WO2013105297A1

WO2013105297A1 - Method for manufacturing amorphous plate and device for manufacturing same

Info

Publication number: WO2013105297A1
Application number: PCT/JP2012/070649
Authority: WO
Inventors: 倉橋　隆郎; 松本　宏; 潤治竹原; 恒裕三村; 尚寿福留; 敬治森本
Original assignee: 株式会社中山製鋼所
Priority date: 2012-01-13
Filing date: 2012-08-13
Publication date: 2013-07-18
Also published as: JP6010554B2; JPWO2013105297A1

Abstract

[Problem] To provide an amorphous alloy sheet and an amorphous alloy film-coated sheet having greater thicknesses and widths compared to conventional manufacturing dimensions. [Solution] An amorphous alloy film is formed by performing spraying on a surface of a heated sheet base material, and the metal sheet with the amorphous alloy film is passed through a rolling machine in a state where the amorphous alloy is maintained in a temperature range in which the amorphous alloy has plastic flowability. Particularly, it is preferable to heat the sheet base material so that the sheet base material is 200-520°C at the time when the amorphous alloy film is formed.

Description

Method and apparatus for manufacturing amorphous plate

The present invention relates to a method and an apparatus for producing an amorphous plate (amorphous film coated plate having an amorphous alloy film on a thin plate base material and an amorphous alloy thin plate formed by separating the film from the thin plate base material). is there.

Amorphous alloys have not been widely deployed as industrial members, although they have many excellent performances such as corrosion resistance, wear resistance, soft magnetism, and catalytic properties. The reason is that the conventional industrial amorphous alloy sheet manufacturing equipment is mainly a single roll or twin roll method, and the manufacturing dimensions are limited to a small size with a thickness of 100 μm or less and a width of 200 mm or less.

The twin roll method was introduced in a paper published by H.S. Chen et al. In 1970 in the United States. Single roll technology was published by Masumoto et al. In 1970, and a patent was issued in 1975 by Allied Chemical Company in the United States. Recently, many patents such as twin rolls, Japanese Patent Laid-Open Nos. 6-7902 and 6-114504 have been filed. That is, there are the following non-patent documents and patent documents as prior art documents.

JP-A-6-7902 JP-A-6-114504

The conventional twin roll method and single roll method are methods in which a molten alloy is directly contacted with a roll and rapidly cooled to produce an amorphous alloy sheet. For this reason, it is impossible to produce an amorphous alloy sheet with a thickness of 100 μm or more at the limit of roll cooling. In addition, it is difficult to produce an amorphous alloy sheet with a wide width and a uniform thickness, and as a result, the maximum width is 220 mm. As an actual industrial material, such a small size has a narrow range of use. As an amorphous alloy thin plate, if a large plate exceeding the maximum dimensions (plate thickness 100μm, width 220mm) manufactured by conventional manufacturing equipment, for example, a plate thickness of 300μm or more, width 300mm or more, can be used as an industrial member. The development of
The present invention provides a new production method and production apparatus for an amorphous plate (amorphous film coating plate having an amorphous alloy film on a thin plate substrate, and an amorphous alloy thin plate formed by separating the film from the thin plate substrate), Thus, for example, a thin plate having a thickness of 300 μm or more and a width of 300 mm or more can be manufactured.

In the present invention, a film of an amorphous alloy (including metal glass, including a non-amorphous rate of 100%) is formed on the surface of a preheated thin plate substrate by thermal spraying, and the plastic fluidity temperature range of the amorphous alloy ( The thin plate substrate with an amorphous alloy film is passed through a rolling mill at approximately 200 to 520 ° C.). As a result, the surface of the amorphous alloy thin plate is smoothed and the consistent holes and vacancies therein are eliminated.
When an amorphous alloy film is formed and rolled with a rolling mill while the amorphous alloy film does not cool (with good plastic fluidity), an amorphous plate with no consistent holes or voids inside the amorphous alloy film (Figure 2 Amorphous Alloy) A cross section of the thin plate) is produced.
In the case where the separating agent (FIG. 3) is not applied to the thin plate base material with a separating agent applicator, it is also possible to produce a thin plate in which an amorphous alloy is plated on the thin plate base material. In that case, the effect which improves the adhesive force of a thin-plate base material and an amorphous alloy membrane | film | coat is also acquired by letting it pass through a rolling mill.

In order to keep the amorphous alloy in a temperature range having plastic fluidity as described above, the thin plate base material is heated before the thermal spraying, and when passing through a rolling mill, the amorphous alloy film becomes 200 to 520 ° C. It is preferable to do this. Thereby, the thin plate substrate with the film can be passed through a rolling mill in a state where the film is in the plastic fluidity temperature range, thereby eliminating the consistent holes and voids inside the amorphous alloy film, and further, In some cases, the adhesion between the thin plate substrate and the amorphous alloy is improved. The purpose of pre-heating the thin plate substrate is to keep the amorphous alloy at the plastic fluidity temperature during rolling. When the temperature of the amorphous alloy film when it is passed through a rolling mill is lower than 200 ° C., when the sprayed amorphous alloy film is rolled, the plastic fluidity is insufficient and cracks occur without deformation. On the other hand, when the film is heated to be higher than 520 ° C., the amorphous alloy film is not formed because the temperature becomes higher than the crystallization temperature during the thermal spraying of the amorphous alloy. It is more preferable that the roll of the rolling mill is heated so that the surface temperature becomes 200 to 520 ° C. This is because the amorphous alloy being rolled can be easily maintained at the plastic fluidity temperature.

When the metal sheet with an amorphous alloy film is passed through a rolling mill and then the amorphous alloy film is peeled from the sheet material, an amorphous alloy sheet having excellent internal and surface properties can be obtained.
With respect to this process, the amorphous coating and the thin plate substrate must be in close contact immediately after spraying and during rolling and peel off after rolling. When the thin plate base material is pickled and iron with a surface roughness Ra of 1 to 2 μm and a linear expansion coefficient of 11 × 10 ^-6 / ° C, there are various materials such as stainless steel and aluminum for the thin plate base material. It is also possible to match the expansion coefficient), and since the thermal shrinkage rate differs greatly, an amorphous film with poor adhesion (for example, Ni base having a linear expansion coefficient of 17 × 10 ⁻⁶ / ° C.) may be peeled off before rolling. Therefore, the surface of the thin plate base material is polished and the surface roughness is set to 2 to 5 μm in Ra to improve the adhesion between the amorphous film and the thin plate base material and roll.
On the other hand, an amorphous film (for example, Fe base having a linear expansion coefficient of 11 × 10 ⁻⁶ / ° C.) having a close thermal contraction rate and good adhesion to the thin plate base material is not polished because it does not peel before rolling. A separating material is applied or sprayed on the surface of an amorphous alloy film (eg Fe base) having good adhesion. By using a different diameter single-drive rolling mill in which the upper and lower rolls have a diameter difference and only one of the upper and lower rolls is driven or an ordinary four-stage {two-stage} rolling mill, The alloy thin plate is preferably peeled from the thin plate base material. Separating agent and different diameter single drive rolling are for peeling the amorphous alloy sheet from the sheet substrate.

As an apparatus for carrying out the invention, there are a pay-off reel for paying out a thin plate base material, a surface treatment device (abrasive device, for example, air blast) for smoothing the surface of the thin plate base material, and shape correction of the base plate thin plate. Leveler, separator applicator or sprayer, substrate thin plate heating device, amorphous alloy film-forming injection device (large super-quenching transition control device), different diameter single drive or normal A four-stage (two-stage) rolling mill, an apparatus for heat insulation and cooling after forming the amorphous alloy thin plate, a winder for winding the thin plate base material, and a winder for winding the amorphous alloy thin plate are preferable. It is advantageous to incorporate a heater in the roll of the rolling mill to be used so that the surface temperature can be adjusted by heating the roll.

Alternatively, instead of separating the amorphous alloy thin plate and the substrate thin plate as described above, the surface roughness of the thin plate substrate is set to 2 to 5 μm in Ra, and the upper and lower rolls have the same upper and lower roll diameters as the rolling mill. By using the same-diameter dual drive system that is driven, not only the consistent holes and voids of the amorphous alloy film are reduced, but also the adhesion of the amorphous alloy film coating layer to the thin plate substrate is improved (amorphous film coating plate Can also be obtained).
As an apparatus for carrying out the invention, there are a payoff reel for paying out a thin plate substrate, a leveler for correcting the shape of the thin plate substrate, and a surface treatment device (polishing) for smoothing the surface of the thin plate substrate. Equipment (for example, air blasting), heating device for thin plate base material, thermal spraying device for forming amorphous alloy coating, rolling mill driven by the same diameter, and winding for winding the produced amorphous alloy coating coated thin plate It is preferable to have a machine and a device for heat insulation and cooling when forming an amorphous alloy thin plate. For the same-diameter dual-drive rolling mill used for this, it is advantageous to incorporate a heater in the roll so that the roll can be heated to adjust the surface temperature.

In the amorphous plate manufacturing apparatus as described above, as the above-mentioned injection device (large-scale ultra-quick transition transition injection device) for forming an amorphous alloy film,
A device that sprays a flame containing material particles from the spray gun toward the base material, melts the material particles by the flame, and cools the material particles and the flame before reaching the base material,
-On the front surface of the spray gun, the material particle spray port and the flame spray port are continuously provided in the width direction of the substrate at least 150 mm,
・ Inert gas (nitrogen gas, etc.) injection ports for rectifying and cooling the flame, and liquid mist (water mist, etc.) for cooling the flames at positions on both sides of the material particle injection port and flame injection port It is advisable to use an apparatus in which the nozzle is continuously provided with 150 mm or more in the width direction of the substrate.
This is because a wide amorphous plate can be efficiently manufactured by using such a wide injection device. When injecting a high-power flame (including material particles) with a width of 150 mm or more, it is necessary to properly rectify the flame and cool it sufficiently, but with the above device, it flows just outside the flame The inert gas performs its rectification and partial cooling, and the liquid mist that flows to the outside strongly supplements the cooling of the flame, thus realizing the necessary rectification and cooling to form a wide amorphous film. enable.
In addition, a dust collection hood is provided in the vicinity of the flame of the injection device that forms the amorphous alloy film, and the dust collection hood is cooled while being cooled by water mist separately supplied to the dust collection hood. It is preferable that the hood is sucked and sent to the dust collector.

According to the present invention, a thin plate made of only an amorphous alloy or a coating plate having an amorphous alloy film on its surface can be smoothly produced, and the thickness is increased to, for example, 300 μm or more, and the width dimension, for example, to 300 mm or more. Is also possible. By rolling down with a rolling mill, there is an effect that the surface of the amorphous alloy can be smoothed and no voids can be contained therein.
Since a preferable thin plate can be manufactured as described above, the range in which an amorphous alloy thin plate can be applied as an industrial member is greatly increased. In addition, the amorphous alloy film coating plate can be applied in place of the plating material to increase the durability of building materials, wall materials, and roof materials.

Figure 1 shows a large quench transition control injector. Each of the figures (a), (b) and (c) is a front view, a side view and a bottom view of the whole including the water mist injection port. A plurality of material particle injection ports, flame injection ports, and rectifying / cooling nitrogen gas injection ports are continuously arranged in the horizontal direction along a straight line. Further, (d) is an external photograph showing a flame or the like during actual injection. FIG. 2 shows the cross section of the amorphous alloy thin plate and the X-ray diffraction analysis result. The composition of this amorphous alloy is 64.5Ni-10Cr-7.5Mo-18B (at%). FIG. 3 is a drawing in which a separating material is applied to a thin plate substrate by a coating apparatus, and a configuration diagram of the separating agent coating apparatus. FIG. 4 is a drawing for separating the single-diameter single-drive rolling mill and the amorphous alloy sheet from the sheet substrate. FIG. 5 is a view showing a dust collector (dust collection hood) around the rolling mill. FIG. 6 (a) is a side view showing an overview of the production line for amorphous alloy thin plates, and FIG. 6 (b) is a diagram showing the temperature transition of the substrate and the amorphous sprayed alloy thin plate. FIG. 7 is a detailed view showing a part of the production line of FIG. FIG. 8 is a side view conceptually showing an example of amorphous alloy film temperature measurement. FIG. 9 is an appearance photograph showing an example of the manufactured amorphous alloy thin plate coil. FIG. 10 shows the cross section of the amorphous film coating plate and the result of X-ray diffraction analysis. The composition of this amorphous alloy is 64.5Ni-10Cr-7.5Mo-18B (at%). FIG. 11 is an appearance photograph showing an example of the manufactured amorphous film-coated plate. FIG. 12 is a photograph showing heating by a heating / soaking device and injection from a large quench transition control injector in a line showing production of an amorphous alloy film.

The apparatus of the present invention is a continuous production equipped with a large-scale ultra-quenching transition control injector (that is, an injection device. Cooling capacity: more than 1 million degrees per second. Fig. 1) that enables the production of amorphous alloy with a thickness of 300 µm or more. Equipment (FIG. 6). The large super rapid cooling transition control injector has material injection holes arranged at equal intervals in the width direction, and has gas injection holes on the outer side. The gas is injected from there to melt the material, and quenching with water mist etc. The gas gun has a structure, and since a material is uniformly injected in the width direction, a thin plate having a uniform thickness in the width direction can be formed.

The large ultra-quenching transition control injector is configured as shown in FIG. That is,
a) A plurality of material particle injection holes 25 and a plurality of flame injection holes 26 are provided along the straight line on the front surface of the spray gun 21 so that the cross section of the flame a containing the material particles is a horizontally long (about 300 mm width). They are arranged continuously.
b) A plurality of nitrogen gas (inert gas) b injection ports 27 for rectifying and cooling the flame a at the positions on both sides of the material particle injection port 25 and the flame injection port 26 along the straight line. They are arranged continuously.
c) At the positions on both sides of the material particle injection port 25, the flame injection port 26 and the inert gas injection port 27, the water mist c injection port 24 for cooling the flame a is aligned along the straight line. A slit is provided in the mist nozzle 23.
The water mist c injection port 24 is angled so that the mist c to be injected approaches the flame a, and the angle can be changed according to the chemical composition of the material particles. Further, the injection pressures of the nitrogen gas b and the water mist c can be similarly changed. Due to the action of nitrogen gas b and water mist c, the cooling rate of flame (a flame containing material particles) a reaches 400,000 to 1 million ° C./second.
The water mist c is decomposed into oxygen and hydrogen by contact with the high thermal power flame a, and the amount of oxygen in the flame a is excessively reduced, so the amount of oxygen injected from the flame injection port 26 is reduced. , 50-80% of the amount of oxygen required for complete combustion.

The pickled thin plate base material (coil) is fitted into a payoff reel, the tip of the thin plate base material is guided to a line with a pinch roll, and the shape correction and curl of the thin plate base material are corrected through the leveler. The sheet width and length direction are made uniform (± 10 degrees) with a heating device including an infrared heater up to a temperature (200 to 520 degrees) that can maintain the plastic fluidity of the amorphous metal injected later on the thin plate substrate. Heat. Then, the powder material is sprayed on the base material with a large ultra-quick quench transition control jet to form an amorphous alloy film, and the amorphous alloy film does not cool, and is rolled with a rolling mill while the plastic fluidity is good. To do. Thus, an amorphous metal thin plate (FIG. 2 cross-section of the amorphous thin plate) having no consistent holes or voids inside the thin plate is produced.
After that, what was sprayed on the thin plate substrate with a large ultra-quick transition control injector, amorphous alloy film, after rolling down with a rolling mill, what was separated from the thin plate substrate, amorphous alloy thin plate, when not separating from the thin plate substrate, The plate is called an amorphous alloy film coated plate. Moreover, an amorphous alloy thin plate and an amorphous alloy film coating plate are generically called an amorphous plate.
The rolling temperature at the time of rolling is a plastic fluid region (temperature of 200 to 520 degrees) regardless of whether the amorphous metal thin plate is an amorphous alloy or metal glass. The rolling reduction in the rolling mill is 2-30% of the thickness of the amorphous alloy sheet, and the rolling speed is 2-20 m / min.
When the separating agent is applied to the base material in advance with a separating agent applicator (Fig. 3), after rolling, the amorphous alloy thin plate is separated from the thin plate base material, and the thin plate base material and the amorphous alloy thin plate are wound up separately to form an amorphous alloy. Thin plates can be manufactured. This is to obtain an amorphous alloy thin plate exceeding the conventional manufacturing dimensions. The rolling mill system used here may be an ordinary four-stage (two-stage) system, but a different diameter piece drive system (FIG. 4) may be employed in order to improve the separability. The advantage of rolling with a different diameter single drive method is that the upper and lower roll diameters are larger when the roll diameter of the upper and lower rolls is different, and the smaller the roll diameter, the higher the roll diameter of the upper roll. If it is smaller, the thin metal substrate and the amorphous alloy thin plate can be separated by utilizing the fact that the amorphous metal thin plate warps upward.
FIG. 3 shows a conceptual diagram showing the state of application (application by spraying) of the separating agent to the surface of the thin plate substrate, and a configuration diagram (system diagram) of the separating agent applying apparatus. The separating agent application device sprays a separating agent (such as grease) in a grease tank onto a thin plate substrate through a plurality of systems each having a pump and an injection nozzle.
The separating agent used here consists of a surfactant with a particle size of 1 to 10 μm and a solid lubricant (Si, etc.) with the same particle size. When the film is formed, the peelability between the film and the thin plate substrate is improved. Table 1 shows typical components and separation effects.

Equipment for producing amorphous alloy sheets is shown in FIGS. 6 and 7. FIG.
In this equipment, an amorphous alloy film is formed on the surface of a thin plate substrate by thermal spraying, and thereafter rolled to eliminate voids / consistent holes, and the amorphous alloy thin plate is peeled off from the thin plate substrate and collected. This facility will be described in detail below.

Specific Form of Equipment The basic equipment and functions that make up the line in FIG. 6 are as follows.
(1) Payoff reel: For receiving a thin plate base coil.
(2) Polishing device: Abrasive material is sprayed onto the substrate surface using compressed air made by a compressor.
(3) Separating agent coating and spraying device: A device for applying a separating material to facilitate separation of the amorphous alloy thin plate and the thin plate base material. In addition, it is good also to provide between a thin-plate base-material heating apparatus and a super quenching transition control injector.
(4) Preheater: A device for heating a thin plate base material from room temperature to 350 degrees. This time, two rows of propane burners were arranged in the width direction. Here, the thin plate base material uses a pickling material to which no rust preventive oil is applied, but since it is manufactured on the same pickling line as the thin plate coated with the rust preventive oil, a very small amount of the rust preventive oil remains. When this is heated, carbides appear on the surface, reducing the adhesion between the amorphous alloy film and the thin plate substrate. Therefore, reducing the required amount of oxygen to propane burner to 0.8 to 0.7 will result in a reducing atmosphere, and will also play a role in preventing the generation of graphite due to rust-preventing oil. (5) Leveler: Shape correction broken by heating the thin plate base material Is what you do.
(6) Thin plate substrate heating / soaking device: A device for heating a thin plate to 200 to 520 ° C. When the thin plate heating temperature is lower than 200 ° C., when rolling an amorphous alloy produced by injection, the plastic fluidity is insufficient and the amorphous film is cracked. On the other hand, when the thin plate base material is heated to a temperature higher than 520 ° C., the molten alloy powder becomes higher than the crystallization temperature at the time of injection with a large ultra-cooled transition control injector, so that an amorphous alloy film is not generated. The equipment here adopted an infrared system.
(7) Large-scale ultra-quick transition control injector: Amorphous alloy film production equipment. It is an apparatus that forms the basis of the production of this amorphous alloy film and amorphous alloy sheet. The configuration and the like are as described above (see FIG. 1).
(8) Dust collector: The dust collector installed at the front of the rolling mill is to recover the amorphous gas residue after injection and surplus gas used in the large ultra-quick transition control injector. The gas energy used to melt the amorphous alloy powder is less than 10% of the total. Therefore, if the surplus gas is not recovered, the ambient temperature around the rolling mill will be 450 degrees, the surface of the amorphous alloy film on the thin plate substrate will be 600 degrees or more, and the amorphous film will begin to crystallize. Since the inside of the dust collector becomes hot because a large amount of gas is collected, the dust collector and the piping before the dust collector are cooled with water mist and the temperature inside the dust collector is controlled to be 80 ° C or lower. Fig. 5 shows the arrangement of dust collection hoods. As shown in the figure, the dust collection hood is provided at the left and right of the passage position of the thin plate base material and the position surrounding the upper part of the rolling mill, and sprays water mist for cooling toward them. Water mist for cooling is also injected into suction ducts connected to each dust collection hood, and suction gas is sent to the dust collector main body (not shown) through the ducts.
(9) Different-diameter single-drive rolling mill (or 2-stage, 4-stage same-diameter rolling mill): The amorphous alloy film is crushed to crush consistent holes and pores, and at the same time, above and below the thin plate substrate and amorphous alloy film By changing the degree of processing, the amorphous alloy film is warped, and the amorphous alloy film and the thin plate base material are separated to form an amorphous alloy thin plate. In this rolling mill, it is preferable that at least the work roll on the side in contact with the amorphous alloy film is a temperature-adjustable one incorporating a bar heater or the like.
(10) Thin plate substrate winding machine: Winds the separated thin plate substrate.
(11) Amorphous alloy sheet take-up machine: Takes up the separated amorphous alloy sheet.
The equipment shown in the figure is basically an amorphous alloy thin plate production line composed of (1) to (11).
Furthermore, facilities such as (12) to (13) may be added.
(12) Amorphous alloy thin plate heating device: A device for holding a separated amorphous alloy thin plate in a plastic flow temperature range.
(13) Warm processing machine: A machine that processes and molds an amorphous alloy sheet kept at a plastic flow temperature.

Table 2 shows the equipment configuration according to the product type.

Contents of work When manufacturing amorphous alloy sheet, the procedure is as follows.
(1) Setting of thin plate base material In other words, the thin plate base material is previously placed on the payoff reel to the tension reel.
(2) Start of threading When the above setting is completed, the payoff reel is activated to feed the thin plate base material from left to right in the figure. The following operations are simultaneously performed by each device on the thin plate substrate to be sent.
(i) Grind the surface with air blast as necessary.
(ii) Using a separating material coating apparatus, a separating agent is coated on the entire width of the thin plate base material for the required amorphous alloy.
(iii) A small amount of remaining rust preventive oil is burned in a thin plate base material preheating device so as not to leave graphite. (iv) The shape of the thin plate base material is corrected with a leveler.
(v) Preheat in the range of 200 ° C to 520 ° C while passing through a thin plate substrate, heating and soaking device.
(vi) An amorphous alloy film is formed with a large ultra-quickly cooled transition controlled injector.
(vii) Roll the amorphous alloy film and the thin plate base material with a rolling mill. Due to the difference in the amorphous alloy composition and production conditions, the rolling reduction is reduced from 2% to 30% 0.1 to 10 seconds after the amorphous alloy film is injected with a large ultra-quick transition control injector. As shown in FIG. 8, the surface temperature of the amorphous film 16 is measured using a thermocouple 17, and the heating of the thin plate base material is controlled accordingly. The base material temperature depends on the temperature of the outside air, and the target temperature ± 30 degrees may vary on the heating and soaking furnace exit side. For variations of 20 degrees or more, adjust the burner heating power of the preheater, and within 20 degrees, adjust it by infrared heating and the electrical output of the soaking furnace. If the temperature of the work roll on the side in contact with the amorphous alloy film in the rolling mill is adjustable, the surface temperature of the roll may be kept in the range of 200 to 520 ° C. during rolling.
(viii) After rolling, winding is performed with a winding machine for each of the separated amorphous alloy thin plate and thin plate base material. In some cases, an amorphous alloy thin plate preheating device and a warm processing machine are placed in front of the amorphous alloy thin plate winder to continuously produce products from the amorphous alloy thin plate.
On the other hand, when producing an amorphous film-coated thin plate, the procedure is performed as follows.
(1) Setting of thin plate base material In other words, the thin plate base material is previously placed on the payoff reel to the tension reel.
(2) Start of threading When the above setting is completed, the payoff reel is activated to feed the thin plate base material from left to right in the figure. The following operations are simultaneously performed by each device on the thin plate substrate to be sent.
(i) If necessary, the surface is ground by air blasting to increase the roughness of the surface of the thin plate substrate.
(ii) Do not apply separation material.
(iii) In a thin plate base material preheating device, a small amount of remaining rust preventive oil is burned so as not to leave graphite.
(iv) The shape of the thin plate substrate is corrected with a leveler.
(v) Preheat in the range of 200 ° C to 520 ° C while passing through a thin plate substrate, heating and soaking device.
(vi) An amorphous alloy film is formed with a large ultra-quickly cooled transition controlled injector.
(vii) Roll the amorphous alloy film and the thin plate base material with a rolling mill. Due to the difference in the amorphous alloy composition and production conditions, the rolling reduction ratio is 2% to 30% in the same diameter roll 0.1 to 10 seconds after the amorphous alloy film is sprayed with a large ultra-quick transition control injector. Even in the case of manufacturing an amorphous coating coated thin plate, it is preferable that the work roll on the side in contact with the amorphous alloy coating at least in the rolling mill is a temperature-adjustable one incorporating a bar heater or the like. This is because by maintaining the surface temperature of the roll or the like in the range of 200 to 520 ° C. during rolling, the amorphous alloy film can be easily maintained at the plastic fluidity temperature.
(viii) After rolling, the amorphous alloy thin plate and the thin plate are not separated and wound by a thin plate substrate winding device.

Introduced below are the production tests of amorphous alloy sheets performed with the equipment shown in Figs. 6 and 7. In this test, the same-diameter dual-drive rolling mill was used as the rolling mill.

An amorphous alloy sheet with a thickness of 300μm and a width of 300mm will be manufactured using a super-quenching transition control injector. Table 3 shows the manufacturing test conditions. The surface temperature of the thin plate substrate before thermal spraying of the amorphous alloy is heated to 400 ° C., and the powder of 64.5Ni-10Cr-7.5Mo-18B (at%) is melted and sprayed from the ultra-quenching transition control injector. In this example, the substrate feed speed is 5.7 m / min and the roll is reduced by 10% with the same diameter roll of φ115. The rolling load after 10% rolling was 24 t.

(2) Test results Fig. 9 shows the amorphous alloy sheet. A thin amorphous alloy sheet with a thickness of 300 μm, a width of 300 mm and a length of 4 m was obtained. The amorphization rate and cross-sectional photograph are shown in FIG.

The production test of the amorphous alloy film coating plate carried out with the equipment shown in FIGS. 6 and 7 followed the steps shown in Table 2. In this test, the same-diameter dual-drive rolling mill was used as the rolling mill.

An amorphous alloy coating sheet with a thickness of 250μm and a width of 300mm will be manufactured using a super-quenching transition control injector. Table 4 shows the main manufacturing test conditions. The surface temperature of the thin plate substrate before thermal spraying of the amorphous alloy is heated to 450 ° C., 64.5Ni-10Cr-7.5Mo-18B (at%) powder is melted and sprayed from an ultra-quenching transition control injector. In this example, the substrate feed speed is 5.7 m / min, and the sheet is reduced by 7% with the same diameter roll of φ115. The rolling load after 7% rolling was 15 t.

(2) Test results Fig. 10 shows the amorphous alloy film coated plate. An amorphous alloy film coated plate having a thickness of 2.25 mm {amorphous film thickness 250 μm} and a width of 300 mm and a length of 150 mm could be obtained. The amorphization rate and cross-sectional photograph are shown in FIG.

The present invention provides a new production method and production apparatus for an amorphous plate (amorphous film coating plate having an amorphous alloy film on a thin plate substrate, and an amorphous alloy thin plate formed by separating the film from the thin plate substrate), Thereby, for example, it is possible to produce a thin plate having a thickness of 300 μm or more and a width of 300 mm or more. If such a large-sized thing can be manufactured, development as an industrial member will spread greatly.

1 Payoff reel
2 Surface polishing equipment
3 Separating material application and jetting machine
4 Preheater
5 Leveler
6 Thin plate substrate heating, soaking device
7 Ultra-cooled transition control injection device
8 Different diameter single drive rolling mill (2 or 4 rolling mill)
9 Dust collector
10 Sheet base material winder
11 Amorphous alloy sheet winding machine
12 Amorphous alloy sheet heating device
13 Warm processing machine
14 Thin plate base material
15 Separation material
16 Amorphous alloy sheet
17 Thermocouple
21 spray gun
23 Mist spray nozzle
24 Mist injection port
25 Material injection port
26 Flame outlet
27 Inert gas outlet
28 Amorphous alloy powder supply pipe
29 Propane gas supply pipe
30 branch route
31 Oxygen supply pipe
32 Inert gas supply pipe
a flame
b Inert gas
c mist

Claims

An amorphous alloy film is formed by jetting on the surface of a heated thin plate base material, and the thin metal plate with the film is passed through a rolling mill in a state where the amorphous alloy is maintained in a temperature range having plastic fluidity. A method for producing an amorphous plate.
In order to keep the amorphous alloy in the temperature range having plastic fluidity as described above, the thin plate substrate is heated before the injection, and the amorphous alloy film is set to 200 ° C. to 520 ° C. when passing through a rolling mill. 2. The method for producing an amorphous plate according to claim 1, wherein:
3. The method for producing an amorphous plate according to claim 2, wherein after the metal thin plate with the amorphous alloy film is passed through a rolling mill, the amorphous alloy film is peeled off from the thin plate base material.
Different diameters in which the separating material is applied or sprayed on the surface of the thin plate substrate before forming the amorphous alloy film, and the upper and lower rolls have a diameter difference in the rolling mill and only one of the upper and lower rolls is driven. 4. The method for producing an amorphous plate according to claim 3, wherein the amorphous alloy film is peeled off from the thin plate base material by using a single drive.
In order to carry out the method for producing an amorphous plate according to claim 4, a payoff reel for paying out the thin plate substrate, a surface treatment device for adjusting the surface roughness of the thin plate substrate, and shape correction of the thin plate substrate A leveler for carrying out, a separating material applicator or sprayer, a heating device for a thin plate substrate, an injection device for forming an amorphous alloy film, the rolling machine driven by different diameter pieces, and the thin plate substrate A device for producing an amorphous plate, comprising: a winder that winds up, a device for heat insulation and cooling of the amorphous alloy thin plate, and a winder that winds up the amorphous alloy thin plate.
By polishing the surface of the thin plate substrate before forming the amorphous alloy film, and using the same diameter double drive system in which the upper and lower roll diameters are equally driven as the rolling mill, the amorphous alloy film The method for producing an amorphous plate according to claim 2, wherein the degree of adhesion to the thin plate base material is improved.
In order to carry out the method for producing an amorphous plate according to claim 6, a payoff reel for paying out the thin plate base material, a surface treatment device for adjusting the surface roughness of the thin plate base material, and shape correction of the thin plate base material A leveler for performing, a heating device for a thin plate base material, an injection device for forming an amorphous alloy film, the above-mentioned rolling mill driven by the same diameter, and an apparatus for heat insulation and cooling at the time of forming an amorphous alloy film coating And a winding machine for winding the produced amorphous alloy film-coated thin plate.
The apparatus for producing an amorphous plate according to claim 5 or 7, wherein the rolling mill has a roll with a built-in heater as a work roll at least in contact with the amorphous alloy film.
As the above injection device for forming an amorphous alloy film,
A device that injects a flame containing material particles toward the substrate from an injection gun, melts the material particles by the flame, and cools the material particles and the flame before reaching the substrate. At the front of the gun, material particle injection ports and flame injection ports are continuously provided in the width direction of the base material by 150 mm or more, and the flame is rectified at positions on both sides of the material particle injection port and flame injection port. Having an apparatus in which an inert gas injection port for cooling and a liquid mist injection port for cooling a flame are continuously provided in a width direction of 150 mm or more in the base material;
The apparatus for producing an amorphous plate according to claim 5 or 7, wherein:
A dust collection hood is provided in the vicinity of the flame of the thermal spraying device that forms the amorphous alloy film, and the generated gas from the injection device is sucked from the dust collection hood while being cooled with water mist and sent to the dust collector. An apparatus for producing an amorphous plate according to claim 5, 7 or 9, wherein