KR102613756B1 - Zirconium-based bulk amorphous alloy with high flowability - Google Patents

Abstract

The present invention relates to a zirconium-based bulk amorphous alloy with excellent fluid flow properties. According to one aspect of the present invention to achieve the above object, the present invention provides an amorphous alloy Zr _a Cu _b Ni _c Al _d Ag _e . Here, a is 46 to 57 at. %, and b is 16 to 33 at. %, and c is 6 to 14 at. %, and d is 6 to 12 at. %, and e is 3 to 10 at. It may be %. The amorphous alloy according to an embodiment of the present invention provides an amorphous alloy containing silver, an element that can increase the stability of the liquid phase while minimizing the decline in amorphous forming ability to increase process efficiency for manufacturing commercial parts, and provides an excellent fluid. By ensuring fluidity, amorphous alloys can be commercialized in various fields through an easy molding process.

Description

Zirconium-based bulk amorphous alloy with excellent fluid fluidity {ZIRCONIUM-BASED BULK AMORPHOUS ALLOY WITH HIGH FLOWABILITY}

The present invention relates to a zirconium-based bulk amorphous alloy with excellent flowability. More specifically, the present invention relates to a zirconium-based bulk amorphous alloy with excellent fluid fluidity that can stabilize the amorphous alloy production process.

Non-crystalline (amorphous) alloy refers to an alloy that is not crystalline. Generally, when metals are solid, they have a crystal structure in which atoms are arranged periodically. In contrast, liquids have a disordered atomic arrangement that lacks translational periodicity due to thermal vibration. When molten metal is rapidly cooled and solidified, the atoms of the solidified metal are not arranged regularly, and it becomes a solid with a liquid structure. This state is called amorphous.

Amorphous alloys have superior thermal conductivity, electrical conductivity, strength, and elasticity compared to crystalline metals, and can be used in various fields such as sporting goods, cell phone cases, watches, and medical tools.

However, amorphous alloys generally have low flowability because alloy elements that can have a highly filled structure are selected for bulking, so the process for mass production is limited and the production process is difficult. Currently, commercialized parts and structures This is almost non-existent.

The following Patent Document 1 discloses the composition of an amorphous metal with excellent amorphous forming ability at a commercially possible level, but the alloy of Patent Document 1 contains expensive niobium and has a high liquidus temperature, so it is used in various fields. It is difficult to apply.

US 5735975 B1

In order to solve the above-mentioned problems, the present invention seeks to provide a technology that can increase the stabilization of the production process for turning amorphous alloy into parts by minimizing the decline in amorphous forming ability while providing excellent flowability.

In addition, the purpose of the present invention is to provide an amorphous alloy containing silver, an element that can increase the stability of the liquid phase while minimizing the decrease in amorphous forming ability in order to increase process efficiency for manufacturing commercial parts, thereby securing excellent fluid fluidity. We aim to ensure that amorphous alloys can be commercialized in various fields through an easy forming process.

According to one aspect of the present invention to achieve the above object, the present invention provides an amorphous alloy Zr _a Cu _b Ni _c Al _d Ag _e . Here, a is 46 to 57 at. %, and b is 16 to 33 at. %, and c is 6 to 14 at. %, and d is 6 to 12 at. %, and e is 3 to 10 at. It may be %.

In one embodiment, a+b+c is 79.0 to 89.1 at. It may be %.

In one embodiment, a-c is 38.4 to 41.6 at. It may be %.

In one embodiment, d+e is 15.4 to 16.6 at. It may be %.

In one embodiment, d/e may be 0.96 to 1.04.

In one embodiment, a is 50 at. %, and b is 24 at. %, and c is 10 at. %, and d is 8 at. %, and e is 8 at. It may be %.

In one embodiment, a is 54 at. %, and b is 16 at. %, and c is 14 at. %, and d is 8 at. %, and e is 8 at. It may be %.

In one embodiment, a is 46 at. %, and b is 32 at. %, and c is 6 at. %, and d is 8 at. %, and e is 8 at. It may be %.

The amorphous alloy according to an embodiment of the present invention improves flowability by providing an amorphous alloy containing silver, an element that can increase the stability of the liquid phase while minimizing the decline in amorphous forming ability to increase process efficiency for manufacturing commercial parts. By doing so, amorphous alloys can be produced stably. Accordingly, the amorphous alloy according to an embodiment of the present invention can be applied to various fields.

1 is a graph showing the ν parameter of an amorphous alloy according to the present invention.
Figure 2 is a graph showing the ε parameter of the amorphous alloy according to the present invention.
Figure 3 is a graph showing the results of XRD analysis of the amorphous alloy according to the present invention.
Figure 4 is a graph showing the liquefaction temperature of the amorphous alloy according to the present invention.
Figure 5 is a photograph showing an example of a mold flowability test of an amorphous alloy according to the present invention.
Figure 6 is a graph showing the surface hardness of the amorphous alloy according to the present invention.

Hereinafter, embodiments disclosed in the present specification will be described in detail with reference to the attached drawings. However, identical or similar components will be assigned the same reference numbers regardless of reference numerals, and duplicate descriptions thereof will be omitted. Additionally, in describing the embodiments disclosed in this specification, if it is determined that detailed descriptions of related known technologies may obscure the gist of the embodiments disclosed in this specification, the detailed descriptions will be omitted. In addition, the attached drawings are only for easy understanding of the embodiments disclosed in this specification, and the technical idea disclosed in this specification is not limited by the attached drawings, and all changes included in the spirit and technical scope of the present invention are not limited. , should be understood to include equivalents or substitutes.

Terms containing ordinal numbers, such as first, second, etc., may be used to describe various components, but the components are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another.

Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this application, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

The amorphous alloy according to the present invention may be represented by the following formula (1).

[Formula 1]

Zr _a Cu _b Ni _c Al _d Ag _e

In Formula 1, a is 46 to 57 atomic percent (hereinafter, at. %), and b is 16 to 33 at. %, and c is 6 to 14 at. %, and d is 6 to 12 at. %, and e is 3 to 10 at. It may be %.

Meanwhile, a+b+c is 79.0 to 89.1 at. It may be %.

Meanwhile, a-c is 38.4 to 41.6 at. It may be %.

Meanwhile, d+e is 15.4 to 16.6 at. It may be %.

Meanwhile, d/e may be 0.96 to 1.04.

Below, the amorphous forming ability of the amorphous alloy according to the present invention will be described. For convenience of explanation, the amorphous forming ability of three types of amorphous alloys having different compositions manufactured according to the present invention will be described, but is not limited thereto.

Here, the compositions of the three types of amorphous alloy are shown in Table 1 below.

Zr
[at. %] Cu
[at. %] Ni
[at. %] Al
[at. %] Ag
[at. %] Composition 1 ('1-Ag)') 46 32 6 8 8 Composition 2 ('3-Ag)') 50 24 10 8 8 Article 3 ('5-Ag)') 54 16 14 8 8

Amorphous forming ability (GFA) indicates how easily an alloy of a specific composition can be amorphized, and the amorphous forming ability of an alloy varies depending on its composition.

In general, the amorphous forming ability is determined by using a thermogravimetric analyzer to characterize the alloy temperature T _g , T _x and the phase change temperature T _l are measured, and the measured values are used to evaluate them as predetermined parameters.

Here, T _g is the glass transition temperature of the alloy, T _x is the crystallization start temperature, and T _l is the liquidus temperature of the alloy.

Glass transition temperature (T _g ) is defined as the temperature at which the supercooled liquid transforms into amorphous form during the solidification process, and can be recognized as a temperature standard representing the stability of the supercooled liquid phase. T _g may vary depending on the cooling rate during amorphous formation during the solidification process and the heating rate during thermal analysis.

Crystallization initiation temperature (T _x ) is the temperature at which crystallization begins when heating an amorphous alloy and varies depending on the heating rate during thermal analysis.

The liquidus temperature (T _l ) represents the stability of the stable liquid, and is closely correlated with the alloy composition and internal energy state and changes sensitively according to changes, so it is recognized as an important factor governing amorphous formation ability.

Various parameters are used to evaluate amorphous formation ability. Among these, two parameters with high reliability will be explained.

First, the ν parameter expressed as Equation 1 below is used.

Second, the ε parameter expressed as Equation 2 below is used.

In Equation 2 above, , and x _i is the mole fraction of the specific metal included in the alloy, is the melting temperature of the metal.

The results of calculating the ν and ε parameters of the amorphous alloy according to the present invention through thermal analysis are shown in Figures 1 and 2. Also, shown in Figures 1 and 2

The _calculated values of ^the amorphous characterization temperature ₍ T _g , _T

Alloy T _g [K] T _x [K] T _l [K] T _m ^mix [K] ν ε Vit. 106 Zr ₅₇ Cu _15.4 Ni _12.6 Al ₁₀ Nb ₅ 676 749 1133
(ref. 1115) 1871 0.41 0.83 Vit. 601 Zr _{50 . 8} Cu _{36 . 1} Ni _{4 Al 9.1} 684 771 1160
(ref. 1026) 1725 0.42 0.82 5) Zr ₆₀ Cu ₁₆ Ni ₁₄ Al ₁₀ 661 746 1126 1829 0.42 0.84 4) Zr ₅₈ Cu ₂₀ Ni ₁₂ Al ₁₀ 671 748 1127 1807 0.42 0.83 3) Zr ₅₆ Cu ₂₄ Ni ₁₀ Al ₁₀ 678 754 1124 1784 0.42 0.84 2) Zr ₅₄ Cu ₂₈ Ni ₈ Al ₁₀ 684 764 1137 1761 0.42 0.83 One) Zr ₅₂ Cu ₃₂ Ni ₆ Al ₁₀ 690 771 1149 1738 0.42 0.83 5-Nb) Zr _56.2 Cu _15.52 Ni _13.58 Al _9.7 Nb ₃ 672 763 1158 1814 0.42 0.83 4-Nb) Zr _56.26 Cu _19.4 Ni _11.64 Al _9.7 Nb ₃ 677 767 1168 1835 0.42 0.83 3-Nb) Zr _54.32 Cu _23.28 Ni _9.7 Al _9.7 Nb ₃ 685 771 1171 1813 0.42 0.83 2-Nb) Zr _52.38 Cu _27.16 Ni _7.76 Al _9.7 Nb ₃ 696 771 1185 1791 0.41 0.81 1-Nb) Zr _50.44 Cu _31.04 Ni _5.82 Al _9.7 Nb ₃ 697 769 1185 1768 0.41 0.81 5-Ag) Zr ₅₄ Cu ₁₆ Ni ₁₄ Al ₈ Ag ₈ 680 756 1126 1782 0.42 0.83 3-Ag) Zr ₅₀ Cu ₂₄ Ni ₁₀ Al ₈ Ag ₈ 684 759 1117 1736 0.42 0.84 1-Ag) Zr ₄₆ Cu ₃₂ Ni ₆ Al ₈ Ag ₈ 691 763 1144 1691 0.42 0.82

Referring to Figure 1, the three inverted triangles shown in the graph correspond to the ν parameter value of the amorphous alloy according to the present invention. Among the three inverted triangles, the amorphous alloy (second composition) corresponding to the inverted triangle located in the center has a higher ν parameter value than the amorphous alloy (Vit 106) disclosed in Patent Document 1.

Meanwhile, referring to FIG. 2, the three inverted triangles shown in the graph correspond to the ε parameter value of the amorphous alloy according to the present invention. Among the three inverted triangles, the amorphous alloy (second composition) corresponding to the inverted triangle located in the center has a higher ε parameter value than the amorphous alloy (Vit 106) disclosed in Patent Document 1.

According to the above results, the amorphous alloy according to the present invention is expected to have very excellent amorphous forming ability. In particular, the alloy having the second composition has a superior amorphous forming ability than a conventional amorphous alloy containing Nb. Accordingly, the amorphous alloy according to the present invention can be formed and post-processed in bulk form more stably than conventional amorphous alloys, thereby enabling high productivity.

In order to confirm the actual amorphous forming ability of the alloys of the present invention, the following will describe the results of X-ray Diffraction Spectroscopy (XRD) for the amorphous alloy according to the present invention.

Using XRD analysis, it can be confirmed whether the manufactured alloy has an amorphous shape. Specifically, a sharp peak is observed in the XRD graph of an alloy with a crystal structure. In contrast, in the case of amorphous alloys, broad peaks are observed over a wide angular range.

Figure 3 is a graph showing the results of XRD analysis of an amorphous alloy of a 6 mm bulk specimen manufactured by a suction casting method according to an embodiment of the present invention.

Referring to Figure 3, no sharp peaks were observed in the XRD graph of the alloys having the first to third compositions, and it can be confirmed that the alloys having the first to third compositions have excellent amorphous forming ability of 6 mm or more.

Meanwhile, when manufacturing an amorphous alloy through a die casting process, etc., material properties such as liquid temperature and fluidity and process conditions such as molten metal temperature and mold temperature are very important factors in the productivity of the amorphous alloy. am. To elaborate, the productivity of amorphous metal increases when the process is possible even at low melt and mold temperatures due to low liquefaction temperature and good flowability.

Referring to Figure 4, it can be seen that in the case of the amorphous alloy (second composition) according to the present invention, the liquefaction temperature is 1117K, which is about 20K lower than that of the amorphous alloy (1133K) disclosed in Patent Document 1.

Meanwhile, in the case of the amorphous alloy disclosed in Patent Document 1, the molten metal temperature is about 1293K and the mold temperature is about 553K. Meanwhile, in the case of the amorphous alloy (second composition) according to the present invention, the molten metal temperature is 1253K and the mold temperature is 503K. As described above, the amorphous alloy according to the present invention has a lower liquidus temperature than the conventional amorphous alloy and can be produced under low temperature conditions. Accordingly, the productivity of the amorphous alloy can be increased.

Meanwhile, the mold flowability of an amorphous alloy is an important factor in the productivity of an amorphous alloy, as described above. To test the mold flowability of the amorphous alloy, the liquid alloy was poured into a mold of a certain shape (thickness 1 mm), and the distance the alloy moved was measured, as shown in Figure 5.

Using the above mold, the mold flow properties of the amorphous alloy disclosed in Patent Document 1 and the amorphous alloy according to the present invention (first and second compositions) were measured.

Here, the molten metal temperature of the amorphous alloy disclosed in Patent Document 1 was 1293K, and the mold temperature was 553K. Meanwhile, the molten metal temperature of the amorphous alloy (first and second compositions) according to the present invention was 1253K, and the mold temperature was 503K. This is a condition for each amorphous alloy to have the best mold flowability.

As a result of the mold flowability test, the moving distance of the amorphous alloy disclosed in Patent Document 1 was 150 mm. In contrast, the movement distances of the amorphous alloy (first and second compositions) according to the present invention were 180 mm and 160 mm, respectively. Through this, the amorphous alloy according to the present invention can be expected to have higher productivity than the conventional amorphous alloy.

Below, the surface hardness of the amorphous alloy according to the present invention will be described.

Figure 6 is a graph showing the surface hardness of the amorphous alloy according to the present invention.

Referring to Figure 6, the surface hardness (509.2Hv) of the amorphous alloy disclosed in Patent Document 1 of the alloy ('1-Ag)', '3-Ag)', '5-Ag)') having the first to third compositions. ) can be confirmed to be higher than that. That is, as explained in FIG. 4, it was confirmed that the amorphous alloy according to the present invention was produced at a lower temperature than the amorphous alloy disclosed in Patent Document 1, and at the same time, it had high surface hardness and exhibited excellent mechanical properties.

Meanwhile, Table 3 below lists the surface hardness of the alloys shown in FIG. 6 and the surface hardness of the amorphous alloy disclosed in Patent Documents 1 and 2.

Alloy Hardness [HV] Vit. 106 Zr ₅₇ Cu _15.4 Ni _12.6 Al ₁₀ Nb ₅ 509.20 Vit. 601 Zr _{50 . 8} Cu _{36 . 1} Ni _{4 Al 9.1} 530.30 5) Zr ₆₀ Cu ₁₆ Ni ₁₄ Al ₁₀ 501.00 4) Zr ₅₈ Cu ₂₀ Ni ₁₂ Al ₁₀ 509.40 3) Zr ₅₆ Cu ₂₄ Ni ₁₀ Al ₁₀ 518.10 2) Zr ₅₄ Cu ₂₈ Ni ₈ Al ₁₀ 523.90 One) Zr ₅₂ Cu ₃₂ Ni ₆ Al ₁₀ 534.90 5-Nb) Zr _56.2 Cu _15.52 Ni _13.58 Al _9.7 Nb ₃ 498.80 4-Nb) Zr _56.26 Cu _19.4 Ni _11.64 Al _9.7 Nb ₃ 511.40 3-Nb) Zr _54.32 Cu _23.28 Ni _9.7 Al _9.7 Nb ₃ 524.50 2-Nb) Zr _52.38 Cu _27.16 Ni _7.76 Al _9.7 Nb ₃ 539.78 1-Nb) Zr _50.44 Cu _31.04 Ni _5.82 Al _9.7 Nb ₃ 537.00 5-Ag) Zr ₅₄ Cu ₁₆ Ni ₁₄ Al ₈ Ag ₈ 513.70 3-Ag) Zr ₅₀ Cu ₂₄ Ni ₁₀ Al ₈ Ag ₈ 531.80 1-Ag) Zr ₄₆ Cu ₃₂ Ni ₆ Al ₈ Ag ₈ 551.90

It is obvious to those skilled in the art that the present invention can be embodied in other specific forms without departing from the spirit and essential features of the present invention.

Additionally, the above detailed description should not be construed as limiting in any respect and should be considered illustrative. The scope of the present invention should be determined by reasonable interpretation of the appended claims, and all changes within the equivalent scope of the present invention are included in the scope of the present invention.

Claims (8)

In the amorphous alloy Zr _a Cu _b Ni _c Al _d Ag _e ,
a is 46 to 54 at. %, and b is 16 to 32 at. %, and c is 6 to 14 at. %, and d/e is 0.96 to 1.04. According to paragraph 1,
a+b+c is 84 at. A zirconium-based bulk amorphous alloy characterized by %. According to paragraph 1,
d is 8 at. % and e is 8 at. A zirconium-based bulk amorphous alloy characterized by %. delete delete According to paragraph 1,
The above a is 50 at. %, and b is 24 at. %, and c is 10 at. %, and d is 8 at. %, and e is 8 at. A zirconium-based bulk amorphous alloy characterized by %. According to paragraph 1,
The above a is 54 at. %, and b is 16 at. %, and c is 14 at. %, and d is 8 at. %, and e is 8 at. A zirconium-based bulk amorphous alloy characterized by %. According to paragraph 1,
The above a is 46 at. %, and b is 32 at. %, and c is 6 at. %, and d is 8 at. %, and e is 8 at. A zirconium-based bulk amorphous alloy characterized by %.

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