JPH08283919A - Iron-base amorphous alloy foil and its production - Google Patents

Abstract

PURPOSE: To produce an Fe-base amorphous alloy foil improved in magnetic properties by incorporating prescribed amounts of P. CONSTITUTION: This foil is an Fe-base amorphous alloy foil excellent in magnetic properties, having an alloy composition represented by (Fea Sib Bc Cd )100-x Px [where 70<=a<=86, 1<=b<=19, 7<=c<=20, and 0<=d<=4 are satisfied and (x) is 0.003-0.1wt.%] and also having 40-90μm sheet thickness. This Fe-base amorphous alloy foil excellent in magnetic properties can be produced by cooling the alloy while regulating average cooling rate, through the temp. region between the melting point and 400 deg.C, to (1×10<5> to 2×10<5> ) deg.C/sec. By this method, the foil excellent in magnetic properties can be easily produced while obviating the necessity of highly advanced manufacturing technique and complicated equipment, even in the region of large sheet thickness and relatively low cooling velocity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an Fe-based amorphous alloy ribbon used for iron cores of power transformers, high frequency transformers and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Centrifugal quenching method, single roll method, twin roll method, and the like are known as methods for continuously producing ribbons by rapidly cooling an alloy from a molten state. In these methods, molten metal is rapidly jetted from an orifice or the like onto the inner peripheral surface or the outer peripheral surface of a metallic drum rotating at high speed to rapidly solidify the molten metal to produce a ribbon or a wire. Furthermore, by appropriately selecting the alloy composition, an amorphous alloy similar to a liquid metal can be obtained, and a material having excellent magnetic properties or mechanical properties can be manufactured.

[0003] In Fe-Si-B- (C) type amorphous ribbons, trace impurity elements that deteriorate the ribbon characteristics are known, and those impurity elements have been reduced as much as possible in order to avoid characteristic deterioration. The method of making has been taken. The inventors of the present invention have disclosed a method for producing a ribbon in which the contents of S and P are reduced in Japanese Patent Laid-Open No. 59-16947. Here, the allowable amount of S is specified to be 0.02% by weight or less and the allowable amount of P is set to 0.015% or less, and the reason is that S is 0.0 or less.
If the content exceeds 2% by weight, embrittlement and a decrease in amorphous forming ability occur, and if the content of P exceeds 0.015% by weight, iron loss deteriorates. Further, in this publication, it is only described that the cooling rate of the ribbon is 10 ⁵ to 10 ⁶ ° C / sec or more, there is no description of the thickness range of the ribbon, and the thickness of Examples is At 30 μm
There is only an example of thickness.

JP-A-57-185957 discloses that in order to improve the saturation magnetic flux density of the ribbon and reduce the loss, the F
In the e-Si-B-C-P system, P is 1% or more and 10% or more.
An alloy composition characterized by being added below (atomic%) is disclosed. However, other than Al, Sn, Ge, Ti,
The condition is that 5 atomic% or less of one or more elements of Zr, Nb, V, Mo, and W are simultaneously added.

In addition to the above, as well-known conventional P additions, there are Fe-Cr-CP and Fe-Cr-B-types.
In the P system, P is added in an amount of 5 atomic% or more to improve the strength and heat resistance of the ribbon (Japanese Patent Publication No. Sho 58-42261), or in the Fe-B-C-P system, P is set to 7
% -35% (atomic%) in order to increase the magnetic permeability (JP-A-51-73920) and the like are disclosed.

As described above, Fe having a large plate thickness has hitherto been used.
In the -Si-B- (C) -based amorphous alloy, it was not possible to use a low-purity raw material from the recognition that P is harmful. Further, there has been no ribbon and a method for producing the ribbon in which iron loss is improved by containing only P in a trace amount.

[0007]

Problem to be Solved by the Invention Fe-Si-B-
In the amorphous ribbon of (C) type, P is conventionally recognized as a harmful element that deteriorates the characteristics, and reducing P is the only method for preventing the deterioration of the characteristics. However, reducing P as conventionally known increases the material cost. From an industrial point of view, it is desirable that an amorphous alloy ribbon which is inexpensive and has good characteristics can be easily obtained.

The present invention, contrary to the prior art, has a certain amount of P
It is an object of the present invention to provide an Fe-based amorphous alloy ribbon having improved magnetic properties by containing the above and a method for producing the same.

[0009]

SUMMARY OF THE INVENTION The present invention has the following features. A ribbon produced by jetting a molten alloy onto a moving cooling substrate and rapidly solidifying it, having a plate thickness of 40 μm or more and 90 μm or less, a plate width of 20 mm or more, and an alloy composition of (Fe _a Si characterized in that _{b B c C d)} is a _{100-x P} x,, superior Fe-based amorphous alloy ribbons of the magnetic properties. However, a, b, c and d are 70% in atomic%.
≤ a ≤ 86, 1 ≤ b ≤ 19, 7 ≤ c ≤ 20,
0 ≦ d ≦ 4, a + b + c + d = 100, and X is 0.003% by weight or more and 0.1% by weight or less. The Fe-based amorphous alloy ribbon having excellent magnetic properties, wherein the P content is 0.004% by weight or more and 0.03% by weight or less. In a method for producing a ribbon that is rapidly solidified by jetting a molten alloy onto a moving cooling substrate, the composition is (Fe _a S
i _b B _c C _d ) _100-x P _x , the average cooling rate from the melting point to 400 ° C. is 1 × 10 ⁵ ° C./sec or more 2
A method for producing an Fe-based amorphous alloy ribbon having excellent magnetic properties, which comprises cooling at × 10 ⁵ ° C / sec or less. However, a, b, c and d are in atomic%, 70 ≤ a ≤
86, 1 ≤ b ≤ 19, 7 ≤ c ≤ 20, 0 ≤ d
≦ 4, a + b + c + d = 100, and X is
It is 0.003% by weight or more and 0.1% by weight or less. The method for producing an Fe-based amorphous alloy ribbon having excellent magnetic properties, wherein the P content is 0.004% by weight or more and 0.03% by weight or less.

The present invention will be described in detail below. The inventors of the present invention have made various studies on the effect of the P content on iron loss.
It has been found that the iron loss can be reduced by including the element. Furthermore, when the ribbon was manufactured, the ribbon temperature was actually measured and the cooling rate was measured.
The effect of improving iron loss was found by the addition of.

First, the reason for limiting the P content will be described. If the content is less than 0.003% by weight, a sufficient iron loss reduction effect cannot be obtained. Further, even if the content exceeds 0.1% by weight, the effect is not improved. Therefore,
The P content was 0.003% by weight or more and 0.1% by weight or less. In order to obtain a large iron loss reducing effect, the P content is preferably 0.004% by weight or more and 0.03% by weight or less.

Regarding the plate thickness, when the thickness is less than 40 μm or more than 90 μm, the effect of P is not clearly recognized, and the effect of P is obtained only when the plate thickness is 40 μm or more and 90 μm or less. It was Therefore, the thickness range is set to 40 μm or more and 90 μm or less. The width of the ribbon was set to 20 mm or more in consideration of productivity.

As a method of obtaining a thin strip having a large plate thickness, the multiple slit method disclosed by the present inventors in Japanese Patent Laid-Open No. 60-255243 can be used. By this method, a ribbon having a plate thickness of 50 μm or more can be easily obtained.

Next, in Fe _a Si _b B _c D _d ,
The reason for limiting a, b, c and d will be described. a is set to 70% or more and 86% or less (atomic%) on condition that a high saturation magnetic flux density of 1.5 T (tesla) or more is obtained as a practical level. That is, when a is lower than 70%, it is difficult to achieve a saturation magnetic flux density of 1.5 T or higher, while when it is higher than 86%, it becomes difficult to form an amorphous material, resulting in large variations in magnetic characteristics. Because. In order to obtain magnetic properties and ribbon manufacturing stability, a is 7
It is desirable to be 7% or more and 83% or less (atomic%).

Si and B are added to improve the amorphous forming ability and the thermal stability. In the alloy of the present invention, b is 1% or more and 19% or less (atomic%), and c is 7% or more and 20% or less (atomic%). If b is less than 1 atom%, or c is less than 7 atom%, the amorphous phase is not stably formed. On the other hand, if b is more than 19 atom% and c is more than 20 atom%, the raw material cost only increases. No improvement in amorphous forming ability and thermal stability was observed. Therefore, b is 1% or more 1
9% or less (atomic%), c is limited to 7% or more and 20% or less (atomic%).

C is an element effective in improving the productivity of the amorphous ribbon. In the alloy of the present invention, the effect can be obtained even if it does not contain C, but it is desirable to contain C in order to obtain more effect. By containing C, the wettability with Cu or the like, which is often used as a material for the cooling substrate, is improved, and a thin strip with good properties can be formed. When C is contained even in a small amount of about 0.01 atomic%, the wettability with the cooling substrate is improved. However, if it exceeds 4 atomic%, the thermal stability is lowered and the ribbon surface layer is easily crystallized. Therefore, d is 0
The above is specified to be 4 atomic% or less.

The present inventors have found that the effect of reducing iron loss by containing P is closely related to the cooling rate of the ribbon, and arrived at the present invention. In the present invention, the effect of P is obtained only when the average cooling rate from the melting point of the alloy to the ribbon temperature of 400 ° C. is 1 × 10 ⁵ ° C./sec or more and 2 × 10 ⁵ ° C./sec or less. To be Therefore, the range of the cooling rate is set to be not less than 1 × 10 ⁵ ° C / sec and not more than 2 × 10 ⁵ ° C / sec. Here, the lower limit of the range in which the average cooling rate is measured is set to 400 ° C. because the amorphous phase is stabilized by cooling to 400 ° C.

The cooling rate of the ribbon during casting can be measured by, for example, a method using a contact type thermometer disclosed in Japanese Patent Laid-Open No. 59-64114. By using this method, it is possible to determine the average cooling rate of the ribbon between just below the melting point and 400 ° C. Also, the average cooling rate of the ribbon can be obtained by using a radiation thermometer.

[0019]

EXAMPLES The present invention will be further described below based on examples. Example 1 alloy composition _{(Fe 80.5 Si 6.5 B 12 C} 1) 100-x P x
Then, the respective alloys mixed by changing x in the range of 0.003% by weight to 0.1% by weight were produced into a quenched ribbon having a width of 25 mm by the single roll method. The nozzle used is a single slit nozzle (width 0.4 mm, length 25 mm),
A double slit nozzle (width 0.4 mm, length 25 mm, slit interval 1 mm) and a triple slit nozzle (width 0.4 mm, length 25 mm, slit interval 1 mm). The molten metal was jetted from each nozzle onto a cooling roll made of Cu alloy having a diameter of 580 mm rotating at 500 to 800 rpm. The thickness of the obtained ribbon is 25 μm to 95 μm
Is. The ribbon was magnetically annealed at 360 ° C. for 1 hour in a nitrogen atmosphere, and the magnetic properties were measured by SST.

As a comparative example, using alloys containing less than 0.003% by weight and 0.15% by weight of x, ribbons were prepared and heat-treated in the same manner as in the examples, and then the magnetic characteristics were measured.

Table 1 shows the iron loss values at 1.3 T and 50 Hz. As is clear from Table 1, the plate thickness is in the range of 40 μm or more and 90 μm or less, and the P content is 0.00
In the range of 3% by weight or more and 0.1% by weight or less (inside the thick frame),
When viewed at the same plate thickness, an effect of reducing iron loss by 5% or more is obtained as compared with a P content below the analysis limit.
When the P content is in the range of 0.004% by weight or more and 0.03% by weight or less (in the double frame), the iron loss improving effect is further increased, and when viewed at the same plate thickness, the P content is Iron loss is reduced by 10% or more as compared with those below the analysis limit.

[0022]

[Table 1]

Example 2 The composition was (Fe _80.5 Si _6.5 B ₁₂ C ₁ ) _100-x P _x
Then, each alloy mixed with x changed in the range of 0.003% by weight to 0.1% by weight was formed into a quenched ribbon using the single roll method. The nozzle used was a single slit nozzle (width 0.4 mm), a double slit nozzle (width 0.
4 mm, slit spacing 1 mm), and triple slit nozzle (width 0.4 mm, slit spacing 1 mm). The molten metal was jetted from each nozzle onto a cooling roll made of Cu alloy having a diameter of 580 mm rotating at 500 to 800 rpm. At this time, the surface temperature of the ribbon being cast was measured using a contact type thermometer to determine the cooling rate of the ribbon. This ribbon was magnetically annealed at 360 ° C. for 1 hour in a nitrogen atmosphere, and SST
The magnetic characteristics were measured with.

Further, as a comparative example, using an alloy containing less than 0.003% by weight and 0.15% by weight of x, a ribbon was prepared and heat treated in the same manner as in the example, and then the magnetic characteristics were measured.

Table 2 shows the cooling rate and iron loss of the ribbon calculated from the measured values. The cooling rate of the ribbon is the average cooling rate on the surface of the ribbon between just below the melting point and 400 ° C. during casting. The iron loss is a value of 1.3 T and 50 Hz.

As is clear from Table 2, when the cooling rate of the ribbon is 1 × 10 ⁵ ° C / sec or more and 2 × 10 ⁵ ° C / sec or less,
Moreover, the P content is 0.003% by weight or more and 0.1% by weight.
In the following range (inside the thick frame), when viewed at the same cooling rate,
An effect of reducing iron loss by 5% or more is obtained as compared with the case where the P content is less than the analysis limit. P content is 0.00
In the range of 4% by weight or more and 0.03% by weight or less (in the double frame), the effect of improving iron loss is further increased, and when viewed at the same cooling rate, P content is below the analysis limit. Then, the iron loss is reduced by 10% or more.

As is clear from Examples 1 and 2, the present invention reduces iron loss by including a trace amount of P at a specific plate thickness or a specific cooling rate.

[0028]

[Table 2]

[0029]

According to the method of the present invention, even in a region where the plate thickness is large and the cooling rate is relatively small, a ribbon having good magnetic characteristics can be obtained without using a high manufacturing technology or a complicated device.
It can be easily manufactured. The Fe-based amorphous alloy ribbon obtained in the present invention has a large plate thickness and a wide material,
Since it shows good characteristics and can use inexpensive raw materials, it can be industrially used in various applications including iron core materials for power transformers, and the application range can be expanded.

Claims (4)

[Claims] 1. A ribbon produced by jetting a molten alloy onto a moving cooling substrate and rapidly solidifying the molten alloy having a plate thickness of 40.
Fe-based amorphous having excellent magnetic properties, characterized in that the alloy composition is (Fe _a Si _b B _c C _d ) _100-x P _x , having a plate width of 20 μm or more and a plate width of 20 mm or more. Alloy ribbon. However, a, b, c and d are in atomic%, 70 ≤ a ≤ 86, 1 ≤ b ≤ 19, 7 ≤ c ≤ 20, 0 ≤ d ≤ 4, and a + b + c + d = 100, and X is It is 0.003% by weight or more and 0.1% by weight or less. 2. The content of P is 0.004% by weight or more and 0.1.
The Fe-based amorphous alloy ribbon excellent in magnetic properties according to claim 1, which is not more than 03% by weight. 3. A method for producing a rapidly solidified ribbon by jetting a molten alloy onto a moving cooling substrate, wherein an alloy having a composition of (Fe _a Si _b B _c C _d ) _100-x P _x is prepared. , The average cooling rate from the melting point to 400 ° C. is 1 × 10 ⁵
A method for producing an Fe-based amorphous alloy ribbon having excellent magnetic properties, which comprises cooling at a rate of not less than ° C / sec and not more than 2 × 10 ⁵ ° C / sec. However, a, b, c and d are in atomic%, 70 ≤ a ≤ 86, 1 ≤ b ≤ 19, 7 ≤ c ≤ 20, 0 ≤ d ≤ 4, and a + b + c + d = 100, and X is 0. It is 0.003% by weight or more and 0.1% by weight or less. 4. The content of P is 0.004% by weight or more and 0.1.
The method for producing an Fe-based amorphous alloy ribbon having excellent magnetic properties according to claim 3, wherein the content is 03% by weight or less.