WO2020206611A1 - METHOD FOR CONTINUOUS AND HIGH-EFFICIENT PREPARATION OF WIDE AMORPHOUS THIN STRIP HAVING THICKNESS OF 80-1,500 μM AT HIGH COOLING SPEED - Google Patents

Abstract

A method for continuous and high-efficient preparation of a wide amorphous thin strip having a thickness of 80-1,500 μm using a double roller method at a high cooling speed. The method comprises the following steps: (1) smelting an amorphous alloy according to set components under an inert atmospheric condition, the components comprising non-alloy component systems, such as zirconium-, copper-, iron-, and nickel-based non-alloy component systems; (2) performing amorphous thin strip preparation by means of slot flow distribution using a vertical thin-strip casting process at an alloy melt cooling speed of 500-75,000°C/s to form a wide cast strip having a thickness of 80-1,500 μm, so as to provide a basic material for a subsequent processing procedure; and (3) shaping and reeling the wide cast strip. For high requirements of amorphous alloy preparation on raw materials and preparation technology, the method implements a continuous casting process of an amorphous strip having a length of more than 12 m and a thickness of 80-1,500 μm.

Description

Method for high-efficiency and continuous high-speed cooling of wide-width amorphous thin ribbons with a thickness of 80-1500 μm Technical field

The invention belongs to the field of amorphous alloy preparation, and specifically relates to a method for preparing a wide amorphous ribbon with a thickness of 80-1500 μm by using a double-roll method with continuous high cooling speed and high efficiency.

Background technique

Amorphous alloy, also known as Metallic Glass or Glassy Alloy, is a new, special, and crystalline alloy material prepared by applying modern rapid solidification metallurgical technology. Due to the unique atomic structure arrangement and metal bond composition of amorphous alloys, amorphous alloys have better mechanical, physical and chemical properties than traditional crystalline metal materials. This makes amorphous alloys have a wide range of application prospects in aerospace, weapon industry, precision instruments, biomedicine and power transmission.

The preparation of early amorphous alloys required a large cooling rate (>10 ⁶ K/s). At that time, amorphous alloys could only exist in the form of powder, wire, thin ribbon, etc., which greatly weakened the performance potential of amorphous alloys and restricted Application of amorphous alloys in industry. Therefore, since the end of the 1980s, how to improve the forming ability of amorphous alloys and prepare large-size amorphous alloys has become one of the key research directions in the field of new materials research. In the decades from the 1980s to the present, through the efforts of a large number of scholars, a large number of glass-forming capabilities such as Zr-based, Ti-based, Fe-based, Co-based, Ni-based, Cu-based, and Pt-based have been developed. Alloy system; develop the preparation technology of various bulk amorphous alloys such as water quenching method, copper mold casting method, directional solidification method, and amorphous powder extrusion method. Among them, the amorphous thin strip with excellent soft magnetic properties produced by the single-roll method has been widely and widely used in China, making outstanding contributions to the energy saving and emission reduction of my country's power system. Moreover, the preparation and application of bulk amorphous alloys have also made great progress. Because of their excellent mechanical properties, they have been used as structural materials and used in electronic products, sports equipment, auto parts, etc. At present, the most important production method of bulk amorphous alloy products in the market is die-casting. Due to its own conditions, only small-size products can be produced. As a sheet and strip material widely used in structural materials, there is still no reliable production method. Therefore, how to achieve continuous, large-volume and stable production of amorphous alloy plates and strips and promote the wide application of bulk amorphous alloys is one of the urgent problems in the current amorphous industry.

At present, the main production methods of amorphous strip include single-roll melt quenching method, double-roll melt quenching method and casting mold casting method. At present, the most widely used and industrialized production is the single-roll melt quenching method, referred to as the single-roll method. The iron-based amorphous strip produced by the single-roll method has excellent soft magnetic properties, which can replace silicon steel and permalloy to make transformer cores, thereby greatly improving transformer efficiency, reducing iron loss of distribution transformers, and reducing volume and weight. However, the single-roll production process limits the thickness (about 20-50μm) and width (less than 220mm) of the strip. The twin-roll melt quenching method is referred to as the twin-roll method. Develop a variety of continuous casting methods for bulk amorphous alloys based on the twin-roll method. The United States Patent (Publication No. US2006/0260782A1) discloses a continuous housing device and method for bulk amorphous alloy plates. The device in the patent uses multiple sets of small-diameter cooling rolls to cool the alloy strip, because the row of rolls can only apply small Contact pressure, the cooling rate of the system can only reach less than 10℃/s, the thickness of the prepared sheet is 0.1-10mm, and it is limited to the forming of the Zr-based amorphous alloy containing Be with strong forming ability, which will also reduce the amorphous life and stability. The technical idea is closer to the Chinese patent (publication number CN 107755652 A), which uses crawler-type cooling to continuously cast amorphous material. The contact force is small and the cooling rate is limited, which will also reduce the life of the amorphous material and prepare the amorphous material. Redundancy of component design. Chinese Patent (Publication No. CN1486800A) discloses a continuous casting and rolling technology for bulk amorphous alloys. The molten metal in the crucible is poured into two relatively rotating water-cooled rolls, and the bulk amorphous sheet is prepared by double-roller casting. , Bars, etc., but the patent does not see specific process protection nodes and technical implementation schemes. At the same time, detailed parameters such as melting temperature, heat preservation measures, flow control measures, cooling speed, casting and rolling force are not disclosed. In addition, a relatively large rolling force can be applied to the roll gap position to achieve a large cooling rate. In theory, its cooling capacity is greater than that of the single-roll method, and it can be used to prepare amorphous alloy plates and strips with large thickness specifications. The mold pull casting method is a kind of master alloy after melting in a crucible, heat preservation, and casting into a water-cooled hole through a flow nozzle, and pulling force on the formed amorphous alloy at a certain speed to realize the amorphous alloy Continuous casting method. Chinese Patent (Publication No. CN101543885A) discloses a device and method for horizontal continuous casting of bulk amorphous alloys. The cooling of the alloys mainly relies on water-cooled copper molds, and the solidified castings are continuously output by the pulling rod driven by the motor.

Summary of the invention

In view of the high requirements on raw materials and preparation technology for the preparation of amorphous alloys, the problem of mass production of amorphous alloy plates and strips has not yet been seen. The wide amorphous thin strip method realizes the continuous casting and rolling process of amorphous strips with a length of 12m or more and a thickness of 80-1500μm.

The technical scheme of the present invention is:

A method for the continuous high-speed and high-efficiency preparation of a wide amorphous thin ribbon with a thickness of 80-1500μm is carried out as follows:

(1) The alloy is discharged into the crucible, and the preheatable draft tube and its position control device are cleaned. The inside of the preheatable draft tube is lined with quartz material and a heating system is attached. The heating temperature is the solidification of the target alloy Above temperature 100～200℃, it can be preheated and protected by cooling water outside the guide tube;

(2) Melt the amorphous master alloy according to the set composition. Its composition is: zirconium-based, copper-based, iron-based or nickel-based amorphous alloy composition system. After the metal is melted, it is uniformly mixed for 5-30 minutes, and the temperature is controlled;

(3) The superheat of the alloy melt is controlled at 50-300℃, and the high-purity argon with a volume purity of more than 99.999% is used for protection during the temperature control. The argon inside the melting chamber is slightly positive, that is, the pressure is not less than 0.11MPa;

(4) During the smelting process, the preparation of the forming cavity is completed. The steps include: a) All valve bodies on the cavity of the forming cavity are closed, and argon is filled after vacuuming. The volume purity is above 99.99%, and the volume is maintained at no less than 0.11MPa. Slightly positive pressure; b) The flow nozzle is preheated. The flow nozzle adopts slit type flow, and it is installed into a fixed position for heating. The heating temperature is 100～200℃ above the solidification temperature of the target alloy; c) Cast roll cooling cycle The water temperature is 3～5℃, and the total water flow is 70～90m ³ /h; d) Prepare the gas cooling system after casting, the argon pressure is 0.6～0.8MPa, and the gas temperature is controlled at 4～6℃;

(5) After alloy smelting, preheating of the preheatable flow guide tube and flow nozzle, and filling of argon in the forming cavity, the vertical thin strip casting and rolling process is used to prepare the amorphous thin strip and enter the continuous thin strip casting process: Open the smelting chamber gate valve, the preheating diversion tube can be lowered, and it is connected with the flow nozzle, the intermediate frequency induction melting furnace dumps the alloy into the preheating diversion tube; the flow nozzle is made of transparent quartz, which is monitored by infrared surveillance cameras. The tilting speed of the intermediate frequency induction melting furnace controls the height of the melt inside the flow nozzle to be 40-60mm. The alloy melt is uniformly distributed in the vertical direction through the flow nozzle through the liquid level and flows into the roll gap of the casting roll. The alloy melt is in the roll gap. The height of the gap liquid level is controlled at 2～10mm, the alloy melt cooling rate is 500～75000℃/s, and the alloy is cooled and cast-rolled. After forming, the amorphous thin strip is led out by the guide roller and enters the post-casting gas cooling system for further cooling. Low temperature argon purge cooling, gas cooling rate 50～800℃/s;

(6) After gas cooling, the thickness range of the amorphous thin strip reaches 80-1500μm, and the width range is 110-550mm; the cast strip with a thickness of 80-800μm is taken up by coiling, and the cast strip with a thickness of more than 800μm is not coiled, but directly Collection in the form of thin ribbons.

The method for preparing wide amorphous thin strip with a thickness of 80-1500μm with continuous high cooling rate and high efficiency. During the casting and rolling process, the alloy is rapidly cooled by heat transfer through the casting rolls, and the casting speed, the casting force and the roll are controlled. The size of the gap is used to control the temperature of the exit roll of the alloy ribbon, and the temperature of the exit roll of the alloy is controlled to be close to or less than the crystallization temperature Tx of the alloy; the casting speed is 0.20～1.8m/s, and the casting force is controlled to every 1cm width. The casting-rolling force of the belt is 2-15kN, the width of the roll gap opening of the casting roll is set to 80-1500μm, and the side sealing plate is not provided.

The method for preparing wide amorphous thin strips with a thickness of 80-1500μm in continuous high cooling rate and high efficiency, through the opening size of the lower end of the flow nozzle, casting roll gap value, casting speed, copper casting roll, steel The casting-rolling process parameters of the casting roll and the cooling water volume of the casting roll control the solidification cooling rate to reach 500-75000℃/s.

In the method for preparing a wide amorphous ribbon with a thickness of 80-1500 μm in continuous high cooling speed and high efficiency, the zirconium-based, copper-based, iron-based or nickel-based amorphous alloy is added with 0.0045-0.020 mass percentage of yttrium element, Used to remove O and N pollution brought into the environment.

The described method for the continuous high-speed and high-efficiency preparation of wide amorphous ribbons with a thickness of 80-1500μm uses a quartz slit-type flow nozzle for flow distribution, and the slit opening width is designed according to different product thicknesses; the flow nozzle is On-line preheating, the preheating temperature is 100～200℃ above the alloy solidification temperature, the open end of the lower end of the flow nozzle conducts heat through the tungsten alloy sheet, and the end temperature of the flow nozzle reaches near the solidification temperature of the alloy. Damping is used to stabilize the flow; the lining of the preheatable diversion tube is quickly replaceable quartz glass, the preheating temperature is 100-200℃ above the alloy solidification temperature, and the outside of the preheating diversion tube can be protected by cooling water.

In the method for the continuous high-speed and high-efficiency preparation of wide amorphous ribbons with a thickness of 80-1500 μm, an infrared monitoring camera is set on the side of the width of the flow nozzle to feed back to the tilt control system to achieve the purpose of flow control; The height control range of the lower end of the nozzle from the kiss line of the casting roll gap is 10-50mm, and the height of the liquid level inside the nozzle is 40-60mm.

The method for preparing wide amorphous ribbons with a thickness of 80-1500μm in continuous high cooling speed and high efficiency. The casting rolls use two horizontally opposed two rolls, and the two rolls are equipped with support rolls on both sides. The diameter of the cast rolls is 280-420mm. , The diameter of each set of supporting rollers is designed to be greater than the diameter of the casting roller by 100mm.

Said method for the preparation of wide amorphous ribbons with a thickness of 80-1500μm with continuous high cooling speed and high efficiency, the melting chamber and forming chamber adopt hierarchical vacuum design, among which: the working vacuum of the melting chamber is below 1×10 ^-2 Pa, The vacuum degree of the forming cavity is below 1Pa; in the pouring state, the environment is in an argon gas protection state, and the melting cavity and the forming cavity are separated by a gate valve. The gate valve is opened before the casting and rolling is filled with argon gas.

The method for preparing wide amorphous ribbons with a thickness of 80-1500μm with continuous high cooling rate and high efficiency adopts intermediate frequency induction melting furnace + high purity graphite (carbon content ≥99.99wt%) crucible for amorphous alloy smelting and heating The temperature does not exceed 400℃ above the melting temperature of the metal to prevent oxidation and burning of metal elements.

In the method for preparing a wide amorphous ribbon with a thickness of 80 to 1500 μm with continuous high cooling rate and high efficiency, no more than 20wt% of cast strip trimming scraps are added to the incoming amorphous master alloy.

The advantages and beneficial effects of the present invention are:

1. For the continuous forming process of bulk amorphous alloy, high cooling rate and good stability are essential. However, the general casting and rolling equipment has a simple casting method and a wide alloy molten pool, which makes the cooling rate of the alloy in the shallow supercooled liquid phase region smaller, and it is difficult to form an amorphous alloy. According to the characteristics of the bulk amorphous solidification, the invention adopts the deep roll gap casting method in combination with the double-roll casting and rolling technology, and the alloy melting pool is narrow, the cooling rate is large, and the deformation is small. Its principle, structure and method have not been reported in public.

2. The present invention can control the solidification cooling speed to reach 500-75000℃ through casting and rolling process parameters such as the slit width of the flow nozzle, the value of the casting roll gap, the casting speed, the copper casting roll, the steel casting roll, and the cooling water volume of the casting roll. /s. A method for continuous forming of thin strips is designed for the series of amorphous metals with a limiting cooling rate between 500 and 75000°C/s, providing basic materials for their subsequent processing procedures.

3. The present invention adopts quartz material slit type flow nozzle for flow distribution, and the slit opening width is designed 0.15-0.8mm according to the thickness of different products. The flow nozzle can be preheated on-line. The preheating temperature is 100-200℃ above the solidification temperature of the alloy. The end of the flow nozzle conducts heat through the tungsten alloy sheet, and the temperature of the end reaches near the solidification temperature of the alloy. There is a dam flush inside the flow nozzle for steady flow.

4. In the present invention, there is an infrared monitoring camera on the width side of the flow nozzle, which feeds back to the tilt control system to achieve the purpose of flow control. Among them, the lower end of the cloth flow nozzle has a height control range of 10-50mm from the kiss line of the casting roll gap (Kiss line refers to the closest line of the double work rolls), and the liquid level inside the cloth flow nozzle is 40-60mm. The casting and rolling system adopts a flow-casting speed matching strategy to control the free flow of the alloy melt roll gap along the vertical direction, eliminating the side sealing plate in the casting and rolling process.

5. The casting-rolling system of the present invention adopts the support roller method with additional casting rollers to improve the lateral stability control and reduce the thickness deviation between the transmission side and the operation side of the casting machine. The diameter of the casting roll is 280～420mm, the diameter of each group of support roll is designed to be larger than the diameter of the work roll (casting roll) by 100mm, and the surface roughness Ra≤10μm.

6. The present invention adopts a diversion design with preheating. The preheating diversion tube is lined with quartz glass that can be replaced quickly. The preheating temperature is 100-200℃ above the solidification temperature of the alloy. Cooling water protection.

7. The grading vacuum design of the melting chamber and the forming chamber of the present invention, wherein the working vacuum of the melting chamber is below 1×10 ^-2 Pa, the vacuum degree of the forming chamber is below 1 Pa, and argon is quickly filled. In the pouring state, the environment is in an argon protection state, and the melting chamber and the forming chamber are separated by a gate valve. The gate valve is opened before the casting and rolling is filled with argon.

8. The post-casting gas cooling system of the present invention adopts low-temperature argon purging and cooling, and the cooling rate is 50-800°C/s.

Description of the drawings

Fig. 1 is a schematic structural diagram of a casting-rolling device for continuous high-speed cooling and high-efficiency preparation of wide amorphous thin strips of the present invention. In the picture, 1 intermediate frequency induction melting furnace; 2 high vacuum melting chamber; 3 preheatable draft tube; 4 gate valve; 5 flow nozzle and infrared camera monitoring device; 51 flow nozzle; 52 infrared monitoring camera; 6 forming Cavity; 7 support rollers; 8 casting rollers; 9 post-casting gas cooling system; 10 coiling equipment; 11 tilting control system.

Figure 2 is a schematic diagram of 0.55 mm thick amorphous strip.

Figure 3 is a microstructure photograph (a) and XRD graph (b). In the figure, the abscissa 2θ represents the diffraction angle (drgee), and the ordinate intensity represents the relative intensity (a.u.).

Figure 4 is the microstructure photograph (a) and XRD graph (b). In the figure, the abscissa 2θ represents the diffraction angle (drgee), and the ordinate intensity represents the relative intensity (a.u.).

detailed description

As shown in Figure 1, the casting and rolling device for the continuous high-speed and high-efficiency preparation of wide amorphous ribbons of the present invention mainly includes: an intermediate frequency induction melting furnace 1, a high vacuum melting chamber 2 (chamber pressure <0.1Pa), Heat guide pipe 3, gate valve 4, flow nozzle and infrared camera monitoring device 5, forming cavity 6, support roller 7, casting roller 8, post-casting gas cooling system 9, coiling equipment 10, tilting control system 11 The specific structure is as follows:

The bottom opening of the high-vacuum melting chamber 2 corresponds to the top opening of the forming chamber 6. The bottom opening of the high-vacuum melting chamber 2 communicates with the top opening of the forming chamber 6 through a gate valve 4; the high-vacuum melting chamber 2 is equipped with an intermediate frequency induction melting Furnace 1, preheatable draft tube 3 and tilting control system 11. The preheatable draft tube 3 is located on one side of the intermediate frequency induction melting furnace 1, and the preheatable draft tube 3 is arranged vertically, and its lower port is formed The upper port of the flow nozzle 51 at the top of the cavity 6 corresponds to the upper port; the intermediate frequency induction melting furnace 1 is installed on the tilt control system 11, and the intermediate frequency induction melting furnace 1 rotates around the tilt control system 11 through a rotating shaft, so that the intermediate frequency induction melting furnace 1 The upper mouth corresponds to the upper mouth of the preheatable draft tube 3.

The flow nozzle and the infrared camera monitoring device 5 include two parts, a flow nozzle 51 and an infrared monitoring camera 52. The flow nozzle 51 is provided with a dam for steady flow. The wider side of the flow nozzle 51 is provided with an infrared monitoring camera. 52. Feed back to the tilt control system 11 through the infrared monitoring camera 52 to achieve the purpose of flow control. When the amorphous master alloy melt is obtained by smelting in the intermediate frequency induction melting furnace 1, it is poured into the preheatable draft tube 3, and the preheatable draft tube 3 moves down through the bottom opening and the gate of the intermediate frequency induction melting furnace 1 In valve 4, the amorphous master alloy melt enters the flow nozzle 51 through the preheatable guide tube 3.

The lower port of the flow nozzle 51 corresponds to the roll gap between the two casting rolls 8. The two casting rolls 8 are provided with support rollers 7 respectively, which can preheat the alloy melt in the draft tube 3 to pass through the flow nozzle 51 is uniformly distributed to the roll gap between the two casting rolls 8, the alloy melt continuously passes through the post-casting gas cooling system 9 under the casting roll 8 to form a cast strip, and the cast strip passes through the coiling device 10 to be rolled.

In the specific implementation process, the method for preparing the wide-width amorphous ribbon of the present invention with continuous high cooling rate and high efficiency is as follows: (1) Smelting amorphous alloys according to the set composition, and its composition includes zirconium-based, copper-based, iron-based, and nickel-based For amorphous metals with a limiting cooling rate between 500 and 75000°C/s, a method for continuous forming of thin strips is designed to provide basic materials for subsequent processing procedures; (2) The thickness of the thin strip is formed after continuous casting 80～1500μm wide cast belt; (3) Melting, forming and coiling under inert atmosphere.

Hereinafter, the present invention will be further described with reference to the drawings and specific embodiments.

Example one

Alloy composition: (Zr _53.5 Hf _1.5 Cu ₃₀ Al ₁₀ Ni ₅ ) _99.9 O _0.1 (atomic percentage at.%, the same below);

Distribution method: deep roll gap cloth flow;

Preparation process:

a. Prepare 20kg of raw materials according to atomic percentage, put them into the intermediate frequency induction melting furnace, and vacuum the melting chamber to 6×10 ^-2 Pa, heat the alloy raw materials until they are completely melted, and continue smelting at 1500°C for 10 minutes.

b. During the smelting process, the preparation of the forming cavity is completed. The steps include: 1) All valve bodies on the cavity of the forming cavity are closed, vacuumed to 0.5Pa, and then filled with argon gas, with a volume purity of 99.99% or more and maintaining 0.12MPa Slightly positive pressure; 2) The cloth flow nozzle is preheated. The cloth flow nozzle adopts a slit type cloth flow. After being installed into a fixed position, it is heated. The heating temperature is 1150℃; 3) The cooling water temperature of the casting roll is 5℃. The water flow rate is 80m ³ /h; 4) Prepare the gas cooling system after casting, the argon pressure is 0.7MPa, and the gas temperature is controlled at 5°C; 5) The roll gap opening width is set to 0.55mm.

c. Turn off the vacuum pump, fill the intermediate frequency induction melting furnace with high-purity argon with a volume purity of 99.999% to a slight positive pressure of 0.12 MPa, open the gate valve, lower the preheatable draft tube, and pass the alloy melt through the The preheating guide tube (the preheating temperature of the guide tube is 1150℃) and the flow nozzle are evenly distributed to the roll gap of the casting roll.

Its parameters are shown in Table 1 below.

Table 1 The main parameters of the experiment

d. The cloth flow nozzle used in the experiment is made of transparent quartz. During the experiment, the infrared monitoring camera and crucible tipping speed were used to monitor and control the melt level inside the flow nozzle to 60mm. Rely on the pressure of the alloy liquid to uniformly distribute the alloy melt into the roll gap of the casting roll through the flow nozzle, control the height of the alloy melt in the roll gap to 5-10mm, and no side sealing plate, the alloy is cooled and cast-rolled , The alloy melt cooling rate is 10000℃/s; during the casting and rolling process, the alloy is rapidly cooled by the heat transfer of the casting roll, and the temperature of the alloy thin strip exit roll is controlled by controlling the casting speed, the casting force and the size of the roll gap, and The temperature of the alloy exit roll is controlled at about 400°C; the amorphous thin strip after forming is led out of the casting and rolling device through the guide roll and enters the post-casting gas cooling system for further cooling to below 100°C. The cooling rate of the gas cooling system is 100°C/s.

The 0.55 mm thick amorphous strip was obtained in the experiment, as shown in Figure 2. The microstructure photo and XRD curve are shown in Figure 3. It can be seen from Fig. 2 to Fig. 3 that the matrix of the cast strip is an amorphous structure with very few crystal impurities.

Example two

Alloy composition: (Zr _53.5 Hf _1.5 Cu ₃₀ Al ₁₀ Ni ₅ ) _99.9 O _0.1 ;

Distribution method: deep roll gap cloth flow;

Preparation process:

a. Prepare 50kg of raw materials according to atomic percentage, put them into the intermediate frequency induction melting furnace, and vacuum the melting chamber to 6×10 ^-2 Pa, heat the alloy raw materials until they are completely melted, and continue smelting at 1400°C for 20 minutes.

b. During the smelting process, the preparation of the forming cavity is completed. The steps include: 1) All valve bodies on the cavity of the forming cavity are closed, vacuumed to 0.5Pa, and then filled with argon gas, with a volume purity of 99.99% or more and maintaining 0.11MPa Slightly positive pressure; 2) The cloth flow nozzle is preheated. The cloth flow nozzle adopts slit-type cloth flow. It is heated after being installed into a fixed position. The heating temperature is 1000°C; 3) The cooling water temperature of the casting roll is 5°C. The water flow rate is 80m ³ /h; 4) Prepare the gas cooling system after casting, the argon pressure is 0.7MPa, and the gas temperature is controlled at 5°C; 5) The roll gap opening width is set to 0.5mm.

c. Turn off the vacuum pump, fill the intermediate frequency induction melting furnace with high-purity argon with a volume purity of 99.999% to a slight positive pressure of 0.11MPa, open the gate valve, lower the preheatable draft tube, and pass the alloy melt through the The preheating guide tube (the preheating temperature of the guide tube is 1150℃) and the flow nozzle are evenly distributed to the roll gap of the casting roll.

Its parameters are shown in Table 2 below.

Table 2 The main parameters of the experiment

d. The cloth flow nozzle used in the experiment is made of transparent quartz. During the experiment, the infrared monitoring camera and crucible tipping speed were used to monitor and control the melt level inside the flow nozzle to 60mm. Rely on the pressure of the alloy liquid to uniformly distribute the alloy melt into the roll gap of the casting roll through the flow nozzle, control the height of the alloy melt in the roll gap to 5-10mm, and no side sealing plate, the alloy is cooled and cast-rolled , The alloy melt cooling rate is 6000℃/s; during the casting and rolling process, the alloy is rapidly cooled by the heat transfer of the casting roll, and the temperature of the alloy strip exit roll is controlled by controlling the casting speed, the casting force and the size of the roll gap, and The temperature of the alloy exit roll is controlled at about 400°C; the amorphous thin strip after forming is led out of the casting and rolling device through the guide roller and enters the post-casting gas cooling system to be further cooled to below 100°C, and the cooling rate of the gas cooling system is 80°C/s.

The test obtained 0.5mm thick amorphous strip. The microstructure photo and XRD curve are shown in Figure 4. It can be seen from Figure 4 that the cast strip is completely amorphous.

Example three

Alloy composition: (Cu ₆₀ Zr ₂₀ Hf ₁₀ Ti ₁₀ ) _99.9 O _0.1 ;

Distribution method: deep roll gap cloth flow;

Preparation process:

a. Prepare 30kg of raw materials according to atomic percentage, put them into an intermediate frequency induction melting furnace, and vacuum the melting chamber to 7×10 ^-2 Pa, heat the alloy raw materials until they are completely melted, and continue smelting at 1500°C for 10 minutes.

b. During the smelting process, the preparation of the forming cavity is completed. The steps include: 1) All valve bodies on the cavity of the forming cavity are closed, vacuumed to 0.5Pa, and then filled with argon gas, with a volume purity of 99.99% or more and maintaining 0.11MPa Slightly positive pressure; 2) The cloth flow nozzle is preheated. The cloth flow nozzle adopts a slit type cloth flow. After being installed into a fixed position, it is heated. The heating temperature is 1150℃; 3) The cooling water temperature of the casting roll is 5℃. The water flow rate is 80m ³ /h; 4) Prepare the gas cooling system after casting, the argon pressure is 0.7MPa, and the gas temperature is controlled at 5°C; 5) The roll gap opening width is set to 0.5mm.

c. Turn off the vacuum pump, fill the intermediate frequency induction melting furnace with high-purity argon with a volume purity of 99.999% to a slight positive pressure of 0.11MPa, open the gate valve, lower the preheatable draft tube, and pass the alloy melt through the The preheating guide tube (the preheating temperature of the guide tube is 1150℃) and the flow nozzle are evenly distributed to the roll gap of the casting roll.

Its parameters are shown in Table 3 below.

Table 3 The main parameters of the experiment

d. The cloth flow nozzle used in the experiment is made of transparent quartz. During the experiment, the infrared monitoring camera and crucible tipping speed were used to monitor and control the melt level inside the flow nozzle to 60mm. Rely on the pressure of the alloy liquid to uniformly distribute the alloy melt into the roll gap of the casting roll through the flow nozzle, control the height of the alloy melt in the roll gap to 5-10mm, and no side sealing plate, the alloy is cooled and cast-rolled , The alloy melt cooling rate is 8000℃/s; during the casting and rolling process, the alloy is rapidly cooled by the heat transfer of the casting roll, and the temperature of the alloy strip exit roll is controlled by controlling the casting speed, the casting force and the size of the roll gap, and The temperature of the alloy exit roll is controlled at about 400°C; the amorphous thin strip after forming is led out of the casting and rolling device through the guide roller and enters the post-casting gas cooling system for further cooling to below 100°C. The cooling rate of the gas cooling system is 60°C/s.

The test obtained 0.5 mm thick amorphous strip.

Example four

Alloy composition: Fe ₆₉ C ₅ Si ₃ B ₅ P ₈ Cr ₃ Al ₂ Mo ₅ ;

Distribution method: deep roll gap cloth flow;

Preparation process:

a. Prepare 20kg of raw materials according to atomic percentage, put them into the intermediate frequency induction melting furnace, and vacuum the melting chamber to 8×10 ^-2 Pa, heat the alloy raw materials until they are completely melted, and continue smelting at 1500°C for 10 minutes.

b. During the smelting process, the preparation of the forming cavity is completed. The steps include: 1) All valve bodies on the cavity of the forming cavity are closed, vacuumed to 0.5Pa, and then filled with argon gas, with a volume purity of 99.99% or more and maintaining 0.11MPa Slightly positive pressure; 2) The cloth flow nozzle is preheated, and the cloth flow nozzle adopts slit type cloth flow, which is installed into a fixed position for heating, and the heating temperature is 1200℃; 3) The cooling water temperature of the casting roll is 5℃, the total The water flow rate is 80m ³ /h; 4) Prepare the gas cooling system after casting, the argon pressure is 0.7MPa, and the gas temperature is controlled at 5°C; 5) The roll gap opening width is set to 0.5mm.

c. Turn off the vacuum pump, fill the intermediate frequency induction melting furnace with high-purity argon with a volume purity of 99.999% to a slight positive pressure of 0.11MPa, open the gate valve, lower the preheatable draft tube, and pass the alloy melt through the The preheating guide tube (the preheating temperature of the guide tube is 1150℃) and the flow nozzle are evenly distributed to the roll gap of the casting roll.

Its parameters are shown in Table 4 below.

Table 4 The main parameters of the experiment

d. The cloth flow nozzle used in the experiment is made of transparent quartz. During the experiment, the infrared monitoring camera and crucible tipping speed were used to monitor and control the melt level inside the flow nozzle to 60mm. Rely on the pressure of the alloy liquid to uniformly distribute the alloy melt into the roll gap of the casting roll through the flow nozzle, control the height of the alloy melt in the roll gap to 5-10mm, and no side sealing plate, the alloy is cooled and cast-rolled , The alloy melt cooling rate is 5000℃/s; during the casting and rolling process, the alloy is rapidly cooled by the heat transfer of the casting roll, and the temperature of the alloy strip exit roll is controlled by controlling the casting speed, the casting force and the size of the roll gap, and The temperature of the alloy exit roll is controlled at about 520℃; after forming, the amorphous thin strip is led out of the casting and rolling device through the guide roll and enters the post-casting gas cooling system to be further cooled to below 100℃. The cooling rate of the gas cooling system is 50℃/s.

The test obtained 0.25 mm thick amorphous strip.

Example five

Alloy composition: Ni ₄₀ Cu ₅ Ti ₁₆ Zr ₂₈ Hf ₁ Al ₁₀ ;

Distribution method: deep roll gap cloth flow;

Preparation process:

a. Prepare 20kg of raw materials according to atomic percentage, put them into the intermediate frequency induction melting furnace, and vacuum the melting chamber to 6×10 ^-2 Pa, heat the alloy raw materials until they are completely melted, and continue smelting at 1500°C for 10 minutes.

b. During the smelting process, the preparation of the forming cavity is completed. The steps include: 1) All valve bodies on the cavity of the forming cavity are closed, vacuumed to 0.5Pa, and then filled with argon gas, with a volume purity of 99.99% or more and maintaining 0.11MPa Slightly positive pressure; 2) The cloth flow nozzle is preheated, and the cloth flow nozzle adopts slit type cloth flow, which is installed into a fixed position for heating, and the heating temperature is 1200℃; 3) The cooling water temperature of the casting roll is 5℃, the total The water flow rate is 80m ³ /h; 4) Prepare the gas cooling system after casting, the argon pressure is 0.7MPa, and the gas temperature is controlled at 5°C; 5) The roll gap opening width is set to 0.5mm.

c. Turn off the vacuum pump, fill the intermediate frequency induction melting furnace with high-purity argon with a volume purity of 99.999% to a slight positive pressure of 0.11MPa, open the gate valve, lower the preheatable draft tube, and pass the alloy melt through the The preheating guide tube (the preheating temperature of the guide tube is 1150℃) and the flow nozzle are evenly distributed to the roll gap of the casting roll.

Its parameters are shown in Table 5 below.

Table 5 The main parameters of the experiment

d. The cloth flow nozzle used in the experiment is made of transparent quartz. During the experiment, the infrared monitoring camera and crucible tipping speed were used to monitor and control the melt level inside the flow nozzle to 60mm. Rely on the pressure of the alloy liquid to uniformly distribute the alloy melt into the roll gap of the casting roll through the flow nozzle, control the height of the alloy melt in the roll gap to 5-10mm, and no side sealing plate, the alloy is cooled and cast-rolled , The alloy melt cooling rate is 7000℃/s; during the casting and rolling process, the alloy is rapidly cooled by the heat transfer of the casting roll, and the temperature of the alloy strip exit roll is controlled by controlling the casting speed, the casting force and the size of the roll gap, and The temperature of the alloy exit roll is controlled at about 520℃; after forming, the amorphous thin strip is led out of the casting and rolling device through the guide roll and enters the post-casting gas cooling system to be further cooled to below 100℃, and the cooling rate of the gas cooling system is 80℃/s.

The test obtained 0.25 mm thick amorphous strip.

The above-mentioned embodiments are only used to illustrate the technical features of the present invention, rather than to limit the protection scope of the present invention, and their purpose is to describe the present invention in detail. However, all equivalent substitutions made according to the spirit of the invention without departing from the technical essence of the invention fall within the protection scope of the invention.

Claims (10)

1. A method for the continuous high-speed and high-efficiency preparation of a wide amorphous thin ribbon with a thickness of 80-1500 μm, which is characterized in that the following steps are performed:

   (1) The alloy is discharged into the crucible, and the preheatable draft tube and its position control device are cleaned. The inside of the preheatable draft tube is lined with quartz material and a heating system is attached. The heating temperature is the solidification of the target alloy Above temperature 100～200℃, it can be preheated and protected by cooling water outside the guide tube;

   (2) Melt the amorphous master alloy according to the set composition. Its composition is: zirconium-based, copper-based, iron-based or nickel-based amorphous alloy composition system. After the metal is melted, it is uniformly mixed for 5-30 minutes, and the temperature is controlled;

   (3) The superheat of the alloy melt is controlled at 50-300℃, and the high-purity argon with a volume purity of more than 99.999% is used for protection during the temperature control. The argon inside the melting chamber is slightly positive, that is, the pressure is not less than 0.11MPa;

   (4) During the smelting process, the preparation of the forming cavity is completed. The steps include: a) All valve bodies on the cavity of the forming cavity are closed, and argon is filled after vacuuming. The volume purity is above 99.99%, and the volume is maintained at no less than 0.11MPa. Slightly positive pressure; b) The flow nozzle is preheated. The flow nozzle adopts slit type flow, and it is installed into a fixed position for heating. The heating temperature is 100～200℃ above the solidification temperature of the target alloy; c) Cast roll cooling cycle The water temperature is 3～5℃, and the total water flow is 70～90m ³ /h; d) Prepare the gas cooling system after casting, the argon pressure is 0.6～0.8MPa, and the gas temperature is controlled at 4～6℃;

   (5) After alloy smelting, preheating of the preheatable flow guide tube and flow nozzle, and filling of argon in the forming cavity, the vertical thin strip casting and rolling process is used to prepare the amorphous thin strip and enter the continuous thin strip casting process: Open the smelting chamber gate valve, the preheating diversion tube can be lowered, and it is connected with the flow nozzle, the intermediate frequency induction melting furnace dumps the alloy into the preheating diversion tube; the flow nozzle is made of transparent quartz, which is monitored by infrared surveillance cameras. The tilting speed of the intermediate frequency induction melting furnace controls the height of the melt inside the flow nozzle to be 40-60mm. The alloy melt is uniformly distributed in the vertical direction through the flow nozzle through the liquid level and flows into the roll gap of the casting roll. The alloy melt is in the roll gap. The height of the gap liquid level is controlled at 2～10mm, the alloy melt cooling rate is 500～75000℃/s, and the alloy is cooled and cast-rolled. After forming, the amorphous thin strip is led out by the guide roller and enters the post-casting gas cooling system for further cooling. Low temperature argon purge cooling, gas cooling rate 50～800℃/s;

   (6) After gas cooling, the thickness range of the amorphous thin strip reaches 80-1500μm, and the width range is 110-550mm; the cast strip with a thickness of 80-800μm is taken up by coiling, and the cast strip with a thickness of more than 800μm is not coiled, but directly Collection in the form of thin ribbons.
2. The method for preparing a wide amorphous thin strip with a thickness of 80 to 1500 μm with a continuous high cooling rate and high efficiency according to claim 1, characterized in that, during the casting and rolling process, the alloy is rapidly cooled by heat transfer from the casting rolls, and the Speed, casting force and roll gap are used to control the temperature of the alloy strip exit roll, and control the alloy exit roll temperature close to or less than the crystallization temperature Tx of the alloy; the casting speed is 0.20～1.8m/s, The force is controlled as the casting rolling force per 1cm width of the cast strip is 2-15kN, the roll gap opening width of the casting roll is set to 80-1500μm, and there is no side sealing plate.
3. The method for preparing a wide amorphous ribbon with a thickness of 80 to 1500 μm with continuous high cooling rate and high efficiency according to claim 1, characterized in that the opening size at the lower end of the flow nozzle, the value of the gap between the casting rolls, and the casting speed , The casting and rolling process parameters of copper casting roll, steel casting roll, and casting roll cooling water volume control the solidification cooling rate to 500-75000℃/s.
4. The method for preparing a wide amorphous ribbon with a thickness of 80-1500 μm with continuous high cooling rate and high efficiency according to claim 1, wherein the zirconium-based, copper-based, iron-based or nickel-based amorphous alloy is added with mass percentage Yttrium element of 0.0045～0.020 is used to remove O and N pollution brought into the environment.
5. The method for preparing a wide amorphous ribbon with a thickness of 80 to 1500 μm with continuous high cooling rate and high efficiency according to claim 1, characterized in that the quartz material slit type nozzle is used for flow, and the slit opening width varies according to Product thickness design; the flow nozzle is preheated online, the preheating temperature is 100～200℃ above the alloy solidification temperature, the open end of the lower end of the flow nozzle conducts heat through the tungsten alloy sheet, and the end temperature of the flow nozzle reaches the alloy solidification temperature Nearby, the flow nozzle is equipped with a dam for steady flow; the preheatable flow guide tube is lined with quick-change quartz glass, and the preheating temperature is 100～200℃ above the solidification temperature of the alloy, which can be preheated. The outside of the flow tube is protected by cooling water.
6. The method for preparing a wide amorphous ribbon with a thickness of 80 to 1500 μm with continuous high cooling rate and high efficiency according to claim 1, characterized in that an infrared monitoring camera is arranged on the side of the width of the flow nozzle to feed back to the tilt control system to achieve the cloth The purpose of flow control: Among them, the height control range of the lower end of the cloth flow nozzle from the kiss line of the casting roll gap is 10-50mm, and the inner liquid level of the cloth flow nozzle is 40-60mm.
7. The method for preparing a wide amorphous thin ribbon with a thickness of 80-1500μm with continuous high cooling rate and high efficiency according to claim 1, characterized in that the casting roll uses two rolls arranged horizontally and oppositely, and supporting rolls are installed on both sides of the two rolls. , The diameter of the casting roll is 280-420mm, and the diameter of each group of support rolls is designed to be greater than the diameter of the casting roll by 100mm.
8. The method for preparing a wide amorphous ribbon with a thickness of 80-1500 μm with continuous high cooling rate and high efficiency according to claim 1, characterized in that the melting chamber and the forming chamber adopt hierarchical vacuum design, wherein: the working vacuum of the melting chamber reaches Below 1×10 ^-2 Pa, the vacuum degree of the forming cavity is below 1Pa; in the pouring state, the environment is in an argon protection state, and the melting chamber and the forming cavity are separated by a gate valve, and after the casting is filled with argon before the start of rolling The gate valve opens.
9. The method for preparing a wide amorphous ribbon with a thickness of 80 to 1500 μm with continuous high cooling rate and high efficiency according to claim 1, characterized in that an intermediate frequency induction melting furnace + a high-purity graphite crucible is used to melt the amorphous alloy, and the heating temperature It does not exceed 400℃ above the melting temperature of the metal to prevent oxidation and burning of metal elements.
10. The method for preparing a wide-width amorphous ribbon with a thickness of 80-1500 μm with continuous high cooling rate and high efficiency according to claim 1, characterized in that no more than 20wt% of cast strip trimming scrap is added to the incoming amorphous master alloy .

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