JPS644866B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method and apparatus for producing a solution quenched material.

In the present invention, the solution quenched material refers to any one of metals, semimetals, semiconductors, and ceramics having a structure consisting of at least one of amorphous and microcrystalline materials manufactured by the present invention. It shall be.

Conventionally, in order to produce an amorphous or microcrystalline ribbon, a single roll method is used, in which a molten material is jetted from a nozzle and is rapidly solidified by spraying it onto the circumferential surface of a single rotating cooling roll, or A production method called the so-called twin roll method using two cooling rolls is known, but in the case of the single roll method, unevenness tends to occur on the free surface side that does not contact the cooling roll surface. The shape is unstable, and in the case of the twin roll method, the contact area of the cooling roll to rapidly cool the molten material is limited to a narrow area close to line contact, making it difficult to produce a wide ribbon. It is difficult to do so, and the surface of the cooling roll is also easily damaged.

In order to eliminate the above drawbacks, the molten material is jetted onto a first roll with low thermal conductivity to perform super rapid cooling.
A method for producing an amorphous ribbon characterized in that rolling is carried out continuously between this roll and a second roll having high thermal conductivity was invented and is known from Japanese Patent Laid-Open No. 55-45551.

However, in the case of the prior invention, it is necessary to provide a certain gap (usually ~200 μm) between the first and second rolls, and this gap is equal to the thickness of the normal ribbon.
Because it is much larger than 30 to 70 μm, it is impossible in principle to forcibly smooth both surfaces of the ribbon by applying pressure to contact with it with sufficient force, and therefore the thickness cannot be controlled with high precision. , it is fundamentally difficult to eliminate surface irregularities.

In view of the above-mentioned conventional circumstances, the present invention jets a molten material from a nozzle onto the surface of a first cooling roll, rapidly cools the molten material in contact with the cooling roll from the contact surface side to form a ribbon, While the free surface side of the ribbon peeled off from the cooling roll is in a temperature range in which it has deformability, the free surface side of the ribbon is brought into planar contact with the circumferential surface of a second cooling roll and pressurized. The method is characterized in that the ribbon is rapidly cooled from both sides with a time difference, and both sides are made smooth.The principle is, for example, as shown in FIG.
Immediately after the thin strip 6, which has been rapidly cooled from the contact surface and has become a thin plate, is peeled off from the cooling roll 1, the free surface side of the thin strip 6, that is, the first cooling roll The free surface of the thin strip 6 is applied to the circumferential surface of the second cooling roll 2, for example, for about 0.001 to 0.5 seconds while the opposite surface that was in contact with the second cooling roll 2 has a temperature range that allows deformation. Pressure is applied by a pressurizing mechanism 3 that brings the side surfaces into planar contact over a relatively wide range and presses from the outside, or a pressurizing mechanism 4 that suctions from the inside. In the case shown in FIG. 2, the second cooling roll 2a is shaped like a drum, and on its inner circumferential surface, the free surface side of the ribbon 6 in the first cooling roll 1 is heated by the kinetic energy of the ribbon. The surface contact is made while applying pressure by impact force or the like.

Next, various embodiments of the present invention will be described based on the drawings.

FIG. 3 is based on the principle shown in FIG. 1, in which a scraper 7 whose tip is brought very close to the circumferential surface, and a scraper 7, which has its tip very close to the circumferential surface, and air or He, Ar,
A wind pressure device 8 that also serves as a guide is provided and has a large number of jet ports 9 that jet a gas such as an inert gas such as N ₂ from below the ribbon, that is, from the side of the contact surface with the first cooling roll 1. The molten material ejected from the nozzle 5 is blown against the first cooling roll 1, and the thin ribbon 6 formed is reliably peeled off by the scraper 7 and guided to the second cooling roll 2, and the molten material is ejected from the spout 9. The ribbon 6 is brought into pressure contact with the second cooling roll 2 over a relatively wide area by the wind pressure of the gas.

Note that the scraper 7 may be omitted if the ribbon 6 is reliably separated from the first cooling roll 1 by centrifugal force, and the pinch roll 10 is provided behind the wind pressure device 8 to remove the second cooling roll 1. Although the free surface side is further made smooth by bringing the ribbon 6 into pressure contact with the roll 2 under a slight tension, this may be omitted.

Furthermore, the molten material is heated in a container 12 equipped with a heating means 11 to a temperature approximately 10 to 150 DEG C. higher than its melting point, and is ejected from a nozzle 5 by the pressure of a gas such as Ar.

The cooling rolls 1 and 2 may be rotated in air, but preferably they are rotated in vacuum, inert gas, or reducing gas. Copper, chromium copper, brass, beryllium copper, phosphor bronze or other copper alloys, silver, silver alloys, carbon steel, stainless steel, heat-resistant steel, high-speed steel are used in consideration of the relationship and to withstand high-speed rotation. , spring steel, cold die steel, hot die steel, bearing steel, nitrided steel, borided steel, other alloy steels, Inconel-based or Incoloy-based heat-resistant alloys, and the like.

In FIG. 4, the second cooling roll 2B is shaped like a non-magnetic hollow drum, and a magnetic pressure device 13 such as a strong permanent magnet or an electromagnet is installed at a fixed position along the inner periphery of the part where the ribbon 6 contacts. The only difference from the case shown in FIG. 3 is that the ribbon 6 is guided and pressurized by the wind pressure device 8 in the case shown in FIG. is added.

Note that if the pressure applied by the magnetic pressure device 13 is sufficient, the wind pressure device 8 may be omitted.

FIG. 5 is characterized in that the pinch roll 14 that comes into pressure contact with the second cooling roll 2 has a flexible structure in which its circumferential portion is easily deformed and restored, and the pressure contact area of the ribbon 6 is widened in planar form. It is something.

That is, as shown in FIG. 6, the pinch roll 14 has a cooling layer 15 on the circumferential surface made of a metal material with good thermal conductivity and sufficient strength, for example, selected from among the cooling roll materials mentioned above, and a metal material on the inner peripheral side. For example, an elastic body 16 such as elastomer or rubber that is easily deformed and restored even under a weak load is provided, or a hollow elastic body 17 is provided as shown in FIG.
It has a structure in which a pressure medium 18 of gas or liquid can be enclosed or circulated to maintain a constant pressure inside the elastic body 16 and the hollow elastic body 17, and there is usually a pressure medium 18 inside the elastic body 16 and the hollow elastic body 17 so as to transmit the rotational motion of the shaft. Shaft center body 19 made of metallic materials, reinforced plastics, etc.
The three layers are bonded or interlocked with sufficient strength.

For example, on the outer peripheral surface of the pinch roll 14 -20
A cooling device 20 that blows cold air at a temperature of .degree. C. to -40.degree. C. or liquid nitrogen spray may be provided.

In FIG. 8, each of the cooling rolls 1 and 2 is used as an electrode so that a direct current flows through the ribbon 6 that runs in contact with the first cooling roll 1 and the second cooling roll 2, and non-magnetic copper, It is made of copper alloy, silver alloy, stainless steel, manganese austenitic steel, etc., and magnetic force generating devices 21 and 22 such as permanent magnets or electromagnets are provided near both sides of the part where the ribbon 6 contacts. When a current is applied and a magnetic field is applied to the magnetic force generator 21 in the front direction perpendicular to the plane of the paper, and to the other magnetic force generator 22 in the opposite direction perpendicular to the plane of the paper, the thin strip 6 is moved to a cooling roll according to Fleming's left hand rule. An electromagnetic force is generated that presses the ribbons 1 and 2, and pressurizes both sides of the ribbon 6 into contact with each other over a wide area, thereby improving the quenching effect and smoothing the surface.

In this case as well, the scraper 7 and the wind pressure device 8 can be used together, and the magnetic force generator 21,
It is also possible to use a pole piece for 22 in order to make the magnetic field strong and stable.

FIG. 9 is based on the principle shown in FIG. 2, and includes a large drum-shaped second cooling roll 2A that accommodates the first cooling roll 1 therein,
The thin strip 6 peeled off from the first cooling roll 1 by centrifugal force is placed on the second cooling roll 2A with its free surface side
The ribbon 6 is brought into contact with the inner circumferential surface of the ribbon 6, and is rapidly cooled while being pressurized by the impact force at the time of collision and the centrifugal force at the time of rotation, so that a thin ribbon 6 with smooth surfaces on both sides is produced.

After one rotation, the next thin strip 6 is placed on the thin strip 6 pressed against the inner circumferential surface of the second cooling roll 2A.
As a means to avoid this, a winding drum 23 is used to wind up the thin ribbon 6 midway through the winding process.
A winding device consisting of a pinch roll 24 or a damper mechanism 25 for mitigating the impact during winding is provided.

Note that a mechanism (not shown) for storing the thin ribbon 6 in the cooling roll 2A that moves in the axial direction so that the ribbon 6 does not run at the same location on the inner circumference of the second cooling roll 2A after one round can be provided. .

Further, the scraper 7 and the wind pressure device 8 are provided between the first cooling roll 1 and the second cooling roll 2A,
The magnetic pressure device 13 along the outer periphery of the second cooling roll 2A, the flexible structure pinch roll 14 rotating inscribed in the second cooling roll 2A, or the eighth
It is also possible to use one type or two or more types of magnetic force generating devices 21, 22, etc. as shown in the drawings.

Next, each example based on each of the above-mentioned embodiments will be described.

Example 1 In the apparatus shown in FIG. 3, a carbon steel roll with a diameter of 300 mm and a width of 50 mm is used as the first cooling roll 1, and a second cooling roll is installed near the cooling roll 1 with an interval of 30 mm. 2 with a diameter of 200mm and a width of 50mm
made of beryllium copper with the same circumferential speed of 25
Rotate at m/sec.

As the scraper 7, a wind pressure device 8 made of carbon steel is used, the surface of which is on the gliding surface side, except for the hardened tip, treated with turcite to provide lubricity.

Pinch roll 10 has a diameter of 100 mm and a width of 50 mm.
A copper roll is used and rotated at the same circumferential speed.

In a container 12 made of silicon nitride and having an outer diameter of 50 mm and an inner diameter of 30 mm, a slit-shaped nozzle 5 with a slit width of 0.35 mm, a length of 30 mm, and a depth of 10 mm is provided at the bottom of the container.
After melting 300gr of sendust alloy containing %, Al7.05%, Mo1.2%, Ni1.0%, Ar gas pressure 1.3
It is pressurized at Kg/cm ² and is continuously ejected onto the outer periphery of the first cooling roll 1.

The ejected metal is cooled from one side by the first cooling roll 1 and becomes a thin strip, and then peels off from the roll surface and glides while floating due to the wind pressure of Ar gas ejected from the wind pressure device 8. The free surface side is pressed against the outer peripheral surface of the second cooling roll 2 to be rapidly cooled again, and then released into the air while being pressurized by the pinch roll 10, with a crystal grain size of about 5 to 10 μm, with a width of 30 mm, a thickness of 40 μm, and a length of about 40 m. A microcrystalline thin ribbon 6 was produced.

Both sides of the obtained ribbon 6 are smooth within a range of ±1 μm, exhibiting a tensile strength of 35 Kg/mm ² , and magnetic properties such as magnetic flux density B ₁₀ , 8600 G, maximum permeability μ max, 155000, and initial transmission. Rate μ _0.01 , 70000, coercive force
It showed satisfactory characteristics of Hc, 0.018Oe.

Example 2 In the apparatus shown in FIG. 4, a hollow drum made of copper with an outer diameter of 300 mm and an inner diameter of 290 mm is used as the second cooling roll 2B, and energy product (BH) max, 23× 10 ⁶ G・Oe samarium cobalt magnets are arranged so that the NS poles are arranged alternately,
The first cooling roll 1, scraper 7, and wind pressure device 8 are completely similar to those in Example 1, and rotate the cooling surfaces of both cooling rolls 1 and 2B at the same speed of 50 m/sec. In this case, the distance between the two cooling rolls 1 and 2B is compared so that the temperature of the ejected material is below the Curie point by the time it peels off from the first cooling roll 1 and reaches the second cooling roll 2B. The target was set to be large, about 150mm.

Using the same container 12 as in Example 1 above,
Melt 300gr of Fe ₇₂ Co ₁₈ Zr ₁₀ amorphous alloy material,
Ar gas is pressurized at a pressure of 1.8 Kg/cm ² and continuously ejected onto the outer periphery of the first cooling roll 1.

The ejected metal is cooled from one side by the first cooling roll 1 to form a thin strip, and then sent to the second cooling roll 2B where it is magnetically attracted and pressurized and rapidly cooled to form a strip with a width of 30 mm and a thickness of 35 μm. , about 40m long
An amorphous ribbon 6 of Fe ₈₀ Co ₁₀ Zr ₁₀ was produced.

The obtained ribbon 6 is smooth on both sides within a range of ±2 μm, has a tensile strength of 200 Kg/mm ² , and has magnetic properties such as saturation magnetic flux density Bs, 16000 G, maximum magnetic permeability μmax, 288000, and coercive force after heat treatment. It showed satisfactory characteristics of Hc, 0.018Oe.

Example 3 In the apparatus shown in FIG.
A first cooling roll 1 with a diameter of 450 mm and a width of 60 mm, and a roller with a diameter of 100 mm and a width of 60 mm with an interval of about 10 mm between this roll.
a second cooling roll 2 made of water-cooled copper with a further diameter of
A flexible pinch roll 14 with a width of 70 mm and a width of 60 mm is placed in circumscribed contact with the second cooling roll 2 with a load of 5 kg, and the above three rolls 1, 2, and 14 are rotated at the same circumferential speed of 30 m/sec.

The pinch roll 14 has a cooling layer 15 with a thickness of 1 mm.
The elastic body 16 was made of silicone rubber with a thickness of 20 mm, and the shaft center body 19 was made of carbon steel with a radius of 14 mm.

Note that the scraper 7 and wind pressure device 8 were the same as those described above.

In a container 12 made of sintered quartz and having an outer diameter of 120 mm and an inner diameter of 100 mm, a slit-shaped nozzle 5 with a slit width of 0.4 mm, a length of 50 mm, and a depth of 10 mm is provided at the bottom of the container.
After melting 500gr of Fe ₈₁ B ₁₃ C ₂ Si ₄ amorphous alloy material,
Ar gas is pressurized at a pressure of 1.1 Kg/cm ² and is continuously ejected onto the outer periphery of the first cooling roll 1.

After the ejected metal is peeled off, it is transferred to the second cooling roll 2.
It is fed into the pressurized contact area with the pinch roll 14 and rapidly cooled, and the width is 50 mm, the thickness is 35 μm, and the length is 20 m.
An amorphous ribbon 6 of Fe ₈₁ B ₁₃ C ₂ Si ₄ was produced.

The obtained ribbon 6 is smooth on both sides within a range of ±2 μm, and its magnetic properties include, after heat treatment, maximum magnetic flux density Bs, 16000G, coercive force Hc, 0.010Oe,
It showed a satisfactory squareness ratio of 88%.

Example 4 In the apparatus shown in FIG.
A first cooling roll 1 equipped with a positive electrode of 300 mm in diameter and 10 mm in width and a second cooling roll 2 made of copper with a negative electrode of 300 mm in diameter and 10 mm in width are used as magnetic force generators 21 and 22. 26000G by effectively utilizing two electromagnets and pole pieces
A magnetic field is provided near each of the cooling rolls 1 and 2 so that the magnetic flux densities are perpendicular to the plane of the paper and in opposite directions, and a direct current of 0.5 A is passed through the running ribbon 6 to a width of 2 mm.
The ribbon is pressed in the direction of each roll with a load of about 13 gr over each 50 mm length portion of the ribbon 6 having a thickness of 35 μm.

In a container 12 made of a quartz tube with an inner diameter of 20 mm,
After melting 60gr of Fe ₈₀ Cr ₁₀ Zr ₁₀ amorphous alloy material, Ar
The gas is pressurized at a gas pressure of 2.5 kg/cm ² and continuously ejected onto the outer peripheral surface of the first cooling roll 1 which is rotating at a circumferential speed of 40 m/sec.

Since the ejected material becomes a thin ribbon 6 and flies through the magnetic field space, it receives a force in the opposite direction to the centrifugal force. Combined with the effect of the wind pressure device 8 manufactured by Chiyu, pressure and rapid cooling are achieved, resulting in smooth surfaces on both sides with a width of 2mm and a thickness of 35μ.
It was possible to produce an amorphous ribbon 6 with a length of 100 m or more, and a satisfactory tensile strength of 280 Kg/mm ² .

Example 5 In the apparatus shown in FIG. 9, the first cooling roll 1 was made of water-cooled carbon steel, diameter 200 mm, width 60 mm.
using a roll made of carbon steel with an outer diameter of 1060 mm,
A large drum-shaped second cooling roll 2A with an inner diameter of 1000 mm and a width of 100 mm is used, and is rotated at a circumferential speed of 30 m/sec.

The distance between the outer periphery of the cooling roll 1 and the inner wall of the cooling roll 2A is about 50 mm, and the cooling roll 2
It is arranged so that it collides with the inner wall of A.

After melting 1 kg of Fe _2.5 Co _71.5 Mn _3.0 Si ₈ B ₁₅ -based amorphous alloy material in a crucible-shaped container 12 made of silicon nitride with an inner diameter of 50 mm, the bottom width is 0.4 mm, the length is 50 mm, and the depth is 10 mm.
It is ejected from the slit-shaped nozzle 5 onto the outer circumferential surface of the first cooling roll 1, becomes a thin ribbon, and immediately collides the free surface side with the inner wall of the second cooling roll 2A to perform pressurized contact quenching. , is wound onto the winding drum 23 via the damper mechanism 25, and the width is
An amorphous ribbon 6 having a size of 50 mm, a thickness of 35 μm, and a length of about 100 m was obtained.

The obtained ribbon 6 has a smooth surface within a range of ±2 μm, and its magnetic properties are saturated magnetization after heat treatment.
It showed satisfactory values of 9500G, coercive force Hc, and 0.02Oe.

In the present invention, as described above, the molten material ejected from the nozzle is first sprayed onto the first cooling roll, so it is possible to form a wide ribbon as in the conventional single roll method, and then it is fed. In the second cooling roll, the free surface side of the first cooling roll is widened by the cooling roll and the ribbon pressure mechanism while the air is in the temperature range in which it has the deformability. By bringing pressure into contact across the surface, it is possible to improve the quenching effect and create a thin strip with extremely smooth surfaces on both surfaces. According to the present invention, the difference between the valleys and peaks of the unevenness, which was about 6 to 8 μm, can be reduced to about 1 to 2 μm as described above, and the effect is obvious.

[Brief explanation of drawings]

Figures 1 and 2 are schematic diagrams showing the principle of the present invention, Figures 3 to 5, Figures 8 and 9, respectively.
The figures are schematic diagrams showing various embodiments of the present invention, respectively;
FIGS. 6A and 6B and FIGS. 7A and 7B are a front view and a longitudinal cross-sectional view, respectively, showing half of each embodiment of the pinch roll shown in FIG. 5. 1: first cooling roll, 2, 2A, 2B: second
cooling roll, 3, 4: pressure mechanism, 5: nozzle,
6: Thin strip, 7: Scraper, 8: Wind pressure device, 9:
spout, 10: pinch roll, 11: heating means,
12: Container, 13: Magnetic pressure device, 14: Pinch roll, 15: Cooling layer, 16: Elastic body, 17: Hollow elastic body, 18: Pressure medium, 19: Axial body, 2
0: Cooling device, 21, 22: Magnetic force generator, 2
3: Winding drum, 24: Pinch roll, 25: Damper mechanism.

Claims (1)

[Claims] 1. Spraying the molten material from a nozzle onto the circumferential surface of the first cooling roll, and rapidly cooling the molten material in contact with the cooling roll from the contact surface side to form a ribbon; While the free surface side of the ribbon peeled off from the circumferential surface of the cooling roll is in a temperature range in which it has deformability, the free surface side of the ribbon is brought into planar contact with the circumferential surface of a second cooling roll. 1. A method for producing a solution-quenched material, characterized in that the ribbon is quenched from both sides with a time difference by applying pressure, and both sides are made smooth. 2. A nozzle for spouting a molten material, and a first cooling roll and a second cooling roll that are spaced apart from each other, and the molten material jetting from the nozzle is sprayed onto the circumferential surface of the first cooling roll. After the ribbon is peeled off from the cooling roll, the free surface side of the ribbon is in contact with the circumferential surface of the second cooling roll while the free surface side of the ribbon is in a temperature range in which the ribbon has deformability, Furthermore, a wind pressure device is provided that blows gas from a large number of jet ports toward the contact surface side of the ribbon, so that the ribbon contacts the second cooling roll in a planar manner and pressurizes the ribbon. An apparatus for producing solution quenched materials, which is characterized by: 3 A nozzle for spouting a molten material, a first cooling roll and a second cooling roll in the form of a non-magnetic hollow drum that are spaced apart from each other, and the molten material jetting from the nozzle is directed to the first cooling roll. After the thin strip formed by blowing onto the circumferential surface is peeled off from the cooling roll, the free surface side is applied to the circumferential surface of the second cooling roll while the free surface side of the thin strip is in a temperature range in which it has deformability. A magnetic pressurizing device is provided along the inner periphery of the second cooling roll at the portion where the ribbon contacts, and the ribbon is sucked into the second cooling roll from the inside to form a planar shape. An apparatus for manufacturing a solution quenched material, characterized in that the material is brought into contact and pressurized. 4 A nozzle for spouting a molten material, and a first cooling roll and a second cooling roll provided at intervals, the molten material jetting from the nozzle being sprayed onto the circumferential surface of the first cooling roll. After the ribbon is peeled off from the cooling roll, the free surface side of the ribbon is in contact with the circumferential surface of the second cooling roll while the free surface side of the ribbon is in a temperature range in which the ribbon has deformability, Furthermore, a pinch roll is provided which contacts the first cooling roll contact surface side of the thin strip and circumscribes the second cooling roll via the thin strip, and has a flexible structure whose circumferential portion is easily deformed and restored. 1. An apparatus for manufacturing a solution quenched material, characterized in that the thin ribbon is brought into planar contact with a second cooling roll and pressurized. 5 A nozzle for spouting a molten material, and a first cooling roll and a second cooling roll provided at intervals, and the molten material spouted from the nozzle is sprayed onto the circumferential surface of the first cooling roll. After the ribbon is peeled off from the cooling roll, the free surface side of the ribbon is in contact with the circumferential surface of the second cooling roll while the free surface side of the ribbon is in a temperature range in which it has deformability, Further, the first cooling roll and the second cooling roll are provided as electrodes so that a current flows through the ribbon, and magnetic force generating devices are provided near both sides of the contact portion of each cooling roll with the ribbon, so that the ribbon An apparatus for manufacturing a solution quenched material, characterized in that the material is pressurized by contacting each cooling roll in a planar manner. 6 comprises a nozzle for spouting the molten material, a first cooling roll, a drum-shaped second cooling roll that stores the cooling roll therein, and a winding device, and the molten material jetting from the nozzle is spouted from the first cooling roll. After the thin strip formed by blowing onto the circumferential surface of the cooling roll is peeled off from the cooling roll, while the free surface side of the ribbon is in a temperature range in which it can be deformed, the free surface side is placed inside the second cooling roll. The thin ribbon is provided so as to be in contact with the circumferential surface, and the thin ribbon is pressed in planar contact with a second cooling roll, and the thin ribbon created is wound up via the second cooling roll. An apparatus for producing solution quenched materials, which is characterized by: