JPH0682576B2 - Method for producing amorphous alloy ribbon with excellent magnetic properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is suitable for use in magnetic cores of power transformers, high-frequency transformers, etc., and is suitable for use in amorphous alloy thin films having excellent magnetic properties, particularly iron loss properties. The present invention relates to a method for manufacturing a belt.

(Prior Art) In recent years, a molten alloy is continuously supplied onto a cooling body whose cooling surface is renewed and moved at a high speed and rapidly solidified, so that an amorphous alloy ribbon can be relatively easily manufactured. became. This amorphous alloy ribbon has excellent properties not only in mechanical properties but also in magnetic properties. In particular, the Fe-based amorphous alloy ribbon has high saturation magnetic flux density and low iron loss. , Is being applied to various iron core materials such as power transformers.

As described above, the amorphous alloy ribbon can obtain a low iron loss if an appropriate component composition is selected, but recently, a material having more excellent iron loss characteristics is required, and therefore, the iron loss is required. Various methods have been proposed for further reducing this.

Many of them reduce eddy current loss by subdividing magnetic domains. For example, in Japanese Patent Laid-Open No. 60-235411, the scratch method in which a linear or point array strain region is introduced by mechanical means. Is proposed.

Further, in JP-A-57-161030 and JP-A-57-161031, in which a magnetic domain is introduced by introducing a linear strain or a heat-affected zone without crystallization of the amorphous alloy ribbon by laser light irradiation. A method of subdividing and reducing iron loss has been proposed.

Furthermore, in JP-A-60-233804 and 61-29103, the beam diameter of the pulsed laser light is reduced to 0.5 mmφ or less,
A method has been proposed in which the surface of an amorphous alloy ribbon is locally and instantaneously melted, and then rapidly solidified to make it amorphous.
It is reported that such a method is effective in reducing iron loss and improving excitation characteristics.

(Problems to be solved by the invention) However, the scratch method using mechanical means is
The amorphous alloy ribbon having a thickness of 40 μm or less tends to deteriorate the iron loss, and therefore cannot be applied to the amorphous alloy having a thickness of 20 to 30 μm as prepared by a normal single roll method.

Although the laser beam irradiation method is effective in improving the magnetic characteristics, unless the laser beam is strictly controlled, it shifts to a low energy region where the laser irradiation is ineffective, the excitation characteristics deteriorate, and crystallization occurs. There is a high possibility that it will shift to the iso-energy region that brings about such problems, and it is difficult to hope for stable operation. Moreover, in addition to the large equipment, there is a drawback that the strip passing speed cannot be made sufficiently high due to restrictions such as the laser power magnitude, the oscillation frequency or the irradiation energy density, and the feed rate of the laser nozzle. It was

The laser light irradiation method is industrially adopted for improving the iron loss of grain-oriented electrical steel sheets. However, when the application to amorphous alloy ribbon is considered, the thickness of the ribbon is electromagnetic steel sheet. Since it is nearly an order of magnitude thinner than the above, from the viewpoint of productivity, it is necessary to increase the strip running speed, and it is also necessary to significantly improve the controllability of the laser light. It was difficult to say that the practicality was sufficient.

The present invention advantageously solves the above-mentioned problems, and an object of the present invention is to propose a method for producing an amorphous alloy ribbon which enables stable reduction of iron loss.

(Means for Solving Problems) As described above, in the method of sweeping a spot such as a laser beam, the strip running speed of the ribbon is restricted,
It is practically advantageous if the magnetically non-uniform portions can be processed linearly or in a dot array over a certain area.

Therefore, the inventors conducted extensive research into batch processing of the magnetically inhomogeneous portions as described above, and found that the plating method was advantageously suitable for achieving the intended purpose. It has been found that in the amorphous alloy ribbon in which the plating bath is locally formed on the surface, the magnetic domains are effectively subdivided and, by extension, excellent iron loss characteristics are exhibited.

The present invention is based on the above findings.

That is, according to the present invention, a metal layer or an alloy layer made of one or more selected from Fe and Ni is formed on the surface of the amorphous magnetic alloy ribbon in a linear or dotted manner by plating. The film thickness is 0.01 to 5 μm, the line width is 0.1 to 2 mm, and the line interval is 2 to 20 mm, and then annealed at a temperature of 300 to 380 ° C. in a magnetic field. It is a method for producing a crystalline alloy ribbon.

(Function) In the present invention, as the amorphous magnetic alloy ribbon, a Fe-based alloy is advantageously suitable, while the alloy or alloy plating layer is
One or two kinds obtained from Fe and Ni.

The preferred component systems of the Fe-based alloy are listed above and are as follows.

・ Fe-Si-B system Fe ₇₈ -Si ₁₂ -B ₁₀ Fe ₈₀ -Si ₇ -B ₁₃・ Fe-Si-BC system Fe ₈₀ -Si ₆ -B ₁₃ -C ₁ On the other hand, for the metal or alloy plating layer, Any material may be used as long as it can introduce a magnetically non-uniform region on the surface of the steel sheet, but the amorphous magnetic alloy ribbon used as the base material in the present invention is subjected to a magnetic field of about 300 to 380 ° C. during the manufacturing process. Since it is necessary to anneal, the melting point of the plated material is preferably 500 ° C. or higher. From this viewpoint, the metal or alloy plating layer is one or two selected from Fe and Ni.
It should be noted that such components can be industrially relatively easily plated by cathodic reduction, and all of them can obtain a certain level of iron loss reducing effect.

The linear or dotted metal or alloy plating layer has a plating film thickness of 0.01 to 5 μm and a plating line width of 0.1 to 2
mm, and the plating line spacing is 2 to 20 mm.

The reason is that if the thickness of the plating layer is less than 0.01 μm, it does not play a sufficient role in subdividing the magnetic domains, and the effect of lowering iron loss is poor, while if it exceeds 5 μm, the space occupied by thin ribbons is occupying. This is because it tends to damage the rate.

If the width of the plated portion exceeds 2 mm, the area of the magnetically non-uniform portion becomes excessively large, which tends to impair iron loss. Therefore, the plating width should be 2 mm or less. However, it is difficult to achieve a line width of less than 0.1 mm stably by electroplating using masking, which will be described later, so the lower limit of the plating width is 0.1 m.
Let m.

Furthermore, if the distance between the linear or point-like plated portions is less than 2 mm, the iron loss tends to be impaired, while if it exceeds 20 mm, it is difficult to realize the iron loss reduction effect by the magnetic domain refinement. To do.

The plating treatment may be either single-sided plating or double-sided plating.

1 (a) to 1 (d) show preferred examples of plating patterns according to the present invention.

FIG. 1 (a) shows a case where a linear plating layer parallel to the width direction of the ribbon is formed. However, in the present invention, the deposition angle of the linear plating layer does not necessarily have to match the width direction of the ribbon, and as shown in FIG. The same effect can be obtained within 30 °.

The figure (c) shows the case where the plating layer indicated by the broken line is formed as in the case of the figure (b).

FIG. 3D shows a case where the plating layer is formed in a dot array.

Next, the manufacturing process of the amorphous alloy ribbon having the plating layer according to the present invention will be described.

FIG. 2 schematically shows a plating apparatus suitable for collectively performing linear or dotted array plating treatment on an amorphous alloy ribbon.

In the figure, numeral 1 is an amorphous alloy ribbon, 2 is an anode, 3 is an electrolytic bath,
4 is a masking screen. In this example, the electrolytic bath immersion portion of the anode 2 is arcuate, and a masking screen is installed so that the amorphous alloy ribbon can pass through the arcuate anode with a uniform gap in the radial direction. The amorphous alloy ribbon is adhered to the back surface of the amorphous alloy ribbon, and a linear or dotted array plating layer is formed while the amorphous alloy ribbon is intermittently threaded.

The masking screen is not limited to the one shown in FIG. 3A, but it is cylindrical 4a as shown in FIG. 2B and is synchronized with the strip of the amorphous alloy ribbon. A rotating mechanism may be used, and such a mechanism may be expected to further improve productivity.

(Example) Example 1 Fe ₈₀ B ₁₃ Si ₇ molten alloy composition, from the nozzle slit, by injection and continuously on the inner water-cooled copper alloy rolls rotating at high speed plate width 50 mm, a thickness of 30μm non A crystalline alloy ribbon was prepared. Next, after degreasing and pickling treatment, FeSO
One-sided Fe plating was performed while flowing N ₂ gas in an electrolytic bath of ₄ · 7H ₂ O 250 g / l, FeCl ₂ · 4H ₂ O 42 g / l, NH ₄ Cl 20 g / l.

This plating treatment was performed using a plating apparatus as shown in FIG. 2 (a) above.

The thickness of the iron plating bath thus obtained is 0.5 μm,
The line width was 0.5 mm, and the line spacing of the plating layer was 5 mm.

Then, it was annealed at 370 ° C. for 1 hour under a magnetic field of 20 Oe in N ₂ gas stream, and cooled as it was.

When the thus obtained iron loss characteristics of the amorphous alloy ribbon was measured by the single plate tester, the iron loss W _13/50 was 0.09 / kg.

In contrast, it was subjected to the same measurements for the amorphous alloy ribbon which is not subjected to a plating treatment, W _13/50 was 0.12 W / kg. That is, according to the present invention, the improvement rate of the iron loss characteristics by plating the amorphous alloy ribbon surface is {(0.
12-0.09) /0.12} × 100 = 25%.

Example 2 An amorphous alloy ribbon having a composition of Fe ₇₈ B ₁₀ Si ₁₂ was produced by the single roll method. The plate width was 100 mm and the plate thickness was 28 μm. Then using a plating apparatus shown in FIG. 2 (a) NiSO ₄ · 6H
₂ O 240 g / l, NiCl ₂ 6H ₂ O 45 g / l, H ₃ BO ₃ 40 g / l in an electrolytic bath
i-plating was applied to both sides of the amorphous alloy ribbon. Here, the thickness of the Ni plating layer is 2 μm, the line width is 1 mm, and the line spacing is 1
It was set to 0 mm. Then, after annealing at 380 ° C. for 1 hour under a magnetic field of 30 Oe, the mixture was cooled.

Thus obtained iron loss W _13/50 of the amorphous alloy ribbon is 0.10W /
It was kg.

On the other hand, when the amorphous alloy ribbon was subjected to the same magnetic field annealing as in Example 2 without performing the plating treatment, the iron loss W
_13/50 was 0.12W / kg. That is, according to the present invention, the improvement rate of the iron loss characteristics by plating the amorphous alloy ribbon surface is {(0.12-0.10) /0.12} × 100 = 16.7%
Met.

Example 3 By the single roll method, Fe ₈₀ B ₁₃ Si ₆ C ₁ composition, plate width 100 mm,
An amorphous alloy ribbon having a plate thickness of 27 μm was produced. Then, using the plating apparatus shown in FIG. 2 (b), FeSO ₄ .7H ₂ O 250 g / l,
Iron plating was applied to one side of the amorphous alloy ribbon in an electrolytic bath of FeCl ₂ .4H ₂ O 42 g / l and NH ₄ Cl ₂₀ g / l. Here, the plating film thickness is 0.
The line width was 0.4 mm and the line interval was 4 mm. Then 2
It was annealed at 360 ° C. for 2 hours in a magnetic field of 0 Oe and then cooled as it was.

The iron loss W _13/50 of the amorphous alloy ribbon thus obtained is 0.08 W /
It was kg.

On the other hand, when the amorphous alloy ribbon which was not subjected to the plating treatment was subjected to the same magnetic field annealing as in Example 3,
Iron loss W _13/50 was 0.12W / kg. That is, the improvement rate of the iron loss characteristics by plating the surface of the amorphous alloy ribbon according to the present invention is {(0.12-0.08) /0.12} × 100 = 33
%Met.

Example 4 NiSO ₄ .6H ₂ O 220 g / g on both sides of the amorphous alloy ribbon of Example 2
Ni, Fe alloy plating was performed in an electrolytic bath of l, FeSO ₄ .7H ₂ O 10 g / l, H ₃ BO _{3 3} g / l. Here, the plating film thickness was 0.3 mm, the line width was 1 μm, and the line interval was 5 mm. Then was annealed in the same manner as in Example 2, the iron loss W _13/50 was 0.09 / kg.

On the other hand, when the amorphous alloy ribbon which was not subjected to the plating treatment was subjected to the same magnetic field annealing as in Example 4,
Iron loss W _13/50 was 0.12W / kg. That is, the improvement rate of the iron loss characteristics by plating the surface of the amorphous alloy ribbon according to the present invention is {(0.12-0.09) /0.12} × 100 = 25
%Met.

(Effects of the Invention) As described above, according to the present invention, the iron loss of the amorphous alloy ribbon can be effectively improved, and therefore, it can be effectively used as a magnetic core of a distribution transformer or the like. Play.

[Brief description of drawings]

FIGS. 1 (a) to 1 (d) are views showing examples of plating patterns in the present invention, and FIGS. 2 (a) and 2 (b) are devices for performing the linear or dotted array plating process of the present invention. FIG. 1 ... Amorphous alloy ribbon, 2 ... Anode 3 ... Electrolytic bath, 4 ... Masking screen

Claims (1)

[Claims] 1. A surface of an amorphous magnetic alloy ribbon is provided with a metal layer or an alloy layer made of one or two selected from Fe and Ni in a linear or dotted manner by plating. Amorphous with excellent magnetic properties, characterized by having a film thickness of 0.01 to 5 μm, a line width of 0.1 to 2 mm and a line spacing of 2 to 20 mm, and then annealing in a magnetic field at a temperature of 300 to 380 ° C. For producing high quality alloy ribbon.