JPH01228652A - Manufacture of amorphous alloy thin strip - Google Patents

Abstract

PURPOSE:To minimize the thickness of an amorphous alloy thin strip by solidifying the two phase separated molten alloy composed by the element selected respectively from specified element group with a liquid rapid cooling method and separating a 1st phase of the amorphous alloy. CONSTITUTION:The thin strip laminating 1st and 2nd phases is formed by solidifying with a liquid rapid cooling method the molten alloy capable of separating in two phases consisting of the amorphous alloy displayed by the XaYb forming the 1st phase and the Z component whose ratio thereto is at 40-90atom.%. In this case X is taken as the element selected from Fe, Co, Ni groups and Y is selected from B, C, SiP and Ge groups. The Z component is selected from Ag, Cu, Pb, Au, Bi, Ba groups. The amorphous alloy thin strip in the extremely thin thickness of about 5-10mum consisting of the 1st phase only is easily obtd. by removing a 2nd phase separated from the laminated thin strip physically by a grinding method, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is suitable for magnetic core materials for electronic devices, high magnetic permeability materials for high frequency use such as magnetic recording heads. The present invention relates to a method for producing a very thin amorphous alloy ribbon.

(Conventional technology) Amorphous alloys have characteristics such as high magnetic permeability, low coercive force, high electrical resistance, high mechanical strength, and excellent wear resistance, and are attracting attention as unique soft magnetic materials. . Utilizing these properties, it is used as a high-permeability material for high frequencies, such as magnetic recording head materials, transformers, and magnetic core materials for various inductors.

With the development of electronic technology in recent years, the level of performance required of various high-frequency magnetic materials has become higher. etc. are required. Various methods have been studied to obtain materials that satisfy these conditions, and one of them is a method of making the thickness of the non-quality alloy (W) band thinner than before.

Among liquid quenching methods, the single roll method, twin roll method, and centrifugal method are used to produce amorphous alloy ribbons (Amorphous Alloys, Physical Properties and Applications, pp. 6-11, published by Agne). In both methods, the alloy is melted in an electric furnace or high-frequency furnace, and the molten metal of one alloy is jetted out from a nozzle using gas pressure, and is solidified by contact on the surface of a rotating cooling body. It is possible to produce a belt in a short time.

However, the thickness of the amorphous alloy ribbon largely depends on the interaction between the amount of molten metal ejected, which depends on the nozzle hole diameter and ejection pressure, and the circumferential speed of the cooling rotor, and these conditions are adjusted by AJfl adjustment. By doing so, a ribbon with a thickness of 15 to 100 μm can be produced, but it is very difficult to uniformly and continuously obtain a ribbon with a thickness of 15 μm or less.

In other words, 1. Even if you try to obtain a ribbon thinner than 15 μm using the normal method, what will happen? 8. If air bubbles are trapped between the field and the surface of the cooling rotor, unevenness or irregularities may occur on the surface of the ribbon, or if the nozzle hole diameter is made smaller.

Difficulties arise, such as the nozzle becoming very easily clogged when blowing air.

On the other hand, an amorphous alloy ribbon is usually a single phase amorphous alloy, as disclosed in JP-A-61-89838.

An amorphous alloy composite material is disclosed in which an Ag coating with a thickness of 1 to 2 μm is formed on the free solidifying surface of an amorphous alloy ribbon by two-phase separation from the amorphous alloy. This is Ag
The purpose of this invention is to composite the amorphous alloy and the amorphous alloy, and is not intended to reduce the thickness of the amorphous alloy ribbon itself as in the present invention. Furthermore, Koyuki U describes that a thin plate of 30 to 50 μm can be easily formed, and the example only shows a thin strip of 30 μm, but it is possible to form a thin plate using two-phase separation. There is no suggestion that the thickness of the crystalline alloy itself be reduced.

Furthermore, Japanese Patent Application Laid-Open No. 61-41733 discloses a method in which a molten metal of a specific two-phase separated alloy is rapidly solidified by a liquid quenching method, and fine second phase metal particles are dispersed in an amorphous matrix. A method for producing a two-phase metal particle-dispersed amorphous alloy has been disclosed, but since the ratio of the metal element forming the second phase is as small as 1 to 10 at%, the second phase is not included in the amorphous matrix. There is no disclosure of reducing the thickness of the amorphous alloy ribbon by dispersing it as particles.

(Problems to be Solved by the Invention) The present invention provides a method for manufacturing an extremely thin amorphous alloy ribbon that cannot be obtained by conventional methods, using a conventional liquid quenching ribbon manufacturing apparatus and manufacturing conditions. The purpose is to

(Means for Solving the Problems) As a result of intensive studies to solve these problems, the present inventors found that when a molten metal of a specific two-phase separated alloy is rapidly solidified by a liquid quenching method, The inventors discovered that it was possible to obtain an extremely thin amorphous alloy ribbon, which could not be obtained by conventional methods, and thus arrived at the present invention.

In other words, in the present invention, x and y form the first phase.

(Here, X is one or more elements selected from the group consisting of Fe, Co, and Ni, and Y is B or C.

One or more elements selected from the group consisting of Si, P, and Ge, where a is atomic % given by too-b,
b is 10 to 40 atomic %) component and Z forming the second phase (here, Z is Ag.

one or more elements selected from the group consisting of Cu, Pb, Au, Bi, and Ba);
A molten metal of an alloy that separates into two phases in which the ratio of Z is 40 to 90 at% is rapidly solidified by a liquid quenching method to form a first phase consisting of an amorphous alloy and a metal or metal that separates into phases from the amorphous alloy. A thin ribbon in which a second phase consisting of an alloy is laminated in layers is obtained.
The gist of the present invention is a method for manufacturing an amorphous alloy ribbon, which is characterized by removing the second phase in the obtained ribbon.

The two-phase-separated alloy in the present invention refers to an alloy in which the second phase-forming metal and the amorphous alloy undergo two-phase separation after rapid solidification. The alloy forming the phase is represented as X, Y, and the metal or alloy forming the second phase is represented as Z. In XaYb, X is Fe.
, Co, and Ni, and is the main metal element constituting the amorphous alloy.

The main metal elements determine the magnetic and electrical properties of the amorphous alloy. For example, Fe-based amorphous alloys have a high saturation magnetic flux density, low coercive force, and high squareness.

It has low iron loss characteristics and is suitable as a transformer core material. The Co-based amorphous alloy has a zero magnetostriction composition.

Suitable for magnetic head materials.

Y is one or more elements selected from the group consisting of B, C, Si, P, and Ge, and is an amorphous element.

a is atomic % given by 100-b, b is 10 to 40 atomic %, and when it is less than 10 atomic % and exceeds 40 atomic %, the ability to form an amorphous state decreases, so the amorphous alloy phase is crystallized and brittle. The preferred range is 15 to 30 at%.

The effect of amorphization is greater when Y is added as a mixture of two elements than as a single element, and the combination of B and Si is particularly effective.

Also, if necessary, the corrosion resistance of amorphous alloy ribbons.

In order to improve wear resistance, magnetic properties, etc., Cr, Mo, and Mn are added within a range that does not reduce the ability to form an amorphous state.

Elements such as V and Nb may be added, and the amount added is preferably 15 at % or less.

Z is a metal or alloy that undergoes phase separation from an amorphous alloy, and the main metal elements of the amorphous alloy are Fc and Co.

In the case of Ni, Ag, Cu, Pb, Au, Bi.

One or more elements selected from the group consisting of Ba. Considering the tendency of separation from amorphous alloys, the difference in melting point, etc., Ag and Ag-Cu alloys are preferable. The ratio of Z is 40
~90 atomic %, and in the case of 40 atomic % ungrooved, the effect of thinning the amorphous alloy is not sufficiently exhibited. Moreover, when it exceeds 90 atomic %, it is difficult for the amorphous alloy phase to become continuous and uniform.

Examples of the liquid quenching method used in the present invention include the usual single roll method, twin roll method, centrifugal method, etc. for making an amorphous alloy ribbon.

For example, when carrying out the present invention using a single roll method, a two-phase separated alloy adjusted to a predetermined composition is put into a molten metal spouting nozzle with a hole at the tip and melted using a high frequency furnace or the like. in this case,? 'g Weir for adjusting the mixing condition of hot water,
A ceramic filter or the like may be installed inside the molten metal spouting nozzle.

Next, the molten metal is blown onto a copper roll or steel roll with a diameter of 10 to 30 cm rotating at 2000 to 8000 rpm and rapidly solidified to obtain a ribbon with a thickness of about 20 to 30 μm. When the cross section of this ribbon is observed with an optical microscope, it is separated into two phases, a first phase and a second phase, and each phase has a structure in which the layers are laminated. Although the thickness of the entire ribbon is the same as that of a conventional ribbon, the thickness of the first phase, which is an amorphous alloy phase, is reduced to 5 to 10 μm due to the presence of the second phase.

In the present invention, it is important to blow out both the molten metal of the amorphous-forming alloy and the second phase-forming metal or alloy from one nozzle hole. Although a single-layer ribbon can be obtained by blowing out the molten forming metal from separate nozzles, the effect of the present invention of thinning the amorphous alloy portion is not achieved.

Next, when the second phase is removed from the two-phase separated ribbon produced in this manner, a very thin amorphous alloy ribbon is obtained. To remove the second phase, 3. For example, use abrasives such as silicon carbide, aluminum oxide, or 6.
A physical method of polishing and removing the second phase with abrasive paper of about 00 to 1200 may be used. Furthermore, a chemical method of removing the second phase by dissolving it with an acid or the like can also be applied.

The thus obtained amorphous alloy ribbon may be heat treated, if necessary, under conditions that do not cause crystallization. In particular, heat treatment to improve magnetic properties is useful, and such heat treatments include methods such as annealing to remove internal strain, annealing above the Curie temperature and water quenching, or cooling in a magnetic field and annealing in a magnetic field with two rotations. You can do it with

(Function) According to the present invention, by utilizing the phenomenon of phase separation,
A very thin amorphous alloy ribbon is obtained.

The manufacturing conditions for the thin strip determine the following: 7;
7 and 2. If a ribbon separated into two phases and each phase is laminated in a layered manner is obtained as in the present invention, the phase-separated second phase is 11
As a result, the thickness of the amorphous alloy phase becomes thinner. By this method, it is possible to easily obtain an extremely thin amorphous alloy ribbon that could not be obtained using conventional methods.

(Example) Next, two embodiments of the present invention will be specifically explained using examples.

Examples 1-6. Comparative Examples 1 to 5 After melting the various alloy phase agreement logs shown in Table 1 in a quartz tube in an argon atmosphere, using a quartz nozzle with a hole diameter of 0.5 mm, the argon injection pressure was 1.5 kg/cI11 and 40
Copper roll (diameter 20 cm) rotating at 00 rpm, m
The thin strip was squirted out and rapidly solidified to obtain a thin strip with a width of about 1 dragon.Next, both sides of the obtained thin strip were polished with No. 1000 silicon carbide abrasive paper (manufactured by Hiki Kenshi Co., Ltd.). The two phases were removed and the amorphous alloy ribbon was taken out (Examples 1 to 6). Comparative examples 1, 2)
.

In addition, for comparison, the alloy phase agreement log that does not contain the metal or alloy forming the second phase was melted in a quartz tube in an argon atmosphere in the same manner as in the example.

Amorphous alloy ribbons were produced by changing the argon ejection pressure, roll rotation speed, and nozzle hole diameter (Comparative Examples 3 to 5).

Table 1 shows the results of the length and thickness of the ribbon produced above. Here, the thickness of the amorphous alloy ribbon is:

Run the NlJ band for 50m using a laser measuring machine.

It was determined by measuring the continuous average thickness.

As is clear from Table 1, in Comparative Example 1, since the amount of 8 get was small, a thin amorphous alloy ribbon could not be obtained.

In Comparative Example 2, since the amount of Ag is large, an amorphous alloy ribbon having a uniform thickness and being continuous cannot be obtained.

On the other hand, as in Examples 1 to 6, if the content of the metal or alloy forming the second phase is within the composition range of the present invention, a very thin amorphous alloy with a thickness of 5 to 10 μm A thin strip was obtained.

However, in Comparative Examples 3 to 5, which were made with an alloy composition that does not contain the metal or alloy that forms the second phase, breaks in the ribbon and nozzle clogging occurred, and the thickness was uniform and continuous amorphous alloy thin film was produced. I didn't get the belt.

Next, the thus obtained amorphous alloy ribbon of Example 2 and the amorphous alloy ribbon of Comparative Example 1 were prepared.

After annealing at 430°C for 3 minutes, water quenching heat treatment was performed and the magnetic permeability was measured using an impedance analyzer 4192A.
(manufactured by Yokogawa Hewlett-Baccard).

The results are shown in FIG. Figure 1 shows the relationship between frequency and magnetic permeability.1 Since the amorphous alloy ribbon obtained by the present invention is thin, the permeability decreases little in the high frequency range. Recognize.

(Effects of the Invention) According to the present invention, it is possible to obtain a very thin (for example, 5 to 10 μm thick) amorphous alloy ribbon that could not be obtained by conventional methods. Such a thin ribbon has a small decrease in magnetic permeability in a high frequency range, and is industrially very useful as a high frequency high permeability material for magnetic heads, inductance cores, and the like.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between frequency and magnetic permeability of a ribbon obtained by the manufacturing method of the present invention and a ribbon obtained by a conventional method. Patent applicant: Ken Masumoto Unico Power Co., Ltd.

Claims (1)

[Claims] (1) X_aY_b forming the first phase (where X is F
one or more elements selected from the group consisting of e, Co, and Ni; Y is one or more elements selected from the group consisting of B, C, Si, P, and Ge; a is 100-
atomic % given by b, b is 10 to 40 atomic %)
component and Z forming the second phase (here, Z is Ag, Cu
, one or more elements selected from the group consisting of Pb, Au, Bi, and Ba), and the ratio of Z is 40 to 90 atomic %. is rapidly solidified by a liquid quenching method to obtain a thin strip in which a first phase consisting of an amorphous alloy and a second phase consisting of a metal or alloy that phase separates from the amorphous alloy are laminated in a layered manner. . A method for producing an amorphous alloy ribbon, which comprises removing the second phase in the obtained ribbon.