JP2000265252A - High strength amorphous alloy and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart remarkably high strength and toughness such as ductility by preparing an alloy consisting of specified ratios of Zr, Ni, Cu, Al, Au, Ag, or the like, and composed of a structure at least having an amorphous phase. SOLUTION: An alloy represented by the general formula of XaMbAlcTdPe (where X denotes one or two kinds of elements of Zr and Hf, M denotes one or more kinds of elements selected from Ni, Cu, Fe, Co and Mn, T denotes elements having negative mixing enthalpy to at least one or more kinds of elements among X, M and Al, P denotes elements having positive mixing enthalpy to at least one or more kinds of elements among X, M and Al, and as to (a), (b), (c), (d) and (e), by atomic%, 25<=a<=85, 5<=b<=70, 0<c<=30, 0<d<=10 and 0<e<=20 are satisfied) and composed of a structure at least having an amorphous phase is prepd. Moreover, the T elements denote one or more kinds of elements among Ru, Os, Rh, Ir, Pd, V, Cr, Mo, W, Au, or the like, and P elements denote one or more kinds of elements among Ag, Au, Nb and Ta.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amorphous alloy having high hardness and strength, excellent ductility, high corrosion resistance, excellent workability, and an amorphous structure, and a method for producing the same. It is about.

[Prior art]

In a conventional Zr-based alloy, a glass transition is observed before crystallization in a specified alloy composition, a wide supercooled liquid region is exhibited, and a large amorphous forming ability is exhibited. Widely used as a base metal for alloys. Since these Zr-based alloys have a large amorphous forming ability as described above, not only a special forming method capable of obtaining a large cooling rate such as a liquid quenching method, but also a Cu mold casting or the like. Even by a general casting method with a relatively slow cooling distance, it becomes amorphous (amorphous), and a tough (high toughness) bulk amorphous can be produced relatively easily.

[0003]

However, when, for example, a quenched thin (high toughness) ribbon produced by a liquid quenching method is heated to a temperature around the crystallization temperature, or the bulk amorphous is formed by the Cu mold casting method. If the cooling rate becomes slower than a predetermined cooling rate during the production in the above, the characteristics of the obtained bulk amorphous phase, particularly the toughness (toughness), are deteriorated due to the precipitation of crystals, and 180 °
There has been a problem that processing such as close contact bending becomes difficult, and the bending strength also decreases.

Accordingly, the present invention has been made in view of the above-mentioned problems, and has been made in a case where heat treatment is performed on a prepared long-strength (high toughness) ribbon or bulk material to precipitate crystals, A composition that can solve the problem of deterioration of properties such as the toughness (toughness) and strength when a crystal is precipitated at a low cooling rate by a mold casting method in order to improve productivity and productivity. An object of the present invention is to provide an amorphous alloy having the same and a method for producing the same.

[0005]

In order to solve the above-mentioned problems, a high-strength amorphous alloy of the present invention has a general formula: XaM
bAlcTdPe (where X is one or two elements selected from Zr and Hf, M; Ni, Cu, Fe, C
at least one element selected from o and Mn, T;
X, M, an element having a negative mixed enthalpy with respect to at least one or more elements of Al; P;
Elements having a positive mixed enthalpy with respect to at least one or more elements of Al, a, b, c, d, and e are atomic percentages, and 25 ≦ a ≦ 85, 5 ≦ b ≦ 70, and 0 <c ≦ 3
0, 0 <d ≦ 10, 0 <e ≦ 20), and is characterized by comprising a structure having at least an amorphous phase. According to this feature, by including the element having the negative mixed enthalpy and the element having the positive mixed enthalpy in the composition as described above, the crystal deposited by slowing the heat treatment and cooling rate. Since the size can be reduced, an alloy having extremely high strength and toughness such as elongation can be obtained without deterioration of properties such as toughness (toughness) and strength.

In the high-strength amorphous alloy according to the present invention, the T element is Ru, Os, Rh, Ir, Pd, Pt, V, Cr, M
It is preferably at least one element selected from o, W, Au, Ga, Ge, Re, Si, Sn, and Ti. In this way, a high effect can be obtained in preventing the above-mentioned property deterioration and improving the properties such as high strength and high toughness.

In the high-strength amorphous alloy of the present invention, the P element is preferably at least one element selected from Ag, Au, Nb, and Ta. In this way, a high effect can be obtained in preventing the above-mentioned property deterioration and improving the properties such as high strength and high toughness.

[0008] In the high-strength amorphous alloy according to the present invention, the structure is preferably a mixed phase of an amorphous phase and a fine crystalline phase. In this way, a high effect can be obtained in preventing the above-mentioned property deterioration and improving the properties such as high strength and high toughness.

The high-strength amorphous alloy of the present invention preferably contains at least a quasicrystalline phase in the amorphous structure.
By doing so, prevention of the characteristic deterioration and high strength,
Improvement of properties such as high toughness, and particularly high effects can be obtained in terms of bending strength.

[0010] The method for producing a high-strength amorphous alloy of the present invention comprises:
XaMbAlcTdPe (where X is one or two elements selected from Zr and Hf, M; Ni,
At least one selected from Cu, Fe, Co and Mn
A kind of element, T; an element having a negative mixed enthalpy with respect to at least one or more of X, M, and Al;
P; elements having a positive mixing enthalpy with respect to at least one or more elements of X, M and Al, a, b, c,
d and e are atomic percent and 25 ≦ a ≦ 85, 5 ≦ b ≦
70, 0 <c ≦ 30, 0 <d ≦ 10, 0 <e ≦ 20) to prepare an amorphous alloy containing at least an amorphous phase, and to prepare a glass transition of the alloy. The ripening process is characterized in that the ripening treatment is performed in a temperature range from the temperature Tg to the first exothermic reaction start temperature (Tx1: crystallization temperature). According to this feature, the heat treatment temperature is equal to the glass transition temperature T.
If it is less than 0.1 g, fine crystalline or quasicrystalline transition is not satisfactorily performed, and if the heat treatment temperature exceeds the starting temperature Tx1 of the first exothermic reaction, the crystal formed in the structure Alternatively, since the properties of the alloy obtained by coarsening the size of the quasicrystal deteriorates, the alloy is contained in the amorphous phase by performing ripening treatment in the temperature range between Tg and Tx1. The amount and size of the fine crystals or quasicrystals can be made appropriate, so that alloys having extremely high strength and toughness such as elongation without deterioration of properties such as toughness (toughness) and strength can be obtained. Obtainable.

[0011] The method for producing a high-strength amorphous alloy of the present invention comprises:
The heat treatment time in the temperature range is preferably set to 1 to 120 minutes. By doing so, the amount and size of the formed fine crystals or quasicrystals can be made appropriate.

[0012] The method for producing a high-strength amorphous alloy of the present invention comprises:
It is preferable that the alloy containing the amorphous phase be an alloy composed of a quasicrystalline single phase in the ripening treatment. In this way, properties such as the toughness (toughness) and strength of the obtained alloy can be significantly improved.

[0013]

Embodiments of the present invention will be described below with reference to the drawings.

(Example) In the above claims, Zr is used as the X element, Ni and Cu as the M element, Au as the T element,
Using Ag as the P element, Zr ₆₅ Al _7.5 Cu _7.5
A master alloy having a composition of Ni ₁₀ Ag ₅ Au ₅ (subscript is atomic%) is melted in an arc melting furnace, and the strip is formed by a generally used single-roll liquid quenching device (melt spinning device). 20 μm, width 1.5 mm).
The roll at that time is made of copper with a diameter of 200 mm, and the rotation speed is 40.
At 00 rpm, the atmosphere is Ar at 10 ⁻³ Torr or less.

Further, as a comparison of the present invention, it is assumed that only the P element having the positive enthalpy is included, and Zr ₅₅ Al ₁₀ Cu ₂₉ N using only Nb as the P element.
i ₅ Nb ₁ and Zr ₅₅ Al ₁₀ containing no P element
A master alloy having a composition of Cu ₃₀ Ni ₅ (subscript: atomic%) was prepared in the same manner as described above to produce a strip.

The obtained amorphous single-phase alloy strips were measured by a differential scanning calorimeter (DSC). In Figure _1, the thermal properties of Zr ₅₅ Al _{10 Cu} 30 Ni ₅ are those represented by _{(a), Zr} 55 Al
The thermal properties of ₁₀ Cu ₂₉ Ni ₅ Nb ₁ are shown by (b) and Zr ₆₅ Al _7.5 Cu _7.5 Ni ₁₀ A
thermal properties of g ₅ Au ₅ is shown in (c).

Based on the measurement by each of the differential scanning calorimeters (DSC), the glass transition temperature (Tg), the crystallization temperature (Tx; Tx1, Tx1, Tx
2) was determined. Explaining how to take these Tg and Tx, the temperature at the point where the endothermic reaction occurs on the differential scanning calorimetric analysis curve and where the extrapolation of the base line intersects with the rising end of the curve is defined as Tg. Where
The temperature obtained in the same manner as above is set as Tx. The supercooled liquid region (ΔT) is a region between the glass transition temperature (Tg) and the crystallization temperature (Tx1). In the present invention, each of the amorphous single phase The alloy strip is heated for a predetermined time at an appropriate temperature selected from the supercooled liquid region.

If the heating time is short, the amorphous phase is not sufficiently transferred to the fine crystals or fine quasicrystals, and if the time is long, the amorphous phase is formed in the structure. Since the size of the crystal or quasicrystal becomes coarse, it is preferable to set the range to 1 to 120 minutes, and in this embodiment, it is set to 2 minutes.

FIG. 2 shows data by X-ray diffraction when the heat treatment is performed on the alloy of this embodiment as described above. From these results, it is shown that the alloy of the present example has no significant difference in peak intensity between the supercooled liquid regions 703K and 753K, and can form a stable crystal in this temperature region. At the same time, a broad diffraction pattern unique to the amorphous phase can also be confirmed, and the obtained alloy is a mixed phase of the amorphous phase and the crystalline phase. It can also be seen that the crystal formed therein is a quasicrystal having the structure shown in FIG.

Each of the alloys heat-treated as described above
FIG. 3 shows the results of measuring the three-point bending strength. This
From the results of the above, Z containing no P element, which is the comparative alloy,
r_{5 5}Al₁₀Cu₃₀Ni₅Positive enthal
By mixing a small amount of Nb as a P element having a peak,
Elongation which is an index of the strength and toughness (toughness) is improved.
And also has positive and negative enthalpies
Example 1 in which Ag and Au coexist as P and T elements
Zr is an alloy of₆₅Al_7.5Cu_7.5Ni ₁₀Ag
₅Au₅In this case, it is even stronger than the above-mentioned mixture of Nb.
It can be seen that the degree has improved,
Close bending was possible.

The alloy of this embodiment (Zr ₆₅ Al _7.5
FIG. 4 shows the results of examining the mechanical properties of Cu _7.5 Ni ₁₀ Ag ₅ Au ₅ ) with respect to the volume fraction of the crystal phase present in the matrix by changing the heat treatment time in the above.
Shown in From this result, it was found that as the volume of the crystalline phase dispersed in the amorphous phase increased, the mechanical properties such as tensile strength, hardness and Young's modulus were improved. The mechanical properties do not deteriorate. From this, it is considered that the crystals formed in the matrix have a quasicrystal structure as shown in FIG. 2A, and even if the volume of the quasicrystalline phase increases,
It is considered that the mechanical properties do not deteriorate.

Although the present invention has been described with reference to the drawings, the present invention is not limited to these embodiments, and changes and additions may be made without departing from the spirit of the present invention. Needless to say, this is included in the present invention.

In the above embodiment, the amorphous single-phase alloy strip is manufactured by a single-roll type liquid quenching apparatus (melt spinning apparatus). However, the present invention is not limited to this. Other methods for obtaining these amorphous single-phase alloys, for example, a twin-neck method, a spinning method in a rotating liquid,
High-pressure gas spraying, spraying, rapid cooling by sputtering or die casting may be used.

[0024]

The present invention has the following effects.

(A) According to the first aspect of the present invention, the heat treatment and the cooling rate are achieved by including the element having the negative mixed enthalpy and the element having the positive mixed enthalpy in the composition as described above. By slowing down, the size of the precipitated crystals can be made finer, and properties such as toughness (toughness) and strength are not deteriorated, and an alloy having extremely high strength and toughness such as elongation can be obtained. Can be.

(B) According to the second aspect of the present invention, a high effect can be obtained in preventing the deterioration of the characteristics and improving the characteristics such as high strength and high toughness.

(C) According to the third aspect of the invention, it is possible to obtain a high effect in preventing the characteristic deterioration and improving characteristics such as high strength and high toughness.

(D) According to the fourth aspect of the invention, a high effect can be obtained in preventing the characteristic deterioration and improving the characteristics such as high strength and high toughness.

(E) According to the fifth aspect of the invention, it is possible to prevent deterioration of the characteristics and to improve characteristics such as high strength and high toughness, and particularly to obtain a high effect in terms of bending strength.

(F) According to the invention of claim 6, when the heat treatment temperature is lower than the glass transition temperature Tg, fine crystalline or quasicrystalline transition is not satisfactorily performed, and
If the heat treatment temperature exceeds the starting temperature Tx1 of the first exothermic reaction, the size of the crystal or quasicrystal formed in the structure becomes coarse, and the characteristics of the obtained alloy are deteriorated. By performing the ripening treatment in the temperature range between Tg and Tx1, it becomes possible to make the amount and size of the fine crystals or quasicrystals contained in the amorphous phase appropriate, and An alloy having remarkably high strength and toughness such as elongation can be obtained without deterioration in properties such as toughness and strength.

(G) According to the invention of claim 7, the amount and size of the fine crystal or quasicrystal to be formed can be made appropriate.

(H) According to the invention of claim 8, characteristics such as toughness (toughness) and strength of the obtained alloy can be remarkably improved.

[0033]

[Brief description of the drawings]

FIG. 1 is a graph showing the results of differential scanning calorimetry of an alloy of this example and an alloy of a comparative example.

FIG. 2 is a graph showing X-ray diffraction data when a predetermined heat treatment is performed on the alloy of this example.

FIG. 3 is a graph showing the three-point bending strength and elongation of the alloy of this example and the alloy of the comparative example.

FIG. 4 is a graph showing the mechanical properties of the alloy of this example.

FIG. 5 is a model diagram showing a structure of a quasicrystal.

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Claims (8)

[Claims] 1. A general formula: XaMbAlcTdPe (where X is one or two elements selected from Zr and Hf, M; at least one element selected from Ni, Cu, Fe, Co and Mn, T An element having a negative mixed enthalpy for at least one or more of the elements X, M, and Al; P; a positive mixed enthalpy for at least one or more of the elements X, M, and Al; Elements,
a, b, c, d, and e are atomic percent and 25 ≦ a ≦ 8
5, 5 ≦ b ≦ 70, 0 <c ≦ 30, 0 <d ≦ 10, 0 <
e ≦ 20), comprising a structure having at least an amorphous phase. 2. The method according to claim 1, wherein the T element is Ru, Os, Rh, Ir,
Pd, Pt, V, Cr, Mo, W, Au, Ga, Ge,
The high-strength amorphous alloy according to claim 1, which is at least one element selected from Re, Si, Sn, and Ti. 3. The high-strength amorphous alloy according to claim 1, wherein the P element is at least one element selected from Ag, Nb, and Ta. 4. The high-strength amorphous alloy according to claim 1, wherein said structure is a mixed phase of an amorphous phase and a fine crystalline phase. 5. The high-strength amorphous alloy according to claim 1, wherein the amorphous structure contains at least a quasicrystalline phase. 6. XaMbAlcTdPe (where X is one or two elements selected from Zr and Hf; M; at least one element selected from Ni, Cu, Fe, Co and Mn; T) An element having a negative mixed enthalpy for at least one or more of the elements X, M, and Al; P; a positive mixed enthalpy for at least one or more of the elements X, M, and Al; Elements,
a, b, c, d, and e are atomic percent and 25 ≦ a ≦ 8
5, 5 ≦ b ≦ 70, 0 <c ≦ 30, 0 <d ≦ 10, 0 <
e ≦ 20), and an amorphous alloy containing at least an amorphous phase is prepared, and the glass transition temperature Tg of the alloy and the start temperature of the first ripening reaction (Tx1: A high-strength amorphous alloy, which is subjected to ripening treatment in a temperature range up to a temperature up to a temperature equal to or higher than the temperature of the amorphous alloy. 7. The heat treatment time in the temperature range is set to 1
7. The method for producing a high-strength amorphous alloy according to claim 6, wherein the heating time is from 120 to 120 minutes. 8. The method for producing a high-strength amorphous alloy according to claim 6, wherein the alloy containing the amorphous phase in the ripening treatment is an alloy composed of a quasicrystalline single phase.