CN109825781B - Method for continuously preparing iron-based amorphous thin strip - Google Patents

Method for continuously preparing iron-based amorphous thin strip Download PDF

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CN109825781B
CN109825781B CN201910277325.7A CN201910277325A CN109825781B CN 109825781 B CN109825781 B CN 109825781B CN 201910277325 A CN201910277325 A CN 201910277325A CN 109825781 B CN109825781 B CN 109825781B
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CN109825781A (en
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张晨阳
袁国
张元祥
王洋
康健
李振磊
王黎筠
王国栋
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Northeastern University China
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Abstract

The invention belongs to the field of amorphous alloy preparation, and particularly relates to a method for continuously preparing an iron-based amorphous alloy thin strip by using a double-roller method. Firstly, smelting alloy raw materials or a preliminarily prepared master alloy in a vacuum induction smelting furnace to obtain an iron-based amorphous master alloy melt, introducing argon gas and opening a gate valve between the vacuum induction smelting furnace and a tundish after the temperature is controlled to meet the requirement, and introducing the melt into the tundish protected by high-purity argon gas through a preheating flow channel. After the flow control plug rod of the tundish is opened, the alloy melt is uniformly distributed by the flow distribution nozzle and then injected into a roll gap of the casting roll, the amorphous strip is formed by cooling the water-cooled casting roll, and the amorphous strip is continuously cooled by the row roll and is guided into the reeling equipment. The whole casting-rolling-cooling-coiling process is completed in a casting machine cavity protected by high-purity argon. The method has the advantages of short amorphous forming process flow, high cooling speed and continuous preparation process, and can efficiently and continuously prepare the iron-based amorphous thin strip and promote the application of the iron-based amorphous alloy.

Description

Method for continuously preparing iron-based amorphous thin strip
Technical Field
The invention belongs to the field of amorphous alloy preparation, and particularly relates to a method for continuously preparing an iron-based amorphous alloy thin strip by using a double-roller method.
Background
Amorphous Alloy, also called Metallic Glass or Glass Alloy, is a new, special Alloy material with a material state obviously different from the crystalline state, which is prepared by applying modern rapid solidification metallurgy technology. Due to the unique atomic structure arrangement and the metal bond composition of the amorphous alloy, the amorphous alloy has more excellent mechanical property, physical property and chemical property compared with the traditional crystalline metal material. The amorphous alloy has wide application prospect in the aspects of aerospace, weapon industry, precise instruments, biomedical treatment, electric power transmission and the like.
Early stage of the processThe preparation of amorphous alloy requires great cooling speed (> 10)6K/s), the amorphous alloy can only exist in the forms of powder, wire, thin strip and the like, the performance potential of the amorphous alloy is greatly weakened, and the application of the amorphous alloy in the industry is limited. Therefore, since the end of the last eighties, how to improve the forming capability of amorphous alloys becomes one of the important research directions in the research field of new materials. In decades from the 20 th century, 80 s to date, a large number of alloy systems having a large glass forming ability, such as Zr-based, Ti-based, Fe-based, Co-based, Ni-based, Cu-based, Pt-based, and the like, have been developed through efforts of a large number of scholars; the preparation technology of various block amorphous alloys such as a water quenching method, a copper mold casting method, a directional solidification method, an amorphous powder extrusion method and the like is developed. The amorphous thin strip with excellent soft magnetic performance produced by the single-roll method is widely applied in China in a large scale, and makes a prominent contribution to energy conservation and emission reduction of electric power systems in China. Moreover, the preparation and application of bulk amorphous alloys have been greatly developed, and due to their excellent mechanical properties, they have been used as structural materials for the production and application of electronic products, sports equipment, automobile parts, etc. At present, the most main production mode of the bulk amorphous alloy products applied to the market is a die casting method, and only small-specification products can be produced due to the limitation of the conditions of the bulk amorphous alloy products. However, there is still no reliable production method for the sheet and strip material widely used as a structural material. Therefore, how to realize continuous, large-scale and stable production of amorphous alloy plates and strips and promote the wide application of bulk amorphous alloys is one of the problems which are urgently needed to be solved by the current amorphous industry.
Currently, the main production methods of amorphous strip include single roll melt quenching, twin roll melt quenching, and cast strip casting. At present, the most widely used method for industrial production is a single-roller melt quenching method, which is called a single-roller method for short. The iron-based amorphous strip produced by the single-roll method has excellent soft magnetic performance, can replace silicon steel and permalloy to manufacture a transformer iron core, further greatly improves the efficiency of the transformer, reduces the iron loss of a distribution transformer, and simultaneously reduces the volume and the weight. However, the single roll process limits the thickness (about 20-50 μm) and width (less than 220mm) of the strip. The twin-roll melt quenching method is abbreviated as twin-roll method. A plurality of continuous casting methods of bulk amorphous alloys are developed based on a double-roller method. U.S. patent (publication No. US2006/0260782A1) discloses a continuous holding device and method for a block amorphous alloy sheet, wherein a plurality of groups of small-diameter cooling rollers are adopted for cooling an alloy strip, the row rollers can only apply small contact pressure, the system cooling speed can only reach less than 10 ℃/s, the thickness of the prepared sheet is 0.1-10 mm, and the sheet is only limited to forming of Zr-based amorphous alloy containing Be with strong forming capacity, and the amorphous life and stability can also Be reduced. The Chinese patent (publication No. CN 107755652A) is close to the technical idea, and uses crawler cooling to continuously cast amorphous, the contact force is small, the cooling speed is limited, and the service life of the amorphous is reduced and the design redundancy of the ingredients for preparing the amorphous is reduced. Chinese patent (publication No. CN1486800A) discloses a continuous casting and rolling technique for bulk amorphous alloy, in which molten metal in a crucible is poured into two water-cooled rollers rotating relatively to each other, and double-roller casting and rolling are used to prepare bulk amorphous plates, bars, etc., but the patent does not have specific process protection nodes and technical implementation schemes, and does not disclose detailed parameters such as melting temperature, heat preservation measures, flow control measures, cooling speed, casting and rolling force, etc. And relatively large rolling force can be applied to the position of the roll gap to realize large cooling speed, the cooling capacity is larger than that of a single-roll method in theory, and the amorphous alloy plate strip with large thickness specification can be prepared. The casting mold drawing casting process is one continuous casting process of smelting mother alloy in a crucible, maintaining temperature, casting the mother alloy into water cooled hole pattern via a nozzle and drawing the amorphous alloy at certain speed to cast amorphous alloy. Chinese patent publication No. CN101543885A discloses a device and method for horizontal continuous casting of bulk amorphous alloy, wherein the cooling of the alloy mainly depends on a water-cooled copper mold, and the solidified casting blank is continuously output by being pulled by a traction rod driven by a motor.
Disclosure of Invention
The invention aims to provide a method for continuously preparing an iron-based amorphous alloy thin strip by using a double-roller method aiming at the problems that the requirements of iron-based amorphous alloy preparation on the purity and the vacuum degree of raw materials are high and the mass production of the iron-based amorphous alloy plate strip is not seen.
The technical scheme of the invention is as follows:
a method for continuously preparing an iron-based amorphous thin strip comprises the following steps:
(1) smelting a master alloy according to set components, wherein the used master alloy comprises the following components: feaCbSicBdPeCrfAlgMohNbiA, b, c, d, e, f, g and h are atomic percent, wherein a is more than or equal to 40 and less than or equal to 80; b is more than or equal to 0 and less than or equal to 20; c is more than or equal to 0 and less than or equal to 10; d is more than or equal to 0 and less than or equal to 15; e is more than or equal to 0 and less than or equal to 15; f is more than or equal to 0 and less than or equal to 30; g is more than or equal to 0 and less than or equal to 5; h is more than or equal to 0 and less than or equal to 20; i is more than or equal to 0 and less than or equal to 5; putting alloy raw materials or a preliminarily prepared master alloy into a melting crucible to be melted completely, continuing to melt after melting, and melting for 5-30 min at a temperature higher than 200 ℃ of the alloy melt to fully melt the alloy;
(2, guiding the alloy melt into a tundish through a preheated flow guide pipe, wherein the temperature of the tundish is 100-300 ℃ higher than the melting point of the alloy, so that the alloy is uniformly heated in the tundish, and controlling the superheat degree of the alloy to be 100-300 ℃ during casting;
(3) forming an amorphous thin strip: opening the stopper rod, uniformly distributing and flowing the alloy melt into a roll gap of the casting roll through a preheated distribution nozzle, and rapidly cooling the alloy for casting and rolling forming; in the casting and rolling process, the alloy is subjected to heat transfer and rapid cooling through a casting roller, the cooling speed is 1000-75000 ℃/s, the casting and rolling speed is controlled to be 0.05-3 m/s, the casting and rolling force is controlled to be 2-15 kN per 1cm width of casting strip, the opening width of a casting roller gap is set to be 0.1-1 mm, the temperature of the alloy thin strip out of the roller is regulated, and the temperature of the alloy out of the roller is controlled to be lower than the crystallization temperature Tx of the alloy;
(4) the alloy cast strip is cooled again through the roller and is guided into a coiler to be coiled; in the process of preparing the cast strip, the whole casting, rolling, cooling and coiling processes are finished in a casting machine cavity protected by high-purity argon.
The method for continuously preparing the iron-based amorphous thin strip uses a double-roller method to continuously and rapidly prepare the iron-based amorphous alloy thin strip with the thickness of 0.1-1 mm.
According to the method for continuously preparing the iron-based amorphous thin strip, the smelting process and the uniform temperature storage process of the master alloy are carried out in a high vacuum condition of less than 0.1Pa or a high-purity argon protective atmosphere with the volume purity of more than or equal to 99.999 percent; the casting and rolling process is carried out under the protection of argon with the volume purity of more than or equal to 99.9 percent.
According to the method for continuously preparing the iron-based amorphous thin strip, the raw alloy materials are directly used for smelting in a smelting crucible, or the smelted master alloy is used for smelting.
According to the method for continuously preparing the iron-based amorphous thin strip, the solidification cooling speed is controlled to reach 1000-75000 ℃/s through the size of a flow distribution port at the lower end of a flow distribution nozzle, the roll gap value of a casting roll, the casting-rolling speed, the casting-rolling technological parameters of the copper casting roll, the steel casting roll and the cooling water amount of the casting roll.
According to the method for continuously preparing the iron-based amorphous thin strip, the flow distribution port at the lower end of the flow distribution nozzle is designed to be rectangular or a row of round, the width of the rectangle is 0.2-1 mm, and the diameter of the round is 0.5-2 mm; the flow distribution mode is divided into three types: direct injection roll seam method, single side casting and coating method or double side casting and coating method; the material of the flow distribution port is SiO which is not easy to react with the alloy melt2Or BN.
The method for continuously preparing the iron-based amorphous thin strip has the preheating temperature range of 1000-1400 ℃ for the flow distribution nozzle and 900-1000 ℃ for the flow guide pipe.
According to the method for continuously preparing the iron-based amorphous thin strip, in the stable casting and rolling process of the thin strip, the height of an alloy molten pool at the upper part of a casting roller is controlled to be stable by controlling the alloy flow, and the width of the surface of the alloy molten pool along the radial direction of the casting roller is controlled within 10 mm.
According to the method for continuously preparing the iron-based amorphous thin strip, the casting roller is made of copper or steel alloy with good heat conductivity, the roller diameter of the casting roller is 220-510 mm, and the roughness Ra of the roller surface is less than or equal to 10 mu m.
According to the method for continuously preparing the iron-based amorphous thin strip, the water inlet temperature of cooling water of a casting roller is controlled to be 5-12 ℃, the water outlet temperature is controlled to be 5-15 ℃, and the water flow is controlled to ensure that the temperature rise interval of water is less than 3 ℃.
The invention has the advantages and beneficial effects that:
1. the invention fully utilizes the thin strip continuous casting technology to continuously prepare the bulk amorphous alloy, the preparation process of the alloy thin strip is formed by one step, and the flow is short; the heat conduction is good under pressure in the alloy cooling and solidifying process, and the cooling speed is high; the amorphous alloy thin strip can be prepared by using industrial raw materials.
2. For the continuous forming process of bulk amorphous alloys, a large cooling rate and good stability are essential. And the casting mode of the common casting and rolling equipment is simple, and the alloy molten pool is wide, so that the cooling speed of the alloy in a shallow supercooled liquid region is low, and the amorphous alloy is difficult to form. According to the characteristics of bulk amorphous solidification, a double-roller casting and rolling technology is combined, deep roll gap casting or a side casting and coating method is adopted, and an alloy molten pool is narrow, the cooling speed is high, and deformation is small. The principle, structure and method are not reported in public. The subject group is also fully technically practiced, and the continuous casting and rolling process of the amorphous strip with the length of more than 12m and the thickness of 0.2-0.75 mm is realized.
3. The invention provides a method for continuously and rapidly preparing an iron-based amorphous alloy thin strip with the thickness of 0.1-1 mm by using industrial raw materials. The invention makes the completely molten metal melt pass through the water distribution flow opening to uniformly widen the liquid flow, and then directly injects the casting opening matched with the roll gap of the roll into the deep part of the roll gap to uniformly fill the whole roll gap. And a slight level control is achieved. The alloy melt filled into the roll gap is contacted with the casting roll, so that heat is conducted and lost through the roll. And deep pouring can ensure that the alloy can obtain a great cooling speed when being injected, thereby inhibiting the formation and the growth of crystal nuclei. In addition, the pressure generated by the casting rolling can accelerate the heat transfer of the alloy to the outside and increase the cooling speed of the alloy. And the reduction of the ratio of the width of the alloy molten pool liquid surface to the width of the roller gap can reduce the casting rolling deformation, thereby reducing the clamping phenomenon of the cooled amorphous alloy due to overhigh strength and ensuring the continuous casting rolling process. And more free volume is obtained, so that the amorphous service life, the stability and the amorphous forming capability are obviously improved.
4. The whole casting and rolling process of the invention is carried out in the sealing cover, Ar gas is filled in the sealing cover as protective gas, thus ensuring that the alloy melt is not contacted with oxygen in the process of solidifying to be solid, preventing oxidation and inhibiting nucleation of the alloy.
Drawings
FIG. 1 is a schematic structural diagram of a casting and rolling device for continuously preparing an iron-based amorphous thin strip. In the figure: the device comprises a vacuum induction smelting furnace 1, a smelting crucible 2, a flow guide pipe 3, a gate valve 4, a tundish 5, a stopper rod 6, a tundish crucible 7, a flow distribution nozzle 8, a casting roller 9, a sealing protective cover 10, a casting belt 11, a row of rollers 12 and a coiling device 13.
FIG. 2 is a schematic structural diagram of an amorphous alloy prepared by a double-roller single-side casting method. In the figure: 8 distribution nozzles, 9 casting rolls, 14 single-side outlets, 15 alloy melts.
FIG. 3 is a schematic structural diagram of an amorphous alloy prepared by a double-roller double-side pouring method. In the figure: 8 distribution nozzles, 9 casting rolls, 15 alloy melt and 16 double-sided outlets.
FIG. 4 is a schematic illustration of a 0.25 mm thick amorphous ribbon.
Figure 5 is an XRD graph of a 0.25 mm thick amorphous ribbon. In the figure, the abscissa 2 θ represents the diffraction angle (drge) and the ordinate intensity represents the relative intensity (a.u.).
Detailed Description
As shown in FIG. 1, the casting and rolling device for continuously preparing the iron-based amorphous thin strip mainly comprises: vacuum induction melting furnace 1, smelt crucible 2, honeycomb duct 3, slide valve 4, middle package 5, stopper stick 6, middle package crucible 7, flow distribution mouth 8, cast roller 9, sealed safety cover 10, cast strip 11, row's roller 12, coiling equipment 13 etc. and specific structure is as follows:
the bottom opening of the vacuum induction melting furnace 1 is communicated with the top opening of the tundish 5 through a gate valve 4, and the bottom opening of the tundish 5 is communicated with the top opening of the sealing protection cover 10; a smelting crucible 2 and a flow guide pipe 3 are arranged in a vacuum induction smelting furnace 1, the flow guide pipe 3 is positioned on one side of the smelting crucible 2, the flow guide pipe 3 is vertically arranged, and the lower end opening of the flow guide pipe corresponds to a tundish crucible 7 in a tundish 5. When the iron-based amorphous mother alloy melt is obtained by smelting in the vacuum induction smelting furnace 1, the melt is poured into the guide pipe 3, the guide pipe 3 moves downwards to penetrate through the bottom opening of the vacuum induction smelting furnace 1 and the top opening of the tundish 5, and the iron-based amorphous mother alloy melt enters the tundish crucible 7 through the guide pipe 3.
The stopper 6 vertically penetrates through the tundish crucible 7, the lower end of the stopper 6 plugs the bottom opening of the tundish 5, the upper side of the flow distribution nozzle 8 is connected with the bottom opening of the tundish 5, and the top opening vertically penetrating through the sealing protective cover 10 is inserted between the two casting rolls 9. Row rollers 12 and a coiling device 13 are arranged below the casting rollers 9 in the sealed protective cover 10, a channel of a casting strip 11 is formed between the oppositely arranged row rollers 12, the row rollers 12 are uniformly distributed in an arc shape, the upper parts of the row rollers 12 correspond to a roller gap between the two casting rollers 9, and the lower parts of the row rollers 12 correspond to an inlet of the coiling device 13. When the stopper 6 is opened, the alloy melt in the tundish crucible 7 is uniformly distributed to the roll gap between the two casting rolls 9 through the distribution nozzle 8 and is cooled at the roll gap to form a casting strip 11, and the casting strip 11 is guided through the opposite row of rolls 12 below the casting rolls 9 and is coiled through the coiling device 13.
As shown in FIG. 2, the structure of the amorphous alloy prepared by the twin-roll single-side casting method has a structure that a single-side outlet 14 is arranged at the position, corresponding to one casting roll 9, of the bottom side in the distribution nozzle 8, and the alloy melt 15 in the distribution nozzle 8 flows through the single-side outlet 14 and flows out along the corresponding casting roll 9 and between the two casting rolls 9 to form an amorphous strip.
As shown in fig. 3, the structure of the amorphous alloy is prepared by the twin-roll double-side pouring method, two opposite sides of the bottom in the distribution nozzle 8 are respectively provided with a double-side outlet 16 corresponding to the casting rolls 9, the alloy melt 15 in the distribution nozzle 8 flows through the double-side outlets 16, converges at the roll gaps of the casting rolls along the corresponding casting rolls 9, and is cast and rolled into the amorphous strip.
In the specific implementation process, the iron-based amorphous alloy comprises the following components: feaCbSicBdPeCrfAlgMohNbiA, b, c, d, e, f, g and h are atomic percent, wherein a is more than or equal to 40 and less than or equal to 80; b is more than or equal to 0 and less than or equal to 20; c is more than or equal to 0 and less than or equal to 10; d is more than or equal to 0 and less than or equal to 15; e is more than or equal to 0 and less than or equal to 15; f is more than or equal to 0 and less than or equal to30, of a nitrogen-containing gas; g is more than or equal to 0 and less than or equal to 5; h is more than or equal to 0 and less than or equal to 20; i is more than or equal to 0 and less than or equal to 5. The preparation method is characterized in that the characteristics of metal double-roll casting and amorphous continuous cooling forming are combined, firstly, alloy raw materials or preliminarily prepared master alloy are smelted in a vacuum induction smelting furnace 1 to obtain an iron-based amorphous master alloy melt. And after the temperature is controlled to meet the requirement, argon is filled, a gate valve 4 between the vacuum induction melting furnace 1 and the tundish 5 is opened, and the iron-based amorphous master alloy melt is introduced into the tundish 5 with high-purity argon protection through a preheating flow passage (a flow guide pipe 3). After the flow control stopper 6 of the tundish 5 is opened, the alloy melt 15 is uniformly distributed by the distribution nozzle 8 and then injected into the roll gap of the casting roll 9, and is cooled by the water-cooled casting roll 9 to form an amorphous strip, and the amorphous strip is continuously cooled by the row roll 12 and is guided into the coiling equipment 13. The whole casting-rolling-cooling-coiling process is completed in a casting machine cavity protected by high-purity argon.
The invention will be further described with reference to the accompanying drawings and specific embodiments.
Example one
Alloy components: fe69C5Si3B5P8Cr3Al2Mo5(atomic percent at.%, the same below);
a flow distribution mode: deeply entering a roller seam for distributing;
the preparation process comprises the following steps:
a. 20kg of raw materials are prepared according to atomic percentage, put into a vacuum induction melting furnace, vacuumized to 0.05Pa, heated until the raw materials are completely melted, and continuously melted at 1500 ℃ for 10 min.
b. And (3) closing the vacuum pump, filling high-purity argon with the volume purity of 99.999 percent into the vacuum induction melting furnace to atmospheric pressure, opening the gate valve, putting down the flow guide pipe, and introducing the alloy into the tundish protected by the high-purity argon through the flow guide pipe (the preheating temperature of the flow guide pipe is 1000 ℃).
c. After the alloy is soaked in the tundish, the stopper rod is opened, and the alloy melt is uniformly distributed and flowed into the roll gap of the casting roll through the distribution nozzle (the preheating temperature of the distribution nozzle is 1200 ℃), so that the alloy is rapidly cooled and cast-rolled and formed, and the cooling speed of the alloy melt is 30000 ℃/s. The parameters are shown in table 1 below.
TABLE 1 Experimental Main parameters
Casting roll speed 0.5m/s Temperature of melting 1500℃
Width of roll gap opening 0.25mm Duration of smelting 10min
Diameter of roller 300mm Tundish temperature 1200℃
Width of casting roll 110mm Force of casting and rolling About 34KN
Water cooling of casting rolls 5℃ Width of the cast strip 25mm
The experiment yielded amorphous ribbon of 0.25 mm thickness as shown in figure 4. The XRD profile is shown in FIG. 5. As can be seen from fig. 4 to 5, the matrix structure of the cast strip is an iron-based amorphous alloy, and only a small amount of grains exist.
Example two
Alloy components: fe69C5Si3B5P8Cr3Al2Mo5
A flow distribution mode: deeply entering a roller seam for distributing;
the preparation process comprises the following steps:
a. 20kg of raw materials are prepared according to atomic percentage, put into a vacuum induction melting furnace, vacuumized to 0.03Pa, heated until the raw materials are completely melted, and continuously melted for 20min at 1500 ℃.
b. And (3) closing the vacuum pump, filling high-purity argon with the volume purity of 99.999 percent into the vacuum induction melting furnace to atmospheric pressure, opening the gate valve, putting down the flow guide pipe, and introducing the alloy into the tundish protected by the high-purity argon through the flow guide pipe (the preheating temperature of the flow guide pipe is 900 ℃).
c. After the alloy is soaked in the tundish, the stopper rod is opened, and the alloy melt is uniformly distributed and flowed into the roll gap of the casting roll through the distribution nozzle (the preheating temperature of the distribution nozzle is 1200 ℃), so that the alloy is rapidly cooled and cast-rolled and formed, and the cooling speed of the alloy melt is 40000 ℃/s. The parameters are shown in table 2 below.
TABLE 2 Experimental Main parameters
Casting roll speed 0.4m/s Temperature of melting 1400℃
Width of roll gap opening 0.3mm Duration of smelting 20min
Diameter of roller 300mm Tundish temperature 1200℃
Width of casting roll 110mm Force of casting and rolling About 50KN
Water cooling of casting rolls 5℃ Width of the cast strip 50mm
The test results in amorphous strips of 0.3mm thickness.
EXAMPLE III
Alloy components: fe69C5Si3B5P8Cr3Al2Mo5
A flow distribution mode: deeply entering a roller seam for distributing;
the preparation process comprises the following steps:
a. 20kg of raw materials are prepared according to atomic percentage, put into a vacuum induction melting furnace, vacuumized to 0.08Pa, heated until the raw materials are completely melted, and continuously melted for 20min at 1400 ℃.
b. And (3) closing the vacuum pump, filling high-purity argon with the volume purity of 99.999 percent into the vacuum induction melting furnace to atmospheric pressure, opening the gate valve, putting down the flow guide pipe, and introducing the alloy into the tundish protected by the high-purity argon through the flow guide pipe (the preheating temperature of the flow guide pipe is 950 ℃).
c. After the alloy is soaked in the tundish, the stopper rod is opened, and the alloy melt is uniformly distributed and flowed into the roll gap of the casting roll through the distribution nozzle (the preheating temperature of the distribution nozzle is 1200 ℃), so that the alloy is rapidly cooled and cast-rolled and formed, and the cooling speed of the alloy melt is 50000 ℃/s. The parameters are shown in table 3 below.
TABLE 3 Experimental Main parameters
Figure BDA0002020442370000061
Figure BDA0002020442370000071
The test results in amorphous strips of 0.35mm thickness.
The above-mentioned embodiments are only for illustrating the technical features of the present invention, and are not to be construed as limiting the scope of the present invention, which is intended to be detailed description of the present invention. It is within the scope of the present invention to cover all equivalent alternatives falling within the spirit of the invention without departing from the technical spirit of the invention.

Claims (10)

1. A method for continuously preparing an iron-based amorphous thin strip is characterized by comprising the following steps:
(1) smelting a master alloy according to set components, wherein the used master alloy comprises the following components: fe a C b Si c B d P e Cr f Al g Mo h Nb i a、b、c、d、e、 f、g、h、iIs in atomic percentage, wherein 40 is less than or equal toa≤80;0≤b≤20;0≤c≤10;0≤d≤15;0≤e≤15;0≤f≤30;0≤g≤5;0≤h≤20;0≤iLess than or equal to 5; putting alloy raw materials or a preliminarily prepared master alloy into a melting crucible to be melted completely, continuing to melt after melting, and melting for 5-30 min at a temperature higher than the melting point of the alloy by more than 200 ℃ to fully melt the alloy;
(2, guiding the alloy melt into a tundish through a preheated flow guide pipe, wherein the temperature of the tundish is 100-300 ℃ higher than the melting point of the alloy, so that the alloy is uniformly heated in the tundish, and controlling the superheat degree of the alloy to be 100-300 ℃ during casting;
(3) forming an amorphous thin strip: opening the stopper rod, uniformly distributing and flowing the alloy melt into a roll gap of the casting roll through a preheated distribution nozzle, and rapidly cooling the alloy for casting and rolling forming; in the casting and rolling process, the alloy is subjected to heat transfer and rapid cooling through a casting roller, the cooling speed is 30000-75000 ℃/s, the casting and rolling speed is controlled to be 0.05-3 m/s, the casting and rolling force is controlled to be 2-15 kN per 1cm width of casting strip, the opening width of a casting roller gap is set to be 0.1-0.35 mm, the temperature of the alloy thin strip out of the roller is regulated, and the temperature of the alloy out of the roller is controlled to be less than the crystallization temperature Tx of the alloy;
(4) the alloy cast strip is cooled again through the roller and is guided into a coiler to be coiled; in the process of preparing the cast strip, the whole casting, rolling, cooling and coiling processes are finished in a casting machine cavity protected by high-purity argon.
2. The method for continuously preparing the iron-based amorphous thin strip according to claim 1, wherein a double-roll method is used for continuously and rapidly preparing the iron-based amorphous alloy thin strip with the thickness of 0.1-0.35 mm.
3. The method for continuously preparing the iron-based amorphous thin strip according to claim 1, wherein the mother alloy melting process and the temperature equalization storage process are both performed under a high vacuum of less than 0.1Pa or a high purity argon protective atmosphere with a volume purity of more than or equal to 99.999%; the casting and rolling process is carried out under the protection of argon with the volume purity of more than or equal to 99.9 percent.
4. The method for continuously manufacturing an iron-based amorphous thin strip according to claim 1, wherein the melting is performed in a melting crucible by directly using alloy raw materials or by using a mother alloy which has been melted.
5. The method for continuously preparing the iron-based amorphous thin strip according to claim 1, wherein the solidification cooling rate is controlled to be 30000-75000 ℃/s by the casting and rolling process parameters of the size of a distribution port at the lower end of a distribution nozzle, the roll gap value of a casting roll, the casting and rolling speed, a copper casting roll, a steel casting roll and the cooling water amount of the casting roll.
6. The method for continuously preparing the iron-based amorphous thin strip according to claim 1, wherein the distribution port at the lower end of the distribution nozzle is designed to be rectangular or a row of round shape, the width of the rectangle is 0.2-1 mm, and the diameter of the round is 0.5-2 mm; the flow distribution mode is divided into three types: direct injection roll seam method, single side casting and coating method or double side casting and coating method; the material of the flow distribution port is SiO which is not easy to react with the alloy melt2Or BN.
7. The method for continuously preparing the iron-based amorphous thin strip according to claim 1, wherein the preheating temperature of the distribution nozzle is in a range of 1000 to 1400 ℃ and the preheating temperature of the flow guide tube is in a range of 900 to 1000 ℃.
8. The method for continuously manufacturing an iron-based amorphous thin strip according to claim 1, wherein the height of the alloy melt pool on the upper part of the casting roll is controlled to be stable by controlling the alloy flow during the stable casting of the thin strip, and the width of the surface of the alloy melt pool along the radial direction of the casting roll is controlled to be within 10 mm.
9. The method for continuously preparing the iron-based amorphous thin strip as claimed in claim 1, wherein the casting roll is made of copper or steel alloy with good heat conductivity, the diameter of the casting roll is 220 mm-510 mm, and the roughness Ra of the surface of the casting roll is less than or equal to 10 μm.
10. The method for continuously preparing the iron-based amorphous thin strip according to claim 1, wherein the water inlet temperature of the cooling water of the casting roller is controlled to be 5-12 ℃, the water outlet temperature is controlled to be 5-15 ℃, and the water flow rate is controlled to ensure that the water temperature rise interval is less than 3 ℃.
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