JPH10212561A - Amorphous alloy with excellent workability - Google Patents

Abstract

(57) [Problem] To provide an amorphous alloy having excellent hardness, high strength, high heat resistance and high corrosion resistance with excellent workability without losing its properties. SOLUTION: General formula: XxMyTz, wherein X: one or two elements selected from Zr and Pd, M: at least one element selected from Al, Si, and transition elements (not including the X element) , T: B or B
And an element having a smaller atomic radius than the X and M elements, x,
y and z are atomic percentages, 5 ≦ y ≦ 70, 0 <z <
6. An amorphous alloy having a composition represented by x = 100-yz and having excellent workability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amorphous alloy which can be easily formed and processed and has excellent workability.

[0002]

2. Description of the Related Art Conventionally, a supercooled liquid region (ΔT) which is a temperature range between a glass transition temperature (Tg) and a crystallization temperature (Tx).
As an amorphous alloy material which is wide and has excellent workability, those disclosed in JP-A-3-158446 and JP-A-3-36243 are known.

However, in the processing of forming an amorphous alloy or the like, strict control of the temperature or the processing time is required, and the forming of the alloy disclosed in the above publication can be performed quite easily. There is a need for an amorphous alloy that can be more easily formed. Further, also in the alloy described in the above publication, the composition excellent in workability and other, for example, the composition excellent in mechanical properties are not necessarily the same, and the case where priority is given to workability and the case where other properties are prioritized. Depending on the composition, the composition is considerably different.

[0004]

Accordingly, the present invention provides a supercooled liquid region having a wider temperature range, thereby providing excellent workability, as well as high hardness, high strength, high heat resistance, and high corrosion resistance. And a new amorphous alloy having the same. That is, although there is a difference in the size of the supercooled liquid region in terms of composition, by adding the T element, for example, a supercooled liquid region having a supercooled liquid region of 20K, 30K, 50K or the like can be reduced to a total of 30K, 40K, 60K. Thus, even if the material has good mechanical properties but insufficient workability, it can be used as a material having excellent workability.

[0005]

According to the present invention, there is provided a compound represented by the general formula: Xx
MyTz, where X: one or two elements selected from Zr and Pd, M: at least one element selected from Al, Si, and transition elements (not including the X element);
T: B or B and an element having an atomic radius smaller than the X and M elements, x, y, and z are 5 ≦ y ≦ 70, 0 in atomic percent.
An amorphous alloy having a composition represented by <z <6, x = 100-yz, and having excellent workability.

In the alloy of the present invention represented by the above general formula, y is in the range of 5 to 70% in atomic percent, and Z is 0.
<Z <6%, and x is limited to the range of 100-yz, because if it is out of the range, it becomes difficult to amorphize, and industrial quenching using a liquid quenching method or the like. This is because it is difficult to obtain an alloy having an amorphous phase by the means. Within the above range, the alloy of the present invention exhibits excellent characteristics such as high hardness, high strength, and high corrosion resistance, which are characteristics of the amorphous alloy. X is 50% or more in atomic percent;
When y is less than 50% by atomic percent, the amorphous alloy has an amorphous phase of at least 50% by volume and has a supercooled liquid region having a wider workability and excellent workability. Can be provided. Further, by limiting z to the range of 3 to 5% in atomic percent, the expansion of the supercooled liquid region due to the addition of the T element becomes more remarkable.

The element X is one or two elements selected from Zr and Pd, and is an essential element that is indispensable in the present invention in producing an alloy having an amorphous phase, and is an amorphous forming element. is there.

[0008] M element is Al, Si, transition element (X
Element is not included), and has the effect of improving the amorphous forming ability in coexistence with the element X and stabilizing the amorphous phase. Also, among the M elements, one or two of Al and Si
M ₁ element consisting of seeds, to expand the supercooled liquid region width has the effect of improving the processability, at least one selected from transition elements of the M element (X element not included) M ₂ The element is effective for improving mechanical properties and for making the material amorphous. Accordingly, the use in combination with the M ₁ element and M ₂ element in order to achieve the object of the present invention is more effective. Among the M ₂ elements, especially Ti, Ni, C
o and Cu are effective elements.

The T element is an element having a smaller atomic radius than the X element and the M element, and specifically includes elements such as B, C, and P. The T element has a strong negative interaction with the X element which is an amorphous forming element. By adding a small amount, a stable amorphous phase having a more close-packed structure can be obtained.
The width of the supercooled liquid region (ΔT) until the amorphous undergoes glass transition at the time of temperature rise and is crystallized can be greatly increased. In particular, B is an indispensable element for increasing the supercooled liquid region which is the object of the present invention.

In the present invention, the supercooled liquid region (ΔT) is a region having a temperature range between a glass transition temperature (Tg) and a crystallization temperature (Tx) of an alloy having an amorphous phase. The amorphous phase is stable,
Various processes can be easily performed. In addition, since this region is wide (the temperature width is large), in the above-mentioned processing, control of temperature, processing time, and the like can be relatively easily performed, and molding of an alloy having an amorphous phase can be easily performed.
Also, in this supercooled liquid region, the alloy having an amorphous phase is in a supercooled liquid state, can be deformed greatly with low stress, and exhibits extremely excellent workability, which can cause a member having a complicated shape or a large plastic flow. It is useful for those requiring necessary processing.

The way of setting the glass transition temperature (Tg) and the crystallization temperature (Tx) in the present invention will be described. FIG. 1 shows Zr ₆₅ Cu _27.5 Al _7.5-x Bx, and FIG.
A differential scanning calorimetry curve for ₇₆ Si _18-x Cu ₆ Bx is shown. In the portion where an endothermic reaction occurs on this curve, the temperature at the point where the rising portion of the curve intersects with the extrapolation of the baseline is defined as Tg, Conversely, the temperature obtained in the same manner as described above at the portion where heat is generated is set as Tx.

The alloy of the present invention shows a supercooled liquid state (supercooled liquid region) in a very wide temperature range, and its temperature range is 5
0K or more. In this supercooled liquid temperature range, plastic deformation is easily and unlimitedly under low pressure, and temperature control during processing and control of processing time can be relaxed. The ribbon and powder can be easily solidified and formed by the method. For the same reason, by mixing with another alloy powder, solidification molding of the composite material at low temperature and low pressure is also facilitated. In addition, the amorphous ribbon of the alloy of the present invention prepared by the liquid quenching method does not crack or peel off from the substrate even by 180 ° close contact bending in a wide composition range. At room temperature,
It shows an elongation exceeding 1.6% and shows excellent spreadability. or,
The alloy of the present invention easily becomes amorphous and can be obtained by water quenching.

The alloy of the present invention can be obtained by rapidly solidifying a molten alloy having the above composition by a liquid quenching method. The liquid quenching method refers to a method of rapidly cooling a molten alloy. For example, a single roll method, a twin roll method, etc. are particularly effective, and in these methods, 10 ⁴ to 10 ⁶ K / s.
A cooling rate of about ec is obtained. In order to produce a ribbon by the single roll method, the twin roll method, or the like, a molten metal is jetted through a nozzle hole onto, for example, a copper or copper roll having a diameter of 30 to 3000 mm rotating at a constant speed in a range of about 300 to 10000 rpm. I do. This makes the width about 1-3
Various ribbon materials having a thickness of about 00 mm and a thickness of about 5 to 500 μm can be easily obtained. Further, in order to produce a thin wire material by the spinning method in a rotating liquid, a depth of about 10 to 100 mm retained by a centrifugal force in a drum rotating at about 50 to 500 rpm at a back pressure of argon gas through a nozzle hole. The thin wire material can be easily obtained by blowing the molten metal into the solution refrigerant layer. In this case, it is preferable that the angle between the molten metal jetted from the nozzle and the refrigerant surface is about 60 to 90 degrees, and the relative speed ratio between the jetted molten metal and the solution refrigerant surface is about 0.7 to 0.9.

It is to be noted that a thin film can be obtained by a sputtering method and a quenched powder by various atomizing methods such as a high-pressure gas spraying method or a spraying method without using the above method.

[0015]

Next, the present invention will be described in detail with reference to examples.

Example 1 Zr ₆₅ Cu _27.5 Al _{7.5-x produced} by an arc melting furnace
Using a Bx (x = 0, 2, 4, 6) (at%) alloy,
A ribbon material having a thickness of about 20 μm and a width of about 1 mm was produced by a single roll method. The quenched phase was identified using X-ray diffraction, and the thermal stability was evaluated using a differential scanning calorimeter (DSC).

As a result of X-ray diffraction, the alloy of the present invention was an amorphous single-phase alloy. FIG. 1 shows the differential scanning calorimetry curve, together with the crystallization temperature (Tx), the glass transition temperature (Tg), and the supercooled liquid region (ΔT). Further, based on FIG. 1, these Tx, Tg, ΔT (Tx−Tg)
2 is shown in FIG.

From FIG. 2, it can be seen from the graph showing the change in Tx that Tx is increased by the addition of B. Also △ T
Was 72K at 0% B, increased with the increase in B content, showed a maximum value of 100K at 4% B, and then decreased with an increase in B content. It can be seen that ΔT is significantly improved when the amount of B is 3 to 5%.

Therefore, Zr ₆₅ Cu _27.5 Al _7.5 alloy has B
By adding a small amount of, it is possible to greatly increase the width of ΔT, and to significantly improve the workability of the material. In particular, a remarkable effect can be expected at B3 to 5%.

Example 2 Pd ₇₆ Si _18-x Cu ₆ Bx produced by an arc melting furnace
(X = 0,1,2,3,4,5,6) (at%) alloy, about 20 μm in thickness and 1 to 4 in width by single roll method
mm amorphous ribbon material was produced. Evaluation of thermal stability was examined using a differential scanning calorimeter (DSC).

The resulting differential scanning calorimetry curve is shown in FIG. 3, together with the crystallization temperature (Tx), glass transition temperature (Tg) and supercooled liquid region (ΔT). Further, based on FIG. 3, these Tx, Tg, ΔT (T
x-Tg) is shown in FIG.

From FIG. 4, it can be seen from the graph showing the change in Tx that Tx is increased by the addition of B. Also, △
T was 42K at B = 0%, but increased with an increase in the amount of B, showed a maximum value of 70K at B = 3, and then decreased with an increase in the amount of B. It can be seen that ΔT is significantly improved when the amount of B is 2 to 4%.

Therefore, by adding a small amount of B to the Pd ₇₆ Si ₁₈ Cu ₆ alloy, the width of ΔT can be greatly increased, and the workability of the material can be significantly improved. In particular, a remarkable effect can be expected when the B content is 2 to 4%.

In the above embodiment, M, Al, Si, C
u is shown using B as a representative T element, but other combinations of the relevant element with the X element and X element being Z
The same effect is obtained in the case of r and Pd.

Example 3 A previously melted Pd ₆₀ P ₄₀ alloy, Pd, Ni, Cu, and B were melted in a high-frequency furnace in an Ar atmosphere to obtain Pd ₄₀ Ni ₁₀ Cu _30.
A five-element mother alloy composed of P _20-x Bx (at%) was produced. A ribbon material was produced from this mother alloy by a single roll method in an Ar atmosphere. The quenched phase was identified using X-ray diffraction, and the thermal stability was evaluated using a differential scanning calorimeter (DSC).

As a result of X-ray diffraction, the alloy of the present invention was an amorphous alloy in the entire range of the B substitution amount of 0 to 20 at%. Also,
As a result of differential scanning calorimetry, the temperature range of the supercooled liquid region (△
T) was 95 K at B = 0 at%, expanded with the addition of B, showed a maximum value of 100 K at B = 2 at%, and thereafter decreased monotonously. The B content was effective at 3-5%.

[0027] Thus, B in Pd ₄₀ Ni ₁₀ Cu ₃₀ P ₂₀ Alloy
By adding a small amount of, it is possible to greatly increase the width of ΔT, and to significantly improve the workability of the material. In particular, a remarkable effect can be expected at a B content of 1 to 3%.

[0028]

Since the alloy of the present invention is an alloy having an amorphous phase, it has excellent characteristics of the amorphous alloy such as high hardness, high strength, high heat resistance and high corrosion resistance. Since the alloy of the present invention has a wide temperature range in the supercooled liquid region, temperature control during processing, control of processing time and the like can be easily performed, processing in multiple stages can be relatively easily performed, and after the above-described processing. Amorphous phase can be maintained, its excellent properties can be maintained, an amorphous alloy can be obtained even at a relatively low cooling rate, and a relatively thick or large solidified material can be obtained in the production of an amorphous alloy.
And so on. Conventionally, alloys that are excellent in other properties such as mechanical properties but have poor workability and are difficult to commercialize can be improved by the present invention, and the range of practical use can be expanded. it can.

[Brief description of the drawings]

1 shows a differential scanning calorimetry curve of the alloy of Example 1. FIG.

FIG. 2 shows the addition amount of element X and ΔT, T in the alloy of Example 1.
9 is a graph showing a relationship between g and Tx.

FIG. 3 shows a differential scanning calorimetry curve of the alloy of Example 2.

FIG. 4 shows the addition amount of element X and ΔT, T in the alloy of Example 2.
9 is a graph showing a relationship between g and Tx.

 ──────────────────────────────────────────────────続 き Continuing from the front page (71) Applicant 000006828 YK-Kei Co., Ltd. 1-cho, Kanda Izumi-cho, Chiyoda-ku, Tokyo (72) Inventor Akihisa Inoue 35-35 Kawachimoto Hasekura, Aoba-ku, Sendai City, Miyagi Prefecture 11-806 (72 Inventor Hisaichi Kimura 44, Fujihirabashi Arahama, Watari-cho, Watari-gun, Miyagi Prefecture (72) Inventor Osamu Haruyama 2641 Yamazaki, Noda-shi, Chiba-ken (72) Inventor Takahiro Aoki 1739 Motoyoshida-cho, Mito-shi, Ibaraki Pref. (72) Inventor Tadahiro Negishi 1-49-402 Haramachi, Miyano-ku, Sendai-shi, Miyagi (72) Inventor Nobuyuki Nishiyama 1-9-9, Yaesu, Chuo-ku, Tokyo Imperial Piston Ring Co., Ltd.

Claims (9)

[Claims] 1. General formula: XxMyTz, wherein X: one or two elements selected from Zr and Pd, M: at least one element selected from Al, Si, and transition elements (excluding the X element) Element: T: B or B and an element having an atomic radius smaller than that of the above X and M elements, x, y, and z are represented by atomic percentages: 5 ≦ y ≦ 70, 0 <z <6, x = 100−yz. Amorphous alloy with excellent composition and workability. 2. An M ₁ element composed of one or two elements whose M elements are selected from Al and Si, and a M ₂ element composed of at least one element selected from transition elements (not including the X element). The amorphous alloy having excellent workability according to claim 1, comprising an element. 3. The amorphous alloy excellent in workability according to claim 1, wherein the M element is an M ₂ element comprising at least one element selected from transition elements (not including the X element). 4. The amorphous alloy having excellent workability according to claim 2, wherein the M ₂ element is at least one element selected from Ti, Ni, Co, and Cu. 5. The amorphous alloy excellent in workability according to claim 1, wherein the T element is B or B and at least one element selected from C and P. 6. The workable amorphous alloy according to claim 1, wherein x is 50% or more in atomic percent and y is less than 50% in atomic percent. 7. The amorphous alloy excellent in workability according to claim 1, wherein z is 1 ≦ z ≦ 5 in atomic percent. 8. The workable amorphous alloy according to claim 1, wherein the amorphous alloy has at least 50% by volume of an amorphous phase. 9. The amorphous alloy having excellent workability according to claim 1, wherein a supercooled liquid region which is a temperature range between a glass transition temperature and a crystallization temperature is widened by adding a T element.