A Pr-Fe-(C, B) rare earth permanent magnetic material and preparation method thereof

Abstract

A Pr-Fe-(C, B) rare earth permanent magnetic material and a preparation method thereof, relating to the technical field of permanent magnetic materials, the Pr-Fe-(C, B) rare earth permanent magnetic material, comprising a substance having a composition calculated by atomic percentage, Pr 15 Fe 79 (C 1‑x ,B x )6, 0.2<x≤0.8; The preparation process includes batching, smelting, melt quenching, and annealing, wherein the melt quenching is carried out in a vacuum quenching furnace with a copper roller speed of 30≤V≤40m / s under a protective atmosphere, and the annealing is carried out in an annealing furnace at 600-950°C under a protective atmosphere. 14 The high stability of the B phase, the atomic size of B atoms is similar to that of C atoms, and the partial replacement of Pr2Fe with B atoms 14 The C atoms in C greatly improve the 14 (C,B) stability, improving Pr2Fe 14 (C, B) phase content greatly improves the coercivity.

Description

Technical Field

[0001] The present invention relates to the technical field of rare earth permanent magnet materials, and in particular to a Pr-Fe-(C, B) rare earth permanent magnet material and a preparation method thereof, and in particular to increasing the Pr2Fe in the Pr-Fe-(C, B) rare earth permanent magnet material by replacing the C element with the B element. 14 The stability and relative content of (C, B) can improve the coercivity. Background Art

[0002] Permanent magnetic materials are widely used in energy, transportation, aerospace, medical and other fields, and have broad application prospects. With the progress of society, the demand for permanent magnetic materials has gradually increased. This has led to the unbalanced utilization of rare earth resources and the scarcity of rare earth elements such as Nd, Tb, and Dy. 14 C permanent magnet material has the same 14 B permanent magnet material has the same tetragonal crystal structure and similar magnetic properties. 14 Compared with the B permanent magnet material, the advantage of this permanent magnet material is that it has a higher magnetocrystalline anisotropy field and can obtain a high coercivity without adding heavy rare earth. 14 C permanent magnetic materials are crucial to solving the problems facing rare earth resources.

[0003] Pr2Fe 14 Pr2Fe in C permanent magnet materials 14 C hard magnetic phase is the main source of its magnetic properties. However, the limitation of Pr2Fe 14 The main reason for the application of C permanent magnet materials is Pr2Fe 14 The stability of C phase is poor. 14 C must undergo a slow solid phase transformation within a specific temperature range to be obtained. Some researchers have obtained Pr2Fe by annealing the ingot for 50 days. 14 C tetragonal phase. However, the coercivity of the permanent magnetic material obtained by this method is very low because the grains grow excessively after long-term annealing. And from the perspective of economic production, such a long annealing time is not conducive to industrial production. The patent with publication number "CN1059618A" mentions a method for preparing anisotropic bonded magnets, in which B is used to replace the known Nd2Fe 14 A small amount of C is added to the Pr-Fe-(C, B) rare earth permanent magnet material, and the coercivity is increased to 500 kA / m by smelting, annealing at 900-1050°C for at least 4 days, and subsequent ball milling. Although this method improves the coercivity to a certain extent, the preparation process is complicated and the coercivity obtained is not very high. Therefore, a preparation method of Pr-Fe-(C, B) rare earth permanent magnet material is needed. Summary of the invention

[0004] The present invention provides a method for preparing a Pr-Fe-(C, B) rare earth permanent magnet material, which adopts the method of doping B element to adjust the composition of Pr-Fe-(C, B) alloy to improve the Pr2Fe 14 (C, B) stability, and combined with rapid quenching and short-time annealing process to obtain Pr2Fe 14 Pr-Fe-(C,B) rare earth alloy permanent magnet material with high (C,B) content and no α-Fe soft magnetic impurity phase.

[0005] In order to achieve the above object, the present invention provides a method for preparing a Pr-Fe-(C, B) rare earth permanent magnet material, wherein the main body of the Pr-Fe-(C, B) rare earth permanent magnet material is composed of a substance having a composition in atomic percentage as shown in Formula 1: Pr 15 Fe 79 (C 1-x ,B x )6(Formula 1); in Formula 1, 0.2<x≤0.8;

[0006] The present invention provides a method for preparing the Pr-Fe-(C, B) rare earth permanent magnet material described in the above scheme, comprising the following steps:

[0007] S1. Weigh each component according to the general formula shown in Formula 1 for mixing, wherein the amount of Pr is increased by 1 to 5% based on the theoretical Pr calculated according to Formula 1;

[0008] S2. The raw materials weighed in S1 are smelted to obtain an ingot;

[0009] S3. The ingot is crushed and the melt is rapidly quenched to obtain a rapidly quenched strip;

[0010] S4. The quenched strip is sequentially annealed and quenched to obtain a Pr-Fe-(C, B) rare earth permanent magnet material;

[0011] Preferably, the ingot preparation process is as follows: the raw materials weighed in S1 are placed in a high-frequency suspension smelting furnace, and the vacuum in the furnace is at least 5×10 -2 Pa; then, argon gas is passed until the pressure in the furnace is 30-80 kPa; the smelting furnace is powered on, the raw materials are melted, and then the power is turned off and poured into a water-cooled copper crucible for standby use;

[0012] Preferably, the smelting process is repeated 3-8 times;

[0013] Preferably, the preparation process of the rapid quenching belt in S3 is as follows: crush the ingot obtained in S2, and put it into a quartz tube of a melt rapid quenching furnace, the nozzle diameter at the bottom of the quartz tube is 0.5-2 mm, and the bottom of the quartz tube is 2-6 mm away from the copper roller; evacuate the cavity of the melt rapid quenching furnace to a vacuum degree of 2×10 -4 ~9×10-4 Pa; then fill the cavity with argon gas to make the pressure inside the cavity greater than the pressure outside the cavity by 60-90 kPa; turn on the heating power supply to melt the ingot in the quartz tube, turn on and adjust the speed of the copper roller; use the spray casting device in the furnace to spray the molten alloy onto the rotating copper roller to obtain a rapid quenching strip;

[0014] Preferably, the rapid quenching of the strip in S3 is carried out in a melt rapid quenching furnace, and during the melt rapid quenching process, the rotation speed of the copper roller is 30 to 40 m / s, and more preferably 40 m / s.

[0015] Preferably, the annealing process in S4 is carried out under argon protection.

[0016] Preferably, the annealing equipment described in S4 is a short-time annealing device built on the basis of a muffle furnace, which consists of a quartz tube with one end open and the other end closed, a quartz gas guide tube, a gas guide hose, and a bottle of argon gas. The device realizes annealing of the sample under argon protection, and at the same time, realizes rapid quenching under argon protection.

[0017] Preferably, the annealing process in S4 is: placing the quick-quenching strip obtained in S3 into a cylinder made of tantalum sheet with one end closed and the other end open; introducing argon gas into the quartz tube in the muffle furnace, and maintaining the gas flow rate at 5-15 l / min; then, placing the tantalum sheet cylinder loaded with the quick-quenching strip at the mouth of the quartz tube and pre-blowing argon for 10 minutes, and then placing the tantalum sheet cylinder loaded with the quick-quenching strip in the quartz tube for annealing at the furnace core position.

[0018] Preferably, the annealing temperature in S4 is 600-1000° C., and the annealing time is 0.5-2 h.

[0019] Preferably, the quenching method in S4 is ice water quenching.

[0020] The present invention provides a Pr-Fe-(C, B) rare earth permanent magnet material having a material composition in terms of atomic percentage as shown in Formula 1: Pr 15 Fe 79 (C 1-x ,B x )6 (Formula 1); wherein 0.2<x≤0.8. The present invention utilizes the close atomic radius of the B atom and the C atom, Nd2Fe 14 B permanent magnet material has high stability. B atoms partially replace C atoms in Pr-Fe-C, which increases the stability of Pr2Fe 14 C stability, inhibited the formation of impurity phase, and improved the hard magnetic phase Pr2Fe 14 The relative content of (C, B) increases the coercive force of the permanent magnet material.

[0021] In the present invention, the process can be a conventional process in the art. The main advantages of the present invention over other existing technologies are:

[0022] The present invention provides a method for preparing a Pr-Fe-(C, B) rare earth permanent magnet material, comprising the following steps: smelting a mixture including Pr, Fe, C and B to obtain an ingot; subjecting the ingot to melt rapid quenching to obtain a rapid quenching strip; and sequentially annealing and quenching the rapid quenching strip to obtain a Pr-Fe-(C, B) rare earth permanent magnet material. The mass of the Pr is increased by 1 to 5% on the basis of the theoretical Pr mass calculated according to Formula 1 to compensate for the loss during the smelting process. The present invention obtains a structure with more uniform composition and finer grains through a melt rapid quenching process, which can reduce the energy barrier of atomic diffusion during annealing, increase the speed of solid phase transformation, and shorten the annealing time; by performing B atom substitution and combining with an annealing process, the α-Fe phase can be eliminated, and the P r2 Fe 14 The stability of the (C,B) phase greatly improves the 14 The relative content of (C, B) phase is conducive to obtaining higher coercivity; the quenching process ensures that Pr2Fe 14 The (C,B) phase will not decompose during the cooling process.

[0023] The results of the examples show that the coercive force of the Pr-Fe-(C, B) rare earth permanent magnet material prepared by the present invention is as high as 19.09 kOe, which indicates that the method of the present invention can improve the coercive force of the permanent magnet material. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The XRD test results of the permanent magnetic materials prepared in Examples 1-5 are as follows;

[0025] Figure 2 is the hysteresis loop of the permanent magnetic material prepared in Example 5;

[0026] Figure 3 The XRD results of the magnetic material prepared in Comparative Example 1 are as follows:

[0027] Figure 4 This is the hysteresis loop of the magnetic material prepared in Comparative Example 1. DETAILED DESCRIPTION

[0028] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments.

[0029] Example 1

[0030] (1) According to the stoichiometric ratio Pr 15 Fe 79 C 3.6 B2.4 Ratio, where the mass of Pr is the same as that of Pr according to the general formula 15 Fe 79 C 3.6 B 2.4 Compared with the calculated mass, it increased by 1%;

[0031] (2) Pr, FeC, and FeB with a purity higher than 99% are placed in a water-cooled copper crucible in a high-frequency induction melting furnace and evacuated to a vacuum degree of 5×10 -2 Pa; then fill the cavity with high-purity argon gas to make the pressure in the furnace reach 70kPa. Turn on the power; raise the temperature to 1600℃ to melt the sample, and stop melting after 60s; repeat the melting 4 times, and take the sample out of the furnace for use after it is completely cooled;

[0032] (3) The ingot is crushed and placed in a quartz tube of a melt quenching furnace. The nozzle diameter at the bottom of the quartz tube is 1 mm, and the bottom of the quartz tube is 4 mm away from the copper roller. The cavity is closed and the melt quenching furnace cavity is evacuated to a vacuum degree of 9 × 10 -4 Pa; then fill argon into the cavity to make the pressure difference between the inside and outside of the cavity reach 80kPa; turn on the heating power to make the ingot re-melt in the quartz tube, open and adjust the copper roller speed to 30m / s; use the spray-casting device in the furnace to vertically spray the re-melted alloy melt onto the rotating copper roller to obtain a quick-quenching strip.

[0033] (4) Place the quenching tape into a cylinder made of tantalum sheet with one end closed and the other end open; introduce argon gas into the quartz tube in the muffle furnace, and keep the gas flow rate at 10 l / min; then, place the tantalum sheet cylinder loaded with the quenching tape at the mouth of the quartz tube and pre-blow argon gas for 10 min, then place the tantalum sheet cylinder loaded with the quenching tape at the center of the furnace in the quartz tube and perform isothermal annealing at 1000°C for 0.5 h; then, quickly place the quartz tube and the sample in the tube into ice water at high temperature for quenching to obtain the sample.

[0034] XRD was used to analyze the phase composition of the product, and the main phase of the sample was Pr2Fe 14 (C, B) phase, and a very small amount of Pr2Fe 17 Mutually,

[0035] Example 2

[0036] (1) According to the stoichiometric ratio Pr 15 Fe 79 C 3.3 B 2.7 Ratio, where the mass of Pr is the same as that of Pr according to the general formula 15 Fe 79 C 3.3 B 2.7 Compared with the calculated mass, it increased by 1%;

[0037] (2) Place Pr, FeC, and FeB with a purity higher than 99% in a crucible of an induction melting furnace and evacuate the furnace to a vacuum degree of 5 × 10 -2 Pa; then fill the cavity with high-purity argon gas to make the pressure in the furnace reach 70kPa. Turn on the power; raise the temperature to 1600℃ to melt the sample, and stop melting after 60s; repeat the melting 5 times, and take the sample out of the furnace for use after it is completely cooled;

[0038] (3) The ingot is crushed and placed in a quartz tube of a melt quenching furnace. The nozzle diameter at the bottom of the quartz tube is 1.5 mm, and the bottom of the quartz tube is 4 mm away from the copper roller. The cavity is closed and the melt quenching furnace cavity is evacuated to a vacuum degree of 9 × 10 -4 Pa; then fill the cavity with argon gas to make the pressure difference between the cavity and the outside reach 90kPa; turn on the heating power supply to make the ingot re-melt in the quartz tube, turn on and adjust the copper roller speed to 40m / s; use the spray casting device in the furnace to vertically spray the re-melted alloy melt onto the rotating copper roller to obtain a quick-quenching belt. (4) Place the quick-quenching belt into a cylinder made of tantalum sheet with one end closed and the other end open; introduce argon gas into the quartz tube in the muffle furnace, and keep the gas flow rate at 10l / min; then, place the tantalum sheet cylinder loaded with the quick-quenching belt at the mouth of the quartz tube and pre-blow argon for 10min, then place the tantalum sheet cylinder loaded with the quick-quenching belt at the center of the furnace in the quartz tube for isothermal annealing at 950℃ for 1h; then, quickly put the quartz tube and the sample in the tube into ice water at high temperature for quenching to obtain the sample.

[0039] (5) XRD was used to analyze the phase composition of the product. The main phase of the sample was Pr2Fe 14 (C, B) phase, indicating that the use of B element substitution can improve the Pr2Fe 14 (C,B) Stability of phases.

[0040] Example 3

[0041] (1) According to the stoichiometric ratio Pr 15 Fe 79 C3B3 ratio, where the mass of Pr is the same as the general formula Pr 15 Fe 79 Compared with the mass calculated by C3B3, it increased by 1%;

[0042] (2) Place Pr, FeC, and FeB with a purity higher than 99% in a crucible of an induction melting furnace and evacuate the furnace to a vacuum degree of 5 × 10 -2 Pa; then fill the cavity with high-purity argon gas to make the pressure in the furnace reach 70kPa. Turn on the power; raise the temperature to 1600℃ to melt the sample, and stop melting after 60s; repeat the melting 5 times, and take the sample out of the furnace for use after it is completely cooled;

[0043] (3) The ingot is crushed and placed in a quartz tube of a melt quenching furnace. The nozzle diameter at the bottom of the quartz tube is 1.5 mm, and the bottom of the quartz tube is 4 mm away from the copper roller. The cavity is closed and the melt quenching furnace cavity is evacuated to a vacuum degree of 9 × 10 -4 Pa; then fill the cavity with argon gas to make the pressure difference between the cavity and the outside reach 90kPa; turn on the heating power supply to make the ingot re-melt in the quartz tube, turn on and adjust the copper roller speed to 30m / s; use the spray casting device in the furnace to vertically spray the re-melted alloy melt onto the rotating copper roller to obtain a quick-quenching belt. (4) Place the quick-quenching belt into a cylinder made of tantalum sheet with one end closed and the other end open; introduce argon gas into the quartz tube in the muffle furnace, and keep the gas flow rate at 10l / min; then, place the tantalum sheet cylinder loaded with the quick-quenching belt at the mouth of the quartz tube and pre-blow argon for 10min, then place the tantalum sheet cylinder loaded with the quick-quenching belt in the center of the furnace in the quartz tube for isothermal annealing at 800℃ for 1.5h; then, quickly put the quartz tube and the sample in the tube into ice water at high temperature for quenching to obtain the sample.

[0044] (5) XRD was used to analyze the phase composition of the product. The main phase of the sample was Pr2Fe 14 (C, B) phase, indicating that the use of B element substitution can improve the Pr2Fe 14 (C,B) Stability of phases.

[0045] Example 4

[0046] (1) According to the stoichiometric ratio Pr 15 Fe 79 C 2.7 B 3.3 Ratio, where the mass of Pr is the same as that of Pr according to the general formula 15 Fe 79 C 2.7 B 3.3 Compared with the calculated mass, it increased by 1%;

[0047] (2) Place Pr, FeC, and FeB with a purity higher than 99% in a crucible of an induction melting furnace and evacuate the furnace to a vacuum degree of 5 × 10 -2 Pa; then fill the cavity with high-purity argon gas to make the pressure in the furnace reach 70kPa. Turn on the power; raise the temperature to 1600℃ to melt the sample, and stop melting after 60s; repeat the melting 5 times, and take the sample out of the furnace for use after it is completely cooled;

[0048] (3) The ingot is crushed and placed in a quartz tube of a melt quenching furnace. The nozzle diameter at the bottom of the quartz tube is 1.5 mm, and the bottom of the quartz tube is 4 mm away from the copper roller. The cavity is closed and the melt quenching furnace cavity is evacuated to a vacuum degree of 9 × 10 -4Pa; then fill the cavity with argon gas to make the pressure difference between the cavity and the outside reach 90kPa; turn on the heating power supply to make the ingot re-melt in the quartz tube, turn on and adjust the copper roller speed to 35m / s; use the spray casting device in the furnace to vertically spray the re-melted alloy melt onto the rotating copper roller to obtain a quick-quenching belt. (4) Place the quick-quenching belt into a cylinder made of tantalum sheet with one end closed and the other end open; introduce argon gas into the quartz tube in the muffle furnace, and keep the gas flow rate at 12l / min; then, place the tantalum sheet cylinder loaded with the quick-quenching belt at the mouth of the quartz tube and pre-blow argon for 10min, then place the tantalum sheet cylinder loaded with the quick-quenching belt at the center of the furnace in the quartz tube for isothermal annealing at 600℃ for 2h; then, quickly put the quartz tube and the sample in the tube into ice water at high temperature for quenching to obtain the sample.

[0049] (5) XRD was used to analyze the phase composition of the product. The main phase of the sample was Pr2Fe 14 (C, B) phase, indicating that the use of B element substitution can improve the Pr2Fe 14 (C,B) Stability of phases.

[0050] Example 5

[0051] (1) According to the stoichiometric ratio Pr 15 Fe 79 C 2.4 B 3.6 Ratio, where the mass of Pr is the same as that of Pr according to the general formula 15 Fe 79 C 2.4 B 3.6 Compared with the calculated mass, it increased by 1%;

[0052] (2) Place Pr, FeC, and FeB with a purity higher than 99% in a crucible of an induction melting furnace and evacuate the furnace to a vacuum degree of 5 × 10 -2 Pa; then fill the cavity with high-purity argon gas to make the pressure in the furnace reach 70kPa. Turn on the power; raise the temperature to 1600℃ to melt the sample, and stop melting after 60s; repeat the melting 5 times, and take the sample out of the furnace for use after it is completely cooled;

[0053] (3) The ingot is crushed and placed in a quartz tube of a melt quenching furnace. The nozzle diameter at the bottom of the quartz tube is 1.5 mm, and the bottom of the quartz tube is 5 mm away from the copper roller. The cavity is closed and the melt quenching furnace cavity is evacuated to a vacuum degree of 9 × 10 -4 Pa; then fill argon into the cavity to make the pressure difference between the inside and outside of the cavity reach 90kPa; turn on the heating power to make the ingot re-melt in the quartz tube, open and adjust the copper roller speed to 40m / s; use the spray-casting device in the furnace to vertically spray the re-melted alloy melt onto the rotating copper roller to obtain a quick-quenching strip.

[0054] (4) Place the quenching tape into a cylinder made of tantalum sheet with one end closed and the other end open; introduce argon gas into the quartz tube in the muffle furnace, and keep the gas flow rate at 14 l / min; then, place the tantalum sheet cylinder loaded with the quenching tape at the mouth of the quartz tube and pre-blow argon gas for 10 minutes, then place the tantalum sheet cylinder loaded with the quenching tape at the center of the furnace in the quartz tube and perform isothermal annealing at 750°C for 1 hour; then, quickly put the quartz tube and the sample in the tube into ice water at high temperature for quenching to obtain the sample.

[0055] (5) XRD was used to analyze the phase composition of the product. The main phase of the sample was Pr2Fe 14 (C, B) phase, indicating that the use of B element substitution can improve the Pr2Fe 14 (C,B) Stability of phases.

[0056] Comparative Example 1

[0057] The parameters of other steps are the same as those of Example 5, except that B is not added during the smelting of step (1). The obtained sample is subjected to XRD test, and the results are as follows: Figure 3 As shown. The main phase in the sample is Pr2Fe 17 and α-Fe, no Pr2Fe 14 (C, B) phase. This indicates that the B element is not doped, Pr2Fe 14 The stability of the (C,B) phase is extremely poor, and it is impossible to obtain Pr2Fe by only rapid quenching and annealing processes. 14 (C, B) phase. The magnetic properties of the prepared samples were tested using VSM. The test results are shown in Figure 4 shown. Figure 4 The coercivity of the comparative sample is only 0.43 kOe, while the coercivity of the sample in Example 5 is 19.09 kOe, indicating that when doped with B element, the Pr2Fe 14 The stability of the (C,B) phase can improve the Pr2Fe 14 The relative content of (C, B) phase increases the coercivity.

[0058] Comparative Example 2

[0059] The parameters of other steps are the same as those of Example 5, except that the melt is not subjected to the rapid quenching in step S3. The obtained sample is subjected to XRD test. The main phase in the sample is Pr2Fe 17 and α-Fe, and a very small amount of Pr2Fe 14 (C, B) phase. This indicates that it is impossible to obtain a large amount of Pr2Fe in a short time without rapid quenching of the melt. 14 (C, B) phase, and Pr2Fe 14 (C,B) pure phase, for Pr2Fe 14(C, B) The magnetic properties of permanent magnet materials will be adversely affected. The coercive force of the final sample was measured to be only 1.32kOe.

[0060] Comparative Example 3

[0061] The parameters of other steps are the same as those of Example 5, except that the annealing treatment in step S4 is not performed. XRD test is performed on the prepared sample, and only Pr2Fe 17 and α-Fe diffraction peaks, but no Pr2Fe 14 The diffraction peaks of the (C, B) phase indicate that solid phase transformation cannot occur without annealing and single Pr2Fe 14 (C, B) phase is not conducive to the magnetic properties of permanent magnet materials. The coercive force of the final sample was measured to be only 0.53kOe.

[0062] The magnetic properties of the examples and comparative examples are compared in Table 1.

[0063]

[0064]

[0065] Although the specific embodiments of the present invention have been described, it will be apparent to those skilled in the art that other various changes and modifications may be made thereto without departing from the spirit and scope of the present invention. Therefore, the appended claims are intended to cover all these changes and modifications falling within the scope of protection of the present invention.

Claims

1. A method for preparing a Pr-Fe-(C, B) rare earth permanent magnetic material, characterized in that: Pr-Fe-(C,B) rare earth permanent magnet material is composed of substances having the following atomic percentage composition: Pr 15 Fe 79 (C 1-x ,B x )6, and no α-Fe soft magnetic impurity phase; wherein 0.2<x≤0.8; The preparation method comprises the following steps: S1. Weigh each component according to the general formula shown in Formula 1 for batching, wherein the mass of Pr is increased by 1 to 5% based on the theoretical mass of Pr calculated according to Formula 1; S2. The raw materials weighed in S1 are smelted to obtain an ingot; S3. The ingot is crushed and the melt is rapidly quenched to obtain a rapidly quenched strip; S4. The quenched strip is sequentially annealed and quenched to obtain a Pr-Fe-(C, B) rare earth permanent magnet material; The preparation process of the rapid quenching belt in S3 is as follows: the ingot obtained in S2 is crushed and loaded into a quartz tube of a melt rapid quenching furnace, the nozzle diameter at the bottom of the quartz tube is 0.5-2 mm, and the bottom of the quartz tube is 2-6 mm away from the copper roller; the cavity of the melt rapid quenching furnace is evacuated to a vacuum degree of 2×10 -4 ~9×10 -4 Pa; then fill the cavity with argon gas to make the pressure difference between the inside and outside of the cavity reach 60-90 kPa; turn on the heating power supply to melt the ingot in the quartz tube, open and adjust the speed of the copper roller; use the spray casting device in the furnace to spray the alloy melt onto the rotating copper roller to obtain a quick-quenching strip; S3 The quick-quenching strip is carried out in a melt quick-quenching furnace, and the speed of the copper roller is 30-40 m / s during the melt quick-quenching process; The quenching method in S4 is ice water quenching; The annealing equipment described in S4 is a short-time annealing device based on a muffle furnace, which consists of a quartz tube with one end open and the other end closed, a quartz gas guide tube, a gas guide hose, and a bottle of argon gas. The device realizes annealing of the sample under argon protection, and at the same time, realizes rapid quenching under argon protection; The annealing process in S4 is as follows: placing the quick-quenching tape obtained in S3 into a cylinder made of tantalum sheet with one end closed and the other end open; introducing argon gas into the quartz tube in the muffle furnace, and maintaining the gas flow rate at 5-15 l / min; then, placing the tantalum sheet cylinder loaded with the quick-quenching tape at the mouth of the quartz tube for pre-blowing argon gas for 10 minutes, and then placing the tantalum sheet cylinder loaded with the quick-quenching tape at the furnace zinc position in the quartz tube for annealing; The annealing temperature in S4 is 600-1000° C., and the annealing time is 0.5-2 h.

2. The preparation method according to claim 1, characterized in that: The ingot preparation process is as follows: the raw materials weighed in S1 are placed in a high-frequency suspension melting furnace, and the vacuum in the furnace is at least 5×10 -2 Pa; then, argon gas is introduced until the pressure in the furnace is 30-80 kPa; the power of the smelting furnace is turned on, the raw materials are melted, and then the power is turned off and poured into a water-cooled copper crucible for standby use.

3. The preparation method according to claim 1, characterized in that: The annealing process is carried out under argon protection.

Images