KR20230169832A - Amorphous alloy, manufacturing method thereof, and product including the same - Google Patents

Abstract

It relates to an amorphous alloy, a method of manufacturing the same, and a product containing the same. The novel amorphous alloy of one embodiment includes a quaternary amorphous alloy matrix comprising Zr, Ni, Cu, and Al; And a complex concentrated alloy (CCA) dispersed within the quaternary amorphous alloy matrix and containing two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo. Includes.

Description

Amorphous alloy, method of manufacturing same, and product containing same {AMORPHOUS ALLOY, MANUFACTURING METHOD THEREOF, AND PRODUCT INCLUDING THE SAME}

It relates to an amorphous alloy, a method of manufacturing the same, and a product containing the same.

Amorphous alloys are attracting attention as next-generation high-quality structural materials. Specifically, an amorphous alloy is an amorphous solid whose constituent atoms are not arranged periodically, and has higher strength and elasticity limits than crystalline alloys, as well as excellent corrosion resistance and formability.

However, amorphous alloys show little ductility near room temperature and have low fracture toughness, which limits their commercialization as structural materials.

In this regard, several attempts are being made to improve the ductility of amorphous alloys.

For example, during the amorphous alloy manufacturing process, various elements are added to control the amorphous structure, or after the amorphous alloy is manufactured, strain is applied to form a shear band or local structural expansion (dilatation).

However, due to the essential characteristics of the amorphous structure, despite the above attempts, the degree of increase in ductility is extremely limited, and in many cases, the material strength is rapidly deteriorated.

Recently, high-entropy alloys and complex concentrated alloys (CCA), which have disordered atomic arrangements of multiple elements within a single crystal lattice structure, have been developed.

First, a high-entropy alloy is an alloy system in which all elements constituting it have the same or similar atomic fractions. In other words, all elements that make up a high-entropy alloy act as main elements and cause high mixing entropy. Accordingly, high-entropy alloys form stable solid solutions without forming intermetallic compounds or intermediate compounds even at high temperatures.

In the case of CCA, it is an expanded concept from high-entropy alloy. The fraction of the substitutional solid solution elements constituting this CCA can range from 5 to 95 element % for each element, and close interactions between solute elements can occur within a single crystal lattice structure. Accordingly, it may exhibit characteristics different from general amorphous alloys that have a disordered liquid structure in which the solute elements are surrounded by base elements.

One embodiment goes further on the concept of CCA and provides a novel amorphous alloy in which CCA is added to a quaternary amorphous alloy matrix.

Another embodiment provides a method for manufacturing the novel amorphous alloy.

Another embodiment provides a product containing the novel amorphous alloy.

One embodiment is a quaternary amorphous alloy matrix containing Zr, Ni, Cu, and Al; And a complex concentrated alloy (CCA) dispersed within the quaternary amorphous alloy matrix and containing two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo. It provides an amorphous alloy containing.

Of the total amount of 100 atomic% of the quaternary amorphous alloy matrix, Ni is contained at 2 to 29 atomic%, Cu is contained at 2 to 29 atomic%, and Al is contained at 6 to 18 atomic%, and Zr is included as a remainder.

The complex over-solidified alloy may have a single-phase body-centered cubic (BCC) structure.

It may further include complex quasicrystal clusters dispersed within the amorphous matrix.

The complex quasicrystal cluster may include a plurality of quasicrystal nuclei (QC) and a free volume region where the quasicrystal nuclei do not exist.

Each quasicrystal nucleus may include a plurality of principle clusters and a glue atom that bonds the plurality of principle clusters.

The basic cluster may include Zr and Ni among the elements constituting the quaternary amorphous alloy matrix.

The basic cluster may include Zr and Ni in an atomic ratio of 1:1 to 3:1 per unit.

The elementary cluster may have an icosahedral structure.

In each basic cluster, 9 Zr and 3 Ni form the basic skeleton of the icosahedral structure, and one Ni may be located at the center of the basic skeleton of the icosahedral structure.

The glue atom may include at least one of the elements constituting the complex oversolubilized alloy.

The overall composition of the amorphous alloy can be expressed as Formula 1:

[Formula 1]

Zr _a Ni _b Cu _cd Al _f (X) _d

In Formula 1, 29, d is 1 to 10, f is 6 to 18, and a is 100-(b+c+f).

X of Formula 1 may satisfy the following Equation 1:

[Equation 1]

10.0 ≤ {(1/3)*(x+n+o+p) + (1/6.9)*y + (1/7)*(z+m)}

In Formula 1, x is the atomic fraction of Ti in Formula 1; y is the atomic fraction of Zr in Formula 1; z is the atomic fraction of Hf in Formula 1; m is the atomic fraction of V in Formula 1; n is the atomic fraction of Nb in Formula 1; o is the atomic fraction of Ta in Formula 1; p is the atomic fraction of Mo in Formula 1 above.

The X may include four or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo.

The supercooled liquid region of the amorphous alloy may be 20 K or more.

The amorphous alloy may have an elongation of 5% or more during a three-point bending test on a 1 mm thick plate-shaped specimen.

The amorphous alloy may have a fracture rate of 0% when a compression test is performed on a specimen with an aspect ratio of 1 to 3.5 until the aspect ratio satisfies 1.

The amorphous alloy may have a fracture toughness of 100 MPa·m ^1/2 or more when subjected to a fracture test on a specimen with a thickness of 0.01 to 2.0 mm.

The fatigue life of the amorphous alloy can be increased by more than two times after continuously performing a fatigue test and 10 heat repetition processes within the elastic range on a specimen with a size of 0.01 to 2.0 mm.

The amorphous alloy has an enthalpy value after 10 thermal deformation cycles on a 2 mm rod-shaped specimen, when one heat deformation cycle is performed alternately in an environment below -50 ℃ and an environment above 100 ℃ for 20 seconds or more, respectively. The reduction rate can be more than 20%.

The amorphous alloy is manufactured by cooling the molten metal containing the first alloy elements and the second alloy elements, and the critical cooling rate when cooling the molten metal is 10 ⁰ K/s or more 10 ⁶ K/s, and The thickness of the molten metal may be 10 ㎛ or more and 20 mm or less.

In another embodiment, a first step of manufacturing a complex concentrated alloy (CCA) containing two or more selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo; A second step of preparing a mixture by mixing Zr, Ni, Cu, and Al with the complex oversolubilized alloy; A third step of melting the mixture to produce molten metal; and a fourth step of cooling the molten metal to obtain an amorphous alloy.

Among the total amount of Zr, Ni, Cu, and Al of 100 atomic%, in the total amount of 100 atomic% of the quaternary amorphous alloy matrix, Ni is included in 2 to 29 atomic%, and Cu is included in 2 to 29 atomic% Al is included in an amount of 6 to 18 atomic%, and Zr is the remainder.

In the fourth step, the critical cooling rate may be 10 ⁰ K/s or more and 10 ⁶ K/s or less.

In the fourth step, the thickness of the molten metal may be 10 ㎛ or more and 20 mm or less.

Another embodiment provides a product containing the amorphous alloy.

The products may be sporting goods, medical devices, watch gears, interior materials of electronic devices, exterior materials of electronic devices, or driving parts of smart robots.

A novel amorphous alloy in one embodiment maximizes both local compositional variation and structural complexity variation by adding CCA to a quaternary amorphous alloy matrix.

Accordingly, compared to conventional amorphous alloys, the novel amorphous alloy of one embodiment has a wide supercooled liquid region, has high toughness characteristics that exceed the brittleness limit, and can have unique healing properties.

Furthermore, a product using the novel amorphous alloy of one embodiment can have dramatically improved lifespan characteristics while maintaining thermal and mechanical stability.

Figure 1 schematically shows the single-phase body-centered cubic (BCC) structure of the complex over-solidifying alloy.
Figure 2 is a diagram for explaining the basis for selecting a candidate group of elements that can be included in the complex high-solidity alloy.
Figure 3 is a schematic diagram showing the complex quasicrystal cluster.
Figure 4 is a schematic diagram showing the formation of a quasicrystal nucleus through the combination of the basic cluster of the icosahedral structure and the adhesive element.
Figure 5 is a graph (above) showing the relationship between cluster volume and cluster level pressure of a conventional amorphous alloy; and a graph (below) showing the relationship between cluster volume and cluster level pressure when the complex quasicrystal cluster is present in the novel amorphous alloy of one embodiment.
Figure 6 is a Zr-Ni-Cu-Al quaternary phase diagram showing a plane with a constant Al content in the quaternary amorphous alloy matrix, a cross section where the Al content is 6 atomic%, 12 atomic%, or 18 atomic%, respectively. is indicated. (Top) Additionally, in the Zr-Ni-Cu-Al quaternary phase diagram, for the Zr-enriched region phase diagram of a cross section with Al contents of 6 atomic%, 12 atomic%, or 18 atomic%, respectively, the critical cooling rate is 10 ⁶ These are graphs (three below) showing the composition range in which an amorphous substance with a thickness of 10 ㎛ or more can be formed at K/s or less and the proeutectoid phase precipitated during heat treatment.
Figure 7 is a 2 mm rod-shaped CCA of each composition of Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ , Ti ₁₅ V ₃₈ Nb ₂₃ Hf ₂₄ , Ti _32.5 Zr _30.8 Nb _14.8 Hf _21.9 , and Ti ₂₀ Nb ₈ Ta ₈ Mo ₃₂ V ₃₂ . This is an X-ray diffraction analysis graph for the specimen.
Figure 8 is an X-ray diffraction analysis graph for a 2 mm rod-shaped amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ .
Figure 9 is a differential scanning calorimetry graph (left) for a 2 mm rod-shaped amorphous alloy specimen of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ composition, X after heat treatment to the peak of the first crystallization behavior. -This is a line diffraction analysis graph (right).
Figure 10 shows a case where, in the Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ (CCA) _d composition, CCA is Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ but the content (d) is set to 0 atomic% (no addition) and 2 This is a graph of compression test results for 2 mm rod-shaped amorphous alloy specimens, respectively, in atomic percent. The attached drawing is a photograph showing the appearance of an amorphous specimen containing CCA at 2 atomic percent after 40% compression strain.
Figure 11 shows the case where, in the Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ (CCA) _d composition, CCA is Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ but the content (d) is set to 0 atomic% (no addition) and 2 This is a graph of the results of a three-point bending test for plate-shaped amorphous alloy specimens with a thickness of 1 mm, each in atomic percent.
Figure 12 shows a single notch (notch length = 2.5 mm ( a / W = 0.5), notch manufactured through thermal plastic processing in the composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) _2. These are the fracture toughness measurement results of a 1 mm thick plate-shaped amorphous alloy specimen with root radius, ρ = 10 μm (top), and scanning electron microscope images showing the crack propagation behavior of the notch tip under each load condition (bottom). )am.
Figure 13 shows rod-shaped amorphous alloy specimens with a size of 2 mm in the composition Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ immediately after casting (as-cast) and after 10 healing cycles after casting, respectively. This is a differential scanning calorimetry analysis graph and an enlarged view of the structural relaxation area (inset).
Figure 14 shows a rod-shaped amorphous alloy specimen with a size of 2 mm immediately after casting (as-cast), after 50% compression strain, and 50% in _the composition Zr ₆₅ Ni ₁₂ Cu ₁₃ Al _{8 (Ti 25 Nb 25} Ta 25 Mo 25 ) ₂ . This is a differential scanning calorimetry analysis graph for a specimen that underwent 10 healing cycles after % compression deformation.
Figure 15 shows a 10 ㎛ thick ribbon amorphous alloy specimen in the composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ without undergoing healing cycle recovery treatment (as-spun specimen). ) and shows the results of a fatigue test performed on a specimen that underwent 10 healing cycle recovery treatment after deformation of 80% of the maximum fatigue deformation.

Hereinafter, specific implementation examples will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein.

(Definition of Terms)

The terminology used herein is for the purpose of describing example implementations only and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

“Combination thereof” means a mixture of constituents, a laminate, a composite, a copolymer, an alloy, a blend, a reaction product, etc.

Terms such as “comprise,” “comprise,” or “have” are intended to designate the presence of an implemented feature, number, step, component, or combination thereof, but are not intended to indicate the presence of one or more other features, numbers, steps, or combinations thereof. It should be understood that the existence or addition possibility of components or combinations thereof is not excluded in advance.

In the drawings, the thickness is enlarged to clearly express various layers and regions, and similar reference numerals are given to similar parts throughout the specification. When a part of a layer, membrane, region, plate, etc. is said to be “on” or “on” another part, this includes not only cases where it is “directly above” another part, but also cases where there is another part in between. Conversely, when a part is said to be “right on top” of another part, it means that there is no other part in between.

“Layer” includes not only the shape formed on the entire surface when observed in plan view, but also the shape formed on some surfaces.

“Thickness” may be measured through photographs taken with a microscope, such as a scanning electron microscope, for example.

“Atomic %” refers to the composition ratio of the number of atoms.

“A and/or B” means “A and B, or A or B”.

“Bulk” means having a thickness of 1 mm or more or an amorphous forming ability below a critical cooling rate of 10 ³ K/s.

(amorphous alloy)

One embodiment provides a novel amorphous alloy.

The novel amorphous alloy of one embodiment includes a quaternary amorphous alloy matrix comprising Zr, Ni, Cu, and Al; And a complex concentrated alloy (CCA) dispersed within the quaternary amorphous alloy matrix and containing two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo. Includes.

Of the total amount of 100 atomic% of the quaternary amorphous alloy matrix, Ni is contained at 2 to 29 atomic%, Cu is contained at 2 to 29 atomic%, and Al is contained at 6 to 18 atomic%, and Zr is included as a remainder. Specifically, Zr may be included in an amount of 55 to 73 atomic%.

When the composition range is satisfied, local compositional variation and structural complexity variation can be maximized at the same time. Accordingly, compared to conventional amorphous alloys, the novel amorphous alloy of one embodiment has a wide supercooled liquid region, has high toughness characteristics that exceed the brittleness limit, and can have unique healing properties.

Furthermore, a product using the novel amorphous alloy of one embodiment can have dramatically improved lifespan characteristics while maintaining thermal and mechanical stability.

Below, the novel amorphous alloy of one embodiment is described in more detail.

Complex Concentrated Alloy (CCA)

As previously mentioned, complex over-dissolved alloys typically exhibit a single-phase microstructure.

In a novel amorphous alloy of one embodiment, the microstructure of the complex hypersolidified alloy may be a single-phase body-centered cubic (BCC) structure. Figure 1 schematically shows the single-phase body-centered cubic (BCC) structure of the complex over-solidifying alloy.

Specifically, in the novel amorphous alloy of one embodiment, the complex hypersolidified alloy is 2, 3, 4, 5 selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo, It may contain 6 or 7 elements. The content of the elements constituting the complex hypersolidified alloy can be selected within a wide range of 5 to 95 element % for each element, and can be selected at an appropriate content depending on the characteristics of the desired final amorphous alloy.

In particular, there are at least two elements constituting the complex over-solidified alloy, and as the number of constituent elements increases, the characteristics of the final amorphous alloy can be improved. In particular, when there are four or more elements constituting the complex over-solidified alloy, the properties of the final amorphous alloy can be significantly improved. The properties of the final amorphous alloy are as described above or below.

Figure 2 is a diagram to explain the basis for selecting a group of element candidates that can be included in the complex over-solidifying alloy, and Table 1 below is a table summarizing the selection results. Specifically, this is a table showing the ratio of Equation A below.

[Equation A]

100%*{(actual radius of the element candidate group) - (atomic radius ideal to be included in the complex oversolubilized alloy)} / (atomic radius ideal to be included in the complex oversolubilized alloy)

The ideal atomic radius to be included in the complex oversolubilized alloy may mean the ideal atomic radius to form quasicrystal nuclei, which will be described later.

For Ti, Zr, Hf, V, Nb, Ta, and Mo, the difference in radius is within the range of -10 to +10%, calculated using Equation A. In particular, the ideal atomic radius corresponds to 0.1445 nm, which is 90.2% of the radius of Zr element. In addition, in the complex over-solidification alloy, elements that have a similar heat of mixing relationship within the range of -10 to 10 kJ/mol may be combined to promote over-solidification in the crystal lattice.

According to the difference in radius and similar heat of mixing relationship, the complex hypersolidified alloy can form a single-phase body-centered cubic structure, bonding a plurality of elementary clusters in the amorphous alloy, and quasicrystalline nuclei containing the plurality of elementary clusters. And complex quasicrystal clusters can be easily formed.

In particular, when adding the complex hypersolidizing alloy to the quaternary amorphous alloy matrix, in contrast to adding individual elements, the elements are smoothly dissolved despite the addition of multiple types of elements, and separate precipitates are formed. to form a homogeneous amorphous structure without forming or segregating.

Furthermore, when adding the complex hypersolidizing alloy to the quaternary amorphous alloy matrix, the type and/or number of elements that can be added may increase compared to adding individual elements. Here, as the type and/or number of elements that can be added increases, complex quasicrystal clusters are created within the amorphous alloy and its structural complexity increases, resulting in thermoplastic formability, toughness against compressive stress, and tensile stress of the amorphous alloy. Toughness, etc. can be comprehensively improved.

A detailed description of the elementary cluster, the complex quasicrystal cluster, etc. will be described later.

Complex over-solubilized alloy
elemental candidates Atomic Radius (nm) Equation A V 0.1316 - 9.0% Mo 0.1362 - 5.8% Nb 0.1429 - 1.2% Ta 0.1430 - 1.0% Ti 0.1462 1.0% Hf 0.1577 9.0% Zr 0.1603 10.0%

Complex quasicrystal cluster

The novel amorphous alloy of one embodiment may further include complex quasicrystal clusters dispersed in the quaternary amorphous alloy matrix. This is because it includes the quaternary amorphous alloy matrix and the complex hypersolidified alloy.

Figure 3 is a schematic diagram showing the complex quasicrystal cluster, and Figure 4 is a schematic diagram showing the formation of a quasicrystal nucleus through the combination of the basic cluster of the icosahedral structure and the adhesive element. Hereinafter, the complex quasicrystal cluster will be described with reference to FIGS. 3 and 4.

First, the complex quasicrystal cluster is described from top to bottom as follows.

The complex quasicrystal cluster may include a plurality of quasicrystal nuclei (QC; a plurality of multi-QCs) and a free volume region where the quasicrystal nuclei do not exist.

The quasicrystal nucleus may be formed by combining basic clusters in the form of vertex sharing, line sharing, or face sharing, and is a region in which constituent atoms are relatively densely packed. In contrast, the free volume region refers to a region where the quasicrystal nuclei do not exist and mainly appears in a region where constituent atoms are relatively loosely packed.

Specifically, each quasicrystal nucleus may include a plurality of principle clusters and a glue atom that bonds the plurality of principle clusters. As shown in FIG. 3, the quasicrystal core may be formed by combining the plurality of elementary clusters and the adhesive elements in the form of vertex sharing, line sharing, or face sharing, depending on the combining method.

More specifically, the basic cluster may include Zr and Ni among the elements constituting the quaternary amorphous alloy matrix. An icosahedral structure can be formed by including Zr and Ni in an atomic ratio of 1:1 to 3:1 per basic cluster. When the atomic ratio of Zr and Ni per one elementary cluster satisfies the above range, the combined shape and size of the elementary clusters can be adjusted, and the elementary clusters are easily connected by the complex hypersolidified alloy to form the complex quasicrystal. Clusters can be easily formed.

More specifically, per basic cluster of the icosahedral structure, 9 Zr and 3 Ni form the basic skeleton of the icosahedral structure (located at the vertices); One Ni may be located at the center of the basic skeleton of the icosahedral structure.

Meanwhile, the adhesive element may include at least one of the elements constituting the complex hypersolidizing alloy. Different elementary clusters may contain different adhesive elements.

The complex quasicrystal cluster is described from bottom to top as follows.

Inside the quaternary amorphous alloy matrix, Zr and Ni can form basic clusters of an icosahedral structure. At least one of the elements constituting the complex over-solidifying alloy can function as an adhesive element to bond the plurality of basic clusters. Accordingly, the plurality of elementary clusters and the adhesive elements may form quasicrystal nuclei.

Specifically, a plurality of quasicrystal nuclei are gathered to form the complex quasicrystal cluster, and within the complex quasicrystal cluster, a free volume region, which is a region in which the quasicrystal nuclei do not exist, also exists.

Other explanations are common to the top to bottom explanation above.

The structure of the complex quasicrystal cluster may serve as a 'basic unit' in a novel amorphous alloy of one embodiment, specifically, a 'basic unit of deformation' such as a shear transformation zone when deformed by external energy application.

Figure 5 is a graph (above) showing the relationship between cluster volume and cluster level pressure of a conventional amorphous alloy; and a graph (below) showing the relationship between cluster volume and cluster level pressure when the complex quasicrystal cluster is present in the novel amorphous alloy of one embodiment.

Here, “cluster level pressure” refers to the pressure that occurs due to misfit between the ‘cluster’ and the ‘cluster periphery’. This occurs due to differences in volume and stiffness resulting from the structural diversity of the ‘cluster’.

Referring to FIG. 5, unlike the conventional amorphous alloy, when the complex quasicrystal cluster is present in the novel amorphous alloy of one embodiment, the dispersion and complexity of cluster level pressure increase.

As a result, in the novel amorphous alloy of one embodiment, the total deviation in level pressure between the complex quasicrystal clusters increases, the stress is effectively distributed when stress is applied, the uniform deformation limit stress is significantly increased, and the activation energy of shear deformation is increased. ) increases, and the total strain induced internally when external energy is applied relatively increases, allowing it to exhibit high toughness characteristics and unique self-healing characteristics even in bulk amorphous substances of 1 mm or more.

A more detailed description of the physical properties exhibited by the novel amorphous alloy of one embodiment will be described later.

Overall composition of amorphous alloy

Basically, of the total amount of 100 atomic% of the quaternary amorphous alloy matrix, the Al content is 6 atomic% or more and 18 atomic% or less. Within this range, it can be adjusted to achieve the excellent amorphous forming ability, and if the content is outside the above range, the amorphous forming ability may rapidly decrease.

Figure 6 is a Zr-Ni-Cu-Al quaternary phase diagram showing a plane with a constant Al content in the quaternary amorphous alloy matrix, showing a cross section where the Al content is 6 atomic%, 12 atomic%, or 18 atomic%, respectively. indicated. (Top) Additionally, in the Zr-Ni-Cu-Al quaternary phase diagram, for the Zr-enriched region phase diagram of a cross section with Al contents of 6 atomic%, 12 atomic%, or 18 atomic%, respectively, the critical cooling rate is 10 ⁶ These are graphs (three below) showing the composition range in which an amorphous substance with a thickness of 10 ㎛ or more can be formed at K/s or less and the proeutectoid phase precipitated during heat treatment. According to the drawing, as described above, in the total amount of 100 atomic % of the quaternary amorphous alloy matrix, Ni is contained at 2 to 29 atomic %, Cu is contained at 2 to 29 atomic %, and Al is contained at 6 atomic %. to 18 atomic%, and Zr is included as the balance.

A detailed description of FIG. 6 will be provided later.

The novel amorphous alloy of one embodiment may have its overall composition represented by Formula 1, considering FIG. 6 above:

[Formula 1]

Zr _a Ni _b Cu _cd Al _f (X) _d

In the above formula (1), where b is 2 to 29 atomic%; (c-d) is 2 to 29 atomic%; where d is 1 to 10 atomic%; where f is 6 to 18 atomic%; The a is 100-(b+c+f).

In Formula 1, the 'Zr _a Ni _b Cu _cd Al _f ' portion may be due to the quaternary amorphous alloy matrix, and the '(X) _d ' portion may be due to the complex hypersolidified alloy.

Specifically, X in Chemical Formula 1 may satisfy the following Equation 1:

[Equation 1]

10.0 ≤ {(1/3)*(x+n+o+p) + (1/6.9)*y + (1/7)*(z+m)}

In Formula 1, x is the atomic fraction of Ti in Formula 1; y is the atomic fraction of Zr in Formula 1; z is the atomic fraction of Hf in Formula 1; m is the atomic fraction of V in Formula 1; n is the atomic fraction of Nb in Formula 1; o is the atomic fraction of Ta in Formula 1; p is the atomic fraction of Mo in Formula 1 above.

As the complex over-solidified alloy satisfies Equation 1, the total distribution of level pressure between the complex quasicrystal clusters is maximized, thereby greatly improving the thermal and mechanical stability of the novel amorphous alloy of one embodiment.

More specifically, the X may include four or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo.

Accordingly, the novel amorphous alloy of one embodiment may be an alloy of eight or more elements in total, and structural complexity and chemical complexity are maximized through the high entropy effect through a large increase in compositional entropy, resulting in not only thermal stability but also ultra-high toughness properties. It can also exhibit more improved self-healing characteristics.

Physical properties of amorphous alloy

In the novel amorphous alloy of one embodiment, the supercooled liquid region may be 20 K or more, and the upper limit is not particularly limited, but may be 200 K or less.

Specifically, in the novel amorphous alloy of one embodiment, as the structure becomes more complex compared to the conventional amorphous alloy, crystallization behavior may be delayed. Accordingly, the novel amorphous alloy of one embodiment may have a wide supercooled liquid region of 20 K or more between the glass transition temperature and the crystallization temperature, and may exhibit excellent thermal stability and thermoplastic forming ability.

In particular, the structural complexity exhibited by the novel amorphous alloy of one embodiment may be due to the presence of the complex quasicrystal cluster.

The novel amorphous alloy of one embodiment may have an elongation of 5% or more during a three-point bending test on a 1 mm thick plate-shaped specimen, and the upper limit is not particularly limited, but may be 50% or less.

Specifically, the novel amorphous alloy of one embodiment exhibits high toughness and can exhibit improved mechanical stability compared to conventional amorphous alloys. Accordingly, when the novel amorphous alloy of one embodiment and the conventional amorphous alloy are bent under the same conditions, the former may have a higher elongation than the latter.

The novel amorphous alloy of one embodiment may have a fracture rate of 0% when compression testing is performed on specimens with an aspect ratio of 1 to 3.5 until the aspect ratio satisfies 1. If the aspect ratio is less than 1, geometrically, compression fracture does not occur, and if it exceeds 3.5, buckling occurs and is excluded from the above range.

In detail, 50% deformation occurred in a rod-shaped specimen (4 mm height for a 2 mm rod shape) with an aspect ratio of 1 or more and 3.5 or less, specifically 2 to 3, more specifically 2 to 3, such as 2. For amorphous alloys; The aspect ratio after 50% deformation approaches 1.

For example, in the novel amorphous alloy of one embodiment, compression fracture does not occur during a 50% compression strain test on a 2 mm rod-shaped specimen, so the fracture rate may be 0%.

As such, the novel amorphous alloy of one embodiment has a superplastic behavior similar to the deformation behavior of a crystalline alloy, and can exhibit improved mechanical stability compared to a conventional amorphous alloy. Accordingly, when a novel amorphous alloy and a conventional amorphous alloy of one embodiment are tested for compression strain under the same conditions, the uniform strain limit stress of the former is much higher than that of the latter, so compression fracture itself may not occur (rupture rate 0%). .

In particular, the superplastic behavior exhibited by the novel amorphous alloy of one embodiment may be due to the presence of the complex quasicrystal clusters, resulting in an increase in the total deviation of level pressure between different complex quasicrystal clusters.

The novel amorphous alloy of one embodiment may have a fracture toughness of 100 MPa m ^1/2 or more when tested on a fracture toughness specimen with a thickness of 0.01 to 2.0 mm, specifically 0.3 mm, and the upper limit is not particularly limited, but is 300 MPa · It may be less than m ^1/2 .

The novel amorphous alloy of one embodiment has unique self-healing properties in which the deformed area is recovered even when external energy including one selected from the group consisting of mechanical energy, electrical energy, thermal energy, magnetic energy, and combinations thereof is applied. It can be expressed.

In this way, the novel amorphous alloy of one embodiment relatively increases the total strain induced internally when external energy is applied, and can effectively recover its original properties through unique self-healing, which is a conventional amorphous alloy. In preparation for this, longevity can be promoted.

Specifically, in the novel amorphous alloy of one embodiment, fatigue life can be increased by more than two times after continuously performing a fatigue test and 10 heat repetition processes within the elastic range on a specimen with a size of 0.01 to 2.0 mm. .

The heat repetition process may be performed alternately in an environment of -50°C or lower and an environment of 100°C or higher for 20 seconds or more, respectively, as one heat deformation cycle.

The elasticity range of the amorphous alloy specimen may be around 2%, and 'fatigue life' may mean 'the number of fatigue failure cycles when the amorphous alloy finally reaches fracture due to the propagation of fatigue cracks.'

For example, the enthalpy value reduction rate (specifically, healing from permanent deformation) after 10 heat deformation cycles for a 2 mm rod-shaped specimen may be 20% or more, and the upper limit is not particularly limited, but may be 100% or less.

The enthalpy value reduction rate can be calculated using Equation 2 below.

[Equation 2]

Enthalpy reduction rate (%) = 100 * ((Enthalpy of amorphous alloy immediately after deformation - Enthalpy of amorphous alloy after thermal deformation cycle after deformation) / (Enthalpy of amorphous alloy immediately after deformation - Enthalpy of amorphous alloy immediately after manufacturing) )

In particular, the self-healing behavior exhibited by the novel amorphous alloy of one embodiment may be due to the presence of the complex quasicrystal cluster. Even when the local strain generated by shear band formation in the novel amorphous alloy of the above embodiment reaches the plastic deformation region, the viscous flow resistance of the quasicrystal nuclei in the complex quasicrystal cluster increases, and the complex quasicrystal cluster The total deviation of inter-level pressure increases and fracture may be delayed.

quite

The novel amorphous alloy of one embodiment can be manufactured by cooling molten metal containing the first alloy elements and the second alloy elements, and when cooling the molten metal, the critical cooling rate and the thickness of the molten metal are set within a specific range. Only when controlled with , a new amorphous alloy containing the complex quasicrystal cluster can be formed.

Here, “thickness of molten metal” may mean the smallest thickness in the three-dimensional shape formed by molten metal. Specifically, in a three-dimensional shape formed by molten metal, it may mean the shortest distance between a straight line passing through the inside of the three-dimensional shape and the distance formed by the outer surface.

With reference to FIG. 6, the cooling process of molten metal in the process of manufacturing a novel amorphous alloy according to one embodiment will be described in detail.

When cooling the molten metal, the critical cooling rate may be 10 ⁰ K/s or more and 10 ⁶ K/s, and the thickness of the molten metal may be 10 ㎛ or more and 20 mm or less.

Here, the composition of the quaternary amorphous alloy matrix (out of 100 atomic% of the total amount of the quaternary amorphous alloy matrix, Ni is included in 2 to 29 atomic% of the total amount of 100 atomic% of the quaternary amorphous alloy matrix, and Cu is contained at 2 to 29 atomic%, Al is contained at 6 to 18 atomic%, and Zr is included as the balance), and only then, the thickness of the molten metal is controlled to be 10 ㎛ or more and 20 mm or less. At the same time, when cooling the molten metal, the critical cooling rate can be controlled within the range of 10 ⁰ K/s or more to 10 ⁶ K/s.

Furthermore, when the critical cooling rate and the thickness of the molten metal satisfy the above ranges during cooling of the molten metal, a new amorphous alloy comprising the quaternary amorphous alloy matrix and the complex hypersolidified alloy dispersed therein can be obtained. there is.

A detailed description of the above manufacturing method will be provided later.

(Method for producing amorphous alloy)

Another embodiment provides a method for manufacturing the novel amorphous alloy of the above-described embodiment.

Specifically, one embodiment is a first step of manufacturing a complex concentrated alloy (CCA) containing two or more selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo. ; A second step of preparing a mixture by mixing Zr, Ni, Cu, and Al with the complex oversolubilized alloy; A third step of melting the mixture to produce molten metal; and a fourth step of cooling the molten metal to obtain an amorphous alloy.

Among the total amount of Zr, Ni, Cu, and Al of 100 atomic%, in the total amount of 100 atomic% of the quaternary amorphous alloy matrix, Ni is included in 2 to 29 atomic%, and Cu is included in 2 to 29 atomic% Al is included at 6 to 18 atomic%, and Zr is included as the remainder.

A complex hypersolidizing alloy of the above composition is first prepared (first step), elements that serve as raw materials for the quaternary amorphous alloy matrix are added (second step), and the mixture is melted to prepare molten metal ( Third step), and finally cooling the molten metal (fourth step), a new amorphous alloy can be produced.

Hereinafter, descriptions that overlap with the above will be omitted, and each step of manufacturing a new amorphous alloy in one embodiment will be described in detail.

Manufacturing steps of complex over-solidifying alloy (first step)

First, a complex hypersolidizing alloy is prepared including two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo. Specifically, a complex hyper-solidifying alloy is prepared including 2, 3, 4, 5, 6, or 7 elements selected from the above group.

When manufacturing the complex hypersolidified alloy, the content of each element can be determined within a wide range of 5 to 95% of elements at which interaction between solute elements is activated, depending on the characteristics of the final amorphous alloy of interest.

As mentioned earlier, there are at least two elements constituting the complex over-solidified alloy, and as the number of constituent elements increases, the characteristics of the final amorphous alloy can be improved. In particular, when there are four or more elements constituting the complex over-solidified alloy, the properties of the final amorphous alloy can be significantly improved. The properties of the final amorphous alloy are as described above or below.

Mixing stage (second stage)

After the first step, the elements that serve as raw materials for the quaternary amorphous alloy matrix (i.e., Zr, Ni, Cu, and Al) and the complex hypersolidified alloy are mixed to prepare a mixture.

When preparing the mixture, the stoichiometric atomic ratio can be determined depending on the composition of the final amorphous alloy.

Molten metal manufacturing step (third step)

After the second step, the mixture is melted to prepare molten metal.

Specifically, the melting temperature range may be 500 to 3500° C., and the melting time may be from 1 second to 1 hour.

Cooling stage (fourth stage)

After the third step, the molten metal is cooled.

In the fourth step, an amorphous alloy including the quaternary amorphous alloy matrix and the complex hypersolidified alloy may be formed.

Specifically, in the fourth step, a plurality of basic clusters are formed, and the adhesive element can bond the plurality of basic clusters to form quasicrystal nuclei. Since this process takes place during a rapid cooling process and the quasicrystal nuclei serve as seeds for crystallization, the quasicrystal nuclei can be referred to as 'quenched nuclei'.

In particular, the critical cooling rate in the fourth step is 10 ⁰ K/s or more and 10 ⁶ K/s or less; The thickness of the molten metal may be 10 ㎛ or more and 20 mm or less. When this range is satisfied, the complex quasicrystal cluster including a plurality of quasicrystal nuclei and a free volume region, which is a region where the quasicrystal nuclei do not exist, can be formed.

(product)

Another embodiment provides a product containing the novel amorphous alloy of the above-described embodiment.

A product using the novel amorphous alloy of one embodiment can have dramatically improved lifespan characteristics while maintaining thermal and mechanical stability.

The products may be sporting goods, medical devices, watch gears, interior materials of electronic devices, exterior materials of electronic devices, or driving parts of smart robots. However, this is just an example and can be applied to a wider range of products.

Hereinafter, examples and comparative examples of the present invention will be described. The following examples are only examples of the present invention, and the present invention is not limited to the following examples.

(Test example)

Test Example 1: XRD after casting of quaternary ribbon amorphous alloy and after first crystallization

After fixing the Al content at 6 atomic%, 12 atomic%, or 18 atomic%, respectively, the respective contents of Ni and Cu were changed according to Table 2 below, and Zr was left as the balance, resulting in Zr, Ni, Cu, and Al. A quaternary amorphous alloy raw material mixture containing was prepared.

The quaternary amorphous alloy raw material mixture was melted at 2000° C. for 10 minutes to prepare molten metal. The molten metal was cooled for less than 1 second at a cooling rate of 10 ⁶ ℃/s, and then molded into a 10 ㎛ ribbon shape to obtain a quaternary amorphous alloy specimen.

The structure was analyzed using _an After confirming whether a phase or quasicrystal phase (Icosahedral phase, I-phase) was formed, the results are summarized in FIG. 6 and Table 2 below.

Furtherance 10 ㎛ ribbon
amorphous formation
Whether cornerstone statue Zr65Ni28Cu1Al6 X - Zr65Ni26Cu3Al6 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni21Cu7Al6 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni18Cu11Al6 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni14Cu15Al6 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni10Cu19Al6 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni6Cu23Al6 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni1Cu28Al6 O Zr2Cu Zr67Ni26Cu1Al6 X - Zr67Ni24Cu3Al6 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni20Cu7Al6 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni16Cu11Al6 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni12Cu15Al6 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni8Cu19Al6 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni4Cu23Al6 O Zr2Ni, ZrAl, Zr2Cu Zr69Ni24Cu1Al6 X - Zr69Ni22Cu3Al6 O Zr2Ni, ZrAl, Zr2Cu Zr69Ni18Cu7Al6 O Zr2Ni, ZrAl, Zr2Cu Zr69Ni14Cu11Al6 O Zr2Ni, ZrAl, Zr2Cu Zr69Ni10Cu15Al6 O Zr2Ni, ZrAl, Zr2Cu Zr69Ni6Cu19Al6 O Zr2Ni, ZrAl, Zr2Cu Zr69Ni1Cu24Al6 O Zr2Cu Zr71Ni22Cu1Al6 X - Zr71Ni20Cu3Al6 O I-phase Zr71Ni16Cu7Al6 O I-phase Zr71Ni12Cu11Al6 O I-phase Zr71Ni8Cu15Al6 O I-phase Zr71Ni4Cu19Al6 O I-phase Zr73Ni20Cu1Al6 X - Zr73Ni18Cu3Al6 O I-phase Zr73Ni14Cu7Al6 O I-phase Zr73Ni10Cu11Al6 O I-phase Zr73Ni6Cu15Al6 O I-phase Zr73Ni1Cu20Al6 X - Zr75Ni18Cu1Al6 X - Zr75Ni16Cu3Al6 O β-Zr Zr75Ni14Cu5Al6 O β-Zr Zr75Ni12Cu7Al6 O β-Zr Zr75Ni10Cu9Al6 O β-Zr Zr75Ni8Cu11Al6 O β-Zr Zr75Ni6Cu13Al6 O β-Zr Zr75Ni4Cu15Al6 O β-Zr Zr75Ni1Cu17Al6 X - Zr77Ni16Cu1Al6 X - Zr77Ni14Cu3Al6 X - Zr77Ni12Cu5Al6 X - Zr77Ni10Cu7Al6 X - Zr77Ni18Cu9Al6 X - Zr77Ni6Cu11Al6 X - Zr77Ni4Cu13Al6 X - Zr77Ni1Cu16Al6 X - Zr59Ni28Cu1Al12 X - Zr59Ni26Cu3Al12 O Zr2Ni, ZrAl, Zr2Cu Zr59Ni21Cu7Al12 O Zr2Ni, ZrAl, Zr2Cu Zr59Ni18Cu11Al12 O Zr2Ni, ZrAl, Zr2Cu Zr59Ni14Cu15Al12 O Zr2Ni, ZrAl, Zr2Cu Zr59Ni10Cu19Al12 O Zr2Ni, ZrAl, Zr2Cu Zr59Ni6Cu23Al12 O Zr2Ni, ZrAl, Zr2Cu Zr59Ni1Cu28Al12 O Zr2Cu Zr61Ni26Cu1Al12 X - Zr61Ni24Cu3Al12 O Zr2Ni, ZrAl, Zr2Cu Zr61Ni20Cu7Al12 O Zr2Ni, ZrAl, Zr2Cu Zr61Ni16Cu11Al12 O Zr2Ni, ZrAl, Zr2Cu Zr61Ni12Cu15Al12 O Zr2Ni, ZrAl, Zr2Cu Zr61Ni8Cu19Al12 O Zr2Ni, ZrAl, Zr2Cu Zr61Ni4Cu23Al12 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni24Cu1Al12 X - Zr63Ni22Cu3Al12 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni18Cu7Al12 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni14Cu11Al12 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni10Cu15Al12 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni6Cu19Al12 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni1Cu24Al12 O Zr2Cu Zr65Ni22Cu1Al12 X - Zr65Ni20Cu3Al12 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni16Cu7Al12 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni12Cu11Al12 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni8Cu15Al12 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni4Cu19Al12 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni20Cu1Al12 X - Zr67Ni18Cu3Al12 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni14Cu7Al12 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni10Cu11Al12 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni6Cu15Al12 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni1Cu20Al12 O Zr2Cu Zr69Ni18Cu1Al12 X - Zr69Ni16Cu3Al12 O I-phase Zr69Ni14Cu5Al12 O I-phase Zr69Ni12Cu7Al12 O I-phase Zr69Ni10Cu9Al12 O I-phase Zr69Ni8Cu11Al12 O I-phase Zr69Ni6Cu13Al12 O I-phase Zr69Ni4Cu15Al12 O I-phase Zr69Ni1Cu17Al12 O Zr2Cu Zr70Ni9Cu9Al12 O I-phase Zr71Ni16Cu1Al12 X - Zr71Ni14Cu3Al12 O I-phase Zr71Ni12Cu5Al12 O I-phase Zr71Ni10Cu7Al12 O I-phase Zr71Ni18Cu9Al12 O I-phase Zr71Ni6Cu11Al12 O I-phase Zr71Ni4Cu13Al12 O I-phase Zr71Ni1Cu16Al12 O Zr2Cu Zr73Ni14Cu1Al12 X - Zr73Ni12Cu3Al12 O I-phase Zr73Ni10Cu5Al12 O I-phase Zr73Ni18Cu7Al12 O I-phase Zr73Ni6Cu9Al12 O I-phase Zr73Ni4Cu11Al12 O I-phase Zr73Ni1Cu14Al12 X - Zr75Ni12Cu1Al12 X - Zr75Ni10Cu3Al12 O β-Zr Zr75Ni18Cu5Al12 O β-Zr Zr75Ni6Cu7Al12 O β-Zr Zr75Ni4Cu9Al12 O β-Zr Zr75Ni2Cu11Al12 X - Zr77Ni8Cu3Al12 X - Zr77Ni6Cu5Al12 X - Zr77Ni3Cu8Al12 X - Zr65Ni8Cu15Al12 O Zr2Ni, ZrAl, Zr2Cu Zr55Ni26Cu1Al18 X - Zr55Ni24Cu3Al18 O Zr2Ni, ZrAl, Zr2Cu Zr55Ni20Cu7Al18 O Zr2Ni, ZrAl, Zr2Cu Zr55Ni16Cu11Al18 O Zr2Ni, ZrAl, Zr2Cu Zr55Ni12Cu15Al18 O Zr2Ni, ZrAl, Zr2Cu Zr5Ni8Cu19Al18 O Zr2Ni, ZrAl, Zr2Cu Zr55Ni4Cu23Al18 O Zr2Ni, ZrAl, Zr2Cu Zr57Ni24Cu1Al18 X - Zr57Ni22Cu3Al18 O Zr2Ni, ZrAl, Zr2Cu Zr57Ni18Cu7Al18 O Zr2Ni, ZrAl, Zr2Cu Zr57Ni14Cu11Al18 O Zr2Ni, ZrAl, Zr2Cu Zr57Ni10Cu15Al18 O Zr2Ni, ZrAl, Zr2Cu Zr57Ni6Cu19Al18 O Zr2Ni, ZrAl, Zr2Cu Zr57Ni1Cu24Al18 O Zr2Cu Zr59Ni22Cu1Al18 X - Zr59Ni20Cu3Al18 O Zr2Ni, ZrAl, Zr2Cu Zr59Ni16Cu7Al18 O Zr2Ni, ZrAl, Zr2Cu Zr59Ni12Cu11Al18 O Zr2Ni, ZrAl, Zr2Cu Zr59Ni8Cu15Al18 O Zr2Ni, ZrAl, Zr2Cu Zr59Ni4Cu19Al18 O Zr2Ni, ZrAl, Zr2Cu Zr61Ni20Cu1Al18 X - Zr61Ni18Cu3Al18 O Zr2Ni, ZrAl, Zr2Cu Zr61Ni14Cu7Al18 O Zr2Ni, ZrAl, Zr2Cu Zr61Ni10Cu11Al18 O Zr2Ni, ZrAl, Zr2Cu Zr61Ni6Cu15Al18 O Zr2Ni, ZrAl, Zr2Cu Zr61Ni1Cu20Al18 O Zr2Cu Zr63Ni18Cu1Al18 X - Zr63Ni16Cu3Al18 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni14Cu5Al18 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni12Cu7Al18 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni10Cu9Al18 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni8Cu11Al18 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni6Cu13Al18 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni4Cu15Al18 O Zr2Ni, ZrAl, Zr2Cu Zr63Ni1Cu17Al18 O Zr2Cu Zr65Ni16Cu1Al18 X - Zr65Ni14Cu3Al18 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni12Cu5Al18 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni10Cu7Al18 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni18Cu9Al18 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni6Cu11Al18 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni4Cu13Al18 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni1Cu16Al18 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni14Cu1Al18 X - Zr67Ni12Cu3Al18 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni10Cu5Al18 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni18Cu7Al18 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni6Cu9Al18 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni4Cu11Al18 O Zr2Ni, ZrAl, Zr2Cu Zr67Ni1Cu14Al18 X - Zr69Ni12Cu1Al18 X - Zr69Ni10Cu3Al18 O Zr2Ni, ZrAl, Zr2Cu Zr69Ni18Cu5Al18 O Zr2Ni, ZrAl, Zr2Cu Zr69Ni6Cu7Al18 O Zr2Ni, ZrAl, Zr2Cu Zr69Ni4Cu9Al18 O Zr2Ni, ZrAl, Zr2Cu Zr69Ni2Cu11Al18 X - Zr71Ni8Cu3Al18 O I-phase Zr71Ni6Cu5Al18 O I-phase Zr71Ni3Cu8Al18 O I-phase Zr73Ni8Cu1Al18 X Zr73Ni6Cu3Al18 O I-phase Zr73Ni4Cu5Al18 O I-phase Zr73Ni2Cu7Al18 X Zr75Ni6Cu1Al18 X - Zr75Ni4Cu3Al18 O β-Zr Zr75Ni2Cu5Al18 O β-Zr Zr75Ni1Cu6Al18 X - Zr77Ni4Cu1Al18 X - Zr77Ni2Cu3Al18 X - Zr77Ni1Cu4Al18 X - Zr65Ni12Cu19Al4 X - Zr65Ni11Cu18Al6 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni10Cu17Al8 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni9Cu16Al10 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni7Cu14Al14 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni6Cu13Al16 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni5Cu12Al18 O Zr2Ni, ZrAl, Zr2Cu Zr65Ni4Cu11Al20 X -

Referring to FIG. 6 and Table 2, in the quaternary amorphous alloy specimen itself, when the Al content is 12 atomic% and the respective contents of Ni and Cu are about 29 atomic% or less, amorphousness is good based on a 10 ㎛ ribbon. It is formed by precipitating Zr ₂ Ni and/or I-phase in which the principle cluster or quenched-in Icosahedral nuclei of Zr ₂ Ni composition are dispersed within the quaternary amorphous alloy matrix. You can check that it happens.

However, in the quaternary amorphous alloy specimen itself, when the Al content is fixed at 12 atomic% and the sum of Ni and Cu contents is less than about 15 atomic%, an amorphous phase and a crystalline phase are formed together based on a 10 ㎛ ribbon, Through X-ray diffraction analysis, it was confirmed that a completely amorphous alloy in which only the halo peak was observed was not formed.

Meanwhile, referring to Table 2, in the quaternary amorphous alloy specimen itself, in the case of a Zr ₇₅ Ni ₁₈ Cu ₅ Al ₁₂ composition with a high Zr content, β-Zr is precipitated in the form of prophylactoid and forms inside the quaternary amorphous alloy matrix. Only a β-Zr cluster is formed, but a principal cluster or quasicrystal quenched nuclei of Zr ₂ Ni composition are not formed.

In addition, in the quaternary amorphous alloy specimen itself, in the case of a Zr ₇₁ Ni ₁ Cu ₁₆ Al ₁₂ composition with an extremely high Cu content, Zr ₂ Cu is precipitated in the form of a superlithe, forming Zr ₂ Cu clusters inside the quaternary amorphous alloy matrix. is formed, but the principle cluster or quenched-in icosahedral nuclei of Zr ₂ Ni composition are not formed.

On the other hand, in the quaternary amorphous alloy specimen itself, in the composition range of the novel amorphous alloy of one embodiment, Zr ₆₅ Cu ₁₅ Ni ₈ Al ₁₂ , Zr ₆₃ Cu ₇ Ni ₁₈ Al ₁₂ , etc., inside the quaternary amorphous alloy matrix Principal clusters of Zr ₂ Ni composition, quenched-in Icosahedral nuclei, or both are formed.

Test Example 2: XRD after casting of quaternary bulk amorphous alloy, after first crystallization

After fixing the Al content at 12 atomic%, the respective contents of Ni and Cu were changed according to Table 3 below, and Zr was the balance, thereby preparing a quaternary amorphous alloy raw material mixture.

The quaternary amorphous alloy raw material mixture was melted at 2000° C. for 10 minutes to prepare molten metal. The molten metal was cooled at a cooling rate of 1000°C/s for 3 seconds or less, and then molded into a 1 mm rod shape to obtain a quaternary amorphous alloy specimen.

The structure was analyzed using _an After confirming whether a phase was formed, the results are summarized in Table 3 below.

Furtherance 1 mm rod
amorphous formation
Whether cornerstone statue Zr59Cu1Ni28Al12 X - Zr59Cu3Ni26Al12 X NiZr2, AlZr, CuZr2 Zr59Cu7Ni21Al12 O NiZr2, AlZr, CuZr2 Zr59Cu11Ni18Al12 O NiZr2, AlZr, CuZr2 Zr59Cu15Ni14Al12 O NiZr2, AlZr, CuZr2 Zr59Cu19Ni10Al12 O NiZr2, AlZr, CuZr2 Zr59Cu23Ni6Al12 O NiZr2, AlZr, CuZr2 Zr59Cu28Ni1Al12 X CuZr2 Zr61Cu1Ni26Al12 X - Zr61Cu3Ni24Al12 X NiZr2, AlZr, CuZr2 Zr61Cu7Ni20Al12 O NiZr2, AlZr, CuZr2 Zr61Cu11Ni16Al12 O NiZr2, AlZr, CuZr2 Zr61Cu15Ni12Al12 O NiZr2, AlZr, CuZr2 Zr61Cu19Ni8Al12 O NiZr2, AlZr, CuZr2 Zr61Cu23Ni4Al12 X NiZr2, AlZr, CuZr2 Zr63Cu1Ni24Al12 X - Zr63Cu3Ni22Al12 X NiZr2, AlZr, CuZr2 Zr63Cu7Ni18Al12 O NiZr2, AlZr, CuZr2 Zr63Cu11Ni14Al12 O NiZr2, AlZr, CuZr2 Zr63Cu15Ni10Al12 O NiZr2, AlZr, CuZr2 Zr63Cu19Ni6Al12 O NiZr2, AlZr, CuZr2 Zr63Cu24Ni1Al12 X CuZr2 Zr65Cu1Ni22Al12 X - Zr65Cu3Ni20Al12 X NiZr2, AlZr, CuZr2 Zr65Cu7Ni16Al12 O NiZr2, AlZr, CuZr2 Zr65Cu11Ni12Al12 O NiZr2, AlZr, CuZr2 Zr65Cu15Ni8Al12 O NiZr2, AlZr, CuZr2 Zr65Cu19Ni4Al12 X NiZr2, AlZr, CuZr2 Zr67Cu1Ni20Al12 X - Zr67Cu3Ni18Al12 X NiZr2, AlZr, CuZr2 Zr67Cu7Ni14Al12 O NiZr2, AlZr, CuZr2 Zr67Cu11Ni10Al12 O NiZr2, AlZr, CuZr2 Zr67Cu15Ni6Al12 O NiZr2, AlZr, CuZr2 Zr67Cu20Ni1Al12 X CuZr2 Zr69Cu1Ni18Al12 X - Zr69Cu3Ni16Al12 X I-phase Zr69Cu5Ni14Al12 O I-phase Zr69Cu7Ni12Al12 O I-phase Zr69Cu9Ni10Al12 O I-phase Zr69Cu11Ni8Al12 O I-phase Zr69Cu13Ni6Al12 O I-phase Zr69Cu15Ni4Al12 X I-phase Zr69Cu17Ni1Al12 X CuZr2 Zr70Cu9Ni9Al12 O I-phase Zr71Cu1Ni16Al12 X - Zr71Cu3Ni14Al12 X I-phase Zr71Cu5Ni12Al12 X I-phase Zr71Cu7Ni10Al12 X I-phase Zr71Cu9Ni18Al12 X I-phase Zr71Cu11Ni6Al12 X I-phase Zr71Cu13Ni4Al12 X I-phase Zr71Cu16Ni1Al12 X CuZr2 Zr73Cu1Ni14Al12 X - Zr73Cu3Ni12Al12 X I-phase Zr73Cu5Ni10Al12 X I-phase Zr73Cu7Ni18Al12 X I-phase Zr73Cu9Ni6Al12 X I-phase Zr73Cu11Ni4Al12 X I-phase Zr73Cu14Ni1Al12 X - Zr75Cu1Ni12Al12 X - Zr75Cu3Ni10Al12 X β-Zr Zr75Cu5Ni18Al12 X β-Zr Zr75Cu7Ni6Al12 X β-Zr Zr75Cu9Ni4Al12 X β-Zr Zr75Cu11Ni2Al12 X - Zr77Cu3Ni8Al12 X - Zr77Cu5Ni6Al12 X - Zr77Cu8Ni3Al12 X - Zr70Cu9Ni9Al12 O I-phase Zr70Cu13Ni13Al4 X - Zr70Cu12Ni12Al6 O I-phase Zr70Cu11Ni11Al8 O I-phase Zr70Cu10Ni10Al10 O I-phase Zr70Cu8Ni8Al14 O I-phase Zr70Cu7Ni7Al16 O I-phase Zr70Cu6Ni6Al18 O I-phase Zr70Cu5Ni5Al20 X -

Referring to Table 3, when the quaternary amorphous alloy specimen is manufactured by itself, the Zr content is 60 to 70 atomic%, the Ni content is 5 to 21 atomic%, and the Cu content is 5 to 21 atomic%. , and when the content of Al is 6 to 18 atomic%, a bulk amorphous alloy having a thickness of 1 mm or more can be formed, and Zr ₂ Ni and/or I phase are precipitated as a proeutectoid phase, forming the bulk amorphous alloy Inside the matrix, principal clusters or quenched-in icosahedral nuclei of Zr ₂ Ni composition may be dispersed.

Test Example 3: XRD of complex concentrated alloy (CCA)

Two or more elements were selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo, and mixed according to the composition in Table 4 below to prepare a raw material mixture.

The raw material mixture was melted at 3500°C for 10 minutes to prepare molten metal. The molten metal was cooled at a cooling rate of 250°C/s for 10 seconds or less, and then molded into a 2 mm rod shape to obtain the CCA specimen of Test Example 3.

The structure was analyzed using an X-ray diffraction analyzer (New D8 Advance, Bruker Corporation), and the crystal structure precipitated inside the CCA specimen was analyzed.

alloy composition phase Ti ₉₅ Nb ₅ BCC Nb ₉₅ Ta ₅ BCC Zr ₅ Hf ₉₅ BCC Zr ₉₅ Hf ₅ BCC Mo ₅ Ta ₉₅ BCC Mo ₉₅ Ta ₅ BCC Ti ₅ Hf ₅ Zr ₉₀ BCC Nb ₅ Ta ₅ Zr ₉₀ BCC Ti ₅ Nb ₅ Ta ₅ Zr ₈₅ BCC Nb ₅ Ta ₅ Mo ₉₀ BCC Ti _33.3 Zr _33.3 Hf _33.3 BCC Ti _33.3 Zr _33.3 V _33.3 BCC Ti _33.3 Zr _33.3 Nb _33.3 BCC Ti ₁₀ Zr ₃₀ Nb ₆₀ BCC Ti ₁₀ Zr ₇₀ Nb ₂₀ BCC Ti _33.3 Zr _33.3 Ta _33.3 BCC Ti ₂₀ Zr ₂₀ Ta ₆₀ BCC Ti ₂₅ Zr ₂₅ Nb ₂₅ Ta ₂₅ BCC Ti ₁₅ Zr ₁₅ Nb ₃₅ Ta ₃₅ BCC Ti _33.3 Hf _33.3 Nb _33.3 BCC Ti _33.3 Hf _33.3 Ta _33.3 BCC Ti ₂₅ Hf ₂₅ Nb ₂₅ Ta ₂₅ BCC V _33.3 Nb _33.3 Ta _33.3 BCC V ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ BCC V _33.3 Nb _33.3 Mo _33.3 BCC V _33.3 Ta _33.3 Mo _33.3 BCC Ti ₂₀ Zr ₂₀ Hf ₂₀ Nb ₂₀ Ta ₂₀ BCC V ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ BCC Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ BCC Ti _16.7 Zr _16.7 Hf _16.7 V _16.7 Nb _16.7 Ta _16.7 BCC Ti ₅ Zr ₅ Hf ₅ V _28.3 Nb _28.3 Ta _28.3 BCC Ti _2.86 Zr _2.86 Hf _2.86 V ₂₀ Nb ₂₀ Ta ₂₀ Mo ₂₀ BCC Ti _14.3 Zr _14.3 Hf _14.3 V _14.3 Nb _14.3 Ta _14.3 Mo _14.3 BCC Ti _32.5 V _15.4 Nb _22.6 Hf _24.1 BCC Ti ₁₅ V ₃₈ Nb ₂₃ Hf ₂₄ BCC Ti _26.5 V _26.5 Nb ₂₃ Hf ₂₄ BCC Ti ₃₈ V ₁₅ Nb ₂₃ Hf ₂₄ BCC (Nb ₅₀ Ta ₅₀ ) _0.2 (Mo ₅₀ V ₅₀ ) _0.8 BCC (Nb ₅₀ Ta ₅₀ ) _0.4 (Mo ₅₀ V ₅₀ ) _0.6 BCC (Nb ₅₀ Ta ₅₀ ) _0.6 (Mo ₅₀ V ₅₀ ) _0.4 BCC (Nb ₅₀ Ta ₅₀ ) _0.8 (Mo ₅₀ V ₅₀ ) _0.2 BCC Ti ₁₀ Nb ₉ Ta ₉ Mo ₃₆ V ₃₆ BCC Ti ₂₀ Nb ₈ Ta ₈ Mo ₃₂ V ₃₂ BCC Ti ₃₀ Nb ₇ Ta ₇ Mo ₂₈ V ₂₈ BCC

Figure 7 shows 2 mm rod-shaped CCA specimens of each composition of Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ , Ti ₁₅ V ₃₈ Nb ₂₃ Hf ₂₄ , Ti _32.5 Zr _30.8 Nb _14.8 Hf _21.9 , and Ti ₂₀ Nb ₈ Ta ₈ Mo ₃₂ V ₃₂ . This is a graph showing the results of X-ray diffraction analysis.

Referring to FIG. 7 and Table 4, it can be seen that CCA containing two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo forms a single-phase BCC structure. Here, the content of each element constituting CCA can be selected within a wide range of 5 to 95 atomic%, at which interaction between solute elements is activated.

Test Example 4: XRD, differential scanning calorimetry, etc. of an amorphous alloy containing CCA using a quaternary amorphous alloy as a matrix

The composition of the quaternary amorphous alloy matrix is Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ , and while changing the composition and content of CCA according to Table 5 below, Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ (CCA) _d composition An amorphous alloy was manufactured.

Specifically, a CCA raw material mixture was prepared according to the composition in Table 5, and the CCA raw material mixture was melted at 3500 ° C. for 10 minutes to prepare CCA molten metal. The CCA molten metal was cooled at a cooling rate of 10°C/s for 10 minutes or less, and then obtained as a CCA specimen. Here, Equation 1 below was calculated from the composition of CCA, and the results are listed in Table 5 below.

[Equation 1]

10.0 ≤ {(1/3)*(x+n+o+p) + (1/6.9)*y + (1/7)*(z+m)}

In Formula 1, x is the atomic fraction of Ti in Formula 1; y is the atomic fraction of Zr in Formula 1; z is the atomic fraction of Hf in Formula 1; m is the atomic fraction of V in Formula 1; n is the atomic fraction of Nb in Formula 1; o is the atomic fraction of Ta in Formula 1; p is the atomic fraction of Mo in Formula 1 above.

Thereafter, to the CCA specimen, Zr, Ni, Cu, and Al were added considering the stoichiometric atomic ratio of Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ , and then the Zr ₆₅ Ni ₁₂ Cu _15-d Al The raw material mixture of ₈ and CCA was melted at 3000°C for 10 minutes to prepare the molten metal of Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ (CCA) _d .

Thereafter, the molten metal was cooled at a cooling rate of 250°C/s for 10 seconds or less, and then molded into a rod shape of 2 mm in size to obtain the amorphous alloy specimen of Test Example 4.

By analyzing the structure using _an After checking whether an image was formed, the results are listed in Table 5 below.

In addition, the crystallization behavior of the amorphous alloy was analyzed using a differential scanning calorimeter (DSC, DSC 8500, Perkin Elmer), and the precipitated phase was analyzed after heat treatment to the peak of the first crystallization behavior, and the results were used to determine the complex It was confirmed whether quasicrystal clusters were formed.

addition alloy Content (at.%) 'Equation 1'
calculated value 10 μm ribbon
amorphous formation
Whether cornerstone statue Nb ₉₅ Ta ₅ 0.5 9.58 O _Zr2Ni 6 11.4 O I-phase 9 12.4 O I-phase Ti _33.3 Zr _33.3 Hf _33.3 0.5 9.5 O _Zr2Ni 6 10.6 O I-phase 9 11.2 O I-phase Ti _33.3 Zr _33.3 V _33.3 0.5 9.5 O _Zr2Ni 6 10.6 O I-phase 9 11.2 O I-phase Ti _33.3 Zr _33.3 Nb _33.3 3 10.2 O I-phase 6 11.0 O I-phase 9 11.9 O I-phase Ti _33.3 Zr _33.3 Ta _33.3 3 10.2 O I-phase 6 11.0 O I-phase Ti ₂₅ Zr ₂₅ Nb ₂₅ Ta ₂₅ 2 10.0 O I-phase 8 11.7 O I-phase Ti _33.3 Hf _33.3 Nb _33.3 0.5 9.5 O _Zr2Ni 3 10.2 O I-phase 6 11.0 O I-phase Ti _33.3 Hf _33.3 Ta _33.3 0.5 9.5 O _Zr2Ni 3 10.2 O I-phase 6 11.0 O I-phase Ti ₂₅ Hf ₂₅ Nb ₂₅ Ta ₂₅ 4 10.5 O I-phase 8 11.7 O I-phase V _33.3 Nb _33.3 Ta _33.3 3 10.2 O I-phase 6 11.0 O I-phase V ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ 4 10.5 O I-phase 8 11.7 O I-phase V _33.3 Nb _33.3 Mo _33.3 3 10.2 O I-phase 6 11.0 O I-phase V _33.3 Ta _33.3 Mo _33.3 3 10.2 O I-phase 6 11.0 O I-phase Ti ₂₀ Zr ₂₀ Hf ₂₀ Nb ₂₀ Ta ₂₀ 4 10.4 O I-phase 8 11.5 O I-phase V ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ 4 10.5 O I-phase 10 11.4 O I-phase Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ 2 10.0 O I-phase 4 10.7 O I-phase Ti _14.3 Zr _14.3 Hf _14.3 V _14.3 Nb _14.3 Ta _14.3 Mo _14.3 4 10.4 O I-phase 8 11.4 O I-phase Ti _32.5 V _15.4 Nb _22.6 Hf _24.1 3 10.1 O I-phase 6 10.8 O I-phase Ti ₁₅ V ₃₈ Nb ₂₃ Hf ₂₄ 4 10.3 O I-phase 8 11.1 O I-phase Ti _26.5 V _26.5 Nb ₂₃ Hf ₂₄ 4 10.4 O I-phase 8 11.3 O I-phase Ti ₃₈ V ₁₅ Nb ₂₃ Hf ₂₄ 4 10.5 O I-phase 8 11.5 O I-phase Ti ₂₀ Nb ₈ Ta ₈ Mo ₃₂ V ₃₂ 0.5 9.5 O _Zr2Ni 4 10.5 O I-phase 10 12.1 O I-phase

According to Table 5, when CCA is added in a single-phase BCC structure with a composition that satisfies Equation 1, the CCA is dispersed in the quaternary amorphous alloy matrix, forming the complex quasicrystal cluster, and forming a level between the complex quasicrystal clusters. The total distribution of pressure can be maximized. Accordingly, the thermal and mechanical stability of the novel amorphous alloy of one embodiment can be greatly improved.

Test Example 5: XRD, differential scanning calorimetry, etc. of an amorphous alloy containing CCA using a quaternary amorphous alloy as a matrix

The composition of the quaternary amorphous alloy matrix is Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ , and the composition of CCA is Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ , but the content is changed as follows, Zr ₆₅ Ni ₁₂ Cu ₁₅ A 2 mm-sized rod-shaped amorphous alloy specimen of _-d Al ₈ (CCA) _d composition was prepared.

Specifically, a CCA raw material mixture was prepared with a composition of Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ , and the CCA raw material mixture was melted at 3500 ° C. for 10 minutes to prepare CCA molten metal. The CCA molten metal was cooled at a cooling rate of 10°C/s for 10 minutes or less, and then obtained as a CCA specimen.

Thereafter, to the CCA specimen, Zr, Ni, Cu, and Al were added considering the stoichiometric atomic ratio of Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ , and then the Zr ₆₅ Ni ₁₂ Cu _15-d Al The raw material mixture of ₈ and CCA was melted at 3000°C for 10 minutes to prepare the molten metal of Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ (CCA) _d .

Afterwards, the molten metal was cooled at a cooling rate of 250°C/s for 10 seconds or less, and then molded into a rod shape of 2 mm in size to obtain the amorphous alloy specimen of Test Example 5.

The structure of the manufactured alloy specimen was analyzed using an X-ray diffraction analyzer (New D8 Advance, Bruker Corporation), and the results are shown in Figure 8.

Referring to FIG. 8, it can be seen that a ₂ mm rod-shaped amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) 2 shows a halo pattern of a typical amorphous structure.

Meanwhile, the amorphous alloy specimen was analyzed using a differential scanning calorimeter (DSC, DSC 8500, Perkin Elmer), and the results are shown in FIG. 9.

Referring to the left drawing of FIG. 9, it can be seen that a 2 mm rod-shaped amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ has a wide supercooled liquid region of about 50 K or more. You can. The stability of this supercooled liquid is directly related to excellent thermoplastic forming ability. It is a son of man.

In addition, the ₂ mm rod-shaped amorphous alloy specimen of the composition Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) 2 is heat-treated to 430 ° C., the peak of the first crystallization behavior, to form a quasicrystal (I-phase). It can be seen that only the superlithic phase precipitates (right drawing of FIG. 9).

In general, when a quasicrystal phase is used as the superlithic phase, nucleation is easy to generate during the cooling process due to the characteristics of the quasicrystal phase, so the formation of clusters is inevitable. In this regard, the manufacturing process of the 2 mm rod-shaped amorphous alloy specimen of the composition Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ (especially , cooling process), it is inferred that complex quasicrystalline clusters are formed inside the amorphous matrix. In addition, during the heat treatment of the ₂ mm rod-shaped amorphous alloy specimen of the composition Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) 2, complex quasicrystal clusters grow inside the amorphous matrix, forming a superlithic phase. It is inferred that it precipitated. This behavior can be confirmed by observing only crystal phase growth and related peaks during isothermal heat treatment from 80% of the glass transition temperature or before the crystallization start temperature.

Furthermore, considering FIGS. 6 and 9 comprehensively, the quaternary amorphous alloy system with the original composition of Zr ₆₅ Ni ₁₂ Cu ₁₅ Al ₈ is converted into a composite phase (ZrAl, Zr ₂ Cu, etc.) containing Zr ₂ Ni during the heat treatment process. A stone phase was formed, but when a new amorphous alloy was manufactured by adding Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ , a type of CCA, it was confirmed that only the quasicrystal (I-phase) phase was precipitated.

Through this, when manufacturing a new amorphous alloy by adding Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ to a quaternary amorphous alloy system of Zr ₆₅ Ni ₁₂ Cu ₁₅ Al ₈ composition, a plurality of quasicrystal nuclei and the quasicrystal nuclei are present. It can be seen that a complex quasicrystal cluster is formed including a free volume region, which is an area that is not free.

Test Example 6: Compression test of an amorphous alloy containing CCA using a quaternary amorphous alloy as a matrix

The composition of the quaternary amorphous alloy matrix is Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ , and the composition of CCA is Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ , but the content is changed as follows, Zr ₆₅ Ni ₁₂ Cu _{15 -d} Al ₈ (CCA) A rod-shaped amorphous alloy specimen with _d composition and size of 2 mm was prepared. Its manufacturing method is the same as Test Example 5.

The amorphous alloy specimen was subjected to a 50% compression strain test under a strain rate of 5*10 ^-4 /s using a universal material tester (Instron 5967, manufacturer: Instron), and the results are shown in Figure 10.

Referring to FIG. 10, a 2 mm rod-shaped amorphous alloy specimen with a CCA content (d) of 0 atomic% (no _addition ) in the composition of Zr ₆₅ Ni ₁₂ Cu _{15 -d} Al ₈ (Ti ₂₅ Nb ₂₅ Ta 25 Mo 25 ) _d is , indicates an elongation within 6%.

On the other hand, in the Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ (CCA) _d composition, CCA is Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ and the content (d) is 2 atomic%. A 2 mm rod-shaped amorphous alloy specimen is, It can be seen that it does not break even when compressed, and the pressure due to compression continues to increase, showing superplastic behavior with maximized mechanical stability.

This superplastic behavior is the result of simultaneously maximizing local compositional variation and structural complexity variation by adding a complex hypersolidified alloy inside a quaternary amorphous alloy matrix with a high Zr content.

Test Example 7: Three-point bending test of an amorphous alloy containing CCA using a quaternary amorphous alloy as a matrix

The composition of the quaternary amorphous alloy matrix is Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ , and the composition of CCA is Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ , but the content is changed as follows, Zr ₆₅ Ni ₁₂ Cu _{15 -d} Al ₈ (CCA) A rod-shaped amorphous alloy specimen with _d composition and size of 2 mm was prepared. Its manufacturing method is the same as Test Example 5.

Thereafter, the amorphous alloy specimen with a size of 2 mm and a height of 50 mm was molded into a plate shape with a thickness of 1 mm through thermoplastic molding at 420 ° C. under a pressure of 10 kN.

Using a universal material tester (device name: Instron 5967, manufacturer: Instron) using a 2810-400 jig, a three-point bending test was performed on the amorphous alloy specimen under the conditions of a span length of 24 mm and a strain rate of 10 ^-4 /s. , the results are shown in Figure 11.

Referring to FIG _. 11, a plate-shaped amorphous alloy with a size of 1 mm with a CCA content (d) of 0 atomic% (no _addition ) in _the composition of Zr ₆₅ Ni ₁₂ Cu _{15 -d} Al ₈ (Ti ₂₅ Nb 25 Ta 25 Mo 25 ) d. The specimen has a short elongation of less than 3.5% and fracture occurs.

On the other hand, in the Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ (CCA) _d composition, CCA is Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ , and the 1 mm-sized plate-shaped amorphous alloy specimen with the content (d) of 2 atomic% is , has excellent elongation of about 7%. In addition, during the three-point bending test, fracture did not occur immediately after the ultimate strength, but the stress gradually decreased, showing that the structural flexibility and mechanical stability of the amorphous alloy were greatly increased.

Test Example 8: Thermoplastic forming and fracture toughness test of an amorphous alloy containing CCA using a quaternary amorphous alloy as a matrix

A plate-shaped amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ and a thickness of 1 mm was prepared. Its manufacturing method is the same as Test Example 7.

The amorphous alloy specimen was thermoplasticized at 420°C to produce a fracture toughness measurement specimen (single edge notched tension (SENT) sample) with a size of 25 × 5 × 0.3 mm. At this time, the size of the single edge notch was notch length = 2.5 mm ( a / W = 0.5), notch root radius, ρ = 10 μm, and fracture toughness was measured under a strain rate of 10 ^-4 /s.

Referring to FIG. 12, it can be seen that the alloy fracture toughness specimen of the Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ composition has a large plastic zone of about 914 μm and 100 MPa · It has excellent toughness of m ^1/2 or more. In addition, during the fracture toughness test, fracture does not occur immediately after the formation of the shear band, but as the stress increases, the shear band gradually propagates and deformation occurs continuously, greatly increasing the structural flexibility and mechanical stability of the amorphous alloy. You can see that

Test Example 9: Healing behavior of an amorphous alloy containing CCA using a quaternary amorphous alloy as a matrix

A rod-shaped amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ and a size of 2 mm was prepared. Its manufacturing method is the same as Test Example 5.

Immediately after casting and after 10 healing cycles after casting, the amorphous alloy specimens were analyzed using a differential scanning calorimeter (DSC, DSC 8500, Perkin Elmer), and the results are shown in FIG. 13.

The healing cycle was carried out through a thermo-cycling process in which one heat deformation cycle was performed alternately in an environment below -50°C and an environment above 100°C for 20 seconds or more.

Hereinafter, the conditions for "analyzing the amorphous alloy specimen immediately after casting and after 10 healing cycles after casting, respectively, using a differential scanning calorimeter" are the same as above.

This thermal repetition process can easily provide a complex environment in which external energy is applied, such as (1) application of heat energy according to temperature change, and (2) application of local mechanical energy by repetition of expansion and contraction of interatomic bonds.

Referring to Figure 13, the conventional amorphous alloy shows an increase in enthalpy change (ΔH) after the healing cycle, while the composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ and size of 2 mm It can be seen that the structural flexibility of the amorphous alloy is increased even in the cast state of the rod-shaped amorphous alloy specimen.

Specifically, when 10 healing cycles are performed after casting of the amorphous alloy specimen, the enthalpy change (ΔH) in the energy region showing a moderate exothermic reaction in the low temperature range below the crystallization temperature is similar due to the amorphous structure relaxation behavior. It can be seen that it has .

This is the result of maximizing both local compositional variation and structural complexity variation by adding a complex hypersolidified alloy to a quaternary amorphous alloy matrix with a high Zr content, and the amorphous structure created through casting is in a stable steady-state. ) means entering the area.

In addition, the novel amorphous alloy of one embodiment is applied even when external energy including one selected from the group consisting of mechanical energy, electrical energy, thermal energy, magnetic energy, and combinations thereof at a level equivalent to the thermal repetition conditions is applied. , it can exhibit unique self-healing properties where the deformed area recovers.

Test Example 10: Compressive deformation and healing behavior of an amorphous alloy containing CCA using a quaternary amorphous alloy as a matrix

A rod-shaped amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ and a size of 2 mm was prepared. Its manufacturing method is the same as Test Example 5.

For the amorphous alloy specimen, after a 50% compression strain test, 10 healing cycles were performed, and the results were analyzed using a differential scanning calorimeter (DSC, DSC 8500, Perkin Elmer). Shown in 14. Here, the 50% compression set test conditions are the same as Test Example 6, and the healing cycle conditions are the same as Test Example 8.

In Figure 14, a rod-shaped amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ and a size of 2 mm is obtained immediately after casting, immediately after 50% compressive strain, and after 50% compressive strain. Immediately after 10 healing cycles, differential scanning calorimetry was performed over 5 times each to show the average changes.

In a rod-shaped amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ and a size of 2 mm, multiple shear bands were formed during differential scanning calorimetry analysis immediately after 50% compression deformation, It has an enthalpy value (ΔH) of amorphous structure relaxation behavior that increases by about 50% compared to immediately after casting.

Furthermore, a rod-shaped amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ and a size of 2 mm, after 50% compressive deformation and after 10 healing cycles, uniquely exhibits approximately 20 It was confirmed that not only structural recovery (Rejuvenation) but also healing of permanent deformation occurred effectively by reducing the enthalpy value of the amorphous structural relaxation behavior by more than %.

This healing behavior of permanent deformation is due to the simultaneous maximization of local compositional variation and structural complexity variation by adding a complex hypersolidified alloy to a quaternary amorphous alloy matrix with a high Zr content. Specifically, the complex quasicrystal cluster is formed inside a quaternary amorphous alloy matrix, and when external energy is applied, interatomic bond expansion and contraction are repeated, and the complex quasicrystal cluster can serve as a healing core unit. .

Test Example 11: Fatigue damage healing behavior of an amorphous alloy containing CCA using a quaternary amorphous alloy as a matrix

A ribbon amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ and a size of 10 ㎛ was prepared.

Specifically, a CCA raw material mixture was prepared with a composition of Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ , and the CCA raw material mixture was melted at 3500 ° C. for 10 minutes to prepare CCA molten metal. The CCA molten metal was cooled at a cooling rate of 10°C/s for 10 minutes or less, and then obtained as a CCA specimen.

Thereafter, to the CCA specimen, Zr, Ni, Cu, and Al were added considering the stoichiometric atomic ratio of Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ , and then the Zr ₆₅ Ni ₁₂ Cu _15-d Al The raw material mixture of ₈ and CCA was melted at 3000°C for 10 minutes to prepare the molten metal of Zr ₆₅ Ni ₁₂ Cu _15-d Al ₈ (CCA) _d .

Thereafter, the molten metal was cooled for less than 1 second at a cooling rate of 10 ⁶ ℃/s, and then molded into a 10 ㎛ ribbon shape to obtain an amorphous alloy specimen.

Figure 15 shows a 10 ㎛ thick ribbon amorphous alloy specimen with a composition of Zr ₆₅ Ni ₁₂ Cu ₁₃ Al ₈ (Ti ₂₅ Nb ₂₅ Ta ₂₅ Mo ₂₅ ) ₂ without undergoing healing cycle recovery treatment (as-spun). It shows the results of a fatigue test on a specimen that underwent 10 healing cycle recovery treatments after deformation of 80% of the maximum fatigue strain. The figure shows that the resistance of a material changes depending on the number of fatigue failure cycles. At this time, as the defect grows larger and a fatigue crack occurs and gradually propagates, the resistance of the material rapidly increases. As can be seen in the figure, it can be seen that the as-spun specimen fractured after receiving fatigue stress about 20,000 times. In particular, it can be seen that the resistance increases significantly through a rapid increase in internal defects above about 18,000 points (= 90% of the rupture cycle). The alloy was subjected to fatigue stress only up to 16,000 cycles, which is 80% of the number of fracture cycles (red dotted line), and then 10 healing cycles were performed. When the recovery treatment was repeatedly performed on the amorphous alloy developed in this way, it was confirmed that it could be repeated more than 100,000 times, exceeding the original material life of 20,000 times. Therefore, it was confirmed that by repeatedly performing the healing cycle according to the present invention, the fatigue deformation area generated in the material can be effectively removed and the lifespan can be extended.

Although the preferred embodiments have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept defined in the following claims are also within the scope of the present invention. It belongs.

Claims (22)

A quaternary amorphous alloy matrix containing Zr, Ni, Cu, and Al; and
It is dispersed within the quaternary amorphous alloy matrix and includes a complex concentrated alloy (CCA) containing two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo. do,
Of the total amount of 100 atomic% of the quaternary amorphous alloy matrix, Ni is contained at 2 to 29 atomic%, Cu is contained at 2 to 29 atomic%, and Al is contained at 6 to 18 atomic%, and Zr is included in the balance,
Amorphous alloy.
According to paragraph 1,
The complex over-solidifying alloy is an amorphous alloy with a single-phase body-centered cubic (BCC) structure.
According to paragraph 1,
An amorphous alloy further comprising complex quasicrystal clusters dispersed within the amorphous matrix.
According to paragraph 3,
The complex quasicrystal cluster includes a plurality of quasicrystal nuclei (QC) and a free volume region where the quasicrystal nuclei do not exist;
Each quasicrystal nucleus includes a plurality of principle clusters and a glue atom that bonds the plurality of principle clusters,
The basic cluster is an amorphous alloy containing Zr and Ni among the elements constituting the quaternary amorphous alloy matrix.
According to paragraph 4,
The basic cluster is an amorphous alloy containing Zr and Ni at an atomic ratio of 1:1 to 3:1 per unit.
According to paragraph 4,
The elementary cluster is an icosahedral structure;
The basic cluster is an amorphous alloy in which 9 Zr and 3 Ni form the basic skeleton of the icosahedral structure, and 1 Ni is located at the center of the basic skeleton of the icosahedral structure.
According to clause 4,
The glue atom is an amorphous alloy containing at least one of the elements constituting the complex oversolubilized alloy.
According to paragraph 1,
The overall composition of the amorphous alloy is an amorphous alloy represented by Chemical Formula 1:
[Formula 1]
Zr _a Ni _b Cu _cd Al _f (X) _d
In Formula 1,
The X includes two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo,
where b is 2 to 29,
(cd) is 2 to 29,
where d is 1 to 10,
where f is 6 to 18,
The a is 100-(b+c+f).
According to clause 8,
X in Formula 1 is an amorphous alloy that satisfies the following equation:
[Equation 1]
10.0 ≤ {(1/3)*(x+n+o+p) + (1/6.9)*y + (1/7)*(z+m)}
In Equation 1 above,
x is the atomic fraction of Ti in Formula 1;
y is the atomic fraction of Zr in Formula 1;
z is the atomic fraction of Hf in Formula 1;
m is the atomic fraction of V in Formula 1;
n is the atomic fraction of Nb in Formula 1;
o is the atomic fraction of Ta in Formula 1;
p is the atomic fraction of Mo in Formula 1 above.
In paragraph 9:
Wherein X is an amorphous alloy containing four or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo.
In paragraph 1:
The amorphous alloy has a supercooled liquid region of 20 K or more.
In paragraph 1:
The amorphous alloy is an amorphous alloy with an elongation of 5% or more during a three-point bending test on a 1 mm thick plate-shaped specimen.
In paragraph 1:
The amorphous alloy is an amorphous alloy with a fracture rate of 0% when a compression test is performed on a specimen with an aspect ratio of 1 to 3.5 until the aspect ratio satisfies 1.
In paragraph 1:
The amorphous alloy has a fracture toughness of 100 MPa·m ^1/2 or more when subjected to a fracture test on a specimen with a thickness of 0.01 to 2.0 mm.
In paragraph 1:
The amorphous alloy is an amorphous alloy whose fatigue life increases by more than two times after continuously performing a fatigue test and 10 heat repetition processes within the elastic range on a specimen with a size of 0.01 to 2.0 mm.
In paragraph 1:
The amorphous alloy has an enthalpy value after 10 thermal deformation cycles on a 2 mm rod-shaped specimen, when one heat deformation cycle is performed alternately in an environment below -50 ℃ and an environment above 100 ℃ for 20 seconds or more. Amorphous alloy with a reduction rate of more than 20%.
In paragraph 1:
The amorphous alloy is manufactured by cooling molten metal containing the first alloy elements and the second alloy elements,
When cooling the molten metal, the critical cooling rate is 10 ⁰ K/s or more and 10 ⁶ K/s,
An amorphous alloy wherein the molten metal has a thickness of 10 ㎛ or more and 20 mm or less.
A first step of manufacturing a complex concentrated alloy (CCA) containing two or more selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and Mo;
A second step of preparing a mixture by mixing Zr, Ni, Cu, and Al with the complex oversolubilized alloy;
A third step of melting the mixture to produce molten metal; and
The fourth step of cooling the molten metal to obtain an amorphous alloy
Including,
Among the total amount of Zr, Ni, Cu, and Al of 100 atomic%, in the total amount of 100 atomic% of the quaternary amorphous alloy matrix, Ni is included in 2 to 29 atomic%, and Cu is included in 2 to 29 atomic% Al is contained at 6 to 18 atomic%, and Zr is the balance,
Method for producing amorphous alloy.
In paragraph 18:
A method of producing an amorphous alloy wherein the critical cooling rate in the fourth step is 10 ⁰ K/s or more and 10 ⁶ K/s or less.
In paragraph 19:
A method of producing an amorphous alloy in which the thickness of the molten metal in the fourth step is 10 ㎛ or more and 20 mm or less.
A product containing the amorphous alloy of any one of claims 1 to 20.
According to clause 21,
The products include sporting goods, medical devices, watch gears, interior materials for electronic devices, exterior materials for electronic devices, or driving parts of smart robots.