CN115287503B - Aluminum-beryllium intermediate alloy and preparation method thereof - Google Patents

Aluminum-beryllium intermediate alloy and preparation method thereof Download PDF

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CN115287503B
CN115287503B CN202210964985.4A CN202210964985A CN115287503B CN 115287503 B CN115287503 B CN 115287503B CN 202210964985 A CN202210964985 A CN 202210964985A CN 115287503 B CN115287503 B CN 115287503B
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aluminum
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tin
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CN115287503A (en
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徐小峰
程龙
姜朋飞
秦明升
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Shanghai Taiyang Technology Co ltd
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C21/00Alloys based on aluminium
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    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04Influencing the temperature of the metal, e.g. by heating or cooling the mould
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/06Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to an aluminum-beryllium intermediate alloy and a preparation method thereof, wherein the raw materials of the aluminum-beryllium intermediate alloy comprise 0.05-0.4 part by weight of tin, 0.05-0.3 part by weight of zinc, 1-5 parts by weight of beryllium and 93-98 parts by weight of aluminum. The aluminum-beryllium intermediate alloy is obtained by firstly uniformly mixing a beryllium-tin-zinc mixed melt with an aluminum melt, naturally cooling the mixture, and rapidly cooling the mixture to room temperature when the temperature of the melt is reduced to 850-900 ℃. According to the invention, a small amount of tin and zinc are doped into the beryllium melt, the uniformly mixed beryllium-tin-zinc mixed melt is obtained under the combined action, and the addition of the tin and the zinc reduces the melting temperature of the mixed melt, so that the tin and the zinc can be better and more uniformly mixed with the aluminum melt. The invention also adopts a two-stage cooling process of natural cooling and rapid cooling, reduces the segregation of beryllium, and ensures that the aluminum-beryllium intermediate alloy shows excellent mechanical property and stress relaxation resistance.

Description

Aluminum-beryllium intermediate alloy and preparation method thereof
Technical Field
The invention belongs to the field of alloys, and particularly relates to an aluminum-beryllium intermediate alloy and a preparation method thereof.
Background
The intermediate alloy is an additive functional material, which is prepared by adding one or more simple substances into a metal serving as a matrix to solve the problems of easy burning loss, difficult melting of high melting point, high density, easy segregation and the like of the simple substances of the metal or improve the performance of the alloy.
The Al-base intermediate alloy is an additive product for regulating the components of molten Al, and is prepared through smelting some metal elements with relatively high smelting temperature to produce intermediate with Al, and the intermediate has obviously lowered smelting temperature, so that some metal elements with relatively high smelting temperature may be added into molten Al at relatively low temperature to regulate the element content in molten Al. The aluminum beryllium can obviously improve the organizational structure of the alloy, refine crystal grains, increase the strength and improve the cleanness, the fluidity and the corrosion resistance of aluminum or magnesium.
The aluminum-beryllium alloy is divided into beryllium-based aluminum alloy and aluminum-based beryllium alloy according to the content of beryllium in the aluminum-beryllium alloy, wherein the aluminum-based beryllium alloy with low beryllium content is called aluminum-beryllium alloy, and the aluminum-beryllium intermediate alloy with the beryllium content lower than 5% is called aluminum-beryllium intermediate alloy and is generally used as an additive material of other alloy materials. The Al-Be-1, al-Be-3 and Al-Be-5 are generally commercialized, wherein the beryllium content is respectively 0.9-1.2%,2-4% and 4-6%, and aluminum-beryllium intermediate alloys with different beryllium contents can Be selected according to different requirements. The aluminum-beryllium intermediate alloy is mainly suitable for smelting aluminum alloy and magnesium alloy, can improve the cleanness, the flowability and the corrosion resistance of magnesium and aluminum, protect the oxidation and the combustion of the magnesium and the aluminum, reduce the oxidation loss of elements, improve the organizational structure of the alloy, refine crystal grains and increase the strength.
In the prior art, the preparation process of the aluminum-beryllium intermediate alloy is mainly obtained by melting and mixing a beryllium melt and an aluminum melt in a furnace under the action of a protective agent or a protective atmosphere. However, the difference between the melting points of beryllium and aluminum is large, with beryllium melting at 1280 ℃ and aluminum melting at 660 ℃. Furthermore, as can be seen from the phase diagram of beryllium aluminum, the alloy is actually subjected to eutectic reaction at about 650 ℃, and is not a pure phase material. The melting time and the solidification time have influence on the performance of the aluminum-beryllium intermediate alloy. After the melting point of aluminum is exceeded, the longer the smelting time is, the higher the content of aluminum oxide is, the formation of metal oxide slag inclusion can influence the performance of the aluminum-beryllium intermediate alloy as an additive, and the compactness, the ductility and the hardness of the alloy are reduced. However, if the smelting time is too short, beryllium particles in the aluminum-beryllium intermediate alloy are uneven in size, and the defects of micro pores can be accompanied, so that the performance of the alloy is influenced. When the solidification time is too short, anisotropic coarse particles or flaky structures can appear, and the defects of micro pores can also be generated; if the solidification time is too long, two phases of beryllium and aluminum can be separated, and phenomena of dendrite and segregation can be generated, so that the performance is deteriorated, and even the product cannot be used.
Therefore, it is highly desirable to develop a new method for preparing an aluminum-beryllium intermediate alloy, which reduces dendrites and segregation phenomena in the preparation process, reduces slag inclusions of oxides in the intermediate alloy, and improves the dispersion condition of beryllium in the aluminum matrix, so as to improve the performance of the aluminum-beryllium intermediate alloy as an additive in the preparation of other aluminum alloys.
CN202010477768.3 discloses a method for preparing aluminum beryllium alloy powder, in which an aluminum source is melted to form a liquid film by an arc method in a vacuum environment, and the liquid film is broken by centrifugal force.
CN201610754243.3 discloses a low beryllium aluminum alloy and a preparation method thereof, which comprises 1-5wt% of beryllium, 93-98wt% of aluminum intermediate alloy and 0.1-2wt% of other trace elements. The low beryllium aluminum alloy is obtained by adjusting the types and the proportions of trace elements and quenching by cooling water. It is quenched directly with cooling water and coarse particles or micro-porosity occurs which leads to deterioration of alloy properties, and thus the toughness of the master alloy obtained by the patented method is insufficient.
CN202110965607.3 discloses a low-density high-modulus aluminum alloy, wherein beryllium accounts for 0.2-1.5%, li accounts for 2.5-3.5%, mn accounts for 1-3%, mg accounts for 0.05-2%, zr accounts for 0.05-0.15%, sc accounts for 0.05-0.15%, and the balance is aluminum. After casting and forming to obtain a cast ingot, annealing treatment, hot extrusion deformation, solid solution treatment and aging treatment are carried out to obtain the low-density high-modulus aluminum alloy. The casting and melting process is complex, and needs to be processed by different devices for many times, so that the operation cost and the operation difficulty of production enterprises are increased.
CN202110777069.5 discloses a method for preparing an aluminum beryllium intermediate alloy, wherein a vacuum furnace is not used in the method, an electric furnace is used for melting in a crucible, preheated metal beryllium is added into the deep part of aluminum liquid in batches, and the metal beryllium is melted in a rotating manner. However, the melting point of beryllium is as high as 1280 ℃, and metal beryllium preheated at 600 ℃ is added into aluminum liquid, and the temperature of the metal beryllium cannot be the melting point of beryllium, so that the patent method is doubtful to fail to obtain the aluminum-beryllium intermediate alloy.
CN20201143840.5 discloses a preparation method of magnesium-aluminum-beryllium intermediate alloy for casting addition, which comprises preheating pure aluminum, pure magnesium and metal beryllium, then adding 3/4 of the preheated pure aluminum, heating and melting to obtain aluminum liquid, overheating to high temperature, adding the preheated metal beryllium in batches and stirring, adding the rest pure aluminum after the metal beryllium is completely melted, and adding the preheated pure magnesium after the pure aluminum is completely melted. And refining and casting to obtain the magnesium-aluminum-beryllium intermediate alloy. But it does not explore the properties of the obtained master alloy.
CN201910196180.8 discloses a preparation method of an aluminum beryllium intermediate alloy wire rod, which comprises the steps of heating aluminum water to 730-750 ℃ under the condition of argon, adding aluminum beryllium 10 alloy, heating to 710-830 ℃, refining, and carrying out hot rolling to obtain the aluminum beryllium intermediate alloy with the beryllium content of 0.1-5%. The patent uses aluminum beryllium 10 alloy (Be content is about 10%) to replace beryllium, and avoids the defect caused by too large difference between melting points of aluminum and beryllium. However, the performance of the master alloy obtained in the patent still needs to be improved.
Aluminum beryllium intermediate alloys are commonly added to magnesium and aluminum alloys to reduce oxidation slag inclusions and to densify the magnesium or aluminum oxide film layer, but aluminum beryllium alloys have a much higher melting point than magnesium and aluminum, making processing difficult, and are themselves susceptible to oxidation during addition to the magnesium and aluminum melt, affecting the ductility and hardness of the product.
Disclosure of Invention
The invention aims to provide an aluminum-beryllium intermediate alloy and a preparation method thereof. Because the difference between the melting points of beryllium and aluminum is large, the conventional smelting method has phase separation in the solidification process, so that the metallic beryllium is not uniformly dispersed in the aluminum melt, and the phenomena of dendritic crystals and segregation are generated, thereby affecting the performance of the alloy. The invention can reduce the dendritic crystal and segregation phenomena caused by the difference of melting points by controlling the cooling speed; however, the cooling speed is too fast, and casting defects such as shrinkage cavities and the like appear in the alloy, so that the mechanical properties such as the tensile strength, the yield strength and the like of the alloy are obviously reduced. The invention firstly carries out a natural cooling process to fully eliminate the casting defects among the melts, and then carries out a rapid cooling process of liquid nitrogen to accelerate cooling and reduce the phenomena of dendrite and segregation, thereby finally obtaining the aluminum-beryllium intermediate alloy with excellent performance.
In order to achieve the purpose, the invention provides an aluminum-beryllium intermediate alloy, the raw materials of which comprise 0.05-0.4 weight part of tin, 0.05-0.3 weight part of zinc, 1-5 weight parts of beryllium and 93-98 weight parts of aluminum.
Tin is a metal with a relatively low melting point, and an alloy with a relatively low melting point can be obtained by utilizing the characteristic of tin, but only a mixed phase of beryllium and tin can be obtained according to a binary phase diagram of beryllium and tin. In order to avoid the large difference between the melting points of beryllium and aluminum, the inventor adds a certain amount of zinc into the beryllium-tin melt, so that the beryllium-tin-zinc mixed melt can be fully and uniformly dispersed to obtain a relatively uniform single phase.
Furthermore, the aluminum-beryllium intermediate alloy comprises, by weight, 0.1-0.2 part of tin, 0.2-0.4 part of zinc, 1-5 parts of beryllium, 93-98 parts of aluminum and less than or equal to 0.3 part of other components.
Further, the aluminum-beryllium intermediate alloy is prepared by uniformly mixing a beryllium, tin and zinc mixed melt and an aluminum melt to obtain a mixed melt.
Furthermore, the mixed melt cooling is a cooling stage of natural cooling-rapid cooling.
The aluminum-beryllium intermediate alloy also contains other components with the weight percent less than or equal to 0.3 percent; the other components, such as impurity elements of iron, silicon, copper, nickel, etc., are impurities inevitably introduced into the raw material.
The second purpose of the invention is to provide a preparation method of the aluminum-beryllium intermediate alloy, which comprises the following steps:
(S1) heating beryllium in specified parts by mass in a smelting furnace until the beryllium is molten, adding tin powder and zinc powder in specified parts by mass in batches under the condition of stirring, and obtaining a beryllium-tin-zinc mixed melt after all metals are molten after the addition;
(S2) heating the aluminum with the specified mass part to be molten to obtain an aluminum melt, and heating the aluminum melt to 1100-1200 ℃;
(S3) slowly adding the beryllium-tin-zinc mixed melt obtained in the step (S1) into the aluminum melt obtained in the step (S2), stirring all the time, completely melting at 1100-1200 ℃, removing surface scum, adding a refining agent, and refining for 3-5 hours under heat preservation to obtain a mixed melt;
and (S4) adding the mixed melt into a casting mold with a cooling device, naturally cooling, starting the cooling device to enable the cooling rate to be 60-100 ℃/min when the melt is cooled to 850-900 ℃, and rapidly cooling to room temperature to obtain the aluminum-beryllium intermediate alloy.
The rapid cooling is realized by a cavity circulating cooling device of the casting mold, and the cooling medium is liquid nitrogen and can provide a cooling rate of 60-100 ℃/min. The invention adopts natural cooling firstly, fully eliminates the casting defects among the melts at a relatively slow cooling rate and inhibits discontinuous precipitation; when the temperature is cooled to 850-900 ℃, the cooling is changed into rapid cooling, which is beneficial to reducing the segregation of beryllium. However, the cooling rate should not be too fast, which may result in destruction of the micro-crystalline phases in the alloy and thus in poor mechanical properties.
Further, in the step (S3), the refining agent is hexachloroethane and is added in an amount of 0.1 to 1wt% of the total mixed melt (the sum of the beryllium-tin-zinc mixed melt and the aluminum melt).
Further, steps (S1) to (S4) are performed under an inert atmosphere, which is one or a mixed gas of argon and nitrogen.
Furthermore, the metal materials used, i.e., metallic beryllium, metallic tin, metallic zinc, and metallic aluminum, need to be subjected to removal of impurities such as oxides on the surface before they are melted by heating.
Compared with the prior art, the invention achieves the following technical progress:
1. according to the invention, a small amount of tin and zinc are doped into the beryllium melt, the uniformly mixed beryllium-tin-zinc mixed melt is obtained under the combined action, the tin and the zinc are added, the mixed melt and the melting temperature are reduced, the aluminum melt can be better and more uniformly mixed, and the aluminum-beryllium intermediate alloy is prepared by cooling.
2. In the preparation process, a two-stage cooling process of natural cooling and rapid cooling is adopted, and the cooling rate of rapid cooling is screened by the time for starting rapid cooling, so that the segregation of beryllium is reduced, and the aluminum-beryllium intermediate alloy has excellent stress relaxation resistance.
Drawings
FIG. 1 is a photograph of an aluminum beryllium master alloy ingot obtained in example 1.
Detailed Description
Example 1
(S1) heating 5 parts by mass of beryllium in a smelting furnace until the beryllium is molten, adding 0.2 part by mass of tin powder and 0.2 part by mass of zinc powder in three batches under the condition of stirring, and obtaining a mixed melt of the beryllium, the tin and the zinc after all metals are molten;
(S2) heating 95 parts by mass of aluminum ingot to be molten to obtain an aluminum melt, and heating the aluminum melt to 1100 ℃;
(S3) slowly adding the beryllium, tin and zinc mixed melt obtained in the step (S1) into the aluminum melt obtained in the step (S2), stirring all the time, completely melting at 1100 ℃, removing surface scum, and refining for 5 hours in a heat preservation manner to obtain a mixed melt;
and (S4) adding the mixed melt into a casting mold with a cavity circulating cooling device, naturally cooling, starting a liquid nitrogen circulating cooling device to enable the cooling rate to be 60 ℃/min when the temperature of the melt is reduced to 850 ℃, and rapidly cooling to room temperature to obtain the aluminum-beryllium intermediate alloy.
The chemical components and impurities of the aluminum-beryllium intermediate alloy are tested according to the GB/T20975 specification, in order to test the segregation condition of the aluminum-beryllium intermediate alloy, 3 samples are respectively taken in each area of an obtained alloy ingot in a central area, an upper layer, a lower layer, two outer sides and five areas in total, the content of Be elements is tested, the average value is calculated, the difference value between the highest value and the lowest value of the content of Be elements in the five areas is calculated, and the obtained result is shown in the following table 1:
TABLE 1 analysis of Al-Be intermediate alloy composition
Figure BDA0003794497700000052
Example 2
Other conditions and operations were the same as in example 1 except that 0.1 part by mass of tin powder and 0.3 part by mass of zinc powder were added. The chemical composition of the aluminum-beryllium intermediate alloy prepared in example 2 was tested, and the results are shown in table 2 below:
TABLE 2 analysis of Al-Be intermediate alloy composition
Figure BDA0003794497700000051
Example 3
The other conditions and operations were the same as in example 1 except that 0.15 parts by mass of tin powder and 0.25 parts by mass of zinc powder were added. The chemical components of the aluminum-beryllium intermediate alloy prepared in example 3 are tested, and the results are shown in the following table 3:
TABLE 3 analysis of Al-Be intermediate alloy composition
Figure BDA0003794497700000061
Example 4
The other conditions and operations were the same as in example 1 except that in (S4), when the melt was cooled to 900 ℃, the liquid nitrogen circulation cooling device was turned on to reduce the temperature at a rate of 100 ℃/min, and the results are shown in the following table, 4:
TABLE 4 analysis of Al-Be intermediate alloy composition
Figure BDA0003794497700000062
Comparative example 1
The other conditions and operations were the same as in example 1 except that 0.4 part by mass of tin powder was added and no zinc powder was added. The chemical components of the aluminum-beryllium intermediate alloy prepared in the comparative example 1 are tested, and the results are shown in the following table 5:
TABLE 5 analysis of Al-Be intermediate alloy composition
Figure BDA0003794497700000063
Comparative example 2
The other conditions and operations were the same as in example 1 except that 0.4 parts by mass of zinc powder was added and no tin powder was added. The chemical composition of the aluminum-beryllium intermediate alloy prepared in the comparative example 2 is tested, and the results are shown in the following table 6:
TABLE 6 analysis of Al-Be intermediate alloy composition
Figure BDA0003794497700000071
Comparative example 3
The other conditions and operations are the same as those in example 1, except that in step (S4), the mixed melt is added to a mold, and natural cooling is performed to cool the mixed melt to room temperature, thereby obtaining an aluminum-beryllium intermediate alloy. Namely, the liquid nitrogen is not cooled rapidly. The chemical components of the aluminum-beryllium intermediate alloy prepared in the comparative example 3 are tested, and the results are shown in the following table 7:
TABLE 7 analysis of Al-Be intermediate alloy composition
Figure BDA0003794497700000072
Comparative example 4
And the other conditions and operations are the same as those in the example 1, except that in the step (S4), the mixed melt is added into a casting mold with a cavity circulating cooling device, the liquid nitrogen circulating cooling device is started to reduce the temperature at a rate of 60 ℃/min, and the aluminum-beryllium intermediate alloy is rapidly cooled to room temperature. Namely, air cooling is not carried out.
The chemical components of the aluminum-beryllium intermediate alloy prepared in the comparative example 4 are tested, and the results are shown in the following table 8:
TABLE 8 analysis of Al-Be intermediate alloy composition
Figure BDA0003794497700000073
Application example
The following performance tests were performed on the aluminum beryllium master alloys obtained in the above examples and comparative examples, and the results are shown in table 9 below:
tensile strength: the tests were carried out according to the standard GB/T228.1-2010.
Yield strength: the test was carried out according to the standard GB/T228.1-2010.
Stress relaxation resistance: the stress is 800MPa, the initial stress and the residual stress after 100 hours are tested after the stress of the test alloy is relaxed for 100 hours at 250 ℃, and the stress is calculated according to the following formula:
Figure BDA0003794497700000081
wherein sigma 0 Denotes the initial stress, σ t The residual stress after t time (100 h) was shown. The smaller the relaxation rate, the better the stress relaxation resistance of the alloy.
TABLE 9 test of Al-Be intermediate alloy Properties
Figure BDA0003794497700000082
It can be seen that the aluminum-beryllium intermediate alloy obtained by the invention has excellent comprehensive performance, less beryllium segregation phenomenon, high mechanical strength and excellent stress relaxation resistance.

Claims (5)

1. The aluminum-beryllium intermediate alloy is characterized by comprising the following raw materials: 0.1-0.2 part of tin, 0.2-0.3 part of zinc, 1-5 parts of beryllium, 93-98 parts of aluminum and less than or equal to 0.3 part of other components, wherein the other components are at least one of iron, silicon, copper and nickel;
the aluminum-beryllium intermediate alloy is prepared by doping tin and zinc into a beryllium melt, obtaining a uniformly mixed beryllium-tin-zinc mixed melt under the combined action, uniformly mixing the uniformly mixed beryllium-tin-zinc mixed melt with an aluminum melt, and preparing the aluminum-beryllium intermediate alloy by adopting a two-stage cooling process of natural cooling and rapid cooling;
the two-stage cooling process of natural cooling and rapid cooling comprises the steps of firstly, naturally cooling and cooling, and rapidly cooling to room temperature when the temperature of a melt is reduced to 850-900 ℃; the rapid cooling is realized by a cavity circulating cooling device of the casting mold, the cooling medium is liquid nitrogen, and the cooling rate of the rapid cooling is 60-100 ℃/min.
2. The method for preparing the aluminum-beryllium intermediate alloy as set forth in claim 1, which comprises the following steps:
(S1) heating beryllium in specified mass parts to be molten in a smelting furnace, adding tin powder and zinc powder in specified mass parts in batches under the stirring condition, and obtaining beryllium-tin-zinc mixed melt after all metals are molten after the addition;
(S2) heating the aluminum with the specified mass part to be molten to obtain an aluminum melt, and heating the aluminum melt to 1100-1200 ℃;
(S3) slowly adding the beryllium, tin and zinc mixed melt obtained in the step (S1) into the aluminum melt obtained in the step (S2), stirring all the time, completely melting at 1100-1200 ℃, removing surface scum, adding a refining agent, and refining for 3-5 hours under heat preservation to obtain a mixed melt;
and (S4) adding the mixed melt into a casting mold with a cooling device, naturally cooling to reduce the temperature, and rapidly cooling to room temperature when the temperature of the melt is reduced to 850-900 ℃ to obtain the aluminum-beryllium intermediate alloy.
3. The method according to claim 2, wherein in the step (S3), the refining agent is hexachloroethane and is added in an amount of 0.1 to 1wt% based on the sum of the beryllium-tin-zinc mixed melt and the aluminum melt.
4. The method according to claim 2, wherein each of steps (S1) to (S4) is performed under an inert atmosphere, and the inert atmosphere is one or a mixture of argon and nitrogen.
5. The method according to claim 2, wherein the metallic material is beryllium, tin, zinc, or aluminum, and the oxide impurities on the surface are removed before the melting.
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