JP2000234156A - Bulky amorphous alloy and high strength member using the alloy - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase the amorphousness forming performance of the alloy by controlling the content of oxygen therein to a specified range and allowing it to contain an amorphous phase by a specified volume ratio. SOLUTION: This bulky amorphous alloy has an amorphous phase, e.g. with the dimensional shape of >=1 mm even as to any direction of the three dimensions and contains the amorphous phase of >=50% by volume ratio. In this alloy, the content of oxygen is controlled, by atom, to 0.005 to 1.0%. By this, the formation of ununiform nuclei is made less to obtain the alloy contg. the amorphous phase of >=50% by volume, so that the excellent characteristics of high hardness and elongation, high mechanical strength or the like can be obtd. The content of oxygen is more preferably controlled to 0.005 to 0.26%, by which its amorphousness forming performance improves to obtain the alloy having large dimensions. Furthermore, the amorphousness forming performance of the alloy is moreover improved by incorporating it with 0.005 to 1.05 oxygen, >0 to 0.2% nitrogen and >0 to 1.0% hydrogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bulk amorphous alloy and a high strength member using the same.

[0002]

BACKGROUND OF THE INVENTION Metals or alloys usually crystallize when cooled from the molten state, but for certain metals or alloys,
It is known that when cooled from a molten state at a sufficiently high cooling rate, it is supercooled to obtain an amorphous metal or alloy at room temperature. The cooling rate in that case is
Conventionally, ultra-rapid cooling of about 10 ⁴ to 10 ⁶ K / sec has been required, and as a result, amorphous metals or alloys have been limited to thin bodies, powders, fine wires, or the like.

However, recently, for example, a certain zirconium alloy or the like has a cooling rate of about 1 K / sec to 10 ³ K / sec as a critical cooling rate, so that an amorphous alloy can be obtained at a relatively low cooling rate. Now you can do it. For this reason, a bulk amorphous alloy can be manufactured, and the characteristics of the amorphous alloy in a bulk state can be applied in addition to a thin body or a thin line. For this reason, various applications utilizing properties unique to amorphous alloys, such as good mechanical properties such as high strength and high hardness, in a bulk state have been considered.

As an alloy capable of obtaining an amorphous phase at a relatively low cooling rate, for example, Japanese Patent Publication No. 7-12
Alloys such as Zr-based alloys disclosed in JP-A-2120, alloys disclosed in JP-A-8-74010 and JP-A-8-199318 to which a platinum group element is added, and US Pat. No. 5,288,344 to which Be is added. Specification, US Patent 536
Alloys and the like disclosed in 8659 are known.

[0005]

However, in the alloy having the composition according to the above-mentioned known example, the method of casting the molten metal as it is into a mold does not make it amorphous. Patent No. 5797443, or
Material Science Forum Vols. 269-272 (1998) pp.797-
As described, for example, in 802, the oxygen content must be limited to practicable levels to reduce heterogeneous nucleation. However, even with these, it was still insufficient to obtain an amorphous alloy. In particular, the alloy of Zr ₅₅ Al ₁₀ Cu ₃₀ Ni ₅ described in the latter has an amorphous content in the range of 0.26 at% to 0.73 at% in oxygen content. In this case, although a part became amorphous, it did not become an amorphous having a size satisfactory as a bulk size. The oxygen content is 0.2
The same was true for the alloy of 8 at% Zr ₆₅ Al _7.5 Cu _17.5 Ni ₁₀ . Materials Transactions, JIM Vo
l.38, pp473-477 (1997) states that heterogeneous nucleation may be caused by the inclusion of carbon and nitrogen in addition to oxygen. Not specifically shown.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a bulk amorphous alloy produced by enhancing the amorphous forming ability of the alloy and the bulk amorphous alloy. An object is to provide a high-strength member made of an alloy.

[0007]

Means for Solving the Problems The present inventors have conducted detailed studies on the amounts of oxygen, nitrogen, and hydrogen contained in the alloy, the ability to form an amorphous phase, and the characteristics of the obtained amorphous alloy. As a result, by controlling the amount of oxygen, the amount of nitrogen and the amount of hydrogen in the alloy composition, the amorphous formation can be clearly controlled, for example, the volume ratio and mechanical properties of the amorphous phase contained in the alloy can be controlled, It has been found that good characteristics can be obtained, and the present invention has been accomplished.

[0008] The bulk amorphous alloy of the present invention is characterized in that the content of oxygen is 0.005 at% or more and 1.0 at% or less and the amorphous phase contains 50% or more by volume. It is.

[0009] In the present invention, the amorphous alloy is 10 ⁴ -
It does not require ultra-rapid cooling of 10 ⁶ K / sec,
Amorphous formation is possible by cooling at a low cooling rate of less than 10 ⁴ K / sec. For this reason, high strength can be obtained in a bulk form.

In the present invention, a bulk amorphous alloy is defined as a dimensional shape having a dimension of, for example, 1 mm or more in any three-dimensional direction without having to have a minute dimension such as a thin body, a powder, or a fine line. And an alloy containing an amorphous phase in a volume ratio of 50% or more.

Since the bulk amorphous alloy of the present invention can be easily formed without requiring rapid cooling as in the prior art, it is possible to produce an amorphous alloy having a larger dimension, and the amorphous alloy can be formed into a thin tape. Compared to the case where the size is limited to a small size such as a shape, the amorphous alloy can be used for a wider application by utilizing the features of the amorphous alloy.

In the present invention, the oxygen content is set to 1.0 at%.
The reason for limiting to the following is that the formation of heterogeneous nuclei is reduced thereby, and a bulk amorphous alloy containing an amorphous phase in a volume ratio of 50% or more can be obtained. However, excellent properties of the amorphous alloy, such as high mechanical strength, can be obtained. Oxygen content is 1.0
If it exceeds at%, the ability to form a bulk amorphous material does not improve, which makes it difficult to form an amorphous material. Amorphous alloys cannot be obtained, and excellent properties of amorphous alloys, such as exhibiting good mechanical properties, are lost.

Further, in the present invention, the oxygen content is limited to 0.005 at% or more because, when the oxygen content is less than 0.005 at%, the hardness of the bulk amorphous alloy material obtained is low. This is because a decrease in elongation is observed along with the decrease, and an advantage in an application utilizing high strength, which is one of the features of the amorphous alloy, is reduced.

In the present invention, the oxygen content is 0.00
More preferably, the content is 5 at% or more and 0.26 at% or less. By making the oxygen content 0.005 at% or more and 0.26 at% or less, the ability to form a bulk amorphous material is further improved, and a bulk amorphous alloy having larger dimensions can be obtained.

Further, the bulk amorphous alloy of the present invention is characterized in that it contains oxygen in an amount of 0.005 to 0.26 at% and an amorphous phase in a volume ratio of 50% or more. is there.

Further, the bulk amorphous alloy of the present invention contains 0.005 at% or more and 1.0 at% or less of oxygen, more than 0 and 0.2 at% or less of nitrogen, and more than 0 and 1.0 at% or less of hydrogen. And an amorphous phase containing at least 50% by volume.

Further, the bulk amorphous alloy of the present invention contains 0.005 at% or more and 1.0 at% or less of oxygen, more than 0 and 0.2 at% or less of nitrogen, and more than 0 and 1.0 at% or less of hydrogen. And an amorphous phase containing at least 50% by volume.

In the present invention, not only the oxygen content is controlled within the specified range but also the oxygen, nitrogen and hydrogen contents are controlled within the specified range, thereby further improving the ability to form a bulk amorphous. However, it is preferable because a bulk amorphous alloy having a larger shape can be obtained. In this case, the oxygen content is set to 0.005 at% or more and 1.0 at% or less, the nitrogen content is set to more than 0 and 0.2 at% or less, and the hydrogen content is set to more than 0 and 1.0 at% or less. Is preferred. If the nitrogen content exceeds 0.2 at%, the ability to form a bulk amorphous material is reduced. The hydrogen content is 1.0at
%, The ability of the alloy to form a bulk amorphous state is reduced.

Further bulk amorphous alloys of the present invention have the general _{formula, (X a M b Al c} ) 100-xyz O x N y H z , however, X is one or selected from Zr and Hf M is at least one element selected from Ni, Cu, Fe, Co and Mn; a, b, c, x,
y and z are atomic percentages, 0.005 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.2, 0 ≦ z ≦ 1.0, 25 ≦ a ≦ 85, 5 ≦ b ≦ 70, 0 <c ≦ 35, a + b + c = 100 can be preferably used.

In the present invention, Ni, Cu, Fe, Co
The element M selected from Mn and Mn improves the ability to form an amorphous phase and increases the crystallization temperature by coexisting with Zr or Hf. Al coexists with the above elements to stabilize the amorphous phase, improve the spreadability, and increase the width of the supercooled liquid region.

In the present invention, the numerical ranges of a, b, and c are defined as described above. Outside of this range, the bulk amorphous forming ability of the alloy is reduced, and the bulk having a certain size is reduced. This makes it impossible to obtain an amorphous amorphous alloy.

The present invention relates to a metal composition of the above alloy,
In particular, by defining the ranges of the contents x, y, and z of oxygen, nitrogen, and hydrogen, respectively, the critical cooling rate can be significantly reduced, and as a result, a bulky amorphous alloy having a large shape can be easily obtained. It is possible to get. It is more preferable that the value of x is 0.005 or more and 0.26 or less.

Further bulk amorphous alloys of the present invention have the general formula _{[(Zr 1-p Ti p} ) a1 (M E) a2 (Cu 1-q Ni q)
_{b1 (M L) b2 Be c} ] 100-xyz O x N y H z , provided that at least one element M _E is V, Nb, selected from Hf and Cr, M _L is Fe, Co, Mn, Ru,
At least one element selected from the group consisting of Ag and Pd;
, A2, b1, b2, c, x, y, z are atomic percentages, p, q are atomic fractions, 0 ≦ p ≦ 1, 0 ≦ q ≦ 1, 30 ≦ a1 + a2 ≦ 75, 5 ≦ b1 + B2≤62, 2≤c≤47, a1 + a2 + b1 + b2 + c = 100, 0≤a1, 0≤a2, 0≤b1, 0≤b2, 0.005≤x≤1.0, 0≤y≤0. Those having a composition represented by 2, 0 ≦ z ≦ 1.0 are preferably used.

In the present invention, a1, a2, b1, b2
The reason for limiting the ranges of c and c in this manner is that if the ratio is outside this range, the ability to form bulk amorphous is reduced, and a bulk amorphous alloy having a certain size cannot be obtained.

In the present invention, the critical cooling rate can be remarkably lowered by having the metal composition of the above alloy, and particularly defining the ranges of the contents x, y and z of oxygen, nitrogen and hydrogen. As a result, a large-sized bulk amorphous alloy can be easily obtained. It is more preferable that the value of x is 0.005 or more and 0.26 or less.

In the amorphous alloy having the above composition, a 1 +
More preferably, a2 is 40 to 67%, b1 + b2 is 10 to 48%, and c is 10 to 35%.

Further, the high-strength member of the present invention is characterized by containing the above-mentioned bulk amorphous alloy. High strength, which is a basic property of an amorphous alloy, can be used in a bulk size.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the content of oxygen, nitrogen and hydrogen in a bulk amorphous alloy depends on the content of oxygen, nitrogen and hydrogen in each metal material used for each metal constituting the alloy. It can be adjusted to a predetermined value by controlling the amount and the content of oxygen, nitrogen and hydrogen in the atmosphere gas when melting these to produce an alloy.

Next, the embodiments of the present invention will be specifically described based on examples.

[Examples] Table 1 is a table collectively showing alloy compositions used in Examples and Comparative Examples of the present invention.

[0031]

[Table 1] In Table 1, A1 to A8 have the general formula: X _a M _b Al _c,
Here, X is one or two selected from Zr and Hf.
The seed element, M, is a specific example of the alloy composition of Ni, Cu, Fe, Co, and Mn. In Table 1, B1 to B8
General _{formula: (Zr 1-x Ti x} ) a1 (M E) a2 (Cu 1-y
_{Ni y) b1 (M L)} b2 Be c, where the M _E is V, Nb,
At least one element selected from Hf and Cr, M _L
Is a specific example of each alloy composition which is at least one element selected from Fe, Co, Mn, Ru, Ag and Pd.

(Examples 1 to 4 and Comparative Examples 1 to 4) First, the relationship between the oxygen content and the amorphous volume fraction, hardness and elongation of the alloy of the present invention will be described.

Regarding the alloy composition of A1, a material containing an oxygen content close to the value shown in the column of oxygen content in Table 2 was set in a crucible, and vacuum melting and casting were performed by high-frequency induction heating to obtain an alloy. The body was made. Here, the degree of vacuum in the vacuum melting was adjusted to a degree of vacuum of 1.33 Pa or less and the oxygen atmosphere was adjusted. After stirring after melting, the mixture was cast into a copper mold set in the same vacuum vessel to obtain a plate having a thickness of 4 mm. A bulk alloy material was obtained. By adjusting the oxygen atmosphere and the degree of vacuum, each alloy body having the value shown in Table 2 as the oxygen content of each alloy composition after casting was obtained. At this time, the copper mold was not subjected to forced cooling such as water cooling, but allowed to cool naturally.

[0034]

[Table 2] The structure of the thus obtained alloy body was observed, and the amorphous volume ratio of the alloy was measured by image analysis. The hardness (Vickers hardness H) of each obtained alloy material
v) and elongation (elongation at break,%) were measured, and both are shown in Table 2.

FIG. 1 shows the relationship between the oxygen content and the amorphous volume ratio of the obtained alloy. FIG. 2 shows the relationship between the oxygen content and the hardness (Hv) and elongation of the obtained alloy body.

From the results shown in Table 2 and FIGS. 1 and 2, the hardness and elongation of the alloy body were determined when the oxygen content was 0.005 at% or more and 1.0
It can be seen that a high value is obtained at at% or less.

(Examples 5 to 8 and Comparative Examples 5 to 7) Next, the relationship between the nitrogen content of the alloy of the present invention and the amorphous volume fraction and elongation will be described.

With respect to the alloy composition of A2, a material containing an amount of nitrogen close to the value shown in the column of nitrogen amount in Table 3 was set in a crucible, and vacuum melting and casting were performed by high frequency induction heating to obtain an alloy. The body was made. Here, the vacuum degree of the vacuum melting was adjusted to a vacuum degree of 1.33 Pa or less, and the nitrogen atmosphere was adjusted. After stirring after melting, the mixture was cast into a copper mold set in the same vacuum vessel to obtain a plate thickness of 4 mm. A bulk alloy material was obtained. By adjusting the nitrogen atmosphere and the degree of vacuum, each alloy body having the value shown in Table 3 as the nitrogen content of each alloy composition after casting was obtained. At this time, the copper mold was not subjected to forced cooling such as water cooling, but allowed to cool naturally.

With respect to the alloy body thus obtained,
The structure was observed, and the amorphous volume fraction of the alloy was measured by image analysis. In addition, the hardness (Vickers hardness Hv) and elongation (%) of each of the obtained alloy materials were measured.

[0040]

[Table 3] FIG. 3 shows the relationship between the nitrogen content and the amorphous volume ratio of the obtained alloy.

From Table 3 and FIG. 3, the nitrogen content is 0.2 at%.
If it is less than or equal to, it can be seen that an alloy body having an amorphous volume fraction of 50% or more can be obtained, and a high value can be obtained as the elongation of the alloy body.

(Examples 9 to 12 and Comparative Examples 8 to 10)
Next, the relationship between the hydrogen content of the alloy of the present invention and the amorphous volume fraction and elongation will be described.

With respect to the alloy composition of A3, a material containing an amount of hydrogen close to the value shown in the column of hydrogen amount in Table 4 was set in a crucible, and vacuum melting and casting were performed by high-frequency induction heating. The body was made. Here, the vacuum degree of the vacuum melting is adjusted to a vacuum degree of 1.33 Pa or less and the hydrogen atmosphere is adjusted, and after stirring after melting, the mixture is poured into a copper mold set in the same vacuum vessel to obtain a plate having a thickness of 4 mm. A bulk alloy material was obtained. By adjusting the hydrogen atmosphere and the degree of vacuum, alloy bodies having the values shown in Table 4 as the hydrogen content of each alloy composition after casting were obtained. At this time, the copper mold was not subjected to forced cooling such as water cooling, but allowed to cool naturally.

With respect to the alloy body thus obtained,
The structure was observed, and the amorphous volume fraction of the alloy was measured by image analysis. In addition, the hardness (Vickers hardness Hv) and elongation (%) of each of the obtained alloy materials were measured.

[0045]

[Table 4] FIG. 4 shows the relationship between the hydrogen content and the amorphous volume fraction of the obtained alloy.

From Table 4 and FIG. 4, it can be seen that the hydrogen content is 1.0 at%.
If it is less than or equal to, it can be seen that an alloy body having an amorphous volume fraction of 50% or more can be obtained, and a high value can be obtained as the elongation of the alloy body.

(Examples 13 to 44 and Comparative Examples 11 to 4)
2) The relationship between the oxygen, nitrogen, and hydrogen contents of the alloy of the present invention and the amorphous volume fraction, hardness, and elongation will be described.

Table 5 shows the contents of oxygen, nitrogen and hydrogen for each of the alloy compositions A1 to A8 and B1 to B8 in Table 1.
A material containing an amount close to the value shown in the column of “alloy gas component” of No. 8 was set in a crucible, and vacuum melting and casting were performed by high-frequency induction heating to produce an alloy.

[0049]

[Table 5]

[Table 6]

[Table 7]

[Table 8] Here, the degree of vacuum in the vacuum melting was adjusted to 1.33 Pa or less and the atmosphere was adjusted. After stirring after melting, the mixture was cast into a copper mold set in the same vacuum vessel to obtain a plate thickness of 1 mm and 4 mm. Of each bulk alloy material were obtained.
By adjusting the atmosphere and the degree of vacuum, each alloy material having the values shown in the alloy gas component columns of Tables 5 to 8 as the contents of oxygen, nitrogen and hydrogen of each alloy composition after casting was obtained. At this time, the copper mold was not subjected to forced cooling such as water cooling, but allowed to cool naturally.

With respect to the alloy material thus obtained,
X-ray diffraction and structure observation were performed, and the amorphous volume fraction of the alloy was measured by image analysis. The results are shown in Tables 5 to 8 in the columns of cast thickness and amorphous volume fraction. The hardness (Vickers hardness) and elongation (%) of each of the obtained alloys were measured and shown in the hardness column and the elongation column of Tables 5 to 8.

FIG. 5 is a micrograph of the alloy of Example 13 having a thickness of 4 mm.
% And 36% are mixed. FIG. 6 shows the second embodiment.
9 is a micrograph of a 4 mm-thick alloy of Example 9, in which a crystal phase is slightly mixed at a volume ratio of 7% with an amorphous phase volume ratio of 93%. FIG. 7 is a micrograph of the alloy of Comparative Example 11 having a thickness of 4 mm, in which the crystal phase has a volume ratio of 72% and the amorphous phase has a volume ratio of 28%.

From the results shown in Tables 5 to 8, in the alloy containing oxygen, nitrogen and hydrogen, the oxygen content was set at 1.0 at.
% Or less, the nitrogen content is set to 0.2 at% or less, and the hydrogen content is set to 1.0 at% or less, a bulk amorphous can be formed well, and the oxygen content is reduced to 0.1 at%.
It can be seen that by setting the content to 005 at% or more, it is possible to prevent the hardness and elongation of the bulk amorphous from decreasing.

[0053]

According to the present invention, since the critical cooling rate for forming an amorphous phase can be reduced, the ability of the alloy to form an amorphous phase can be improved. Therefore, the alloy having the ability to form a bulk amorphous material of the present invention is used as a master alloy for producing a bulk amorphous alloy, and is melted and cast using a mold to form a bulk amorphous alloy. Can be manufactured. Further, since the bulk amorphous alloy of the present invention can be formed more easily than in the past, the characteristics of the amorphous alloy can be utilized for wider applications such as larger dimensions.

[Brief description of the drawings]

FIG. 1 is a view showing a relationship between an oxygen content of an alloy material and an amorphous volume ratio.

FIG. 2 is a diagram showing the relationship between the oxygen content of an alloy material, hardness (Hv), and elongation.

FIG. 3 is a diagram showing the relationship between the nitrogen content of an alloy material, the amorphous volume ratio, and the elongation.

FIG. 4 is a diagram showing the relationship between the amount of hydrogen in the alloy material, the amorphous volume ratio, and the elongation.

FIG. 5 is a micrograph of an alloy of one example of the present invention.

FIG. 6 is a micrograph of an alloy according to another embodiment of the present invention.

FIG. 7 is a micrograph of an alloy of a comparative example for the present invention.

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[Procedure amendment]

[Submission date] May 15, 2000 (2000.5.1)
5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

Further, the bulk amorphous alloy of the present invention contains oxygen in a range of 0.005 to 0.26 at%, nitrogen in a range of more than 0 to 0.2 at%, and hydrogen in a range of more than 0 to 1.0 at%. , Containing at least 50% by volume of the amorphous phase.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction contents]

[0049]

[ Table 5 ]

[ Table 6 ]

[ Table 7 ]

[ Table 8 ] Here, the degree of vacuum in the vacuum melting was adjusted to 1.33 Pa or less, the atmosphere was adjusted, and after stirring after melting, the mixture was cast into a copper mold set in the same vacuum vessel to obtain a plate pressure of 1 mm and 4 mm. Of each bulk alloy material were obtained.
By adjusting the atmosphere and the degree of vacuum, each alloy material having the values shown in the alloy gas component columns of Tables 5 to 8 as the contents of oxygen, nitrogen and hydrogen of each alloy composition after casting was obtained. At this time, the copper mold was not subjected to forced cooling such as water cooling, but allowed to cool naturally.

Claims (10)

[Claims] 1. A bulk amorphous alloy comprising 0.005 at% or more and 1.0 at% or less of oxygen and 50% or more by volume of an amorphous phase. 2. The oxygen content is 0.005 at% or more and 0.26 at%.
A bulk amorphous alloy containing the following, and containing an amorphous phase in a volume ratio of 50% or more. 3. The composition contains 0.005 at% or more and 1.0 at% or less of oxygen, more than 0 and 0.2 at% or less of nitrogen, and more than 0 and 1.0 at% or less of hydrogen. A bulk amorphous alloy containing 50% or more. 4. The composition contains oxygen in an amount of 0.005 to 1.0 at%, nitrogen in an amount of more than 0 and 0.2 at% and hydrogen in an amount of more than 0 and 1.0 at% or less. A bulk amorphous alloy containing 50% or more. 5. A general _{formula, (X a M b Al c} ) 100-xyz O x N y H z where either or both of the two elements X are selected from Zr and Hf, M is Ni, Cu, At least one element selected from the group consisting of Fe, Co and Mn, a, b, c, x,
y and z are atomic percentages, 0.005 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.2, 0 ≦ z ≦ 1.0, 25 ≦ a ≦ 85, 5 ≦ b ≦ 70, 0 <c ≦ 35. A bulk amorphous alloy having a composition represented by: a + b + c = 100. 6. general _{formula, (X a M b Al c} ) 100-xyz O x N y H z where either or both of the two elements X are selected from Zr and Hf, M is Ni, Cu, At least one element selected from the group consisting of Fe, Co and Mn, a, b, c, x,
y and z are atomic percentages, 0.005 ≦ x ≦ 0.26, 0 ≦ y ≦ 0.2, 0 ≦ z ≦ 1.0, 25 ≦ a ≦ 85, 5 ≦ b ≦ 70, 0 <c ≦ 35. A bulk amorphous alloy having a composition represented by: a + b + c = 100. 7. A general _{formula, [(Zr 1-p Ti} p) a1 (M E) a2 (Cu 1-q Ni q)
_{b1 (M L) b2 Be c} ] 100-xyz O x N y H z , provided that at least one element M _E is V, Nb, selected from Hf and Cr, M _L is Fe, Co, Mn, Ru,
At least one element selected from the group consisting of Ag and Pd;
, A2, b1, b2, c, x, y, z are atomic percentages, p, q are atomic fractions, 0 ≦ p ≦ 1, 0 ≦ q ≦ 1, 30 ≦ a1 + a2 ≦ 75, 5 ≦ b1 + B2≤62, 2≤c≤47, a1 + a2 + b1 + b2 + c = 100, 0≤a1, 0≤a2, 0≤b1, 0≤b2, 0.005≤x≤1.0, 0≤y≤0. 2. A bulk amorphous alloy having a composition represented by the formula: 0 ≦ z ≦ 1.0. 8. A general _{formula, [(Zr 1-p Ti} p) a1 (M E) a2 (Cu 1-q Ni q)
_{b1 (M L) b2 Be c} ] 100-xyz O x N y H z , provided that at least one element M _E is V, Nb, selected from Hf and Cr, M _L is Fe, Co, Mn, Ru,
At least one element selected from the group consisting of Ag and Pd;
, A2, b1, b2, c, x, y, z are atomic percentages, p, q are atomic fractions, 0 ≦ p ≦ 1, 0 ≦ q ≦ 1, 30 ≦ a1 + a2 ≦ 75, 5 ≦ b1 + B2≤62, 2≤c≤47, a1 + a2 + b1 + b2 + c = 100, 0≤a1, 0≤a2, 0≤b1, 0≤b2, 0.005≤x≤0.26, 0≤y≤0. 2. A bulk amorphous alloy having a composition represented by the formula: 0 ≦ z ≦ 1.0. 9. The bulk amorphous alloy according to claim 5, wherein the amorphous phase contains at least 50% by volume of an amorphous phase. 10. A high-strength member comprising the bulk amorphous alloy according to any one of claims 1 to 9.