US20140144554A1

US20140144554A1 - Ternary-Alloy Metallic Glass and Method for Making the Same

Info

Publication number: US20140144554A1
Application number: US13/684,246
Authority: US
Inventors: Yee-Wen Yen; Bo-jyun Chen
Original assignee: National Taiwan University of Science and Technology NTUST
Current assignee: National Taiwan University of Science and Technology NTUST
Priority date: 2012-11-23
Filing date: 2012-11-23
Publication date: 2014-05-29

Abstract

The present invention relates to a ternary-alloy metallic glass and a method for making the same, wherein the ternary-alloy metallic glass is a Cu/Zr/Ag ternary-alloy metallic glass. Comparing to the traditional metal and current conventional alloy metallic glass, the Cu/Zr/Ag ternary-alloy metallic glass performs good mechanical properties of high strength, well wear and corrosion resistance, and capable of being processed to precision instruments, machinery or components for further applying to military, high-tech products, as well as nano medical industries. Moreover, the wide supercooled liquid region of Zr-based metallic glass not only facilitates the three metals of Cu, Zr and Ag capable of being fabricated to the ternary-alloy metallic glass easily, but also makes the manufacturing process of the Cu/Zr/Ag ternary-alloy metallic glass become simple and convenient.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention
The present invention relates to a metallic glass alloy, and more particularly to a ternary-alloy metallic glass and a method for making the same; comparing to the traditional metal and current conventional alloy metallic glass, the ternary-alloy metallic glass shows performs good mechanical properties of high strength, well wear and corrosion resistance.
2. Description of the Prior Art
Metals, ceramics and polymer materials are currently widely applied in clothes, foods, shelters, and transportations of people life, wherein the metal materials further include the highest application. Comparing to polymer or composite materials, metal materials show better fatigue resistance and creep resistance; besides, because people have been studied metal materials for a very long time, they have sufficient experience for utilizing and processing the metal materials to various industrial and commercial products. However, metal materials still cannot meet the requirements of some specific industries due to their crystal structures and limited ductility, for example, aerospace industry.
Different from crystalline metals, amorphous metals (i.e., so-called metallic glass) include the excellent mechanical properties of high strength, high hardness, and well corrosion resistance, therefore the compositions and manufacturing method of the metallic glasses have been became an important issue; in which, because bulk metallic glass (BMG) has the advantages of simple manufacturing process and low cost, it becomes one of the most popular amorphous metal materials.
For instance, pure copper (Cu) is hard to be processed due to its over-soft property, but copper alloy having the elements of tin (Sn), aluminum (Al), silicon (Si), and nickel (Ni) can be processed to some specific products, so as to increase the application of copper. Herein taking a copper alloy having cobalt (Co), nickel (Ni) and silicon (Si) for example, this copper alloy consists of Ni having the weight percent of 1 wt %˜2.5 wt %, Co having the weight percent of 0.5 wt %˜2.0 wt %, Si having the weight percent of 0.5 wt %˜1.5 wt %, remaining copper, and some unavoidable impurity elements. This copper alloy includes above 40% IACS (International Annealing Copper Standard) conductivity because the ratio of (Ni+Co) and Si thereof is ranged between 2:1 and 7:1. Thus, this copper alloy can mainly applied in automobile and multimedia industry which demand high requirements on miniaturization, high strength and high conductivity of metal-made products. Accordingly, since the copper alloy having Co, Ni and Si is mainly applied in those metal-made products having miniaturization, high strength and high conductivity, it is able to know that this copper alloy includes an narrow application and is hard to be applied in the technology industries having high-tech threshold.
Another one metallic alloy is Cu/Zn/Si alloy, which consists of Cu having the weight percent of 70 wt %˜80 wt %, Si having the weight percent of 1 wt %˜5 wt %, B having the weight percent of 0.0001 wt %˜0.5 wt %, and P or As having the weight percent of 0 wt %˜0.2 wt %. This Cu/Zn/Si alloy has the properties of uniform reformation, so that it can be further processed to contact points of electrical device, recyclable components and drop forged components. However, resulting from that Zn alloy includes high fragility and low ductility, the Cu/Zn/Si alloy is unsuitable for being applied in precision industries, such as military, high-tech and nano medical products.
Thus, through above descriptions, it can know that although above-mentioned various metallic alloys have different advantages and related applications, however, these metallic alloys still have drawbacks and shortcomings and cannot be applied in aerospace, military, high-tech, and nano medical industries. For above reasons, the inventor of the present application has made great efforts to make inventive research thereon and eventually provided a ternary-alloy metallic glass and method for making the same.

SUMMARY OF THE INVENTION

The primary objective of the present invention is to provide a ternary-alloy metallic glass, which performs good mechanical properties of high strength, well wear and corrosion resistance comparing to the traditional metal and current conventional alloy metallic glass; therefore this ternary-alloy metallic glass can be processed to precision instruments, machinery or components for further applying to military, high-tech products, as well as nano medical industries.
Accordingly, to achieve the primary objective of the present invention, the inventors propose a ternary-alloy metallic glass, comprising a first metal material, a second metal material and a third metal material, wherein each of the first metal material, the second metal material and the third metal material have a specific composition ratio, and are further manufactured to the ternary-alloy metallic glass having high strength, wear resistance and corrosion resistance by using an arc smelting furnace and a copper mould formation; wherein the first metal material, the second metal material and the third metal material of the ternary-alloy metallic glass are selected from the group consisting of Cu, Zr, Ag, Ni, Fe, and Mg; moreover, the specific composition ratio of the first metal material is ranged from 35 at % to 50 at %, the specific composition ratio of the second metal material being ranged from 40 at % to 55 at %, and the specific composition ratio of the third metal material being ranged from 10 at % to 20 at %.
The another objective of the present invention is to provide a method for manufacturing ternary-alloy metallic glass, which is used for fabricating the ternary-alloy metallic glass under a complete processing flow; the method comprises the steps of:
(1) fabricating copper (Cu) having atomic percent ranged from 35 at % to 50 at %, zirconium (Zr) having atomic percent ranged from 40 at % to 55 at %, and silver (Ag) having atomic percent ranged from 10 at % to 20 at %, and then and then disposing the three metal materials by melting points level thereof.
(2) disposing the product obtained from the step (1) in an arc smelting furnace for smelting, so as to smelt the three metal materials of Cu, Zr and Ag to a ball-tablet shape alloy;
(3) soaking a pure copper mould in a liquid nitrogen for a specific soak time, and then disposing a copper gasket and the ball-tablet shape alloy on the pure copper mould after removing the pure copper mould from the liquid nitrogen;
(4) disposing the product obtained from the step (3) into the arc smelting furnace and connecting a vacuum pump to the bottom of the pure copper, and then evacuating the pure copper mould for a specific vacuum-pump time;
(5) smelting the ball-tablet shape alloy to a molten metal alloy, and making the molten metal alloy flow into the pure copper mould; and
(6) rapidly cooling the molten metal alloy, and then a ternary-alloy metallic glass is obtained.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention as well as a preferred mode of use and advantages thereof will be best understood by referring to the following detailed description of an illustrative embodiment in conjunction with the accompanying drawings, wherein:

FIG. 1 is a flowchart of a method for manufacturing ternary-alloy metallic glass according to the present invention;

FIG. 2 is a flowchart of the detailed steps of step (S02);

FIG. 3A and FIG. 3B are schematic structure diagrams of a pure copper mould used in the method for manufacturing ternary-alloy metallic glass;

FIG. 4 is a backscattered electron image (BEI) of a ternary-alloy metallic glass;

FIG. 5 is an X-ray diffraction image of the ternary-alloy metallic glass;

FIG. 6 is a DSC thermal analysis plot of the ternary-alloy metallic glass;

FIG. 7 is a DTA thermal analysis plot of the ternary-alloy metallic glass;

FIG. 8 is a transmission electron microscope image of the ternary-alloy metallic glass;

FIG. 9 is a thermal property analysis table of the ternary-alloy metallic glass; and

FIG. 10 is an amorphous composition region drawing of the ternary-alloy metallic glass.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

To more clearly describe a ternary-alloy metallic glass and a method for making the same according to the present invention, embodiments of the present invention will be described in detail with reference to the attached drawings hereinafter.
The ternary-alloy metallic glass of the present invention is made of Cu having the atomic percent of 35 at %˜50 at %, Zr having the atomic percent of 40 at %˜55 at %, and Ag having the atomic percent of 10 at %˜20 at %. Each of the three metal materials of Cu, Zr and Ag have a specific composition ratio, and the three metal materials are further manufactured to the ternary-alloy metallic glass having high strength, wear resistance and corrosion resistance by using an arc smelting furnace and a copper mould formation. In which, the specific composition ratio of Cu is ranged from 35 at % to 50 at %, the specific composition ratio of Zr is ranged from 40 at % to 55 at %, and the specific composition ratio of Ag is ranged from 10 at % to 20 at %.
Because Cu-based metallic glass performs high strength, high hardness and the plastic deformation greater than 1%, Ag shows better flowability and easy to be obtained, as well as Zr-based metallic glass includes high corrosion resistance and wide supercooled liquid region, the ternary-alloy metallic glass of the present invention performs good mechanical properties of high strength, well wear and corrosion resistance comparing to the traditional metal and current conventional alloy metallic glass. Besides, the wide supercooled liquid region of Zr-based metallic glass not only facilitates the three metals of Cu, Zr and Ag capable of being fabricated to the ternary-alloy metallic glass easily, but also makes the manufacturing process of the Cu/Zr/Ag ternary-alloy metallic glass become simple and convenient.
Thus, through above descriptions, the composition and property of the ternary-alloy metallic glass of the present invention have been completely introduced; next, the method for manufacturing ternary-alloy metallic glass will be described in follows. Please refer to FIG. 1, which illustrates a flowchart of the method for manufacturing ternary-alloy metallic glass according to the present invention; moreover, please simultaneously refer to FIG. 3A and FIG. 3B, there are schematic structure diagrams of a pure copper mould used in the method for manufacturing ternary-alloy metallic glass. As shown in FIG. 1, the ternary-alloy metallic glass manufacturing method includes the following steps.
The method is firstly proceeds to step (S01) for fabricating copper (Cu) having atomic percent of 35 at %˜50 at %, zirconium (Zr) having atomic percent of 40 at %˜55 at %, and silver (Ag) having atomic percent of 10 at %˜20 at %, and then disposing the three metal materials by melting points level thereof. Next, the method proceeds to step (S02) for disposing the product obtained from the step (S01) in an arc smelting furnace for smelting, so as to smelt the three metal materials of Cu, Zr and Ag to a ball-tablet shape alloy 1. Continuously, the method proceeds to step (S03) for soaking a pure copper mould 2 in a liquid nitrogen for a specific soak time, and then disposing a copper gasket 21 and the ball-tablet shape alloy 1 on the pure copper mould 2 after removing the pure copper mould 2 from the liquid nitrogen.
After completing the step (S03), step (S04) of the method is then proceeded for disposing the product obtained from the step (S03) into the arc smelting furnace and connecting a vacuum pump to the bottom of the pure copper 2, and then evacuating the pure copper mould for a specific vacuum-pump time of 1 minutes. Next, in step (S05), argon is accessed into the arc smelting furnace for 1 minute, then the ball-tablet shape alloy 1 is smelted to a molten metal alloy by 150 A˜250 A current, and then the molten metal alloy flows into the pure copper mould 2 through the evacuation executed by the vacuum pump. The method finally proceeds to step (S06) for rapidly cooling the molten metal alloy, so as to obtain a ternary-alloy metallic glass.
In addition, please refer to FIG. 2, which illustrates a flowchart of the detailed steps of step (S02). As shown in FIG. 2, the step (S02) in the aforesaid manufacturing method consists of following detailed steps: in step (S021) and step (S022), the product obtained from the step (1) is disposed in the arc smelting furnace and executing the evacuation for 5 minutes, and then accessing argon into the arc smelting furnace for 5 minutes; and after that, step (S023) is next proceeded for repeating the aforesaid steps (21) and (22) for once. Continuously, in step (S024) and step (S024), the three metal materials of Cu, Zr and Ag are smelted to the ball-tablet shape alloy 1 by 150 A˜250 A current, and then the ball-tablet shape alloy 1 is turned over for continuously smelting; and eventually, the aforesaid steps (24) and (25) for four times in step (S026).
Referring to FIG. 2, FIG. 3A and FIG. 3B again, the pure copper mould 2 used in the ternary-alloy metallic glass manufacturing method includes a hollow-penetration pure copper column 22 in the interior thereof, and the hollow-penetration pure copper column 22 has a specific inner diameter of 1 mm˜5 mm. The copper gasket 21 is used for covering the hollow-penetration pure copper column 22 of the pure copper mould 2, and center of the copper gasket 21 is also hollow.
Thus, through the descriptions, the ternary-alloy metallic glass and the manufacturing method thereof have been completely introduced. Next, experiment data is presented for proving that the ternary-alloy metallic glass made by the present invention's method is indeed an amorphous alloy in follows.
Please refer to FIG. 4, there is shown a backscattered electron image (BEI) of the ternary-alloy metallic glass. The ternary-alloy metallic glass shown in FIG. 4 is obtained by smelting the ball-tablet shape alloy made of 50 at % Cu, 40 at % Zr and 10 at % Ag, and shows uneven color and non-obviously precipitation phase. Furthermore, it can find that the composition of this ternary-alloy metallic glass consists of 37.5 at % Cu, 48.7 at % Zr and 13.8 at % Ag.
Continuously referring to FIG. 5, which illustrates an X-ray diffraction image of the ternary-alloy metallic glass, and please refer to FIG. 6 and FIG. 7, there are shown the DSC and DTA thermal analysis plots of the ternary-alloy metallic glass; wherein the X-ray diffraction image reveals that the ternary-alloy metallic glass has no obvious crystallographic diffraction peaks. Furthermore, to analyze the glass transition temperature and the recrystallization temperature of the ternary-alloy metallic glass by differential scanning calorimetry (DSC) and differential thermal analysis (DTA), it can find that a slight slope change and an endothermic peak respectively occur at 375° C. and 440° C. of the DSC curve in FIG. 6. Thus, it is able to know that the glass transition temperature (T_g) and the recrystallization temperature (T_x) of the ternary-alloy metallic glass are 375° C. and 440° C. In addition, it can also know that the liquefaction temperature (T_l) of the ternary-alloy metallic glass is 886.3° C. through the DTA curve of FIG. 7.
Continuously, please refer to FIG. 8, which illustrates transmission electron microscope image of the ternary-alloy metallic glass, and please simultaneously refer to FIG. 9 and FIG. 10, there are shown a thermal property analysis table and an amorphous composition region drawing of the ternary-alloy metallic glass. As shown in FIG. 8, the micro structure of the ternary-alloy metallic glass is observed by using scanning electron microscope (SEM), and it can find that the ternary-alloy metallic glass is indeed an amorphous alloy. Besides, through the thermal property analysis table of FIG. 9, it is able to know that the composition of the ternary-alloy metallic glass consists of Cu having the atomic percent ranged from 35 at % to 50 at %, Zr having the atomic percent ranged from 40 at % to 55 at %, and Ag having atomic percent ranged from 10 at % to 50 at %; moreover, the composition of the ternary-alloy metallic glass includes 45 at % Cu, 45 at % Zr and 10 at % Ag performs the best glass forming ability (GFA) of 0.36.
Thus, through the descriptions, the ternary-alloy metallic glass and the manufacturing method thereof have been completely introduced and disclosed; in summary, the present invention has the following advantages:
1. The ternary-alloy metallic glass proposed by the present invention mainly consists of Cu having the atomic percent ranged from 35 at % to 50 at %, Zr having the atomic percent ranged from 40 at % to 55 at %, and Ag having atomic percent ranged from 10 at % to 50 at %, and performs good mechanical properties of high strength, high hardness, well wear resistance and corrosion resistance; in addition, since the ternary-alloy metallic glass has good ductability, it can easily be processed to precision instruments, machinery or components for further applying to military, high-tech products, as well as nano medical industries.
2. Inheriting to above point 1, moreover, the wide supercooled liquid region of Zr-based metallic glass not only facilitates the three metals of Cu, Zr and Ag capable of being fabricated to the ternary-alloy metallic glass easily, but also makes manufacturing process of the Cu/Zr/Ag ternary-alloy metallic glass become simple and convenient.
The above description is made on embodiments of the present invention. However, the embodiments are not intended to limit scope of the present invention, and all equivalent implementations or alterations within the spirit of the present invention still fall within the scope of the present invention.

Claims

What is claimed is:

1. A ternary-alloy metallic glass, comprising:

a first metal material, being selected from the group consisting of: Cu, Zr, Ag, Ni, Fe, and Mg;

a second metal material, being selected from the group consisting of: Cu, Zr, Ag, Ni, Fe, and Mg; and

a third metal material, being selected from the group consisting of: Cu, Zr, Ag, Ni, Fe, and Mg;

wherein each of the first metal material, the second metal material and the third metal material have a specific composition ratio, and the three metal materials are further manufactured to the ternary-alloy metallic glass having high strength, wear resistance and corrosion resistance by using an arc smelting furnace and a copper mould formation;

wherein the specific composition ratio of the first metal material is ranged from 35 at % to 50 at %, the specific composition ratio of the second metal material being ranged from 40 at % to 55 at %, and the specific composition ratio of the third metal material being ranged from 10 at % to 20 at %.

2. The ternary-alloy metallic glass of claim 1, wherein the specific composition ratio of the first metal material is ranged from 35 at % to 50 at %, the specific composition ratio of the second metal material being ranged from 40 at % to 55 at %, and the specific composition ratio of the third metal material being ranged from 10 at % to 20 at %.

3. The ternary-alloy metallic glass of claim 1, wherein the purity of the first metal material, the second metal material and the third metal material are all at least 99.99%.

4. A method for manufacturing ternary-alloy metallic glass, comprising the steps of:

(1) fabricating copper (Cu) having atomic percent ranged from 35 at % to 50 at %, zirconium (Zr) having atomic percent ranged from 40 at % to 55 at %, and silver (Ag) having atomic percent ranged from 10 at % to 20 at %, and then disposing the three metal materials by melting points level thereof.

(2) disposing the product obtained from the step (1) in an arc smelting furnace for smelting, so as to smelt the three metal materials of Cu, Zr and Ag to a ball-tablet shape alloy;

(3) soaking a pure copper mould in a liquid nitrogen for a specific soak time, and then disposing a copper gasket and the ball-tablet shape alloy on the pure copper mould after removing the pure copper mould from the liquid nitrogen;

(4) disposing the product obtained from the step (3) into the arc smelting furnace and connecting a vacuum pump to the bottom of the pure copper, and then evacuating the pure copper mould for a specific vacuum-pump time;

(5) smelting the ball-tablet shape alloy to a molten metal alloy, and making the molten metal alloy flow into the pure copper mould; and

(6) rapidly cooling the molten metal alloy, and then a ternary-alloy metallic glass is obtained.

5. The method for manufacturing ternary-alloy metallic glass of claim 4, wherein the center of the copper gasket is hollow.

6. The method for manufacturing ternary-alloy metallic glass of claim 4, wherein the pure copper mould comprises a hollow-penetration pure copper column in the interior thereof, and the hollow-penetration pure copper column having a specific inner diameter.

7. The method for manufacturing ternary-alloy metallic glass of claim 4, wherein the step (2) further comprising the detailed steps of:

(21) disposing the product obtained from the step (1) in the arc smelting furnace and executing the evacuation for 5 minutes;

(21) accessing argon into the arc smelting furnace for 5 minutes;

(23) repeating the aforesaid steps (21) and (22) for once;

(24) smelting the three metal materials of Cu, Zr and Ag to the ball-tablet shape alloy by 150 A-250 A current;

(25) turning over and continuously smelting the ball-tablet shape alloy; and

(26) repeating the aforesaid steps (24) and (25) for four times.

8. The method for manufacturing ternary-alloy metallic glass of claim 4, wherein the specific soak time in the step (3) is 10 minutes.

9. The method for manufacturing ternary-alloy metallic glass of claim 4, wherein the purity of the three meal materials of Cu, Zr and Ag are at least 99.99%.

10. The method for manufacturing ternary-alloy metallic glass of claim 4, wherein the step (5) further comprising the detailed steps of:

(51) accessing argon into the arc smelting furnace for 1 minute; and

(52) smelting the ball-tablet shape alloy by 150 A-250 A current, so as to make the molten metal alloy flow into the pure copper mould through the evacuation executed by the vacuum pump.

11. The method for manufacturing ternary-alloy metallic glass of claim 6, wherein the specific inner diameter is ranged from 1 mm to 5 mm.

12. The method for manufacturing ternary-alloy metallic glass of claim 4, wherein the specific vacuum-pump time is 1 minute.