KR20040104317A - Cu-based amorphous alloy composition - Google Patents

Abstract

PURPOSE: To provide a Cu-based amorphous alloy composition which is more excellent in glass forming ability and has wide supercooled liquid region compared with a conventional alloy, and which is consisted of commercial metal elements only so that the alloy is utilized industrially and economically and commercialized more easily. CONSTITUTION: The Cu-based amorphous alloy composition is represented by the following chemical formula 1 : CuaNib(Zr1-xTx)c where a, b, and c are respectively 44 atom%<=a<=60 atom%, 1 atom%<=b<=20 atom%, 36 atom%<=a<=44 atom%, and x is 0.34<=x<=0.47, wherein a glass forming ability of the alloy composition is 1 mm or more of diameter, wherein a, b, c and x in the above chemical formula 1 respectively are 48 atom%<=a<=55 atom%, 6 atom%<=b<=10 atom%, 39 atom%<=a<=43 atom%, and 0.39<=x<=0.46, wherein a glass forming ability of the alloy composition is 4 mm or more of diameter, wherein an amorphous phase in the composition is 90 wt.% or more based on the total weight of the composition.

Description

Cu-based amorphous alloy composition

The present invention relates to a Cu-based amorphous alloy composition, and more particularly, to an amorphous alloy composition composed of a quaternary system containing copper as a main component and containing zirconium, titanium, and nickel.

The amorphous alloy composition according to the present invention has excellent amorphous forming ability and can be bulked when cooled to a temperature below the glass transition temperature (glass transition temperature) at a cooling rate of 10 ³ ° C./s or less from the liquid phase, and a supercooled liquid region of 31 ° C. or more. A Cu-based amorphous alloy composition having a supercooled liquid region.

In general, a rapid cooling rate of 10 ⁴ -10 ⁶ ° C / s is required to obtain an amorphous phase, so that a rapid quenching technique is used for amorphous production, and the prepared specimen has a thin plate or fine powder shape. As described above, the amorphous alloys produced by the rapid solidification method have limited form and size, so the practical application is very limited. Therefore, in order to utilize the amorphous alloy as a commercial metal material, excellent amorphous forming ability with low critical cooling rate is required, and therefore, development of an alloy having such a property has been required.

If the amorphous forming ability is excellent, it is possible to produce the amorphous in the bulk state by the general casting method. In addition, having a large supercooled liquid region in an amorphous alloy is very important from an industrial point of view, because the viscous flow in the supercooled liquid region enables the molding of the bulk amorphous alloy to produce a certain type of part. Because there is.

According to PCT WO 96/24702, a Cu-based bulk amorphous alloy having a thickness of about 4 mm has been developed with a critical cooling rate of several thousand deg. C / s and excellent amorphous formability for forming an amorphous alloy.

However, the conventional Cu-based amorphous alloys such as the supercooled liquid region and the relatively small amorphous forming ability, there is still a need for the development of alloys having excellent amorphous forming ability.

Accordingly, the Cu-based amorphous alloy composition according to the present invention has been proposed to solve the above problems, and the Cu-based amorphous alloy has high strength and high industrial and economic utility. Therefore, it can be very usefully used as a structural material if it can be produced in bulk form. Papers Journal of Applied Physics, Vol. 78, No 11, pp. According to 6514-6519, a bulk amorphous alloy having a maximum thickness of 4 mm was obtained by the copper mold casting method, and it is known to have a supercooled liquid region of about 45 ° C. In addition to this alloy, it is possible to manufacture a new Cu-based bulk amorphous alloy in various alloy systems through an appropriate alloy design, and for practical use, development of Cu-based amorphous alloy with superior amorphous forming ability and wide supercooled liquid region is necessary.

Accordingly, the present invention provides a Cu-based amorphous alloy which is superior in industrial and economic feasibility and is more practical to use, consisting only of commercial metal elements, having an amorphous forming ability and a wider subcooled liquid region than the conventional alloy. have.

1 is a quasi-ternary composition diagram of a copper-nickel- (zirconium + titanium) alloy showing a region in which bulk amorphous formation of 1 mm or more is confirmed in the alloy composition according to the present invention.

Figure 2 is an X-ray diffraction pattern (diffraction pattern) of Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ prepared by the casting method according to an embodiment of the present invention.

Figure 3 is a high resolution transmission electron micrograph of Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ prepared by the casting method according to an embodiment of the present invention.

Figure 4 is a graph of compressive strength of Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ prepared by the casting method according to an embodiment of the present invention.

In order to achieve the object of the present invention, the present invention is represented by the following formula 1

Cu _a Ni _b (Zr _1-x Ti _x ) _c

(Where a, b, and c represent atomic% of copper, nickel and zirconium + titanium, respectively, 44 atomic% ≤ a ≤ 60 atomic%, 1 atomic% ≤ b ≤ 20 atomic%, 36 atomic% ≤ c ≤ 44 atomic% and x is 0.34? X? 0.47.

As used herein, "amorphous" does not mean that the composition of the composition is 100% amorphous, the amorphous structure as a whole, the X-Ray diffraction pattern is usually in the art such as halo (halo) form If it has a known amorphous phase, it is called "amorphous." Therefore, some of the crystalline structure may exist in the amorphous structure, and such crystalline is not included to the extent that the amorphous structure is present more than the amorphous structure.

In general, the rule of thumb is that an amorphous alloy can have excellent amorphous forming ability by combining a multicomponent system of three or more components, a large atomic radius difference of 10% or more, and a negative mixed heat atom.

With this in mind, the present inventors first satisfied copper, zirconium, and titanium with four components by first adding nickel to it. In addition, the atomic radius for each element is Cu (atomic radius = 1.27Å), Zr (atomic radius = 1.61Å), Ti (atomic radius = 1.45Å), and Ni (atomic radius = 1.24Å). -23 kJ / mol, -17 kJ / mol, and -49 kJ / mol and -35 kJ / mol, respectively, between Cu and Zr and Cu and Ti as main components Having the heat of mixing satisfies the above rule of thumb. For this reason, the composition can be obtained by dissolving by arc in a vacuum or argon gas atmosphere, and then filling the copper mold by suction casting to obtain a certain bulk amorphous. Of course, the composition may be prepared by injection casting, which is obtained by dissolving the composition by high frequency induction heating in a vacuum or argon gas atmosphere, and then filling the water-cooled copper mold into a predetermined bulk form.

In the present invention, the alloy composition is preferably in the range of 44-60 atomic% of Cu and 36-44 atomic% of Zr + Ti with respect to the total composition in order to improve amorphous forming ability and to secure a large subcooled liquid region of 40 ° C or higher. Do. On the other hand, the addition amount of Ni is preferably 1-20 atomic% with respect to the whole composition, but it is difficult to expect sufficient amorphous forming ability when Ni is not added, and even when it exceeds 20 atomic%, the amorphous forming ability tends to decrease. . In addition, it was confirmed that the fraction x of the zirconium and titanium exhibits excellent amorphous forming ability when the value of 0.34 ≦ x ≦ 0.47.

The amorphous alloy according to the present invention can be produced by a rapid solidification method, a die casting method, a high pressure casting method, an atomizing method and the like.

On the other hand, the amorphous alloy according to the present invention is excellent in high temperature workability and can be produced through forging, rolling, extrusion or other processing steps.

In the Cu-based bulk amorphous alloy composition of the present invention, the liquid phase is completely solidified to amorphous under a cooling rate of 10 ³ ° C./s or much lower, and the glass transition temperature (Tg) is 428-481 ° C., and the crystallization temperature (Tx) Has a range of 475-522 ° C. In addition, the supercooled liquid phase region (ΔT = Tx-Tg), which is an important factor of the amorphous forming ability, is 31-68 ° C. and has a much wider area and excellent amorphous forming ability than the conventional quaternary Cu-based amorphous alloy. In particular, the alloy composition specified in the present invention enables the production of bulk amorphous alloys up to 6 mm in diameter by suction casting.

In the Cu-based bulk amorphous alloy composition of the present invention, an alloy composition range showing a diameter of 1 mm or more is shown in the ternary composition diagram of FIG. 1. The composition of copper, nickel, zirconium + titanium is shown in the ternary composition diagram of FIG. 1, and as mentioned in the description of the chemical formula, the ratio of zirconium and titanium is 0.66 to 0.53: 0.34 to 0.47.

In the composition region shown in FIG. 1, a bulk amorphous phase of 1 mm or more was formed at a cooling rate of 10 ³ ° C./s, and the supercooled liquid phase region was 31 ° C. or higher. Particularly, the composition represented by 가능 can form amorphous particles with a diameter of 4 mm or more. In this case, the alloy composition has the structure of Chemical Formula 1, wherein a, b, c, and x are 48 atomic% ≤ a ≤ 55 atomic%, 6 Atomic% ≦ b ≦ 10atomic%, 39 atomic% ≦ c ≦ 43atomic%, and 0.39 ≦ x ≦ 0.46. In addition, the composition denoted by 가능 can form a bulk amorphous with a diameter of 5 to 6 mm or more, and the alloy composition at this time is in the structure of Chemical Formula 1, wherein a, b, c, and x are 50 atomic% ≦ a ≦ 54 Atomic%, 6 atomic% ≦ b ≦ 8 atomic%, 40 atomic% ≦ c ≦ 43 atomic%, 0.39 ≦ x ≦ 0.46.

In addition, the compressive fracture strength of the bulk amorphous material was 1.9-2.2 GPa, indicating excellent mechanical properties.

The Cu-based bulk amorphous alloy composition of the present invention has a wider supercooled liquid phase region (ΔT) than the conventional quaternary bulk amorphous alloy composition, and has a superior amorphous forming ability. The bulk amorphous production method may be a rapid solidification method such as melt spinning, atomizing, and the like. In particular, the composition according to the present invention has a wide range of high temperature processing so that high temperature processing is easy, and thus, processing such as rolling, drawing, forging, molten forging, etc. Through bulk amorphous alloys can be produced.

In view of the above, according to the present invention, it is possible to obtain a very large supercooled liquid zone of 31-68 ° C. and to ensure excellent workability. Thus, a plate, rod, or other bulk amorphous alloy is produced by a casting method, and then in the supercooled liquid zone. Advantageously, the viscous flow can be easily formed into a specific type of part. In addition, it is possible to prepare the amorphous powder of the Cu-based amorphous alloy of the present invention by the atomizing method, and then to preform the powder into a bulk amorphous component while maintaining the amorphous structure by applying a high pressure at a high temperature in the supercooled liquid region.

The inventors have found that a certain proportion of crystalline can be included in the alloy composition in the amorphous alloy composition according to the present invention. As a result of the researches of the present inventors, when the crystallites of 1 to 10 nano units are uniformly distributed in the amorphous alloy composition prepared according to the present invention, the overall characteristics of the amorphous properties are maintained, but the mechanical strength is 100% amorphous. It turns out that it has better properties than that. In the amorphous alloy composition according to the present invention, it is preferable that the proportion of uniformly distributed crystals does not exceed 10% by weight (based on the total weight of the alloy composition). For example, when the crystal phase is an intermetallic compound exhibiting fragile characteristics without being matched with an amorphous matrix, when the crystal phase increases, the strength and toughness may be reduced. Therefore, the amorphous phase in the Cu-based amorphous alloy composition according to the present invention is preferably 90% or more. Hereinafter, the present invention will be described in detail based on the following examples. However, the present invention is not limited by the following examples.

Example 1-23: Alloy Composition Prepared by Casting Method

First, the alloy of each composition given in Table 1 was melt | dissolved by the arc melting method, and it produced by the suction casting method into the rod shape of 1-50 mm in diameter and 10-50 mm in length. As a result of the X-ray diffraction analysis of the specimen thus prepared, it was confirmed that the specimen had an amorphous characteristic as showing a halo-type diffraction peak. 2 shows the diffraction pattern results of Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ (Sample 5 in Table 1) prepared by the casting method.

In addition, the glass transition temperature (Tg), crystallization temperature (Tx), and the amount of exothermic enthalpy generated during crystallization were measured through differential thermal analysis, and are shown in Table 1. In addition, the supercooled liquid phase region (ΔT = Tx-Tg) was determined by the glass transition temperature (Tg) and the crystallization temperature (Tx).

In general, the larger the supercooled liquid region, the easier the high temperature molding using the viscous flow of the amorphous alloy. In the composition of the present invention, an alloy composition having a 60 ° C supercooled liquid region needs to be noted from the viewpoint of forming and manufacturing the bulk amorphous structural component.

Example Alloy composition T _g (℃) Tx (℃) ΔT (℃) ΔH (J / g) One Cu ₅₅ Ni ₆ Zr ₂₁ Ti ₁₈ 437 496 59 67.0 2 Cu ₅₅ Ni ₆ Zr ₂₃ Ti ₁₆ 444 502 58 64.9 3 Cu ₅₄ Ni ₇ Zr ₂₂ Ti ₁₇ 442 502 60 66.4 4 Cu ₅₂ Ni ₉ Zr ₂₂ Ti ₁₇ 443 505 62 63.3 5 Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ 439 496 57 60.8 6 Cu ₅₄ Ni ₆ Zr ₂₄ Ti ₁₆ 444 503 59 67.5 7 Cu ₅₃ Ni ₇ Zr ₂₂ Ti ₁₈ 440 500 60 66.5 8 Cu ₅₂ Ni ₈ Zr ₂₃ Ti ₁₇ 441 506 65 56.6 9 Cu ₅₁ Ni ₉ Zr ₂₂ Ti ₁₈ 439 502 63 62.9 10 Cu ₅₀ Ni ₁₀ Zr ₂₂ Ti ₁₈ 442 507 65 67.1 11 Cu ₅₂ Ni ₇ Zr ₂₅ Ti ₁₆ 440 494 54 61.9 12 Cu ₅₁ Ni ₈ Zr ₂₃ Ti ₁₈ 442 501 59 61.1 13 Cu ₅₀ Ni ₉ Zr ₂₄ Ti ₁₇ 438 498 60 57.1 14 Cu ₅₁ Ni ₇ Zr ₂₃ Ti ₁₉ 435 485 50 58.0 15 Cu ₅₀ Ni ₇ Zr ₂₄ Ti ₁₉ 431 475 44 58.7 16 Cu ₄₈ Ni ₉ Zr ₂₃ Ti ₂₀ 428 477 49 53.3 17 Cu ₅₁ Ni ₆ Zr ₂₄ Ti ₁₉ 437 470 33 59.4 18 Cu ₄₄ Ni ₂₀ Zr ₂₃ Ti ₁₃ 481 522 41 48.1 19 Cu ₄₄ Ni ₁₂ Zr ₂₅ Ti ₁₉ 444 484 40 57.4 20 Cu ₅₅ Ni ₁ Zr ₂₅ Ti ₁₉ 430 462 32 47.5 21 Cu ₆₀ Ni ₁ Zr ₂₃ Ti ₁₆ 451 487 36 38.9 22 Cu ₆₀ Ni ₄ Zr ₂₃ Ti ₁₃ 467 498 31 41.2 23 Cu ₅₅ Ni ₉ Zr ₂₃ Ti ₁₃ 472 506 34 59.7

Some of the prepared alloy compositions were tested for compressive strength and the results are shown. The critical diameter of each composition is shown together. The breaking strength was 1.9GPa-2.2GPa, and the critical diameter was 1 ~ 6mm. In particular, Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ has to be noted as a structural material with a critical diameter of 6 mm, a supercooled liquid region of 57 ° C, and a compressive strength of 2.1 GPa.

Example Alloy composition Breaking strength (MPa) Critical diameter (mm) One Cu ₅₅ Ni ₆ Zr ₂₁ Ti ₁₈ 2,080 4 2 Cu ₅₅ Ni ₆ Zr ₂₃ Ti ₁₆ 1,990 4 3 Cu ₅₄ Ni ₇ Zr ₂₂ Ti ₁₇ 2,100 4 4 Cu ₅₂ Ni ₉ Zr ₂₂ Ti ₁₇ 2,040 4 5 Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ 2,130 6 6 Cu ₅₄ Ni ₆ Zr ₂₄ Ti ₁₆ 2,040 5 7 Cu ₅₃ Ni ₇ Zr ₂₂ Ti ₁₈ 2,000 5 8 Cu ₅₂ Ni ₈ Zr ₂₃ Ti ₁₇ 2,070 5 9 Cu ₅₁ Ni ₉ Zr ₂₂ Ti ₁₈ 2,030 4 10 Cu ₅₀ Ni ₁₀ Zr ₂₂ Ti ₁₈ 2,080 4 11 Cu ₅₂ Ni ₇ Zr ₂₅ Ti ₁₆ 2,040 5 12 Cu ₅₁ Ni ₈ Zr ₂₃ Ti ₁₈ 2,020 5 13 Cu ₅₀ Ni ₉ Zr ₂₄ Ti ₁₇ 2,080 4 14 Cu ₅₁ Ni ₇ Zr ₂₃ Ti ₁₉ 2,200 5 15 Cu ₅₀ Ni ₇ Zr ₂₄ Ti ₁₉ 2,140 5 16 Cu ₄₈ Ni ₉ Zr ₂₃ Ti ₂₀ 1,990 4 17 Cu ₅₁ Ni ₆ Zr ₂₄ Ti ₁₉ 2,100 4 18 Cu ₄₄ Ni ₂₀ Zr ₂₃ Ti ₁₃ 2,120 One 19 Cu ₄₄ Ni ₁₂ Zr ₂₅ Ti ₁₉ 2,000 One 20 Cu ₅₅ Ni ₁ Zr ₂₅ Ti ₁₉ 2,020 2 21 Cu ₆₀ Ni ₁ Zr ₂₃ Ti ₁₆ 2,150 One 22 Cu ₆₀ Ni ₄ Zr ₂₃ Ti ₁₃ 2,060 One 23 Cu ₅₅ Ni ₉ Zr ₂₃ Ti ₁₃ 2,040 One

Examples 24 to 47: Alloy composition prepared by the melt spinning method

After the alloys of each composition given in Table 3 were fabricated by the arc melting method, they were dissolved in a quartz tube in a vacuum high frequency induction furnace, and then sprayed on a copper wheel rotating at about 3000 rpm through a nozzle of about 1 mm in diameter to a thickness of about 60 μm. Ribbon was produced. As a result of X-ray diffraction analysis, the sample prepared by the melt spinning method showed an amorphous characteristic as showing a diffraction peak in the form of halo. Also, the differential thermal analysis was used to measure the glass transition temperature (Tg), crystallization temperature (Tx), and the amount of exothermic enthalpy generated during crystallization.The supercooled liquid phase region was measured at the glass transition temperature (Tg) and crystallization temperature (Tx). Determined and shown.

Example Alloy composition T _g (℃) Tx (℃) ΔT ΔH (J / g) 24 Cu ₅₅ Ni ₆ Zr ₂₁ Ti ₁₈ 455 502 47 70.2 25 Cu ₅₅ Ni ₆ Zr ₂₃ Ti ₁₆ 465 509 44 67.0 26 Cu ₅₄ Ni ₇ Zr ₂₂ Ti ₁₇ 466 509 43 93.1 27 Cu ₅₂ Ni ₉ Zr ₂₂ Ti ₁₇ 458 508 50 72.0 28 Cu ₅₀ Ni ₁₁ Zr ₂₁ Ti ₁₈ 459 512 53 95.0 29 Cu ₅₀ Ni ₁₁ Zr ₂₃ Ti ₁₆ 465 518 53 92.2 30 Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ 458 505 47 65.6 31 Cu ₅₄ Ni ₆ Zr ₂₄ Ti ₁₆ 461 509 48 69.5 32 Cu ₅₃ Ni ₇ Zr ₂₂ Ti ₁₈ 468 512 44 62.4 33 Cu ₅₂ Ni ₈ Zr ₂₃ Ti ₁₇ 457 506 49 72.6 34 Cu ₅₁ Ni ₉ Zr ₂₂ Ti ₁₈ 465 513 48 66.6 35 Cu ₅₀ Ni ₁₀ Zr ₂₂ Ti ₁₈ 454 512 58 67.3 36 Cu ₄₇ Ni ₁₃ Zr ₂₄ Ti ₁₆ 460 519 59 84.6 37 Cu ₄₇ Ni ₁₃ Zr ₂₂ Ti ₁₈ 459 518 59 84.1 38 Cu ₅₂ Ni ₇ Zr ₂₅ Ti ₁₆ 467 515 48 66.5 39 Cu ₅₁ Ni ₈ Zr ₂₃ Ti ₁₈ 457 512 55 66.8 40 Cu ₅₀ Ni ₉ Zr ₂₄ Ti ₁₇ 455 508 53 67.8 41 Cu ₅₁ Ni ₇ Zr ₂₃ Ti ₁₉ 424 479 55 64.9 42 Cu ₅₀ Ni ₇ Zr ₂₄ Ti ₁₉ 461 506 45 60.9 43 Cu ₅₁ Ni ₆ Zr ₂₃ Ti ₂₀ 453 496 43 67.1 44 Cu ₅₁ Ni ₆ Zr ₂₆ Ti ₁₇ 452 498 46 62.9 45 Cu ₄₈ Ni ₉ Zr ₂₃ Ti ₂₀ 466 512 48 59.7 46 Cu ₄₈ Ni ₉ Zr ₂₆ Ti ₁₇ 464 510 46 61.8 47 Cu ₄₅ Ni ₁₅ Zr ₂₂ Ti ₁₈ 458 526 68 57.0

In the case of the Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ alloy composition prepared by the casting method, it was confirmed that the crystalline content was contained in about 10% by weight as follows.

In Example 5 and Example 30, the production method is a casting method and a melt spinning method, respectively, and the alloy composition is the same as Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ . It is known that almost 100% amorphous phase is formed when rapid solidification method such as melt spinning method is used. Therefore, Example 30 according to the melt spinning method is set to 100% amorphous, and as a result of comparing the exothermic enthalpy of Example 5 prepared by the casting method, the exothermic enthalpy of Example 5 is about 90%, Example It can be inferred that about 10% by weight of the crystalline is contained in the alloy composition of 5.

The X-ray diffraction pattern and the high-resolution transmission electron microscope (HRTEM) photograph of Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ of Example 5 prepared by the casting method are shown in FIGS. 2 and 3, respectively. In the X-Ray diffraction pattern shown in Figure 2, it can be seen that the alloy composition prepared in accordance with the present invention exhibits the overall amorphous characteristics, but this alone can not be determined to be 100% amorphous structure. As a result of examining the alloy composition of Example 5 with a higher resolution by the high resolution TEM photograph of FIG. 3, it can be seen that the crystal phase of about 3 nm is shown inside the structure.

Compression test result graph of the alloy composition Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ according to Example 5 is attached to FIG. Compression experiments were carried out with a uniaxial compression strain rate of 1x10 ^-4 / s, total strain was 3.3%, plastic elongation was 1.5%, and fracture strength was 2.1 GPa. The Cu-based amorphous alloy composition containing crystalline has high mechanical strength and excellent elongation compared to a composition which is 100% amorphous, and thus can be applied to a wider range of applications and products.

As described above, the Cu-based amorphous alloy composition according to the present invention can be fabricated as a bulk amorphous having a size of 1 mm or more as a quaternary system, and the super-cooled liquid region has a high temperature forming process of up to 68Δ. It is easy compared to the composition. Particularly, in the case of Cu ₅₄ Ni ₆ Zr ₂₂ Ti ₁₈ in which nano size crystals are evenly distributed in the amorphous alloy composition, a bulk amorphous alloy with improved elongation can be prepared while maintaining overall amorphous characteristics, and high strength and It can be applied to various products requiring high toughness.

Claims (7)

Formula 1 (Formula 1) Cu _a Ni _b (Zr _1-x T _x ) _c Where a, b and c are 44 atomic% ≤ a ≤ 60 atomic%, 1 atomic% ≤ b ≤ 20 atomic%, 36 atomic% ≤ c ≤ 44 atomic%, and x is 0.34 ≤ x ≤ 0.47 felled Cu-based amorphous alloy composition. The method of claim 1, Amorphous forming ability of the alloy composition is characterized in that 1mm or more in diameter Cu-based amorphous alloy composition. The method of claim 1, A, b, c, x in Formula 1 is 48 atomic% ≤ a ≤ 55 atomic%, 6 atomic% ≤ b ≤ 10 atomic%, 39 atomic% ≤ c ≤ 43 atomic%, 0.39 ≤ x ≤ 0.46 Characterized by Cu-based amorphous alloy composition. The method of claim 3, The amorphous forming ability of the alloy composition is characterized in that the diameter of 4mm or more. Cu-based amorphous alloy composition. The method of claim 1, The amorphous phase in the composition is characterized in that at least 90% by weight based on the total weight of the composition Cu-based amorphous alloy composition. Cu-based amorphous alloy composition, the formula (Formula 1) Cu _a Ni _b (Zr _1-x Ti _x ) _c Where a, b and c are 44 atomic% ≤ a ≤ 60 atomic%, 1 atomic% ≤ b ≤ 20 atomic%, 36 atomic% ≤ c ≤ 44 atomic%, and x is 0.34 ≤ x ≤ 0.47, respectively. Notation, 10 wt% or less of the crystalline structure contained in the composition Cu-based amorphous alloy composition. The method of claim 6, The crystalline Cu-based amorphous alloy composition, characterized in that uniformly distributed in the composition in the size of 1-10nm.