CN109865808B - Horizontal continuous casting method for wide amorphous thin strip with thickness of 200-1500 mu m - Google Patents
Horizontal continuous casting method for wide amorphous thin strip with thickness of 200-1500 mu m Download PDFInfo
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Abstract
The invention belongs to the field of amorphous alloy preparation, and particularly relates to a method for horizontally continuously casting a wide amorphous thin strip with the thickness of 200-1500 mu m by using a double-roller method. 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 200-1500 mu m after a thin belt continuous casting process; (3) smelting, forming and coiling are carried out under the condition of inert atmosphere. The amorphous forming process has short flow, high cooling speed and continuous preparation process, and the method can be used for efficiently and continuously preparing the amorphous thin strip and promoting the application of the amorphous alloy.
Description
Technical Field
The invention belongs to the field of amorphous alloy preparation, and particularly relates to a method for horizontally continuously casting a wide amorphous thin strip with the thickness of 200-1500 mu m 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.
The preparation of early amorphous alloys required very high cooling rates (> 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
Aiming at the problems that the requirements of amorphous alloy preparation on the purity and the vacuum degree of raw materials are high and the mass production of amorphous alloy plate strips is not seen, the invention aims to provide a method for horizontally continuously casting a wide amorphous thin strip with the thickness of 200-1500 mu m by using a double-roller method, the amorphous forming process is short in flow, the cooling speed is high, the preparation process is continuous, and the method can be used for efficiently and continuously preparing the amorphous thin strips and promoting the application of the amorphous alloy.
The technical scheme of the invention is as follows:
a method for horizontally continuously casting a wide amorphous thin strip with the thickness of 200-1500 mu m comprises the following steps:
(1) alloy discharging enters a crucible, a preheating guide pipe and a position control device thereof are cleaned, the inner part of the preheating guide pipe is a quartz lining and is attached with a heating system, the heating temperature is 100-200 ℃ above the solidification temperature of the target alloy, and cooling water is introduced to the outer part of the preheating guide pipe for protection;
(2) smelting a master alloy according to set components, wherein the master alloy comprises the following components: melting metals in a zirconium-based, copper-based, iron-based or nickel-based amorphous alloy component system, uniformly mixing for 5-30 minutes, and controlling the temperature;
(3) controlling the superheat degree of an alloy melt to be 50-300 ℃, protecting by adopting high-purity argon with volume purity of more than 99.999% in the temperature control process, and controlling the argon in a smelting cavity to be micro-positive pressure, namely, the pressure is not lower than 0.11 MPa;
(4) in the smelting process, the preparation work of the forming cavity is completed, and the method comprises the following steps: a) all valve bodies of the cavity of the forming cavity are closed, argon is filled after vacuum pumping, the volume purity is more than 99.99 percent, and the micro positive pressure not lower than 0.11MPa is kept; b) preheating a current distributor, distributing current at one side of the current distributor by using a slit type current distribution port, and heating the current distributor after the current distributor is installed at a fixed position, wherein the heating temperature is 100-200 ℃ above the solidification temperature of a target alloy; c) the temperature of the cooling circulating water of the casting roller is 3-5 ℃, and the total water flow is 70-90 m3H; d) preparing a gas cooling system after casting, wherein the argon pressure is 0.6-0.8 MPa, and the gas temperature is controlled to be 4-6 ℃;
(5) alloy smelting, preheating of a preheating guide pipe and a flow distributor, and argon filling of a forming cavity, preparing an amorphous thin strip by adopting a horizontal thin strip casting and rolling process, and performing a thin strip continuous casting process: opening a gate valve of the smelting cavity, descending the preheating guide pipe and corresponding to the current distributor, and pouring alloy into the preheating guide pipe by the medium-frequency induction smelting furnace body; the flow distributor is made of transparent quartz, the height of a melt inside the flow distributor is controlled to be 60-160 mm through the monitoring of an infrared monitoring camera and the tipping speed of the medium-frequency induction smelting furnace, the alloy melt horizontally flows through a flow distribution port on one side of the flow distributor by controlling the liquid level of the alloy melt in the flow distributor, and the alloy melt is uniformly distributed and flowed into a roll gap of the casting roll; the casting rollers are arranged in a reducing way by adopting upper rollers and lower rollers, the diameter of the lower rollers is larger, the diameter of the lower rollers is 450-800 mm, the diameter ratio of the upper rollers to the lower rollers is 1: 1.5-1: 2, and the roughness Ra of the roller surface is less than or equal to 5 mu m; setting the thickness of a roll gap to be 200-1500 mu m, cooling the alloy melt to be 500-75000 ℃, and cooling, casting and rolling the alloy to be formed; guiding the formed amorphous thin belt out through a guide roller, further cooling the amorphous thin belt in a cast gas cooling system, and adopting low-temperature argon for blowing and cooling, wherein the gas cooling speed is 50-800 ℃/s;
(6) after the gas is cooled, the thickness range of the amorphous thin strip reaches 200-1500 mu m, and the width range is 110-550 mm; the casting strip with the thickness of 200-800 μm is wound to form a strip coil, and the casting strip with the thickness of more than 800 μm is directly collected in a thin strip form without being wound.
According to the method for horizontally continuously casting the wide amorphous thin strip with the thickness of 200-1500 mu m, in the casting and rolling process, the alloy is rapidly cooled through heat transfer of a casting roller, the temperature of the alloy thin strip out of the roller is regulated and controlled by controlling the casting and rolling speed, the casting and rolling force and the roll gap, and the temperature of the alloy out of the roller is controlled to be close to or less than the crystallization temperature Tx of the alloy; the casting and rolling speed is 0.20-1.8 m/s, the casting and rolling force is controlled to be 2-15 kN per 1cm width of casting strip, the width of a roll gap opening of a casting roll is set to be 200-1500 mu m, and no side sealing plate is arranged.
According to the method for horizontally continuously casting the wide amorphous thin strip with the thickness of 200-1500 mu m, the solidification cooling speed is controlled to reach 500-75000 ℃/s through the casting and rolling process parameters of the size of a flow distribution port on one side of a flow distributor, 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.
According to the method for horizontally continuously casting the wide amorphous thin strip with the thickness of 200-1500 mu m, yttrium element with the mass percentage of 0.0045-0.020 is added into a zirconium-based, copper-based, iron-based or nickel-based amorphous alloy and is used for removing O, N pollution brought by the environment.
According to the method for horizontally continuously casting the wide amorphous thin belt with the thickness of 200-1500 mu m, a flow distribution port on one side of a quartz flow distributor is adopted for flow distribution, and the opening width of the flow distribution port is designed according to the thickness of different products; the flow distributor is preheated on line, the preheating temperature is 100-200 ℃ above the alloy solidification temperature, the end part of the flow distribution port conducts heat through the tungsten alloy sheet, and the temperature of the end part of the flow distribution port reaches the vicinity of the alloy solidification temperature.
According to the method for horizontally continuously casting the wide amorphous thin strip with the thickness of 200-1500 mu m, the lining of the preheating guide pipe is made of quartz glass which can be quickly replaced, the preheating temperature is 100-200 ℃ above the solidification temperature of the alloy, and cooling water is introduced to the outside of the preheating guide pipe for protection.
According to the method for horizontally continuously casting the wide amorphous thin strip with the thickness of 200-1500 mu m, an infrared monitoring camera is arranged on the side surface of a current distributor and is fed back to a tipping control system to achieve the purpose of controlling the current distribution; wherein, the liquid level in the flow distributor is higher than the Kiss line height control range of the casting roll gap and is 60-160 mm.
The method for horizontally continuous casting the wide amorphous thin strip with the thickness of 200-1500 mu m comprises the step of vacuum design of a smelting cavity and a forming cavity, wherein the working vacuum degree of the smelting cavity reaches 1 × 10-2The vacuum degree of the forming cavity reaches below 1 Pa; and in the pouring state, the environment is in an argon protection state, the smelting cavity and the forming cavity are separated by a gate valve, and the gate valve is opened after the argon is filled before the casting and rolling are started.
According to the method for horizontally continuously casting the wide amorphous thin strip with the thickness of 200-1500 mu m, an intermediate frequency induction smelting furnace and a high-purity graphite crucible are adopted for smelting amorphous alloy, the heating temperature is not more than 400 ℃ above the melting temperature of metal, and oxidation and burning loss of metal elements are prevented.
According to the method for horizontally continuously casting the wide amorphous thin strip with the thickness of 200-1500 mu m, not more than 20wt% of cast strip trimming waste is added into an amorphous master alloy incoming material.
The invention has the advantages and beneficial effects that:
1. 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, a deep roll gap casting method is adopted, and the alloy molten pool is narrow, the cooling speed is high, and the deformation is small. The principle, structure and method are not reported in public. The invention carries out sufficient technical practice and realizes the continuous casting and rolling process of the amorphous strip with the length of more than 12m and the thickness of 200-1500 mu m.
2. The method adopts a horizontal thin strip casting and rolling process to prepare the amorphous thin strip, wherein the thickness range of the amorphous strip reaches 200-1500 mu m, and the width range of the amorphous strip is 110-550 mm. The invention can control the solidification cooling speed to reach 500-75000 ℃/s through casting and rolling technological parameters such as the slit width of the flow distributor, the roll gap value of the casting roll, the casting speed, the copper casting roll, the steel casting roll, the cooling water quantity of the casting roll and the like. The invention designs a method for continuously forming a thin strip of amorphous metal with a series forming limit cooling rate of 500-75000 ℃/s, and provides a base material for the subsequent processing procedures.
3. The invention adopts a flow distribution port on one side of the quartz slit type flow distributor to distribute flow, and the opening degree of the slit is designed to be 0.15-0.8 mm according to the thickness of different products. The flow distributor can be preheated on line at a working position, the preheating temperature is 100-200 ℃ above the alloy solidification temperature, the end part of the flow distribution opening on one side of the flow distributor conducts heat through a tungsten alloy sheet, and the temperature of the end part of the flow distribution opening reaches the temperature close to the alloy solidification temperature.
4. According to the invention, the infrared monitoring camera is arranged on the side surface of the current distributor and feeds back to the tipping control system to achieve the purpose of controlling the current distribution. Wherein the liquid level of the flow distributor is higher than the Kiss line of the roll gap of the casting roll (the Kiss line refers to the line closest to the double working rolls), and the height control range is 60-160 mm. The casting and rolling system adopts a flow-casting speed matching strategy to control the alloy melt to flow freely along the transverse direction of a roll gap, and a side sealing plate in the casting and rolling process is eliminated.
5. The casting rolls are arranged in different diameters, the diameter of the lower roll is larger, the diameter of the lower roll is 450-800 mm, and the ratio of the diameter of the upper roll to the diameter of the lower roll is 1: 1.5-1: 2. The invention adopts a flow guide design with preheating, the lining of the preheating flow guide pipe is made of quartz glass which can be quickly replaced, the preheating temperature is 100-200 ℃ above the alloy solidification temperature, and the preheating flow guide pipe can be protected by introducing cooling water to the outside.
6. The melting cavity and the forming cavity are designed in a graded vacuum mode, wherein the working vacuum degree of the melting cavity reaches 1 × 10-2And when the vacuum degree of the forming cavity is less than 1Pa, rapidly filling argon. And in the pouring state, the environment is in an argon protection state, the smelting cavity and the forming cavity are separated by a gate valve, and the gate valve is opened after the argon is filled before the casting and rolling are started.
7. The roll gap opening degree of the casting roll is set to be 200-1500 mu m, and the roll speed is designed to be 0.20-1.8 m/s. And the gas cooling system after casting is subjected to purging cooling by adopting low-temperature argon, and the cooling speed is 50-800 ℃/s. And controlling the superheat degree of the metal liquid to be 50-300 ℃ in the casting and rolling process. The amorphous alloy is smelted by adopting a medium-frequency induction smelting furnace and a high-purity graphite (the carbon content is more than or equal to 99.99 wt%) crucible, the heating temperature is not more than 400 ℃ above the melting temperature of the metal, and oxidation and burning loss of metal elements are prevented. In addition, no more than 20% of cast strip scrap can be added to the amorphous master alloy feed.
Drawings
FIG. 1 is a schematic structural diagram of a casting and rolling apparatus for horizontally and continuously producing a wide amorphous ribbon according to the present invention. In the figure, 1 a medium frequency induction melting furnace; 2, a high vacuum smelting cavity; 3, the guide pipe can be preheated; 4, a gate valve; 5, a flow distributor and an infrared camera monitoring device; 51 a flow distributor; 52 infrared monitoring camera; 6 forming a cavity; 7, rolling; 8, rolling the roller; 9, a post-casting gas cooling system; 10, a coiling device; 11 a tip-over control system; 12 flow distribution ports.
FIG. 2 is a schematic illustration of a 0.55 mm thick amorphous ribbon.
FIG. 3 shows a microstructure photograph (a) and an XRD graph (b) of a 0.55 mm thick amorphous strip. In the figure, the abscissa 2 θ represents the diffraction angle (drge) and the ordinate intensity represents the relative intensity (a.u.).
FIG. 4 shows a microstructure photograph (a) and an XRD graph (b) of a 0.6mm thick amorphous strip. In the figure, the abscissa 2 θ represents the diffraction angle (drge) and the ordinate intensity represents the relative intensity (a.u.).
FIG. 5 shows a microstructure photograph (a) and an XRD graph (b) of a 0.25 mm thick amorphous strip. 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 horizontally and continuously preparing the wide amorphous thin strip mainly comprises: intermediate frequency induction melting furnace 1, high vacuum melting chamber 2 (chamber pressure < 0.1Pa), honeycomb duct 3, slide valve 4, water distributor and infrared camera monitoring device 5, forming chamber 6, go up roller 7, lower roll 8, the gas cooling system 9 after casting, coiling equipment 10, control system 11 of tumbling etc. can preheat, and concrete 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 a gate valve 4; a medium frequency induction smelting furnace 1, a preheating guide pipe 3 and a tipping control system 11 are arranged in the high vacuum smelting chamber 2, the preheating guide pipe 3 is positioned at one side of the medium frequency induction smelting furnace 1, the preheating guide pipe 3 is vertically arranged, and the lower end port of the preheating guide pipe corresponds to the top opening of a flow distributor 51 at the upper part in the forming chamber 6; the intermediate frequency induction smelting furnace 1 is installed on the tilting control system 11, and the intermediate frequency induction smelting furnace 1 rotates around the tilting control system 11 through a rotating shaft, so that the upper opening of the intermediate frequency induction smelting furnace 1 corresponds to the upper opening of the preheating guide pipe 3.
The current distributor and infrared camera monitoring device 5 comprises a current distributor 51 and an infrared monitoring camera 52, the side surface of the current distributor 51 is provided with the infrared monitoring camera 52, and the purpose of controlling the current distribution is achieved by feeding back to the tipping control system 11 through the infrared monitoring camera 52. When the amorphous master alloy melt is obtained by smelting in the medium-frequency induction smelting furnace 1, the amorphous master alloy melt is poured into the preheating guide pipe 3, the preheating guide pipe 3 moves downwards to penetrate through the bottom opening of the medium-frequency induction smelting furnace 1 and the gate valve 4, and the amorphous master alloy melt enters the flow distributor 51 through the preheating guide pipe 3.
One side of the flow distributor 51 corresponds to a roll gap on one side between two casting rolls (an upper roll 7 and a lower roll 8) through a flow distribution port 12, so that alloy melt in the guide pipe 3 can be preheated and uniformly distributed to the roll gap between the upper casting roll and the lower casting roll through the flow distributor 51, the alloy melt continuously passes through a cast gas cooling system 9 on the other side between the upper casting roll and the lower casting roll to form a casting strip, and the casting strip is coiled through a coiling device 10.
In the specific implementation process, the method for horizontally continuously casting the wide amorphous thin strip comprises the following steps: (1) smelting amorphous alloy according to set components, wherein the components comprise zirconium-based, copper-based, iron-based titanium-based and the like, and amorphous metal with the ultimate cooling rate of 500-75000 ℃/s is formed to design 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 200-1500 mu m after a thin belt continuous casting process; (3) smelting, forming and coiling are carried out under the condition of inert atmosphere. The amorphous forming process has short flow, high cooling speed and continuous preparation process, and the method can be used for efficiently and continuously preparing the amorphous thin strip and promoting the application of the amorphous alloy.
The invention will be further described with reference to the accompanying drawings and specific embodiments.
Example one
Alloy components: (Zr)53.5Hf1.5Cu30Al10Ni5)99.9O0.1(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. 50kg of raw materials are prepared according to the atomic percentage, put into an intermediate frequency induction melting furnace and vacuumized to 7 × 10-2Pa, heating the alloy raw materials until the alloy raw materials are completely melted, and continuously smelting at 1500 ℃ for 10 min.
b. In the smelting process, the preparation work of the forming cavity is completed, and the method comprises the following steps: 1) all valve bodies of the cavity of the forming cavity are closed, argon is filled after vacuum pumping, the volume purity is more than 99.99 percent, and the micro positive pressure of 0.12MPa is kept; 2) preheating a flow distributor, distributing flow at one side of the flow distributor by adopting a slit type flow distribution port, and heating after the flow distributor is installed into a fixed position;3) the temperature of the cooling circulating water of the casting roller is 5 ℃, and the total water flow is 80m3H; 4) preparing a gas cooling system after casting, wherein the argon pressure is 0.7MPa, and the gas temperature is controlled to be 5 ℃; 5) the nip opening width was set to 550 μm.
c. And (3) closing the vacuum pump, filling high-purity argon with the volume purity of 99.999 percent into the medium-frequency induction smelting furnace to the micro-positive pressure of 0.12MPa, opening the gate valve, putting down the preheating guide pipe, and introducing the alloy melt into the high-purity argon-protected flow distributor through the preheating guide pipe (the preheating temperature of the guide pipe is 1150 ℃).
d. Alloy liquid flows to a roll gap of a casting roll through uniform distribution of a distribution device, the distribution device is made of transparent quartz, the alloy liquid flows horizontally through a distribution port on one side of the distribution device by controlling the liquid level of alloy melt in the distribution device and the uniform distribution to the roll gap of the casting roll through monitoring by an infrared monitoring camera, the tilting speed of a medium-frequency induction smelting furnace controls the height of the melt in the distribution device to be 100mm, and the alloy melt is cooled to about 400 ℃ at a cooling speed of 10000 ℃/s. And guiding the formed amorphous thin belt out through a guide roll, further cooling the amorphous thin belt in a cast gas cooling system, and purging and cooling by adopting low-temperature argon at the cooling speed of the gas cooling system of 100 ℃/s.
The parameters are shown in table 1 below.
TABLE 1 Experimental Main parameters
The experiment yielded amorphous ribbon of 0.55 mm thickness as shown in figure 2. The microstructure photograph and XRD curve are shown in FIG. 3. As can be seen from fig. 2-3, the cast strip is an amorphous alloy.
Example two
Alloy components: (Zr)53.5Hf1.5Cu30Al10Ni5)99.9O0.1；
A flow distribution mode: deeply entering a roller seam for distributing;
the preparation process comprises the following steps:
a. in atomic percent50kg of raw materials are added into an intermediate frequency induction melting furnace and are vacuumized to 6 × 10-2Pa, heating the alloy raw materials until the alloy raw materials are completely melted, and continuously smelting at 1400 ℃ for 20 min.
b. In the smelting process, the preparation work of the forming cavity is completed, and the method comprises the following steps: 1) all valve bodies of the cavity of the forming cavity are closed, argon is filled after vacuum pumping, the volume purity is more than 99.99 percent, and the micro positive pressure of 0.12MPa is kept; 2) preheating a flow distributor, distributing flow at one side of the flow distributor by adopting a slit type flow distribution port, and heating after the flow distributor is installed into a fixed position; 3) the temperature of the cooling circulating water of the casting roller is 5 ℃, and the total water flow is 70m3H; 4) preparing a gas cooling system after casting, wherein the argon pressure is 0.6MPa, and the gas temperature is controlled to be 4 ℃; 5) the nip opening width was set to 600 μm.
c. And (3) closing the vacuum pump, filling high-purity argon with the volume purity of 99.999 percent into the medium-frequency induction smelting furnace to the micro-positive pressure of 0.12MPa, opening the gate valve, putting down the preheating guide pipe, and introducing the alloy melt into the high-purity argon-protected flow distributor through the preheating guide pipe (the preheating temperature of the guide pipe is 1150 ℃).
d. Alloy liquid flows to a roll gap of a casting roll through uniform distribution of a distributor, the distributor is made of transparent quartz, the alloy liquid flows horizontally through a distribution port on one side of the distributor by controlling the liquid level of alloy melt in the distributor and the uniform distribution of the alloy liquid flows to the roll gap of the casting roll through monitoring of an infrared monitoring camera, the height of the melt in the distributor is controlled to be 80mm through the tilting speed of a medium-frequency induction smelting furnace, so that the alloy is rapidly cooled and cast-rolled to be formed, and the cooling speed of the alloy melt is 6000 ℃/s and is cooled to about 400 ℃. And guiding the formed amorphous thin belt out through a guide roll, further cooling the amorphous thin belt in a cast gas cooling system, and purging and cooling by adopting low-temperature argon at the cooling speed of 80 ℃/s of the gas cooling system.
The parameters are shown in table 2 below.
TABLE 2 Experimental Main parameters
The test results in amorphous strips of 0.6mm thickness. The microstructure photograph and XRD curve are shown in FIG. 4. As can be seen from fig. 4, the cast strip has no crystalline structure and is an amorphous alloy.
EXAMPLE III
Alloy components: (Zr)53.5Hf1.5Cu30Al10Ni5)99.9O0.1；
A flow distribution mode: deeply entering a roller seam for distributing;
the preparation process comprises the following steps:
a. 50kg of raw materials are prepared according to the atomic percentage, put into an intermediate frequency induction melting furnace and vacuumized to 6 × 10-2Pa, heating the alloy raw materials until the alloy raw materials are completely melted, and continuously smelting at 1500 ℃ for 10 min.
b. In the smelting process, the preparation work of the forming cavity is completed, and the method comprises the following steps: 1) all valve bodies of the cavity of the forming cavity are closed, argon is filled after vacuum pumping, the volume purity is more than 99.99 percent, and the micro positive pressure of 0.16MPa is kept; 2) preheating a flow distributor, distributing flow at one side of the flow distributor by adopting a slit type flow distribution port, and heating after the flow distributor is installed into a fixed position; 3) the temperature of the cooling circulating water of the casting roller is 5 ℃, and the total water flow is 90m3H; 4) preparing a gas cooling system after casting, wherein the argon pressure is 0.8MPa, and the gas temperature is controlled to be 6 ℃; 5) the nip opening width was set to 300 μm.
c. And (3) closing the vacuum pump, filling high-purity argon with volume purity of 99.999 percent into the medium-frequency induction smelting furnace to a micro positive pressure of 0.11MPa, opening the gate valve, putting down the preheating guide pipe, and introducing the alloy melt into the high-purity argon-protected flow distributor through the preheating guide pipe (the preheating temperature of the guide pipe is 1150 ℃).
d. Alloy liquid flows to a roll gap of a casting roll through uniform distribution of a distributor, the distributor is made of transparent quartz, the alloy liquid flows horizontally through a distribution port on one side of the distributor by controlling the liquid level of alloy melt in the distributor and the uniform distribution of the alloy liquid flows to the roll gap of the casting roll through monitoring of an infrared monitoring camera, the height of the melt in the distributor is controlled to be 120mm through the tilting speed of a medium-frequency induction smelting furnace, so that the alloy is rapidly cooled and cast-rolled to be formed, and the cooling speed of the alloy melt is 8000 ℃/s and is cooled to about 400 ℃. And guiding the formed amorphous thin belt out through a guide roll, further cooling the amorphous thin belt in a cast gas cooling system, and purging and cooling by adopting low-temperature argon at the cooling speed of 60 ℃/s.
The parameters are shown in table 3 below.
TABLE 3 Experimental Main parameters
The test yielded amorphous ribbon of 0.25 mm thickness. The microstructure photograph and XRD curve are shown in FIG. 5. As can be seen in fig. 5, the cast ribbon matrix is amorphous with only a very small crystal structure.
Example four
Alloy components: (Cu)60Zr20Hf10Ti10)99.9O0.1；
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 the atomic percentage, put into an intermediate frequency induction melting furnace and vacuumized to 1 × 10-1Pa, heating the alloy raw materials until the alloy raw materials are completely melted, and continuously smelting at 1500 ℃ for 20 min.
b. In the smelting process, the preparation work of the forming cavity is completed, and the method comprises the following steps: 1) all valve bodies of the cavity of the forming cavity are closed, argon is filled after vacuum pumping, the volume purity is more than 99.99 percent, and the micro positive pressure of 0.20MPa is kept; 2) preheating a flow distributor, distributing flow at one side of the flow distributor by adopting a slit type flow distribution port, and heating after the flow distributor is installed into a fixed position; 3) the temperature of the cooling circulating water of the casting roller is 5 ℃, and the total water flow is 80m3H; 4) a post-casting gas cooling system was prepared, argon pressure 0.7MPa, gas temperature 5 ℃ 5) was controlled, and the opening width of the roll gap was set to 500 μm.
c. And (3) closing the vacuum pump, filling high-purity argon with the volume purity of 99.999 percent into the medium-frequency induction smelting furnace to the micro-positive pressure of 0.13MPa, opening the gate valve, putting down the preheating guide pipe, and introducing the alloy melt into the high-purity argon-protected flow distributor through the preheating guide pipe (the preheating temperature of the guide pipe is 1150 ℃).
d. Alloy liquid flows to a roll gap of a casting roll through uniform distribution of a distributor, the distributor is made of transparent quartz, the alloy liquid flows horizontally through a distribution port on one side of the distributor by controlling the liquid level of alloy melt in the distributor through monitoring of an infrared monitoring camera, the alloy liquid flows to the roll gap of the casting roll through uniform distribution by controlling the tilting speed of a medium-frequency induction smelting furnace, so that the alloy is rapidly cooled and cast-rolled to be formed, and the cooling speed of the alloy melt is 5000 ℃/s and is cooled to about 400 ℃. And guiding the formed amorphous thin belt out through a guide roll, further cooling the amorphous thin belt in a cast gas cooling system, and purging and cooling by adopting low-temperature argon at the cooling speed of the gas cooling system of 50 ℃/s.
The parameters are shown in table 4 below.
TABLE 4 Experimental Main parameters
The test yielded amorphous ribbon of 0.5 mm thickness.
EXAMPLE five
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 the atomic percentage, put into an intermediate frequency induction melting furnace and vacuumized to 8 × 10-2Pa, heating the alloy raw materials until the alloy raw materials are completely melted, and continuously smelting at 1500 ℃ for 10 min.
b. In the smelting process, the preparation work of the forming cavity is completed, and the method comprises the following steps: 1) all valve bodies of the cavity of the forming cavity are closed, argon is filled after vacuum pumping, the volume purity is more than 99.99 percent, and the micro positive pressure of 0.18MPa is kept; 2) preheating a flow distributor, distributing flow at one side of the flow distributor by adopting a slit type flow distribution port, and heating after the flow distributor is installed into a fixed position; 3) the temperature of the cooling circulating water of the casting roller is 5 ℃, and the total water flow is 90m3H; 4) gas after preparation for castingA cooling system, wherein the argon pressure is 0.8MPa, and the gas temperature is controlled to be 6 ℃; 5) the nip opening width was set to 250 μm.
c. And (3) closing the vacuum pump, filling high-purity argon with volume purity of 99.999 percent into the medium-frequency induction smelting furnace to a micro positive pressure of 0.11MPa, opening the gate valve, putting down the preheating guide pipe, and introducing the alloy melt into the high-purity argon-protected flow distributor through the preheating guide pipe (the preheating temperature of the guide pipe is 1150 ℃).
d. Alloy liquid flows to a roll gap of a casting roll through uniform distribution of a distribution device, the distribution device is made of transparent quartz, the alloy liquid flows horizontally through a distribution port on one side of the distribution device by controlling the liquid level of alloy melt in the distribution device and the uniform distribution to the roll gap of the casting roll through monitoring by an infrared monitoring camera, the tilting speed of a medium-frequency induction smelting furnace controls the height of the melt in the distribution device to be 160mm, and the alloy melt is cooled to about 400 ℃ at a cooling speed of 7000 ℃/s. And guiding the formed amorphous thin belt out through a guide roll, further cooling the amorphous thin belt in a cast gas cooling system, and purging and cooling by adopting low-temperature argon at the cooling speed of 80 ℃/s of the gas cooling system.
The parameters are shown in table 5 below.
TABLE 5 Experimental Main parameters
The test yielded amorphous ribbon of 0.25 mm 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 horizontal continuous casting method of a wide amorphous thin strip with the thickness of 200-1500 mu m is characterized by comprising the following steps:
(1) feeding the amorphous master alloy into a crucible, cleaning a preheating guide pipe and a position control device thereof, wherein the preheating guide pipe is internally provided with a quartz lining and is attached with a heating system, the heating temperature is 100-200 ℃ above the solidification temperature of the amorphous master alloy, and cooling water is introduced to the outside of the preheating guide pipe for protection;
(2) the amorphous master alloy is smelted according to set components and comprises the following components: melting an amorphous master alloy, uniformly mixing for 5-30 minutes, and controlling the temperature;
(3) controlling the superheat degree of an alloy melt to be 50-300 ℃, protecting by adopting high-purity argon with volume purity of more than 99.999% in the temperature control process, and controlling the argon in a smelting cavity to be micro-positive pressure, namely, the pressure is not lower than 0.11 MPa;
(4) in the smelting process, the preparation work of the forming cavity is completed, and the method comprises the following steps: a) all valve bodies of the forming cavity are closed, argon is filled after vacuum pumping, the volume purity is more than 99.99 percent, and the micro positive pressure not lower than 0.11MPa is kept; b) preheating a flow distributor, distributing flow at one side of the flow distributor by adopting a slit type flow distribution port, and heating after the flow distributor is installed and enters a fixed position, wherein the heating temperature is 100-200 ℃ above the solidification temperature of the amorphous master alloy; c) the temperature of the cooling circulating water of the casting roller is 3-5 ℃, and the total water flow is 70-90 m3H; d) preparing a gas cooling system after casting, wherein the argon pressure is 0.6-0.8 MPa, and the gas temperature is controlled to be 4-6 ℃;
(5) after the amorphous master alloy is smelted, the preheating guide pipe and the flow distributor are preheated, and the argon is filled into the forming cavity, the horizontal thin strip casting and rolling process is adopted to prepare the amorphous thin strip, and the thin strip continuous casting process is carried out: opening a gate valve of the smelting cavity, descending the preheating guide pipe and corresponding to the flow distributor, and pouring the alloy melt into the preheating guide pipe by the medium-frequency induction smelting furnace; the flow distributor is made of transparent quartz, the height of alloy melt in the flow distributor is controlled to be 60-160 mm through the monitoring of an infrared monitoring camera and the tipping speed of a medium-frequency induction smelting furnace, the alloy melt flows horizontally through a flow distribution port on one side of the flow distributor by controlling the liquid level of the alloy melt in the flow distributor, and the alloy melt is uniformly distributed and flowed into a roll gap of the casting roll; the casting rollers are arranged in a reducing way by adopting upper rollers and lower rollers, the diameter of the lower rollers is larger, the diameter of the lower rollers is 450-800 mm, the diameter ratio of the upper rollers to the lower rollers is 1: 1.5-1: 2, and the roughness Ra of the roller surface is less than or equal to 5 mu m; setting the roll gap of the casting roll to be 200-1500 mu m, cooling the alloy melt at a speed of 500-75000 ℃/s, and cooling, casting and rolling the alloy melt to form; guiding the formed amorphous thin belt out through a guide roller, further cooling the amorphous thin belt in a cast gas cooling system, and adopting low-temperature argon for blowing and cooling, wherein the gas cooling speed is 50-800 ℃/s;
(6) after the gas is cooled, the thickness range of the amorphous thin strip reaches 200-1500 mu m, and the width range is 110-550 mm; and coiling the 200-800 mu m thick amorphous thin strip, and directly collecting the amorphous thin strip with the thickness of more than 800 mu m in an amorphous thin strip form without coiling.
2. The method for horizontally and continuously casting the wide amorphous thin strip with the thickness of 200-1500 microns according to claim 1, wherein in the casting and rolling process, an alloy melt is rapidly cooled through heat transfer of a casting roller, the temperature of an amorphous thin strip outlet roller is regulated and controlled by controlling the casting and rolling speed, the casting and rolling force and the roll gap of the casting roller, and the temperature of the amorphous thin strip outlet roller is controlled to be lower than the crystallization temperature Tx of an amorphous master alloy; the casting and rolling speed is 0.20-1.8 m/s, the casting and rolling force is controlled to be 2-15 kN per 1cm width of the amorphous thin strip, and a side sealing plate is not arranged in the casting and rolling process.
3. The method of claim 1, wherein the solidification cooling rate is controlled to 500-75000 ℃/s by the casting process parameters of the flow distribution port size on one side of the flow distributor, the set thickness of the roll gap of the casting rolls, the casting speed, the amount of cooling water of the copper casting rolls, the steel casting rolls and the casting rolls.
4. The method for horizontally and continuously casting the wide amorphous ribbon with the thickness of 200-1500 μm as claimed in claim 1, wherein yttrium element with the mass percent of 0.0045-0.020 is added into zirconium-based, copper-based, iron-based or nickel-based amorphous alloy for removing O, N pollution brought by the environment.
5. The method for horizontally continuously casting the wide amorphous thin belt with the thickness of 200 to 1500 μm as claimed in claim 1, wherein a flow distribution port on one side of a quartz material flow distributor is adopted for flow distribution, and the opening width of the flow distribution port is designed according to different product thicknesses; the flow distributor is preheated on line, the preheating temperature is 100-200 ℃ above the solidification temperature of the amorphous master alloy, the end part of the flow distribution port conducts heat through the tungsten alloy sheet, and the temperature of the end part of the flow distribution port reaches the temperature close to the solidification temperature of the amorphous master alloy.
6. The method for horizontally and continuously casting the wide amorphous thin ribbon with the thickness of 200 to 1500 μm as claimed in claim 1, wherein the lining of the preheating draft tube is made of quartz glass which can be rapidly replaced, the preheating temperature is 100 to 200 ℃ above the solidification temperature of the amorphous master alloy, and the outside of the preheating draft tube is protected by cooling water.
7. The method for horizontally continuously casting the wide amorphous thin strip with the thickness of 200-1500 microns according to claim 1, wherein an infrared monitoring camera is arranged on the side surface of a current distributor and feeds back to a tipping control system to achieve the purpose of current distribution control; wherein the liquid level in the flow distributor is higher than a Kiss line of a roll gap of the casting roll.
8. The method for horizontally continuously casting the wide amorphous thin strip with the thickness of 200-1500 mu m according to claim 1, wherein a smelting cavity and a forming cavity are designed in a graded vacuum mode, wherein the working vacuum degree of the smelting cavity reaches 1 × 10-2The vacuum degree of the forming cavity reaches below 1 Pa; and in the pouring state, the environment is in an argon protection state, the smelting cavity and the forming cavity are separated by a gate valve, and the gate valve is opened after the argon is filled before the casting and rolling are started.
9. The method for horizontally continuously casting the wide amorphous thin strip with the thickness of 200-1500 microns according to claim 1, characterized in that an intermediate frequency induction smelting furnace and a high-purity graphite crucible are adopted for smelting amorphous master alloy, the heating temperature is not more than 400 ℃ above the melting temperature of metal, and oxidation and burning loss of metal elements are prevented.
10. The method for horizontally and continuously casting the wide amorphous thin strip with the thickness of 200-1500 μm according to claim 1, wherein the amorphous master alloy incoming material is added with the amorphous thin strip trimming scrap with the thickness not exceeding 20 wt%.
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