A method of manufacturing an amorphous ribbon

Abstract

The application discloses a preparation method of amorphous strip, and belongs to the field of rapid solidification technology, and solves the problem of low yield of the amorphous strip prepared by using the existing method. The method comprises the following steps: step 1, the master alloy is loaded into the smelting crucible of a smelting device, the vacuum quick-quenching equipment is vacuumized, and then inert gas is filled into the vacuum quick-quenching equipment; step 2, the smelting device is started to melt the master alloy until the master alloy is completely melted; step 3, the melted master alloy is transferred to a tundish and is placed; step 4, the rotating cooling roller is started, the tundish is pressurized to spray the strip, and the tundish and the quick-quenching vacuum chamber maintain a pressure difference; step 5, the spraying condition is observed, the roller speed is adjusted according to the strip condition, and the vacuum quick-quenching process is ended.

Description

Technical Field

[0001] This invention relates to the field of rapid solidification technology, and in particular to a rotating cooling roller, a vacuum rapid quenching device, and a method for preparing amorphous ribbon. Background Technology

[0002] Vacuum rapid quenching technology (vacuum single-roller spinning) is the main technique for mass production of amorphous alloy foils (10-50 μm thick). Due to the special state of vacuum, the alloy melt can only solidify and form amorphous foils through heat conduction with the cooling roller. To achieve a cooling rate of 10... 4 ~10 9 K / s, which requires the cooling roller to provide sufficient cooling intensity.

[0003] The internal water channel design of the cooling roller is the main means to improve the cooling intensity. The applicant has described the relevant details in the patent (ZL201621099453.5) and achieved certain results in actual use, but the cooling intensity still needs to be further improved. Summary of the Invention

[0004] In view of the above, the present invention aims to provide a method for preparing amorphous ribbons to solve the problem of low yield of amorphous ribbons prepared by existing methods.

[0005] The objective of this invention is mainly achieved through the following technical solutions:

[0006] In a first aspect, the present invention provides a method for preparing amorphous ribbon, comprising the following steps:

[0007] Step 1: Load the master alloy into the melting crucible of the melting device, evacuate the vacuum rapid quenching equipment, and then fill the vacuum rapid quenching equipment with inert gas.

[0008] Step 2: Start the melting device to melt the master alloy until the master alloy is completely melted;

[0009] Step 3: Transfer the molten master alloy to the tundish and let it stand.

[0010] Step 4: Start the rotating cooling roller, pressurize the tundish with spray belt, and maintain a pressure difference between the tundish and the rapid quenching vacuum chamber;

[0011] Step 5: Observe the condition of the sprayed strip and adjust the roller speed according to the condition of the strip until the vacuum rapid quenching process is completed.

[0012] Optionally, in step 2, the melting temperature is 1000-1400℃.

[0013] Optionally, in step 3, the settling time is 2-10 minutes.

[0014] Optionally, in step 4, the spray belt pressure is 40-60 kPa.

[0015] Optionally, in step 1, the vacuum degree is ≤4×10 -2 Pa.

[0016] Optionally, in step 5, the roller speed is 15-40 m / s.

[0017] Optionally, in step 5, the spray pattern is observed through the viewing window of the vacuum rapid quenching equipment.

[0018] Optionally, in step 4, the pressure in the intermediate ladle is 20-30 kPa higher than that in the rapid quenching vacuum chamber.

[0019] Optionally, in step 2, the melting temperature is 1100-1300℃.

[0020] Secondly, the present invention also provides a vacuum rapid quenching device used in the above-mentioned preparation method, comprising a melting furnace vacuum chamber, a rapid quenching vacuum chamber, and a vacuum material chamber arranged in sequence; the rapid quenching vacuum chamber is provided with a rotating cooling roller.

[0021] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0022] a) In the preparation method of amorphous ribbon, the present invention improves the yield of amorphous ribbon to more than 80% by strictly controlling the process parameters.

[0023] b) The method for preparing amorphous ribbon in this invention uses a vacuum rapid quenching device with high cooling intensity and good cooling uniformity, which can increase the yield of amorphous ribbon to more than 80% (the yield of amorphous ribbon in the prior art is about 50%).

[0024] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention may be realized and obtained by means of what is particularly pointed out in the written description and the accompanying drawings. Attached Figure Description

[0025] The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Throughout the drawings, the same reference numerals denote the same parts.

[0026] Figure 1 This is a schematic diagram of the rotating cooling roller structure of the present invention;

[0027] Figure 2 The velocity cloud diagram (longitudinal section) of the rotating cooling roller of the present invention is shown; (a) the core barrel rotates, (b) the core barrel moves accordingly;

[0028] Figure 3 This is a vector diagram (longitudinal section) of the flow field velocity of the rotating cooling roller of the present invention; (a) the core barrel rotates, (b) the core barrel moves accordingly;

[0029] Figure 4 The strip prepared in Example 9 of this invention;

[0030] Figure 5 The strip prepared in Example 6 of this invention;

[0031] Figure 6 This is a schematic diagram of the vacuum rapid quenching equipment of the present invention;

[0032] Figure 7 The strip material prepared for the rotary cooling roller (core barrel follower) of this invention;

[0033] Figure 8 Fracture diagram of a tensile specimen used to test the tensile strength of a brazed joint after the amorphous ribbon of the present invention was used as a brazing filler metal.

[0034] Figure label:

[0035] 1-Rotating shaft; 2-Flange; 3-Cooling copper sleeve; 4-Core barrel; 5-Rotary dynamic seal; 6-Rolling bearing; D-Width of spiral groove; h-Height of spiral groove; 7-Vacuum chamber of melting furnace; 8-Smelting device; 9-Rapid quenching vacuum chamber; 10-Vacuum hopper; 11-Online instant grinding device; 12-Rotary cooling roller; 13-Rotary tundish system; 14-Strip guide cooling roller; 15-Strip anti-accumulation track. Detailed Implementation

[0036] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form part of the present invention and, together with the embodiments of the present invention, serve to illustrate the principles of the present invention.

[0037] In a first aspect, the present invention provides a method for preparing amorphous ribbon, which is prepared using the following vacuum rapid quenching equipment and includes the following steps:

[0038] Step 1: Load an appropriate amount of brazing master alloy into the melting crucible of the vacuum rapid quenching equipment, evacuate the vacuum rapid quenching equipment, and then fill the vacuum rapid quenching equipment with inert gas.

[0039] Step 2: Start the medium-frequency induction melting furnace to melt the brazing master alloy until it is completely melted;

[0040] Step 3: Transfer the molten brazing master alloy to the tundish, and let the tundish stand in a sealed state.

[0041] Step 4: Start the rotating cooling roller, pressurize the tundish with spray belt, and maintain a certain pressure difference between the tundish and the rapid quenching vacuum chamber;

[0042] Step 5: Observe the strip spraying condition through the viewing window of the vacuum rapid quenching equipment, and adjust the roller speed according to the strip condition until the vacuum rapid quenching process is completed.

[0043] Preferably, in step 1, the vacuum degree is ≤4×10 -2 Pa, for example, 1×10 -2 Pa, 2×10 -2 Pa, 3×10 -2 Pa, 4×10 -2 Pa.

[0044] Preferably, in step 1, the pressure inside the vacuum rapid quenching equipment after filling with inert gas is 20-30 kPa, for example, 20 kPa, 22 kPa, 24 kPa, 25 kPa, 27 kPa, 28 kPa, or 30 kPa.

[0045] Preferably, in step 2, the melting temperature is 1000-1400℃, for example, 1000℃, 1050℃, 1100℃, 1150℃, 1200℃, 1250℃, 1300℃, 1350℃, 1400℃, and more preferably 1100-1300℃.

[0046] Preferably, in step 3, the settling time is 2-10 minutes, for example, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 7 minutes, 8 minutes, 9 minutes, or 10 minutes.

[0047] Preferably, in step 4, the spray pressure is 40-60 kPa, for example, 40 kPa, 45 kPa, 50 kPa, 55 kPa, or 60 kPa.

[0048] Preferably, in step 4, the pressure in the intermediate ladle is 20-30 kPa higher than that in the rapid quenching vacuum chamber, for example, 20 kPa, 22 kPa, 25 kPa, 27 kPa, or 30 kPa.

[0049] Preferably, in step 5, the roller speed is 15-40 m / s, for example, 15 m / s, 20 m / s, 25 m / s, 30 m / s, 35 m / s, or 40 m / s.

[0050] Specifically, the composition of amorphous ribbons can be TiZrCuNiNb.

[0051] Preferably, the composition of the amorphous ribbon, by mass percentage, includes: Zr, 5%-30%, Cu, 10%-15%, Ni, 10%-15%, Nb, 0.5%-3.5%, rare earth elements, 0.1%-0.3%; the balance being Ti and unavoidable trace impurities.

[0052] Preferably, the rare earth element of the present invention is one or more of La, Ce and Y.

[0053] The following details the function and dosage selection of the components contained in this invention:

[0054] Zr: The addition of Zr can improve the fluidity of the brazing filler metal and enhance wettability during brazing, thereby facilitating the formation of uniform brazed joints. Therefore, this invention limits the Zr content to 5%-30%.

[0055] Cu: In solder, Cu plays a role in lowering the melting point and increasing fluidity, which helps the solder better fill the joint gap. It also facilitates element diffusion and phase transformation. Therefore, this invention limits the Cu content to 10% to 15%.

[0056] Ni: The addition of Ni can further improve the corrosion resistance and mechanical properties of the brazing filler metal, and enhance the durability and service life of the brazed joint. Therefore, this invention limits the Ni content to 10% to 15%.

[0057] Nb: Adding an appropriate amount of Nb can effectively improve the mechanical properties and corrosion resistance of amorphous alloys, while excessive Nb may lead to a decline in performance. Therefore, this invention limits the Nb content to 0.5% to 3.5%.

[0058] Rare earth elements: Rare earth elements can undergo internal oxidation to form high-melting-point compounds, reducing the oxygen content of the matrix and improving the high-temperature oxidation resistance and mechanical properties of the alloy. In this invention, rare earth elements enhance the mechanical properties of the titanium alloy through solid solution and the formation of intermetallic compounds. Therefore, this invention limits the rare earth element content to 0.1% to 0.3%.

[0059] Ti: Ti element is the balance, and its content is >50%.

[0060] The amorphous ribbon of this invention was used as a brazing filler metal for welding components made of TA15 titanium alloy at a temperature of 920°C and a vacuum degree of 1×10⁻⁶. -2 Brazing was performed at 10 MPa and held at that temperature for 10 minutes. The tensile strength of the brazed joint was tested, and the results showed that the tensile strength of the brazed joint was 930-950 MPa, the elongation after fracture was 11%-15%, and the typical microstructure of the brazed joint was lamellar, with lamellar structure accounting for 75%-90%.

[0061] See the fracture diagram of the tensile specimen. Figure 8 ,Depend on Figure 8 It is evident that when brazing is performed on brazing strips, the corresponding brazed joints break off in the matrix after room temperature tensile testing, indicating that the brazing performance is equal to or stronger than that of the matrix.

[0062] The microstructure of the amorphous ribbon (solder metal) of the present invention includes: rapid diffusion of Cu and Ni elements into the matrix at the brazing interface, and rapid diffusion of Ti elements into the solder, forming a diffusion layer near both sides of the matrix. This diffusion layer gradually widens with increasing brazing temperature and holding time. Subsequently, β-Ti nucleates and grows in the liquid solder. At this time, the remaining liquid phase mainly contains Ti, Zr, Cu, and Ni elements, which solidify to form the (Ti,Zr)2(Cu,Ni) phase. As the temperature decreases, the high-temperature β-Ti gradually undergoes eutectoid decomposition, generating α-Ti distributed in a lamellar pattern. The addition of rare earth elements and Nb elements is beneficial to the precipitation of lamellar α-Ti, reducing the volume content of the brittle (Ti,Zr)2(Cu,Ni) phase, thereby increasing the joint toughness.

[0063] The design concept of the amorphous ribbon (brazing filler metal) composition of this invention is as follows: By adding rare earth elements to titanium-based alloys, high-melting-point compounds are formed through the internal oxidation of rare earth elements, reducing the oxygen content of the matrix and improving the high-temperature oxidation resistance and mechanical properties of the alloy. Rare earth elements enhance the mechanical properties of the titanium alloy through solid solution and the formation of intermetallic compounds. While improving the strength of the brazed joint (tensile strength of 930-950 MPa and toughness) and reducing the brittleness of the brazed joint (elongation after fracture of 11%-15%, far exceeding the elongation after fracture of <5% in existing technologies), this broadens the application range of titanium and its alloys, enabling them to be used in applications requiring high joint performance.

[0064] Secondly, the present invention provides a rotating cooling roller. For example... Figure 1 As shown, the rotating cooling roller includes a rotating shaft 1, a flange 2, a cooling jacket 3, a core barrel 4, a rotating dynamic seal 5, and a rolling bearing 6.

[0065] Flange 2, core barrel 4 and cooling jacket 3 form an internal flow path, through which the cooling medium flows. Figure 1 The middle arrow indicates the direction of the cooling medium flow.

[0066] The cooling jacket 3 is a hollow cylinder without end faces. Each end of the cooling jacket is connected to a flange 2, and the other ends of the two flanges 2 are connected to a rotating shaft 1. The two flanges 2 and the cooling jacket 3 form a spindle-shaped internal space. The core 4 is located within this internal space, with gaps between it and both flanges 2 and the cooling jacket 3 to allow the cooling medium to flow through. Specifically, as shown... Figure 1 As shown, the longitudinal section of the structure formed by flange 2 and cooling jacket 3 is similar to a hexagon.

[0067] Flange 2 has a tapered structure with a tapered angle of 40°-70°, for example, 40°, 50°, 60°, 70°. The inner wall of flange 2 is provided with guide grooves, which enable the cooling medium (e.g., water) to be quickly distributed after entering the cooling roller.

[0068] Specifically, the larger diameter end of the flange 2 is connected to the cooling jacket 3, and the smaller diameter end is connected to the rotating shaft 1.

[0069] The core barrel 4 has a spindle-shaped sealed cavity structure, the shape of which corresponds to the spindle-shaped internal space. Both ends of the core barrel 4 are connected to the rotating shaft 1. A rolling bearing 6 is fixed at the connection between the core barrel 4 and the rotating shaft 1, which allows the core barrel 4 to be in a follow-up state (water flow) when the rotating shaft 1 and the cooling jacket 3 rotate.

[0070] The flange 2, core barrel 4, and cooling jacket 3 together form a spindle-shaped streamlined internal flow path. The streamlined structural design helps to overcome centrifugal force, reducing the impact of the centrifugal force of the high-speed rotation of the cooling roller on the cooling medium, especially the cooling medium in the annular water channel between the cooling jacket and the core barrel. This facilitates the rapid distribution of the cooling medium through the inlet and its rapid convergence at the outlet through the internal flow path, thereby improving the cooling intensity.

[0071] In a preferred embodiment, the longitudinal section of the core barrel 4 is similar to a hexagon.

[0072] In another embodiment, the rotary cooling roller further includes a locking element (e.g., a snap-fit), which is located at the connection between the core barrel 4 and the rotating shaft 1 to fix the core barrel 4 to the rotating shaft 1. In this case, the core barrel 4 is in a rotating state, meaning it rotates along with the rotating shaft 1. By providing the locking element, this invention enables the switching between a following state and a rotating state for the core barrel 4. The cooling intensity differs between the following and rotating states (see Table 1), thereby achieving adjustment of the cooling intensity and expanding the application range of the rotary cooling roller of this invention.

[0073] Specifically, the rotating shaft 1 is hollow inside to allow the cooling medium to flow through. The rotating shaft 1 comprises two sections: one for the inflow of the cooling medium and the other for its outflow. Each section of the rotating shaft is connected to the smaller diameter end of the flange 2. One end of the rotating shaft 1 is open, and the other end is closed. Each section of the rotating shaft has a through-hole on its side wall, located in the gap between the flange 2 and the core barrel 4. This allows the cooling medium to flow in or out of the rotating shaft and its internal flow path, either flowing into the internal flow path or flowing out of the rotating shaft 1, thus allowing the cooling medium to collect at the outlet after flowing through the internal flow path.

[0074] Specifically, there are multiple through holes, and these through holes are evenly distributed around the rotation axis 1.

[0075] In a preferred embodiment, a rotary dynamic seal 5 is provided at the connection between the core barrel and the rotating shaft to prevent the cooling medium in the internal flow path from flowing into the cavity of the core barrel 4.

[0076] It should be noted that, compared with the solid structure, the hollow structure of the core barrel 4 helps to reduce the weight of the cooling roller, save raw materials, and reduce costs.

[0077] The inner wall of the cooling jacket 3 is provided with single or multiple spiral grooves to form a spiral water channel. Multiple spiral grooves are preferred, for example, 3-5 parallel spiral grooves. In use, this invention increases the system's cooling capacity by controlling the flow direction of the cooling medium to be opposite to the rotation direction of the cooling roller.

[0078] Specifically, the pitch S of the spiral groove is 50-100mm. The cross-section of the spiral groove is semi-elliptical, semi-circular, triangular, rectangular, or trapezoidal. When the cross-section of the spiral groove is semi-elliptical or rectangular, the width-to-height ratio is 2-3.5. This invention, by providing spiral grooves on the inner wall of the cooling jacket 3, can reduce the area (dead zone) where the cooling medium, formed by high-speed rotation, is relatively stationary with the inner surface of the cooling roller when flowing in the spiral channel. The existence of the dead zone causes the cooling medium water to vaporize upon contact with the inner surface of the cooling roller, forming a gas film that hinders heat transfer, and in severe cases (excessive vapor pressure), can easily lead to danger. This invention, by providing spiral grooves on the inner wall of the cooling jacket 3, improves both cooling intensity and production safety.

[0079] The cooling jacket 3 is made of copper, copper alloy, or other materials with high thermal conductivity. The gap between the cooling jacket 3 and the core barrel 4 is 5-10 mm on one side, for example, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, or 10 mm. The gap between the flange 2 and the core barrel 4 is 30-40 mm on one side, for example, 30 mm, 32 mm, 35 mm, 37 mm, 39 mm, or 40 mm.

[0080] Compared with the prior art, the present invention has the following technical effects:

[0081] 1) The flange of this invention has a conical structure, which, when connected to a hollow cooling jacket without end faces, forms a spindle-shaped internal space. The core barrel is a spindle-shaped sealed cavity structure, corresponding to the spindle-shaped internal space formed by the flange and the cooling roller, and leaving gaps between it and the flange and the cooling jacket, thereby constructing an internal flow path of a streamlined spindle structure. The streamlined structural design helps to overcome the effect of centrifugal force, reducing the impact of the centrifugal force of the high-speed rotation of the cooling roller on the poor flow of the cooling medium, especially the cooling medium in the annular water channel between the cooling jacket and the core barrel. This facilitates the rapid distribution of the cooling medium through the inlet and its rapid convergence to the outlet through the internal flow path, ensuring that the cooling medium can pass through quickly. On the one hand, it can remove more heat in a short time, achieving efficient heat exchange and thus improving the cooling intensity; on the other hand, it can increase the cooling uniformity and improve the yield of amorphous ribbon to over 80% (the yield of amorphous ribbon in the prior art is about 50%).

[0082] 2) By connecting a rolling bearing to the connection end between the core barrel and the rotating shaft, the core barrel can be in a follow-up state when the rotating shaft and cooling jacket rotate. This is equivalent to applying a shear force perpendicular to the centrifugal force to the internal cooling medium. The purpose is to offset part of the centrifugal force, increase the axial movement efficiency of the cooling medium, and improve the cooling intensity of the rotating cooling roller.

[0083] 3) This invention fixes the core barrel to the rotating shaft by setting a locking component, thus enabling the core barrel to be in a rotating state, that is, the core barrel rotates with the rotating shaft. The cooling intensity of the core barrel in the following state and the rotating state are different (see Table 1), thereby realizing the adjustment of the cooling intensity and expanding the application range of the rotary cooling roller of this invention.

[0084] 4) By setting a flow guide groove on the inner wall of the flange, the present invention can realize the rapid distribution of the cooling medium, ensuring that the cooling medium can pass through quickly and remove more heat in a short time, thereby achieving the purpose of efficient heat exchange and further improving the cooling intensity.

[0085] 5) The present invention provides single or multiple spiral grooves on the inner wall of the cooling jacket. By controlling the flow direction of the cooling medium to be opposite to the rotation direction of the cooling roller, the cooling capacity of the system is increased, thereby improving the cooling intensity.

[0086] 6) The cooling roller of the present invention has great promotion and practical value. When applied to vacuum rapid quenching equipment, it can prepare amorphous foil strips of alloy systems that are urgently needed in the aerospace field but do not have strong amorphous forming ability. After its widespread promotion and application, it will generate good economic and social benefits.

[0087] 7) The rotating cooling roller in the vacuum rapid quenching equipment of the present invention constructs a spindle-shaped streamline internal flow path, which helps to overcome the centrifugal force and reduce the impact of the centrifugal force of the high-speed rotation of the cooling roller on the poor flow of the cooling medium inside, especially the cooling medium in the annular water channel between the cooling jacket and the core barrel. This facilitates the rapid distribution of the cooling medium through the inlet and its rapid convergence to the outlet through the internal flow path, ensuring that the cooling medium can pass through quickly. On the one hand, it can remove more heat in a short time, achieving the purpose of efficient heat exchange and thus improving the cooling intensity. On the other hand, it can increase the cooling uniformity and improve the yield of amorphous ribbon to more than 80% (the yield of amorphous ribbon in the prior art is about 50%).

[0088] Thirdly, the present invention provides a vacuum rapid quenching device, such as... Figure 6 As shown, it includes a melting furnace vacuum chamber 7, a rapid quenching vacuum chamber 9, and a vacuum material hopper 10 arranged in sequence; the melting furnace vacuum chamber 7, the rapid quenching vacuum chamber 9, and the vacuum material hopper are independent and closed structures, and can each perform corresponding operations after being connected to the atmospheric environment without affecting each other.

[0089] The vacuum chamber 7 of the melting furnace is equipped with a melting device 8, and the melting device 8 is equipped with a melting crucible for placing the master alloy.

[0090] The rapid quenching vacuum chamber 9 is equipped with the aforementioned rotary cooling roller 12, turntable tundish system 13, strip guide cooling roller 14, and strip anti-stacking track 15 in sequence.

[0091] In one specific embodiment, the melting device 8 is a medium-frequency melting furnace. The capacity of the medium-frequency melting furnace is 10-300 kg, preferably 50-150 kg.

[0092] The rotary intermediate bale system 13 comprises 3-5 rotatable independent intermediate bales, each driven by a horizontal disc to rotate and / or stop along the circumference of the disc. A rotating cooling roller 12 is located below the intermediate bales, and each intermediate bale has a nozzle below it to spray cooling medium onto the rotating cooling roller 12. Exemplarily, the capacity of the intermediate bales is 25-100 kg.

[0093] In a preferred embodiment, the vacuum rapid quenching equipment also includes an online instant polishing device 11, which is arranged facing the working surface of the rotating cooling roller 12, and can trim and polish the surface of the rotating cooling roller 12 when the melting device 8 is feeding and melting.

[0094] The strip guide cooling roller 14 is a two-roll adjustable slit structure, which is set at the exit end of the strip after it leaves the rotating cooling roller 12. It controls the flight state of the strip after it leaves the roller, guides the strip through the slit into the strip anti-accumulation track 15, and performs secondary cooling on the strip.

[0095] Example 1 (Spindle-shaped cooling roller, core barrel follows)

[0096] This embodiment uses a rotating cooling roller with a shaft diameter of 100mm, a cooling jacket material of copper, an outer diameter of 380mm, a core barrel outer diameter of 304mm, and four parallel spiral grooves on the inner wall of the copper jacket. The width-to-height ratio of the spiral grooves D / h is 2.5, and the pitch S is 80mm.

[0097] Example 2 (spindle-shaped cooling roller, core barrel rotating)

[0098] This embodiment is basically the same as embodiment 1, except that it also includes a locking component (bucket) to fix the core barrel 4 to the rotating shaft 1, so that the core barrel is in a rotating state.

[0099] Comparative Example 1 (Right-angled cooling roller, rotating core barrel)

[0100] Compared with Example 1, the structure of the rotating cooling roller is the structure involved in the patent with patent number ZL201621099453.5.

[0101] Under the same simulation conditions, the velocity and temperature fields during the cooling process of the rotating cooling rollers in Examples 1, 2, and Comparative Example 1 were analyzed using finite element simulation. The results are as follows: Figure 2 and Figure 3 As shown, the simulation data is listed in Table 1.

[0102] Table 1 Simulation Data Analysis Table

[0103]

[0104] As can be seen from the data in Table 1, the outlet velocity of the spindle-shaped cooling roller (Examples 1 and 2) of the present invention is significantly greater than that of the right-angled cooling roller (Comparative Example 1). The faster outlet velocity of the cooling medium after passing through the spindle-shaped copper roller indicates that the cooling medium can remove more heat in a short time, thereby making the outlet temperature of the spindle-shaped cooling roller (Examples 1 and 2) significantly higher than that of the right-angled cooling roller (Comparative Example 1). This proves that the cooling intensity of the spindle-shaped cooling roller is significantly greater than that of the right-angled cooling roller.

[0105] Furthermore, comparing the data from Examples 1 and 2 in Table 1 reveals that, compared to the core barrel rotation (Example 2), the core barrel follow-up (Example 1) exhibits a faster outlet velocity and a lower tangential velocity of the cooling medium between the cooling jacket and the core barrel. A lower tangential velocity of the cooling medium between the cooling jacket and the core barrel indicates a smaller effect of centrifugal force. Therefore, it can be concluded that, compared to core barrel rotation (Example 2), core barrel follow-up (Example 1) better reduces the influence of centrifugal force, improves the axial flow capacity of the cooling medium, further enhances cooling efficiency, and consequently increases cooling intensity.

[0106] In addition, by Figure 2 and Figure 3 It can be seen that, although Figure 2 In the velocity cloud diagram, the left-hand core barrel is rotating, and the cooling water flow rate is relatively fast (the cloud diagram is red), but from... Figure 3 It can be further seen that the high speed is due to the large tangential speed, which means it is greatly affected by centrifugal force, ultimately resulting in a slow outlet speed.

[0107] The following specific embodiments and comparative examples demonstrate the superior advantages of precise control of process parameters in the preparation method of amorphous ribbon of the present invention.

[0108] Examples 3-8 of this invention provide a method for preparing amorphous ribbons. The amorphous ribbons have a composition of TiZrCuNiNb. The ribbons prepared in Example 3 are shown in [reference needed]. Figure 7 .

[0109] The preparation methods of Examples 3-8 include: vacuuming in a vacuum rapid quenching equipment, melting the master alloy, transferring it from a converter to an intermediate ladle, starting the rotating cooling roller, and applying pressure to the spray belt.

[0110] It should be noted that the equipment used in the vacuum rapid quenching process of Examples 3-8 is a vacuum rapid quenching equipment, and the rotating cooling roller in the vacuum rapid quenching equipment is the cooling roller of Example 1.

[0111] The specific process parameters for Examples 3-8 are shown in Table 2, and the strip yield is shown in Table 3.

[0112] Table 2 Production Process Parameters

[0113]

[0114]

[0115] Table 3 Yield of Amorphous Ribbons

[0116] Number Yield / % Number Yield / % Example 3 85 Comparative Example 2 48 Example 4 87 Comparative Example 3 70 Example 5 88 Comparative Example 4 85 Example 6 87 Comparative Example 5 72 Example 7 90 Comparative Example 6 75 Example 8 86 Comparative Example 7 73 Example 9 81 Comparative Example 8 71

[0117] Example 9

[0118] This embodiment is basically the same as Embodiment 6, except that the rotating cooling roller in the vacuum rapid quenching equipment is the same as the cooling roller in Embodiment 2. The yield of the strip is shown in Table 3.

[0119] like Figure 4As shown, when this alloy system was subjected to vacuum rapid quenching experiments using a spindle-shaped copper roller (Example 2, with rotating core barrel) for a rotating cooling roller, localized crystallization occurred at the edges of the strip, indicating that the cooling intensity of the cooling roller was insufficient to prepare a completely amorphous strip. However, using the spindle-shaped copper roller of this invention (Example 1, with a moving core barrel) can produce a strip with a bright surface quality, complete strip shape, and complete amorphous properties, such as... Figure 5 As shown.

[0120] Comparative Example 2

[0121] The comparative example is basically the same as Example 6, except that the rotating cooling roller in the vacuum rapid quenching equipment is the same as the cooling roller in Comparative Example 1, and the strip yield is shown in Table 3.

[0122] In addition, the inventors conducted a large number of experimental studies during the research process. Some solutions with poor performance are now used as comparative examples. The strip yield of comparative examples 3-8 is shown in Table 3.

[0123] Comparative Example 3

[0124] This comparative example is basically the same as Example 6, except that the melting temperature is 900°C.

[0125] Comparative Example 4

[0126] This comparative example is basically the same as Example 6, except that the melting temperature is 1500°C.

[0127] Comparative Example 5

[0128] This comparative example is basically the same as Example 6, except that the spray pressure is 35 kPa.

[0129] Comparative Example 6

[0130] This comparative example is basically the same as Example 6, except that the spray pressure is 65 kPa.

[0131] Comparative Example 7

[0132] The comparative example is basically the same as Example 6, except that the pressure difference between the tundish and the rapid quenching vacuum chamber is 15 kPa.

[0133] Comparative Example 8

[0134] The comparative example is basically the same as Example 6, except that the pressure difference between the tundish and the rapid quenching vacuum chamber is 35 kPa.

[0135] As shown in Table 3, the strip yield of Examples 3-8 (85%-90%) is significantly higher than that of Comparative Examples 3 and 5-8 (70%-75%, but still higher than the approximately 50% amorphous strip yield of the prior art). This indicates that excessively low melting temperature, excessively high or low spraying pressure, and excessively high or low pressure difference between the tundish and the rapid quenching vacuum chamber all reduce the strip yield, thus demonstrating the importance of process parameter control in the preparation method of amorphous strips. Furthermore, the strip yield of Comparative Example 4 is comparable to that of Examples 3-8, indicating that excessively high melting temperature does not contribute to improving the strip yield.

[0136] Furthermore, Table 3 shows that the strip yield rates of Examples 3-8 (85%-90%) and Example 9 (81%) are significantly higher than those of Comparative Example 2, indicating that using a spindle-shaped cooling roller can improve the strip yield rate more effectively than using a right-angled cooling roller. Moreover, the strip yield rates of Examples 3-8 (85%-90%) are also higher than those of Example 9 (81%), indicating that a spindle-shaped cooling roller with a core barrel following motion can improve the strip yield rate more effectively than a spindle-shaped cooling roller with a core barrel rotating motion.

[0137] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing an amorphous ribbon, characterized in that, Includes the following steps: Step 1: Load the master alloy into the melting crucible of the melting device, evacuate the vacuum rapid quenching equipment, and then fill the vacuum rapid quenching equipment with inert gas. Step 2: Start the melting device to melt the master alloy until the master alloy is completely melted; Step 3: Transfer the molten master alloy to the tundish and let it stand. Step 4: Start the rotating cooling roller, pressurize the tundish with spray belt, and maintain a pressure difference between the tundish and the rapid quenching vacuum chamber; Step 5: Observe the condition of the sprayed strip and adjust the roller speed according to the condition of the strip until the vacuum rapid quenching process is completed; The rotary cooling roller is used to improve the yield of amorphous ribbon. The rotary cooling roller includes a rotating shaft, a flange, a cooling jacket, a core barrel, and a rolling bearing. The cooling jacket is a hollow cylinder without end faces. Each end of the cooling jacket is connected to a flange, and the other ends of the two flanges are connected to the rotating shaft. The rotating shaft is hollow inside to allow the cooling medium to flow through. The two flanges and the cooling jacket form a spindle-shaped internal space. The core barrel is located in the spindle-shaped internal space and has gaps between itself and the flanges and the cooling jacket, thereby constructing an internal flow path of the spindle-shaped streamline structure for the cooling medium to flow through. The streamlined structural design helps to overcome the centrifugal force and can reduce the impact of the centrifugal force of the high-speed rotation of the cooling roller on the poor flow of the cooling medium. The outer shape of the core barrel corresponds to the spindle-shaped internal space, and its two ends are respectively connected to the rotating shaft, with rolling bearings provided at the connection points; It also includes a locking element, which is located at the connection between the core barrel and the rotating shaft to fix the core barrel and the rotating shaft.

2. The preparation method according to claim 1, characterized in that, In step 2, the melting temperature is 1000-1400℃.

3. The preparation method according to claim 2, characterized in that, In step 3, the settling time is 2-10 minutes.

4. The preparation method according to claim 1, characterized in that, In step 4, the spray pressure is 40-60 kPa.

5. The preparation method according to claim 1, characterized in that, In step 1, the vacuum degree is ≤4×10 -2 Pa.

6. The preparation method according to claim 1, characterized in that, In step 5, the roller speed is 15-40 m / s.

7. The preparation method according to any one of claims 1-6, characterized in that, In step 5, the spray pattern is observed through the viewing window of the vacuum rapid quenching equipment.

8. The preparation method according to claim 7, characterized in that, In step 4, the pressure in the intermediate ladle is 20-30 kPa higher than that in the rapid quenching vacuum chamber.

9. The preparation method according to claim 2, characterized in that, In step 2, the melting temperature is 1100-1300℃.

10. A vacuum rapid quenching apparatus used in the preparation method according to any one of claims 1-9, characterized in that, It includes a melting furnace vacuum chamber, a rapid quenching vacuum chamber, and a vacuum material hopper arranged in sequence; the rapid quenching vacuum chamber is equipped with a rotating cooling roller.

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