TWI540210B - Ternary-alloy metallic glass and method for making the same - Google Patents

Description

Ternary alloy metal glass and manufacturing method thereof

The invention relates to a metallic glass alloy, in particular to a ternary alloy metallic glass composed of copper/zirconium/aluminum and a manufacturing method thereof, which is compared with a conventional metallic material and a conventional alloy metallic glass. / Aluminum ternary alloy metal glass system exhibits high strength, wear resistance, corrosion resistance, and good mechanical properties.

At present, metal, ceramic and polymer materials are widely used in people's food, clothing, housing, and travel, and metal materials are the most widely used. Compared with polymers or composite materials, metal materials have better fatigue resistance and creep resistance, and metal materials have a long history of research, so metal materials are widely used because of their mature technology. In a variety of industrial and commercial products. However, due to the fact that the metal materials used in the past are mostly crystalline structures and have limited ductility, they cannot meet the needs of specific industries, such as aerospace industry.

Unlike crystalline structural metals, amorphous metals (also known as metallic glasses) have excellent mechanical properties such as high strength, high hardness, and good corrosion resistance. Therefore, the material composition and manufacturing method of metallic glass Gradually become the key to development. Among them, bulk metallic glass (BMG) is one of the most popular amorphous metal materials due to its advantages of easy process and low cost.

For example, pure copper is too soft to process, but copper alloys containing elements such as tin, aluminum, bismuth, and nickel are easy to process and can be used for copper metal applications. Taking a copper alloy containing cobalt, nickel and bismuth as an example, the copper alloy is composed of 1 wt% to 2.5 wt% of nickel (Ni), 0.5 wt% to 2.0 wt% of cobalt (Co), and 0.5 wt% to 1.5 wt%. The bismuth (Si), the balance of copper, and the inevitable impurities. Wherein, since the ratio of (Ni+Co):Si is between 2:1 and 7:1, the copper alloy has electrical conductivity of more than 40% IACS, and is mainly suitable for miniaturization, high strength and high Conductive metal products have special needs in the automotive and multimedia industries. Further, as apparent from the above, the copper alloy containing cobalt, nickel and bismuth mainly uses metal products of miniaturization, high strength and high electrical conductivity, so that the application range is small and it is difficult to be applied to the high-tech threshold technology industry.

Another conventional metal alloy material is a copper/zinc/bismuth alloy, which comprises 70 wt% to 80 wt% of copper, 1 wt% to 5 wt% of niobium, 0.0001 wt% to 0.5 wt% of boron, and 0 wt% to 0.2 wt%. Phosphorus or arsenic. The copper/zinc/bismuth alloy has the property of reforming uniformity and can be processed into contact points of a motor device, a recyclable component and a drop forged component; however, since the zinc alloy is high in brittleness and low in ductility, This copper/zinc/bismuth alloy is not suitable for use in sophisticated military machinery, high-tech and nanomedicine products.

Therefore, it can be seen from the above that although the various metal alloys described above have their advantages and applications, respectively, these metal alloys still have disadvantages and disadvantages, that is, they cannot be applied to aerospace industry, military machinery, high-tech industries, and nanomedicine. In view of this, the inventors of the present invention have vigorously studied and finally developed a ternary alloy metallic glass of the present invention and a manufacturing method thereof, because the metallic glass of the ternary alloy has high strength and wear resistance. Special magnetic properties, corrosion resistance and good mechanical properties, so it can replace the current metal alloys, and then used in aerospace industry, military machinery, high-tech industries, and nanomedicine industry.

The main object of the present invention is to provide a ternary alloy metallic glass and a manufacturing method thereof, wherein the ternary alloy metallic glass system of the present invention exhibits high strength, compared with the conventional metallic material and the conventional alloy metallic glass. Wear resistance, corrosion resistance, and good mechanical properties can be processed into precision instruments, machinery or components for use in military, high-tech products, and nanomedicine industries.

Therefore, in order to achieve the above object of the present invention, the inventors of the present invention have proposed a ternary alloy metallic glass comprising: a first metallic material selected from any one of the following groups: copper (Cu), Zirconium (Zr), aluminum (Al), nickel (Ni), iron (Fe), and silver (Ag); a second metal material selected from any of the following groups: copper (Cu), zirconium (Zr), aluminum (Al), nickel (Ni), iron (Fe), and silver (Ag); a third metal material selected from the group consisting of copper (Cu), zirconium (Zr), aluminum (Al), nickel (Ni), iron (Fe), and silver (Ag); The first metal material, the second metal material and the third metal material are formed into a metal glass of the ternary alloy by an arc melting furnace and a copper mold cooling method; and wherein the first metal material is The atomic percentage in the metallic glass of the ternary alloy is between 40 at% and 47.5 at%, and the atomic percentage of the second metal material in the metallic glass of the ternary alloy is between 45 at% and 50 at% The atomic percentage of the third metal material in the metallic glass of the ternary alloy is between 5 at% and 10 at%.

In addition, in order to achieve the above object of the present invention, the inventors of the present invention have further proposed a method for producing a ternary alloy metallic glass, which comprises the following steps: (1) preparing 40 at% to 47.5 at% of copper, 45 at% to 50 at % zirconium and 5at% to 10at% aluminum, and the three metals are sequentially arranged according to the melting point; (2) the product obtained in the above step (1) is placed in an arc melting furnace for smelting, and then Copper, zirconium and aluminum are smelted into an alloy ingot; (3) a pure copper mold is immersed in a liquid nitrogen, so that the temperature of the pure copper mold reaches a first specific low temperature; (4) the pure copper mold is taken out, and then And sequentially placing a copper gasket and the alloy ingot on the pure copper mold; (5) placing the product of the foregoing step (4) into the arc melting furnace, connecting a pumping pump and a cooling device to the bottom of the pure copper mold, and then vacuuming the pure copper mold with a specific vacuuming time. At the same time, an ice water machine is used to control the temperature of the cooling device to be maintained at a second specific low temperature; (6) the alloy ingot is smelted to become a melt under the operation of the pumping pump and the cooling device; a metal alloy to flow into the pure copper mold; and (7) rapidly cooling the molten metal alloy to produce a ternary alloy metallic glass.

<present invention>

S01~S07‧‧‧ method steps

S021~S026‧‧‧ method steps

1‧‧‧Pure copper mould

11‧‧‧Pure copper column

2‧‧‧ button alloy ingots

21‧‧‧ copper gasket

3‧‧‧Cooling device

4‧‧‧Exhaust pump

The first drawing is a flow chart of a method for manufacturing a ternary alloy metallic glass according to the present invention; the second drawing A and the second B are a structural schematic view of a pure copper mold which is applied to a method for manufacturing a ternary alloy metallic glass; The third figure is a detailed step flow chart of the step (S02); the fourth A picture is a backscattered electron image of the ternary alloy metallic glass; the fourth B is the X-ray diffraction of the ternary alloy metallic glass Figure 5; Figure 5 is a backscattered electron image of a ternary alloy of metallic glass; Figure 5B is an X-ray diffraction pattern of a ternary alloy of metallic glass; and the sixth figure is a ternary alloy metallic glass The DSC curve; and the seventh figure is the amorphous region composition diagram of the Cu/Zr/Al ternary alloy.

In order to more clearly describe a ternary alloy metallic glass and a method of manufacturing the same according to the present invention, a preferred embodiment of the present invention will be described in detail below with reference to the drawings.

A ternary alloy metallic glass according to the present invention is produced by a first metal material, a second metal material and a third metal material passing through an arc melting furnace and a copper mold cooling method. In the present invention, the first metal material, the second metal material and the third metal material may be copper (Cu), zirconium (Zr), aluminum (Al), nickel (Ni), iron (Fe), Or any of silver (Ag). Preferably, the present invention is a copper metal (Cu) having an atomic percentage of between 40 at% and 47.5 at%, a zirconium metal (Zr) having an atomic percentage of between 45 at% and 50 at%, and an atomic percentage system. Aluminum metal (Al) between 5 at% and 10 at% is used to make the ternary alloy metallic glass. Here, it must be particularly noted that the purity of the selected copper metal, zirconium metal and silver metal is at least 99.99%.

According to the above description, the copper-based metallic glass has the characteristics of high strength and high hardness, and the plastic deformation can reach more than 1%; and the aluminum element is easy to obtain and has better ductility; further, the zirconium-based metallic glass It has excellent corrosion resistance and a wide subcooled liquid region. Therefore, compared with the conventional metal material and the conventional alloy metallic glass, the metallic glass system of the ternary alloy of the present invention exhibits high strength and wear resistance. Good corrosion resistance, etc. Mechanical properties. Furthermore, since the zirconium-based metallic glass has a broad supercooled liquid region, the copper/zirconium/aluminum trimetal is easy to form the metallic glass of the ternary alloy, thereby improving the simplicity of the process.

The composition and characteristics of the metallic glass of the ternary alloy of the present invention have been fully described in the above description. Next, the manufacturing method of the ternary alloy metallic glass proposed by the present invention will be further described hereinafter. It is a flow chart of a method for manufacturing a ternary alloy metallic glass according to the present invention; at the same time, please refer to the second A diagram and the second B diagram, which is applied to one of the manufacturing methods of the ternary alloy metallic glass. Schematic diagram of the mold. As shown in FIG. 2A and FIG. 2B, the pure copper mold 1 used in the manufacturing method of the present invention is internally provided with a hollow copper pillar 11 which is hollow, and the pure copper pillar 11 has a diameter of 1 mm to 5 mm. The specific inner diameter between. Further, the copper spacer 21 for carrying the button-shaped alloy ingot 2 is designed to have a hollow center. Further, in particular, in the method of the present invention, a cooling device 3 and an evacuation pump 4 are provided at the bottom of the pure copper mold 1.

After the basic introduction of the process equipment is completed, the following describes the manufacturing method of the ternary alloy metallic glass of the present invention; as shown in the first figure, the manufacturing method of the ternary alloy metallic glass of the present invention includes the following steps: The method performs the step (S01) of preparing 40 at% to 47.5 at% of copper, 45 at% to 50 at% of zirconium, and 5 at% to 10 at% of aluminum, and sequentially arranging the three metals according to the melting point. Next, the step (S02) is performed, and the product obtained in the foregoing step (S01) is placed in an arc melting furnace for performing The smelting further melts three metals of copper, zirconium and aluminum into a button-shaped alloy ingot 2. As shown in the detailed step flow chart of the third figure, the step (S02) includes six detail steps as follows: in the detail step (S021), the product obtained in the foregoing step (S01) is placed. After the arc melting furnace, vacuum was applied for 5 minutes; and then step (S022) was carried out, and argon gas was introduced into the arc melting furnace for 5 minutes. Thereafter, the step (S023) is performed, and the steps (21) to (22) are repeatedly performed, which are repeated once in total. Continuing, steps (S024) and (S025) are performed, and three metals of copper, zirconium, and aluminum are smelted into the button alloy ingot 2 at a current of 150 to 250 amps, and the button alloy ingot 2 is turned over. Repeat to smelt it with a current of 150~250A. Finally, the step (S026) is performed, and the steps (S024) to (S025) are repeatedly performed for a total of four repetitions.

After completing all the detailed steps of the step (S02), the method of the present invention then performs the step (S03), immersing a pure copper mold 1 in a liquid nitrogen, so that the temperature of the pure copper mold 1 reaches -10 ° C to -15 ° C. The low temperature between. Next, the step (S04) is performed, the pure copper mold 1 is taken out, and then a copper gasket 21 and the button alloy ingot 2 are sequentially placed on the pure copper mold 1. Then, the step (S05) is performed, the product of the foregoing step (S04) is placed in the arc melting furnace, and a pumping pump 4 and a cooling device 3 are connected to the bottom of the pure copper mold 1, followed by the pure copper mold. 1 Vacuuming was performed for 1 minute; at the same time, the copper cooling device 3 was maintained at a low temperature of -20 ° C to -40 ° C by means of an ice water machine. Continuing, the method performs the step (S06), The button-shaped alloy ingot 2 is smelted by the pumping pump 4 and the cooling device 3 to be melted into a molten metal alloy to flow into the pure copper mold 1. Finally, the method performs the step (S07) to rapidly cool the molten metal alloy to produce a ternary alloyed metallic glass.

Thus, the metal glass of the ternary alloy proposed by the present invention and the method for producing the same have been fully described above, and in addition, in order to prove that the metallic glass of the ternary alloy produced by the manufacturing method of the present invention is indeed an amorphous alloy, the following will It is explained by multiple sets of experimental data. Please refer to the fourth A picture, which is a backscattered electron image of the ternary alloy metal glass; and, please refer to the fourth B picture, which is the X-ray diffraction pattern of the ternary alloy metallic glass (X-Ray). Diffraction, XRD). Among them, the ternary alloy metallic glass shown in the fourth A diagram and the fourth panel B is formed by an arc melting furnace and a copper mold cooling method, but the cooling device 3 is not attached to the bottom of the pure copper mold 1. From the backscattered electron image of Figure A, we can find that there is a clear crystal phase precipitation in the solidified structure of the ternary alloy; correspondingly, the XRD pattern of the fourth B graph also shows the winding of the crystalline phase. Shoot the peak.

Please continue to refer to Figure 5A, which is a backscattered electron image of a ternary alloy metallic glass; and, see also Figure 5B, an X-ray diffraction pattern of a ternary alloy metallic glass (X -Ray Diffraction, XRD). Among them, the ternary alloy metallic glass shown in the fifth A diagram and the fifth panel B is produced by an arc melting furnace and a copper mold cooling method, and a cooling device 3 is attached to the bottom of the pure copper mold 1. Backscattered electron image by Figure 5A As shown in the figure, we can find that there is no precipitation of any crystal phase in the solidified structure of the ternary alloy; correspondingly, the XRD pattern of the fifth B graph does not show any significant crystal phase diffraction peak.

Further, in the experimental procedure, the glass transition temperature and the recrystallization temperature of the metallic glass of the ternary alloy shown in FIG. 5A were analyzed by differential scanning calorimetry (DSC). As shown in the DSC graph of the ternary alloy metallic glass in Fig. 6, it can be found that the DSC thermal analysis curve shows a slight slope change at a temperature of 702.1 K, and an endothermic peak appears at 771.2 K; From this, it can be judged that the glass transition temperature (Tg) of the ternary alloy metallic glass is 447 °C. Therefore, it has been confirmed through experimental results that when the arc melting furnace and the copper mold cooling method are performed, if the cooling device 3 is installed at the bottom of the pure copper mold 1, the temperature of the cooling device 3 is controlled by the ice water machine at -20 ° C to At a very low temperature of -40 ° C, a ternary alloyed metallic glass of Cu _40-47.5 Zr _45-50 Al _5-10 can be successfully produced.

Finally, please refer to the seventh figure, which is the amorphous region composition diagram of the Cu/Zr/Al ternary alloy. As shown in the seventh figure, the Cu/Zr/Al ternary alloy having a composition area of Cu _40-47.5 Zr _45-50 Al _5-10 may be an amorphous metallic glass; and, judging by the supercooled liquid phase, The optimum composition of the Cu/Zr/Al ternary alloy to form the metallic glass is Cu ₄₀ Zr ₅₀ Al ₁₀ . In addition, it was found through experiments that the Cu/Zr/Al ternary alloy with Cu _50-52.5 Zr _40-42.5 Al _7.5-10 is an amorphous alloy, and the amorphous alloy is entrained with fine crystal particles, so Cu is judged. The /Zr/Al ternary alloy can form an amorphous and polycrystalline metal alloy in this region.

Thus, the metal glass of the ternary alloy of the present invention and the method for producing the same have been completely and clearly disclosed by the above detailed description, and it is understood from the above that the present invention has the following advantages:

1. The metallic glass of the ternary alloy of the present invention is composed of 40 to 47.5 at% of copper, 45 to 50 at% of zirconium, and 5 to 10 at% of aluminum; wherein copper-based metallic glass has high strength and high hardness. The characteristics of the plastic deformation can reach more than 1%; and the aluminum element is easy to obtain and has better ductility; further, the zirconium-based metallic glass has excellent corrosion resistance and a wide subcooled liquid region. Therefore, compared with the conventional metal material and the conventional alloy metallic glass, the metallic glass system of the ternary alloy of the present invention exhibits good mechanical properties such as high strength, wear resistance, corrosion resistance, etc., and thus is easily processed into precision. Instruments, machinery or components are used in military, high-tech products and industries such as nanomedicine.

2. In accordance with the above first aspect, in addition, in the manufacturing method of the present invention, the metal glass of the ternary alloy is mainly processed by an arc melting furnace and a copper mold cooling method; and, more particularly, the bottom of the pure copper mold is added. A cooling device is installed to control the temperature of the cooling device 3 through an ice water machine at an extremely low temperature between -20 ° C and -40 ° C, thereby successfully producing Cu _40-47.5 Zr _45-50 Al _{5 . -10} ternary alloyed metallic glass.

It must be emphasized that the above detailed description is for this The detailed description of the present invention is not intended to limit the scope of the invention, and the equivalents and modifications of the invention are intended to be included in the scope of the invention.

S01~S07‧‧‧ method steps

Claims (8)

A ternary alloy metal glass comprising: a first metal material, which is copper (Cu); a second metal material, which is zirconium (Zr); and a third metal material, which is aluminum (Al) Wherein the first metal material, the second metal material and the third metal material are formed into a metal glass of the ternary alloy by an arc melting furnace and a copper mold cooling method; wherein the first metal material is The atomic percentage in the metallic glass of the ternary alloy is between 40 at% and 47.5 at%, and the atomic percentage of the second metal material in the metallic glass of the ternary alloy is between 45 at% and 50 at% The atomic percentage of the third metal material in the metallic glass of the ternary alloy is between 5 at% and 10 at%. The metallic glass of the ternary alloy according to claim 1, wherein the first metal material, the second metal material and the third metal material have a purity of at least 99.99%. The metallic glass of the ternary alloy as described in claim 1 is obtained by the following manufacturing steps: (1) preparing 40 at% to 47.5 at% of copper, 45 at% to 50 at% of zirconium, and 5 at% to 10at% aluminum, and set sequentially according to the melting point The three metals; wherein, the purity of copper, zirconium and silver is at least 99.99%; (2) the product obtained in the above step (1) is placed in an arc melting furnace for smelting, and then three metals of copper, zirconium and aluminum Melting into an alloy ingot; (3) cooling a pure copper mold to a first specific low temperature; wherein the first specific low temperature system is between -10 ° C and -15 ° C; (4) taking out the pure copper mold, and then Sequentially placing a copper gasket and the alloy ingot on the pure copper mold; (5) placing the product of the foregoing step (4) into the arc melting furnace, and connecting a pumping pump and a cooling Device to the bottom of the pure copper mold, and then vacuuming the pure copper mold with a specific vacuum time; meanwhile, controlling the temperature of the cooling device to maintain a second specific low temperature by using an ice water machine; wherein the second specific low temperature system Between -20 ° C and -40 ° C; (6) under the operation of the pumping pump and the cooling device, the alloy ingot is smelted to become a molten metal alloy to flow into the pure copper mold And (7) rapidly cooling the molten metal alloy to produce the third Metallic glass alloy. A metallic glass of a ternary alloy as described in claim 3 of the patent application, The center of the copper gasket is hollow. The metal glass of the ternary alloy according to claim 3, wherein the pure copper mold has a hollow copper column penetrating inside, and the hollow copper column has a specific inner diameter; and, the specific inner portion The diameter is between 1mm and 5mm. The metal glass of the ternary alloy according to claim 3, wherein the step (2) further comprises the following detailed steps: (21) after the product obtained in the foregoing step (1) is placed in the arc melting furnace , vacuuming for 5 minutes; (22) introducing argon into the arc melting furnace for 5 minutes; (23) repeating steps (21) to (22), repeating once; (24) to 150~ 250 amps of current smelting three metals of copper, zirconium and aluminum into the alloy ingot; (25) turning the alloy ingot and repeating it to smelt at a current of 150 to 250 A; and (26) repeating the step (24) To step (25), repeat a total of four times. The metallic glass of the ternary alloy according to claim 3, wherein in the aforementioned step (5), the specific vacuuming time is 1 minute. The metallic glass of the ternary alloy according to claim 3, wherein the cooling device is a copper device.