CN109967703B - Method for continuously and efficiently preparing wide amorphous thin strip with thickness of 80-1500 mu m at high cooling speed - Google Patents

Abstract

The invention belongs to the field of amorphous alloy preparation, and particularly relates to a method for efficiently preparing a wide amorphous thin strip with the thickness of 80-1500 mu m by using a double-roll method at a continuous high cooling speed. The method comprises the following steps: (1) smelting amorphous alloy according to set components, wherein the components comprise zirconium base, copper base, iron base, nickel base and the like, and the amorphous metal with the ultimate cooling rate of 500-75000 ℃/s is used for designing a method for continuously forming a thin strip of the amorphous alloy, so that a base material is provided for the subsequent processing procedures; (2) forming a wide casting belt with the thickness of 80-1500 mu m after a thin belt continuous casting process; (3) smelting, forming and coiling are carried out under the condition of inert atmosphere. Aiming at the problems that the requirements of amorphous alloy preparation on raw materials and preparation technology are high and mass production of amorphous alloy plate strips is not available, the invention realizes the continuous casting and rolling process of amorphous strips with the length of more than 12m and the thickness of 80-1500 mu m.

Description

Continuous and efficient preparation of a wide amorphous thin ribbon with a thickness of 80-1500 μm at a large cooling rate Methods

technical field

The invention belongs to the field of amorphous alloy preparation, and in particular relates to a method for efficiently preparing a wide amorphous thin ribbon with a thickness of 80-1500 μm by using a twin-roll method with a continuous high cooling rate.

Background technique

Amorphous alloy, also known as Metallic Glass or Glassy Alloy, is a new type of special alloy material whose material state is obviously different from that of crystalline state prepared by modern rapid solidification metallurgical technology. Due to the unique atomic structure arrangement and metal bond composition of amorphous alloys, amorphous alloys have more excellent mechanical properties, physical properties and chemical properties than traditional crystalline metal materials. This makes amorphous alloys have broad 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 strip, etc., which greatly weakened the performance potential of amorphous alloys. Industrial applications of amorphous alloys. Therefore, since the late 1980s, how to improve the formation ability of amorphous alloys and prepare large-scale 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 Zr-based, Ti-based, Fe-based, Co-based, Ni-based, Cu-based, Pt-based, etc. with large glass-forming ability 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 ribbon with excellent soft magnetic properties produced by the single-roll method has been widely used in China on a large scale and has made 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 produced as structural materials and used in electronic products, sports equipment, and auto parts. 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-sized products can be produced. As a widely used sheet and strip in structural materials, there is still no reliable production method. Therefore, how to realize continuous, large-scale and stable production of amorphous alloy sheets and strips and promote the wide application of bulk amorphous alloys is one of the urgent problems to be solved in the current amorphous industry.

At present, the main production methods of amorphous strip include single-roll melt quenching method, twin-roll melt quenching method and casting mold casting method. At present, the most widely used method that has been used in industrial 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, and can replace silicon steel and permalloy to make transformer cores, thereby greatly improving the efficiency of transformers, reducing the iron loss of distribution transformers, and reducing volume and size. weight. However, the single roll production process limits the thickness (about 20-50 μm) and width (less than 220 mm) of the strip. The twin-roll melt quenching method is referred to as the twin-roll method. A variety of continuous casting methods for bulk amorphous alloys have been developed based on the twin-roll method. U.S. Patent (Publication No. US2006/0260782A1) discloses a continuous living device and method for bulk amorphous alloy sheet. In the patent, the device uses multiple groups of small-diameter cooling rollers to cool the alloy strip, because the row rollers can only apply a small amount of pressure. The contact pressure, the cooling rate of the system can only reach less than 10℃/s, the thickness of the prepared plate is 0.1-10mm, and it is only limited to the forming of Zr-based amorphous alloys containing Be with strong forming ability, which will also reduce the life of amorphous and stability. The one that is closer to the technical idea is the Chinese patent (publication number CN 107755652 A), which uses crawler cooling and continuously casts amorphous materials, with small contact force and limited cooling speed, which will also reduce the life of amorphous materials and prepare amorphous materials. Ingredient design redundancy. Chinese Patent (Publication No. CN1486800A) discloses a continuous casting and rolling technology for bulk amorphous alloys. The molten metal in the crucible is injected into two relatively rotating water-cooled rolls, and the bulk amorphous plate is prepared by double roll casting and rolling. , bars, etc., but the patent does not see specific process protection nodes and technical implementation plans, and also does not disclose detailed parameters such as smelting temperature, heat preservation measures, flow control measures, cooling rate, casting and rolling force. 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 prepare amorphous alloy sheets and strips with large thickness specifications. The casting mold casting method is a method of melting the master alloy after melting in a crucible, keeping it warm, and then pouring it into a water-cooled hole shape through a flow nozzle, and by applying tension to the formed amorphous alloy at a certain speed, the amorphous alloy is realized. Method of continuous casting. Chinese Patent (Publication No. CN101543885A) discloses a device and method for horizontal continuous casting of bulk amorphous alloys. The cooling of the alloy mainly relies on a water-cooled copper mold, and the solidified billet is pulled by a traction rod driven by a motor and continuously output.

SUMMARY OF THE INVENTION

In view of the high requirements on raw materials and preparation technology for the preparation of amorphous alloys, and the mass production of amorphous alloy sheets and strips has not yet been seen, the purpose of the present invention is to provide a continuous and high cooling rate using the twin-roll method to efficiently prepare the thickness of 80-1500μm. The method of wide amorphous thin strip realizes the continuous casting and rolling process of amorphous strip with a length of more than 12 m and a thickness of 80-1500 μm.

The technical scheme of the present invention is:

A method for efficiently preparing a wide-width amorphous thin strip with a thickness of 80-1500 μm in a continuous large cooling rate is carried out according to the following steps:

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

(2) Smelting the amorphous master alloy according to the set composition, the 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 degree of the alloy melt is controlled at 50-300°C, and high-purity argon gas with a volume purity of more than 99.999% is used for protection during the temperature control process. The argon gas inside the melting chamber is slightly positive pressure, that is, the pressure is not lower than 0.11MPa;

(4) During the smelting process, the preparation of the forming cavity is completed, and the steps include: a) all valve bodies on the cavity of the forming cavity are closed, and argon gas is filled after vacuuming, the volume purity is more than 99.99%, and the temperature is not less than 0.11MPa. Slight positive pressure; b) Preheating the flow distribution nozzle. The distribution nozzle adopts a slit type flow distribution. After installation and entering a fixed position, the heating temperature is 100-200 °C above the solidification temperature of the target alloy; c) The cooling cycle of the casting roll 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 guide tube and flow nozzle, and filling of the forming cavity with argon gas, the vertical thin strip casting and rolling process is used to prepare the amorphous thin strip and enter the thin strip continuous casting process: Open the gate valve of the smelting chamber, the preheating guide tube goes down and connects with the flow distribution nozzle. The intermediate frequency induction melting furnace pours the alloy into the preheatable guide tube; the flow distribution nozzle is made of transparent quartz, which is monitored by an infrared monitoring camera. The tipping speed of the intermediate frequency induction melting furnace controls the height of the melt inside the distribution nozzle to be 40-60mm, and the alloy melt is uniformly distributed vertically through the distribution nozzle to the roll gap of the casting roll through the liquid level. The height of the slit liquid level is controlled at 2-10mm, the cooling rate of the alloy melt is 500-75000℃/s, and the alloy is cooled by casting and rolling. Low temperature argon purge cooling, gas cooling rate 50～800℃/s;

(6) After gas cooling, the thickness of the amorphous thin strip ranges from 80 to 1500 μm, and the width ranges from 110 to 550 mm; the cast strip with a thickness of 80 to 800 μm is coiled and taken up. Collection in thin strip form.

The method for continuously and efficiently preparing a wide amorphous thin strip with a thickness of 80-1500 μm at a large cooling rate, during the casting and rolling process, the alloy is rapidly cooled by heat transfer through the casting roll, and by controlling the casting and rolling speed, the size of the casting and rolling force and the rollers. The temperature of the alloy thin strip is controlled by the gap size, and the temperature of the alloy roll is controlled to be close to or less than the crystallization temperature Tx of the alloy; The casting rolling force of the strip is 2-15 kN, the opening width of the casting roll is set to be 80-1500 μm, and no side sealing plate is provided.

The method for continuously and efficiently preparing a wide amorphous thin strip with a thickness of 80-1500 μm at a large cooling rate is based on the opening size of the lower end of the flow nozzle, the roll gap value of the casting roll, the casting rolling speed, the copper casting roll, the steel casting The casting and 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 continuously and efficiently preparing a wide amorphous thin strip with a thickness of 80-1500 μm at a large cooling rate, the zirconium-based, copper-based, iron-based or nickel-based amorphous alloys are added with 0.0045-0.020 mass percent of yttrium element, It is used to remove O and N pollution brought into the environment.

The method for continuously and efficiently preparing a wide amorphous thin strip with a thickness of 80-1500 μm at a large cooling rate adopts a slit-type flow-distribution nozzle made of quartz material to distribute the flow, and the slit opening width is designed according to the thickness of different products; the flow-distribution 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 distribution nozzle conducts heat through the tungsten alloy sheet, and the temperature of the end of the distribution nozzle reaches near the alloy solidification temperature. The dam is flushed to stabilize the flow; the lining of the preheatable guide tube is quick-replaceable quartz glass, the preheating temperature is 100-200°C above the alloy solidification temperature, and the outside of the preheatable guide tube is protected by cooling water.

In the method for continuously and efficiently preparing a wide amorphous thin strip with a thickness of 80-1500 μm at a large cooling rate, an infrared monitoring camera is arranged on the side of the width of the flow distribution nozzle, and the feedback is fed to the tipping control system to achieve the purpose of flow distribution control; The height control range of the opening at the lower end of the flow nozzle from the Kiss line of the casting roll gap is 10-50mm, and the height of the liquid level inside the flow-distributing nozzle is 40-60mm.

In the method for continuously and efficiently preparing a wide amorphous thin strip with a thickness of 80-1500 μm at a large cooling rate, the casting rolls use double rolls arranged opposite horizontally, and support rolls are installed on both sides of the double rolls, and the diameter of the casting rolls is 280-420mm , the diameter of each set of backup rolls is designed to be 100mm larger than the diameter of the casting rolls.

In the method for continuously and efficiently preparing a wide amorphous thin strip with a thickness of 80-1500 μm at a large cooling rate, the smelting cavity and the forming cavity adopt a graded vacuum design, wherein: the working vacuum of the smelting cavity 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 cavity and the forming cavity are separated by a gate valve. The gate valve is opened after filling with argon before casting and rolling.

The method for continuously and efficiently preparing a wide amorphous thin strip with a thickness of 80-1500 μm at a large cooling rate adopts an intermediate frequency induction melting furnace + a high-purity graphite (carbon content ≥ 99.99 wt%) crucible to smelt the amorphous alloy, and heat the 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 continuously and efficiently preparing a wide amorphous thin strip with a thickness of 80-1500 μm at a large cooling rate, no more than 20wt% of cast strip trimming waste is added to the incoming amorphous mother alloy.

The advantages and beneficial effects of the present invention are:

1. For the continuous forming process of bulk amorphous alloys, large cooling rate and good stability are essential. In general casting and rolling equipment, due to its simple casting method and wide alloy molten pool, the cooling rate of the alloy in the shallow supercooled liquid phase region is small, and it is difficult to form an amorphous alloy. According to the characteristics of bulk amorphous solidification, combined with the twin-roll casting and rolling technology, the invention adopts the deep roll gap casting method, and the alloy molten pool is narrow, the cooling rate is large, and the deformation is small. Its principle, structure and method have not been publicly reported.

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

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

4. In the present invention, an infrared monitoring camera is provided on the side of the width of the flow distribution nozzle, which is fed back to the tipping control system to achieve the purpose of flow distribution control. The height control range of the opening at the lower end of the flow nozzle is 10-50mm from the Kiss line of the roll gap (Kiss line refers to the line closest to the double work rolls), and the liquid level inside the nozzle is 40-60mm. The casting and rolling system adopts the flow-casting speed matching to control the alloy melt roll gap along the vertical free flow strategy, and cancel the side sealing plate in the casting and rolling process.

5. The casting and rolling system of the present invention adopts the method of adding a backup roll of the casting roll 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 set of backup rolls is designed to be 100mm larger than the diameter of the work roll (casting roll), and the roughness of the roll surface Ra≤10μm.

6. The present invention adopts the diversion design with preheating. The lining of the preheating diversion tube is quartz glass that can be quickly replaced. Cooling water protection.

7. The grading vacuum design of the smelting cavity and the forming cavity of the present invention, wherein the working vacuum degree of the smelting cavity reaches below 1×10 ^-2 Pa, the vacuum degree of the forming cavity reaches below 1Pa, and the argon gas is quickly filled. In the pouring state, the environment is protected by argon gas, and the smelting cavity and the forming cavity are separated by a gate valve. The gate valve is opened after filling with argon gas before casting and rolling.

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 drawings

FIG. 1 is a schematic structural diagram of a casting and rolling device for continuous large cooling rate and efficient preparation of wide amorphous thin strips according to the present invention. In the figure, 1 medium frequency induction melting furnace; 2 high vacuum melting chamber; 3 preheatable guide pipe; 4 gate valve; 5 flow nozzle and infrared camera monitoring device; 51 flow nozzle; 52 infrared monitoring camera; 6 forming Cavity; 7 Support Rolls; 8 Casting Rolls; 9 Post-Casting Gas Cooling System; 10 Coiling Equipment; 11 Tipping Control System.

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

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

Detailed ways

As shown in FIG. 1 , the casting and rolling device for continuous large cooling rate and high efficiency preparation of wide amorphous thin strip of the present invention mainly includes: a medium frequency induction melting furnace 1, a high vacuum melting chamber 2 (chamber pressure < 0.1Pa), a preheatable Heat diversion tube 3, gate valve 4, flow nozzle and infrared camera monitoring device 5, forming cavity 6, support roll 7, casting roll 8, post-casting gas cooling system 9, coiling equipment 10, tipping control system 11 etc., the specific structure is as follows:

The bottom opening of the high vacuum melting cavity 2 corresponds to the top opening of the forming cavity 6, and the bottom opening of the high vacuum melting cavity 2 is communicated with the top opening of the forming cavity 6 through the gate valve 4; Furnace 1, preheatable guide tube 3 and tipping control system 11, the preheatable guide tube 3 is located on one side of the intermediate frequency induction melting furnace 1, the preheatable guide tube 3 is arranged vertically, and its lower port is connected with the forming The upper port of the flow distribution nozzle 51 on the top of the cavity 6 corresponds to the upper port; the intermediate frequency induction melting furnace 1 is installed on the tipping control system 11, and the intermediate frequency induction melting furnace 1 rotates around the tipping control system 11 through the rotating shaft, so that the intermediate frequency induction melting furnace 1 is rotated around the tipping control system 11. The upper port corresponds to the upper port of the preheatable guide tube 3 .

The flow distribution nozzle and the infrared camera monitoring device 5 include two parts: the flow distribution nozzle 51 and the infrared monitoring camera 52. The flow distribution nozzle 51 is provided with a dam rush to stabilize the flow, and the wider side of the flow distribution nozzle 51 is provided with an infrared monitoring camera. 52. Feedback to the tipping 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 melting in the intermediate frequency induction melting furnace 1, it is poured into the preheatable guide tube 3, and the preheatable guide tube 3 is moved down through the bottom opening and the gate of the intermediate frequency induction melting furnace 1. Valve 4, the amorphous mother alloy melt enters into the distribution nozzle 51 through the preheatable guide tube 3.

The lower port of the flow distribution nozzle 51 corresponds to the roll gap between the two casting rolls 8. The outer sides of the two casting rolls 8 are respectively provided with support rolls 7, which can preheat the alloy melt in the guide tube 3 to pass through the flow distribution nozzle. 51 is evenly 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 into a coil.

In the specific implementation process, the method for continuously and efficiently preparing the wide amorphous thin strip of the present invention with a large cooling rate is as follows: (1) smelting the amorphous alloy according to the set composition, and its composition includes zirconium-based, copper-based, iron-based, nickel-based Design a method for continuous forming of thin strips of amorphous metals with a limiting cooling rate between 500 and 75000 °C/s, and provide basic materials for subsequent processing; (2) After thin strip continuous casting, the thickness is 80-1500μm wide cast strip; (3) Smelting, forming and coiling under inert atmosphere.

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

Example 1

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: in-depth roll gap distribution;

Preparation process:

a. Prepare 20kg of raw material by atomic percentage, put it into the intermediate frequency induction melting furnace, and vacuum the melting chamber to 6×10 ^-2 Pa, heat the alloy raw material until it is completely melted, and continue to melt at 1500℃ for 10min.

b. During the smelting process, the preparation of the forming cavity is completed. The steps include: 1) Close all valve bodies on the cavity of the forming cavity, evacuate to 0.5Pa, and then fill with argon gas, the volume purity is above 99.99%, and the temperature is maintained at 0.12MPa. Slight positive pressure; 2) The distribution nozzle is preheated, and the distribution nozzle adopts a slit type distribution, which is heated after being installed in a fixed position, and the heating temperature is 1150 °C; The water flow rate was 80 m ³ /h; 4) The post-casting gas cooling system was prepared, the argon pressure was 0.7 MPa, and the gas temperature was controlled at 5°C; 5) The roll gap opening width was set to 0.55 mm.

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 0.12MPa, open the gate valve, put down the preheatable guide tube, and pass the alloy melt through the The preheating draft tube (the preheating temperature of the draft tube is 1150°C) and the distribution nozzle are uniformly distributed into 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 flow nozzle used in the experiment is made of transparent quartz. During the experiment, the liquid level of the melt inside the flow nozzle was monitored and controlled to be 60 mm through the infrared monitoring camera and the tipping speed of the crucible. Relying on the alloy liquid pressure, the alloy melt is evenly distributed into the roll gap of the casting roll through the flow nozzle, and the liquid level of the alloy melt in the roll gap is controlled at 5-10mm, and no side sealing plate is provided, and the alloy is cooled and cast and formed. , the cooling rate of the alloy melt 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 is regulated by controlling the casting and rolling speed, the size of the casting force and the size of the roll gap, and the The temperature of the alloy roll out 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 100°C/s.

The test obtained 0.55 mm thick amorphous ribbon, as shown in Figure 2. Its microstructure photos and XRD curves are shown in Figure 3. It can be seen from Fig. 2-Fig. 3 that the matrix of the cast belt is an amorphous structure with only a few crystalline impurities.

Embodiment 2

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

Distribution method: in-depth roll gap distribution;

Preparation process:

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

b. During the smelting process, the preparation of the forming cavity is completed. The steps include: 1) Close all the valve bodies on the cavity of the forming cavity, evacuate to 0.5Pa, and then fill with argon gas, the volume purity is above 99.99%, and the temperature is maintained at 0.11MPa. Slight positive pressure; 2) The distribution nozzle is preheated, and the distribution nozzle adopts a slit type distribution, which is heated after being installed into a fixed position, and the heating temperature is 1000 °C; 3) The temperature of the cooling circulating water of the casting roll is 5 °C, and the total The water flow rate was 80 m ³ /h; 4) The post-casting gas cooling system was prepared, the argon pressure was 0.7 MPa, and the gas temperature was controlled at 5°C; 5) The roll gap opening width was set to 0.5 mm.

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, put down the preheatable guide tube, and pass the alloy melt through the The preheating draft tube (the preheating temperature of the draft tube is 1150°C) and the distribution nozzle are uniformly distributed into 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 flow nozzle used in the experiment is made of transparent quartz. During the experiment, the liquid level of the melt inside the flow nozzle was monitored and controlled to be 60 mm through the infrared monitoring camera and the tipping speed of the crucible. Relying on the alloy liquid pressure, the alloy melt is evenly distributed into the roll gap of the casting roll through the flow nozzle, and the liquid level of the alloy melt in the roll gap is controlled at 5-10mm, and no side sealing plate is provided, and the alloy is cooled and cast and formed. , the cooling rate of the alloy melt is 6000°C/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 out of the roll is regulated by controlling the casting and rolling speed, the size of the casting force and the size of the roll gap. The temperature of the alloy exit roll is controlled at about 400℃; 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 to be further cooled to below 100℃, and the cooling rate of the gas cooling system is 80℃/s.

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

Embodiment 3

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

Distribution method: in-depth roll gap distribution;

Preparation process:

a. Prepare 30kg of raw material by atomic percentage, put it into the intermediate frequency induction melting furnace, and vacuum the melting chamber to 7×10 ^-2 Pa, heat the alloy raw material until it is completely melted, and continue to melt at 1500℃ for 10min.

b. During the smelting process, the preparation of the forming cavity is completed. The steps include: 1) Close all the valve bodies on the cavity of the forming cavity, evacuate to 0.5Pa, and then fill with argon gas, the volume purity is above 99.99%, and the temperature of 0.11MPa is maintained. Slight positive pressure; 2) The distribution nozzle is preheated, and the distribution nozzle adopts a slit type distribution, which is heated after being installed in a fixed position, and the heating temperature is 1150 °C; The water flow rate was 80 m ³ /h; 4) The post-casting gas cooling system was prepared, the argon pressure was 0.7 MPa, and the gas temperature was controlled at 5°C; 5) The roll gap opening width was set to 0.5 mm.

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, put down the preheatable guide tube, and pass the alloy melt through the The preheating draft tube (the preheating temperature of the draft tube is 1150°C) and the distribution nozzle are uniformly distributed into 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 flow nozzle used in the experiment is made of transparent quartz. During the experiment, the liquid level of the melt inside the flow nozzle was monitored and controlled to be 60 mm through the infrared monitoring camera and the tipping speed of the crucible. Relying on the alloy liquid pressure, the alloy melt is evenly distributed into the roll gap of the casting roll through the flow nozzle, and the liquid level of the alloy melt in the roll gap is controlled at 5-10mm, and no side sealing plate is provided, and the alloy is cooled and cast and formed. , the cooling rate of the alloy melt 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 thin strip out of the roll is regulated by controlling the casting and rolling speed, the size of the casting force and the size of the roll gap. The temperature of the alloy 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 to be further cooled to below 100 °C, and the cooling rate of the gas cooling system is 60 °C/s.

The test obtained 0.5 mm thick amorphous strip.

Embodiment 4

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

Distribution method: in-depth roll gap distribution;

Preparation process:

a. Prepare 20kg of raw material by atomic percentage, put it into the intermediate frequency induction melting furnace, and vacuum the melting chamber to 8×10 ^-2 Pa, heat the alloy raw material until it is completely melted, and continue to melt at 1500℃ for 10min.

b. During the smelting process, the preparation of the forming cavity is completed. The steps include: 1) Close all the valve bodies on the cavity of the forming cavity, evacuate to 0.5Pa, and then fill with argon gas, the volume purity is above 99.99%, and the temperature of 0.11MPa is maintained. Slight positive pressure; 2) The distribution nozzle is preheated, and the distribution nozzle adopts a slit type distribution, which is heated after being installed in a fixed position, and the heating temperature is 1200 °C; 3) The cooling water temperature of the casting roll is 5 °C, and the total The water flow rate was 80 m ³ /h; 4) The post-casting gas cooling system was prepared, the argon pressure was 0.7 MPa, and the gas temperature was controlled at 5°C; 5) The roll gap opening width was set to 0.5 mm.

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, put down the preheatable guide tube, and pass the alloy melt through the The preheating draft tube (the preheating temperature of the draft tube is 1150°C) and the distribution nozzle are uniformly distributed into 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 flow nozzle used in the experiment is made of transparent quartz. During the experiment, the liquid level of the melt inside the flow nozzle was monitored and controlled to be 60 mm through the infrared monitoring camera and the tipping speed of the crucible. Relying on the alloy liquid pressure, the alloy melt is evenly distributed into the roll gap of the casting roll through the flow nozzle, and the liquid level of the alloy melt in the roll gap is controlled at 5-10mm, and no side sealing plate is provided, and the alloy is cooled and cast and formed. , the cooling rate of the alloy melt is 5000℃/s; in the process of casting and rolling, the alloy is rapidly cooled by heat transfer of the casting roll, and the temperature of the alloy strip is regulated by controlling the casting and rolling speed, the size of the casting force and the size of the roll gap. The temperature of the alloy roll is controlled at about 520 °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 to be further cooled to below 100 °C, and the cooling rate of the gas cooling system is 50 °C/s.

The test obtained 0.25 mm thick amorphous ribbon.

Embodiment 5

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

Distribution method: in-depth roll gap distribution;

Preparation process:

a. Prepare 20kg of raw material by atomic percentage, put it into the intermediate frequency induction melting furnace, and vacuum the melting chamber to 6×10 ^-2 Pa, heat the alloy raw material until it is completely melted, and continue to melt at 1500℃ for 10min.

b. During the smelting process, the preparation of the forming cavity is completed. The steps include: 1) Close all the valve bodies on the cavity of the forming cavity, evacuate to 0.5Pa, and then fill with argon gas, the volume purity is above 99.99%, and the temperature of 0.11MPa is maintained. Slight positive pressure; 2) The distribution nozzle is preheated, and the distribution nozzle adopts a slit type distribution, which is heated after being installed in a fixed position, and the heating temperature is 1200 °C; 3) The cooling water temperature of the casting roll is 5 °C, and the total The water flow rate was 80 m ³ /h; 4) The post-casting gas cooling system was prepared, the argon pressure was 0.7 MPa, and the gas temperature was controlled at 5°C; 5) The roll gap opening width was set to 0.5 mm.

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, put down the preheatable guide tube, and pass the alloy melt through the The preheating draft tube (the preheating temperature of the draft tube is 1150°C) and the distribution nozzle are uniformly distributed into 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 flow nozzle used in the experiment is made of transparent quartz. During the experiment, the liquid level of the melt inside the flow nozzle was monitored and controlled to be 60 mm through the infrared monitoring camera and the tipping speed of the crucible. Relying on the alloy liquid pressure, the alloy melt is evenly distributed into the roll gap of the casting roll through the flow nozzle, and the liquid level of the alloy melt in the roll gap is controlled at 5-10mm, and no side sealing plate is provided, and the alloy is cooled and cast and formed. , the cooling rate of the alloy melt is 7000°C/s; during the casting and rolling process, the alloy is rapidly cooled by heat transfer of the casting roll, and the temperature of the alloy strip is regulated by controlling the casting rolling speed, the size of the casting force and the size of the roll gap. The temperature of the alloy roll is controlled at about 520 °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 to be further cooled to below 100 °C, and the cooling rate of the gas cooling system is 80 °C/s.

The test obtained 0.25 mm thick amorphous ribbon.

The above 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 the purpose is to describe the present invention in detail. However, all equivalent substitutions made according to the spirit of the present invention without departing from the technical spirit of the present invention are all within the protection scope of the present invention.

Claims (10)

1. a method for the efficient preparation of a wide-width amorphous thin strip with a thickness of 80 to 1500 μm in a continuous large cooling rate, is characterized in that, carry out according to the following steps: (1) The amorphous mother alloy is discharged into the crucible, and the preheatable guide tube and its position control device are cleaned. The inside of the preheatable guide tube is lined with quartz material, and is equipped with a heating system. The heating temperature is When the solidification temperature of the amorphous mother alloy is 100~200℃ above the solidification temperature, the outside of the preheating guide tube can be protected by cooling water; (2) Smelting 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 degree of the alloy melt is controlled to be 50-300°C. During the temperature control process, high-purity argon gas with a volume purity of more than 99.999% is used for protection. The argon gas inside the melting chamber is slightly positive pressure, that is, the pressure is not lower 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 gas is filled after vacuuming. Slight positive pressure; b) Preheating the flow distribution nozzle, the distribution nozzle adopts a slit type flow distribution, and is heated after being installed in a fixed position. The heating temperature is 100~200 °C above the solidification temperature of the target alloy; c) The cooling cycle of the casting roll 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 guide tube and flow nozzle, and filling of the forming cavity with argon gas, the vertical thin strip casting and rolling process is used to prepare the amorphous thin strip and enter the thin strip continuous casting process: Open the gate valve of the smelting chamber, the preheating guide tube goes down and connects with the flow distribution nozzle. The intermediate frequency induction melting furnace pours the alloy into the preheatable guide tube; the flow distribution nozzle is made of transparent quartz, which is monitored by an infrared monitoring camera. The tipping speed of the intermediate frequency induction melting furnace controls the height of the melt inside the distribution nozzle to be 40~60mm, and the alloy melt is uniformly distributed vertically through the distribution nozzle to the roll gap of the casting roll through the liquid level. The height of the seam liquid level is controlled at 2~10mm, the cooling rate of the alloy melt is 500~75000℃/s, and the alloy is cooled by casting and rolling. Adopt low temperature argon purging and cooling, the gas cooling rate is 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 coiled and taken up, and the cast strip with a thickness of more than 800μm is not coiled and directly Collection in thin strip form. 2. The method according to claim 1 for the continuous and efficient preparation of a wide amorphous thin strip with a thickness of 80 to 1500 μm, characterized in that in the casting and rolling process, the alloy melt is rapidly cooled by heat transfer of the casting roll, By controlling the casting speed, the casting force and the roll gap, the temperature of the alloy strip roll is regulated, and the temperature of the alloy roll is controlled to be less than the crystallization temperature Tx of the alloy; the casting speed is 0.20~1.8m/s, The casting and rolling force is controlled to be 2~15kN per 1cm width of the cast strip, the opening width of the casting roll gap is set to 80~1500μm, and no side sealing plate is provided. 3. The method according to claim 1 for the continuous and high-efficiency preparation of wide-width amorphous thin strips with a thickness of 80 to 1500 μm, characterized in that, through the opening size of the lower end of the distribution nozzle, the opening width of the casting roll gap, The casting and rolling process parameters of casting speed, copper casting roll, steel casting roll and casting roll cooling water quantity control the solidification cooling speed to reach 500~75000℃/s. 4. The method according to claim 1 for the efficient preparation of wide-width amorphous thin strips with a thickness of 80 to 1500 μm, characterized in that zirconium-based, copper-based, iron-based or nickel-based amorphous alloys are added The yttrium element with a mass percentage of 0.0045~0.020 is used to remove the O and N pollution brought into the environment. 5. the method according to claim 1 is that the wide-width amorphous thin strip with a thickness of 80-1500 μm is continuously prepared with a large cooling rate and efficiently, it is characterized in that, adopting the quartz material slit type flow nozzle for flow distribution, the slit opening width It is designed according to different product thicknesses; the nozzle is preheated online, and the preheating temperature is 100~200°C above the solidification temperature of the alloy. The open end of the lower end of the nozzle conducts heat through the tungsten alloy sheet, and the temperature at the end of the nozzle reaches the temperature of the alloy. Near the solidification temperature, there is a baffle punch inside the flow distribution nozzle to stabilize the flow; the lining of the preheatable guide tube is quartz glass that can be quickly replaced, and the preheating temperature is 100~200℃ above the alloy solidification temperature. The outside of the guide tube is protected by cooling water. 6. The method according to claim 1 for the continuous and efficient preparation of wide-width amorphous thin strips with a thickness of 80-1500 μm, characterized in that an infrared monitoring camera is arranged on the side of the width of the flow distribution nozzle, which is fed back to the tipping control system. To achieve the purpose of flow control; among them, the height control range of the opening at the lower end of the flow nozzle from the Kiss line of the roll gap is 10~50mm, and the height of the liquid level inside the flow nozzle is 40~60mm. 7. The method for efficiently preparing wide-width amorphous thin strips with a thickness of 80-1500 μm according to claim 1, characterized in that the casting rolls use horizontally opposite twin rolls, and both sides of the twin rolls are installed Backup roll, the diameter of the casting roll is 280~420mm, and the diameter of each set of backup rolls is designed to be larger than the diameter of the casting roll by 100mm. 8. The method according to claim 1 for the continuous and efficient preparation of wide amorphous thin strips with a thickness of 80-1500 μm, characterized in that the smelting cavity and the forming cavity adopt a graded vacuum design, wherein: the working vacuum of the smelting cavity is The degree of vacuum of the forming cavity is below 1×10 ^{- 2} Pa, and the vacuum degree of the forming cavity is below 1Pa; in the pouring state, the environment is in the state of argon gas protection, the melting cavity and the forming cavity are separated by a gate valve, and the casting and rolling are filled with argon before starting. The rear gate valve opens. 9. the method according to claim 1 is that the wide-width amorphous thin strip of 80～1500 μm is continuously prepared with high cooling rate and high efficiency, it is characterized in that, adopt intermediate frequency induction melting furnace+high-purity graphite crucible to carry out amorphous alloy smelting, The heating temperature does not exceed 400°C above the melting temperature of the metal to prevent oxidation and burning of metal elements. 10. The method for efficiently preparing wide-width amorphous thin strips with a thickness of 80 to 1500 μm according to claim 1, characterized in that, adding no more than 20wt% of cast strip cutting to the amorphous mother alloy incoming material. side waste.

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