JP3432661B2 - Fe-based amorphous alloy ribbon - Google Patents

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.

[0002]

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

The amorphous alloy ribbon is regarded as a promising industrial material in many applications because of its excellent properties. Among them, as an application of iron core materials such as power transformers and high frequency transformers, Fe-based amorphous alloy ribbons such as FeSiB are used because of their low iron loss, high saturation magnetic flux density and high magnetic permeability. System, etc. are adopted.

When casting an amorphous ribbon of this system, impurities deteriorate iron loss and the like, so that alloy materials in which impurities are suppressed as low as possible have been conventionally used. That is, electrolytic iron was used as the iron source. Impurities that have been specifically suppressed include P and S.
In Japanese Patent No. 947, S is 0.02 wt% or less and P is 0.
It is specified to be 015% by weight or less. In this publication, P is described as an element that deteriorates iron loss, and S is described as an element that promotes brittleness. The composition is 86-9 Fe.
5% by weight, 0 to 11% by weight of Si, 2 to 4% by weight of B,
C is specified to be 0 to 1.5% by weight, and when converted into an atomic% display, Fe is 65.9 to 85.4 atomic% and S is S.
i is 0 to 18.3 atomic%, B is 8.3 to 17.6 atomic%, and C is 0 to 6.1 atomic%.

Further, Japanese Unexamined Patent Publication No. 57-137451 discloses maximum allowable amounts of various impurity elements in the Fe-Si-B type amorphous ribbon, for example, P is 0.00
8 atomic% or less, Mn is 0.12 atomic% or less, S is 0.0
It is specified to be 2 atomic% or less. In this publication, Fe is 7
More than 8.5 atomic% and less than 80 atomic%, Si 5 atomic% or more 1
Since 0 atom% or less and B are regulated to 13 atom% or more and 16 atom% or less, the maximum allowable amount of each impurity element is wt%.
Converted to a display, P is 0.0053% by weight or less, Mn
Is 0.14% by weight or less, and S is 0.0136% by weight or less. In this publication, the impurity element is also an element that deteriorates the characteristics.

Since the allowable value of each impurity amount in the case of producing an amorphous alloy ribbon is considerably small as shown in these publications, it is produced by a usual steelmaking process using iron ore as a raw material. It has been considered difficult to use steel as the iron source for amorphous alloy ribbons. This is because these iron sources contain more impurities than the allowable amount.

[0007]

As described above, conventionally, since the allowable amount of the impurity element was considerably low, it was necessary to use a high-purity iron source such as electrolytic iron. Since the high-purity iron source is expensive, the ribbon alloy cost is high, which has been one of the factors that increase the ribbon manufacturing cost. In order to popularize the ribbon as an industrial material,
The manufacturing cost must be reduced, and therefore, it has been strongly desired to reduce the ribbon alloy cost. Further, conventionally, there are variations in characteristics within one lot, which has been a cause of lowering the yield and increasing the manufacturing cost.

An object of the present invention is to provide an alloy ribbon which exhibits good characteristics even when an inexpensive iron source is used as a ribbon alloy material without using a high-purity iron source such as electrolytic iron. It is to provide a thin strip with improved yield of the strip.

[0009]

In order to reduce the cost of the alloy, for example, a low-grade iron source containing impurities to some extent can be used as the iron source.
This is because, in general, a low-grade iron source is inexpensive, so the alloy cost can be reduced. The present inventors paid particular attention to P, Mn, and S as impurity elements, and conducted experiments using various Fe-Si-B-C alloys having different contents of these impurity elements. As a result, it was found that when a small amount of P is contained, the characteristics of the ribbon are not deteriorated even if other impurities are contained in a larger amount than before. That is, they have come to the knowledge that the amount of impurities can be made larger than ever.

Further, in the component system containing a trace amount of P, Mn, and S, by limiting the amounts of Fe, Si, B, and C to a certain narrow range, iron loss is improved and one lot It has been found that a thin ribbon with little variation in characteristics in the can be stably obtained and the yield is improved. The present invention has been completed through repeated studies based on these findings.

The present invention is as follows. (1) A thin ribbon composed of main elements of Fe, Si, B, and C and impurities, and the composition of the main elements is Fe _a Si _b.
It is represented by B _c C _d and is 0.01 % by weight as an impurity.
7 % or more and 0.1% or less of P, 0.15% or more and 0.5% or less of Mn, and 0.004% or more and 0.05% or less of S are contained.
For single plate measurement with magnetic flux density of 1.3T and frequency of 50Hz
A Fe-based amorphous alloy ribbon having excellent soft magnetic characteristics in alternating current, characterized by having an iron loss of 0.12 W / kg or less . However, a, b, c, and d are atomic%, 80 <a ≦ 82 , 2 ≦ b <5, 14 ≦ c ≦ 16, 0.02 ≦ d ≦ 4, and a + b + c + d = 100. ( 2 ) Magnetic flux density 1.3T, frequency 5 in 1 lot
When the maximum value of the iron loss measured by the single plate at 0 Hz is W _max and the minimum value thereof is W _min , (W _max −W _min ) /
The above (1 ), wherein W _min ≦ 0.15
The Fe-based amorphous alloy ribbon having excellent soft magnetic characteristics under alternating current as described in 1. (3) Fe, Si, B, C main elements and impurities
It is a thin ribbon composed of Fe _a Si _b whose main element composition is
It is represented by B _c C _d and is 0.01% by weight as an impurity.
7% or more and 0.1% or less P, 0.15% or more and 0.5% or less
Lower Mn, containing 0.004% to 0.05% S
However, the magnetic flux density in one lot is 1.3T and the frequency is 50H.
The maximum value of iron loss measured by a single plate at z is W _max , and the minimum value is
Is defined as W _min , (W _max −W _min ) / W
_For soft magnetic characteristics characterized by _min ≤ 0.15
Excellent Fe-based amorphous alloy ribbon. However, a, b, c and
And d are atomic%, 80 <a ≦ 82, 2 ≦ b <5, 14 ≦ c ≦ 16, 0.02 ≦ d ≦ 4, and a + b + c + d = 100.

The present invention will be described in detail below. The feature of the present invention is that P, which has been regarded as an element that deteriorates the characteristics, is
By positively containing 0.017 wt% or more and 0.1 wt% or less, Mn is 0.15 wt% or more and 0.5 wt% or less, and S is 0.004 wt% or more and 0.05
This makes it possible to use an inexpensive iron source containing Mn and S in an amount not less than the conventional permissible amount, such as Wt% or less. Further, when searching for the optimum component range in the system containing these impurities, it was found that Fe was more than 80 atomic% and 82 atomic% or less, and S
i is 2 atomic% or more and less than 5 atomic% and B is 14 atomic% or more and 1
It is possible to improve the iron loss and reduce the variation of the iron loss in one lot and improve the yield of the ribbon by limiting the iron loss to a narrow limited range of 6 atomic% or less.

The function of each element and the proper range of the content will be described. When P is in the range of 0.017 % by weight or more and 0.1% by weight or less, the iron loss W _13/50 (flux density 1.3 T, frequency 50 Hz) measured by a single plate even when the above-mentioned inexpensive raw material is used. Loss of 0.12W
It shows a low value of / kg or less. When the Fe—Si—B type amorphous alloy ribbon is used as an iron core of a power transformer or the like, iron loss is required to be as low as possible _.
Is 0.12 W / kg or less, sufficient characteristics can be exhibited as an amorphous ribbon. On the other hand, if the P content is
If it is less than 0.017 % by weight, the effect of expanding the allowable amounts of the impurity elements Mn and S does not appear, and the iron loss W
_13/50 can not be below 0.12 W / kg a. When the content of P exceeds 0.1% by weight, the effect of increasing the allowable amount of impurities by adding P no longer appears. Therefore, the content of P is limited to 0.017 % by weight or more and 0.1% by weight or less. Furthermore, in order to obtain a large effect of expanding the allowable amount of impurities, the P content is preferably 0.017 % by weight or more and 0.03% by weight or less.

Next, the reasons for limiting the contents of Mn and S will be described. When Mn is contained by more than 0.5% by weight and S by more than 0.05% by weight, the iron loss value of the ribbon is 0 even if P is contained in the range of 0.017 % by weight or more and 0.1% by weight or less. .12 W / kg
You will not be able to: Therefore, Mn is limited to 0.5 wt% or less and S is limited to 0.05 wt% or less. On the other hand, when Mn is less than 0.15% by weight,
When S is less than 0.004% by weight, it is no longer possible to use an inexpensive iron source, and it is necessary to use an expensive and highly pure iron source as in the past.
As a result, alloy cost increases, which is not preferable. Therefore, Mn is 0.15% by weight or more and S is 0.004% by weight.
Limited to the above. Further, the content of the impurity elements of Mn and S is preferably as small as possible within the range limited by the present invention, and Mn is 0.15% by weight or more and 0.3% by weight or less, and S is 0.004% by weight or more. It is preferably 0.02% by weight or less.

Further, while searching for the optimum value in the component system containing impurities, Fe, which is the main constituent element,
Si, B, Wmax when limited to a narrow limited range the content of each element and C, together with the iron loss W _13/50 is below 0.12 W / kg, the maximum value of the iron loss in one lot, the minimum When the value is Wmin, (Wmax-Wmin) / Wmin
It has been found that ≦ 0.15 and a thin strip having uniform properties over the entire length of one lot can be obtained. This is F
It is considered that by limiting the range of each element of e, Si, B, and C, the amorphous forming ability is stabilized, and as a result, a ribbon having a uniform structure over the entire length can be obtained. . If the Fe content is usually 70 atomic% or more, a practical level of saturation magnetic flux density can be obtained as an iron core, but in order to obtain a higher saturation magnetic flux density of 1.6 T or more, Fe is 80 atomic%. Need to be super. On the other hand, if the Fe content exceeds 86 atom%, it becomes difficult to form an amorphous material. However, in order to stably obtain an amorphous material, the Fe content is 8% or less.
It has been found that the content should be 2 atomic% or less. From the above, the Fe content was limited to the range of more than 80 atomic% and 82 atomic% or less.

Si and B are added in order to improve the amorphous forming ability and the thermal stability. If Si is less than 2 atomic% and B is less than 14 atomic%, an amorphous material cannot be stably obtained and (Wmax-Wmin) /Wmin≤0.15 cannot be satisfied. When using an iron source containing impurities as in the present invention, when Si is set to 5 atomic% or more,
It becomes impossible to satisfy (Wmax-Wmin) /Wmin≦0.15. On the other hand, if B exceeds 16 atom%, embrittlement progresses when an iron source containing impurities is used, which is not preferable and the raw material cost increases.
Therefore, Si is 2 atomic% or more and less than 5 atomic% and B is 1
It was limited to a narrow range of 4 atom% or more and 16 atom% or less.

C is an element effective in improving the castability of the ribbon. By containing C, the wettability of the molten metal and the cooling substrate is improved, and a good ribbon can be formed.
When C is less than 0.02 atomic%, this effect cannot be obtained. Further, even if C is contained in an amount of more than 4 atomic%, this effect is not improved. Therefore, C is 0.0
It is limited to 2 at% or more and 4 at% or less.

As described above, in the past, low iron loss could not be obtained unless an expensive high-purity iron source was used.
Low iron loss of W _13/50 ≦ 0.12W / kg be used as the iron source include conventional allowable value or more impurities of the present invention is obtained. Further, by narrowing the contents of Fe, Si, B, and C to a much narrower range than in the past, a thin strip with a stable iron loss of (Wmax-Wmin) /Wmin≤0.15 can be obtained in one lot. It became so. As a result, the alloy cost of the ribbon can be reduced, and further, the improvement of the yield enables the ribbon to be manufactured at a low cost.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION When determining the components of the ribbon of the present invention, first, the contents of Fe, Si, B and C are determined in atomic%, and then P is 0.017 wt%. % Or more and 0.1% by weight or less, Mn is 0.15% by weight or more and 0.5% by weight or less, and S is 0.004% by weight or more and 0.05% by weight or less so as to fall within the range of the present invention. It determines the component specifications of an inexpensive iron source containing the impurities of. For example, the preferable alloy composition of Fe, Si, B, and C is, in atomic%, Fe _bal Si _3.3 B _15.5 C ₁ , Fe.
_bal Si _2.2 B _15.1 C ₁ , etc.

According to the present invention, it is possible to use, for example, some steel types produced in a steelmaking process in which iron ore is a raw material as an iron source of an alloy. Iron sources are not limited to the steel grades produced in this steelmaking process.

The ribbon of the present invention is a method of melting the alloy component of the present invention, jetting the molten metal through a slot nozzle or the like onto a cooling substrate moving at a high speed, and rapidly solidifying the molten metal, for example, a simple method. It can be manufactured by a roll method or a twin roll method. The single roll device includes a centrifugal quenching device that uses the inner wall of the drum, a device that uses an endless type belt,
In addition, a casting machine under reduced pressure or in a vacuum, or in an inert gas, which is an improved type of those equipped with an auxiliary roll or a roll surface temperature control device, is also included. In the present invention, the thickness and width of the thin strip are not particularly limited, but the thickness of the thin strip is preferably 10 μm or more and 100 μm or less. The plate width is preferably 20 mm or more.

[0022]

EXAMPLES The present invention will be further described below with reference to examples. Example 1 An Fe-Si-B-C alloy containing 0.018% by weight of P, 0.21% by weight of Mn, and 0.006% by weight of S was melted in an argon atmosphere and thinned by a single roll method. Cast into a belt. The casting atmosphere is the atmosphere. At this time, as shown in Table 1, the contents of Fe, Si, B, and C were changed, and the relationship between the contents of these elements and the ribbon characteristics was investigated. F
The ratio of e, Si, B and C is Fe + Si + B + C = 10
It is expressed as 0 atom%. The single roll ribbon manufacturing apparatus used comprises a copper alloy cooling roll having a diameter of 580 mm, a high frequency power source for sample melting, a quartz crucible with a slot nozzle at its tip, and the like. In this experiment, length 2
A double slot nozzle having a width of 5 mm and a width of 0.4 mm was used. The slot spacing is 1 mm. The plate thickness of the obtained ribbon was about 50 μm.

The iron loss of the thin ribbon is SST (Single Strip Tes
ter). The measurement conditions are a magnetic flux density of 1.3 T and a frequency of 50 Hz. As the samples for measuring iron loss, thin strips cut from 12 locations to 120 mm length over the entire length of one lot were used, and these thin strips were annealed in a magnetic field at 360 ° C. for 1 hour and subjected to measurement. . The atmosphere during annealing is nitrogen.

The values of Wmax and Wmin and the deviation ((Wmax
The values of -Wmin) / Wmin) are shown in Table 1. Wmax,
Wmin is the maximum and minimum values of iron loss in each lot.

[0025]

[Table 1]

Sample No. 1 in Table 1 As is clear from the results of 1 to 24, P, Mn and S are contained within the range of the present invention, and
e more than 80 atomic% and 82 atomic% or less, Si 2 atomic% or more and less than 5 atomic%, B 14 atomic% or more and 16 atomic% or less, C
Of 0.02 atomic% or more and 4 atomic% or less within the narrow range of the present invention, the magnetic flux density is 1.3 T and the frequency is 50 H.
the iron loss at z is 0.12 W / kg or less, and
(Wmax-Wmin) / Wmin is 0.15 or less, and a ribbon having excellent soft magnetic characteristics is obtained over the entire length of the ribbon. On the other hand, the sample No. In the composition range of the comparative examples shown in Nos. 25 to 34, there is a portion where the iron loss is larger than 0.12 W / kg, and (Wmax-Wmin) / Wmin is also 0.
It becomes larger than 15 or (Wmax-
Even when Wmin) / Wmin was 0.15 or less, embrittlement of the ribbon became large. From the above, it was found that according to the present invention, a lower quality material containing P, Mn, and S than before can be used.

Example 2 Fe, Si, B, and C, which are main constituent elements, are atomic% and F
e _80.2 Si _3.3 B _15.5 C ₁ composition, P, M
Thin strips were cast by the single roll method using alloys containing n and S in various ratios. The apparatus used is the same as that of the first embodiment. However, the slot nozzle is 25m long
A single slot nozzle with m and a width of 0.6 mm was used. The plate thickness of the obtained ribbon was about 35 μm. The method for collecting the measurement pieces and the measurement conditions for evaluating the iron loss of the ribbon are the same as in Example 1. The evaluation results are shown in Table 2.

[0028]

[Table 2]

Sample No. 2 in Table 2 As is clear from the results of 1 to 11 , P is 0.017 wt% or more and 0.1 wt% or less, Mn is 0.15 wt% or more and 0.5 wt% or less, and S is 0.004 wt% or more and 0 or less. When it is within the range of the present invention of 0.05% by weight or less, the magnetic flux density is 1.3 T, the iron loss at a frequency of 50 Hz is 0.12 W / kg or less, and (W
_max- W _min ) / W _min becomes 0.15 or less,
It is possible to obtain a thin ribbon having excellent uniform soft magnetic characteristics over the entire length of the thin ribbon. On the other hand, the sample No. As shown in 12 to 21, when at least one element of P, Mn, and S is out of the range of the present invention, there is a portion where the iron loss becomes larger than 0.12 W / kg. Further, the sample No. 18
In _{~ 21 (W max -W min)} / W min also 0.1
It's bigger than 5.

No. From the results of No. 12 , when there is no impurity, that is, when conventional electrolytic iron is used, 0.12 W is obtained in the narrow composition range of Fe—Si—B—C of the present invention.
Iron loss of less than / kg cannot be obtained. Therefore, it can be seen that the composition range of the present invention is a low iron loss region that appears only when the impurities of P, Mn, and S are present in a predetermined amount. From the above, according to the present invention, a lower quality material containing P, Mn and S than before can be used.

Example 3 A steel strip produced by the steelmaking process was used as an iron source, and a ribbon was produced using the same single-roll ribbon production apparatus and production conditions as in Example 1. The composition of the iron source used is 0.003
3 wt% C, 0.82 wt% Si, 0.0178 wt%
P, 0.21 wt% Mn, 0.006 wt% S, balance F
It is e. The composition of the obtained ribbon is Fe _80.4 Si.
_3.2 0.01% by weight of P, 0.20% by weight of Mn, and 0.005% by weight of S relative to B _15.4 C _1.0 (atomic%). The thickness of the ribbon was about 50 μm.

The maximum value Wmax of the iron loss of the ribbon measured in the same manner as in Example 1 was 0.094 W / kg, the minimum value Wmin was 0.088 W / kg, and (Wmax-Wmin) / Wmi
With n = 0.07, a thin ribbon having excellent soft magnetic properties over the entire length of the thin ribbon was obtained. From the above, it can be seen that according to the present invention, a lower quality material containing P, Mn and S can be used.

[0033]

According to the present invention, it is possible to use a low-grade material for the iron source of the alloy ribbon, and as a result, it is possible to reduce the alloy cost at the time of producing the ribbon and to manufacture an inexpensive ribbon. can do.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-16947 (JP, A) JP-A-9-95760 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C22C 38/00-45/10

Claims (3)

(57) [Claims] 1. A thin ribbon composed of main elements of Fe, Si, B, and C and impurities, and the composition of the main elements is Fe _a S.
i _b is represented by B _c C _d, as an impurity, in weight percent, 0.
017 % or more and 0.1% or less P, 0.15% or more 0.5
% Mn, 0.004% or more and 0.05% or less S, and has a magnetic flux density of 1.3 T and a frequency of 50 Hz.
A Fe-based amorphous alloy ribbon having excellent soft magnetic characteristics in alternating current, characterized in that the iron loss according to a constant value is 0.12 W / kg or less . However, a, b, c, and d are atomic%, 80 <a ≦ 82 , 2 ≦ b <5, 14 ≦ c ≦ 16, 0.02 ≦ d ≦ 4, and a + b + c + d = 100. 2. When W _{max is} the maximum value and W _min is the minimum value of the iron loss measured by a single plate at a magnetic flux density of 1.3 T and a frequency of 50 Hz in one lot, (W _max −
W _min ) / W _min ≦ 0.15, F having excellent soft magnetic characteristics under alternating current according to claim 1.
e-type amorphous alloy ribbon. 3. Main elements and impurities of Fe, Si, B and C
It is a thin ribbon composed of a material and the composition of the main elements is Fe _a S.
i _b B _c C _d , and as impurities, in% by weight, 0.
017% or more and 0.1% or less P, 0.15% or more 0.5
% Or less Mn, 0.004% or more and 0.05% or less S
Containing flux density 1.3T in one lot, the frequency 5
When the maximum value of the iron loss measured by the single plate at 0 Hz is W _max and the minimum value thereof is W _min , (W _max −W _min ) /
Fe-based amorphous alloy ribbon having excellent soft magnetic properties you being a W _min ≦ 0.15. However, a, b, c, and d are atomic%, 80 <a ≦ 82, 2 ≦ b <5, 14 ≦ c ≦ 16, 0.02 ≦ d ≦ 4, and a + b + c + d = 100.