JP3651538B2 - Metal strip manufacturing apparatus and method - Google Patents

Description

【００７３】
【発明の効果】
以上説明のように、本発明によると、チャンバのような大がかりで、かつ作業性に劣る付帯設備を設けることなく溶湯ノズル近傍雰囲気の酸素濃度を低減し、連続生産をすることが可能となった。
特に本発明において、ロール表面大気遮断板を備えるとともに、ロール側面大気遮断板を備えること、ガスフロー供給手段を２つ、溶湯ノズルを基準として後方側であって、ロール表面大気遮断手段と溶湯ノズルの間に配置し、しかも、一方のガスフロー供給手段のガスフローを溶湯ノズル先端に望むようにしてそのガスに他方のガスフロー供給手段からのガスを供給できるようにすることで、付帯設備を設けることなく溶湯ノズル近傍雰囲気の酸素濃度を低減できるという効果を確実に得ることができる。
【図面の簡単な説明】
【図１】 本発明金属薄帯製造装置の１実施の形態を示す側面図である。
【図２】 第１のガスフローノズルを示す図である。
【図３】 第３のガスフローノズルを示す図である。
【図４】 第２及び第４のガスフローノズルを示す図である。
【図５】 ロール表面大気遮断板の配置を示す図である。
【図６】 ロール後方大気遮断板及びロール側面大気遮断板の配置を示す図である。
【図７】 ロール外周大気遮断板及びロール前方大気遮断板の配置を示す図である。
【図８】 ロール正面上大気遮断板及びロール正面大気遮断板の配置を示す図である。
【図９】 本発明金属薄帯製造装置の他の実施形態を示す側面図である。
【図１０】 実施例１における酸素濃度の変動を示すグラフである。
【図１１】 実施例１における冷却ロール表面からの距離と酸素濃度の関係を示すグラフである。
【図１２】 実施例２における酸素濃度の変動を示すグラフである。
【図１３】 実施例３における酸素濃度の変動を示すグラフである。
【図１４】 実施例４における酸素濃度の変動を示すグラフである。
【図１５】 実施例５における酸素濃度の変動を示すグラフである。
【図１６】 実施例６における酸素濃度の変動を示すグラフである。
【図１７】 実施例７における酸素濃度の変動を示すグラフである。
【図１８】 実施例８における酸素濃度の変動を示すグラフである。
【図１９】 実施例９における酸素濃度の変動を示すグラフである。
【図２０】 実施例１０における酸素濃度の変動を示すグラフである。
【図２１】 実施例１１における酸素濃度の変動を示すグラフである。
【図２２】 実施例１２における酸素濃度の変動を示すグラフである。
【図２３】 実施例１３における酸素濃度の変動を示すグラフである。
【図２４】 実施例１４における酸素濃度の変動を示すグラフである。
【図２５】 実施例１５におけるリボン長さと板厚、ピンホール数の関係を示す図である。
【図２６】 （ａ）Ａｒガスを用いた場合のパドル部分の状態を示す図、（ｂ）Ｎ₂ガスを用いた場合のパドル部分の状態を示す図である。
【図２７】 実施例１５におけるリボン長さと薄帯自由表面の表面粗さの関係を示すグラフである。
【図２８】 実施例１５におけるリボン長さと薄帯ロール面の表面粗さの関係を示すグラフである。
【図２９】 実施例１５においてＮ₂ガスを用いた薄帯のＸ線回折を示す図である。
【図３０】 実施例１５においてＡｒガスを用いた薄帯のＸ線回折を示す図である。
【図３１】 実施例１５において得られた薄帯の透磁率（μ'）を示すグラフである。
【図３２】 実施例１５において得られた薄帯の保持力（Ｂs）、保磁力（Ｈｃ）を示すグラフである。
【図３３】 単ロール法による薄帯製造を示す図である。
【符号の説明】
１・・・冷却ロール
２・・・溶湯ノズル
３・・・るつぼ
４・・・加熱コイル
５１・・・第１のガスフローノズル
５２・・・第２のガスフローノズル
５３・・・第３のガスフローノズル
５４・・・第４のガスフローノズル
６１・・・ロール表面大気遮断板
６２・・・ロール後方大気遮断板
６３・・・ロール側面大気遮断板
６４・・・ロール外周大気遮断板
６５・・・ロール前方大気遮断板
６６・・・ロール正面上大気遮断板
６７・・・ロール正面大気遮断板[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an apparatus and a manufacturing method for manufacturing a metal ribbon such as an amorphous metal.
[0002]
[Prior art]
As a method for producing a metal ribbon, a single roll method using a single cooling roll is currently most popular. FIG. 33 shows the main part of the apparatus for carrying out the single roll method. By rotating the cooling roll 101 at a high speed and ejecting the molten metal 103 from the molten metal nozzle 102 close to the top of the cooling surface, While the molten metal 103 is rapidly cooled and solidified on the cooling surface of the cooling roll 101, the molten metal 103 is drawn out in the rotation direction of the cooling roll (arrow A direction).
[0003]
The molten metal 103 ejected from the molten metal nozzle 102 forms a pool (hereinafter “paddle”) 104 between the tip of the molten metal nozzle 102 and the cooling surface of the cooling roll 101, and sequentially from the paddle 104 as the cooling roll 101 rotates. The molten metal 103 is pulled out and rapidly solidified on the surface of the cooling roll 101, and the ribbon 105 is continuously formed.
[0004]
When the material used for the single roll method has a composition that is easily oxidized, the melt nozzle 102 may be clogged due to the oxidation of the material, and the ejection of the molten metal may be delayed. In order to solve this problem, conventionally, the entire thin ribbon manufacturing apparatus is placed in a chamber, and the inside of the chamber is made an inert gas atmosphere, thereby reducing the oxygen concentration in the vicinity of the molten metal nozzle and oxidizing the material. A method for preventing this problem has been proposed.
[0005]
[Problems to be solved by the invention]
The method of setting the inside of the chamber to an inert gas atmosphere is an extremely effective means for preventing clogging of the molten metal nozzle, but has a problem in terms of workability because the entire apparatus is inside the chamber. For example, a complicated operation of opening the chamber for each charge, loading the molten base material into a melting furnace or a crucible, sealing the chamber again, and replacing with an inert gas atmosphere is necessary. There is also a problem that the cost of incidental equipment for maintaining the inside of the chamber in an inert gas atmosphere is high.
[0006]
Accordingly, it is an object of the present invention to provide an apparatus and a method for manufacturing a ribbon that can reduce the oxygen concentration in the atmosphere near the molten metal nozzle without providing a large facility such as a chamber and inferior workability. To do.
[0007]
[Means for Solving the Problems]
In order to prevent clogging of the molten metal nozzle, if the amount of oxygen can be reduced by making only the vicinity of the molten metal nozzle an inert gas atmosphere, it is necessary to place the entire ribbon production apparatus in an inert gas atmosphere as before. There is no. And if it is the installation which makes only the molten metal nozzle vicinity inert gas atmosphere, it will become possible to aim at the improvement of workability | operativity compared with the conventional chamber, and reduction of equipment cost.
Therefore, the present inventors focused attention on this point and conducted an examination. As a result, an inert gas was supplied around the molten metal nozzle for ejecting molten metal, and the entrainment of the atmosphere around the molten nozzle due to the rotation of the cooling roll was prevented. It has been found that the amount of oxygen around the molten metal nozzle can be efficiently reduced by arranging the air blocking plate to be disposed at an appropriate position.
[0008]
  The present invention has been made on the basis of the above knowledge, and is disposed on both sides of the cooling roll, a cooling roll having a cooling surface for cooling the molten metal, a molten metal nozzle for ejecting the molten metal to the cooling surface, and the like. A roll side air blocking plate that is provided over the entire circumference of the cooling roll and blocks air entrainment from the side of the cooling roll, and a gas flow supply means that supplies an inert gas around the molten metal nozzle, A roll surface atmospheric blocking means is provided, and the two gas flow supply means are arranged on the rear side with respect to the molten metal nozzle, and are arranged between the roll surface atmospheric blocking means and the molten nozzle and arranged on the rear side. The two gas flow supply means are slits of one gas flow supply means.And gas flowThe other gas flow supply means is arranged between the melt nozzle and the one gas flow supply means, and the other gas flow supply means is disposed on the gas flow from the one gas flow supply means. A gas flow is supplied from the gas flow supply means, and the roll surface air blocking means is on the rear side with respect to the molten metal nozzle, and to the paddle portion of the air adhering to the surface of the cooling roll. It is a metal strip manufacturing apparatus characterized by being arranged so that the inflow of water is cut off and the tip portion is in contact with the cooling roll.
[0009]
  In the present invention, the gas flow supply means can be arranged on either the front side, the rear side, or both with respect to the molten metal nozzle. In the present invention, on the basis of the molten metal nozzle, the side in the roll rotation direction is defined as “front” and the opposite is defined as “rear”. As for the arrangement of the molten metal nozzles, there are two on the rear side.EstablishmentThe two gas flow supply means disposed on the rear side are preferably slits of one gas flow supply means, as will be described in particular in the embodiments described later.And gas flowAnd the other gas flow supply means is disposed between the melt nozzle and the one gas flow supply means, and the other gas flow supply means is disposed on the gas flow from the one gas flow supply means. It is more desirable to supply the gas flow from the gas flow supply means.
[0010]
  In the present invention, it is preferable that a roll outer peripheral air blocking plate is provided, and the roll outer peripheral air blocking plate is disposed so as to surround the outer periphery of the cooling roll at the outer peripheral edge of the roll side air blocking plate.The specific structure of the air shielding plate will be shown in the embodiments described later.
[0011]
The method for producing a metal ribbon of the present invention is a method for producing a metal ribbon by continuously injecting molten metal from a molten metal nozzle onto a cooling surface of a cooling roll and rapidly solidifying it. An inert gas is supplied to the periphery of the molten metal nozzle while blocking inflow of air from the side.
In the method for producing the metal ribbon of the present invention, it is desirable to supply the inert gas before rotating the cooling roll. This is because, as will be apparent from the examples described later, the oxygen concentration decreases more quickly when the gas flow is performed before the cooling roll is rotated than when the inert gas is supplied after the cooling roll is rotated. is there. Therefore, it is desirable in terms of production efficiency if the oxygen concentration in the atmosphere near the molten metal nozzle is measured and the cooling roll is rotated after reaching a predetermined oxygen concentration.
[0012]
In the present invention, the inert gas may be supplied under conditions of a flow rate of 2 to 100 m / sec and a flow rate of 5 to 120 l / sec. If the flow velocity is less than 2 m / sec, there is no effect in reducing the amount of oxygen in the atmosphere near the molten metal nozzle, while if it exceeds 100 m / sec, the effect of reducing the oxygen concentration is reduced due to the entrainment of the atmosphere from the surroundings due to the gas flow. Because. Also, if the flow rate is less than 5 l / sec, there is no effect in reducing the oxygen amount in the atmosphere near the molten metal nozzle, while if it exceeds 120 l / sec, no effect commensurate with the supply amount can be expected.
[0013]
The inert gas can be supplied from one or both of the rear side and the front side with reference to the molten metal nozzle. It is desirable to supply two gas flows from the rear side and one gas flow from the front side. In this case, if one of the two gas flows from the rear side is supplied from the tangential direction of the cooling roll and the other gas flow is supplied from above the one gas flow, the effect of reducing the oxygen concentration is remarkable. It becomes.
[0014]
In that case, of the two gas flows from the rear side, the one gas flow (first gas flow) has a flow rate of 10 to 35 m / sec, a flow rate of 5 to 20 l / sec, and the other gas flow (second gas flow). Gas flow) is a flow rate of 2 to 10 m / sec, a flow rate of 5 to 20 l / sec, and a gas flow supplied from the front side (third gas flow) is a flow rate of 10 to 50 m / sec and a flow rate of 5 to 20 l / sec. It is desirable. The more desirable ranges of the first to third gas flows are as follows: first gas flow; flow rate 15 to 25 m / sec; flow rate 5 to 15 l / sec; second gas flow; flow rate 3 to 7 m / sec; flow rate 5-15 l / sec, third gas flow; flow rate 30-45 m / sec, flow rate 5-15 l / sec.
[0015]
  The above gas flow is relatively local at a position close to the molten metal nozzle. However, in order to supplement this, the gas flow extends over a wide range including at least the cooling roll from above, below, and / or from the side. It is also effective to supply a gas flow. As an inert gas used in the method for producing a metal ribbon of the present invention, N₂, He, Ar, Kr, Xe and Rn are selected from one or more of them, and Ar is desirable as will be apparent from the examples described later.
  Further, in the previous manufacturing method, a cooling roll having a cooling surface for cooling the molten metal, a molten metal nozzle for ejecting the molten metal to the cooling surface, and both side surfaces of the cooling roll, the entire cooling roll is disposed. A roll side air blocking plate that is provided over the circumference and blocks air entrainment from the side surface of the cooling roll, a gas flow supply unit that supplies an inert gas around the molten metal nozzle, and a roll surface air blocking unit. The two gas flow supply means are arranged on the rear side with respect to the melt nozzle, and are arranged between the roll surface atmosphere blocking means and the melt nozzle, and are arranged on the rear side. Is the slit of one gas flow supply meansAnd gas flowThe other gas flow supply means is arranged between the melt nozzle and the one gas flow supply means, and the other gas flow supply means is disposed on the gas flow from the one gas flow supply means. A gas flow is supplied from the gas flow supply means, and the roll surface air blocking means is on the rear side with respect to the molten metal nozzle, and to the paddle portion of the air adhering to the surface of the cooling roll. Injecting molten metal continuously from the molten metal nozzle to the cooling surface of the cooling roll using a metal ribbon manufacturing apparatus characterized in that the inflow of the metal is cut off and the tip portion is arranged to contact the cooling roll. It is preferable to produce a metal ribbon by rapid solidification.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the metal ribbon manufacturing apparatus of the present invention will be described below with reference to FIGS.
FIG. 1 is a side view showing a basic configuration part (excluding some atmospheric shielding plates) of a metal ribbon manufacturing apparatus of the present invention, and FIGS. 2 to 4 are diagrams showing details of a gas flow nozzle as gas flow supply means, 5-8 is a figure for demonstrating each atmospheric | air barrier board and its arrangement position.
The metal ribbon manufacturing apparatus according to the present embodiment includes a cooling roll 1, a molten metal nozzle 2 connected to the lower end of a crucible 3 for holding molten metal, a heating coil 4 wound and arranged on the outer periphery of the crucible 3, It is basically composed of first to fourth gas flow nozzles 51 to 54 for flowing the active gas, and atmospheric blocking plates 61 to 67 for the purpose of blocking atmospheric inflow to the vicinity of the molten metal nozzle.
[0017]
The cooling roll 1 is rotationally driven in an arrow (counterclockwise) direction by a motor (not shown). It is desirable that at least the surface of the cooling roll 1 is made of carbon steel, for example, an Fe-based alloy such as JIS S45C, brass (Cu—Zn alloy), or pure Cu. When at least the surface of the cooling roll 1 is brass or pure Cu, the thermal conductivity is high, so that the cooling effect is high and suitable for quenching the molten metal. In order to improve the cooling effect, it is desirable to provide a water cooling structure inside.
[0018]
The molten metal melted in the crucible 3 is ejected from the molten metal nozzle 2 at the lower end. The upper part of the crucible 3 is connected to a gas supply source 8 such as Ar gas through the supply pipe 7, and a pressure adjusting valve 9 and an electromagnetic valve 10 are incorporated in the supply pipe 7. A pressure gauge 11 is incorporated between the pressure regulating valve 9 and the electromagnetic valve 10. An auxiliary pipe 12 is connected in parallel to the supply pipe 7, and a pressure adjustment valve 13, a flow rate adjustment valve 14, and a flow meter 15 are incorporated in the auxiliary pipe 12. Therefore, a gas such as Ar gas is supplied from the gas supply source 8 into the crucible 3 and the molten metal is ejected from the molten metal nozzle 2 to the cooling roll 1.
[0019]
At the time of metal strip production, the cooling roll 1 is rapidly cooled on the surface of the cooling roll 1 by rotating the cooling roll 1 at a high speed and ejecting the molten metal from the nozzle 2 disposed near the top or slightly in front of the top. While solidifying, it is pulled out in the form of a belt in the rotation direction of the cooling roll 1. Although the molten metal outlet of the molten metal nozzle 2 has a rectangular shape, it is desirable that the blowing width (width in the rotation direction of the cooling roll 1) is about 0.2 to 0.8 mm. If it is less than 0.2 mm, clogging of the melt nozzle tends to occur depending on the composition of the melt, and if it exceeds 0.8 mm, sufficient cooling may be difficult.
[0020]
What is necessary is just to select the space | interval of the cooling roll 1 at the time of metal strip manufacture and the molten metal nozzle 2 in the range of 0.2-0.8 mm. If the thickness is less than 0.2 mm, it is difficult to eject the molten metal, which may cause damage to the molten metal nozzle 2, and if it exceeds 0.8 mm, it is difficult to produce a thin ribbon having good properties. The crucible 3 can be moved up and down by lifting means (not shown) so that the distance between the cooling roll 1 and the molten metal nozzle 2 can be adjusted. Since the surface of the chill roll 1 is expanded due to the temperature rise after the start of the production of the metal ribbon, the diameter of the chill roll 1 is increased. Therefore, the gap between the chill roll 1 and the molten metal nozzle 2 is gradually increased after the manufacture is started. It is desirable for producing a ribbon with high thickness accuracy.
[0021]
The first gas flow nozzle 51 is disposed on the rear side with respect to the molten metal nozzle 2. The first gas flow nozzle 51 is for flowing the gas from the substantially tangential direction behind the cooling roll 1 to the vicinity of the tip of the molten metal nozzle 2 (hereinafter referred to as a paddle portion). As shown in FIG. 3, the first gas flow nozzle 51 has a relatively thin slit 510 having a width of 5 mm, and flows gas at a relatively high flow rate.
[0022]
The second gas flow nozzle 52 is connected to the melt nozzle 2 in order to supply a gas flow that blocks the gas flow supplied from the first gas flow nozzle 51 from the atmosphere and prevents the atmosphere from being caught. The gas flow nozzle 51 is installed. As shown in FIG. 2, the second gas flow nozzle 52 has a slit 520 that is 20 mm wider than the first gas flow nozzle 51, and performs gas flow at a slower flow rate than the first gas flow.
[0023]
As shown in FIG. 4, the third gas flow nozzle 53 is formed by winding a Φ5 mm copper pipe having 10 Φ2 mm gas flow slits 530 opened at one end on the one end side in an arc shape. To place. The third gas flow nozzle 53 is installed for the purpose of preventing air from being caught inside the paddle by supplying gas so as to surround the melt nozzle 2 from the top to the bottom of the melt nozzle 2. is there.
[0024]
The fourth gas flow nozzle 54 is intended to prevent the inflow of air from the front front direction of the cooling roll 1. The shape of the fourth gas flow nozzle is the same as that of the second gas flow nozzle 52, but the slit width is as narrow as 2.5 mm.
The above first to fourth gas flow nozzles can be used alone or in combination. The oxygen reduction effect of the paddle portion is the largest in the first and second gas flow nozzles as described in the examples below.
[0025]
The above first to fourth gas flow nozzles are mainly intended for local gas flow. However, as shown in FIG. 1, like the fifth gas flow nozzle 55 and the sixth gas flow nozzle 56, A gas flow supply means for supplying a gas flow in a wide range including the diameter of the cooling roll 1 can also be provided. By performing a gas flow from the fifth gas flow nozzle 55 and the sixth gas flow nozzle 56, it is possible to further enhance the oxygen concentration reduction effect by the first to fourth gas flow nozzles. In addition, it is desirable that the supply amount of the gas flow by the fifth gas flow nozzle 55 and the sixth gas flow nozzle 56 is 25 to 100 l / sec, 20 to 120 l / sec, respectively.
[0026]
A gas supply source is connected to each of the above gas flow nozzles via a connection pipe 17 to which a pressure regulating valve 16 is connected, as illustrated for the first gas flow nozzle 51 of FIG.
[0027]
Next, the air blocking plate will be described.
The roll surface air blocking plate 61 is installed for the purpose of blocking the inflow of the air adhering to the surface of the cooling roll 1 to the paddle portion, and has a plate-like structure having a sharp tip. The sharp tip is disposed so as to contact the surface of the cooling roll 1 (see FIG. 5). Therefore, when the cooling roll 1 is rotated at a high speed, the atmosphere that adheres to the surface of the cooling roll 1 and flows into the paddle portion is blocked by scraping the roll surface atmospheric blocking plate 61. As shown in FIG. 1, since the first and second gas flow nozzles 51 and 52 are disposed between the roll surface atmospheric shielding plate 61 and the molten metal nozzle 2, Immediately after shutting off, an inert gas flow is supplied, and the effect of reducing the oxygen concentration in the paddle portion is improved. In order to more effectively block the inflow of air into the paddle part, a plurality of roll surface air blocking plates 61 may be provided.
[0028]
The roll rear air blocking plate 62 is installed for the purpose of blocking the inflow of air from the rear upper part of the cooling roll 1, and has a flat plate structure having a width larger than the width of the cooling roll 1 (FIG. 6). reference).
[0029]
The roll side air blocking plate 63 is installed for the purpose of blocking air entrainment from the side of the cooling roll 1, has a disk shape larger in diameter than the cooling roll 1, and has both sides of the cooling roll 1. It is in contact with the surface (see FIGS. 1 and 6).
[0030]
The roll outer peripheral air blocking plate 64 is disposed so as to surround the outer periphery of the cooling roll 1 at the outer peripheral edge of the roll side air blocking plate 63 (see FIG. 7). The air blocking effect by the roll surface air blocking plate 61 can be further improved.
[0031]
The roll front air blocking plate 65 is installed for the purpose of blocking the inflow of air from both front sides of the cooling roll 1, and extends from the roll side air blocking plate 63 to the front of the cooling roll 1. (See FIG. 7).
[0032]
The roll upper air blocking plate 66 is installed for the purpose of blocking the inflow of air from above the cooling roll 1, and the roll front air blocking plate 65 installed on both side surfaces of the cooling roll 1. It is mounted and fixed on the upper edge (see FIG. 8).
[0033]
The roll front air blocking plate 67 is installed for the purpose of blocking the inflow of air from the front facing the cooling surface of the cooling roll 1, and is fixed to the front end of the roll front air blocking plate 65. (See FIG. 8).
[0034]
Each of the above air shielding plates 61 to 67 can be used alone or in plural. When all the air shielding plates 61 to 67 are installed, the cooling roll 1 is almost surrounded, and the gas flow from the first to fourth gas flow nozzles 51 to 54 improves the oxygen concentration reduction effect of the paddle portion most. can do. In addition, when each of the above air blocking plates 61 to 67 is used alone, the effect of reducing the oxygen amount of the roll surface air blocking plate 61 and the roll side air blocking plate 63 is most remarkable.
[0035]
Since the ribbon manufacturing apparatus shown in FIG. 1 uses a crucible 3 having a small capacity, when a large amount of metal ribbon is continuously manufactured, the metal ribbon manufacturing apparatus having the basic configuration shown in FIG. The gas flow of the invention and the air blocking plate can be applied. 9, the molten metal 19 is held in the melting furnace 20, and is supplied to the tundish 22 from the bottom outlet of the melting furnace 20 through the outflow pipe 21. . A melt nozzle 2 is provided at the bottom of the tundish 22 and is ejected from the melt nozzle 2 onto the surface of the cooling roll 1 that rotates at a high speed and solidifies to form a ribbon. According to this apparatus, when the molten metal in the tundish 22 is reduced, the molten metal can be replenished to the tundish 22 sequentially from the melting furnace 20, so that it is suitable for continuous production.
[0036]
The following materials are effective as materials applicable to the present invention.
Fe_bB_xM_y
M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W (including any of Zr, Hf, and Nb), and b Is 75 atomic% to 93 atomic%, x is 0.5 atomic% to 18 atomic%, and y is 4 atomic% to 9 atomic%.
(Fe_1-aZ_a)_bB_xM_y
However, Z is one or two of Ni and Co, M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W (Zr, Hf , And Nb), a is 0.2 or less, b is 75 atom% or more and 93 atom% or less, x is 0.5 atom% or more and 18 atom% or less, and y is 4 atom% or more. 9 atomic% or less.
[0037]
Fe_bB_xM_yX_z
However, M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W (including Zr, Hf, and Nb), and X is Cu. , Ag, Cr, Ru, Rh, Ir, one or two or more elements selected, b is 75 atomic% or more and 93 atomic% or less, x is 0.5 atomic% or more and 18 atomic% or less, y Is 4 atomic% or more and 9 atomic% or less, and Z is 5 atomic% or less.
[0038]
(Fe_1-aZ_a)_bB_xM_yX_z
However, Z is one or two of Ni and Co, M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W (Zr, Hf X is one or more elements selected from Cu, Ag, Cr, Ru, Rh, and Ir, a is 0.2 or less, and b is 75 atoms. % Is 93 atomic% or less, x is 0.5 atomic% or more and 18 atomic% or less, y is 4 atomic% or more and 9 atomic% or less, and Z is 5 atomic% or less.
[0039]
Fe_bB_xM_yX '_t
However, M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W (including Zr, Hf, and Nb), and X ′ is One or more elements selected from Si, Al, Ge, Ga, b is 75 atomic% to 93 atomic%, x is 0.5 atomic% to 18 atomic%, y is 4 atoms % To 9 atomic%, t is 4 atomic% or less.
[0040]
(Fe_1-aZ_a)_bB_xM_yX '_t
Where Z is one or two of Ni and Co, and M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W (Zr, Hf X ′ is one or more elements selected from Si, Al, Ge, and Ga, a is 0.2 or less, and b is 75 atomic% or more 93 Atomic% or less, x is 0.5 atomic% or more and 18 atomic% or less, y is 4 atomic% or more and 9 atomic% or less, and t is 4 atomic% or less.
[0041]
Fe_bB_xM_yX_zX '_t
However, M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W (including Zr, Hf, and Nb), and X is Cu. , Ag, Cr, Ru, RhIr, one or more elements selected from X, X ′ is one or more elements selected from Si, Al, Ge, Ga, and b is 75 atoms. % Is 93 atom% or less, x is 0.5 atom% or more and 18 atom% or less, y is 4 atom% or more and 9 atom% or less, Z is 5 atom% or less, and t is 4 atom% or less.
[0042]
(Fe_1-aZ_a)_bB_xM_yX_zX '_t
However, Z is one or two of Ni and Co, M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W (Zr, Hf , And Nb), X is one or more elements selected from Cu, Ag, Cr, Ru, and RhIr, and X ′ is 1 selected from Si, Al, Ge, and Ga A or 0.2 or less, b is 75 to 93 atom%, x is 0.5 to 18 atom%, y is 4 to 9 atom% Hereinafter, Z is 5 atomic% or less, and t is 4 atomic% or less.
[0043]
If an amorphous alloy ribbon having the above composition is obtained according to the present invention and then subjected to a heat treatment of heating to its crystallization temperature or higher (eg, 500 to 600 ° C.) and slow cooling, 100 to 200 Å A soft magnetic alloy ribbon having a fine crystal structure composed of crystals can be obtained.
[0044]
【Example】
The result of investigating the variation of the inert gas flow time and the oxygen concentration using the metal ribbon manufacturing apparatus described above will be described. In the following examples, the cooling roll 1 having a diameter of 300 to 350 mm was used, and the position of the molten metal nozzle 2 was set at a position 4 mm ahead of the top of the cooling roll 1.
[0045]
Example 1
The oxygen concentration was measured when the gas flow nozzle and the air blocking plate were under the following conditions. N as flow gas₂The rotation speed of the cooling roll 1 was 1600 rpm (circumferential speed 27.6 m / sec). The oxygen concentration was measured using LC-700H manufactured by Toray Industries, Inc. at a position of 0.3 mm from the surface of the cooling roll 1 on the front side of the molten metal nozzle 2. In addition, it measured, without performing the ejection of a molten metal. The result is shown in FIG.₂It can be seen that the oxygen concentration (wt.%, The same applies hereinafter) after 3 minutes of gas supply can be reduced to about 4%.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7l / sec, flow rate 19m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Air blocking plate conditions
Roll surface air barrier plate, roll side air barrier plate
[0046]
Under the same conditions as above, the fluctuation of the oxygen concentration due to the distance from the surface of the cooling roll 1 was investigated. The result is shown in FIG. 11, but from the surface of the cooling roll 1 to about 1 mm, it is about the same as 0.4% or less.₂The gas layer is estimated to have a thickness of about 1 mm from the surface of the cooling roll 1. Since the gap between the surface of the cooling roll 1 and the molten metal nozzle 2 at the time of manufacturing the ribbon is about 0.3 mm, an inert gas atmosphere having a low oxygen concentration can be formed around the paddle at the time of actual ribbon manufacturing.
[0047]
(Example 2)
The oxygen concentration was measured when the gas flow nozzle and the air blocking plate were under the following conditions. Other conditions are the same as in the first embodiment. The results are shown in FIG. 12, and the effect of reducing the amount of oxygen similar to that in Example 1 could be confirmed.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7l / sec, flow rate 19m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Air barrier plate behind the roll
[0048]
(Example 3)
The oxygen concentration was measured when the gas flow nozzle and the air blocking plate were under the following conditions. Other conditions are the same as in the first embodiment. The results are shown in FIG. 13, and it was possible to confirm the same amount of oxygen reduction effect as in Example 1.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7l / sec, flow rate 19m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll air barrier plate, roll outer air barrier plate
[0049]
Example 4
The oxygen concentration was measured when the gas flow nozzle and the air blocking plate were under the following conditions. Other conditions are the same as in the first embodiment. The results are shown in FIG. 14, and it was confirmed that the oxygen concentration can be reduced from Examples 1 to 3 by performing the gas flow from the third gas flow nozzle.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7l / sec, flow rate 19m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Third gas flow nozzle (flow rate 10.7 l / sec, flow rate 76.0 m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll air barrier plate, roll outer air barrier plate
[0050]
(Example 5)
The oxygen concentration was measured when the gas flow nozzle and the air blocking plate were under the following conditions. Other conditions are the same as in the first embodiment. The result is shown in FIG. 15, and it was confirmed that the oxygen concentration can be reduced to about 2% lower than that of Example 4 by adding the upper front blocking plate 66.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7l / sec, flow rate 19m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Third gas flow nozzle (flow rate 10.7 l / sec, flow rate 76.0 m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
[0051]
(Example 6)
The oxygen concentration was measured when the gas flow nozzle and the air blocking plate were under the following conditions. Other conditions are the same as in the first embodiment. The results are shown in FIG. 16, and it was confirmed that the oxygen concentration can be reduced to 2% or less.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7 l / sec, flow rate 19.0 m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Third gas flow nozzle (flow rate 10.7 l / sec, flow rate 76.0 m / sec)
Fourth gas flow nozzle (flow rate 10.7l / sec, flow rate 38.0m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
[0052]
(Example 7)
The oxygen concentration was measured when the gas flow nozzle and the air blocking plate were under the following conditions. Other conditions are the same as in the first embodiment. The results are shown in FIG. 17, and it was confirmed that the oxygen concentration can be reduced to about 1.5%.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7 l / sec, flow rate 19.0 m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Third gas flow nozzle (flow rate 10.7 l / sec, flow rate 76.0 m / sec)
Fourth gas flow nozzle (flow rate 10.7l / sec, flow rate 38.0m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
Roll front air barrier plate
[0053]
(Example 8)
In Examples 1 to 7 above, N₂The gas was supplied by two or more of the first to fourth gas flow nozzles, but in this embodiment, only one of the four nozzles is used for N.₂The oxygen concentration reduction effect of each nozzle was investigated by supplying gas.
The conditions of the gas flow nozzle and the air blocking plate are as follows.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7 l / sec, flow rate 19.0 m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Third gas flow nozzle (flow rate 10.7 l / sec, flow rate 76.0 m / sec)
4th gas flow nozzle (flow rate 10.7l / sec, flow rate 38.0m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
Roll front air barrier plate
The results are shown in FIG. 18, and it is understood that the oxygen concentration reduction effect of the first and second nozzles is great. In addition, as can be seen from the comparison of the result of Example 7 under the same conditions with the installation of the air entrainment plate blocking plate, the oxygen concentration is obtained by combining a plurality of nozzles as compared with the case where the gas flow is supplied by a single nozzle. It can be seen that the reduction effect is improved.
[0054]
Example 9
The variation of the oxygen concentration when the flow rate and flow rate of the first gas flow nozzle were changed was investigated. The conditions of the gas flow nozzle and the air blocking plate are as follows.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 0 to 16.4 l / sec, flow rate 0 to 32.3 m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Third gas flow nozzle (flow rate 10.7 l / sec, flow rate 76.0 m / sec)
Fourth gas flow nozzle (flow rate 10.7l / sec, flow rate 38.0m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
Roll front air barrier plate
The results are shown in FIG. N₂Although the oxygen concentration tends to decrease as the gas flow rate and flow rate increase, the oxygen concentration increases at the flow rate of 16.4 l / sec and the flow rate of 32.3 m / sec, and the gas flow rate and flow rate increase. If too much, it is estimated that the oxygen concentration is adversely affected.
[0055]
(Example 10)
Changes in the oxygen concentration when the flow rate and flow rate of the second gas flow nozzle were changed were investigated. The conditions of the gas flow nozzle and the air blocking plate are as follows.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7 l / sec, flow rate 19.0 m / sec)
Second gas flow nozzle (flow rate 0 to 16.4 l / sec, flow rate 0 to 8.06 m / sec)
Third gas flow nozzle (flow rate 10.7 l / sec, flow rate 76.0 m / sec)
4th gas flow nozzle (flow rate 10.7l / sec, flow rate 38.0m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
Roll front air barrier plate
The results are shown in FIG. N₂As the gas flow rate and flow rate increased, the oxygen concentration decreased, and the oxygen concentration decreased most at a flow rate of 10.7 l / sec and a flow rate of 4.75 m / sec. However, when the flow rate and flow rate are exceeded, the oxygen concentration tends to increase. Even in the second gas flow nozzle, if the flow rate and flow rate are excessively increased, it is estimated that the oxygen concentration is adversely affected.
[0056]
(Example 11)
Next, the variation of the oxygen concentration when the flow rate and flow rate of the third gas flow nozzle were changed was investigated. The conditions of the gas flow nozzle and the air blocking plate are as follows.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7 l / sec, flow rate 19.0 m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Third gas flow nozzle (flow rate 0-12.5l / sec, flow rate 91.3m / sec)
4th gas flow nozzle (flow rate 10.7l / sec, flow rate 38.0m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
Roll front air barrier plate
The results are shown in FIG. Compared with the first and second gas flow nozzles, the flow rate and flow velocity have little effect on the oxygen concentration, but N₂The oxygen concentration tends to decrease as the flow rate and flow rate increase until the gas flow rate of 10.7 l / sec and the flow rate of 4.75 m / sec. However, the oxygen concentration increases at higher flow rate and flow rate conditions. Therefore, it is presumed that the oxygen concentration is adversely affected if the gas flow rate and flow velocity are excessively increased.
[0057]
(Example 12)
Next, the variation of the oxygen concentration when the flow rate and flow rate of the fourth gas flow nozzle were changed was investigated. The conditions of the gas flow nozzle and the air blocking plate are as follows.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7 l / sec, flow rate 19.0 m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Third gas flow nozzle (flow rate 10.7 l / sec, flow velocity 76 m / sec)
Fourth gas flow nozzle (flow rate 0 to 10.7 l / sec, flow rate 0 to 38.0 m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
Roll front air barrier plate
The results are shown in FIG. It was confirmed that the oxygen concentration could be reduced most under the conditions of a flow rate of 10.7 l / sec and a flow rate of 4.75 m / sec.
[0058]
(Example 13)
An investigation was made as to whether or not there was a difference in fluctuations in oxygen concentration when Ar gas was supplied before roll rotation and after roll rotation. The conditions of the gas flow nozzle and the air blocking plate are as follows.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7 l / sec, flow rate 19.0 m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
Third gas flow nozzle (flow rate 10.7 l / sec, flow velocity 76 m / sec)
4th gas flow nozzle (flow rate 10.7l / sec, flow rate 38.0m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
Roll front air barrier plate
The result is shown in FIG.₂Even if the gas supply is performed after the roll rotation, a sufficiently low oxygen concentration can be obtained. However, it can be seen that the oxygen concentration is reduced more rapidly if the gas is supplied before the roll rotation. The reason is not clear, but it is presumed that if the cooling roll is rotated while a large amount of oxygen remains in the blocking plate, the airflow in the blocking plate is disturbed. Therefore, in the actual manufacturing process, if the gas is supplied from the roll stop state and then the roll is rotated, the manufacturing process can be shortened.
[0059]
(Example 14)
Next, an oxygen concentration measurement result when an actual thin strip manufacturing work procedure is assumed is shown. The conditions for the gas flow nozzle and the air blocking plate are as follows. Also, 0.68 kg / cm into the molten metal nozzle 2^ThreeN₂Gas flow was also performed
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7 l / sec, flow rate 19.0 m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
4th gas flow nozzle (flow rate 10.7l / sec, flow rate 38.0m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
Roll front air barrier plate
[0060]
First, N with the roll stopped₂Gas supply was performed for 10 minutes. At this stage, the molten metal nozzle 2 was in a heating position above the ejection position, and the oxygen concentration measurement was arranged in front of the molten metal nozzle 2.
N₂Assuming heating of the ingot inserted into the crucible 3 after 10 minutes from the start of the gas flow, heating of the heating coil 4 was started. At the same time, the cooling roll 1 started to rotate. However, the rotational speed at this time is 100 rpm, which is smaller than that at the time of manufacturing the ribbon. This low-speed cooling roll rotation is to prevent local heating of the cooling roll accompanying heating of the crucible 3.
[0061]
N₂After 11.5 minutes from the start of gas flow, N₂The gas supply was stopped. This assumes that the ingot in the crucible 3 has melted.
N₂After 14.5 minutes from the start of the gas flow, the number of revolutions of the cooling roll was increased to 1600 rpm, and 0.5 minutes later, the molten metal nozzle 2 was lowered to the ejection position.
FIG. 24 shows the oxygen concentration fluctuation during this period. The oxygen concentration is reduced to 0.33% after 10 minutes from the start of the gas flow, and the oxygen concentration slightly increases when the cooling roll 1 rotates at a low speed. It was confirmed that the oxygen concentration was reduced again and could be reduced to 0.27% after 15 minutes.
[0062]
(Example 15)
Examples 1-14 are N as inert gas.₂In the present example, N was used as an inert gas.₂Using gas and Ar gas, the influence of the type of flow gas on the present invention was investigated.
Specific conditions are as follows.
Gas flow nozzle conditions
First gas flow nozzle (flow rate 10.7 l / sec, flow rate 19.0 m / sec)
Second gas flow nozzle (flow rate 10.7 l / sec, flow rate 4.8 m / sec)
4th gas flow nozzle (flow rate 10.7l / sec, flow rate 38.0m / sec)
Air blocking plate conditions
Roll surface air shield plate, roll side air shield plate, roll front air shield plate
Roll rear air barrier plate, roll outer peripheral air barrier plate, roll front upper barrier plate
Roll front air barrier plate
Applicable alloy composition
Fe₈₄Nb₇B₉(at.%),
Oxygen concentration measurement
A position at a height of 0.3 mm from the surface of the cooling roll, on the front side from the molten metal nozzle
[0063]
The gas supply and the molten metal jetting were performed in the same manner as in Example 14 except that the gas supply was performed from the state where the cooling roll was stopped, and the cooling roll was rotated at 100 rpm after 16.5 minutes had elapsed from the start of the gas flow. After 5 minutes, heating of the ingot in the crucible 3 was started. When heating was performed for 3 minutes, the rotation of the cooling roll was increased to 1700 rpm (circumferential speed 31.1 m / sec), and injection of molten metal was started. The oxygen concentration at the time of molten metal ejection was 0.248%.
[0064]
X-ray diffraction of the thickness of the manufactured ribbon, pinholes (holes penetrating the front and back surfaces of the ribbon), surface roughness (Ry), and the precipitation state of crystals on the free surface and roll surface of the ribbon It was measured by. In addition, the obtained ribbon was subjected to heat treatment (heated at 180 ° C./min, held at 650 ° C. for 10 minutes and then allowed to cool), and magnetic permeability (μ ′), saturation magnetic flux density (Bs), coercive force (Hc ) Was measured.
[0065]
The plate thickness and pinhole measurement results are shown in FIG.
It can be seen that the ribbon thickness is about 1.5 to 2.0 μm thicker when Ar gas is used. This is the Ar or N supplied₂The gas is caught in the paddle part, but it is understood that it is due to the difference in thermal expansion between the two after being caught in the paddle. That is, the gas entrained in the paddle part is generated in a very short time from entrainment to solidification, but N₂Since gas has a smaller molecular weight and higher thermal conductivity than Ar gas, the entrained gas is heated by the molten metal in a short time and expands greatly. On the other hand, Ar having a large molecular weight has low thermal conductivity, and only the peripheral portion in contact with the molten metal in the entrained gas is heated and expanded.₂It is estimated that the expansion does not increase as much.
[0066]
This is shown in FIG. FIG. 26A shows the paddle 104 portion when Ar gas is used, and FIG.₂The paddle 104 portion in the case of using gas is shown. When Ar gas is used, since the bubbles in the paddle 104 are small, the solidification interface 106 in the paddle is N₂Compared with the case where gas is used, it approaches the melt nozzle 2 and the cooling capacity of the paddle portion is increased. Therefore, it is presumed that the plate pressure of the ribbon becomes thicker when Ar gas is used.
[0067]
N for pinholes₂It was observed that there was no occurrence in the thin strip due to the Ar gas flow, whereas the thin strip due to the gas flow occurred in the first half of the production. Thickness is one of the factors that cause pinholes. That is, as the plate thickness increases, the generation of pinholes tends to be suppressed. However, it is considered that the thin strip due to the Ar gas flow is one of the factors that did not cause pinholes due to the large plate thickness.
[0068]
FIG. 27 shows the surface roughness (Ry) in the length direction and width direction of the free surface, and FIG. 28 shows the surface roughness (Ry) in the length direction and width direction of the roll surface. The roughness is in the range of 12 mm centering on the measurement position in the length direction, and in the range of 12 mm in the center of the width in the width direction.
As shown in FIG. 27, Ar gas, N₂There is no difference in the roughness of the gas, but as shown in FIG.₂It can be seen that the roughness is smaller than that of the ribbon by gas flow. This is because, as mentioned above, N₂It is presumed that Ar gas has a smaller thermal expansion in the paddle than gas.
[0069]
29 and 30 show the crystal precipitation state of the free surface and roll surface of the ribbon (unheat-treated). N₂In the ribbon due to gas flow, bcc (200) orientation peaks are observed on both the free surface and the roll surface, whereas no precipitation of crystals is observed in the ribbon due to Ar gas flow. It is presumed that Ar gas has a smaller thermal expansion in the paddle, so that the area where the cooling roll and the paddle are in close contact with each other is larger and the cooling capacity is higher. In the figure, “S8” indicates a position 8 m from the start end of the ribbon.
[0070]
FIG. 31 shows the measurement results of the magnetic permeability (μ ′) at 1 kHz and 10 kHz after the heat treatment, and it can be seen that the thin ribbon by Ar gas flow shows superior magnetic permeability. FIG. 32 shows the saturation magnetic flux density (Bs) and coercive force (Hc) after the heat treatment, and it can be seen that the ribbon by Ar gas flow has more excellent characteristics. This is because the thin ribbon by Ar gas flow has fewer pinholes and smaller surface roughness, and further, there is no precipitation of crystals in the state before heat treatment, so the crystal grain size after heat treatment becomes uniform. It is presumed to be based on this. In addition, when the structure | tissue after heat processing was observed, it became a fine crystal structure with an average crystal grain diameter of 150 angstroms.
[0071]
(Example 16)
Under the same conditions as in Example 15, Fe₈₄Nb_3.5Zr_3.5B₈Cu₁An alloy ribbon having a composition of (at.%) Is manufactured, and the obtained ribbon (strip Nos. 1 to 3) is subjected to heat treatment (heated to 650 ° C. at 40 ° C./min and then allowed to cool). , Magnetic permeability (μ ′), saturation magnetic flux density (B_Ten) And the coercive force (Hc) were measured. The results are as follows. The properties of the ribbon (No. 4) of the same composition produced by the conventional method in which the ribbon production apparatus is installed in an inert atmosphere chamber are also shown. The ribbon according to the present invention is obtained by the conventional method. It was confirmed that the same magnetic properties as the ribbon could be obtained.
[0072]

[0073]
【The invention's effect】
  As described above, according to the present invention, the oxygen concentration in the atmosphere in the vicinity of the molten metal nozzle can be reduced and continuous production can be performed without providing a large facility such as a chamber and inferior workability. .
  In particular, in the present invention, a roll surface air blocking plate and a roll side air blocking plate are provided, two gas flow supply means are provided on the rear side with respect to the molten metal nozzle, and the roll surface atmospheric blocking device and the molten nozzle are provided. Gas flow supply means arranged betweenGas flow into the gas as desired at the tip of the melt nozzleGas from the other gas flow supply meansTheBy being able to supply, the effect that the oxygen concentration of the atmosphere in the vicinity of the molten metal nozzle can be reduced can be reliably obtained without providing any incidental equipment.
[Brief description of the drawings]
FIG. 1 is a side view showing an embodiment of a metal ribbon manufacturing apparatus of the present invention.
FIG. 2 is a view showing a first gas flow nozzle.
FIG. 3 is a diagram showing a third gas flow nozzle.
FIG. 4 is a diagram showing second and fourth gas flow nozzles.
FIG. 5 is a view showing an arrangement of roll surface air blocking plates.
FIG. 6 is a view showing an arrangement of a roll rear air blocking plate and a roll side air blocking plate.
FIG. 7 is a view showing the arrangement of a roll outer periphery air shielding plate and a roll front air shielding plate.
FIG. 8 is a view showing an arrangement of a roll front air blocking plate and a roll front air blocking plate.
FIG. 9 is a side view showing another embodiment of the metal ribbon manufacturing apparatus of the present invention.
10 is a graph showing fluctuations in oxygen concentration in Example 1. FIG.
11 is a graph showing the relationship between the distance from the surface of the cooling roll and the oxygen concentration in Example 1. FIG.
12 is a graph showing fluctuations in oxygen concentration in Example 2. FIG.
13 is a graph showing fluctuations in oxygen concentration in Example 3. FIG.
14 is a graph showing fluctuations in oxygen concentration in Example 4. FIG.
15 is a graph showing fluctuations in oxygen concentration in Example 5. FIG.
FIG. 16 is a graph showing changes in oxygen concentration in Example 6.
FIG. 17 is a graph showing changes in oxygen concentration in Example 7.
18 is a graph showing fluctuations in oxygen concentration in Example 8. FIG.
FIG. 19 is a graph showing changes in oxygen concentration in Example 9.
20 is a graph showing changes in oxygen concentration in Example 10. FIG.
FIG. 21 is a graph showing changes in oxygen concentration in Example 11.
22 is a graph showing a change in oxygen concentration in Example 12. FIG.
23 is a graph showing fluctuations in oxygen concentration in Example 13. FIG.
24 is a graph showing changes in oxygen concentration in Example 14. FIG.
25 is a graph showing the relationship between ribbon length, plate thickness, and number of pinholes in Example 15. FIG.
FIG. 26A is a diagram showing a state of a paddle portion when Ar gas is used, and FIG.₂It is a figure which shows the state of the paddle part at the time of using gas.
FIG. 27 is a graph showing the relationship between the ribbon length and the surface roughness of the ribbon free surface in Example 15.
28 is a graph showing the relationship between the ribbon length and the surface roughness of the ribbon roll surface in Example 15. FIG.
FIG. 29 shows N in Example 15.₂It is a figure which shows the X-ray diffraction of the thin strip using gas.
30 is a diagram showing X-ray diffraction of a ribbon using Ar gas in Example 15. FIG.
31 is a graph showing the magnetic permeability (μ ′) of the ribbon obtained in Example 15. FIG.
32 is a graph showing the coercive force (Bc) and coercive force (Hc) of the ribbon obtained in Example 15. FIG.
FIG. 33 is a diagram showing ribbon production by a single roll method.
[Explanation of symbols]
1 ... Cooling roll
2 ... Molten metal nozzle
3 ... crucible
4 ... Heating coil
51 ... 1st gas flow nozzle
52 ... Second gas flow nozzle
53 ... Third gas flow nozzle
54 ... Fourth gas flow nozzle
61 ... Roll surface air blocking plate
62 ... Roll rear air blocking plate
63 ... Roll side air blocking plate
64 ... Roll outer peripheral air blocking plate
65 ... Roll front air blocking plate
66 ... Air barrier plate on the front of the roll
67 ... Roll front air blocking plate

Claims (23)

A cooling roll having a cooling surface for cooling the molten metal, a molten metal nozzle for ejecting the molten metal to the cooling surface, and disposed on both sides of the cooling roll and provided over the entire circumference of the cooling roll, cooling A roll side surface air blocking plate for blocking air entrainment from the side surface of the roll, a gas flow supply means for supplying an inert gas around the molten metal nozzle, and a roll surface air blocking means,
Two gas flow supply means, on the rear side with respect to the melt nozzle, disposed between the roll surface air blocking means and the melt nozzle,
The two gas flow supply means arranged on the rear side are arranged so that the slit and gas flow of one gas flow supply means face the tip of the melt nozzle, and the other gas flow supply means is the melt nozzle and the one gas. The gas flow from the other gas flow supply means is supplied on the gas flow from the one gas flow supply means.
The roll surface air blocking means is arranged on the rear side with respect to the molten metal nozzle so as to block the flow of the air adhering to the surface of the cooling roll to the paddle part and to contact the tip part with the cooling roll. An apparatus for producing a thin metal strip,   2. The metal according to claim 1, further comprising a roll outer peripheral air blocking plate, wherein the roll outer peripheral air blocking plate is disposed so as to surround an outer periphery of the cooling roll at an outer peripheral edge of the roll side air blocking plate. Thin strip manufacturing equipment.   The metal ribbon manufacturing apparatus according to claim 1, wherein the gas flow supply means is disposed on the front side with respect to the molten metal nozzle. The metal ribbon manufacturing apparatus according to any one of claims 1 to 3 , wherein the slit of the gas flow supply means is disposed so as to face the tip of the molten metal nozzle.   The metal strip manufacturing apparatus according to any one of claims 1 to 4, wherein the slit width of the gas flow supply means is substantially the same as the cooling roll width.   The metal ribbon manufacturing apparatus according to any one of claims 1 to 5, further comprising a gas flow supply unit configured to supply a gas flow to a range including at least the cooling roll from above, below, and / or from the side of the cooling roll.   The metal ribbon manufacturing apparatus in any one of Claims 1-6 which has a roll back air | atmosphere interruption | blocking board which interrupts | blocks the inflow of air | atmosphere on the back side on the basis of a molten metal nozzle.   The metal ribbon manufacturing apparatus in any one of Claims 1-7 which has a roll front air | atmosphere interruption | blocking board which interrupts | blocks inflow of air | atmosphere on the front side on the basis of a molten metal nozzle. In a metal ribbon manufacturing method for manufacturing a metal ribbon by continuously injecting molten metal from a molten metal nozzle onto the cooling surface of a cooling roll and rapidly solidifying it,
A cooling roll having a cooling surface for cooling the molten metal, a molten metal nozzle for ejecting the molten metal to the cooling surface, and disposed on both sides of the cooling roll and provided over the entire circumference of the cooling roll, cooling A roll side surface air blocking plate that blocks air entrainment from the side surface of the roll, a gas flow supply unit that supplies an inert gas around the molten metal nozzle, and a roll surface atmospheric block unit, the gas flow supply unit comprising: Two, on the rear side with respect to the melt nozzle, disposed between the roll surface air blocking means and the melt nozzle,
The two gas flow supply means arranged on the rear side are arranged so that the slit and gas flow of one gas flow supply means face the tip of the melt nozzle, and the other gas flow supply means includes the melt nozzle and the one gas. The gas flow from the other gas flow supply means is supplied on the gas flow from the one gas flow supply means. A metal that is located on the rear side with respect to the molten metal nozzle and is arranged so as to block the inflow of the air adhering to the surface of the cooling roll to the paddle part and to contact the tip part with the cooling roll. Using a ribbon manufacturing device,
A method for producing a metal ribbon, wherein an inert gas is supplied from the two gas flow supply means to the periphery of the molten metal nozzle while blocking air inflow from the roll side surface by the roll side air blocking plate.   The method for producing a metal ribbon according to claim 9, wherein the inert gas is supplied before the cooling roll is rotated.   The method for producing a metal ribbon according to claim 10, wherein the oxygen concentration in the atmosphere in the vicinity of the molten metal nozzle is measured, and the cooling roll is rotated after reaching a predetermined oxygen concentration.   The method for producing a metal ribbon according to claim 11, wherein the rotation of the cooling roll is initially performed at a low speed, and then the molten metal is ejected after the rotation necessary for the production of the ribbon is performed.   The method for producing a metal ribbon according to any one of claims 9 to 12, wherein the inert gas is supplied under conditions of a flow rate of 2 to 100 m / sec and a flow rate of 5 to 120 l / sec.   The method for producing a metal ribbon according to claim 13, wherein the inert gas is supplied from the rear side with reference to the molten metal nozzle.   The method of Claim 14 which supplies an inert gas from the front side on the basis of a molten metal nozzle.   The method for producing a metal ribbon according to claim 15, wherein the inert gas is supplied from the rear side and the front side with reference to the molten metal nozzle.   The method for producing a metal ribbon according to claim 16, wherein two systems of gas flow are supplied from the rear side and one system of gas flow is supplied from the front side with reference to the molten metal nozzle.   Of the two gas flows from the rear side, one is supplied from the tangential direction of the cooling roll, and the other gas flow is supplied from above the one gas flow and one gas flow from the front side. The method for producing a metal ribbon according to claim 17, wherein   Of the two gas flows from the rear side, the one gas flow has a flow rate of 10 to 35 m / sec and a flow rate of 5 to 20 l / sec, and the other gas flow has a flow rate of 2 to 10 m / sec and a flow rate of 5 to 20 l / sec. 19. The method for producing a metal ribbon according to claim 18, wherein the gas flow supplied from the front side is 10 to 50 m / sec and the flow rate is 5 to 20 l / sec. Inert _{gas, N 2, He, Ar,} Kr, method for producing a metal strip according to any one of claims 9 to 19 is one or more of Xe, and Rn. In a metal ribbon manufacturing method for manufacturing a metal ribbon by continuously injecting molten metal from a molten metal nozzle onto the cooling surface of a cooling roll and rapidly solidifying it,
A cooling roll having a cooling surface for cooling the molten metal, a molten metal nozzle for ejecting the molten metal to the cooling surface, and disposed on both sides of the cooling roll and provided over the entire circumference of the cooling roll, cooling A roll side surface air blocking plate that blocks air entrainment from the side surface of the roll, a gas flow supply unit that supplies an inert gas around the molten metal nozzle, and a roll surface atmospheric block unit, the gas flow supply unit comprising: Two, on the rear side with respect to the melt nozzle, disposed between the roll surface air blocking means and the melt nozzle,
The two gas flow supply means arranged on the rear side are arranged so that the slit and gas flow of one gas flow supply means face the tip of the melt nozzle, and the other gas flow supply means includes the melt nozzle and the one gas. The gas flow from the other gas flow supply means is supplied on the gas flow from the one gas flow supply means. A metal that is located on the rear side with respect to the molten metal nozzle and is arranged so as to block the inflow of the air adhering to the surface of the cooling roll to the paddle part and to contact the tip part with the cooling roll. Using a ribbon manufacturing device,
While the air inflow from the roll side is blocked by the roll side air blocking plate, the inert gas is supplied from the two gas flow supply means to the periphery of the melt nozzle, and one of the gas flows is from the tangential direction of the cooling roll. A method for producing a metal ribbon, wherein the gas flow is supplied and the other gas flow is supplied from above the one gas flow.   The method for producing a metal ribbon according to claim 21, wherein the flow rate of the one gas flow is larger than the flow rate of the other gas flow. Method for producing a metal strip according to any of claims 9-2 2 thickness of the inert gas layer on the cooling roll surface formed by the gas flow is 0.1 to 0.4 mm.

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