JPS63239906A - Manufacture of fe alloy thin band having excellent high-frequency magnetic characteristic - Google Patents

Abstract

PURPOSE:To obtain an Fe group alloy thin band having excellent magnetic characteristics with less core loss in a high frequency band by forming an amorphous alloy thin band by a liquid quenching method from an alloy mainly formed with Fe including, in addition to Cu, at least one of Nb, W, Ta, Zr, Hf, Mo and Ti and then executing local heating the thin band in the form of a line of points or a continuous line to form a region having locally distorted area. CONSTITUTION:After an alloy, mainly consisting of Fe which may form amorphous, including Cu of 0.1-3 atomic% and at least a kind of element selected from Nb, W, Ta, Zr, Hf, Mo, Ti is melted into liquid, the amorphous alloy thin band is formed by a liquid quenching method and then the Fe group alloy thin band having excellent magnetic characteristic in which a greater part of organization is formed of super fine crystal particles can be obtained by a heat treatment of the thin band. This alloy is subjected to local heating in the form of points or continuous line within at least the one period before, during or after the heat treatment to form the region having a local distorted area or different local crystal grain organization and moreover to improve the high frequency magnetic characteristics.

Description

[Detailed description of the invention] [Industrial application field] The present invention is a saturable reactor and high frequency transformer.

The present invention relates to a method for manufacturing an Fe-based alloy ribbon that has excellent magnetic properties and particularly low core loss at high frequencies and is used as a magnetic core in Chirok coils, columnar transformers, and the like.

[Prior Art] Conventionally, silicon steel, permalloy, and the like have been used as metal materials for magnetic cores and the like. Recently, amorphous alloys have been used. Each of these magnetic alloys has its own advantages and disadvantages, and they cannot necessarily be said to have sufficient properties. Silicon steel sheets have a high saturation magnetic flux density, but they suffer from large losses at high frequencies. be. Permalloy also has a problem of large core loss at high frequencies when it has a composition with a high saturation magnetic flux density, although it does not necessarily have sufficient properties. In the case of amorphous alloys as well, there is a problem in that Co-based alloys have a fairly low core loss, but the saturation magnetic flux density is low, and Fe-based alloys have a high saturation magnetic flux density, but the core loss is much larger than that of the Co-based alloys.

In particular, in the case of a magnetic alloy that exhibits a hysteresis curve with a high squareness ratio, abnormal eddy current loss increases, resulting in a large core loss, which poses a problem.

For example, in the case of amorphous alloys, as a method to deal with such problems, crystallization in a line or dot array in the width direction of an Fe-based amorphous alloy ribbon is described in JP-A No. 57-97606. Methods for reducing abnormal eddy current loss by forming regions and subdividing magnetic domains, and
ings of 4th International
Conference on Rapidly Que
nched Metals (1982) P1001~
A method of reducing abnormal eddy current loss by heat-treating an Fe-based amorphous alloy ribbon and then scribing the surface of the ribbon to introduce strain is described in Japanese Patent Laid-Open No. 60-233804. A method of reducing abnormal eddy current loss by locally and instantaneously melting the surface of an Fe-based amorphous alloy ribbon, then rapidly solidifying it to make it amorphous again.The above method has also been applied to silicon steel sheets. There is.

[Problem that the invention seeks to solve]

However, even if the above method is applied to conventional magnetic alloys, although it is effective to some extent in reducing core loss, the core loss of the material itself is inherently large, and even with the above treatment, the core loss cannot be sufficiently reduced, especially at high frequencies. This is not a sufficient characteristic.

An object of the present invention is to provide a method for manufacturing an Fe-based alloy ribbon that has excellent high frequency magnetic properties and low core loss.

[Means for solving problems]

As a result of intensive research in view of the above objectives, the present inventors have discovered that Cu is 0.1 to 3 atoms, Nb+W, TauZr.
* After making an Fe-based alloy that can form an amorphous state into a molten metal and containing 0.1 or more elements of at least one element selected from Hf + Mo + Tt, it is made into an amorphous state by a liquid quenching method. It was discovered that by preparing a high-quality alloy ribbon and then heat-treating the ribbon, a Fe-based alloy ribbon can be obtained in which most of the structure consists of fine crystal grains and has excellent magnetic properties. As a result of further examination of the alloy, it was found that at least 1 of
At the same time, the ribbon is locally heated in a dot array or powder form to form a locally strained region, or to form a region with a locally different crystal grain structure, thereby further increasing the frequency. They found that the magnetic properties were improved and came up with the present invention.

Furthermore, the same effect can be obtained even if the above method is applied to an alloy ribbon produced at a cooling rate of 102 to 10 b grains during the liquid quenching method.

When applying local strain or forming regions with different crystal grain structures, the effect is particularly great after heat treatment, and favorable results can be obtained.

In the present invention, the remainder of the fine grain structure of the Fe-based alloy ribbon may be amorphous, or the structure may be substantially composed of fine crystal grains.

Preferably, when the crystal grains have an average grain size of 500X or less, excellent soft magnetic properties are easily obtained, and especially when the average grain size is 200X or less, high frequency magnetic properties are equal to or higher than that of a Co-based amorphous alloy ribbon. .

The Fe-based alloy ribbon in the present invention has a general formula: %) (where M is Co and/or Ni, M is Nb
+W+Ta tZr tHf tAt least one element selected from the group consisting of Ti and Mo, M is V, C
r, Mn, Al m white metal element + Se + Y
+ Textile element* Au e Zn + Sn + Re
at least one element selected from the group consisting of, X is B
e l cr Ge t p + Ga t sb
At least one member different from the group consisting of l As l In
The seed element is a + X * y, z, α, β and r are 0≦a≦0.3, 0.1≦x≦3, respectively. y
≦25, 5≦2≦25, 0.1≦α≦10.0≦β≦
10, 0≦γ≦20 and 15≦y+z+γ≦30 are satisfied. ) In the case of having a composition represented by the following, it is easy to obtain a product particularly excellent in high frequency magnetic properties by the manufacturing method of the present invention.

The effects of the present invention are more apparent when a heat treatment step in a magnetic field is included, and is particularly noticeable when the magnetic field is applied in the longitudinal direction of the ribbon.

Also, when the method includes a step of heat-treating the ribbon without applying tension to it, the effect of improving the cylindrical frequency magnetic properties, especially the core loss, is remarkable.

In addition, as shown in Fig. 1, if the average angle with the width direction of the ribbon is within 30, it is possible to form dot-like or linear local strain regions, or regions with different crystal grain structures. The effect of improving properties is remarkable and more favorable results can be obtained. Also, adjacent lines or dots do not need to be parallel, nor do they need to be straight as shown in FIG.

In addition, in the present invention, it is possible to use a laser beam as a means of local heating, or to apply electricity by bringing either a metal needle or a metal edge close to or in contact with the surface of the ribbon, which can be used for forest production or mass production. More favorable results can be obtained in terms of performance.

When using a laser beam, more preferable results can be obtained by concentrating the laser beam to a diameter of 0.5 mφ or less, in particular, because a heat-affected zone can be formed locally and the influence on the surroundings can be reduced.

The Fe-based alloy ribbon according to the present invention is produced by a known single roll method.

It can be manufactured by a manufacturing method such as a centrifugal quenching method or a twin roll method.

The heat treatment is usually performed in an inert gas such as N2 gas or Ar gas, but it may also be performed in the atmosphere.

The alloy ribbon of the present invention can be surface-coated as necessary to improve magnetic properties and corrosion resistance. It is also possible to form an insulating layer on the surface to perform interlayer insulation when laminated or spread.

The alloy of the present invention usually has a thickness of about 5 μfrL to 100 μm, but for sinus frequency applications, a thickness of 25 μm or less is suitable.

Cu and Nb, W, Ta, Zr + H in the present invention
At least one element selected from f, Mo*Ti has the effect of refining crystal grains, and the presence of these elements improves the soft magnetic properties. The desired Cr content is 0.1 to 3 atoms! If L<, less than 0.1 atomic atoms, the effect of reducing core loss due to the addition of Cu is negligible, while if it exceeds 3 atomic atoms, the core loss will be even greater than that without addition. A particularly preferable Cu content is 0.
It should be between 5 and 2 atoms, and within this range the core loss is particularly small. The reason for this is not clear enough, but Cu
Although the addition facilitates crystallization, Nb r Ta rW
* It is believed that due to the simultaneous presence of Zr, Hf + Mo + Ti, etc., it is difficult for crystal grains to grow after crystallization, and many crystal grains are generated, making the crystal grains finer and improving soft magnetic properties. It will be done. Cu and Nb +Ta +
Unless at least one element selected from WtZr, Hf, and Mo+Ti is added, the soft magnetic properties will not be good and the effects of the present invention will hardly be obtained.

Nb owl Ta, Zr, Hf, Mo
At least one pole element selected from TTi must be contained in an amount of 0.1 or more atoms.If the amount is less than this, there will be little effect of addition, and core loss will increase.

〔Example〕

The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example 1゜F@50゜25μm thick Fe73.
5 atom%, Cu j atom%, St 10.5 atom%.

An amorphous alloy ribbon having a composition of 12 atomic % B and 3 atomic % Nb was prepared, the ribbon was cut out, and then heated from room temperature at 530'C1 in a N2 gas atmosphere while applying a magnetic field of 100 e in the longitudinal direction of the ribbon. The temperature was raised at a rate of 5 C/min, and 1
After holding for a period of time, it was cooled to 100° C.1 at a cooling rate of 5° C./min, and then cooled to room temperature 1 at a cooling rate of 20° C./min.

Next, a YAG laser was used to introduce local melting zones onto the free surface of the ribbon after heat treatment, and an experiment was conducted to examine the effect on core loss. The irradiation conditions were a pulse mode with a frequency of 400 Hz and a sweep speed of 10 cm/see.

The direction of the dot row is parallel to the width direction of the ribbon, and the interval between the dot rows is 5.
blasphemed. The size of the spot-like melted area was controlled by the power of the irradiation energy and the beam diameter.

Next, the core loss W 12150 of the ribbon at 50 Hz and Bm 12 KG was measured using a single plate tester.

W 12150 was 0.045 W/kf, which was significantly improved from the value of 0.060 W/1w without laser treatment.

This value is for Fe-based amorphous (Fe, , St, B, ,
) is significantly smaller than the value of the alloy o, osow/kf.

Example 2゜By single roll method') @ 10 wg, thickness 25 μm
An amorphous alloy having the composition shown in Table 1 was prepared.

Next, the ribbon was cut and pasted, and heat treated in an Ar gas atmosphere while applying a magnetic field of 100 e in the longitudinal direction of the ribbon.
Core loss was measured at KHz, Bm 2KG. In addition, as a result of tissue observation using a transmission electron microscope, 5
0% or more were fine crystal grains with a grain size of 5ooX or less.

Next, apply a YAG laser to the free image of this thin strip.

Local strain was introduced by scratching with an electron beam or a diamond needle. The direction in which the local strain was applied was parallel to the width direction of the ribbon, and the interval was 5fi. Next, the core loss 2/100K of this ribbon at 100 KHz and Bm2 KG was measured. The results are shown in the first light.

Table 1 When the manufacturing method of the present invention is applied, it has a remarkable effect on reducing core loss, and is suitable as a magnetic core material for high frequency.

Example 3: F'' with a width of 10 m and a thickness of 40 ttm by the twin roll method.
? ! , 7Cu 0. @ Mo 2 S i +s, s
B, C, Amorphous alloy ribbons were prepared and heat-treated at 520° C. for 1 hour to obtain a microcrystalline structure, and then locally melted using a YAG laser to introduce strain.

Figure 3 shows the angle between the linear strain introduction direction and the ribbon width direction, and 1
The relationship between core loss Wt/100 at 00KHz and 2KG is shown.

The angle between the direction of the linear strain introduction region and the ribbon width direction is 30
In the case where the core loss is low, favorable results can be obtained.

Example 4゜ Fe with a width of 5 m and a baseness of 18 μm by a single roll method. ,.

Create an amorphous alloy ribbon of Cu, st 14 B@Nb4 Zr, and irradiate it with a YAG laser and an electron beam.

By bringing a metal needle or a metal edge close to the surface of the ribbon and applying electricity, a linear or dot array crystallization region was formed. The interval between dots or lines was 511II. Next, the above alloy ribbon was wound to an outer diameter of 19 cm and an inner diameter of 15 m, and Ar
Heat treatment was performed at 570°C for 1 hour in an atmosphere while applying a magnetic field in the longitudinal direction of the ribbon to form microcrystalline grains, and then heated at 100K.
The core loss Wz/100K at Hz and 2KG was determined as −j.

For comparison, core loss when a conventional manufacturing method without forming a crystallized region is also shown.

Table 2 The core loss can be reduced when the manufacturing method of the present invention is applied compared to when it is not applied.

Example 5 Fe 74 Cu 2 S 1 u B consisting of fine crystal grains with a width of 10 mm and a thickness of 15 μm was produced using a single roll method.
After producing a Ta 3 alloy ribbon and cutting out the ribbon, it was heat-treated at 500°C for 1 hour while applying tension in the longitudinal direction of the ribbon, and then cooled to room temperature at a rate of 2°C/mt n.

Next, YAG laser irradiation was performed to form local strain regions in the form of a dot array parallel to the υ width direction. The spacing is 5mm, 90mm, and the core loss of this thin strip is 100KHz and 2KG.
When 00K was measured, a value of 480 fnW/c1d was obtained, and the core loss was significantly reduced compared to the value of 880 mW/ad before laser treatment.

〔Effect of the invention〕

According to the present invention, F
E-based alloy ribbons can be produced, and the effects are remarkable.

4 Wplj4L explanation of the drawings Figures 1 (a), (b), (c) and 2 are diagrams explaining the Fe-based alloy ribbon subjected to the method of the present invention, and Figure 3 is the direction of the linear strain introduction region. The angle formed by the width direction and the core loss W2/
100. FIG.

Figure / Figure (a) (b) (c)
No. 2, Figure 3, Figure I (Angle (°) of width direction in a certain direction) Procedural amendment band 62.10.14 Showa year, month, day 1, case description 1988 Patent Application No. 73718 2 , Name of the invention Method for producing Fe-based alloy ribbon with excellent high frequency magnetic properties 3.
Relationship with the case of the person making the amendment Patent Applicant Office 2-1-2 Marunouchi, Chiyoda-ku, Tokyo, "Claims" column and "Detailed description of the invention" column 5, Content ■: The statement in the "Claims" column of the specification is amended as shown in the attached sheet.

■The column "Detailed Description of the Invention" in the same book is amended as follows.

1. Delete lines 9 to 12 on page 9.

÷ Claim 1, Cu that can form an amorphous state is 0.1 atomic % or more and 3 atomic % or less, Nb, W, Ta, Zr, Hf, Mo
, An alloy mainly composed of Fe containing at least 0.1 atomic % of at least one element selected from Ti is made into a molten state, and then an amorphous alloy ribbon is produced by a liquid quenching method, and then the ribbon is In a method for producing an Fe-based alloy ribbon for a magnetic core material in which at least 50% of the structure is made into fine crystal grains by heat treatment,
Before, during, or after the heat treatment process, the ribbon is locally heated in a dot array or line to form a locally strained region, or A method for producing a Fe-based alloy ribbon having excellent high frequency magnetic properties, which is characterized by forming regions with different amorphous phases and crystal grain structures.

Winter In the method for producing an Fe-based alloy ribbon having excellent high frequency magnetic properties as set forth in claim 1, instead of the local heating in the form of dots or lines, heating is performed in an array of dots on the surface of the ribbon. A method for producing an Fe-based alloy ribbon having excellent high frequency magnetic properties, which is characterized by forming a locally strained region by creating a flaw in the form of a shape or a line.

3. The method for producing a Fe-based alloy ribbon having excellent high frequency magnetic properties as set forth in claim 1 or 1, characterized in that the remainder of the structure of the alloy ribbon is amorphous. A method for producing a Fe-based alloy ribbon having excellent high frequency magnetic properties.

4. In the method for producing an Fe-based alloy ribbon having excellent high frequency magnetic properties as set forth in claim 1 or 2,
A method for producing an Fe-based alloy ribbon having excellent high frequency magnetic properties, characterized in that the structure of the alloy ribbon is substantially composed of fine crystal grains.

5. In the method for producing an Fe-based alloy ribbon having excellent high frequency magnetic properties according to any one of claims 1 to 4, the crystal grains have an average grain size of 500 Å or less. A method for producing a Fe-based alloy ribbon having excellent high frequency magnetic properties.

6. In the method for producing an Fe-based alloy ribbon having excellent high frequency magnetic properties according to any one of claims 1 to 5, the Fe alloy ribbon has the general formula: %) ( However, M is Co and/or Ni, and M' is Nb
.

At least one element selected from the group consisting of W, Ta, Zr, If, Ti, and A0, M' is V, C
r, Mn, 8l.

White metal element, Sc, Y, rare earth element, 8us ZJ
At least one element selected from the group consisting of 5JRo, X is Be, C, Ge, P, Ga, Sb
, 8s, In (both are one type of element, a, x.

y, z, cr, β and T are respectively 0≦a≦
0.3゜0.1≦x≦3. y≦25, 5≦2≦25.0
．． 1≦α≦10.0≦β≦10.0≦T≦20 and work 5
≦y+z+γ≦30.) A method for producing an Fe-based alloy ribbon having excellent high frequency magnetic properties.

7. The method for producing a Fe-based alloy ribbon having excellent high frequency magnetic properties, characterized by including the step of Ti1i in-situ heat treatment.

8. A method for producing a Fe-based alloy ribbon with excellent high frequency magnetic properties as claimed in claim 11, characterized in that the direction of application of the magnetic field during heat treatment in a magnetic field is the longitudinal direction of the ribbon. .

9. The Fe-based alloy ribbon having excellent high frequency magnetic properties according to any one of claims 1 to 8, which includes a step of heat-treating the ribbon while applying tension to the ribbon. manufacturing method.

VO8, Claim 1, characterized in that it forms dot-like or cotton-like locally strained regions whose average angle with the I+1 direction of the ribbon is within 30 degrees, or regions with different crystal grain structures. A method for producing an Fe-based alloy ribbon having excellent high-frequency magnetic properties according to any one of items 1 to 1.

1. A method for producing a Fe-based alloy ribbon having excellent high frequency magnetic properties as claimed in any one of the claims, characterized in that a laser beam or an electron beam is used as means for local heating.

A patent claim characterized in that a metal needle, a metal needle, or a metal edge is brought close to or in contact with the surface of the ribbon, and electricity is applied to locally heat the ribbon to locally apply strain or to form a crystallized region. Range 1, 3, 4, 5, 5.

A method for producing an Fe-based alloy ribbon having excellent high frequency magnetic properties according to any one of Items U, O, O, II, and H.

13. A method for producing a Fe-based alloy ribbon having excellent high frequency magnetic properties as set forth in claim L↓, which comprises irradiating a laser beam focused to 0.5 inφ or less.

Claims (1)

[Claims] 1. 0.1 atomic % or more and 3 atomic % or less of Cu capable of forming an amorphous state, and at least one element selected from Nb, W, Ta, Zr, Hf, Mo, and Ti. An alloy mainly containing Fe containing 0.1 atomic % or more is brought into a molten state, an amorphous alloy ribbon is produced by a liquid quenching method, and then the ribbon is heat-treated to reduce at least 50% of the structure to a fine grain. In the method for manufacturing an Fe-based alloy ribbon for magnetic core material to be used as crystal grains, the ribbon is locally heated in a dot array or a line at least one time before, during, or after the heat treatment step. A method for producing a Fe-based alloy ribbon having excellent high-frequency magnetic properties, characterized by forming a locally strained region or locally forming a region with a different crystal grain structure. 2. 0.1 atomic % to 3 atomic % of Cu capable of forming an amorphous state, and 0.1 atomic % of at least one element selected from Nb, W, Ta, Zr, Hf, Mo, and T. After making the Fe-based alloy containing the above into a molten state, 10^2 ~
After rapidly cooling at a cooling rate of 10^6°C/sec to make at least 50% of the structure into fine crystal grains, the ribbon is locally heated in a dot array or line to remove locally strained regions. A method for producing an Fe-based alloy ribbon having excellent high-frequency magnetic properties, characterized by forming or forming regions with locally different crystal grain structures. 3. In the method for manufacturing an Fe-based alloy ribbon having excellent high-frequency magnetic properties as set forth in claim 1 or 2, instead of the local heating in the form of dots or lines, the surface of the ribbon is A method for producing an Fe-based alloy ribbon having excellent high-frequency magnetic properties, which is characterized by forming locally strained regions by creating dotted or linear flaws in the strip. 4. In the method for producing a Fe-based alloy ribbon with excellent high-frequency magnetic properties as set forth in any one of claims 1 to 3, the remainder of the structure of the alloy ribbon is amorphous. A method for producing a Fe-based alloy ribbon having excellent high-frequency magnetic properties. 5. The method for producing an Fe-based alloy ribbon having excellent high-frequency magnetic properties according to any one of claims 1 to 3, wherein the structure of the alloy ribbon is substantially composed of fine crystal grains. A method for producing a Fe-based alloy ribbon having excellent high-frequency magnetic properties. 6. The method for producing a Fe-based alloy ribbon having excellent high-frequency magnetic properties according to any one of claims 1 to 5, characterized in that the crystal grains have an average grain size of 500 Å or less. A method for producing a Fe-based alloy ribbon having excellent high-frequency magnetic properties. 7. In the method for producing an Fe-based alloy ribbon having excellent high-frequency magnetic properties according to any one of claims 1 to 5, the Fe-based alloy ribbon has the general formula: (Fe_1_-_aMa )_1_0_0_-_x_-_
y_-_z_-_α_-_β_-_γCu_xSi_y
B_zM′_αM″_βX_γ (atomic %) (M is Co and/or Ni, M′ is Nb
, W, Ta, Zr, Hf, Ti and Mo, M″ is V, Cr, Mn,
Al, platinum metal element, Sc, Y, rare earth element, Au, Zn
, Sn, and Re, and X is Be, C, Ge, P, Ga, Sb, As, and I.
At least one element selected from the group consisting of n,
a, x, y, z, α, β and γ are respectively 0≦a≦0
．． 3, 0.1≦x≦3, y≦25, 5≦z≦25, 0.
1≦α≦10, 0≦β≦10, 0≦γ≦20 and 15≦
Satisfies y+z+γ≦30. ) A method for producing a Fe-based alloy ribbon having excellent high-frequency magnetic properties, characterized by having the composition represented by: 8. A method for producing a Fe-based alloy ribbon with excellent high-frequency magnetic properties as set forth in claims 1 to 7, which includes a step of heat treatment in a magnetic field. 9. The method for producing a Fe-based alloy ribbon with excellent high-frequency magnetic properties as set forth in claim 8, wherein the direction of application of the magnetic field during the magnetic field heat treatment is the longitudinal direction of the ribbon. 10. A method for producing an Fe-based alloy ribbon with excellent high frequency magnetic properties as set forth in claims 1 to 9, which includes the step of heat-treating the ribbon while applying tension to the ribbon. . 11.Claims 1 to 1, characterized in that a dot array or linear local strain region or a region with a different crystal grain structure is formed with an average angle of 30 or less with respect to the width direction of the ribbon. 11. A method for producing an Fe-based alloy ribbon having excellent high-frequency magnetic properties according to any one of Item 10. 12. Claim 1, characterized in that a laser beam or an electron beam is used as means for local heating;
Fe-based alloy with excellent high-frequency magnetic properties according to any one of Items 2, 4, 5, 6, 7, 8, 9, 10, and 11 Method for manufacturing thin strips. 13. A patent claim characterized in that either a metal needle or a metal edge is brought close to or in contact with the surface of the ribbon, and electricity is applied to locally heat the ribbon to locally apply strain or to form a crystallized region. Range 1st, 2nd, 4th
Section 5, Section 6, Section 7, Section 8, Section 9, Section 10
A method for producing an Fe-based alloy ribbon having excellent high-frequency magnetic properties according to any one of Items 1 and 11. 14. A method for producing a Fe-based alloy ribbon having excellent high-frequency magnetic properties as claimed in claim 12, characterized in that a laser beam focused to a diameter of 0.5 mm or less is irradiated.