KR102367916B1 - amorphous ally - Google Patents

Abstract

An object of the present invention is to provide a cobalt-based amorphous alloy having high rigidity with suppressed magnetic properties.
The amorphous alloy according to an embodiment includes cobalt (Co), iron (Fe), nickel (Ni), chromium (Cr), molybdenum (Mo), carbon (C) and boron (B), and cobalt (Co) , the sum of the iron (Fe) and nickel (Ni) content has a range of 12 to 50 at% relative to the total element content of the amorphous alloy.

Description

amorphous alloy { amorphous ally }

The disclosed invention relates to an amorphous alloy, and more particularly, to an amorphous alloy containing cobalt (Co).

An amorphous alloy is a metal material having a non-periodic atomic arrangement structure, unlike a crystalline alloy, and has superior characteristics such as high strength, corrosion resistance, and wear resistance compared to crystalline alloys.

The amorphous alloy may be manufactured by a method of inhibiting crystallization through a rapidly solidification process or an alloying design.

In general, alloy design for the manufacture of amorphous alloys starts with a multi-component eutectic alloy system with a large bonding force between constituent atoms and a large atomic radius difference, and other elements are added in the alloy system with at least 40 at% of the main element. The way I went was the main thing.

Since this method forms amorphous material in an extremely limited composition range, it is difficult to escape the limit of the composition range, and the cost of developing an amorphous alloy based on a relatively expensive element such as cobalt (Co) or precious metals and rare earths has been a cause of increase. .

In particular, in the case of an amorphous alloy containing iron (Fe), although it has excellent mechanical properties due to intrinsic magnetic properties, there is a limit in the application of electronic components and the like.

The disclosed invention is intended to provide a cobalt-based amorphous alloy having high rigidity with suppressed magnetic properties to solve the above-described problems.

Amorphous alloy according to an embodiment for achieving the above object, cobalt (Co), iron (Fe), nickel (Ni), chromium (Cr), molybdenum (Mo), carbon (C) and boron (B) Including the element, the sum of the cobalt (Co), iron (Fe) and nickel (Ni) element content has a range of 12 to 50 at% compared to the total element content of the amorphous alloy.

In addition, cobalt (Co) may have a content within the range of 16 to 25 at% with respect to the total element content of the amorphous alloy.

In addition, cobalt (Co), iron (Fe), nickel (Ni), chromium (Cr), molybdenum (Mo), carbon (C) and boron (B) elements, respectively, 25 at% of the total element content of the amorphous alloy It may have the following content.

In addition, cobalt (Co), iron (Fe), nickel (Ni), chromium (Cr), molybdenum (Mo), carbon (C) and boron (B) elements, respectively, 5 to 25 relative to the total element content of the amorphous alloy It may have a content within the at% range.

In addition, it may have a fracture strength of 3000 Mpa or more.

In addition, it may have a Young's modulus of 150 Gpa or more.

In addition, it may be represented by the following [Formula 1].

[Formula 1]

(Co, Fe, Ni) ₅₀ (Cr,Mo) _x (C,B) _50-x

Here, x is assumed to be an atomic percent within the range of 20 to 40.

In addition, cobalt (Co), iron (Fe), and nickel (Ni) are at least 1:1:1, 2:1:1, 2:2:1, 3:2:1 and 3:3:1, respectively. It can have only one ratio.

In addition, chromium (Cr) and molybdenum (Mo) may have a ratio of 1:1.

In addition, carbon (C) and boron (B) may have a ratio of 1:1.

In addition, iron (Fe) may have a content within the range of 12 to 22 at% based on the total element content of the amorphous alloy.

In addition, nickel (Ni) may have a content within the range of 12 to 22 at% based on the total element content of the amorphous alloy.

In addition, chromium (Cr) may have a content within the range of 10 to 20 at% based on the total element content of the amorphous alloy.

In addition, molybdenum (Mo) may have a content within the range of 10 to 20 at% based on the total element content of the amorphous alloy.

In addition, carbon (C) may have a content within the range of 5 to 15 at% with respect to the total element content of the amorphous alloy.

In addition, boron (B) may have a content within the range of 5 to 15 at% relative to the total element content of the amorphous alloy.

In addition, the amorphous alloy according to an embodiment may be formed in a ribbon shape (ribbon shaped).

According to the amorphous alloy configured as described above, the following effects can be expected.

First, it is possible to implement excellent strength and rigidity while maintaining the intrinsic physical properties of the amorphous.

In addition, by providing an amorphous alloy with suppressed magnetic properties, it can be applied as a material for electronic components.

1 is a diagram illustrating a yield strength and a Young's modulus of a cobalt-based amorphous alloy according to an embodiment.
2 is a triangular graph showing an example of controlling the content of a (Co, Fe, Ni) group, a (Cr, Mo) group, and a (C, B) group.
3A to 3F are views showing the surface morphology of alloy samples according to Examples 1 to 6;
4 is a view showing the surface shape of the alloy sample according to Comparative Example 1.
5A to 5F are views showing X-ray diffraction peaks according to Examples 1 to 6;
6 is a diagram illustrating an X-ray diffraction peak according to Comparative Example 1. Referring to FIG.
7A to 7F are diagrams showing DSC curves according to Examples 1 to 6;

The configurations shown in the embodiments and drawings described in this specification are only preferred examples of the invention, and there may be various modifications and examples that can replace the embodiments and drawings of the present specification at the time of filing of the present application. Hereinafter, exemplary embodiments will be described in detail with reference to the contents described in the accompanying drawings.

The amorphous alloy according to an embodiment includes cobalt (Co), iron (Fe), nickel (Ni), chromium (Cr), molybdenum (Mo), carbon (C), and boron (B).

Each element may have a content of 25 at% or less relative to the total element content of the amorphous alloy, and more specifically, may have a content within the range of 5 to 25 at% relative to the total element content of the amorphous alloy.

In addition, the sum of the content of cobalt (Co), iron (Fe) and nickel (Ni) may have a range of 12 to 50 at% based on the total element content of the amorphous alloy.

Cobalt (Co) may have a content within the range of 16 to 25 at% relative to the total element content of the amorphous alloy. The amorphous alloy according to an embodiment may secure price competitiveness by containing a relatively low proportion of cobalt (Co).

In addition, magnetic properties can be suppressed, and it can be applied to electronic materials.

In addition, strength and rigidity can be implemented by controlling the ratio of alloy materials included in addition to cobalt (Co). The amorphous alloy material according to an embodiment may be included in the following ratio.

Iron (Fe) may have a content within the range of 12 to 22 at% with respect to the total element content of the amorphous alloy, and nickel (Ni) may have a content within the range of 12 to 22 at% with respect to the total element content of the amorphous alloy, Chromium (Cr) may have a content within the range of 10 to 20 at% relative to the total element content of the amorphous alloy, and molybdenum (Mo) may have a content within the range of 10 to 20 at% relative to the total element content of the amorphous alloy, Carbon (C) may have a content within the range of 5 to 15 at% with respect to the total element content of the amorphous alloy, and boron (B) may have a content within the range of 5 to 15 at% with respect to the total element content of the amorphous alloy. Examples of the content of each element should be broadly understood as a concept including changes within a range easily conceivable to those skilled in the art.

The amorphous alloy according to an embodiment may be represented by the following [Formula 1].

[Formula 1]

(Co, Fe, Ni) ₅₀ (Cr,Mo) _x (C,B) _50-x

Here, x is assumed to be an atomic percent within the range of 20 to 40.

In addition, 50, x, and 50-x each represent a group containing additional elements cobalt (Co), iron (Fe) and nickel (Ni), a group containing additional elements chromium (Cr) and molybdenum (Mo), and addition It may mean atomic% of a group containing the elements carbon (C) and boron (B).

50 may include the meaning of atomic percent when at least one of the additional elements cobalt (Co), iron (Fe) and nickel (Ni) is added simultaneously from the group, and x is the additional elements chromium (Cr) and molybdenum (Mo) may include the meaning of atomic percent when one or more is simultaneously added from the group containing (Mo), and 50-x is added at the same time from the group containing the additional elements carbon (C) and boron (B) It may include the meaning of atomic percent when

In [Formula 1], the case where the sum of cobalt (Co), iron (Fe) and nickel (Ni) contents is 50 is taken as an example, but the sum of cobalt (Co), iron (Fe) and nickel (Ni) contents is It is not limited thereto, and the sum of the content of cobalt (Co), iron (Fe) and nickel (Ni) may have a range of 7 to 50 at% relative to the total element content of the amorphous alloy, and accordingly, chromium (Cr) and molybdenum The content of (Mo) and carbon (C) and boron (B) elements can be adjusted.

By controlling the ratio of cobalt (Co), iron (Fe), and nickel (Ni), excellent strength and rigidity can be implemented while maintaining the intrinsic properties of amorphous material, and cobalt (Co), iron ( The ratio of Fe) and nickel (Ni) elements is adjusted to be included in at least one of 1:1:1, 2:1:1, 2:2:1, 3:2:1, and 3:3:1, respectively. can be

In addition, chromium (Cr) and molybdenum (Mo) may be adjusted to be included in a ratio of 1:1, respectively. In addition, carbon (C) and boron (B) may be adjusted to be included in a ratio of 1:1, respectively.

The amorphous metal according to the above-described embodiment may be an amorphous metal having high rigidity in which magnetic properties are suppressed. That is, by controlling the content of cobalt (Co), magnetic properties are suppressed, and by controlling the content of other metals, excellent strength and rigidity can be realized while maintaining the intrinsic properties of amorphous properties such as tensile strength and abrasion resistance.

1 is a diagram illustrating a yield strength and Young's modulus of a cobalt-based amorphous alloy according to an embodiment.

Referring to FIG. 1 , a cobalt-based amorphous alloy according to an embodiment may have a yield strength of 3000 Mpa or more, and may have a Young's modulus of 150 Gpa or more.

On the other hand, the magnesium-based amorphous alloy, the aluminum-based amorphous alloy, the zirconium-based amorphous alloy, the titanium-based amorphous alloy, and the copper-based amorphous alloy each have a yield strength of 3000 Mpa or less, and it can be confirmed that they have a Young's modulus of 150 Gpa or less. That is, it can be confirmed that the cobalt-based amorphous alloy according to an embodiment can implement excellent strength and rigidity.

Hereinafter, exemplary embodiments of the disclosed invention will be described in detail for better understanding.

For the measurement of the physical properties of the amorphous alloy, alloy samples having composition ratios of [Example 1] to [Example 6] and [Comparative Example 1] were prepared.

[Example 1]

The amorphous alloy according to [Example 1] has a chemical formula of (Co ₂ Fe ₁ Ni ₁ )50(CrMo) ₃₀ (CB) ₂₀ . That is, the (Co, Fe, Ni) group, the (Cr, Mo) group, and the (C, B) group each have a ratio of 50:30:20, and each element has a Co:Fe:Ni ratio of 2: It has a ratio of 1:1, Cr:Mo has a ratio of 1:1, and C:B has a ratio of 1:1.

[Example 2]

The amorphous alloy according to [Example 2] has a chemical formula of (Co ₂ Fe ₂ Ni ₁ ) ₅₀ (CrMo) ₃₀ (CB) ₂₀ . That is, the (Co, Fe, Ni) group, the (Cr, Mo) group, and the (C, B) group each have a ratio of 50:30:20, and each element has a Co:Fe:Ni ratio of 2: It has a ratio of 2:1, Cr:Mo has a ratio of 1:1, and C:B has a ratio of 1:1.

[Example 3]

The amorphous alloy according to [Example 3] has a chemical formula of (Co ₃ Fe ₂ Ni ₁ ) ₅₀ (CrMo) ₃₀ (CB) ₂₀ . That is, the (Co, Fe, Ni) group, the (Cr, Mo) group, and the (C, B) group each have a ratio of 50:30:20, and each element has a Co:Fe:Ni ratio of 3: It has a ratio of 2:1, Cr:Mo has a ratio of 1:1, and C:B has a ratio of 1:1.

[Example 4]

The amorphous alloy according to [Example 4] has a chemical formula of (Co ₂ Fe ₁ Ni ₁ ) ₅₀ (CrMo) ₂₅ (CB) ₂₅ . That is, the (Co, Fe, Ni) group, the (Cr, Mo) group, and the (C, B) group each have a ratio of 50:25:25, and each element has a Co:Fe:Ni ratio of 2: It has a ratio of 1:1, Cr:Mo has a ratio of 1:1, and C:B has a ratio of 1:1.

[Example 5]

The amorphous alloy according to [Example 5] has a chemical formula of (Co ₂ Fe ₂ Ni ₁ ) ₅₀ (CrMo) ₂₅ (CB) ₂₅ . That is, the (Co, Fe, Ni) group, the (Cr, Mo) group, and the (C, B) group each have a ratio of 50:25:25, and each element has a Co:Fe:Ni ratio of 2: It has a ratio of 2:1, Cr:Mo has a ratio of 1:1, and C:B has a ratio of 1:1.

[Example 6]

The amorphous alloy according to [Example 6] has a chemical formula of (Co ₃ Fe ₂ Ni ₁ ) ₅₀ (CrMo) ₂₅ (CB) ₂₅ . That is, the (Co, Fe, Ni) group, the (Cr, Mo) group, and the (C, B) group each have a ratio of 50:25:25, and each element has a Co:Fe:Ni ratio of 3: It has a ratio of 2:1, Cr:Mo has a ratio of 1:1, and C:B has a ratio of 1:1.

[Comparative Example 1]

The alloy according to [Comparative Example 1] has a chemical formula of (Co ₂ Fe ₂ Ni) ₅₀ (CrMo) ₁₀ (CB) ₄₀ . That is, the (Co, Fe, Ni) group, the (Cr, Mo) group, and the (C, B) group each have a ratio of 50:10:40, and each element has a Co:Fe:Ni ratio of 2: It has a ratio of 2:1, Cr:Mo has a ratio of 1:1, and C:B has a ratio of 1:1.

The composition ratios of [Example 1] to [Example 6] and [Comparative Example 1] can be summarized as shown in Table 1 below.

element cobalt
(at%) steel
(at%) nickel
(at%) chrome
(at%) molybdenum
(at%) carbon
(at%) boron
(at%)


content


Example 1 25 12.5 12.5 15 15 10 10 Example 2 20 20 10 15 15 10 10 Example 3 25 16.66667 8.333333 15 15 10 10 Example 4 25 12.5 12.5 12.5 12.5 12.5 12.5 Example 5 20 20 10 12.5 12.5 12.5 12.5 Example 6 25 16.66667 8.333333 12.5 12.5 12.5 12.5 Comparative Example 1 20 20 10 5 5 20 20

[Table 1] shows the at of cobalt (Co), iron (Fe), nickel (Ni), chromium (Cr), molybdenum (Mo), carbon (C), and boron (B) compared to the total amorphous alloy for each example % is expressed as a percentage.

[Example 1] to [Example 3] of [Table 1] show the element content of the (Co, Fe, Ni) group versus the (Cr, Mo) group versus the (C, B) group in a 50:30:20 ratio, respectively. is an example adjusted to, [Example 4] to [Example 6] are (Co, Fe, Ni) group to (Cr, Mo) group to (C, B) the content of the group 50: 25: 25 ratio, respectively This is an example of adjustment with

2 is a triangular graph showing an example of controlling the content of a (Co, Fe, Ni) group, a (Cr, Mo) group, and a (C, B) group.

2, P1 is an amorphous alloy having a composition ratio of (Co, Fe, Ni)50(Cr, Mo)30(C, B)20　, and the content of (Co, Fe, Ni) groups is 50, ( Cr, Mo) group content is 30, (C, B) group content is 20, and [Example 1] to [Example 3] correspond here.

P2 is an amorphous alloy having a composition ratio of (Co, Fe, Ni)50(Cr, Mo)25(C, B)25. The content of (Co, Fe, Ni) groups is 50, and the content of (Cr, Mo) groups is 50. The content of this 25, (C, B) group is 25, and [Example 4] to [Example 6] correspond to this.

P3 is an amorphous alloy having a composition ratio of (Co, Fe, Ni) ₅₀ (Cr, Mo) ₁₀ (C, B) ₄₀ , the content of the (Co, Fe, Ni) group is 50, the content of the (Cr, Mo) group The content of this 10, (C, B) group is 40, and [Comparative Example 1] corresponds to this.

Next, analysis results of samples having the compositions of [Example 1] to [Example 6] and [Comparative Example 1] will be described.

[Experimental Example 1]: Analysis of the surface morphology of the sample

To confirm the surface morphology of the sample, the sample was analyzed using a scanning electron microscope (SEM), and the results are shown in FIGS. 3A to 3F, and 4A, respectively.

3A to 3F are views showing the surface shape of the alloy samples according to [Example 1] to [Example 6], and FIG. 4 is a view showing the surface shape of the alloy sample according to [Comparative Example 1].

Referring to FIGS. 3A to 3F , it can be seen that the alloy samples according to Examples 1 to 6 have a uniform composition, and the molecular arrangement lacks periodic regularity. Referring to FIG. 4 , in the alloy sample according to [Comparative Example 1], it can be confirmed that the molecular arrangement has regularity.

That is, it can be confirmed that the alloy samples according to [Example 1] to [Example 6] have amorphous properties, and the alloy samples according to [Comparative Example 1] have crystalline properties.

[Experimental Example 2]: Analysis of the crystal structure of the sample

To confirm the crystal structure of the sample, the crystal structure was analyzed using X-ray diffraction (XRD). In this experimental example, the crystal structure of the sample was analyzed by irradiating Cu Ka lines at an angle of 2 theta, and the results are shown in FIGS. 5A to 5F and FIG. 6A .

X-ray diffraction method is a method of determining the crystal structure or compound structure by using the X-ray intensity or diffraction angle of the X-ray irradiated to the sample changes depending on the type or structure of the crystal. A graph having a smooth shape without a specific peak is derived, and in the case of a crystalline alloy, a graph having a specific peak is derived.

5A to 5C are views showing X-ray diffraction peaks according to [Example 1] to [Example 3], and FIGS. 5D to 5F are X-rays according to [Example 4] to [Example 6] It is a diagram illustrating a diffraction peak, and FIG. 6 is a diagram illustrating an X-ray diffraction peak according to [Comparative Example 1].

As shown in Figures 5a to 5f, the samples according to [Example 1] to [Example 6] were derived a graph having a gentle shape without a specific peak, and it was confirmed that it had an amorphous characteristic. As shown in FIG. 6 , a graph having a specific peak was derived for the sample according to [Comparative Example 1], and it could be confirmed that it had crystalline properties.

[Experimental Example 3]: Heat flow analysis of amorphous alloy samples

In order to confirm the amorphous characteristics of the sample, the sample was analyzed by differential scanning calorimetry (DSC).

7A to 7C are diagrams showing DSC curves according to [Example 1] to [Example 3], and FIGS. 7D to 7F show DSC curves according to [Example 4] to [Example 6] it is one drawing

Referring to FIG. 7A , the DSC curve of the alloy sample according to [Example 1] has an exothermic peak due to crystallization at the crystallization initiation temperature (T _X ) and a supercooled liquid phase region exists. 7B to 7F, the DSC curves of the alloy samples according to [Example 2] to [Example 6] also have an exothermic peak due to crystallization at the crystallization initiation temperature (T _X ), and the supercooled liquid phase region is exist.

In general, the DSC curve of an amorphous metal has an exothermic peak at the crystallization initiation temperature (TX) and a supercooled liquid phase region peculiar to amorphous is present. The alloy samples according to Examples 1 to 6 have amorphous properties. can confirm.

[Experimental Example 4]: Analysis of hardness and elastic modulus of the sample

In order to confirm the mechanical properties of the sample, the hardness and elastic modulus of the sample were analyzed by the nanoindentation method.

[Table 2] shows the analysis results of hardness (hardness) and elastic modulus (elastic modulus) of the samples according to [Example 1] to [Example 6].

Hardness
(GPa) modulus of elasticity
(GPa) Example 1 23.5 199.5 Example 2 15.75 201.7 Example 3 16.63 166.2 Example 4 17.2 207.5 Example 5 15.5 171.5 Example 6 17.4 244.4

Referring to the results of [Table 2], it can be seen that the alloys according to [Example 1] to [Example 6] have high hardness and elastic modulus.

As described above, the cobalt-based amorphous alloy according to an embodiment has been described. The above-described embodiments are merely exemplary compositions of the invention and should be broadly understood as concepts including changes within a range that can be easily implemented by those skilled in the art.

Claims (17)

containing cobalt (Co), iron (Fe), nickel (Ni), chromium (Cr), molybdenum (Mo), carbon (C) and boron (B),
The sum of the cobalt (Co), iron (Fe) and nickel (Ni) elemental content has a range of 12 to 50 at% compared to the total element content of the amorphous alloy,
The cobalt (Co) has a content of 25 at% or less relative to the total element content of the amorphous alloy,
Iron (Fe) and nickel (Ni) each have a content of 22 at% or less relative to the total element content of the amorphous alloy,
Chromium (Cr) and molybdenum (Mo) each have a content of 20 at% or less relative to the total element content of the amorphous alloy,
Carbon (C) and boron (B) are, respectively, an amorphous alloy having a content of 15 at% or less relative to the total element content of the amorphous alloy. The method of claim 1,
The cobalt (Co) is,
An amorphous alloy having a content within the range of 16 to 25 at% relative to the total element content of the amorphous alloy. delete The method of claim 1,
The iron (Fe), nickel (Ni), chromium (Cr), molybdenum (Mo), carbon (C) and boron (B),
An amorphous alloy having a content within the range of 5 to 22 at%, respectively, based on the total element content of the amorphous alloy. The method of claim 1,
An amorphous alloy having a fracture strength of 3000 Mpa or more. The method of claim 1,
An amorphous alloy having a Young's modulus of 150 Gpa or more. The method of claim 1,
Amorphous alloy represented by the following [Formula 1]:
[Formula 1]
(Co, Fe, Ni) ₅₀ (Cr,Mo) _x (C,B) _50-x
Here, x is assumed to be an atomic percent within the range of 20 to 40. 8. The method of claim 7,
The cobalt (Co), iron (Fe) and nickel (Ni) are
An amorphous alloy having a ratio of at least one of 1:1:1, 2:1:1, 2:2:1, 3:2:1 and 3:3:1, respectively. 8. The method of claim 7,
The chromium (Cr) and molybdenum (Mo) are,
Amorphous alloy having a ratio of 1:1. 8. The method of claim 7,
The carbon (C) and boron (B) are,
Amorphous alloy having a ratio of 1:1. The method of claim 1,
The iron (Fe) is
An amorphous alloy having a content within the range of 12 to 22 at% relative to the total element content of the amorphous alloy. The method of claim 1,
The nickel (Ni) is,
An amorphous alloy having a content within the range of 12 to 22 at% relative to the total element content of the amorphous alloy. The method of claim 1,
The chromium (Cr) is,
An amorphous alloy having a content within the range of 10 to 20 at% relative to the total element content of the amorphous alloy. The method of claim 1,
The molybdenum (Mo) is,
An amorphous alloy having a content within the range of 10 to 20 at% relative to the total element content of the amorphous alloy. The method of claim 1,
The carbon (C) is,
An amorphous alloy having a content within the range of 5 to 15 at% relative to the total element content of the amorphous alloy. The method of claim 1,
The boron (B) is,
An amorphous alloy having a content within the range of 5 to 15 at% relative to the total element content of the amorphous alloy. The method of claim 1,
Amorphous alloy formed into a ribbon shaped.

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