JPH0625807A - Ni-base amorphous metal filament - Google Patents

Abstract

PURPOSE:To obtain an Ni-base amorphous metal filament having high strength and superior toughness and excellent in thermal embrittlement and corrosion resistance by providing an alloy having a specific composition consisting of Ni, Pd, Si, B, and Al and also forming a cross section into circular shape. CONSTITUTION:This filament is a paramagnetic Ni-base amorphous metal filament which consists of an alloy having a composition represented by a composition formula Ni100-a-b-c-dPdaSibBcAld [where the symbols (a), (b), (c), and (d) stand for, by atom, 1-5%, 5-15%, 5-15%, and 0.2-3%, respectively] and further containing, if necessary, 0.5-10% M (where M means one or more elements among Nb, Ta, W, Co, Fe, Cr, and Mo) and whose cross section has a circular shape. Further, this filament has about >=60% roundness, <= about 6% wire diameter variance, and a strength as high as about 300kgf/mm<2>. This filament can be obtained by, using a spinning method in rotating liquid, a conveyer method, etc., and spraying a molten alloy with the prescribed composition via a nozzle into a coolant, such as water, to rapidly solidify this molten alloy.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Ni-based amorphous metal filament having a high strength and a circular cross section.

[0002]

2. Description of the Related Art By quenching a molten alloy,
It is well known that amorphous metal materials having various shapes such as a ribbon shape, a filament shape, and a granular shape can be obtained. Amorphous metal ribbons can be easily manufactured by methods such as the one-roll method and the twin-roll method.
Numerous amorphous metal ribbons have been obtained for alloys of the Ni, Ni, Co, Pd, Ti, Cu or Zr alloys. Among them, the Ni-Si-B system amorphous metal ribbon is excellent in corrosion resistance and heat embrittlement and has a low Curie point, so it is paramagnetic at room temperature. It has unique properties such as the ability to obtain materials with a low temperature coefficient of resistance.

On the other hand, the production of amorphous metal filaments is
It is more difficult than thin ribbons, and particularly high technology is required to manufacture amorphous metal filaments having a circular cross section. Fe system having a wire diameter, Co
Amorphous metal filaments made of Ni-based and Ni-based alloys have been obtained (JP-A-56-165016, JP-A-57-79052 and JP-A-62-5792).
(See Japanese Patent Publication No. 3).

[0004]

The Ni-Si-B system amorphous metal filament is required to avoid the influence of a magnetic field by utilizing the unique characteristics of the Ni-Si-B system amorphous metal material described above. It has been proposed to apply it to a strength material of a certain portion (for example, a dot wire of a dot printer, a covering strength material for electric wires). However, JP-A-62-1
Ni-Si-B based amorphous metal filaments disclosed in Japanese Patent No. 57923 were manufactured and their characteristics were examined. The strength of the rapidly solidified material was about 280 kgf / mm ² at the maximum, and it was suitable for the above applications. It did not reach the required strength. Further, the heat resistance is also poor, and if it is kept at 350 ° C. for 10 minutes, it becomes brittle to the point that it cannot be practically used, and it cannot be applied to the above-mentioned applications including the heat treatment step. Therefore, there is a need for a paramagnetic amorphous metal filament having higher strength and excellent heat embrittlement as compared with the filament disclosed in JP-A-62-57923.

[0005]

Therefore, the present inventors have
In view of these circumstances, as a result of earnest research aimed at providing a paramagnetic amorphous metal filament having high strength and excellent heat embrittlement, a specific amount of Pd was added to a Ni-Si-B alloy. The present invention has been completed by finding the fact that the above object is achieved by melting the added alloy and cooling and solidifying the melt.

That is, the first invention is the composition formula Ni
_100-abcd Pd _a Si _b B _c Al _d (1 atomic% ≤ a <5 atomic%, 5 atomic% ≤ b ≤ 15 atomic%, 5 atomic% ≤ c ≤ 15 atomic%, 0.2 atomic% ≤ d ≦ 3 atom%), and a Ni-based amorphous metal filament characterized by having a circular cross section. The second invention is the composition formula Ni
_{100-abcde M a Pd b Si} c B d Al e ( where
M is one or more elements selected from the group of Nb, Ta, W, Co, Fe, Cr, Mo, and 0.5 atomic%
≦ a ≦ 10 atom%, 1 atom% ≦ b <5 atom%, 5 atom%
≦ c ≦ 15 atomic%, 5 atomic% ≦ d ≦ 15 atomic%, 0.2 atomic% ≦ e ≦ 3 atomic%. The present invention is directed to a Ni-based amorphous metal filament, which is characterized in that it is made of an alloy represented by (4) and has a circular cross section.

The present invention will be described in detail below. The amorphous metal filament of the present invention has a content of 60% or more, preferably 8% or more.
Having a roundness of 0% or more, particularly preferably 90% or more,
In particular, it is a metal filament that has a uniform shape of 6% or less of wire diameter irregularity and is substantially composed of an amorphous phase, and can contain a crystalline phase to the extent that toughness is not impaired.

Further, since the amorphous metal filament of the present invention is of high quality as described above, cold working can be continuously carried out, and in order to further improve dimensional accuracy or mechanical properties, Wire drawing processing etc. can be given. Furthermore, a heat treatment such as annealing can be performed if necessary.

The metal filament of the present invention is a material having high strength, excellent thermal stability, and high toughness, and its alloy composition must be limited as follows in order to satisfy the above characteristics. Is.

That is, the Si content is 5 to 15 atomic%.
It is necessary to be, and preferably 7.5 to 12.5 atomic%. Si content is less than 5 atomic% or 15
If it exceeds atomic%, the obtained filament becomes brittle and cannot be put to practical use. Similarly, the content of B is 5
~ 15 atom% is required, preferably 7.5-1
It is 2.5 atomic%. When the content of B is less than 5 atom% or exceeds 15 atom%, the obtained filament becomes brittle and cannot be put to practical use. Al is an essential element for obtaining an amorphous metal filament, and it is necessary that its content is 0.2 to 3 atomic%. However,
When the Al content is less than 0.2 atomic%, spherical powder or a fine metal wire with an elliptical cross section is formed, and a high quality filament having a circular cross section according to the present invention cannot be obtained. Also, A
When l exceeds 3 atomic%, the amorphous forming ability decreases,
The obtained filament crystallizes and becomes brittle, making it unusable for practical use. Pd is an essential element for obtaining the high strength and toughness of the metal filament of the present invention, and its range is required to be 1 to 5 atom%, preferably 2 to
It is 4.5 atom%. When the content of Pd is less than 1 atom%, the strength sharply decreases, and when it exceeds 5 atom%,
Since it becomes brittle, it cannot be put to practical use.

The metal filament of the present invention comprises Nb, T
When one or more elements selected from the group consisting of a, W, Co, Fe, Cr and Mo are added in an amount of 0.5 atom% or more and 10 atom% or less, the toughness is improved without significantly lowering the toughness. Can be made. However, if the amount added is less than 0.5 at%, no improvement in strength is observed and 10 at%
If it exceeds, the amorphous forming ability is extremely lowered and a tough metal filament cannot be obtained.

The amorphous metal filament of the present invention can be obtained by melting an alloy having the above composition and cooling and solidifying it in a cooling liquid. There are various methods for solidifying, and a preferable method is, for example,
JP-A-56-165016 or JP-A-57-7
The so-called rotating submerged spinning method described in Japanese Patent No. 9052 is mentioned. This method puts the cooling body in the rotating drum,
A cooling body film is formed on the inner wall of the drum by centrifugal force, and the alloy having the above composition melted in the cooling body film is spouted from the spinning nozzle to cool and solidify. In order to obtain a continuous thin wire with less heat, the peripheral speed of the rotating drum should be 5 to more than the speed of the molten metal flow ejected from the spinning nozzle
It is preferable to make it 30% faster, and to set the angle between the molten metal flow ejected from the spinning nozzle and the cooling body film formed on the inner wall of the drum to 20 to 70 °. The hole diameter of the spinning nozzle is 50 to 200 μm, especially 80 to 180 μmφ
Is preferred. If the pore size is less than 50 μm, it is difficult for the molten metal to be ejected from the nozzle, and it is difficult to obtain a quenched wire rod. On the other hand, when it exceeds 200 μm, the roundness tends to be low, the wire diameter unevenness becomes large, and it tends to be difficult to obtain a high-quality filament.

The so-called conveyor method described in JP-A-58-173059 can also be used.
In this conveyor method, molten metal is spouted from a spinning nozzle and brought into contact with a cooling liquid layer formed on a running grooved conveyor belt for rapid cooling and solidification. In order to obtain a continuous metal filament according to the present invention with few spots, the velocity of the traveling cooling liquid on the conveyor is 300 m / min or more, and the velocity ratio between the molten metal jet and the traveling cooling liquid exceeds 1 to 1.3. It is desirable to accelerate the running cooling liquid at the following ratio, to make its contact angle larger than 30 °, and to make the spinning nozzle hole diameter 0.2 mmφ or less.

As the cooling liquid used for producing the above-mentioned metal filament, in addition to inexpensive water, in order to further increase the cooling rate, a 10 to 25 wt% sodium chloride aqueous solution and 5 to 15 wt% caustic soda are used. It is preferable to use an aqueous solution, an aqueous solution of 5 to 25% by weight of magnesium chloride, lithium chloride and an aqueous solution of 50% by weight of zinc chloride.

The amorphous metal filament of the present invention has a number of excellent properties in industrial view as follows. For example, an amorphous metal filament composed of Ni ₇₇ Pd _2.5 Si ₁₀ B ₁₀ Al _0.5 has a tensile strength of 310 kgf / mm ² in a rapidly solidified material, and heat treatment at 350 ° C for 100 minutes and 400 ° C for 10 minutes. Even afterwards, the strength does not change, contact bending is possible, and it has excellent heat embrittlement properties. Moreover, since the Curie temperature of the amorphous metal filament of the present invention is room temperature or lower, it is not affected by the magnetic field and is not magnetized. Therefore, it has a circular cross section, high strength, and high thermal stability.
It can be used as a dot wire for dot printers, electric wire coating reinforcement, etc. Furthermore, the amorphous metal filament of the present invention has excellent corrosion resistance, and therefore, it can be used as a filament material or the like because it can be a strong material or woven / knitted material in a corrosive environment.

[0016]

EXAMPLES Next, the present invention will be specifically described by way of examples.

Examples 1 to 14 and Comparative Examples 1 to 11 After alloys having various compositions shown in Tables 1 and 2 were melted in a quartz tube under an argon atmosphere, the pore size was 100 to 140.
Approximately 280-350rp using quartz spinning nozzle of μmφ
Argon gas was ejected at a pressure of 4.4 kg / cm ² into a film of cooling water having a temperature of 4 ° C and a depth of 2.5 cm formed in a cylindrical drum having an inner diameter of 500 mm and rotating at m, and was rapidly cooled and solidified. . At this time, the distance between the spinning nozzle and the rotary cooling liquid surface was 1 mm or less, and the angle between the molten metal flow ejected from the spinning nozzle and the rotary cooling liquid surface was 45 °.

The average wire diameter, structure, strength, adhesion bendability and shape of these produced filaments were measured, and the results are shown in Tables 1 and 2.

The strength was measured by using an Instron type tensile tester with a sample length of 12 cm and a strain rate of 4.17 × 10 ^-3.
/ S was measured. The determination of the amorphous phase was made by obtaining a halo pattern peculiar to the amorphous by X-ray diffraction measurement. For roundness, select 10 points in the length direction of the thin line,
The cross section of each point is the ratio of the major axis (R) to the minor axis (r), r /
The average diameter of R × 100 (%) was calculated. The wire diameter unevenness was obtained by running a thin wire for 200 m with a laser wire diameter measuring machine and measuring the continuous average wire diameter. This is the variation rate of.

[0020]

[Table 1]

[0021]

[Table 2]

As is clear from Tables 1 and 2, Comparative Example 1 is a conventional Ni-based amorphous metal filament having a strength of about 260 kgf / mm ² and having the strengths of Examples 1 to 14 of the present invention. Weak in comparison. On the other hand, the amorphous metal filaments of Examples 1 to 14 according to the present invention are 300 kgf / mm ²
It is an amorphous metal filament with high toughness and high toughness that allows close bending. However, Si
In Comparative Examples 2 to 5 in which the content or B content deviates from the composition range of the present invention, the amorphous filaments having excellent strength cannot be obtained because they are crystallized and become brittle. Also, A
Comparative Example 6 in which the 1 content is less than the composition range of the present invention
Becomes spherical powder, and the high quality filament of the present invention cannot be obtained. On the other hand, in Comparative Example 7 containing Al in the composition range of the present invention or more, it is crystallized and becomes brittle, and an amorphous filament excellent in strength cannot be obtained. Comparative Examples 8 and 9 in which the Pd content deviated from the composition range in the present invention are filaments having a good circular cross section, but inferior in toughness because they cannot be bent by 180 °. Further, Comparative Example 10 in which the additive element Co is less than the range of the present invention does not have high strength as compared with Example 1, and the effect of the additive element cannot be obtained. Comparative Example 11 containing Co in an amount not less than the range of the present invention is a filament that is good but is brittle and inferior in toughness.

[0023]

The Ni-based amorphous metal filament containing a small amount of Pd of the present invention has a high strength of 300 kgf / mm ² or more, is rich in toughness, and is excellent in heat embrittlement and corrosion resistance. Moreover, since the cross section is circular and there are few irregularities in the wire diameter, it is easy to perform drawing, woven, and other processing. Therefore, it can be widely used as a material such as a dot wire for a dot printer, a filter requiring high strength, or a covering reinforcing material for electric wires, which has been difficult to apply with a conventional Ni-based amorphous metal filament.

Claims (2)

[Claims] 1. A composition formula Ni _100-abcd Pd _a Si _b B
_c Al _d (However, 1 atomic% ≤ a <5 atomic%, 5 atomic%
≦ b ≦ 15 atomic%, 5 atomic% ≦ c ≦ 15 atomic%, 0.2 atomic% ≦ d ≦ 3 atomic%. ) A Ni-based amorphous metal filament, which is characterized by comprising an alloy represented by (4) and having a circular cross section. 2. A composition formula _{Ni 100-abcde M a Pd b} S
i _c B _d Al _e (where M is Nb, Ta, W, Co,
One or more elements selected from the group of Fe, Cr, Mo, 0.5 atomic% ≤ a ≤ 10 atomic%, 1 atomic%
≤b <5 atom%, 5 atom% ≤c≤15 atom%, 5 atom%
≦ d ≦ 15 atomic%, 0.2 atomic% ≦ e ≦ 3 atomic%. ) A Ni-based amorphous metal filament, which is characterized by comprising an alloy represented by (4) and having a circular cross section.