JPH07300657A - Amorphous alloy ribbon manufacturing method - Google Patents

Abstract

(57) Abstract: [configuration] formula _{(Fe 1-a M a)} 100-xyzb Cu x S
i _y B _{z M'b} (In the formula, M represents at least one element selected from the group consisting of Nb, Mo, W, and Ta;
x, y, z and b are 0 ≦ a ≦ 0.1, 0.5 ≦ x ≦
2, 5 ≦ y ≦ 20, 5 ≦ z ≦ 11, 14 ≦ y + z ≦ 2
5, 2 ≦ b ≦ 5 (atomic%) are satisfied, and the ratio of y and z (y / z) is in the range of 0.5 ≦ y / z ≦ 3. ), A molten alloy having a composition indicated by (1) is injected from a slot provided at the end of the nozzle onto a cooling roll made of a Cu alloy containing 0.05 to 3.0% by weight of Be, and is amorphous by a single roll method. A method for producing an amorphous alloy ribbon, which comprises producing an alloy ribbon. [Effects] It is possible to provide a manufacturing method capable of controlling the peeling position of the amorphous alloy ribbon formed on the cooling roll.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a ribbon of amorphous metal by a single roll type liquid quenching method.

[0002]

BACKGROUND OF THE INVENTION In recent years, various soft magnetic alloys having a high saturation magnetic flux density have been developed as magnetic core materials for various transformers, magnetic heads, choke coils and the like.

As such a soft magnetic alloy, for example, Japanese Patent Kokoku 4-4393, general _{formula: (Fe 1-a M a} ) 100-xyzb Cu x Si y B z M 'b ( where, Where M is Co and / or Ni,
M'is Nb, W, Ta, Zr, Hf, Ti and Mo
At least one element selected from the group consisting of
a, x, y, z and b are 0 ≦ a ≦ 0.5 and 0.
1 ≦ x ≦ 3, 0 ≦ y ≦ 30, 0 ≦ z ≦ 25, 5 ≦ y + z
≦ 30 and 0.1 ≦ b ≦ 30 are satisfied. ), A soft magnetic alloy is shown in which at least 50% of the structure is composed of fine crystal grains having an average grain size of 1000Å or less, and the balance is substantially amorphous. It has been shown that this microcrystalline soft magnetic alloy is a soft magnetic alloy with low core loss and low magnetostriction.

Further, among the microcrystalline soft magnetic alloys having the above composition, M'is at least one element selected from the group consisting of Nb, W, Ta and Mo, and a,
x, y, z, and q are a = 0, 0.5 ≦ x ≦, respectively.
2, 5 ≦ y ≦ 20, 5 ≦ z ≦ 11, 14 ≦ y + z ≦ 25
And the microcrystalline soft magnetic alloy satisfying 2 ≦ b ≦ 5 have particularly high saturation magnetic flux density, low loss, and low magnetostriction. JP-B-4-393, Yoshizawa, Yamauchi: Journal of Japan Society for Applied Magnetics. , 13 , 231 (1989), Yoshizawa, Yamauchi: The Japan Institute of Metals, 53 , 241 (1989), and Y. Yoshizawa and K. Yamauch.
i: Material Science and Engineering, A133 , 176 (1991)
In detail.

By the way, a basic method for producing the above-mentioned microcrystalline soft magnetic alloy is disclosed in Japanese Patent Laid-Open No. 3-219909. This method for producing a microcrystalline soft magnetic alloy comprises the steps of quenching a molten metal having the above composition into an amorphous alloy and performing a heat treatment for forming fine crystal grains having an average grain size of 1000Å or less. Has become. However, this publication does not disclose details of how to carry out each step. Further, regarding the industrial mass production technology of the amorphous ribbon, which is the first step of producing the microcrystalline soft magnetic alloy ribbon, it is not known what to do specifically. It has been considered difficult to industrially mass-produce the amorphous alloy ribbon suitable for producing the microcrystalline soft magnetic alloy ribbon.

When the present inventors produce an amorphous alloy having the above composition by the single roll method, Fe--S
As compared with the alloy made of i-B, it was easily peeled off from the rotating cooling roll, and the peeling position was irregular, which made industrial mass production difficult. If the position where the strip is peeled off from the cooling roll is irregular as described above, it becomes difficult to collect the strip for winding or the like, and the productivity of the strip is significantly reduced.

As a method of avoiding such a problem, US Pat. No. 3,586,074 discloses a method in which a metal filament is sandwiched between a cooling wheel and a roller to retain the metal filament formed on the outer peripheral surface of the cooling wheel. The method of doing is proposed.

Further, in US Pat. No. 3,862,658, a gas is blown against a metal filament formed on the outer peripheral surface of a cooling wheel, a belt or a roller,
A method has been proposed in which the contact time between the metal filament and the cooling wheel is lengthened by sandwiching the metal filament with the cooling wheel.

Further, in US Pat. No. 4,202,404, the cooling roll and the outer peripheral surface of the cooling roll are
A method of holding a metal filament by sandwiching the metal filament between a cooling roll and a belt using a flexible belt covering three or more has been proposed. In addition, in the specification,
It is disclosed that a Cu alloy containing Be is used as the material of the cooling roll.

However, each of these methods requires the introduction of a special device, which raises the problem of increased manufacturing cost. On the other hand, as a means for improving the adhesion between the ribbon and the cooling roll, the material of the cooling roll is Cu-
A method of using an alloy such as Ag alloy and using a cooling roll having a coating layer of a metal such as Fe and Cr having good wettability with the molten metal on the surface of the cooling roll is used.
No. 61 is disclosed. However, this method has a problem in terms of wear resistance of the cooling roll and manufacturing cost.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and in producing an amorphous alloy ribbon by a single roll method, a molten alloy is jetted from a nozzle onto a cooling roll. The amorphous alloy ribbon formed by the above process adheres sufficiently to the cooling roll, which allows the position where the amorphous alloy ribbon separates from the cooling roll to be accurately controlled. It is characterized by providing a method for manufacturing a belt.

[0012]

Method for producing an amorphous alloy ribbon according to the SUMMARY OF THE INVENTION The present invention has the general formula _{(Fe 1-a M a)} 100-xyzb Cu x Si y B z M 'b ( wherein, M represents, Co And / or Ni element,
M ′ represents at least one element selected from the group consisting of Nb, Mo, W and Ta, and a, x, y, z and b
Are 0 ≦ a ≦ 0.1, 0.5 ≦ x ≦ 2 (atomic%), 5 ≦ y ≦ 20 (atomic%), 5 ≦ z ≦ 11 (atomic%), 14 ≦ y + z ≦ 25 (atomic, respectively) %), 2 ≦ b ≦ 5 (atomic%), and the ratio of y and z (y / z) is 0.5.
It is in the range of ≦ y / z ≦ 3. ), A molten alloy having a composition indicated by (1) is injected from a slot provided at the end of the nozzle onto a cooling roll made of a Cu alloy containing 0.05 to 3.0% by weight of Be, and is amorphous by a single roll method. It is characterized by producing a ribbon of alloy.

In the present invention, a = 0 in the above general formula.
It is preferable to use a molten alloy having a composition of Also,
In the present invention, in the composition of the alloy, it is particularly preferable that the ratio of y to z (y / z) is in the range of 0.7 ≦ y / z ≦ 2.

In the present invention, it is preferable to produce the amorphous alloy ribbon under the following conditions. Circumferential velocity (R) of cooling roll: 10≤R≤40 (m / sec) Injection pressure (P) of molten alloy (gauge pressure): P≤0.6 (kgf / cm ² ) In the present invention, the following conditions are satisfied. It is more preferable to manufacture the amorphous alloy ribbon by.

Peripheral velocity of cooling roll (R): 10 ≦ R ≦ 40 (m / sec) Cast temperature (Tc): 1150 ≦ Tc ≦ 1600 (° C.) Injection pressure (P) (gauge pressure) of molten alloy: P ≦ 0.6 (kgf / cm ² ) Slot width at nozzle tip (d): 0.2 ≦ d ≦ 0.9 (mm) Distance between nozzle tip and cooling roll (g): 0.05 ≦ g ≦ 0.3 (mm) In the present invention, it is particularly preferable to produce the amorphous alloy ribbon under the following conditions.

Circumferential velocity (R) of cooling roll: 15 ≦ R ≦ 30 (m / sec) Cast temperature (Tc): 1150 ≦ Tc ≦ 1500 (° C.) Injection pressure (P) (gauge pressure) of molten alloy: P ≦ 0.4 (kgf / cm ² ) Slot width at nozzle tip (d): 0.3 ≦ d ≦ 0.6 (mm) Distance between nozzle tip and cooling roll (g): 0.08 ≦ g ≤0.2 (mm)

[0017]

DETAILED DESCRIPTION OF THE INVENTION The method for producing an amorphous alloy ribbon according to the present invention will be specifically described below. FIG. 1 is a conceptual diagram showing a method for producing an amorphous alloy ribbon according to the present invention. FIG. 2 is an enlarged sectional view of the end portion of the nozzle used in the present invention.

As shown in FIGS. 1 and 2, in the method for producing an amorphous alloy ribbon according to the present invention, a molten alloy 5 is rotated from a slot 2 provided at an end of a nozzle 1 to rotate a cooling roll. Then, the amorphous alloy ribbon 7 is formed.

The amorphous alloy ribbon in the present invention means an alloy ribbon having a crystal content (x _c (%)) of 30% or less.
The crystal content is the ratio (%) of the crystal phase in the alloy (volume fraction of the crystal phase in the alloy structure (%)), and this value is the amorphous alloy ribbon produced by the single roll method. In the X-ray diffraction pattern measured from the free surface side of, the area of the diffraction peak from the crystalline phase (S _C ) and the area of the broad diffraction pattern due to the amorphous phase (S _A ) as shown in FIG. With and

[0020]

[Equation 1]

Is defined as Since the alloy ribbon having a crystal content (x _c ) of 30% or less has excellent mechanical strength, it is easy to automatically wind the ribbon or slit the alloy ribbon. . The alloy ribbon obtained by heat-treating the amorphous alloy ribbon to precipitate fine crystals exhibits excellent magnetic characteristics. When the amorphous alloy ribbon is mass-produced particularly stably, the amorphous alloy ribbon according to the present invention has a crystal content (x _c ) of 5% or less, particularly substantially 0%. It is preferably a belt.

The alloys used in the production of the amorphous alloy ribbon in the present invention have the general formula _{(Fe 1-a M a)} 100-xyzb Cu x S
It is a Fe-based alloy represented by i _y B _z M ′ _b .

In the above general formula, M represents a Co and / or Ni element, and M ′ represents at least one element selected from the group consisting of Nb, Mo, W and Ta. Further, x, y, z and b are represented by atomic%.

A is 0≤a≤0.1, preferably 0≤a
Satisfying ≦ 0.05, more preferably a = 0,
x is 0.5 ≦ x ≦ 2 (atomic%), preferably 0.5 ≦ x
≦ 1.5 (atomic%), y satisfies 5 ≦ y ≦ 20 (atomic%), z satisfies 5 ≦ z ≦ 11 (atomic%), and b satisfies 2 ≦ b ≦ 5 ( Atomic%), preferably 2 ≦ b ≦
Satisfy 4 (atomic%),

Further, y and z are 14≤y + z≤25.
(Atomic%) is satisfied. The alloy used in the present invention satisfies the above composition, and the ratio y / z (atomic ratio) of y and z satisfies 0.5 ≦ y / z ≦ 3. y / z
Preferably satisfies 0.7 ≦ y / z ≦ 2.

If necessary, the alloy used in the present invention may contain V, Cr, and V in addition to the composition represented by the above general formula.
Elements such as Mn, Ti, Zr, Hf, C, Ge, P, Ga, platinum group elements, and Au may be contained in an amount of 5 atomic% or less.

The alloy having the above composition has excellent adhesion to a cooling roll as described later. Further, an amorphous alloy ribbon having a high saturation density and low magnetostriction can be produced from the alloy having the above composition.

The cooling roll 3 used in the present invention (the entire cooling roll or at least the surface portion of the cooling roll which comes into contact with the molten alloy) contains Be in an amount of 0.05 to 3.0% by weight, preferably 0.1 to 2. It is formed from a Cu alloy containing in an amount of 0.0% by weight. A Cu alloy containing 0.05 to 3.0% by weight of Be is an alloy containing Cu as a main essential component and 0.05 to 3.0% by weight of Be.
Cu containing 0.05 to 3.0% by weight and the balance being Cu
-Be alloys as well as alloys containing Cu and 0.05 to 3.0 wt% Be and other elements, such as elements such as Fe, Co and Ni, in an amount of 1 wt% or less are included. In the present invention, among these alloys, a Cu-Be alloy in which Be is 0.05 to 3.0% by weight, preferably 0.1 to 2.0% by weight and the balance is Cu is particularly preferable.

Since the cooling roll used in the present invention is formed of a Cu alloy containing 0.05 to 3.0 wt% of Be, it has excellent adhesion to the alloy having the above composition, It is difficult for the amorphous ribbon to spontaneously peel off from the cooling roll (the sticking angle is large), and it is easy to accurately control the peeling position of the amorphous alloy ribbon from the cooling roll.
Further, since this chill roll has excellent adhesion to the molten alloy having the above composition, the heat conduction at the interface between the chill roll and the molten alloy is good, and the cooling rate of the molten alloy is high, and therefore standard. The amorphous alloy ribbon can be easily manufactured under the conditions, and the amorphous alloy ribbon can be industrially mass-produced.

The cooling roll used in the present invention is made of a Cu-based alloy having excellent thermal conductivity, and has excellent cooling performance for the molten alloy. Further, since the Cu alloy containing 0.05 to 3.0 wt% of Be as described above is excellent in Vickers hardness, the cooling roll is also excellent in wear resistance.

The cooling roll used in the present invention may be equipped with a mechanism for passing a liquid such as water through the inside of the cooling roll to forcibly cool it in order to increase the cooling capacity of the cooling roll.

In the present invention, the peripheral velocity (R) of the cooling roll 3 when the molten alloy 5 is jetted onto the rotating cooling roll 3
Is 10 to 40 m / sec, particularly preferably 15 to 35 m / sec.
A range of seconds is desirable.

When the peripheral velocity (R) of the cooling roll 3 when the molten alloy 5 is jetted onto the cooling roll 3 is in the range of 10 to 40 m / sec, an Fe-based amorphous alloy ribbon is formed. In addition, a sufficient cooling rate can be obtained, and the formed ribbon is not separated from the cooling roll by the centrifugal force.

In the present invention, the molten alloy 5 is placed at the end of the nozzle 1.
Injection pressure when injecting from the slot 2 provided in the
(P) (gauge pressure) is 0.6 kgf / cm²Below (0
0.6 kgf / cm²), Preferably 0.5 kgf / cm²
Below (0 to 0.5 kgf / cm ²), More preferably
0.4 kgf / cm²Below (0 to 0.4 kgf / cm²)so
Is desirable.

The injection pressure (P) when the molten alloy 5 is injected from the slot 2 provided at the end of the nozzle 1 is 0.6.
If it is less than or equal to kgf / cm ² , the amorphous alloy ribbon formed has a thickness sufficient to adhere to the cooling roll.
Further, the thickness is such that a sufficient cooling rate for forming the amorphous alloy ribbon can be obtained.

The casting temperature (Tc), which is the temperature at which the molten alloy is injected, varies depending on the composition of the amorphous alloy ribbon to be produced, but is 1150 to 1600 ° C., preferably 115.
It is preferably in the range of 0 to 1500 ° C.

Casting temperature (Tc) is 1150 to 160
Within the range of 0 ° C., the viscosity of the molten alloy becomes low, and the molten alloy can be easily jetted from the nozzle. Further, the molten alloy sprayed onto the cooling roll can obtain a sufficient cooling rate to form the amorphous alloy ribbon.

Examples of means for melting the alloy include high frequency heating. As a means for injecting the molten alloy, an inert gas pressure such as Ar gas is usually used.

At the end of the nozzle 1 used in the present invention,
A slot 2 is provided, and the molten alloy is injected from this slot 2. The width (d) of the slot 2 at the tip of the nozzle 1 is 0.2 to 0.9 mm, preferably 0.1.
It is desirable to be in the range of 3 to 0.6 mm.

When the width (d) of the slot 2 at the tip of the nozzle 1 is in the range of 0.2 to 0.9 mm, the amorphous alloy ribbon formed has such a thickness that it can be sufficiently adhered to the cooling roll. It becomes Further, the thickness is such that a sufficient cooling rate for forming the amorphous alloy ribbon can be obtained.

The distance (g) between the tip of the nozzle provided with the slot 2 and the cooling roll 3 is 0.05 to 0.3 m.
m, preferably 0.08 to 0.2 mm.

When the distance (g) between the tip of the nozzle 1 and the cooling roll 3 is in the range of 0.05 to 0.3 mm, the amorphous alloy ribbon formed is sufficiently adhered to the cooling roll. It will be thick. Further, there is no risk that the front surface of the nozzle will be destroyed due to the contact between the solidified front surface of the molten metal and the nozzle.

The amorphous alloy ribbon of the present invention can be manufactured in vacuum, in the air, or in an inert atmosphere such as nitrogen or argon. Among them, in industrial mass production, it is desirable to carry out the production in the atmosphere because the production equipment can be simplified. At that time, He,
Any gas such as N ₂ may be blown onto the nozzle tip and the surface of the cooling roll.

According to the manufacturing method of the present invention, since the formed amorphous alloy ribbon adheres sufficiently to the cooling roll, the peeling position can be controlled by a method such as forced peeling with an air knife. According to the invention, for example Fe-C
Industrial mass production of amorphous ribbons made of u-Si-B-Nb alloy or the like is possible.

The amorphous alloy ribbon produced as described above may be subjected to heat treatment to form fine crystal grains to form a microcrystalline soft magnetic alloy.

[0046]

The manufacturing method of the present invention uses a molten alloy having a specific composition and a cooling roll made of a Cu alloy containing a specific amount of Be when manufacturing an amorphous alloy ribbon. Adhesion between the formed amorphous alloy ribbon and the cooling roll is improved. Therefore, it is possible to accurately control the peeling position of the amorphous alloy ribbon from the cooling roll, and it becomes easy to collect the ribbon for winding, etc., and it is possible to mass-produce the amorphous alloy ribbon. In addition, the thermal conductivity at the interface between the chill roll and the molten alloy becomes good, so the cooling rate of the molten alloy is fast, and therefore, the amorphous alloy ribbon can be easily manufactured under standard conditions, and industrially Can also mass-produce the amorphous alloy ribbon.

[0047]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0048]

Example 1 In order to determine the optimum composition for producing an amorphous alloy ribbon, alloy ribbons are formed by using alloys of various compositions, and the adhesion of the alloy ribbon to a cooling roll at that time is formed. As an evaluation means, the sticking angle (θ) of the alloy ribbon was measured.
Further, the X-ray diffraction pattern of the formed alloy ribbon was measured to examine the presence / absence of crystallinity in the ribbon.

Fe _96-yz Cu ₁ Si _y B _z Nb ₃ (atomic%)
Using an alloy having the composition shown in (where y and z are shown in Table 1), an alloy ribbon having a thickness of about 25 μm is formed by the single roll method under the following conditions, and the sticking angle of the alloy ribbon at that time is formed. (Θ) and X-ray diffraction pattern were measured.

The results are shown in Table 1. At this time, supply pressure (P)
Was finely adjusted with each alloy so that the thickness of the ribbon was about 25 μm.

As for the sticking angle (θ) of the alloy ribbon, the state at the time of manufacturing the alloy ribbon was photographed with a video camera, and the sticking angle (θ) was read from the image. Further, as shown in FIG. 1, the sticking angle (θ) is a line passing through the slot center of the nozzle and the center of the cooling roll, the point where the formed alloy ribbon starts to peel from the cooling roll, and the center of the cooling roll. It is the angle formed by the line passing through.

Further, since the upper limit for quantitatively observing the sticking angle (θ) is about 60 °, when the observed angle exceeds 60 °, it is described as “> 60 °”. Cooling roll material: Cu-Be alloy containing 0.4% by weight of Be Peripheral velocity of cooling roll (R): 30 (m / sec) Cast temperature (Tc): 1450 (° C) Injection pressure (P) of molten alloy (Gauge pressure): 0.30 to 0.35 (kgf / cm ² ) Slot width at nozzle tip (d): 0.3 (mm) Distance between nozzle tip and cooling roll (g): 0.2 (Mm) Atmosphere: Atmosphere From these results, the alloy having the composition described in Example 1 of Table 1 has the sticking angle (θ) of 60 ° or more, and the adhesion between the ribbon and the cooling roller is good. It can be seen that it is. Further, the formed ribbons were all amorphous as a result of X-ray diffraction.

[0053]

[Comparative Example 1] A thickness of about 2 was obtained in the same manner as in Example 1 except that alloys having Si and B contents shown in Table 1 were used.
An alloy ribbon of 5 μm was formed, and the sticking angle (θ) of the alloy ribbon at that time and the X-ray diffraction pattern of the formed alloy ribbon were measured.

The results are shown in Table 1. The alloy having the composition described in Comparative Example 1 in Table 1 had a small sticking angle (θ) and had poor adhesion between the ribbon and the cooling roller. Also,
As a result of X-ray diffraction, the formed ribbon contained 30% or more of crystalline material.

[0055]

Comparative Example 2 The thickness was about 25 in the same manner as in Example 1 except that a Cu cooling roll was used as the cooling roll and four kinds were selected from the alloy compositions used in Example 1.
An alloy ribbon having a thickness of μm was formed, and the sticking angle (θ) of the alloy ribbon at that time and the X-ray diffraction pattern of the formed alloy ribbon were measured.

The results are shown in Table 1. The thin ribbon manufactured under the conditions described in Comparative Example 2 in Table 1 had a small sticking angle (θ), and the adhesiveness between the thin ribbon and the cooling roller was poor. Moreover, as a result of X-ray diffraction, the formed ribbon contained 30% or more of crystalline material.

[0057]

[Table 1]

From Table 1, as a cooling roll, 0.05-
Using a Cu-Be alloy containing 3.0 wt% Be,
Si content (y) and B content (z) are 14 ≦ y
When an amorphous alloy ribbon is manufactured by a single roll method using an alloy having a composition satisfying + z ≦ 25 (atomic%) and 0.5 ≦ y / z ≦ 3, the adhesion between the ribbon and the roller Excellent,
It can be seen that the sticking angle is large.

[0059]

Example 2 Using an alloy having a composition represented by Fe _73.5 Cu ₁ Si _13.5 B ₉ Nb ₃ , the casting temperature (T _C ), the peripheral velocity (R) of the cooling roll and the injection pressure (P) of the molten alloy are shown. 2, the other production conditions were set as follows, and an amorphous alloy ribbon was produced by the single roll method.
The sticking angle (θ) of the alloy ribbon and the thickness (h) of the formed alloy ribbon at that time were measured in the same manner as in Example 1,
In addition, the crystal content (Xc) of the obtained alloy ribbon was measured in Example 1
It was obtained by the same method as.

The results are shown in Table 2. Cooling roll material: Cu-Be alloy containing 0.4 wt% of Be Slot width at nozzle tip (d): 0.3 (mm) Distance between nozzle tip and cooling roll (g): 0.2 ( mm) Atmosphere: Atmosphere

[0061]

[Table 2]

[0062]

Example 3 Using an alloy having a composition represented by Fe ₇₆ Cu ₁ Si ₁₁ B ₉ Nb ₃ (atomic%), the casting temperature (T _C ), the peripheral velocity (R) of the cooling roll and the injection pressure of the molten alloy ( An amorphous alloy ribbon was produced by the single roll method in the same manner as in Example 2 except that P) was changed as shown in Table 3. The sticking angle (θ) of the alloy ribbon and the thickness (h) of the formed alloy ribbon at that time were measured in the same manner as in Example 1, and the crystal content (Xc) of the obtained alloy ribbon was measured. It was determined in the same manner as in Example 1.

The results are shown in Table 3.

[0064]

[Table 3]

[0065]

Example 4 Using an alloy having a composition represented by Fe ₇₉ Cu ₁ Si ₈ B ₉ Nb ₃ (atomic%), the casting temperature (T _C ), the peripheral velocity (R) of the cooling roll and the injection pressure of the molten alloy ( P)
Amorphous metal ribbons were manufactured by the single roll method in the same manner as in Example 2 except that was changed as shown in Table 4. The sticking angle (θ) of the alloy ribbon and the thickness (h) of the formed alloy ribbon at that time were measured in the same manner as in Example 1, and the crystal content (Xc) of the obtained alloy ribbon was measured. It was determined in the same manner as in Example 1.

The results are shown in Table 4.

[0067]

[Table 4]

From Tables 2 to 4, the peripheral speed of the cooling roll (R)
Is in the range of 10 ≦ R ≦ 40 (m / sec) and the injection pressure (P) is 0.6 kgf / cm ² (gauge pressure) or less, the adhesion between the amorphous metal ribbon and the cooling roll is particularly high. It can be seen that the property is good.

[0069]

Examples 5 to 20 Using alloys having the compositions shown in Table 5, amorphous alloy ribbons were manufactured by the single roll method under the following conditions, and the sticking angle (θ) of the alloy ribbons at that time was produced. Was measured in the same manner as in Example 1. In addition, in Examples 5 to 20, the crystal content (Xc) of the obtained alloy ribbon was calculated as in Example 1.
When determined by the same method as above, all were 0%.

The results are shown in Table 5. The injection pressure (P) of the molten alloy was 25 to 30 when the average thickness of the amorphous metal ribbon was 25 to 30.
It was adjusted within the following range so as to be μm. The casting temperature (Tc) was adjusted according to the composition of the alloy.

Material of cooling roll: Cu-Be alloy containing 0.4 wt% of Be Cooling roll peripheral velocity (R): 30 (m / sec) Casting temperature (Tc): Injection pressure of molten alloy shown in Table 5 (P): shown in Table 5 Slot width at nozzle tip (d): 0.3 (mm) Distance between nozzle tip and cooling roll (g): 0.2 (mm) Atmosphere: Atmosphere

[0072]

[Table 5]

[0073]

Example 21 Using an alloy having a composition represented by Fe _96-yz Cu ₁ Si _y B _z Nb ₃ (atomic%) and under various atmospheres, the thickness was about 25 Thirty
Amorphous alloy ribbon having a thickness of μm is formed, the sticking angle (θ) of the alloy ribbon at that time and the thickness (h) of the formed alloy ribbon
Was measured in the same manner as in Example 1, and the crystal content (Xc) of the obtained alloy ribbon was determined by the same method as in Example 1.

The results are shown in Table 6. Cooling roll material: Cu-Be alloy containing 0.4% by weight of Be Peripheral velocity of cooling roll (R): 30 (m / sec) Casting temperature (TC): 1450 ° _C Injection pressure of molten alloy (P) ( Gauge pressure): 0.35 kgf / cm ² Slot width at nozzle tip (d): 0.3 (mm) Distance between nozzle tip and cooling roll (g): 0.2 (mm)

[0075]

[Table 6]

From Table 6, it can be seen that the amorphous metal ribbon is sufficiently attached to the cooling roll even in an atmosphere other than the air.

[0077]

Example 22 Fe ₇₆ Cu ₁ Si ₁₁ B ₉ Nb ₃ (atomic%)
Using the alloy having the composition shown in Fig. 5, the gap width (g) between the nozzle tip and the cooling roll is variously changed, and an amorphous alloy ribbon having a thickness of about 25 to 30 µm is formed by the single roll method under the following conditions. Formed, and the adhesion angle of the alloy ribbon at that time (θ)
The thickness (h) of the formed alloy ribbon was measured in the same manner as in Example 1, and the crystal content (X
c) was determined by the same method as in Example 1.

The results are shown in Table 7. Even in an atmosphere other than the air, the amorphous ribbon adheres well to the cooling roller. Cooling roll material: Cu-Be alloy containing 0.4% by weight of Be Peripheral velocity of cooling roll (R): 30 (m / sec) Casting temperature (TC): 1450 ° _C Injection pressure of molten alloy (P) ( Gauge pressure): 0.35 kgf / cm ² Slot width at nozzle tip (d): 0.3 (mm) Distance between nozzle tip and cooling roll (g): 0.2 (mm)

[0079]

[Table 7]

[0080]

Example 23 Fe _96-yz Cu ₁ Si _y B _z Nb ₃ (atomic%) (however, y and z are shown in Table 8) were used and the single roll method was conducted under the following conditions. Thickness is about 25
An amorphous alloy ribbon of ˜30 μm was formed, the sticking angle (θ) of the alloy ribbon and the thickness (h) of the formed alloy ribbon were measured in the same manner as in Example 1 and obtained. The crystal content (Xc) of the obtained alloy ribbon was determined by the same method as in Example 1.

The results are shown in Table 8. Amorphous alloy ribbon is B
As in the case of the cooling roll using the Cu-Be alloy containing 0.4% by weight of e, it adheres sufficiently. The material of the cooling roll: peripheral speed of Cu-Be alloy cooling roll containing 1.9% by weight of Be (R): 30 (m / sec) Cast temperature (T _C): the 1450 ° C. molten alloy injection pressure (P) ( Gauge pressure): 0.30 kgf / cm ² Slot width at nozzle tip (d): 0.3 (mm) Distance between nozzle tip and cooling roll (g): 0.15 (mm) Atmosphere: Atmosphere

[0082]

[Table 8]

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing a method for producing an amorphous alloy ribbon according to the present invention.

FIG. 2 is an enlarged cross-sectional view of a nozzle end portion used in the present invention.

FIG. 3 is a conceptual diagram of an X-ray diffraction pattern measured from a free area of an amorphous alloy ribbon manufactured by a single roll method.

[Explanation of symbols]

1 ... Nozzle 2 ... Slot 3 ... Cooling roll 5 ... Molten alloy 7 ... Amorphous alloy ribbon d ... Slot width P ... Injection pressure S _C ... Area of diffraction peak from crystalline phase S _A ... Due to amorphous phase Broad diffraction pattern area

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C22C 38/00 303 V 38/16 H01F 1/153

Claims (6)

[Claims] 1. A general formula _{(Fe 1-a M a)} 100-xyzb C
u _x Si _y B _z M ′ _b (wherein M is Co and / or N
i represents an element, M ′ represents at least one element selected from the group consisting of Nb, Mo, W and Ta, and a, x,
y, z and b are 0 ≦ a ≦ 0.1 and 0.5 ≦ x, respectively.
≦ 2 (atomic%), 5 ≦ y ≦ 20 (atomic%), 5 ≦ z ≦ 1
1 (atomic%), 14 ≦ y + z ≦ 25 (atomic%), 2 ≦ b
Satisfies ≦ 5 (atomic%), and the ratio of y and z (y / z)
Is in the range of 0.5 ≦ y / z ≦ 3. ), A molten alloy having a composition shown by
A method for producing an amorphous alloy ribbon, characterized in that the amorphous alloy ribbon is produced by a single roll method by spraying onto a cooling roll made of a Cu alloy containing about 3.0% by weight. 2. The general formula: Fe _100-xyzb Cu _x Si _y B _z
M'b (In the formula, M represents Co and / or Ni element,
M ′ represents at least one element selected from the group consisting of Nb, Mo, W and Ta, and x, y, z and b are
0.5 ≦ x ≦ 2 (atomic%), 5 ≦ y ≦ 20 (atomic%), 5 ≦ z ≦ 11 (atomic%), 14 ≦ y + z ≦ 25, respectively
(Atomic%), 2 ≦ b ≦ 5 (atomic%) are satisfied, and the ratio of y to z (y / z) is in the range of 0.5 ≦ y / z ≦ 3. The method for producing an amorphous alloy ribbon according to claim 1, wherein a molten alloy having a composition shown in (4) is used. 3. The ratio of y to z in the alloy composition (y
/ Z) is in the range of 0.7 ≦ y / z ≦ 2, The method for producing an amorphous alloy ribbon according to claim 1. 4. The method for producing an amorphous alloy ribbon according to claim 1, wherein the amorphous alloy ribbon is produced under the following conditions: peripheral velocity (R) of cooling roll: 10 ≦ R ≦ 40 (m / sec) Injection pressure (P) of molten alloy (gauge pressure): P ≦ 0.6 (kgf / cm ² ). 5. The method for producing an amorphous alloy ribbon according to claim 1, wherein the amorphous alloy ribbon is produced under the following conditions: peripheral speed (R) of a cooling roll: 10 ≦ R ≦ 40 (m / sec) Cast temperature (Tc): 1150 ≦ Tc ≦ 1600 (° C.) Injection pressure (P) of molten alloy (gauge pressure): P ≦ 0.6 (kgf / cm ² ) Slot width at the nozzle tip (D): 0.2 ≦ d ≦ 0.9 (mm) Interval between nozzle tip and cooling roll (g): 0.05 ≦ g ≦ 0.3 (mm). 6. The method for producing an amorphous alloy ribbon according to claim 1, wherein the amorphous alloy ribbon is produced under the following conditions: peripheral speed (R) of a cooling roll: 15 ≦ R ≦ 30 (m / sec) Cast temperature (Tc): 1150 ≦ Tc ≦ 1500 (° C.) Injection pressure (P) of molten alloy (gauge pressure): P ≦ 0.4 (kgf / cm ² ) Slot width at nozzle tip (D): 0.3 ≦ d ≦ 0.6 (mm) Distance between nozzle tip and cooling roll (g): 0.08 ≦ g ≦ 0.2 (mm).