JPS6217020B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a high silicon steel ribbon containing 4 to 10% silicon, less than 10% cobalt, and less than 3% nickel, and a method for producing the same. Silicon steel ribbon, which is made by adding about 3% silicon to iron, is widely used as a core material for electrical equipment such as transformers. These silicon steel sheets are usually divided into non-oriented silicon steel sheets, in which the crystal axis orientation of the crystal grains varies in various directions, and grain-oriented silicon steel sheets, in which the [100] axis of the crystal grains is aligned in the rolling direction. The former is mainly used for core materials of rotating machines and generators where magnetic flux is applied in various directions, while the latter is used for iron core materials such as transformers where magnetic flux is applied only in one direction. In such applications, the most strongly required point is firstly to minimize the core loss of the material. This is expected to become more and more demanded due to soaring energy prices. The second goal is to keep equipment noise caused by magnetostrictive vibration of the material as low as possible. This demand is also expected to become even stronger. In order to meet these demands, technology has been developed to minimize the amount of impurities such as carbon, nitrogen, oxygen, and sulfur that degrade iron loss in non-oriented silicon steel, and to align the [100] axis with the plate surface. , the effects are increasing. On the other hand, for grain-oriented silicon steel, technologies have been developed to further increase the degree of integration in the rolling direction of the [100] axis, and to reduce iron loss and apparent magnetostriction by applying tension to the steel plate through coating treatment. Ta. However, the technology of conventional silicon steel sheets has almost reached the stage of completion, and improvements in magnetic properties and magnetostrictive properties are on the verge of saturation. The improvement is expected to be small. By the way, high-silicon steel, which is made by adding about 6.5% silicon to iron, has a low saturation magnetic flux density of about 1.80T (Tesla), but magnetostriction virtually disappears.
In addition, since the magnetic anisotropy is halved, the soft magnetic properties (high permeability μ, coercivity
It has been known since the 1950s to exhibit low Hc). When this material is assembled into a transformer or the like, it has extremely low iron loss at a suitable excitation magnetic flux density and virtually eliminates noise, making it an extremely attractive material for applications. However, when the amount of silicon exceeds about 4%, the material matrix hardens and becomes rapidly brittle as an ordered lattice (Fe ₃ Si) appears. This makes rolling extremely difficult, making it virtually impossible to manufacture, and also making processing such as shearing and punching impossible. Under these circumstances, high-silicon steels with a silicon content of 4% or more, especially high-silicon steels with a silicon content of about 6.5%, are not put into practical use despite their excellent magnetic properties. On the other hand, the present inventors added silicon by 4 to 10%,
The ribbon obtained by ultra-quenching a silicon steel melt containing less than 10% cobalt and less than 3% nickel has extremely fine crystal grains, virtually no regular lattice, and is flexible and workable. They discovered that a high-silicon steel ribbon with extremely high silicon content and excellent magnetic properties could be obtained, and conducted extensive research to complete the present invention. The present invention is as follows. First invention Consisting of 4 to 10% silicon by weight, the remainder substantially consisting of iron and unavoidable impurities, and 10% cobalt as a subcomponent.
% or less, 3% or less of nickel, the crystal grains are 1 to 100 μm, and there is substantially no regular lattice Fe ₃ Si, and the crystal grains are close to the surface of the ribbon. A high-silicon steel ribbon consisting of vertically grown columnar crystals with excellent workability and magnetic properties. 2nd invention Consisting of 4 to 10% silicon by weight, the remainder substantially consisting of iron and unavoidable impurities, and 10% cobalt as a subcomponent.
% or less, 3% or less of nickel, and 2% or less of aluminum, 2% or less of manganese, and has crystal grains of 1 to 100 μm, and A high-silicon steel ribbon with excellent workability and magnetic properties, with virtually no regular lattice Fe ₃ Si and consisting of columnar crystals with crystal grains grown perpendicular to the ribbon surface. Third invention Contains 4 to 10% silicon by weight, the balance consists of iron and unavoidable impurities, and cobalt 10 as a subcomponent.
% or less, or 3% or less of nickel, is ultra-quenched at a cooling rate of 10 ³ to 10 ⁶ °C/sec, and the crystal grains are 1 to 100 μm and the ordered lattice Fe ₃ Manufacture of high-silicon steel ribbon with excellent workability and magnetic properties, which is characterized by the fact that it is substantially free of Si and consists of columnar crystals with crystal grains grown perpendicular to the ribbon surface. Method. Fourth invention Contains 4 to 10% silicon by weight, the balance consists of iron and unavoidable impurities, and cobalt 10 as a subcomponent.
% or less, or 3% or less of nickel, is ultra-quenched at a cooling rate of 10 ³ to 10 ⁶ °C/sec, and the crystal grains are 1 to 100 μm and the ordered lattice Fe ₃ The process of obtaining a ribbon consisting of columnar crystals in which Si is substantially absent and crystal grains grown perpendicular to the surface of the thin body, and the process of annealing the obtained silicon steel ribbon at 400 to 1300℃ to obtain crystal grains. A method for producing a high-silicon steel ribbon with excellent workability and magnetic properties, characterized by a step of growing Fe ₃ Si to a thickness of 0.05 to 10 mm to obtain a ribbon in which an ordered lattice Fe 3 Si substantially exists. Fifth invention Silicon 4-10%, Cobalt 10% or less Nickel 3%
Contains the following, with the remainder consisting essentially of iron and unavoidable impurities, with fine crystal grains and a regular lattice.
A high-silicon steel ribbon substantially free of Fe ₃ Si is rolled and further annealed at 400 to 1300℃ to reduce the grain size to 0.05 to 10.
A method for producing a high-silicon steel ribbon with excellent workability and magnetic properties, which is characterized by obtaining a ribbon in which a regular lattice of Fe ₃ Si is grown to a size of 3 mm and substantially contains Fe 3 Si. Sixth invention Silicon 4-10%, Cobalt 10% or less, Nickel 3
% or less, the remainder substantially consisting of iron and unavoidable impurities, crystal grains of 1 to 100 μm, and substantially no ordered lattice Fe ₃ Si for electrical equipment. Iron core. 7th invention Silicon 4-10%, Cobalt 10% or less, Nickel 3
% or less, the remainder substantially consists of iron and unavoidable impurities, the crystal grains are 0.05 to 10 mm, and the ordered lattice Fe ₃ Si is substantially present. Iron core. Here, it is preferable that the total amount of unavoidable impurity elements is 0.1% or less of carbon, nitrogen, oxygen, and sulfur. Furthermore, as subcomponents added to the high silicon steel ribbon, in addition to one or more of the following: 10% or less of cobalt, 3% or less of nickel, 1 or more of the following: 2% or less of aluminum, 2% or less of manganese. Or two or more types can be contained. When molten high-silicon steel is ultra-rapidly cooled on a cooling body, the temperature is 10 ³ to 10 ⁶ until it reaches at least 400°C.
Preferably, the rapid cooling is performed at a rate of °C/sec. The melting temperature of high-silicon steel is 300℃ above the melting point.
It is preferable that the temperature is no higher than that. In addition, when it is desired to obtain a wide ribbon, this can be achieved by ejecting the melt from a multi-hole nozzle having two or more ejection holes arranged close to each other in a row over the required width of the ribbon. In addition, as an impurity element, any one or two of chromium, molybdenum, tungsten, vanadium, and titanium may be contained in an amount of 0.1% or less. When manufacturing an iron core for electrical equipment using the high silicon steel ribbon obtained according to the present invention, either the thin ribbon obtained by ultra-quenching as described above is laminated, or the laminated iron core is heated at 400°C to 650°C. It is obtained by annealing at a temperature of from 10 minutes to 5 hours to generate an ordered lattice Fe ₃ Si. When the iron core is annealed in this way, the crystal grains grow to 0.05 to 10 mm, further improving the magnetic properties. Figures 1A and 1B show an example of a microstructure photograph of a silicon steel ribbon of the present invention consisting of 6.5% silicon and the remainder substantially iron; A shows the surface of the ribbon obtained by ultra-quenching; Tissue B is its cross-sectional structure, and from this photo, approximately 5
It can be seen that crystal grains with a diameter of ~10 μm are arranged and grown in a direction perpendicular to the thin plate surface. Figure 2 shows the bending workability of a similar thin strip.
FIG. 2A shows the thin ribbon of the present invention wound around a rod-shaped body having a diameter of 4 mm, and FIG. 2B shows the ribbon in a bent state. As is clear from Figures 2 A and B, this was not possible in the past.
It will be appreciated that it can be bent well. On the other hand, Figure 3 shows a melt containing various proportions of 3 to 11% silicon, with the remainder essentially consisting of 10 ³ to 10 ⁴
The coercive force Hc (A curve) when a ribbon obtained by ultra-quenching at ℃/sec is magnetized to a maximum of 10 kg is shown in comparison with high silicon steel made by the conventional method (B curve). . As is clear from Fig. 3, the ribbon of the present invention is similar to the conventional high-silicon steel in the high-silicon region.
A phenomenon in which Hc gradually decreased was observed, and silicon 6.5%
In the vicinity, it is comparable to conventional 3% silicon steel.
Indicates Hc. The ribbon of the present invention has a higher Hc than conventional products when it is rapidly cooled from the molten state, but it can be improved by annealing as described below, and it is at the level of conventional high-silicon iron materials. It can be done. These characteristics regarding workability of the present invention are due to the fact that the crystal grains are fine as shown in FIGS. 1A and 1B, and that no regular lattice is substantially observed. However, in the ultra-rapid cooling state, the crystal grains are reduced to 100.
If it exceeds .mu.m, the workability will be reduced, which is undesirable.On the other hand, even if it is made finer than 1 .mu.m, there will be no substantial improvement in the workability, and too high-speed cooling will be required, which will impair economic efficiency. When the silicon steel ribbon obtained by the method of the present invention is heat-treated, the crystals become coarser and the magnetic properties (Hc) are significantly improved. This can be explained using microscopic photographs as follows. Figures C and D show silicon steel ribbons with a composition of 6.4%Si-93.6%Fe at 1200℃ in an argon gas atmosphere.
Showing the results of heat treatment for 40 minutes, C is a photograph of the surface structure;
D is a photograph of the cross-sectional structure. The size of the crystal grains shown in the photograph indicates that grain growth has progressed due to heat treatment and the crystal grain size has become significantly coarser. As can be seen from the photo, the crystal grain size is approximately 150 μm or more. The grain size of the crystal grains in this ribbon is a function of heat treatment time and heat treatment temperature. The magnetic properties (Hc) were significantly improved as the ribbon crystals became coarser. Even after the above-mentioned heat treatment, the ribbon has sufficient workability, but this is because the crystal grains are developed in a direction perpendicular to the sheet surface, as shown in the micrograph in Figure 1D. It is presumed that this and the substantial absence of regular grids are contributing factors. Next, the component composition will be explained. The high silicon steel ribbon of the present invention basically contains 4 to 4 silicon.
10%, less than 10% cobalt, less than 3% nickel, and the remainder essentially consists of iron and unavoidable impurities. If the silicon content is less than 4%, the magnetic properties will be comparable to those of conventional products, and if the silicon content exceeds 10%, it will not only become brittle but also deteriorate in magnetic properties.
Note that since silicon exhibits the best magnetic properties when the content is 5 to 7%, this range is suitable. Oxygen, sulfur, carbon, and nitrogen are unavoidable impurities mixed into silicon steel, but if these are present in the product, they will deteriorate the iron loss characteristics, make the ribbon brittle, and deteriorate the workability. It is desirable to keep it as low as possible. If the total amount of these impurities exceeds 0.1%, the iron loss increases and is inferior to conventional silicon steel, so the upper limit is set at 0.1%. In addition, in the current steelmaking technology, 0<50ppm, S<80ppm, C<100ppm, N
Since it can be <50 ppm, it is particularly preferable to keep it within this range. The composition of the present invention may further include up to 2% aluminum and up to 2% manganese. Aluminum is a stronger deoxidizing element than silicon, so by adding aluminum, a material with lower oxygen content can be obtained. Further, since it increases electrical resistance, it is preferable in terms of lowering eddy current loss. However, since aluminum increases magnetostriction, it is not preferable to add more than 2%, so the upper limit is set at 2%.
shall be. Manganese is an unavoidable mixed element and is contained at approximately 0.05% in ordinary steel manufacturing. Unlike oxygen and sulfur, this element is known to be preferable for silicon steel in terms of rollability and magnetic properties. In the present invention, the addition of 2% or less, preferably 0.2 to 1.3%, not only improves the magnetic properties but also improves the shape of the ribbon (no holes or cracks at the ends in the width direction) when ultra-quenched. It was found that a thin strip could be obtained. The cause of these phenomena is not clear, but by adding manganese, the impurity sulfur changes from a solid solution state or a fine precipitate state to a large MnS precipitate, which improves rolling properties and magnetic properties. It is thought that However, if manganese exceeds 2%, the magnetic properties will deteriorate and the product will become more difficult to process due to further hardening, so the maximum content was reduced to 2%.
limited to. Since the ribbon of the present invention has a high silicon content, it has the disadvantage of inevitably having a low saturation magnetic flux density. Adding cobalt to the Fe-Si alloy increases the saturation magnetic flux density, so in the present invention as well, cobalt can be added as needed to compensate for the above disadvantages. However, since cobalt is an extremely expensive element, the upper limit of cobalt is set at 10% in the present invention. Nickel is an element that increases the toughness of Fe-Si alloys, and in the present invention, 3% nickel is used.
Hereinafter, it has been found that adding preferably 0.2 to 1.5% makes it possible to produce a high-quality ultra-quenched ribbon. In addition to the above-mentioned impurity elements such as chromium, molybdenum, tungsten, vanadium, titanium, tin, etc. may be contained in trace amounts of about 0.1% or less, this does not impede the effects of the present invention in any way. Now, in the conventional manufacturing of silicon steel sheets, steel ingots or continuous cast slabs are hot-rolled to
After forming a hot strip with a thickness of 1 mm, a product with a thickness of 0.28 to 0.50 mm is usually produced by combining appropriate cold rolling and heat treatment.In the present invention, a silicon steel melt having the above-mentioned composition ^is 10 ⁶ ℃/
The material is directly ultra-quenched at a cooling rate of 1.0 seconds to immediately produce a thin ribbon with a predetermined thickness. That is, a silicon steel melt is directly made into a finished product or a semi-finished product, completely eliminating the hot rolling and cold rolling steps that are essential to conventional processes. Any method can be used to ultra-quench a molten material to form a thin ribbon, as long as it is wide enough, has a specified thickness, is uniform in thickness, and can be drawn out continuously into a coil. However, typically, as shown in Figures 4 and 5, the molten material is jetted out continuously from holes of an appropriate shape on a continuously moving moving surface, rapidly solidified, and formed into a predetermined shape. It is better to obtain a thick strip in the form of a coil. FIG. 4a shows a schematic diagram of an apparatus that uses a bowl-shaped rotating body 2 as a moving surface and ejects a melt 4 from a jet nozzle 1 onto the inner rotating surface to obtain a rapidly solidified continuous ribbon 3. has been done. Also, in Fig. 4b and c, molten silicon steel is continuously ejected from the ejection holes on one rotating roll 5 or between two adjacent rotating rolls 5' and 5'', which are not necessarily of the same size. A schematic diagram of an apparatus for obtaining a continuous ribbon by ultra-quenching between two rolls is shown. FIG. A schematic diagram of an apparatus for continuously obtaining a ribbon by rapid cooling is shown below. When manufacturing a silicon steel ribbon according to the present invention using the above apparatus, the important thing is that the molten material solidifies and cools at a sufficiently fast rate. First, if it takes a long time for the ejected molten material to solidify when it hits the moving cooling body, the flow of the ejected molten material will become uneven, which may result in the formation of holes or voids, or the thickness may increase. In addition to producing uneven ribbons, if the product is manufactured in the atmosphere, it may be oxidized or nitrided, making it impossible to produce a ribbon with a good shape, or even if it is produced, it may become magnetic due to the presence of oxygen or nitrogen in the product. On the other hand, if it takes a long time after solidification to reach a temperature of approximately 400°C at which no grain growth or regular lattice formation occurs, the obtained ribbon will partially have an ordered lattice, and As the crystal grains become coarser, subsequent shearing, punching, or rolling performed as necessary becomes difficult. As a result of experiments with different values, it was found that a desirable ribbon could not be obtained if the average cooling rate during the period from when the melt was ejected from the nozzle to when it was solidified and cooled until the temperature of the ribbon reached 400℃ was less than 10 ³ ℃/sec. In other words, when manufacturing in an atmosphere that cools slower than this critical cooling rate, it may not be possible to obtain a continuous ribbon with a good shape due to oxidation, or even if it is obtained, problems such as grain growth may occur. Therefore, it is extremely fragile.
In order to economically and reliably obtain a ribbon with sufficiently fine grains and virtually no ordered lattice, it is recommended to cool to 400°C at a cooling rate of 10 ³ to 10 ⁶ °C/sec. . Incidentally, the high-silicon steel ribbon according to the present invention must also be manufactured industrially with a sufficiently wide width. Generally, a nozzle with a slit-shaped ejection hole over the required width is used for this purpose, but in order to obtain a thin strip with a uniform thickness across the width, it is necessary to As shown in the figure, it is preferable to use nozzles 1 in which two or more ejection holes 10 are placed close to each other and arranged in a line over a necessary width. At this time, if an auxiliary jet hole 10' is provided at the end of the nozzle, a more uniform melt jet 9 can be obtained over the entire width in the width direction. Therefore, by doing so, a ribbon having a uniform thickness can be obtained. In addition, in order to continuously produce high-silicon steel ribbons industrially, it is necessary to eject the melt continuously from the nozzle over a long period of time, resulting in significant damage to the nozzle. Nozzles are typically made of refractory materials with high melting points, such as boron nitride ceramics, in which case continuous cooling of the area around the nozzle with water, liquid metal, or gas to prevent damage may cause the nozzle to melt. This is advantageous because the life of the product is significantly extended. Furthermore, in order to reliably prevent oxidation and nitridation and obtain a ribbon with few impurities, the entire ribbon manufacturing apparatus is placed in one tank under a protective gas atmosphere or under vacuum, as shown in Figure 7. It's also good. Argon or helium or other protective gas near the nozzle
It is also a good idea to spray CO ₂ gas etc. FIG. 7 shows a manufacturing apparatus for obtaining a silicon steel ribbon according to the present invention under vacuum. 11 is a vacuum chamber, and a rotating roll 5 is installed in this vacuum chamber 11. The rotating roll 5 is made of a material with good thermal conductivity, such as copper, and is connected to a motor that drives it. Directly above the rotating roll 5, a nozzle 1 for storing a high-silicon steel material is installed so as to be movable up and down. 12 is a pipe, and the high silicon iron material is connected to the nozzle 1.
It is intended for use in Further, 13 is a pipe for injecting gas to jet the molten high-silicon steel material from the nozzle 1. 14 is a cylinder that moves the nozzle 1 up and down, and adjusts the distance between the nozzle 1 and the rotating roll 5. 15 is a vacuum bellows that expands and contracts in accordance with the vertical movement of the nozzle 1 and seals the gap between the vacuum chamber 11 and the nozzle 1.
16 is a heater, which is placed around the tip of the nozzle 1, and for example, heats the nozzle 1 at a temperature of 1400 to 1600°C.
is heated to melt the high-silicon iron material housed in the nozzle 1. 17 is an exhaust port of the vacuum chamber 11 and is connected to an exhaust system. 18 is a collection port for the silicon-iron ribbon produced by this apparatus. When a molten crystalline high-silicon steel material is ejected from the nozzle 1 and ultra-quenched on the rotating surface of the rotating roll 5 to obtain a silicon steel ribbon, the inside of the vacuum chamber 11 may be a natural atmosphere under atmospheric pressure, or A protective atmosphere such as Ar or _N2 may be used. In the silicon steel ribbon manufacturing apparatus shown in FIGS. 4 to 7 described above, it is important to select the material of the rotary cooling body in consideration of the wettability between the cooling body and silicon iron. Also, the melting temperature of the silicon steel melt is lower than the melting point.
If the temperature rises by 300℃ or more, the viscosity of the melt decreases, causing the melt to ooze out from the nozzle while heating the melt.
When ejected from the nozzle, the jet stream may become mist-like, or it may spread widely over the surface of the rotating cooling body and may not form a ribbon of a constant width, resulting in the ribbon becoming too thin or forming a sash-like shape. I feel relaxed.
On the other hand, if the melting temperature of the molten material is too low, the viscosity of the molten material will increase, and the jet flow of the molten material will not be able to sufficiently adhere to the surface of the rotary cooling body and move, resulting in ultra-rapid cooling of the molten material. and the initial effect cannot be obtained. Furthermore, if the injection pressure of the molten material from the nozzle is too high, the jet stream of the molten material becomes irregularly shaped fine particles and scatters. Therefore, when carrying out the invention, the viscosity must be chosen such that the melt builds up on the cooling body with a contact angle of 10° to 170°, preferably approximately 90°. For this purpose, the temperature of the melt must be lower than the melting point.
Preferably, the temperature is 100°C to 150°C higher. According to the present invention, the pressure at which the molten material is ejected from the nozzle is preferably in the range of 0.01 to 1.5 atm. This is because if the ejection pressure of the molten material is too high, the molten material may become a mist, become scattered in the form of fine particles, or the resulting thin ribbon may form a sash-like shape, depending on the viscosity of the molten material. Note that if the melt is ejected in a vacuum, the resulting thin strip will collide with the air, and the above-mentioned drawbacks such as slits, hangnails on the periphery, or porousness can be eliminated. By the method described above, a high-silicon steel ribbon is produced immediately from the melt into a coil. The crystal grains of the ribbon thus obtained are extremely fine, usually ranging from 1 to 100 μm. Such a ribbon has a good shape and magnetic properties so that it can be made into a finished product in this state, but in order to exhibit even higher magnetic properties,
This is preferably annealed for a short time at 400 to 1300°C, preferably 800 to 1250°C, to remove internal strain and at the same time grow crystal grains to a grain size of 0.05 to 10 mm. When this process is performed, for example, the coercive force Hc is significantly reduced. If the heat treatment temperature exceeds 1300°C, the ribbon becomes brittle and cannot be put to practical use. Also, 400℃
It is not possible to remove internal distortions below.
This heat treatment may be carried out by any method, but industrially it is best to anneal for about 60 seconds in a continuous annealing furnace and cool it as quickly as possible. Figure 8 shows a ribbon A with an average grain size of 5 μm and a thickness of 80 μm, consisting of 6.5% silicon and essentially iron, and a ribbon B with a similar composition and an average grain size of 15 μm and a thickness of 80 μm at various temperatures. This is the result of annealing for 2 minutes. As a result of annealing, it is understood that Hc decreases at temperatures above 400°C and reaches saturation at approximately 1300°C. On the other hand, from a practical point of view, it is desirable that the space factor of the core be as high as possible when incorporating it into the core. For this purpose, the surface of the ribbon needs to be smooth. In the present invention, the thin ribbon in the ultra-rapidly solidified state exhibits a sufficiently smooth surface condition under appropriate manufacturing conditions, but when an even higher level of smoothness is required, It is desirable that the rapidly cooled and solidified ribbon is subjected to heat treatment if necessary, then rolled at a rolling reduction of 5% or more and annealed at the above temperature. Rolling can be carried out satisfactorily in a normal cold rolling mill, but if the silicon content is particularly high (7-10%) and cracking during rolling is a concern, it is recommended to roll at a warm temperature of 100°C to 500°C. Ru. Appropriate rolling heat treatment makes the surface of the ribbon smooth, and at the same time, the rolling heat treatment improves the magnetic properties. Although the cause of this is not clear at present, it is presumed that the texture changes due to the rolling heat treatment after cold rolling. The ribbons produced as described above are laminated and used as cores for electrical equipment such as transformers and cores for rotating machines. At that time, the laminated iron core is annealed in that state,
Generating a regular lattice in the ribbon can significantly reduce Hc. In this case, even if a regular lattice occurs, it does not pose any problem since the iron core has already been formed, and it can be said that this is a reasonable method of use. Figure 9 shows a ribbon consisting of 6.5% silicon, 0.2% manganese, and the remainder essentially iron after being annealed at 1200°C for 3 minutes.
This figure shows changes in magnetic properties (Hc) obtained by annealing at temperatures of 350 to 700°C for various times. Apparently, good results are obtained when the temperature is maintained at 400-650°C for 30 minutes or more. Therefore, the annealing in the core state described above is preferably performed within this temperature range. Next, the present invention will be specifically explained with reference to Examples. Example 1 Silicon 6.5%, manganese 0.6%, aluminum 0.3%
Molten iron containing 0.007% carbon, 0.004% nitrogen, 0.003% oxygen, and 0.005% sulfur as unavoidable impurities is jetted into a copper (300 mmφ) rotary cooling body rotating at 800 rpm to form an 80 μm thick ribbon. I made it. Table 1 shows the magnetic properties (Hc) and workability of this ribbon. The ribbon was annealed at 1200°C for 3 minutes, rolled to 65 μm, and further annealed at 1000°C for 3 minutes. Finally, this was wound into a coil and annealed at 500°C for 3 hours.

[Table] The magnetic properties (Hc) indicate the values when magnetized up to 1.5T (Tesla). In addition, the minimum radius of curvature indicates the minimum radius that does not cause breakage when wrapped around glass rods of various radii, and regarding shearing properties, 〇... shows good shearing properties with no shearing burrs △... shows no shearing burrs. Although there are some, shearing is sufficient.×...Means that shearing is difficult. Example 2 Molten silicon iron containing 9.5% silicon, 1.5% manganese, 2% cobalt, 0.1% aluminum, 0.7% nickel, and containing 0.004% carbon, 0.0025% nitrogen, 0.0023% oxygen, and 0.003% sulfur as inevitable impurities. ,
A thin ribbon with a thickness of 100 μm was produced by ejecting it into a twin rotating body made of stainless steel (100 mmφ) rotating at 700 rpm.
This was immediately rolled to 50 μm and annealed at 950° C. for 2 minutes. This was further annealed at 420°C for 10 hours. The magnetic properties and workability after each of these treatments are shown in Table 2.

[Table] Note that the measurement conditions for each item are the same as in Example 1. According to the method of the present invention, an extremely flexible high-silicon iron ribbon can be produced continuously at high speed, and the high-silicon iron ribbon can be easily processed, and rolling and heat treatment are also possible. According to the present invention, a high-silicon iron ribbon without an ordered lattice, which has excellent bendability and shearability, is manufactured, and after being formed into a transformer core or the like, heat treatment is performed to generate an ordered lattice, and the magnetic properties (Hc ), which is extremely useful industrially.

[Brief explanation of the drawing]

Figure 1 A and B are 6.4%Si− in the ultra-quenched state.
Figures 2A and B are micrographs of the surface and cross section of a silicon-iron ribbon containing Fe; 3 is a drawing showing a state in which a silicon-iron ribbon is wound around a rod-shaped body having a diameter of 4 mm and a state in which it is bent. Fig. 3 is a magnetic characteristic diagram showing the relationship between silicon content and coercive force (Hc) of the silicon-iron ribbon of the present invention in comparison with a conventional one, and Fig. 4 a, b, c, and d are graphs of the present invention. A schematic diagram showing an example of an apparatus for manufacturing a silicon-iron ribbon according to the present invention, and FIGS. 5A and 6B, and FIGS. 6A and B are cross-sectional views of a nozzle showing an example of a multi-hole nozzle for manufacturing a silicon-iron ribbon according to the present invention, respectively. FIG. FIG. 7 is an explanatory diagram showing an example of an apparatus for manufacturing a silicon-iron ribbon according to the present invention. Figure 8 shows the magnetic properties (Hc) (A curve) of the silicon-iron ribbon of the present invention before annealing.
A heat treatment characteristic diagram comparing the magnetic properties after annealing and FIG. 9 shows the heat treatment temperature for the silicon-iron ribbon of the present invention,
FIG. 3 is a magnetic characteristic diagram showing the relationship between heat treatment time and coercive force (Hc). 1... Spout nozzle, 2... Bowl-shaped rotating body, 3...
Continuous ribbon, 4... Molten material, 5, 5', 5''...
Rotating roll, 6...Backup roll, 7...
Conveyor, 9... Melt jet, 10... Spout hole,
10'...Auxiliary spout, 11...Vacuum chamber, 12...
...pipe, 13 ... gas injection pipe, 14 ... cylinder, 15 ... vacuum bellows, 16 ... heater, 17 ... exhaust port, 18 ... ribbon collection port.

Claims (1)

[Claims] 1% by weight, consisting of 4 to 10% silicon and the remainder substantially iron and unavoidable impurities, with cobalt as a subcomponent.
10% or less, nickel 3% or less, either one or two
The crystal grains are 1 to 100 μm in size, and there is virtually no regular lattice Fe ₃ Si, and the crystal grains are columnar crystals grown perpendicular to the ribbon surface, resulting in excellent workability and magnetic properties. Excellent high silicon steel ribbon. 2. The high silicon steel ribbon according to claim 1, wherein the unavoidable impurity elements include carbon, nitrogen, oxygen, and sulfur in a total amount of 0.1% or less. 3 wt% silicon, 4 to 10% silicon, and the balance essentially consists of iron and unavoidable impurities, with cobalt as a subcomponent.
10% or less, nickel 3% or less, either one or two
Species or more, aluminum 2% or less, manganese 2%
A columnar type containing one or more of the following, with crystal grains of 1 to 100 μm, substantially no regular lattice Fe ₃ Si, and with crystal grains grown perpendicular to the ribbon surface. High-silicon steel ribbon with excellent workability and magnetic properties. 4. The high silicon steel ribbon according to claim 1, which contains 0.1% by weight or less of any one or both of chromium, molybdenum, tungsten, vanadium, and titanium as impurity elements. 5. Contains 4 to 10% silicon by weight, the balance consists of iron and unavoidable impurities, and cobalt as a subcomponent.
A melt containing either one or two of 10% or less of nickel and 3% or less of nickel is ultra-quenched at a cooling rate of 10 ³ to 10 ⁶ °C/sec to obtain crystal grains of 1 to 100 μm and regular lattice Fe. ₃ Production of high-silicon steel ribbon with excellent workability and magnetic properties, which is characterized by the fact that Si is substantially absent and the ribbon consists of columnar crystals with crystal grains grown perpendicular to the ribbon surface. Method. 6. A method for producing a high silicon steel ribbon according to claim 5, which comprises rapidly cooling the melt on an ultra-quenched body at a rate of 10 ³ to ^{10 6} °C/sec until it reaches 400 °C. 7. The method for producing a high-silicon steel ribbon according to claim 5, wherein the melting temperature of the melt is not higher than the melting point by more than 300°C. 8. Claim 5 consisting of ejecting the molten material from a multi-hole nozzle formed by arranging two or more ejection holes close to each other in a row over the required ribbon width.
A method for producing a high silicon steel ribbon as described in . 9% by weight, containing 4 to 10% silicon, the balance consisting of iron and unavoidable impurities, and cobalt as a subcomponent.
10% or less, nickel 3% or less, either one or two
The melt containing the seeds is ultra-quenched at a cooling rate of 10 ³ to ^{10 6} °C/sec, and the crystal grains are 1 to 100 μm, there is substantially no regular lattice Fe ₃ Si, and the crystal grains are in the form of thin ribbons. A process of obtaining a ribbon consisting of columnar crystals grown perpendicular to the surface, and heating the obtained silicon steel ribbon at 400 to 1300℃.
A high-silicon steel ribbon with excellent workability and magnetic properties, characterized by the process of annealing to grow crystal grains to 0.05 to 10 mm to obtain a ribbon in which ordered lattice Fe ₃ Si substantially exists. manufacturing method. 10 3 to 10% by weight of a melt containing 4 to 10% silicon, the balance consisting of iron and unavoidable impurities, and containing one or both of cobalt 10% or less and nickel 3 ^% or less as subcomponents. Ultra-quenched at a cooling rate of 10 ⁶ °C/sec to obtain a high-silicon steel ribbon with crystal grains of 1 to 100 μm and substantially no ordered lattice Fe ₃ Si, which was then rolled at a rolling reduction of 5% or more. And further
A high-silicon steel ribbon with excellent workability and magnetic properties, which is annealed at 400-1300°C to grow crystal grains to 0.05-10 mm to obtain a ribbon in which ordered lattice Fe ₃ Si substantially exists. Production method. 11 Contains 4 to 10% silicon, 10% or less cobalt, and 3% or less nickel, with the remainder essentially consisting of iron and unavoidable impurities, with crystal grains of 1 to 100 μm and substantially regular lattice Fe ₃ Si. An iron core for electrical equipment made of laminated high-silicon steel ribbons. 12 Contains 4 to 10% silicon, 10% or less cobalt, and 3% or less nickel, with the remainder essentially consisting of iron and unavoidable impurities, crystal grains of 0.05 to 10 mm, and substantially regular lattice Fe ₃ Si. An iron core for electrical equipment made of laminated high-silicon steel ribbons.