 49.0 at % or less, B: 5.0 at % or less, and C: 5.0 at % or less, with the balance being Cu and impurities.
- a raw material contained nickel (Ni), titanium (Ti), and silicon (Si).
- One kilogram of the raw material in a mixed state was heated to 1450° C. to be produced into molten metal.
- the molten metal was supplied from the tundish onto the cooling roll.
- the cooling roll was one the outer peripheral surface of which is covered with copper and the inside of which is cooled by water.
- the cooling roll had a diameter of 20 cm and a width of 18 cm.
- the peripheral speed of the roll was 120 m/min.
- the thin metal strips made of Si alloy obtained in Example 1 to Example 3 were cut, and cross sections were observed under a scanning electron microscope (SEM).
- Example 1 the producing apparatus according to the present embodiment was used to produce a thin metal strip made of Si alloy.
- the thin metal strip made of Si alloy was produced using the molten metal remover.
- the molten metal remover was a flat alumina plate having a thickness of 3 mm.
- the width of the gap between the molten metal remover and the outer peripheral surface of the cooling roll was 80 ⁇ m.
- Example 2 a thin metal strip made of Si alloy was produced using the producing apparatus according to the present embodiment from which the molten metal remover was detached. In other words, the thin metal strip made of Si alloy was produced without using the molten metal remover.
- Example 3 a thin metal strip made of Si alloy was produced under the same conditions as those of Example 1 except that a producing apparatus with no cooling zone on the cooling roll in a region between the tundish and the molten metal remover was used. In other words, without the free surface, the molten metal was supplied to the molten metal remover.
- FIG. 9 is a picture of a cross section of the thin metal strip produced by the producing method according to the present embodiment (with the molten metal remover), taken under the electron microscope (SEM).
- the thin metal strip produced by the method according to the present embodiment had an average coating thickness of 80 ⁇ m.
- the size of a grain in a Si phase of the thin metal strip produced by the method according to the present embodiment was not more than 2 ⁇ m.
- FIG. 10 is a picture of a cross section of the thin metal strip produced by a conventional method (without the molten metal remover), taken under the electron microscope (SEM).
- the thin metal strip produced by the conventional method had an average coating thickness of 440 ⁇ m.
- the size of a grain in a Si phase of the thin metal strip produced by the conventional method was 20 to 30 ⁇ m.
- Example 3 in which the production was made by removing the molten metal without the free surface with the molten metal remover, the size of a grain in a Si phase of the thin metal strip was 10 to 15 ⁇ m.
- the method according to the present embodiment provides a thin metal strip with finer crystal grain than the conventional method.
- Each of the thin metal strip had a chemical composition, containing 20.0 at % of Sn and 8.0 at % of Si, with the balance being Cu and impurities.
- the ratio (mass %) of D0 3 phase (phase having D0 3 structure) in the produced thin metal strip was determined.
- test numbers 1 to 3 and 5 to 8 thin metal strips were produced by the production method (with a blade member) of this embodiment.
- test number 4 a thin metal strip was produced by a conventional manufacturing method (without a blade member).
- molten metal of each test number was provided onto the cooling roll from the tundish.
- the composition of the coating film on the surface of the cooling roll used was as shown in Table 1. That is, in test numbers. 1 and 2, the surface of the cooling roll was Cu, and in test numbers 3 and 4, the surface of the cooling roll was a Cr plating film.
- the interior of the cooling roll was cooled with water. The diameter of the cooling roll was 20 cm, and the width was 18 cm.
- the ratio occupied by D0 3 phase in the produced thin metal strips of each test numbers 1 to 8 was determined by the following method.
- X-ray diffraction measurement was conducted on the thin metal strips and measurement data of the X-ray diffraction profile was obtained. Specifically, an X-ray diffraction profile of the thin metal strip was obtained, using a SmartLab (rotor target maximum output 9 KW; 45 kV-200 mA) manufactured by Rigaku Corporation. Based on the obtained X-ray diffraction profile (measured data), the crystal structure in the thin metal strip was analyzed by the Rietveld method. The X-ray diffraction apparatus and measurement conditions are described below.
- the crystal structure of D0 3 phase is cubic, and in terms of classification of a space group, No. 225(Fm-3m) of International Table (Volume-A).
- a calculated value of diffraction profile (hereinafter, referred to as a calculated profile) of each thin metal strip was found by Rietveld method.
- Rietan-2000 program name
- the ratio of D0 3 phase is shown in Table 1. Referring to Table 1, the ratio of D0 3 phase in the thin metal strips of test numbers 1 to 3 and 5 to 8 produced by the product method (with a blade member) of the present embodiment was higher than the ration of D0 3 phase in the thin metal strip of test number 4 produced by the conventional production method).
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Abstract
Description
- The present invention relates to an apparatus for producing a thin metal strip and a method for producing a thin metal strip using the apparatus.
- It is known that rapid solidification process can provide metal materials with various properties. The rapid solidification process refers to a process for solidifying molten metal at a certain cooling rate or higher. The rapid solidification process enables, for example, refining crystal structures of a metal material, homogenizing a solute distribution, increasing a solid-solubility limit, producing amorphous layers (amorphous), and producing thermodynamic non-equilibrium phases. Specifically, known methods for producing a cast piece by the rapid solidification process include the strip casting process, the melt spinning process, the atomization process, the melt spinning process, and the like.
- For example, International Application Publication No. WO2012/099056 (Patent Literature 1) describes producing Si alloy by the atomization process. For another example, Japanese Patent Application Publication No. 2013-161785 (Patent Literature 2) describes producing Si alloy by the melt spinning process.
- In the rapid solidification processes, the higher the cooling rate of molten metal is, the finer the resultant grains become. Among the rapid solidification processes, one producing method with a particularly high cooling rate is, for example, the melt spinning process. The melt spinning process is a method in which molten metal is jetted and rapidly cooled on a roll rotating at high speed to produce a ribbon-shaped thin metal strip in a flying manner. In the melt spinning process, a jet of a small amount of molten metal is supplied onto the roll. Therefore, the cooling rate is high.
- The melt spinning process enables the production of a thin metal strip including fine grains. However, in the melt spinning process, a small amount of the molten metal is supplied onto the roll. Therefore, the melt spinning process has its limitation in production capability and has a difficulty of producing a thin metal strip in volume.
- Meanwhile, in the rapid solidification processes, a method capable of producing a thin metal strip in volume is, for example, a single roll strip casting process. The single roll strip casting process is a method for producing a thin metal strip by continuously supplying molten metal onto a rotating roll to rapidly cool the molten metal. Methods for producing a cast piece using the strip casting process are, for example, described in Japanese Patent Application Publication No. 2011-206835 (Patent Literature 3) and Japanese Patent Application Publication No. 2001-291514 (Patent Literature 4).
- The producing apparatus described in Japanese Patent Application Publication No. 2011-206835 (Patent Literature 3) is a producing apparatus for an aluminum clad plate. This producing apparatus includes a first roll with a cooling capability and a first pool for storing first molten alloy. The first pool is surrounded by a surface of the first roll, a first front plate, a rear member, and both-side members. The first front plate lies forward of the first roll in a rotation direction. The rear member lies rearward of the first roll in the rotation direction. The first front plate includes a front edge portion and is movably provided such that the distance between the front edge portion and the surface of the first roll can vary. The first roll cools the first molten alloy in the first pool to form a first metallic layer in a semi-solidified state or a solidified state on the surface of the first roll and rotates with the first metallic layer. The first front plate is urged so that the front edge portion of the first front plate always abuts against a semi-solidified surface of the first metallic layer moving with the rotation of the first roll, at given force.
- The producing method described in Japanese Patent Application Publication No. 2001-291514 (Patent Literature 4) is a producing method for a negative electrode material for a non-aqueous electrolyte secondary battery. This producing method is characterized by melting an alloy raw material having a composition selected such that a Si phase and intermetallic compounds of Si and other metallic elements are crystallized in solidification, and then solidifying the alloy raw material using the strip casting process or the centrifugal casting process to form a columnar structure.
- In the strip casting process, the amount of molten metal supplied onto a roll is large as compared with the melt spinning process. Therefore, the strip casting process enables the production of a thin metal strip in large volume. However, in the strip casting process, the cooling rate of the molten metal is low as compared with the melt spinning process. Therefore, the strip casting process has a difficulty of refining grains. For that reason, the strip casting process is requested to provide more refined grains.
- Patent Literature 1: International Application Publication No. WO2012/099056
- The production methods disclosed in the Patent Literatures described above fail in some cases to efficiently produce thin metal strips including fine grains.
- An objective of the present invention is to provide an apparatus for producing a thin metal strip that is capable of efficiently producing a thin metal strip including fine grains.
- A producing apparatus according to the present embodiment is an apparatus for producing a thin metal strip by a single roll strip casting process. The producing apparatus includes a cooling roll, a tundish, and a molten metal remover. The cooling roll includes an outer peripheral surface and is configured to cool and solidify molten metal on the outer peripheral surface while rotating. The tundish can accommodate the molten metal and is configured to supply the molten metal onto the outer peripheral surface of the cooling roll. The molten metal remover is disposed downstream of the tundish in the rotating direction of the cooling roll with a gap provided between the molten metal remover and the outer peripheral surface of the cooling roll. The molten metal remover is configured to remove a portion of a thickness of the molten metal on the outer peripheral surface of the cooling roll that is larger than the width of the gap described above. As a result, the thickness of the molten metal on the outer peripheral surface of the cooling roll is cut down to the width of the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- A method for producing a thin metal strip according to the present embodiment is a method for producing a thin metal strip by a single roll strip casting process using the producing apparatus described above. The producing method includes a supplying step, a rapid cooling step, and a thickness adjustment step. In the supplying step, the molten metal in the tundish is supplied onto the outer peripheral surface of the cooling roll. In the rapid cooling step, the molten metal on the outer peripheral surface is rapidly cooled with the cooling roll to be formed into the thin metal strip. In the thickness adjustment step, a portion of a thickness of the molten metal on the outer peripheral surface of the cooling roll that is larger than the width of the gap described above is removed by the molten metal remover. As a result, the thickness of the molten metal on the outer peripheral surface is cut down to the width of the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- Using the apparatus for producing a thin metal strip according to the present embodiment enables a thin metal strip including fine grains to be produced efficiently.
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FIG. 1 is a cross-sectional view of an apparatus for producing a thin metal strip according to the present embodiment. -
FIG. 2 is a cross-sectional view of the vicinity of a front edge of a molten metal remover of the producing apparatus in an enlarging manner. -
FIG. 3 is a diagram illustrating an attachment angle of the molten metal remover. -
FIG. 4 is a cross-sectional view of a producing apparatus according to another embodiment, which is different from that illustrated inFIG. 1 toFIG. 3 . -
FIG. 5 is a cross-sectional view of a producing apparatus according to another embodiment, which is different from that illustrated inFIG. 1 toFIG. 4 . -
FIG. 6 is a diagram illustrating the cross sectional shape of a molten metal remover. -
FIG. 7 is a diagram illustrating the cross sectional shape of a molten metal remover different from that illustrated inFIG. 6 . -
FIG. 8 is a diagram illustrating the cross sectional shape of a molten metal remover different from those illustrated inFIG. 6 andFIG. 7 . -
FIG. 9 is a picture of a cross section of a thin metal strip produced by a production method according to the present embodiment, taken under an electron microscope (SEM). -
FIG. 10 is a picture of a cross section of a thin metal strip produced without using the molten metal remover, taken under the electron microscope (SEM). - A producing apparatus according to the present embodiment is an apparatus for producing a thin metal strip by a single roll strip casting process. The producing apparatus includes a cooling roll, a tundish, and a molten metal remover. The cooling roll includes an outer peripheral surface and is configured to cool and solidify molten metal on the outer peripheral surface while rotating. The tundish can accommodate the molten metal and is configured to supply the molten metal onto the outer peripheral surface of the cooling roll. The molten metal remover is disposed downstream of the tundish in the rotating direction of the cooling roll with a gap provided between the molten metal remover and the outer peripheral surface of the cooling roll. The molten metal remover is configured to remove a portion of a thickness of the molten metal that is larger than the width of the gap described above (hereafter, also referred to as a surface portion). As a result, the thickness of the molten metal on the outer peripheral surface of the cooling roll is cut down to the width of the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- The producing apparatus according to the present embodiment includes a molten metal remover. The molten metal remover is configured to be in contact with the molten metal when a free surface of the molten metal (a surface of the molten metal on a side on which the molten metal is not in contact with the cooling roll) in a liquid state or a semi-solidified state. The molten metal remover is configured to remove the surface portion of the molten metal on the outer peripheral surface. As a result, the thickness of the molten metal on the outer peripheral surface of the cooling roll is cut down to the width of the gap between the outer peripheral surface of the cooling roll and the molten metal remover. As a result, the molten metal on the outer peripheral surface of the cooling roll becomes thin. As the molten metal becomes thin, the cooling rate of the molten metal increases. As a result, grains in the thin metal strip become small. In other words, by using the strip casting, it is possible to efficiently produce a thin metal strip including fine grains. In addition, by cutting down the width of the thickness of the molten metal to the width of the gap as described above, it is possible to perform rapid solidification without being affected not much by viscosity of the molten metal, wettability to the roll material, supply amount of the molten metal, and the like.
- It is preferable that the width of a gap between the outer peripheral surface of the cooling roll and the molten metal remover is smaller than the thickness of the molten metal on the outer peripheral surface of the cooling roll on an upstream side of the molten metal remover in the rotating direction of the cooling roll.
- In this case, the molten metal on the outer peripheral surface of the cooling roll becomes thinner. Therefore, the cooling rate of the molten metal becomes higher. As a result, the grains in the thin metal strip are more refined.
- It is preferable that the tundish is disposed in the vicinity of the outer peripheral surface of the cooling roll and includes a supply end configured to guide the molten metal onto the outer peripheral surface of the cooling roll. In addition, the molten metal remover is disposed above the supply end of the tundish.
- In this case, the molten metal is cooled while being wound up by the cooling roll. Therefore, the time for which the molten metal is in contact with the outer peripheral surface of the cooling roll is long, and the cooling time of the molten metal is long. As a result, the grains in the thin metal strip are more refined.
- It is preferable that molten metal remover is disposed opposite to the outer peripheral surface of the cooling roll and includes a heat dissipation surface configured to be in contact with the molten metal passing through the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- In this case, the molten metal is subjected to heat dissipation from a surface in contact with the molten metal remover, as well as a surface in contact with the cooling roll (hereafter, also referred to as a solidified portion). Therefore, the cooling rate of the molten metal becomes high. As a result, the grains in the thin metal strip are more refined.
- A method for producing a thin metal strip according to the present embodiment is a method for producing a thin metal strip by a single roll strip casting process using the producing apparatus described above. The producing method includes a supplying step, a rapid cooling step, and a thickness adjustment step. In the supplying step, the molten metal in the tundish is supplied onto the outer peripheral surface of the cooling roll. In the rapid cooling step, the molten metal on the outer peripheral surface is rapidly cooled with the cooling roll to be formed into the thin metal strip. In the thickness adjustment step, a portion of a thickness of the molten metal on the outer peripheral surface of the cooling roll that is larger than the width of the gap described above is removed by the molten metal remover. As a result, the thickness of the molten metal on the outer peripheral surface is cut down to the width of the gap between the outer peripheral surface of the cooling roll and the molten metal remover.
- The producing method according to the present embodiment includes the thickness adjustment step. Through the thickness adjustment step, the molten metal on the outer peripheral surface of the cooling roll becomes thin. Therefore, the cooling rate of the molten metal becomes high. As a result, the grains in the thin metal strip are refined. In other words, by using the strip casting process, it is possible to efficiently produce a thin metal strip including fine grains.
- The thin metal strip produced by the above production method of a thin metal strip may contain a chemical composition that includes Cu and Sn, and may contain a phase having D03 structure in the Strukturbericht notation. The powder obtained by pulverizing this thin metal strip can be used as a negative electrode active material for a nonaqueous electrolyte secondary battery, such as a lithium ion secondary battery. This negative electrode active material has excellent charge-discharge capacity and capacity retention characteristics. A chemical composition of the above thin metal strip consists of, for example, 10 to 20 at % or 21 to 27 at % of Sn, with the balance being Cu and impurities. The chemical composition of the above thin metal strip may further contain one or more selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Al, Si, B, and C in place of a part of Cu.
- With the producing method according to the present embodiment, in case of the above chemical composition, the ratio of the phase having D03 structure (hereinafter referred to as D03 phase) can be increased. Therefore, battery characteristics (capacity retention rate etc.) are increased.
- The present embodiment will be described below in detail with reference to the accompanying drawings. The same or equivalent elements will be denoted by the same reference numerals, and the description thereof will not be repeated.
- [Producing Apparatus]
-
FIG. 1 is a cross-sectional view of an example of an apparatus for producing a thin metal strip according to the present embodiment. A producingapparatus 1 includes acooling roll 2, atundish 4, and amolten metal remover 5. - [Cooling Roll]
- The
cooling roll 2 has an outer peripheral surface and is configured to cool and solidifymolten metal 3 on the outer peripheral surface while rotating. Thecooling roll 2 includes a column-shaped barrel portion and a shaft portion not illustrated. The barrel portion includes the outer peripheral surface described above. The shaft portion is disposed at a central axis position of the barrel portion and attached to a driving source not illustrated. Thecooling roll 2 is configured to be rotated about acentral axis 9 of thecooling roll 2 by the driving source. - The starting material of the
cooling roll 2 is preferably a material having a high hardness and a high thermal conductivity. The starting material of thecooling roll 2 is, for example, one selected from the group consisting of copper and copper alloys. The starting material of thecooling roll 2 is preferably copper. Thecooling roll 2 may further include a coating on its surface. This inclusion of the coating increases the hardness of thecooling roll 2. Therefore, it is advantageous, particularly in mass production. The coating is, for example, one or two selected from the group consisting of plating coating and cermet coating. The plating coating is, for example, one or two selected from the group consisting of chromium plating and nickel plating. The cermet coating contains, for example, one, or two or more selected from the group consisting of tungsten (W), cobalt (Co), titanium (Ti), chromium (Cr), nickel (Ni), silicon (Si), aluminum (Al), boron (B), and carbides, nitrides, and carbo-nitrides of these elements. It is preferable that the outer layer of thecooling roll 2 is made of copper, and thecooling roll 2 further includes a chromium plating coating on its surface. - Reference character X illustrated in
FIG. 1 denotes the rotating direction of thecooling roll 2. In producing athin metal strip 6, thecooling roll 2 rotates in a given direction X. By this rotation, inFIG. 1 , themolten metal 3 coming into contact with thecooling roll 2 is partially solidified on the outer peripheral surface of thecooling roll 2 and moves with the rotation of thecooling roll 2. - The
cooling roll 2 includes a cooling zone that lies downstream of thetundish 4 to be described later in the rotating direction of thecooling roll 2 but does not reach themolten metal remover 5 to be described later. In the cooling zone, themolten metal 3 supplied onto the outer peripheral surface of thecooling roll 2 has a free surface. Therefore, rapid cooling is enabled. If themolten metal 3 has no free surface, that is, if a solidified portion of themolten metal 3 is covered with another portion ofmolten metal 3, the solidified portion cannot be subjected to sufficient heat dissipation. This is because heat is continuously added to the solidified portion from themolten metal 3 lying on the solidified portion. In the cooling zone, themolten metal 3 is made to have the free surface by being supplied onto the outer peripheral surface of thecooling roll 2. Therefore, the solidified portion can be subjected to sufficient heat dissipation, which enables the rapid cooling. As a result, it is possible to obtain thethin metal strip 6 including more refined grains. - The roll peripheral speed of the
cooling roll 2 is set as appropriate in consideration of the cooling rate and the efficiency of manufacturing of themolten metal 3. The higher the roll peripheral speed is, the more easily thethin metal strip 6 peels off from the outer peripheral surface of thecooling roll 2. Therefore, the lower limit of the roll peripheral speed is preferably 50 m/min, more preferably 80 m/min, and still more preferably 120 m/min. The upper limit of the roll peripheral speed is not particularly limited but, for example, 500 m/min in consideration of a plant capacity. The roll peripheral speed can be determined from the diameter and the number of revolutions of the roll. - The inside of the
cooling roll 2 may be filled with solvent for the heat dissipation. It is thereby possible to subject themolten metal 3 to the heat dissipation efficiently. The solvent is, for example, one, or two or more selected from the group consisting of water, organic solvent, and oil. The solvent may stay inside thecooling roll 2 or may be circulated through the outside. - [Tundish]
- The
tundish 4 can accommodate themolten metal 3 and is configured to supply themolten metal 3 onto the outer peripheral surface of thecooling roll 2. - In the present embodiment, the
tundish 4 may always be heated. In this case, the melted state of themolten metal 3 having a high fusing point can be maintained. As a result, themolten metal 3 can be removed remaining in the melted state, with themolten metal remover 5 to be described later. A heating temperature is not particularly limited as long as the heating temperature is equal to or higher than the liquidus temperature of a raw material. In a case of producing a Si alloy, the heating temperature is, for example, 1200° C. or more, and a more preferable heating temperature is 1500° C. or more. In a case of producing an alloy material for a magnet, the heating temperature is, for example, 1000° C. or more. - The shape of the
tundish 4 is not particularly limited as long as themolten metal 3 can be supplied onto the outer peripheral surface of thecooling roll 2. As shown inFIG. 1 , the shape of thetundish 4 may be a box-like shape with an open top, or may be other shapes. - The
tundish 4 includes asupply end 7 for guiding themolten metal 3 on the outer peripheral surface of thecooling roll 2. Themolten metal 3 is supplied from a crucible (not shown) to thetundish 4, and then supplied to the outer peripheral surface of thecooling roll 2 through thesupply end 7. The shape of thesupply end 7 is not particularly limited. The cross section of thesupply end 7 may be rectangular as shown inFIG. 1 or it may be inclined. Alternatively, thesupply end 7 may be in the form of a nozzle. - Preferably, the
tundish 4 is disposed in the vicinity of the outer peripheral surface of thecooling roll 2. Thereby, themolten metal 3 can be stably supplied onto the outer peripheral surface of thecooling roll 2. The gap between thetundish 4 and thecooling roll 2 is appropriately set within a range where themolten metal 3 does not leak. - The material of the
tundish 4 is preferably refractory. Thetundish 4 is made of, for example, one or more selected from the group consisting of aluminum oxide (Al2O3), silicon monoxide (SiO), silicon dioxide (SiO2), chromium oxide (Cr2O3), magnesium oxide (MgO), titanium oxide (TiO2), aluminum titanate (Al2TiO5), And zirconium oxide (ZrO2). - [Molten Metal Remover]
- The
molten metal remover 5 is a member that extends along the shaft direction of thecooling roll 2. An example of themolten metal remover 5 is a plate-shaped member that is disposed in parallel to the shaft direction of thecooling roll 2, as illustrated inFIG. 1 . Themolten metal remover 5 is disposed downstream of thetundish 4 in the rotating direction of thecooling roll 2 with a gap provided between themolten metal remover 5 and the outer peripheral surface of thecooling roll 2. Themolten metal remover 5 consists amain body 51 and afront edge portion 50 that is disposed opposite to the outer peripheral surface of thecooling roll 2. The shape of thefront edge portion 50 is not particularly limited. -
FIG. 2 is a cross-sectional view illustrating the vicinity of thefront edge portion 50 of themolten metal remover 5 included in the producing apparatus 1 (a region surrounded by a broken line inFIG. 1 ) in an enlarging manner. Referring toFIG. 2 , themolten metal remover 5 is disposed with a gap A between themolten metal remover 5 and the outer peripheral surface of thecooling roll 2. Themolten metal remover 5 is configured to cut down the thickness of themolten metal 3 on the outer peripheral surface of thecooling roll 2 to the width of the gap A between the outer peripheral surface of thecooling roll 2 and themolten metal remover 5. Specifically, there is a case where themolten metal 3 lying upstream of themolten metal remover 5 in the rotating direction of thecooling roll 2 has a large thickness as compared with the width of the gap A. In this case, an amount ofmolten metal 3 corresponding to a thickness by which the thickness of themolten metal 3 is more than the width of the gap A is removed by themolten metal remover 5. By this removal, the thickness of themolten metal 3 is reduced to the width of the gap A. The reduced thickness of themolten metal 3 makes the cooling rate of themolten metal 3 higher. As a result, the grains in thethin metal strip 6 are refined. - The width of the gap A is preferably smaller than a thickness B of the
molten metal 3 on the outer peripheral surface on an upstream side of themolten metal remover 5 in the rotating direction of thecooling roll 2. In this case, themolten metal 3 on the outer peripheral surface of thecooling roll 2 becomes thinner. Therefore, the cooling rate of themolten metal 3 becomes higher. As a result, the grains in thethin metal strip 6 are more refined. - The width of the gap A between the outer peripheral surface of the
cooling roll 2 and themolten metal remover 5 is a shortest distance between themolten metal remover 5 and the outer peripheral surface of thecooling roll 2. The width of the gap A is set as appropriate in accordance with a target cooling rate and a target efficiency of manufacturing. The smaller the width of the gap A, the thinner themolten metal 3 subjected to thickness adjustment. Therefore, the cooling rate of themolten metal 3 becomes higher. As a result, the grains in thethin metal strip 6 are more easily refined. Consequently, the upper limit of the gap A is preferably 400 more preferably 250 μm, still more preferably 100 μm, even still more preferably 50 μm, even still more preferably 30 μm. In a case where thecooling roll 2 includes chromium plating and nickel plating on its surface, the cooling rate is slow as compared with a case where the surface of thecooling roll 2 is made of copper. Therefore, in this case, the gap A is preferably narrowed. The lower limit of the gap A is not particularly limited but, for example to, 10 μm. - Of the outer peripheral surface of the
cooling roll 2, the distance between a location where themolten metal 3 is supplied from thetundish 4 and a location where themolten metal remover 5 is disposed is set as appropriate. Themolten metal remover 5 may be disposed in a region where the free surface of the molten metal 3 (a surface of themolten metal 3 on a side on which themolten metal 3 is not in contact with the cooling roll 2) is in contact with themolten metal remover 5 in the liquid state or the semi-solidified state. -
FIG. 3 is a diagram illustrating an attachment angle of themolten metal remover 5. Referring toFIG. 3 , for example, themolten metal remover 5 is disposed such that an angle θ formed by aplane PL 1 including thecentral axis 9 of thecooling roll 2 and asupply end 7, and a plane PL2 including thecentral axis 9 of thecooling roll 2 and thefront edge portion 50 of themolten metal remover 5 is constant (Hereafter, this angle θ will be referred to as an attachment angle θ.). The attachment angle θ can be set as appropriate. The upper limit of the attachment angle θ is, for example, 45°. The upper limit of the attachment angle θ is preferably 30°. The lower limit of the attachment angle θ is not particularly limited but is preferably within such a range that does not cause themolten metal remover 5 not to directly come into contact with themolten metal 3 on thetundish 4. - Referring to
FIG. 1 toFIG. 3 , it is preferable that themolten metal remover 5 includes aheat dissipation surface 8. Theheat dissipation surface 8 is disposed opposite to the outer peripheral surface of thecooling roll 2. Theheat dissipation surface 8 is configured to come into contact with themolten metal 3 passing through a gap between the outer peripheral surface of thecooling roll 2 and themolten metal remover 5. - The starting material of the
molten metal remover 5 is preferably a refractory material. Themolten metal remover 5 contains, for example, one, or two or more selected from the group consisting of aluminum oxide (Al2O3), silicon monoxide (SiO), silicon dioxide (SiO2), chromium oxide (Cr2O3), magnesium oxide (MgO), titanium oxide (TiO2), aluminum titanate (Al2TiO5), and zirconium oxide (ZrO2). It is preferable that themolten metal remover 5 contains one, or two or more selected from the group consisting of aluminum oxide (Al2O3), silicon dioxide (SiO2), aluminum titanate (Al2TiO5), and magnesium oxide (MgO). - In the producing
apparatus 1 described above, themolten metal remover 5 removes a surface portion of themolten metal 3 on the outer peripheral surface of thecooling roll 2. The surface portion of themolten metal 3 means a portion of a thickness of themolten metal 3 on the outer peripheral surface of thecooling roll 2 that is larger than the width of the gap A between the outer peripheral surface of thecooling roll 2 and themolten metal remover 5. This cuts down the thickness of themolten metal 3 on the outer peripheral surface of thecooling roll 2. As a result, themolten metal 3 on the outer peripheral surface of thecooling roll 2 becomes thin. The reduction of themolten metal 3 in thickness makes the cooling rate of themolten metal 3 higher. Therefore, by producing a thin metal strip using the producingapparatus 1, it is possible to obtain thethin metal strip 6 including more refined grains. - The apparatus for producing a thin metal strip according to the present embodiment is not limited to the producing
apparatus 1 described above. - In the producing
apparatus 1 illustrated inFIG. 1 , themolten metal 3 is supplied from a lateral side of thecooling roll 2. However, themolten metal 3 can be supplied above thecooling roll 2. -
FIG. 4 is a cross-sectional view of a producingapparatus 10 according to another embodiment, which is different from that illustrated inFIG. 1 toFIG. 3 . Referring toFIG. 4 , thetundish 4 and thesupply end 7 are disposed above thecooling roll 2. Themolten metal remover 5 is disposed below thesupply end 7. The rest of the configuration of the producingapparatus 10 is the same as that of the producingapparatus 1. In the producingapparatus 10, themolten metal 3 is supplied from above thecooling roll 2 onto the outer peripheral surface of thecooling roll 2. The thickness of themolten metal 3 supplied onto the outer peripheral surface of thecooling roll 2 is cut down by themolten metal remover 5 as with the producingapparatus 1. As a result, the thickness of themolten metal 3 on the outer peripheral surface of thecooling roll 2 is reduced to the width of the gap A between the outer peripheral surface of thecooling roll 2 and themolten metal remover 5. - In the producing
apparatus 10, themolten metal 3 is cooled while descending from the top of thecooling roll 2 along the outer peripheral surface of thecooling roll 2. Meanwhile, in the producingapparatus 1 illustrated inFIG. 1 , themolten metal 3 is supplied from a lateral side of thecooling roll 2 in the same direction as the rotating direction of thecooling roll 2. In addition, themolten metal 3 is wound up by thecooling roll 2 to reach the top of thecooling roll 2 and then descends on the outer peripheral surface of thecooling roll 2 to be cooled. For that reason, in a case of using the producingapparatus 1, the time for which themolten metal 3 is in contact with the outer peripheral surface of thecooling roll 2 is long as compared with the producingapparatus 10. As a result, the cooling time of themolten metal 3 is long. In this case, the grains in thethin metal strip 6 are more refined. Consequently, the producingapparatus 1 illustrated inFIG. 1 , that is, disposing themolten metal remover 5 above thesupply end 7 of thetundish 4 is preferable. - The number of
molten metal removers 5 to be disposed may be one as illustrated inFIG. 1 toFIG. 4 , or a plurality ofmolten metal removers 5 may be disposed continuously in the rotating direction of thecooling roll 2. In a case where a plurality ofmolten metal removers 5 are disposed, the molten metal remover(s) 5 disposed on a downstream side in the rotating direction of thecooling roll 2 are disposed to be closer to thecooling roll 2 than the molten metal remover(s) 5 disposed on an upstream side in the rotating direction of thecooling roll 2. In addition, amolten metal remover 5 at a most downstream position in the rotating direction of thecooling roll 2 is disposed such that a gap A between themolten metal remover 5 and the outer peripheral surface of thecooling roll 2 becomes the narrowest. Disposing a plurality ofmolten metal removers 5 enables stepwise removal of themolten metal 3. In this case, a load applied to onemolten metal remover 5 is lower. In this case, moreover, precise control of the thickness of themolten metal 3 is facilitated. - The
molten metal remover 5 may be disposed in a direction along a normal line of thecooling roll 2 as illustrated inFIG. 1 toFIG. 4 or may be disposed in a direction different from a normal line of thecooling roll 2 as illustrated inFIG. 5 . InFIG. 5 , themolten metal remover 5 is disposed such as to incline from a normal direction of thecooling roll 2 toward the rotating direction of thecooling roll 2. In this case, it is easy to remove a portion of themolten metal 3 on the outer peripheral surface of thecooling roll 2 that is higher than the width of the gap A. In other words, it is easy to cut down the thickness of themolten metal 3 on the outer peripheral surface of thecooling roll 2. InFIG. 5 , moreover, themolten metal remover 5 is configured to have a cross sectional shape different from that illustrated inFIG. 1 toFIG. 4 , which will be described later. In this case, the removal of themolten metal 3 can be performed even more efficiently. The direction of themolten metal remover 5 is set as appropriate such that the cut-down of the thickness of themolten metal 3 is easy. - The cross sectional shape of the
front edge portion 50 of the molten metal remover 5 (an edge of themolten metal remover 5 to be in contact with the molten metal 3) in a cross section perpendicular to the shaft of the roll may be a rectangle as illustrated inFIG. 1 toFIG. 4 or may be in another shape. Another shape may be, for example, a triangle as illustrated inFIG. 6 . Alternatively, as illustrated inFIG. 5 andFIG. 7 , thefront edge portion 50 of themolten metal remover 5 may be in a shape in which the width of a gap between thefront edge portion 50 of themolten metal remover 5 on an entrance side for themolten metal 3 and the outer peripheral surface of thecooling roll 2 is different from the width of a gap between thefront edge portion 50 of themolten metal remover 5 on an exit side for themolten metal 3 and the outer peripheral surface of thecooling roll 2. The cross sectional shape of thefront edge portion 50 of themolten metal remover 5 is set as appropriate such that the thickness of themolten metal 3 is easily cut down. - [Producing Method]
- A method for producing the
thin metal strip 6 according to the present embodiment is a producing method using the producingapparatus - First, the
molten metal 3 is prepared. The composition of themolten metal 3 is set as appropriate in accordance with an intended composition of thethin metal strip 6. For example, in a case of producing Si alloy, themolten metal 3 contains, for example, one, or two or more selected from the group consisting of silicon (Si), titanium (Ti), chromium (Cr), vanadium (vanadium), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), copper (Cu), and tin (Sn), with the balance being impurities. In the case of producing a metal ribbon for a negative electrode active material used in a lithium secondary battery or the like, it is preferable to produce themolten metal 3 so as to obtain a metal ribbon having the chemical composition described below. Alternatively, in a case of producing an alloy material for a neodymium magnet, themolten metal 3 consists, for example, neodymium (Nd), boron (B), and iron (Fe), with the balance being impurities. Themolten metal 3 is produced by heating a raw material having the chemical composition described above to the fusing point of the raw material or higher. - By putting the raw material having the chemical composition described above in a crucible and heating the raw material, the
molten metal 3 is produced. Examples of the method of the heating include high-frequency induction heating, arc heating, plasma arc heating, electric resistance heating, and electron beam heating. A heating temperature is not particularly limited as long as the heating temperature is equal to or higher than the liquidus temperature of the raw material. In a case of producing a Si alloy, the heating temperature is, for example, 1200° C. or more, more preferably 1500° C. or more. In a case of producing an alloy material for a magnet, the heating temperature is, for example, 1000° C. or more. - [Supplying Step]
- In the supplying step, the
molten metal 3 in thetundish 4 is supplied onto the outer peripheral surface of thecooling roll 2. First, themolten metal 3 is supplied from the crucible to thetundish 4. The supply of themolten metal 3 from the crucible to thetundish 4 may be made by tilting the crucible to pour themolten metal 3 directly. Alternatively, a nozzle or the like may be used to supply themolten metal 3 from the crucible to thetundish 4. Subsequently, from thesupply end 7 of thetundish 4, themolten metal 3 is supplied onto the outer peripheral surface of thecooling roll 2. Thecooling roll 2 rotates, as described above, about thecentral axis 9 of thecooling roll 2 at a given speed. When themolten metal 3 supplied from thetundish 4 comes into contact with the outer peripheral surface of thecooling roll 2, themolten metal 3 is partially solidified to be transferred to thecooling roll 2. Themolten metal 3 moves with the rotation of thecooling roll 2. At this point, a surface of themolten metal 3 not in contact with the outer peripheral surface of the cooling roll 2 (free surface) is in a liquid state or a semi-solidified state. - In the supplying step, the
tundish 4 may always be heated. In this case, the melted state of themolten metal 3 having a high fusing point can be maintained. Therefore, themolten metal 3 can be removed by themolten metal remover 5 while being in the melted state. A heating temperature is not particularly limited as long as the heating temperature is equal to or higher than the liquidus temperature of the raw material. In a case of producing a Si alloy, the heating temperature is, for example, 1200° C. or more, and a more preferable heating temperature is 1500° C. or more. In a case of producing an alloy material for a magnet, the heating temperature is, for example, 1000° C. or more. - [Rapid Cooling Step]
- In the rapid cooling step, the
molten metal 3 on the outer peripheral surface is rapidly cooled with thecooling roll 2 to be formed into thethin metal strip 6. The rapid cooling step is started when themolten metal 3 is supplied onto the outer peripheral surface of thecooling roll 2 in the supplying step described above. In the rapid cooling process, themolten metal 3 is cooled from a solidified portion. - In the rapid cooling step, the
cooling roll 2 includes a cooling zone that lies downstream of thetundish 4 in the rotating direction of thecooling roll 2 but does not reach themolten metal remover 5. In the cooling zone, themolten metal 3 supplied onto the outer peripheral surface of thecooling roll 2 includes a free surface. Therefore, rapid cooling is enabled. If themolten metal 3 has no free surface, that is, if the solidified portion is covered with another portion ofmolten metal 3, the solidified portion cannot be subjected to sufficient heat dissipation. This is because heat is continuously added to the solidified portion from themolten metal 3 lying on the solidified portion. In the cooling zone, themolten metal 3 is made to have the free surface by being supplied onto the outer peripheral surface of thecooling roll 2. Therefore, the solidified portion can be subjected to sufficient heat dissipation, which enables the rapid cooling. As a result, thethin metal strip 6 including more refined grains can be produced. - [Thickness Adjustment Step]
- In the thickness adjustment step, the thickness of the
molten metal 3 on the outer peripheral surface of thecooling roll 2 is cut down by themolten metal remover 5, in the middle of the rapid cooling step, to the width of the gap A between the outer peripheral surface of thecooling roll 2 and themolten metal remover 5. Immediately after supplied onto the outer peripheral surface of thecooling roll 2, themolten metal 3 is not solidified as a whole but gradually solidified from a solidified portion. The free surface of themolten metal 3 comes into contact with themolten metal remover 5, in a liquid state or a semi-solidified state. The hardness of themolten metal 3 in the liquid state or the semi-solidified state is low. Therefore, when the thickness of themolten metal 3 is larger than the width of the gap A, the free surface of themolten metal 3 in the liquid state or the semi-solidified state is blocked or removed. Themolten metal 3 thereby becomes thin. As themolten metal 3 is thinner, the cooling rate of themolten metal 3 increases. As a result, thethin metal strip 6 including more refined grains can be produced. - The disposition of the
heat dissipation surface 8 enables themolten metal 3 to be subjected to heat dissipation from theheat dissipation surface 8 as well as the solidified portion. In this case, the cooling rate of themolten metal 3 becomes high. The area and shape of theheat dissipation surface 8 are set as appropriate. For example, as illustrated inFIG. 8 , by forming thefront edge portion 50 of themolten metal remover 5 into an L shape, the area of theheat dissipation surface 8 can be increased. In this case, the cooling rate of themolten metal 3 can be made higher. - The
molten metal 3 reduced in thickness through the thickness adjustment step is subsequently cooled on thecooling roll 2. At this point, themolten metal 3 is thin. Therefore, the cooling rate is remarkably high. As a result, grains in thethin metal strip 6 are fine. The entiremolten metal 3 is solidified into thethin metal strip 6. Thethin metal strip 6 is separated from the outer peripheral surface of thecooling roll 2 and collected. Through the above steps, thethin metal strip 6 according to the present embodiment can be produced. - [Production of Thin Metal Strip for Negative Electrode Active Material]
- As a negative electrode active material made of a metal, it is preferable that the ratio of a phase having D03 structure in Strukturbericht notation (hereinafter also referred to as D03 phase) is large. When pulverizing the thin metal strip and using it as a negative electrode active material (powder) for a lithium secondary battery, the D03 phase acts as a host for occlusion and release a lithium. Therefore, the greater the ratio of D03 phase in the metal strip is, the better the electric capacity and the cycle life of a battery are.
- In the manufacturing method of this embodiment, it is easy to generate D03 phase. Therefore, it is suitable for the production of a metal ribbon for a negative electrode active material used in a lithium secondary battery.
- A preferable chemical composition of the thin metal strip as a negative electrode active material is Sn, with the balance being Cu and impurities. More preferably, the chemical composition of the thin metal strip contains 10 to 20 at % or 21 to 27 at % of Sn, with the balance being Cu and impurities. In the chemical composition of the thin metal strip, the more preferable Sn content is 13 to 16 at %, 18.5 to 20 at %, or 21 to 27 at %.
- The chemical composition may contain 10 to 20 at % or 21 to 27 at % of Sn, and one or more selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Al, Si, B, and C, with the balance being Cu and impurities. More specifically, the above chemical composition may contain: Sn: 10 to 20 at % or 21 to 27 at % of Sn, and one or more selected from the group consisting of Ti: 9.0 at % or less, V: 49.0 at % or less, Cr: 49.0 at % or less, Mn: 9.0 at % or less, Fe: 49.0 at % or less, Co: 49.0 at % or less, Ni: 9.0 at % or less, Zn: 29.0 at % or less, Al: 49.0 at % or less, Si: 49.0 at % or less, B: 5.0 at % or less, and C: 5.0 at % or less, with the balance being Cu and impurities.
- Using a producing apparatus described in the following Example 1 to Example 3, thin metal strips made of Si alloy were produced. A raw material contained nickel (Ni), titanium (Ti), and silicon (Si). The composition of the raw material was, in mass ratio, Ni:Ti:Si=25:17:58. One kilogram of the raw material in a mixed state was heated to 1450° C. to be produced into molten metal. The molten metal was supplied from the tundish onto the cooling roll. The cooling roll was one the outer peripheral surface of which is covered with copper and the inside of which is cooled by water. The cooling roll had a diameter of 20 cm and a width of 18 cm. The peripheral speed of the roll was 120 m/min. The thin metal strips made of Si alloy obtained in Example 1 to Example 3 were cut, and cross sections were observed under a scanning electron microscope (SEM).
- In Example 1, the producing apparatus according to the present embodiment was used to produce a thin metal strip made of Si alloy. In other words, the thin metal strip made of Si alloy was produced using the molten metal remover. The molten metal remover was a flat alumina plate having a thickness of 3 mm. The width of the gap between the molten metal remover and the outer peripheral surface of the cooling roll was 80 μm.
- In Example 2, a thin metal strip made of Si alloy was produced using the producing apparatus according to the present embodiment from which the molten metal remover was detached. In other words, the thin metal strip made of Si alloy was produced without using the molten metal remover.
- In Example 3, a thin metal strip made of Si alloy was produced under the same conditions as those of Example 1 except that a producing apparatus with no cooling zone on the cooling roll in a region between the tundish and the molten metal remover was used. In other words, without the free surface, the molten metal was supplied to the molten metal remover.
-
FIG. 9 is a picture of a cross section of the thin metal strip produced by the producing method according to the present embodiment (with the molten metal remover), taken under the electron microscope (SEM). The thin metal strip produced by the method according to the present embodiment had an average coating thickness of 80 μm. In addition, the size of a grain in a Si phase of the thin metal strip produced by the method according to the present embodiment (equivalent to the width of a gray portion inFIG. 9 ) was not more than 2 μm. -
FIG. 10 is a picture of a cross section of the thin metal strip produced by a conventional method (without the molten metal remover), taken under the electron microscope (SEM). The thin metal strip produced by the conventional method had an average coating thickness of 440 μm. In addition, the size of a grain in a Si phase of the thin metal strip produced by the conventional method (equivalent to the width of a gray portion inFIG. 10 ) was 20 to 30 μm. - In Example 3, in which the production was made by removing the molten metal without the free surface with the molten metal remover, the size of a grain in a Si phase of the thin metal strip was 10 to 15 μm.
- From the above, the method according to the present embodiment provides a thin metal strip with finer crystal grain than the conventional method.
- Metallic ribbons were produced under various producing conditions. Each of the thin metal strip had a chemical composition, containing 20.0 at % of Sn and 8.0 at % of Si, with the balance being Cu and impurities. The ratio (mass %) of D03 phase (phase having D03 structure) in the produced thin metal strip was determined.
- [Experimental Method]
- Initially, molten metals with the chemical composition of
test numbers 1 to 8 shown in Table 1 were prepared. -
TABLE 1 Gap between Cooling Blade Roll Member D03Fase Peripheral and Ratio in Melting Speed Cooling Cooling Thin Test Temperature (m/ Roll Blade Roll Strip No. Chemical Composition of Alloy (° C.) minute) Surface Member (μm) (mass %) Note 1 Cu—20.0at % Sn—8.0at % Si 1250 120 Cu Installed 109 77.8 Inventive Example 2 Cu—20.0at % Sn—8.0at % Si 1250 360 Cu Installed 89 78.1 Inventive Example 3 Cu—20.0at % Sn—8.0at % Si 1250 360 Cr Installed 89 44.9 Inventive plated Example 4 Cu—20.0at % Sn—8.0at % Si 1250 120 Cr Not — 6.9 Comparative plated installed Example 5 Cu—20.0at % Sn—7.0at % Si—1.0at % Ti 1250 360 Cu Installed 89 70.2 Inventive Example 6 Cu—20.0at % Sn—7.0at % Si—1.0at % V 1250 360 Cu Installed 89 71.6 Inventive Example 7 Cu—20.0at % Sn—6.0at % Si—1.0at % Al—1.0at % Zn 1250 360 Cu Installed 89 72.5 Inventive Example 8 Cu—20.0at % Sn—6.0at % Si—1.0at % Cr—1.0at % Ni 1250 360 Cu Installed 89 68.3 Inventive Example - The composition of raw material of the molten metal was Cu:Sn:Si=63.8:33.1:3.1 by mass ratio at each test number. 1 kg of the raw material was heated to 1250° C. to produce molten metal.
- Using the molten metal described above, in
test numbers 1 to 3 and 5 to 8, thin metal strips were produced by the production method (with a blade member) of this embodiment. Intest number 4, a thin metal strip was produced by a conventional manufacturing method (without a blade member). - Specifically, molten metal of each test number was provided onto the cooling roll from the tundish. The composition of the coating film on the surface of the cooling roll used was as shown in Table 1. That is, in test numbers. 1 and 2, the surface of the cooling roll was Cu, and in
test numbers - With the peripheral velocity of the cooling roll shown in Table 1, molten metal was provided onto the cooling role at the temperature shown in Table 1 to produce a thin metal strip. At this time, in test numbers. 1 to 3, a blade member was used. The material of the blade member was alumina and the blade member was a flat plate having a thickness of 3 mm. The gap between the blade member and the cooling roll of each
test numbers 1 to 3 was as shown in Table 1. Intest number 4, no blade member was used. - The ratio occupied by D03 phase in the produced thin metal strips of each
test numbers 1 to 8 was determined by the following method. - X-ray diffraction measurement was conducted on the thin metal strips and measurement data of the X-ray diffraction profile was obtained. Specifically, an X-ray diffraction profile of the thin metal strip was obtained, using a SmartLab (rotor target
maximum output 9 KW; 45 kV-200 mA) manufactured by Rigaku Corporation. Based on the obtained X-ray diffraction profile (measured data), the crystal structure in the thin metal strip was analyzed by the Rietveld method. The X-ray diffraction apparatus and measurement conditions are described below. - (X-Ray Diffraction Apparatus and Measurement Conditions)
-
- Apparatus: SmartLab manufactured by Rigaku Corporation
- X-ray tube: Cu—Kα ray
- X-ray output: 40 kV, 200 mA
- Incident monochrometer: Johannson type crystal (which filters out Cu-Kα2 ray and Cu—Kβ ray)
- Optical system: Bragg-Brentano geometry
- Incident parallel slit: 5.0 degrees
- Incident slit: ½ degrees
- Length limiting slit: 10.0 mm
- Receiving slit 1: 8.0 mm
- Receiving slit 2: 13.0 mm
- Receiving parallel slit: 5.0 degrees
- Goniometer: SmartLab goniometer
- X-ray source—mirror distance: 90.0 mm
- X-ray source—selection slit distance: 114.0 mm
- X-ray source—sample distance: 300.0 mm
- Sample—receiving
slit 1 distance: 187.0 mm - Sample—receiving
slit 2 distance: 300.0 mm - Receiving
slit 1—receivingslit 2 distance: 113.0 mm - Sample—detector distance: 331.0 mm
- Detector: D/Tex Ultra
- Scan range: 10 to 120 degrees
- Scan step: 0.02 degrees
- Scan mode: Continuous scan
- Scanning speed: 0.1 degrees/min
- The crystal structure of D03 phase is cubic, and in terms of classification of a space group, No. 225(Fm-3m) of International Table (Volume-A).
- Accordingly, with the structure model of this space group number being as the initial structure model of Rietveld analysis, a calculated value of diffraction profile (hereinafter, referred to as a calculated profile) of each thin metal strip was found by Rietveld method. Rietan-2000 (program name) was used for Rietveld analysis.
- From the each diffraction peaks at the powder X-ray diffraction profile and the Rietveld method, the existence of D03 phase in the thin metal strips was confirmed. When the D03 phase was present, the ratio (mass %) of the D03 phase was determined.
- [Result of Evaluation]
- The ratio of D03 phase is shown in Table 1. Referring to Table 1, the ratio of D03 phase in the thin metal strips of
test numbers 1 to 3 and 5 to 8 produced by the product method (with a blade member) of the present embodiment was higher than the ration of D03 phase in the thin metal strip oftest number 4 produced by the conventional production method). - Furthermore, when comparing
test numbers 1 to 3 and 5 to 8, when the surface of the cooling roll was Cu, the ratio of D03 phase was higher as compared with the case of the Cr plating film on the surface of the cooling roll. It is thought that Cu had a higher heat transfer property than the Cr plating film and it was easy to quench the molten metal. - The embodiment according to the present invention has been described above. However, the aforementioned embodiment is merely an example for practicing the present invention. Therefore, the present invention is not limited to the aforementioned embodiment, and the aforementioned embodiment can be modified and implemented as appropriate without departing from the scope of the present invention.
-
- 1, 10 producing apparatus
- 2 cooling roll
- 3 molten metal
- 4 tundish
- 5 molten metal remover
- 6 thin metal strip
- 7 supply end
- 8 heat dissipation surface
Claims (20)
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JP2015233354 | 2015-11-30 | ||
JP2015-233354 | 2015-11-30 | ||
JP2016099864 | 2016-05-18 | ||
JP2016-099864 | 2016-05-18 | ||
PCT/JP2016/085458 WO2017094741A1 (en) | 2015-11-30 | 2016-11-29 | Device for manufacturing thin metal strip, and method of manufacturing thin metal strip employing same |
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US20190176224A1 true US20190176224A1 (en) | 2019-06-13 |
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US15/779,741 Abandoned US20190176224A1 (en) | 2015-11-30 | 2016-11-29 | Apparatus for producing thin metal strip and method for producing thin metal strip using the same |
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US (1) | US20190176224A1 (en) |
JP (1) | JP6593453B2 (en) |
KR (1) | KR102070271B1 (en) |
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WO (1) | WO2017094741A1 (en) |
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- 2016-11-29 CN CN201680069534.7A patent/CN108290212A/en active Pending
- 2016-11-29 KR KR1020187018138A patent/KR102070271B1/en active IP Right Grant
- 2016-11-29 WO PCT/JP2016/085458 patent/WO2017094741A1/en active Application Filing
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US4771819A (en) * | 1985-04-12 | 1988-09-20 | Nippon Metal Industry Co., Ltd. | Manufacturing apparatus for sheet metal according to continuous casting |
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JPWO2017094741A1 (en) | 2018-09-13 |
WO2017094741A1 (en) | 2017-06-08 |
JP6593453B2 (en) | 2019-10-23 |
CN108290212A (en) | 2018-07-17 |
KR20180088854A (en) | 2018-08-07 |
KR102070271B1 (en) | 2020-01-28 |
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