JP4332647B2 - High-strength amorphous alloy and method for producing the same - Google Patents

Description

[0001]
[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 having an amorphous structure, and a method for producing the same.
[Prior art]
[0002]
In a conventional Zr-based alloy, a glass transition is observed before crystallization in a specific alloy composition, a wide supercooled liquid region is shown, and a large amorphous forming ability is exhibited. Widely used as metal material. 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. Do relatively slow cooling speed common casting method by even amorphous turned into, Ne if have (high toughness) can be produced relatively easily the bulk amorphous.
[0003]
[Problems to be solved by the invention]
However, for example, when a thick (high toughness) quenching ribbon produced by a liquid quenching method is heated to a temperature around the crystallization temperature, or when the bulk amorphous is produced by the Cu mold casting method, the cooling rate is low. in the case of slower than a predetermined cooling rate, properties of the bulk amorphous obtained, degraded by particular viscosity of (toughness) is precipitated crystal, together become Dzu pleasure to machining such as bending 180 ° adhesion There was a problem that the bending strength also decreased.
[0004]
Therefore, the present invention has been made by paying attention to the above-mentioned problems. When the prepared thick (high toughness) ribbon or bulk material is subjected to heat treatment to precipitate crystals, workability and productivity are increased. Amorphous composition that can solve the problems of deterioration of properties such as stickiness (toughness) and strength when crystals are precipitated by slowing the cooling rate in the mold casting method to improve It is an object of the present invention to provide a quality alloy and a method for producing the same.
[0005]
[Means for Solving the Problems]
In order to solve the aforementioned problems, a high strength amorphous alloy of the present invention have the general formula; XaMbAlcTdPe (However, X; 1 kind or two kinds of elements selected from Zr and Hf, M; Ni, Cu, At least one element selected from Fe, Co and Mn, T; an element having a negative mixed enthalpy with respect to at least one element selected from the group consisting of X, M and Al; P; Elements having a positive mixed enthalpy with respect to one or more elements, a, b, c, d, and e are atomic percentages, 25 ≦ a ≦ 85, 5 ≦ b ≦ 70, 0 <c ≦ 30, 0 < d ≦ 10, 0 <e ≦ 20), and is characterized by comprising a structure having at least an amorphous phase. According to this feature, the size of crystals precipitated by slowing down the heat treatment and cooling rate by including in the composition an element having a negative mixed enthalpy and an element having a positive mixed enthalpy as described above. Thus, it is possible to obtain an alloy having extremely high strength and toughness such as elongation without deterioration of properties such as stickiness (toughness) and strength.
[0006]
In the high-strength amorphous alloy of the present invention, the element T is selected from Ru, Os, Rh, Ir, Pd, Pt, V, Cr, Mo, W, Au, Ga, Ge, Re, Si, Sn, and Ti. It is preferable that it is at least one kind of element. In this way, it is possible to obtain a high effect in preventing the characteristic deterioration and improving the characteristics such as high strength and high toughness.
[0007]
In the high-strength amorphous alloy of the present invention, the P element is preferably at least one element selected from Ag, Nb and Ta. In this way, it is possible to obtain a high effect in preventing the characteristic deterioration and improving the characteristics such as high strength and high toughness.
[0008]
In the high-strength amorphous alloy of the present invention, the structure is preferably a mixed phase of an amorphous phase and a fine crystalline phase. In this way, it is possible to obtain a high effect in preventing the characteristic deterioration and improving the characteristics such as high strength and high toughness.
[0009]
The high-strength amorphous alloy of the present invention preferably contains at least a quasicrystalline phase in the amorphous structure. In this way, it is possible to obtain a high effect in terms of prevention of the characteristic deterioration and improvement of characteristics such as high strength and high toughness, particularly in terms of bending strength.
[0010]
The method of manufacturing high-strength amorphous alloy of the present invention have the general formula; XaMbAlcTdPe (However, X; 1 kind or two kinds of elements selected from Zr and Hf, M; Ni, Cu, Fe, Co and Mn At least one element selected, T; an element having a negative mixed enthalpy with respect to at least one element selected from the group consisting of X, M and Al; P; at least one element selected from X, M and Al; In contrast, elements having a positive mixed enthalpy, a, b, c, d, and e are atomic percentages, 25 ≦ a ≦ 85, 5 ≦ b ≦ 70, 0 <c ≦ 30, 0 <d ≦ 10, 0 <. has a composition represented by e ≦ 20), to produce an amorphous alloy containing at least an amorphous phase, which alloy glass transition temperature Tg and the starting temperature of the first exothermic reaction (Tx1: forming crystallization Japanese to process pressure heat set at a temperature range up to temperature) It is set to. According to this feature, if the heat treatment temperature is lower than the glass transition temperature Tg, the fine crystalline or quasicrystalline transition is not improved, and the heat treatment temperature is lower than that of the first exothermic reaction. If the starting temperature Tx1 is exceeded, the characteristics of the alloy obtained by coarsening the size of the crystals or quasicrystals formed in the structure will deteriorate, so the temperature will be increased in the temperature range between Tg and Tx1. by heat treatment, said possible to make the amount and size of fine crystals or quasi-crystals contained in the amorphous phase suitable as the result, deterioration of the characteristics such as Nebasa (toughness) and strength Therefore, an alloy having a remarkably high strength and toughness such as elongation can be obtained.
[0011]
In the method for producing a high-strength amorphous alloy of the present invention, the heat treatment time in the temperature range is preferably 1 to 120 minutes. In this way, the amount and size of fine crystals or quasicrystals formed can be made appropriate.
[0012]
Method of producing a high strength amorphous alloys of the present invention, it is preferable that the alloy of the alloy containing the amorphous phase from the quasicrystalline single phase at the pressurized heat treatment. In this way, characteristics such as the toughness (toughness) and strength of the obtained alloy can be remarkably improved.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0014]
(Example)
The Zr as the element X in the claims, Ni and Cu as M elements, Au as the T element, _Zr 65 Al ₇ using Ag as a P _{element. 5 Cu 7. 5 Ni 10} Ag 5 Au 5 ( suffixes atomic%) A master alloy composed of the following composition was melted in an arc melting furnace, and a book band (thickness: 20 μm, width 1.5 mm) was produced by a commonly used single roll liquid quenching device (melt spinning device). The roll at that time is made of copper having a diameter of 200 mm, the rotational speed is 4000 rpm, and the atmosphere is Ar of 10 ⁻³ Torr or less.
[0015]
Further, as a comparison of the present invention, Zr ₅₅ Al ₁₀ Cu ₂₉ Ni ₅ Nb ₁ using only Nb as the P element, and not including the P element, including only the P element having the positive enthalpy. _{Zr 55 Al 10 Cu 30 Ni 5} ( suffixes atomic%) the mother alloy having a composition of, to prepare the carrying band in the same manner as above.
[0016]
Each of the obtained amorphous single-phase alloy band was measured by a differential scanning calorimeter (DSC). In FIG. 1, the thermal characteristics of Zr ₅₅ Al ₁₀ Cu ₃₀ Ni ₅ are shown by (a), and the thermal characteristics of Zr ₅₅ Al ₁₀ Cu ₂₉ Ni ₅ Nb ₁ are shown by (b). _{There, Zr 65 Al 7. 5 Cu} 7. thermal properties of ₅ Ni ₁₀ Ag ₅ Au ₅ is shown in (c).
[0017]
Based on the measurement by each differential scanning calorimeter (DSC), the glass transition temperature (Tg) and the crystallization temperature (Tx; Tx1, Tx2) were determined for each of the alloys. Explaining how Tg and Tx are taken, the endothermic reaction occurs on the differential scanning calorimetry curve. The temperature at the point where the rising edge of the curve and the extrapolation of the baseline intersect is Tg, and the exothermic reaction is reversed. The temperature obtained in the same manner as described 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 amorphous single phase produced above is used. The alloy band is heated for a predetermined time at an appropriate temperature selected from the supercooled liquid region.
[0018]
As the time for these heat treatments, if this time is short, the transition of the amorphous phase to fine crystals or fine quasicrystals will not be sufficient, and if this time is long, crystals or quasi-forms formed in the structure will be formed. Since the size of the crystal becomes coarse, it is preferably in the range of 1 to 120 minutes, and in this example, it is 2 minutes.
[0019]
FIG. 2 shows data by X-ray diffraction when the alloy of this example is heat-treated as described above. From these results, it can be seen that the alloy of this example has no significant difference in peak intensity between the supercooled liquid regions 703K and 753K, and stable crystals can be formed in this temperature region. At the same time, a broad diffraction pattern peculiar to the amorphous phase can be confirmed, and the resulting alloy is a mixed phase of an amorphous phase and a crystalline phase. It can also be seen that the crystals formed therein are quasicrystals having the structure shown in FIG.
[0020]
FIG. 3 shows the results of measuring the three-point bending strength for each alloy heat-treated as described above. From this result, it was found that the Zr ₅₅ Al ₁₀ Cu ₃₀ Ni ₅ that does not contain the P element as the comparative alloy was mixed with a small amount of Nb as a P element having a positive enthalpy, thereby obtaining the strength and stiffness (toughness). indicator extends understand that improves a of), _Zr 65 Al ₇ a further Ag as P and T elements having positive and negative enthalpy, the alloy of this embodiment are allowed to coexist _{Au. 5} Cu _{7. 5} In Ni ₁₀ Ag ₅ Au ₅ , it was found that the strength was further improved as compared with the mixture of Nb, and the 180 ° contact bending was possible.
[0021]
Alloys of this embodiment _{(Zr 65 Al 7. 5 Cu} 7. 5 Ni 10 Ag 5 Au 5) by changing the heat treatment time in the the mechanical properties with respect to the volume of the crystal phase present in Matrigel Tsu box FIG. 4 shows the result of examination. From this result, it can be seen that as the volume of the crystalline phase dispersed in the amorphous phase increases, the mechanical properties of tensile strength, hardness, and Young's modulus improve, and these crystalline phases are close to 100%. Even if it becomes, this mechanical characteristic does not fall. This also crystals formed during Matrigel Tsu box, believed to have a quasicrystalline structure as shown in the diagram (a), even if the increase in the volume of the quasi-crystalline phase, It is considered that the mechanical properties do not deteriorate.
[0022]
The present invention has been described with reference to the drawings. However, the present invention is not limited to these embodiments, and the present invention can be modified or added without departing from the spirit of the present invention. Needless to say, it is included.
[0023]
Moreover, in the said Example, although the said amorphous single phase alloy book band is produced with the single roll-type liquid quenching apparatus (melt spinning apparatus), this invention is not limited to this, These amorphous | non-crystalline materials Other methods such as a double neck method, spinning in a rotating liquid, high-pressure gas spraying method, spraying method, rapid cooling by sputtering or die casting method may be used as a method for obtaining a porous single phase alloy.
[0024]
【The invention's effect】
The present invention has the following effects.
[0025]
(A) According to the invention of claim 1, by including in the composition the element having a negative mixed enthalpy and the element having a positive mixed enthalpy as described above, the heat treatment and the cooling rate are reduced. The size of crystals to be precipitated can be made finer, and properties such as stickiness (toughness) and strength are not deteriorated, and an alloy having extremely high strength and toughness such as elongation can be obtained.
[0026]
(B) According to invention of Claim 2, a high effect can be acquired in prevention of the said characteristic deterioration and characteristic improvement, such as high intensity | strength and high toughness.
[0027]
(C) According to the invention of claim 3, it is possible to obtain a high effect in preventing the characteristic deterioration and improving the characteristics such as high strength and high toughness.
[0028]
(D) According to the invention of claim 4, it is possible to obtain a high effect in preventing the characteristic deterioration and improving the characteristics such as high strength and high toughness.
[0029]
(E) According to the invention of claim 5, it is possible to obtain a high effect in terms of prevention of the characteristic deterioration and improvement of characteristics such as high strength and high toughness, particularly bending strength.
[0030]
(F) According to the invention of claim 6, when the heat treatment temperature is lower than the glass transition temperature Tg, the fine crystalline or quasicrystalline transition is not improved, and the heat treatment temperature is If the temperature of the first exothermic reaction exceeds the start temperature Tx1, the characteristics of the alloy obtained by coarsening the crystal or quasicrystal formed in the structure deteriorates. of by processed under heat at a temperature region, the possible the amount and size of fine crystals or quasi-crystals contained in the amorphous phase as a suitable one and will, Nebasa (toughness) and strength or the like Thus, an alloy having extremely high strength and toughness such as elongation can be obtained.
[0031]
(G) According to the invention of claim 7, the amount and size of fine crystals or quasicrystals to be formed can be made appropriate.
[0032]
(H) According to the invention of claim 8, characteristics such as the 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 a comparative example alloy.
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 this example alloy and a comparative example alloy.
FIG. 4 is a graph showing mechanical properties of the alloy of this example.
FIG. 5 is a model diagram showing the structure of a quasicrystal.

Claims (8)

Formula; ZraMbAlcAudAge (and only, M; Ni and Cu do we selected Ru elements, a, b, c, d , e in atomic percent, 25 ≦ a ≦ 85,5 ≦ b ≦ 70,0 <c ≦ 30, 0 <d ≦ 10, 0 <e ≦ 20), and has a structure having at least an amorphous phase. The high-strength amorphous alloy according to claim 1, wherein the M element is Ni + Cu . The high-strength amorphous alloy according to claim 1 or 2, which is an alloy represented by a composition of Zr ₆₅ Al _7.5 Cu _7.5 Ni ₁₀ Ag ₅ Au ₅ (subscript is atomic%) .    The high-strength amorphous alloy according to any one of claims 1 to 3, wherein the structure is a mixed phase of an amorphous phase and a fine crystalline phase.    The high-strength amorphous alloy according to any one of claims 1 to 4, wherein the amorphous structure includes at least a quasicrystalline phase. Formula; and Zr aMbAlc Au d Ag e (free, M; Ni and Cu do we selected that elemental, a, b, c, d , e in atomic percent, 25 ≦ a ≦ 85,5 ≦ b ≦ 70, 0 <c ≦ 30, 0 <d ≦ 10, 0 <e ≦ 20), and an amorphous alloy containing at least an amorphous phase is produced. temperature Tg and the starting temperature of the first shot Hydrothermal: high strength method for producing an amorphous alloy, which comprises processed under heat at a temperature range of up to (Tx1 sintering crystallization temperature).   The method for producing a high-strength amorphous alloy according to claim 6, wherein the heat treatment time in the temperature region is 1 to 120 minutes. Method of producing a high strength amorphous alloy as claimed in claim 6 or 7, alloy of an alloy containing the amorphous phase from the quasicrystalline single phase at the pressurized heat treatment.

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