JPH0929399A - Manufacture of amorphous metallic thin wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new manufacturing method for a thin wire made of amorphous metal having excellent roundness and capable of manufacturing the amorphous metal thin wire of excellent quality with less irregularity in the wire diameter in manufacturing the wire of large with diameter at high cooling speed. SOLUTION: A rotary roll 1 having a tip of V-shaped projection whose thermal conductivity is >=0.40 (cal/cm.s.deg) in the temperature range of 0-100 deg.C is brought into contact with the surface of the molten alloy 2 heated in the temperature range of 1.02-1.4Tm relative to the melting point Tm(K), and the supercooled liquid of the molten alloy 2 is jetted to be cooled.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an amorphous metal thin wire. More specifically, the present invention has a particularly circular cross section and has a small wire diameter unevenness,
The present invention relates to a method for producing a high-quality amorphous metal thin wire.

[0002]

2. Description of the Related Art Conventionally, a method utilizing a rapid solidification method has been known as a method for producing metal fibers. As this method, for example, spinning in a spinning liquid disclosed in JP-A-56-165015 is disclosed. Method and the melt extraction method disclosed in JP-A-48-4340.

In the rotating submerged spinning method, a molten metal is ejected from a nozzle hole into a refrigerant held by a centrifugal force on the inner wall of a rotating drum by a gas pressure, and the molten metal is cooled and solidified to form an amorphous metal. This is a method for producing fine wires and crystalline metal fine wires. On the other hand, the melt extraction method is a method in which a V-shaped projection type roll (rotating roll having surface projections) is brought into contact with the surface of the molten metal stored in the crucible, and the molten metal is solidified into a fine wire. is there.

In recent years, the melt-extraction method has been improved, and a V-shaped protrusion roll made of Mo having a tip of 60 degrees is brought into contact with the surface of the molten metal having a diameter of 5 to 10 mm to melt the molten metal. An improved method for producing amorphous metal wires by quenching has been announced (Material Science
and Engineering, A133 (1991), p158-161).

[0005]

However, in order to produce an amorphous metal thin wire by the conventional rotary submerged spinning method, it is necessary to stably jet a molten metal jet into the rotary cooling liquid layer. However, when a nozzle having a hole diameter of 100 μm or less is used, it is very difficult to stabilize the molten metal jet ejected into the cooling liquid layer, and therefore, the amorphous metal thin wire having a wire diameter of 100 μm or less is used. There were problems such as difficulty in manufacturing.

On the other hand, with respect to the melt extraction method, even in the improved method, since the material of the rotating roll is Mo having a low thermal conductivity, the cooling rate is slow and the wire diameter is 60 μm.
There is a problem that even if the Fe-Co-Si-B-based amorphous metal fine wire having a thickness of m or more is produced, the amorphous metal fine wire having excellent bending toughness cannot be produced. In the case of the improved melt extraction method, the wire diameter is 50 μm.
In the production of the above thick amorphous metal fibers, the roundness of the cross section of the produced amorphous metal fine wire is low, and the variation in the diameter of the produced amorphous metal fine wire in the longitudinal direction (uneven diameter irregularity) is also caused. There was a problem such as getting bigger.

Therefore, the present invention has been made in view of the above circumstances, and has a high cooling rate and a wire diameter of 50.
A new amorphous metal thin wire capable of producing a high-quality amorphous metal thin wire having excellent roundness even when producing a thin wire having a diameter of μm or more and having a small diameter unevenness. It is intended to provide a way.

[0008]

The present invention is intended to solve the above problems, and the gist of the present invention is 0
Thermal conductivity of 0.40 (cal /
cm-s-deg) or more tip V-shaped rotating roll is brought into contact with the surface of the combined financial liquid heated to a temperature range of 1.02 to 1.4 Tm with respect to the melting point Tm (K), and the combined financial liquid The method for producing an amorphous metal thin wire is characterized in that the supercooled liquid of (1) is jetted to cool.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the material of the rotating roll used in the apparatus for producing amorphous metal fine wire has a thermal conductivity of 0.4 in the temperature range of 0 to 100 ° C. as described above.
It needs to be 0 (cal / cm · s · deg) or more. The thermal conductivity of the rotary roll is 0.40 (cal /
If the wire diameter is smaller than cm ・ s ・ deg), the wire diameter will be 5
When manufacturing a thin wire having a diameter of 0 μm or more, the supercooled liquid of the combined financial liquid cannot be ejected, and only an amorphous metal thin wire having inferior bending toughness can be obtained, or Only amorphous thin wires with low wire diameter unevenness can be obtained. Specifically, Cu, Cu alloy, Al, Al alloy, W or the like can be used as the material of the rotating roll of the present invention.

FIG. 1 of the accompanying drawings shows a tip V-projection type rotating roll (1) of the present invention made of these materials. For example, as shown in FIG. 1, the rotating roll (1) has a V-shaped protrusion at the tip, and the V-shaped protrusion has a tip angle of 3 mm.
It is in the range of 0 to 120 ° and the radius of curvature of the tip is 30.
It is preferable to use one having a shape of 0 μm or less. Also,
Even if the tip cross-section is not triangular V-shaped, the radius of curvature that can contact the molten alloy in a small area is 300μ.
Rolls having protrusions of m or less can also be used.

As described above, it is necessary to control the temperature of the financial liquid to be brought into contact with the rotating roll within a temperature range of 1.02 to 1.4 Tm with respect to the melting point Tm (K) of the alloy. Yes, it is more preferable to control in the range of 1.03 to 1.2 Tm. When the temperature of the synthetic liquid is less than 1.02 Tm, amorphization occurs during the contact between the roll and the melt, and it cannot be jetted into the atmosphere as a supercooled liquid. The roundness of the cross section becomes low and the unevenness of the wire diameter becomes large. On the other hand, when the temperature of the molten liquid contacted with the rotating roll is higher than 1.4 Tm, only amorphous fine wires including a crystallized part cannot be produced during the contact between the roll and the melt and a completely supercooled liquid cannot be produced. Disappear.

The temperature of the synergistic liquid according to the present invention is
The temperature of the surface of the melt can be measured by a measuring instrument using an optical measuring means such as an optical pyrometer or a two-color thermometer, but the temperature near the surface of the melt is directly detected by a thermocouple. The temperature can be measured by the method. FIG. 2 is a schematic view of an apparatus for producing the amorphous metal thin wire of the present invention.

Rotating roll (1) as described above according to the present invention
Is brought into contact with the surface of the synthetic liquid (2) while rotating. The synergistic liquid (2) is heated to the temperature required by the present invention, for example, by a high frequency induction heating device (3). The financial liquid (2) is supplied to the contact portion with the rotating roll (1) by the elevating means (4). Combined financial liquid (2)
Is sprayed and cooled by the contact of the rotating roll (1) to become a thin metal wire (5).

With respect to such a method and apparatus, in the present invention, as described above, it is essential to control the thermal conductivity of the rotating roll (1) and the heating temperature of the financial liquid within a specific range. As a temperature control method for carrying out the present invention, various methods such as a method using resistance heating and a method using high frequency induction heating can be used, but an appropriate shape as shown in FIG. 2 is used. The method of operating the input power in the induction heating using the high frequency coil is preferable because the temperature controllability is good.

Further, in the method for producing an amorphous metal fine wire of the present invention, the melt is applied to a roll rotating at a peripheral speed of 10 m / s to 80 m / s and the melt is applied to 8 to 350 mm ³ / sec.
It is desirable to contact them at a feeding rate of. If the melt supply rate to the roll surface is less than 8 mm ³ / s or if the supply rate exceeds 350 mm ³ / s, it becomes difficult to jet the supercooled liquid into the atmosphere, and the obtained amorphous There is a tendency that the roundness of the fine wire becomes low and the unevenness of the wire diameter tends to be large, or an amorphous fine wire containing microcrystals and having poor bending toughness can be obtained.

Further, in the manufacturing method of the present invention,
It is necessary that the supercooled liquid of the synergistic liquid is cooled in an atmosphere, and the atmosphere for that purpose is to be cooled in an inert gas atmosphere containing 50% or more of a rare gas component such as Ar or He. preferable. In the manufacturing method of the present invention, a very high cooling rate is realized by the alloy leaving the rotating roll in the state of supercooled liquid and being jetted into the atmosphere to be cooled. According to the manufacturing method of the present invention, Fe-Si-B having a wire diameter of 60 μm or more and which can be bent in close contact
A system amorphous metal thin wire or a Co-Fe-Si-B system amorphous metal thin wire is obtained.

Further, in the present invention, an amorphous alloy having an arbitrary composition is extracted in an atmosphere of a supercooled liquid and cooled to produce an amorphous metal fine wire having a wire diameter of 50 μm or more. In particular, it is possible to obtain a high quality amorphous metal thin wire having a circularity of 75% or more and a wire diameter unevenness of 20% or less in the cross section of the thin wire. The wire diameter of the thin wire according to the present invention is an average value of the minimum diameter and the maximum diameter in an arbitrary cross section, and the circularity (%) is (minimum diameter / maximum diameter) × 100 in the cross section of the thin wire. Value of. The wire diameter unevenness (fluctuation in wire diameter in the longitudinal direction) means the value of the following expression (1) obtained when the wire diameter of any 10 cross sections in the longitudinal direction of the thin wire is measured.

[0018]

[Equation 1]

The amorphous metal fine wire manufactured according to the present invention has a cross-section that is almost circular, but as shown in FIGS. 3 (a) and 3 (b), a part of the cross-section is shown. It may also include where the curvature has changed. In addition, according to the method for producing an amorphous metal thin wire of the present invention,
An alloy having an arbitrary alloy composition that forms an amorphous single phase at a cooling rate of 0 ⁴ K / s or more is produced. That is, the composition range of the alloy is not particularly limited. For example, a Fe group-based amorphous alloy that has been known in the past and exhibits excellent magnetic properties,
It is possible to manufacture high-quality amorphous metal fine wires such as an Al-based amorphous alloy exhibiting a high specific strength and a Ti-based amorphous alloy exhibiting excellent corrosion resistance.

Specifically, an example of the alloy composition to which the method for producing an amorphous metal fine wire of the present invention is exemplified, in the Fe group, {Fe, Co and N
contains at least 50 atomic% of at least one element selected from i} and contains at least 10 atomic% of at least one element selected from {Si, B, C, P, Zr, Ga} In the amorphous alloys and Al-based amorphous alloys,
Contains 0 atom% or more and {Y, La, Ce, Nd, S
m, Ga, Mm (Misch metal), Nb, Si}, an amorphous alloy containing a total of 1 atomic% or more of one or more elements selected from {Ti, Z
contains at least 40 atomic% of at least one element selected from r}, and contains at least 20 atomic% of at least one element selected from {Cu, Ni, Fe, Co, Si, B} Amorphous metals and the like can be mentioned.

[0021]

EXAMPLES Hereinafter, a method of manufacturing an amorphous metal thin wire will be described in more detail with reference to examples. Example 1 Amorphous alloy thin wires were manufactured as the structure of the method and apparatus illustrated in FIG. That is, it has the cross-sectional shape shown in FIG.
A rotating roll (1) made of copper having a V-shaped tip (tip angle of 60 degrees) and a diameter of 20 cm and a thermal conductivity of 0.96 (cal / cm · s · deg) was used, and the rotation speed was 2000 pm (peripheral speed 20. 9
While rotating at m / s), the surface of the synthetic financial liquid (2) was brought into contact with it, and the supercooled liquid of the synthetic financial liquid was ejected into the atmosphere to be rapidly cooled to prepare a thin metal wire (5). Here financial liquid (2)
Is composed of Fe ₇₅ Si ₁₀ B ₁₅ (melting point 1420K), and melt surface temperature 1523K by the high frequency induction heating device (3).
Is melted by 100 mm on the surface of the rotating roll (1)
It is supplied by the lifting means (4) at a speed of ³ / s.
The rotating roll (1), the molten alloy (2), the high frequency induction heating device (3), the elevating means (4), and the thin metal wire (5) are in a vacuum chamber (not shown),
The atmosphere in this chamber is filled with 500 mmHg of Ar gas.

When the structure of the prepared Fe ₇₅ Si ₁₀ B ₁₅ thin wire (5) was examined by X-ray diffraction using Cu-Kα radiation, it was found to be a thin wire composed of an amorphous single phase. Further, regarding the cross-sectional morphology in the longitudinal direction of the thin wire, when the thin wire was embedded in a resin and observed by an optical microscope, the minimum circularity in 10 cross sections was 92%, and the average line system was 68 μm.
The wire diameter unevenness calculated by the above equation (1) is 14%.
Met. When the bending toughness at 10 places was examined by a manual contact bending test, it was found that all of them were capable of complete contact bending. Example 2 By the same method as in Example 1, a fine wire of Ti ₄₈ Zr ₁₂ Cu ₄₀ alloy (melting point 1107K) was produced. The melting temperature (melting surface temperature) is 1300K, and the supply rate of the combined financial liquid is 100
mm ³ / s, chamber atmosphere is 500 mmHg-Ar
And

The structure, cross-sectional morphology and toughness of the produced Ti ₄₈ Zr ₁₂ Cu ₄₀ thin wire were examined in the same manner as in Example 1. As a result, a thin wire composed of an amorphous single phase, roundness, average wire diameter and wire diameter unevenness were observed. Had 95%, 72 μm, and 12%, respectively, and had a toughness capable of tight bending. Examples 3 to 8 According to the same method as in Example 1, Fe ₇₅ Si ₁₀ B ₁₅ alloy (alloy 1) and Ti _{48 having} various melting temperatures (melting surface temperatures) were used.
Amorphous metal wires of Zr ₁₂ Cu ₄₀ (alloy 2) were produced.
The manufacturing conditions of the thin wire are shown in Table 1. With respect to the thin wire produced under each condition, the structure observation, cross-section observation (roundness, wire diameter, wire diameter unevenness) and adhesion bending test were performed in the same manner as in Example 1. The results are also shown in Table 1.

[0024]

[Table 1]

Examples 9 to 12 By the same method as in Example 1, the melting temperature (melting surface temperature)
The 1523K Fe ₇₅ Si ₁₀ B ₁₅ alloy was supplied while changing the supply speed to the contact portion with the rotating roll (1) in FIG. 2 to manufacture the thin metal wire (5) at various roll peripheral speeds. Table 2 shows the manufacturing conditions of the thin wire in this case. Further, with respect to the thin wire produced under each condition, the structure observation, cross-section observation (roundness, wire diameter, wire diameter unevenness) and close contact bending test were performed in the same manner as in Example 1. The results are shown in Table 2.

[0026]

[Table 2]

Examples 13 to 16 By the same method as in Example 1, the melting temperature (melting surface temperature)
1100K Al ₈₅ Ce ₅ Ni ₁₀ alloy (Tm = 889
K) was supplied while changing the supply speed to the contact portion with the rotating roll, and metal thin wires were manufactured at various roll peripheral speeds. Table 3 shows the manufacturing conditions of the thin wire. Further, with respect to the thin wire produced under each condition, the structure observation, cross-section observation (roundness, wire diameter, wire diameter unevenness) and close contact bending test were performed in the same manner as in Example 1. The results are also shown in Table 3.

[0028]

[Table 3]

Example 17 Cu-13 wt% with a V-shaped tip (tip angle 60 degrees) having a thermal conductivity of 0.41 (cal / cm · s · deg) and a diameter of 20 cm
Rotation speed 2000 rpm using a Zn alloy rotating roll
1523K while rotating at a peripheral speed of 20.9 m / s
The surface of the molten Fe ₇₅ Si ₁₀ B ₁₅ alloy of was contacted with, and the supercooled liquid was ejected into the atmosphere to prepare a thin metal wire in the same manner as in Example 1.

Then, in the same manner as in Example 1, the produced thin wire was subjected to structure observation, cross-section observation (roundness, wire diameter, wire diameter unevenness) and a contact bending test. As a result, it was found that the produced thin wire was a thin wire (5) composed of an amorphous single phase. In addition, the minimum circularity in the cross section was 89%, the average wire diameter was 70 μm, and the wire diameter unevenness calculated by the above formula (1) was 17%. In addition, when the bending toughness at 10 places was examined by a contact bending test by hand,
All of them were completely bendable. Examples 18 to 20 The same V-shaped tip (tip angle 60 °) of Cu having a thermal conductivity of 0.41 (cal / cm · s · deg) and a diameter of 20 cm as in Example 9 was used.
A rotating roll made of a 13 wt% Zn alloy was used, and Co ₇₅ Si ₁₀ B ₁₅ alloys (melting point 1
393 K) amorphous thin metal wires were produced. The roll peripheral speed at the time of producing the fine wire was 20.9 m / s, and the supply speed of the synthetic financial liquid to the surface of the rotating roll was 100 mm ³ / s. In the same manner as in Example 1, the obtained thin wire was subjected to structure observation, cross-section observation (roundness, wire diameter, wire diameter unevenness) and a contact bending test. The results are shown in Table 4 together with the production conditions.

[0031]

[Table 4]

Comparative Examples 1 and 2 In the same manner as in Example 1, using a copper V-shaped rotating roll, Fe ₇₅ Si ₁₀ B having various melting temperatures (melting surface temperatures) was used.
_A thin metal wire of ₁₅ alloy was manufactured. Table 5 shows the manufacturing conditions of the thin wire. Further, with respect to the thin wire produced under each condition, the structure observation, cross-section observation (roundness, wire diameter, wire diameter unevenness) and close contact bending test were performed in the same manner as in Example 1. The results are also shown in Table 5.

[0033]

[Table 5]

In Table 5, the circularity of the cross section is 10
The maximum (best) roundness obtained from the measurement result of the cross section is shown. Further, the structures in Table 5 are expressed as crystalline when diffraction lines from crystals are observed as a result of X-ray diffraction. Comparative Example 3 Using a V-shaped tip (60 degree tip angle) 20 cm diameter rotary roller made of Mo with a thermal conductivity of 0.34 (cal / cm · s · deg), a rotation speed of 2000 pm (peripheral speed 20.9 m / S) while making contact with the surface of the molten Fe ₇₅ Si ₁₀ B ₁₅ alloy of 1523K while rotating at a speed of / s), a thin metal wire was produced in the same manner as in Example 1.

Then, in the same manner as in Example 1, the thin wire produced was subjected to structure observation, cross-section observation (roundness, wire diameter, wire diameter unevenness) and a contact bending test. As a result, the circular shape of the produced fine wire (5) was 74 μm, and the circularity was 72% even at the maximum in 10 cross sections. In addition, the unevenness of the thin wire diameter was 25%. As a result of observing the structure, the produced thin wire was composed of an amorphous single phase, but there was no portion capable of being completely adhered and bent.

As is clear from the above results, in Examples 1 to 20 of the present invention, the thermal conductivity was 0.40 (cal / cm ·
s · deg) or more of a V-shaped protrusion type rotating roll with a tip of 1.0 against the melting point Tm (K) of the alloy.
A very high cooling rate can be obtained by contacting the surface of the combined financial liquid heated in the temperature range of 2 Tm or more and 1.4 Tm or less and ejecting the supercooled liquid of the alloy into the atmosphere to produce the amorphous metal thin wire. Has been realized. Therefore, wire diameter 60μ
Fe-Si-B system and Co-Si that can be closely bent to m or more
-B type, Ti-Zr-Cu type and Al-Ce-Ni type amorphous metal fine wires are obtained, and even in the amorphous metal fine wire (5) having a wire diameter of 50 μm or more, the roundness of the thin wire cross section is obtained. Is 85
%, And high-quality amorphous metal fine wires having a wire diameter unevenness of 20% or less are obtained.

On the other hand, in Comparative Example 1, the thermal conductivity is 0.40.
Even if a rotating roll of (cal / cm · s · deg) or more is used, the manufacturing temperature is too high, so the supercooled liquid cannot be jetted into the atmosphere, and the generation of crystals during manufacturing cannot be suppressed. . In Comparative Example 2, the thermal conductivity is 0.40 (cal / cm
・ Even if a rotating roll of s ・ deg) or more is used, the manufacturing temperature is too low, so that the synthetic financial liquid is amorphized before it separates from the roll (1), and the roundness of the cross section is poor, Only low-quality amorphous alloy fine wires with large wire diameter unevenness have been obtained.

Further, in Comparative Example 3, the thermal conductivity is 0.4.
Since it is manufactured by using a rotating roll made of Mo with a value smaller than 0 (cal / cm · s · deg), the cooling rate is not high, the roundness is low, and the wire diameter is large and amorphous. It is a thin line. Moreover, the bending toughness of the obtained amorphous thin wire is also poor.

[0039]

As described in detail above, according to the present invention, the supercooled liquid of various alloys having an amorphous forming ability can be jetted into the atmosphere and rapidly solidified, so that the circularity of the cross section is high. In addition, it is possible to easily manufacture a high-quality amorphous metal fine wire with a small wire diameter unevenness (a small wire diameter distribution in the longitudinal direction).

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view showing an example of a V-shaped protrusion type rotary roll of the present invention.

FIG. 2 is a schematic view of an apparatus for producing an amorphous metal thin wire of the present invention.

3 (a) and 3 (b) are cross-sectional views each exemplifying an amorphous metal thin wire of the present invention having a part with a changed curvature in a part of the cross-section.

[Explanation of symbols]

 1 rotating roll 2 combined financial liquid 3 high frequency induction heating device 4 lifting means 5 thin metal wire

 ─────────────────────────────────────────────────── ─── Continuation of the front page (71) Applicant 000004640 3-10 Fukuura, Kanazawa-ku, Yokohama-shi, Kanagawa, Japan (72) Inventor Ken Masumoto 3-8-22, Uesugi, Aoba-ku, Sendai-shi, Miyagi (72) ) Inventor Akihisa Inoue Kawauchi Mugenji, Aoba-ku, Sendai City, Miyagi Prefecture Kawauchi Housing 11-806 (72) Inventor Kenji Amitani 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Central Research Laboratories (72) Inventor Katsuya Akihiro Kanagawa 4-1206 Honmokubara, Naka-ku, Yokohama-shi, Japan

Claims (1)

[Claims] 1. A tip V-shaped protrusion type rotating roll having a thermal conductivity of 0.40 (cal / cm · s · deg) or more in a temperature range of 0 to 100 ° C. with respect to a melting point Tm (K) of 1. 02-1.
A method for producing an amorphous metal thin wire, which comprises contacting the surface of a synthetic financial liquid heated to a temperature range of 4 Tm, and jetting a supercooled liquid of the synthetic financial liquid to cool it.