JPH11302823A - Manufacture of iron-base amorphous alloy foil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for improving iron loss by forming an extra thin oxide layer on the surface of a foil by carrying out atmosphere control according to the temperature of the foil in the course of casting. SOLUTION: An alloy which has a composition represented by Fea Sib Bc Cd [where the symbols (a), (b), (c), and (d) satisfy, by atomic%, 70<=a<=86, 1<=b<=19, 7<=c<=20, 0.02<=d<=4, and a+b+c+d+100, respectively] is melted, and the resultant molten alloy is sprayed through a slot nozzle onto a moving cooling substrate and rapidly solidified to manufacture an amorphous foil. In this method for manufacturing an amorphous foil, foil tempratures are measured at least at two spots in the longitudinal direction of the foil in the course of casting, and a region of foil where foil temperature is within the temperature range of the whole or a part of 800 to 150 deg.C is held in an atmosphere containing 1 to 30 vol.% oxygen and a region of foil having a temperature outside the above temperature range is held in a nonoxidizing atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Centrifugal quenching, a single roll method, a twin roll method, and the like are known as methods for continuously producing a ribbon or a wire by rapidly cooling an alloy from a molten state. In these methods, a molten metal is ejected from an orifice or the like onto the inner peripheral surface or the outer peripheral surface of a high-speed rotating metal drum, thereby rapidly solidifying the molten metal to produce a ribbon or a wire. Furthermore, by properly 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. This amorphous alloy is regarded as a promising industrial material in many applications because of its excellent properties. Among them, iron core materials such as power transformers and high-frequency transformers are used for low iron loss and high saturation magnetic flux density and high magnetic permeability. -Si-B type is adopted.

Conventionally, the following methods have been disclosed as methods for improving the magnetic properties of an Fe-based amorphous ribbon used for an iron core material by focusing on the ribbon surface layer or surface film.
Thickness 20 to 30 for giving compressive stress in the in-plane direction of the ribbon
In order to form a 0 nm oxide film layer on the surface of the ribbon, a heat treatment is performed in a mixed atmosphere of an inert gas and oxygen (JP-A-61-250162). A method of improving the magnetic permeability by increasing the insulating properties between layers when a toroidal core is formed by applying an oxide film of several tens to 100 nm on the surface of a thin strip by introducing the same (JP-A-6-346219);
When annealing an iron-based amorphous alloy ribbon with an alumina insulating film obtained by baking an aqueous treatment liquid containing colloidal alumina hydrate as a main component, oxygen is introduced into the annealing atmosphere to oxidize Si on the surface of the ribbon. A method for preventing oxidation of B by forming a film and preventing crystallization of the ribbon surface (Japanese Patent Laid-Open No. 4913/1990)
Publication), 5 nm to 1000 nm carbide by ion plating on the surface of the ribbon to improve iron loss,
A method of forming an ultra-thin film of a boride, a silicide, or a nitride (Japanese Patent Application Laid-Open No. 61-246356).
A method of preventing iron loss deterioration by forming an oxide of Ti, Zr, Cr, Al, Si or a nitride of Al, Si on the surface of an amorphous material with a thickness of ~ 3.7 µm No. 150081).

In all of these prior arts, after a ribbon is cast, the surface of the ribbon itself is changed by heat treatment in an oxygen atmosphere, or another material is attached to the ribbon by ion plating or vapor deposition. And requires a new process.

[0005]

As described above, conventionally, in order to modify the surface layer of a Fe-based non-quality ribbon and to provide a surface film thereon, the surface of the amorphous ribbon is processed in a separate step other than the casting step. A process of providing an oxide film, etc. The present invention implements atmosphere control according to the ribbon temperature during casting, so that an ultra-thin oxide layer or at least one of P and S is formed on the ribbon surface without providing an oxide layer in a separate step. Forming a segregation layer and an ultra-thin oxide layer containing
An object of the present invention is to provide a method for improving iron loss of an e-based amorphous alloy ribbon.

[0006]

The gist of the present invention is as follows. (1) An alloy whose composition is represented by FeaSib Bc Cd is melted, and a molten alloy is jetted through a slot nozzle onto a moving cooling substrate to rapidly solidify the alloy to produce an amorphous ribbon. In the method, the ribbon temperature is measured at least at two points in the longitudinal direction of the ribbon during casting, and all or a part of the ribbon portion where the ribbon temperature is within a temperature range of 800 ° C. or less and 150 ° C. or more is 1 vol% or more. A method for producing an Fe-based amorphous alloy ribbon, wherein the ribbon is held in an atmosphere containing 30 vol% or less of oxygen, and a ribbon portion at a temperature outside the temperature range is kept in a non-oxidizing atmosphere.

Wherein a, b, c and d are atomic%,
70 ≦ a ≦ 86, 1 ≦ b ≦ 19, 7 ≦ c ≦ 20, 0.0
2 ≦ d ≦ 4, and a + b + c + d = 100. (2) The thickness of the amorphous alloy ribbon having a thickness of 10 μm or more and 100 μm or less is at least 5 nm or more on at least one surface of the ribbon.
The method for producing an Fe-based amorphous alloy ribbon according to the above (1), wherein an ultrathin oxide layer having a thickness of 0 nm or less is formed.

(3) The composition is (FeaSib Bc Cd)
Was dissolved alloy represented by _100-X M _X, and is ejected through the slot nozzle onto a cooling substrate which is moving the molten alloy, thereby rapidly solidifying the alloy in the process for producing the amorphous ribbon, During casting, the ribbon temperature is measured at least at two places in the longitudinal direction of the ribbon, and all or a part of the ribbon portion whose ribbon temperature is within a temperature range of 800 ° C. or less and 150 ° C. or more is subjected to 1 vol.
A method for producing an Fe-based non-quality alloy ribbon, comprising maintaining the ribbon in an atmosphere containing 1% or more and 30% by volume or less of oxygen and maintaining the ribbon portion at a temperature outside the temperature range in a non-oxidizing atmosphere. .

Wherein a, b, c and d are atomic%,
70 ≦ a ≦ 86, 1 ≦ b ≦ 19, 7 ≦ c ≦ 20, 0.0
2 ≦ d ≦ 4, a + b + c + d = 100, M is at least one of P and S, and 0.0003 ≦ X by weight%.
≦ 0.1. (4) an ultrathin oxide layer on at least one side of the amorphous alloy ribbon having a thickness of 10 μm or more and 100 μm or less,
The method for producing an Fe-based amorphous alloy ribbon according to the above (3), further comprising forming a segregation layer containing at least one of P and S below the oxide layer.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A feature of the present invention is that a liquid quenching method such as a single roll method is used to produce an amorphous alloy ribbon having reduced iron loss by forming an extremely thin oxide layer on the surface of the ribbon. When casting an amorphous alloy ribbon containing Fe-Si-B as a main component using the method, the temperature of the ribbon during casting is measured, and the amount of oxygen in the atmosphere is controlled according to the temperature. . The present inventors have proposed Fe-Si-BC and Fe-Si-B-
When casting C (P, S) -based and amorphous alloy ribbons of unavoidable impurities, the cooling rate of the ribbon, the peeling temperature, the thickness of the ribbon, and the oxygen concentration in the atmosphere are changed to change the thickness of each ribbon. The iron loss of the obi was examined. As a result, various values, such as low and high iron loss, were obtained, but carefully examined the structure of the cast ribbon to clarify why the iron loss changed,
I started by looking for factors that affect iron loss. The analysis methods include the presence or absence of crystallization by X-ray diffraction, measurement of the concentration distribution of each element in the surface layer by GDS (glow discharge emission spectroscopy),
And so on. As a result of investigating a number of ribbons, it was newly found that changing the casting conditions described above changed the thickness of the oxide layer on the amorphous surface. It turns out that there is a relationship.
That is, the thickness of the Fe-Si-BC-based amorphous ribbon is 5 nm on the surface of the ribbon having a thickness of 10 μm or more and 100 μm or less.
When there is an ultrathin oxide layer having a thickness of not less than 20 nm and less, a low iron loss ribbon can be obtained, and an amorphous alloy thin film of Fe-Si-BCM type, wherein M is at least one of P and S, It was found that a low iron loss ribbon can be obtained when there is a segregation layer containing at least one of P and S below the ultra-thin oxide layer on the surface of the ribbon having a thickness of 10 μm or more and 100 μm or less.

Based on the above findings, the present inventors have made intensive studies on how to form an optimum ultrathin oxide layer on the surface of the ribbon with good reproducibility during casting. The oxide layer can also be formed in a heat treatment step after casting, but in the case where the oxide layer has become too thick during casting, in the next heat treatment step,
It is no longer possible to optimize the oxide layer thickness. Therefore, by controlling the formation of the oxide layer in the casting step, an effect of stably obtaining a low iron loss ribbon and improving the yield can be expected.

As a result of the study, it has been found that, in a method of producing an amorphous alloy ribbon by casting a molten alloy through a slot nozzle onto a moving cooling substrate and rapidly solidifying the alloy, the length of the ribbon during casting is reduced. The ribbon temperature is measured at least at two locations in the direction, and 1 vol% is defined as the ribbon portion where the ribbon temperature is within 800% or less and 150 ° C or more in all or part of the temperature range.
It is kept in an atmosphere containing at least 30 vol% of oxygen,
It has been found that by maintaining the ribbon portion at a temperature outside the temperature range in a non-oxidizing atmosphere, a ribbon having a controlled ultrathin oxide layer on the ribbon surface can be obtained. Here, the reason why the ribbon temperature is measured at least at two locations during casting is to accurately predict the ribbon temperature at each ribbon portion during casting. Since the melting point of the alloy is known, if the ribbon temperature is measured at at least two other locations, it is at least 3
Since the temperatures at the three ribbon positions are known, the cooling curve of the ribbon can be accurately drawn. The position where the ribbon temperature is 800 ° C. can be found from the cooling curve thus obtained. When the ribbon temperature is higher than 800 ° C., the oxidation rate is high, and it is difficult to form a uniform ultra-thin oxide layer. The whole or part of the ribbon is 800 ℃ or less15
1 vol% or more 30 in the temperature range of 0 ° C or more
By maintaining the part in an atmosphere containing oxygen of not more than vol%, the ultrathin oxide layer targeted by the present invention can be formed on the surface of the ribbon. The lower limit was set to 150 ° C.
This is because, in a temperature range lower than 150 ° C., the growth rate of the oxide layer becomes slow, so that the thickness of the ultrathin oxide layer hardly increases, and further reduction of iron loss cannot be expected. In order to form a more uniform oxide layer, when all or a part of the ribbon portion is in a temperature range of 600 ° C. or less and 150 ° C. or more, the portion is placed in an atmosphere containing 1 vol% or more and 30 vol% or less of oxygen. And it is preferable to keep the ribbon portion at a temperature outside the temperature range in a non-oxidizing atmosphere.

Regarding the oxygen concentration, if the oxygen concentration is less than 1 vol%, the oxide layer cannot grow to a predetermined thickness.
If the content exceeds vol%, the thickness of the oxide layer becomes uneven depending on the location. Therefore, the oxygen concentration is set in the range of 1 vol% to 30 vol%. In order to form a more uniform oxide layer, it is preferable that the oxygen concentration be 5 vol% or more and 25 vol% or less. Here, as the atmosphere, a mixed gas of oxygen and an inert gas can be used. Under these conditions, a thin ribbon having a thickness of 10 μm or more and 100 μm or less and a composition of Fea
An alloy which is Sib Bc Cd, where a, b, c and d are atomic%, 70 ≦ a ≦ 86, 1 ≦ b ≦ 19, 7 ≦ c
An ultrathin oxide layer having a thickness of 5 nm or more and 20 nm or less can be formed on the surface of the ribbon satisfying ≦ 20, 0.02 ≦ d ≦ 4, and a + b + c + d = 100. By forming an ultra-thin oxide layer having this thickness, the magnetic domains are subdivided, eddy current loss is reduced, and iron loss is improved. The thickness of the oxide layer is 5 nm
When the thickness is thinner, the iron loss reduction effect is not sufficient,
When the thickness is larger than nm, the effect of reducing iron loss is not recognized.

Next, the reasons for limiting the composition will be described. When a ribbon is used for the iron core, the saturation magnetic flux density of the iron core needs to be a high value of 1.5T or more. For this purpose, the content of Fe must be 7
Must be at least 0 atomic%. On the other hand, if the Fe content exceeds 86 atomic%, it becomes difficult to form an amorphous phase, and good ribbon properties cannot be obtained. Therefore, if Fe is 70
It must be at least 86 atomic%. Si and B are for improving the ability to form an amorphous phase and the thermal stability. If Si is less than 1 at% and B is less than 7 at%, amorphous is not formed stably. On the other hand, if Si is more than 19 at% and B is more than 20 at%, the cost of raw materials is only high, No improvement in amorphous forming ability and thermal stability is observed. Therefore, Si is not less than 1 atomic% and not more than 19 atomic%,
B is preferably at least 7 atomic% and at most 20 atomic%. C is an element effective for improving the castability of the ribbon. By containing C, the wettability between the molten metal and the cooling substrate is improved, and a good ribbon can be formed. If less than 0.02 atomic%, this effect cannot be obtained. Further, even if C exceeds 4 atomic%, this effect is not improved. Therefore, C is 0.02
It is preferably at least 4 atomic% but not more than 4 atomic%. In order to further stabilize the magnetic properties, it is preferable that the content of Fe is 77 to 83 atomic%, the content of Si is 2 to 9 atomic%, and the content of B is 11 to 17 atomic%. Further, the alloy used in the present invention may contain, as unavoidable impurities, elements contained in a normal Fe-based non-quality alloy ribbon such as Ti, Al, Sn, Mn, and Cr in addition to the above-described elements. .

[0015] The ribbon thickness is less than 10 µm,
Alternatively, if it exceeds 100 μm, it becomes difficult to perform stable casting, so that it is preferably 10 μm or more and 100 μm or less. More preferably, the thickness is 10 μm or more and 70 μm or less, because the strip casting is more stable. The width of the ribbon is not particularly limited, but is preferably 20 mm or more. We have:
Alloy of composition FeaSib Bc Cd, where a, b,
c and d are atomic%, 70 ≦ a ≦ 86, 1 ≦ b ≦ 1
9, 7 ≦ c ≦ 20, 0.02 ≦ d ≦ 4, a + b + c + d
It has been found that iron loss is further reduced by including at least one of P and S in an amount of 0.0003% or more and 0.1% or less by weight in an amorphous alloy ribbon having a thickness of = 100. P is 0.003% or more and 0.1% or less by weight, S
Is preferably 0.0003% or more and 0.01% or less. The effect of P or S results from the segregation layer of P or S generated between the amorphous ribbon and the ultrathin oxide layer. These segregation layers have the effect of reducing hysteresis loss. In the case of a ribbon having a structure in which at least one segregation layer of P or S is present between the amorphous ribbon and the ultrathin oxide layer, the ultrathin oxide layer has an iron loss improving effect up to a thickness of about 100 nm. Can be contributed to. Even if the thickness is more than 100 nm, no further effect of improving iron loss is observed. Further, the thickness of at least one segregation layer of P or S formed between the non-quality ribbon and the ultrathin oxide layer is preferably 0.2 nm or more, and more preferably the thickness is 0.2 nm to 15 nm.

It should be noted that at least one kind of P or S is contained in a trace amount, for example, 0.003% or less (% by weight).
In the case of the Fe-based non-quality alloy ribbon represented by eaSib Bc Cd, the segregation layer does not exist but cannot be detected even if it exists. The present invention is a method of melting a predetermined alloy component, ejecting the molten metal through a slot nozzle onto a moving cooling substrate, and rapidly cooling and solidifying the alloy, for example, a single-roll method, a twin-roll method. it can. As the single roll device, a centrifugal quenching device using the inner wall of the drum, a device using an endless type belt, and the like can be used. FIGS. 1 and 2 show an apparatus configuration for carrying out the present invention using a single roll method as an example. When the molten alloy 2 melted in the crucible 3 is jetted onto the rotating cooling roll 1 to cast the amorphous ribbon 6, the temperature of the ribbon is adjusted by contact thermocouples 4 and 5.
Online temperature measurement. A radiation thermometer may be used. The ribbon temperature distribution on the cooling roll is estimated using a total of three ribbon temperatures including the melting point of the alloy and two points measured during casting. Although the estimation accuracy of the temperature distribution is improved as the number of the temperature measuring points increases, the handling becomes complicated when the number is too large. Usually, it is sufficient to measure the temperature at about 2 to 4 places. When the casting amount is small and there is no time for obtaining the temperature distribution of the ribbon during casting, the temperature distribution of the ribbon may be obtained by a preliminary experiment. A position where the ribbon temperature is 800 ° C. is determined from the ribbon temperature distribution thus determined, and, for example, a nozzle having a double structure shown in 7 and 8 in FIG. An inert gas such as argon or nitrogen is ejected from the nozzle 7, and an inert gas containing 1 vol% or more and 30 vol% or less oxygen is ejected from the nozzle 8. In this manner, the ribbon portion having a ribbon temperature of 800 ° C. or less and 150 ° C. or more is maintained in an atmosphere containing oxygen of 1 vol% or more and 30 vol% or less, and the ribbon portion having a temperature outside the temperature range is not oxidized. The atmosphere can be made sexual. However, in the case of FIG. 1, although the ribbon temperature range lower than 150 ° C. is exposed to the atmosphere, the oxidation rate is slow in this temperature range, so that even if the temperature is not maintained in the non-oxidizing atmosphere, the oxide layer thickness is hardly affected. do not do.

More surely, all or a part of the ribbon portion within a temperature range of 800 ° C. or less and 150 ° C. or more is 1 vol%
In order to maintain an atmosphere containing oxygen of 30 vol% or less and a ribbon portion at a temperature outside the temperature range in a non-oxidizing atmosphere, for example, the apparatus shown in FIG. 2 is used. In FIG. 2, the inside of the container 9 whose atmosphere can be controlled is set to an inert gas atmosphere such as argon or nitrogen, and 1 vol% or more is passed through the nozzle 10 to a ribbon position in a predetermined temperature range obtained in the same manner as in FIG. An inert gas containing 30 vol% or less of oxygen is jetted. This gas is supplied to the nozzle 11
Through the container. In this manner, the ribbon portion whose ribbon temperature is in the whole or part of the temperature range of 800 ° C. or lower and 150 ° C. or higher is 1 vol% or more and 30 vol% or less.
An inert atmosphere containing the following oxygen can be used. By changing the length 12 of the part that contacts the roll,
It is possible to easily control the temperature range of the ribbon portion held in the oxygen-containing atmosphere. In order to form a more uniform oxide layer, the same method is used when all or a part of the ribbon portion whose ribbon temperature is in a temperature range of 600 ° C. or less and 150 ° C. or more is kept in an oxygen-containing atmosphere. can do.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. (Example 1) An alloy having a composition of Fe _80.5 Si _2.5 B ₁₆ C ₁₉ was passed through a nozzle having a slot width of 0.4 mm and a length of 25 mm.
In the step of jetting onto a copper roll rotating at a peripheral speed of 25 m / sec to obtain an amorphous alloy ribbon having a thickness of 25 μm, the amorphous alloy ribbon is held in an oxygen-containing nitrogen gas atmosphere using the apparatus shown in FIG. The upper and lower limits of the ribbon temperature were controlled. In this experiment, air (20 vol% oxygen + nitrogen) was used as the oxygen-containing nitrogen gas. Since the inside of the container 9 was kept in a nitrogen gas atmosphere, the ribbon was kept in a nitrogen atmosphere outside the above temperature range. For comparison, conventional atmospheric casting was also performed. The thickness of the oxide layer on the free surface (the side not in contact with the roll) of the As-cast ribbon produced under each condition was determined by GDS.
(Glow discharge emission spectroscopy). The magnetic properties of the ribbon were determined by annealing the ribbon in a magnetic field at 360 ° C. for 1 hour in a nitrogen atmosphere, and then performing SST (Single Strip).
(Tester) and evaluated under the conditions of a frequency of 50 Hz and a magnetic flux density of 1.3 T. The thickness of the oxide layer hardly changed before and after annealing. Table 1 shows the results.

[0019]

[Table 1]

From the above results, No. 1 to No. If the upper limit of the ribbon temperature of No. 4 is more than 800 ° C., the oxide layer becomes non-uniform, and excellent iron loss cannot be obtained. Also, N
o. 7 and no. From the comparison of 10, the lower limit of the ribbon temperature is 15
It can be seen that even if the temperature is lower than 0 ° C., no further improvement in iron loss is observed. From the comparison between the oxide layer thickness and iron loss, by controlling the temperature of all or a part of the ribbon in contact with the oxygen-containing gas of the present invention within a temperature range of 800 ° C. or less and 150 ° C. or more, a low iron loss ribbon is obtained. It can be seen that it can be obtained.

Here, No. 3 and No. When No. 7 was compared, the temperature range in which air was exposed was No. 7; No. 3 is No. 3. 7
Oxide layer thickness is N
o. No. 3 is No. 3. The result is thinner than 7. This is presumably because once a non-uniform oxide layer is formed at a high temperature, growth of the entire oxide layer thereafter is hindered. (Embodiment 2) In the process of casting a ribbon using the same alloy and casting method as in Embodiment 1, the temperature of the ribbon is 650 ° C. or less.
The casting was carried out by changing the oxygen concentration of the atmosphere gas in contact with the ribbon portion at 80 ° C. or higher. However, the number of roll rotations and the thickness of the ribbon were also changed by using a multi-slot nozzle.
The evaluation method of the ribbon is the same as that of the first embodiment. Table 2 shows the results.

[0022]

[Table 2]

From the above results, by maintaining the ribbon portion in an atmosphere casting containing 1 vol% to 30 vol% oxygen, an ultrathin oxide layer of 5 nm to 20 nm is formed, and the low iron loss ribbon is formed. It can be seen that it can be obtained. (Example 3) A master alloy having a composition of Fe _80.5 Si _2.5 B ₁₆ C ₁ , and 0.05 wt% of P and 0.
An amorphous ribbon having a thickness of 25 μm was cast using a master alloy to which 005 wt% of S was added. The apparatus used was that shown in FIG. 1, and the partition wall between the nozzles 7 and 8 was arranged so that the ribbon temperature was at a position of 580 ° C. Nozzle 7
By ejecting a nitrogen gas and a nitrogen gas containing 24 vol% oxygen from Nos. 8 and 8, respectively, the ribbon portion at 580 ° C or lower was kept in an oxygen-containing atmosphere, and the ribbon portion at 580 ° C or more was kept in a non-oxidizing atmosphere. . Under the experimental conditions this time, the lower limit temperature of the ribbon held in the nitrogen gas containing 24 vol% oxygen was about 200 ° C. Evaluation of the ribbon is the same as that of the first embodiment. FIG. 3 shows the result of measuring the distribution of each element in the depth direction of the ribbon to which both P and S are added by GDS (sputtering rate: 50 nm / sec). It turns out that the segregation layer of P and S exists between the amorphous alloy ribbon and the oxide layer. However, in FIG. 3, the sensitivity of P is made five times. Table 3 shows the results of iron loss.

[0024]

[Table 3]

From the above results, the production of the amorphous ribbons of the P and S additive components by the method of the present invention results in the formation of an ultrathin oxide layer including their segregated layers, and further low iron loss. It can be seen that a ribbon is obtained.

[0026]

According to the present invention, by controlling the atmosphere according to the temperature of the ribbon during casting, an ultra-thin oxide layer can be formed on the surface of the ribbon without providing an oxide layer in a separate step.
Alternatively, by forming a segregation layer containing at least one of P and S below the ultrathin oxide layer, a Fe-based amorphous alloy ribbon with low iron loss can be manufactured.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of an apparatus for implementing the present invention.

FIG. 2 is a diagram showing an example of another apparatus for carrying out the present invention.

FIG. 3 is a view showing an example (measured by GDS) of an element distribution in a depth direction of a ribbon manufactured according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Cooling roll 2 ... Molten alloy 3 ... Crucible 4 ... Temperature meter (contact type thermocouple etc.) 5 ... Thermometer (contact type thermocouple etc.) 6 ... Thin ribbon 7 ... Non-oxidizing atmosphere gas introduction nozzle 8 ... Oxygen containing Atmosphere gas introduction nozzle 9 ... Container 10 ... Oxygen-containing atmosphere gas introduction nozzle 11 ... Oxygen-containing atmosphere gas discharge nozzle 12 ... Oxygen-containing atmosphere gas flow path guide

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[Procedure amendment]

[Submission date] May 22, 1998

[Procedure amendment 1]

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[Correction target item name] Claim 3

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[Correction target item name] 0005

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[0005]

As described above, conventionally, in order to modify the surface layer of an Fe-based amorphous ribbon and to provide a surface film, the amorphous ribbon must be formed in a separate step other than the casting step. A process of providing an oxide film or the like on the surface has been employed. The present invention implements atmosphere control according to the ribbon temperature during casting, so that an ultra-thin oxide layer or at least one of P and S is formed on the ribbon surface without providing an oxide layer in a separate step. Forming a segregation layer and an ultra-thin oxide layer containing
An object of the present invention is to provide a method for improving iron loss of an e-based amorphous alloy ribbon.

[Procedure amendment 3]

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(3) The composition is (FeaSib Bc Cd)
Was dissolved alloy represented by _100-X M _X, and is ejected through the slot nozzle onto a cooling substrate which is moving the molten alloy, thereby rapidly solidifying the alloy in the process for producing the amorphous ribbon, During casting, the ribbon temperature is measured at least at two places in the longitudinal direction of the ribbon, and all or a part of the ribbon portion whose ribbon temperature is within a temperature range of 800 ° C. or less and 150 ° C. or more is subjected to 1 vol.
Manufacturing an Fe-based amorphous alloy ribbon, wherein the ribbon is maintained in an atmosphere containing 1% or more and 30% by volume or less of oxygen and a ribbon portion at a temperature outside the temperature range is maintained in a non-oxidizing atmosphere. Method.

[Procedure amendment 4]

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Wherein a, b, c and d are atomic%,
70 ≦ a ≦ 86, 1 ≦ b ≦ 19, 7 ≦ c ≦ 20, 0.0
2 ≦ d ≦ 4, a + b + c + d = 100, M is at least one of P and S, and 0.0003 ≦ X by weight%.
≦ 0.1. (4) an ultrathin oxide layer on at least one side of the amorphous alloy ribbon having a thickness of 10 μm or more and 100 μm or less,
The method for producing an Fe-based amorphous alloy ribbon according to the above (3), further comprising forming a segregation layer containing at least one of P and S below the oxide layer.

[Procedure amendment 5]

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[Correction target item name] 0010

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[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A feature of the present invention is that a liquid quenching method such as a single roll method is used to produce an amorphous alloy ribbon having reduced iron loss by forming an extremely thin oxide layer on the surface of the ribbon. When casting an amorphous alloy ribbon containing Fe-Si-B as a main component using the method, the temperature of the ribbon during casting is measured, and the amount of oxygen in the atmosphere is controlled according to the temperature. . The present inventors have proposed Fe-Si-BC and Fe-Si-B-
When casting C (P, S) -based and amorphous alloy ribbons of unavoidable impurities, the cooling rate of the ribbon, the peeling temperature, the thickness of the ribbon, and the oxygen concentration in the atmosphere are changed to change the thickness of each ribbon. The iron loss of the obi was examined. As a result, various values, such as low and high iron loss, were obtained, but carefully examined the structure of the cast ribbon to clarify why the iron loss changed,
I started by looking for factors that affect iron loss. The analysis methods include the presence or absence of crystallization by X-ray diffraction, measurement of the concentration distribution of each element in the surface layer by GDS (glow discharge emission spectroscopy),
And so on. As a result of investigating a number of ribbons, it was newly found that changing the casting conditions described above changed the thickness of the oxide layer on the amorphous surface. It turns out that there is a relationship.
That is, the thickness of the Fe-Si-BC-based amorphous ribbon is 5 nm on the surface of the ribbon having a thickness of 10 μm or more and 100 μm or less.
When there is an ultrathin oxide layer having a thickness of not less than 20 nm, a low iron loss ribbon can be obtained, and an amorphous alloy thin film of Fe-Si-BCM type, wherein M is at least one of P and S, It was found that a low iron loss ribbon can be obtained when there is a segregation layer containing at least one of P and S below the ultra-thin oxide layer on the surface of the ribbon having a thickness of 10 μm or more and 100 μm or less.

[Procedure amendment 6]

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[0015] The ribbon thickness is less than 10 µm,
Alternatively, if it exceeds 100 μm, it becomes difficult to perform stable casting, so that it is preferably 10 μm or more and 100 μm or less. More preferably, the thickness is 10 μm or more and 70 μm or less, because the strip casting is more stable. The width of the ribbon is not particularly limited, but is preferably 20 mm or more. We have:
Alloy of composition FeaSib Bc Cd, where a, b,
c and d are atomic%, 70 ≦ a ≦ 86, 1 ≦ b ≦ 1
9, 7 ≦ c ≦ 20, 0.02 ≦ d ≦ 4, a + b + c + d
It has been found that iron loss can be further reduced by including at least one of P and S in an amount of 0.0003% or more and 0.1% or less by weight in an amorphous alloy ribbon of = 100. P is 0.003% or more and 0.1% or less by weight, S
Is preferably 0.0003% or more and 0.01% or less. The effect of P and S results from the segregation layer of P and S generated between the amorphous ribbon and the ultrathin oxide layer. These segregation layers have the effect of reducing hysteresis loss. In the case of a ribbon having a structure in which at least one segregation layer of P and S is present between the amorphous ribbon and the ultrathin oxide layer, the ultrathin oxide layer has an iron loss improving effect up to a thickness of about 100 nm. Can be contributed to. Even if the thickness is more than 100 nm, no further effect of improving iron loss is observed. The thickness of at least one segregation layer of P and S formed between the amorphous ribbon and the ultrathin oxide layer is preferably 0.2 nm or more, and more preferably the thickness is 0.2 nm to 15 nm. .

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[Correction method] Change

[Correction contents]

According to the present invention, a predetermined alloy component is melted, and the molten metal is jetted onto a moving cooling substrate through a slot nozzle to rapidly cool and solidify the alloy, for example, by a single roll method or a twin roll method. can do. As the single roll device, a centrifugal quenching device using the inner wall of the drum, a device using an endless type belt, and the like can be used. FIGS. 1 and 2 show an apparatus configuration for carrying out the present invention using a single roll method as an example.
When the molten alloy 2 melted by the crucible 3 is jetted onto the rotating cooling roll 1 and the amorphous ribbon 6 is cast, the ribbon temperature is measured online by the contact thermocouples 4 and 5. A radiation thermometer may be used. The ribbon temperature distribution on the cooling roll is estimated using a total of three ribbon temperatures including the melting point of the alloy and two points measured during casting. Although the estimation accuracy of the temperature distribution is improved as the number of the temperature measuring points increases, the handling becomes complicated when the number is too large. Usually, it is sufficient to measure the temperature at about 2 to 4 places. When the casting amount is small and there is no time for obtaining the temperature distribution of the ribbon during casting, the temperature distribution of the ribbon may be obtained by a preliminary experiment. A position where the ribbon temperature is 800 ° C. is determined from the ribbon temperature distribution thus determined, and, for example, a nozzle having a double structure shown in 7 and 8 in FIG. An inert gas such as argon or nitrogen is ejected from the nozzle 7, and 1 vol% or more and 30 vol from the nozzle 8.
An inert gas containing 1% or less of oxygen is jetted. In this manner, the ribbon portion having a ribbon temperature of 800 ° C. or less and 150 ° C. or more is maintained in an atmosphere containing oxygen of 1 vol% or more and 30 vol% or less, and the ribbon portion having a temperature outside the temperature range is not oxidized. The atmosphere can be made sexual. However, in the case of FIG. 1, although the ribbon temperature range lower than 150 ° C. is exposed to the atmosphere, the oxidation rate is slow in this temperature range, so that even if the temperature is not maintained in a non-oxidizing atmosphere, the thickness of the oxide layer is hardly affected. do not do.

Claims (4)

[Claims] 1. An alloy having a composition represented by FeaSib Bc Cd is melted, and a molten alloy is jetted through a slot nozzle onto a moving cooling substrate to rapidly solidify the alloy to form an amorphous ribbon. In the manufacturing method, the ribbon temperature is measured at at least two places in the longitudinal direction of the ribbon during casting, and all or a part of the ribbon portion where the ribbon temperature is within a temperature range of 800 ° C. or less and 150 ° C. or more is 1 vol. % Or more 30vol
%. A method for producing an Fe-based amorphous alloy ribbon, wherein the ribbon is maintained in an atmosphere containing not more than 0.1% of oxygen, and the ribbon portion having a temperature outside the temperature range is maintained in a non-oxidizing atmosphere. However, a, b, c and d are atomic%, 70 ≦ a ≦ 86,
1 ≦ b ≦ 19, 7 ≦ c ≦ 20, 0.02 ≦ d ≦ 4, a +
b + c + d = 100. 2. An amorphous alloy ribbon having a thickness of 10 μm or more and 100 μm or less has a thickness of 5n on at least one surface of the ribbon.
The method for producing an Fe-based amorphous alloy ribbon according to claim 1, wherein an ultrathin oxide layer having a thickness of not less than m and not more than 20 nm is formed. 3. The composition having a composition of (FeaSib Bc Cd) _100-X
It was dissolved alloy represented by M _X, and is ejected through the slot nozzle onto a cooling substrate which is moving the molten alloy, thereby rapidly solidifying the alloy in the process for producing the amorphous ribbon, during casting The ribbon temperature is measured at least at two places in the longitudinal direction of the ribbon, and the whole or a part of the ribbon portion where the ribbon temperature is within a temperature range of 800 ° C. or less and 150 ° C. or more is 1 vol%.
It is kept in an atmosphere containing at least 30 vol% of oxygen,
A method for producing an Fe-based non-quality alloy ribbon, comprising maintaining a ribbon portion at a temperature outside the temperature range in a non-oxidizing atmosphere. However, a, b, c and d are atomic%, and 7
0 ≦ a ≦ 86, 1 ≦ b ≦ 19, 7 ≦ c ≦ 20, 0.02
≦ d ≦ 4, a + b + c + d = 100, M is at least one of P and S, and 0.0003 ≦ X ≦% by weight.
0.1. 4. An amorphous alloy ribbon having a thickness of 10 μm or more and 100 μm or less has an ultrathin oxide layer on at least one surface of the ribbon, and further has at least one of P and S under the oxide layer. The method for producing an Fe-based amorphous alloy ribbon according to claim 3, wherein a segregation layer containing the alloy is formed.