WO2018137270A1

WO2018137270A1 - Iron-based amorphous alloy

Info

Publication number: WO2018137270A1
Application number: PCT/CN2017/075158
Authority: WO
Inventors: 李晓雨; 庞靖; 李庆华; 杨东; 刘红玉
Original assignee: 青岛云路先进材料技术有限公司
Priority date: 2017-01-25
Filing date: 2017-02-28
Publication date: 2018-08-02
Also published as: CN106636984A

Abstract

Disclosed is an iron-based amorphous alloy, FeaSibBcMd, wherein a, b, c and d respectively represent an atomic percentage content of the corresponding component; 81.0≤a≤83.0, 0.5≤b≤4.5, 12.5≤c≤16.0, d≤0.4, and a+b+c+d＝100; and M represents an impurity element. The alloy material has a saturation magnetic induction not less than 1.62 T.

Description

Iron-based amorphous alloy

The present application claims priority to Chinese Patent Application No. JP-A No. No. No. No. No. No. No. No. No. No. No. No. No. .

Technical field

The invention relates to the technical field of soft magnetic materials, in particular to an iron-based amorphous alloy.

Background technique

Iron-based amorphous ribbon is a new type of energy-saving material. It is prepared by rapid quenching and solidification production process. This new material is used in transformer core. Compared with traditional silicon steel transformer, the magnetization process is quite easy, which greatly reduces the no-load of the transformer. loss, if the transformer oil for further reduction CO, SO, NO _x and other harmful gases, known as "green material" 21 century.

At present, in the preparation process of amorphous transformers at home and abroad, iron-based amorphous ribbons with a saturation magnetic induction of about 1.56T are generally used. Compared with the saturation magnetic induction strength of silicon steel close to 2.0T, iron-based amorphous has the disadvantage of increasing volume when preparing a transformer. In order to enhance the competitiveness of iron-based amorphous materials in the transformer industry, it is necessary to develop an iron-based amorphous material having a saturation magnetic induction of more than 1.6T.

The development of amorphous materials with high saturation magnetic induction has been carried out for many years. The most representative is an alloy developed by Allied-Signal of the United States under the brand name Metglas 2605Co. The alloy has a saturation magnetic induction of 1.8T, but the alloy contains 18% of Co. Application in production.

Hitachi Metals, in Chinese Patent Application Publication No. CN1721563A, discloses a Fe-Si-BC alloy of the name HB1 having a saturation magnetic induction strength of 1.64T, but the disclosed process conditions mentions blowing in the preparation process. The process of controlling the C element content distribution on the surface of the strip by C gas, which directly leads to the difficulty in controlling the production process conditions of the product, and the stability of industrial production cannot be guaranteed.

Nippon Steel Corporation announced a Fe-Si-BPC alloy in the patent CN1356403A. Although its saturation magnetic induction intensity reaches 1.75T, its amorphous Fe formation capacity is too high, resulting in its industrial production. The amorphous state is formed, and the magnetic properties of the strip are poor. At the same time, in the patent, the problem of adding P element is not mentioned on the one hand, and the addition content of P element is large on the other hand, combined with the actual situation of the domestic and international ferrophosphorus industry. The preparation conditions of ferrophosphorus are relatively extensive, and the impurity content is too high to be reached. Conditions of use of amorphous alloys. In the preparation process, the extensive use of conventional conditions of ferrophosphorus causes the strip to be crystallized, brittle, and poor in performance after heat treatment. If such alloy composition is used for industrial production, it is necessary to add a step of phosphorus iron refining, on the one hand, increasing the complexity of the process flow, on the other hand, it is necessary to raise the current level of smelting, which makes the industrial production more difficult.

Summary of the invention

The technical problem to be solved by the present invention is to provide an iron-based amorphous alloy. The iron-based amorphous alloy provided by the present application has high saturation magnetic induction strength and amorphous forming ability.

In view of this, the present application provides an iron-based amorphous alloy as shown in formula (I).

Fe _a Si _b B _c M _d (I);

Where a, b, c and d respectively represent the atomic content of the corresponding component; 81.0 ≤ a ≤ 83.0, 0.5 ≤ b ≤ 4.5, 12.5 ≤ c ≤ 16.0, d ≤ 0.4, a + b + c + d = 100 ; M is an impurity element.

Preferably, the iron-based amorphous alloy has a saturation magnetic induction of ≥ 1.62T.

Preferably, the atomic percentage of the Fe is 81.3 ≤ a ≤ 82.8.

Preferably, the atomic percentage of the Fe is 81.5 ≤ a ≤ 82.5.

Preferably, the atomic percentage of the Si is 2.5 ≤ b ≤ 4.2.

Preferably, the atomic percentage of the B is 13.0 ≤ c ≤ 15.5.

Preferably, the atomic percentage of the B is 13.7 ≤ c ≤ 14.7.

Preferably, in the iron-based amorphous alloy, a = 81.5, 2.5 ≤ b ≤ 4.5, and 14.0 ≤ c ≤ 16.0.

Preferably, in the iron-based amorphous alloy, a = 82, 3.0 ≤ b ≤ 4.0, and 14.0 ≤ c ≤ 15.0.

Preferably, in the iron-based amorphous alloy, 82.3 ≤ a ≤ 82.8, 2.5 ≤ b ≤ 4.5, and 13.0 ≤ c ≤ 15.0.

Preferably, the iron-based amorphous alloy having the composition according to the above scheme is prepared into a strip, and then subjected to longitudinal magnetic field heat treatment to obtain a heat-treated strip; the heat treatment temperature is 300-360 ° C, and the heat preservation time is 60 ～. At 120 min, the magnetic field strength is 800 to 1400 m/A.

Preferably, the iron core loss of the heat-treated strip is ≤0.1800 W/kg, the excitation power is ≤0.2200 VA/kg, and the coercive force is ≤4 A/m.

The present application provides an iron-based amorphous alloy represented by the formula Fe _a Si _b B _c M _d , which comprises Fe, Si, B, wherein the Fe element acts as a ferromagnetic element and is the main magnetic of the iron-based amorphous alloy. The source is to ensure the high saturation magnetic induction intensity of the amorphous alloy; Si and B are amorphous forming elements, and the proper amount can ensure the iron-based amorphous alloy has good amorphous forming ability. In the high Fe content range, the present invention uses a low silicon and high boron ratio to make the iron-based amorphous alloy have high saturation magnetic induction and amorphous forming ability.

DRAWINGS

1 is an XRD pattern of an iron-based amorphous alloy having different thicknesses according to an embodiment of the present invention;

Figure 2 is a graph showing the relationship between magnetic properties and heat treatment temperature of an embodiment of the present invention and a comparative example;

Figure 3 is a graph comparing the loss curves of the embodiment of the present invention and the comparative example at 50 Hz.

detailed description

The present invention has been described in detail with reference to the preferred embodiments of the present invention.

The embodiment of the invention discloses an iron-based amorphous alloy as shown in formula (I),

Fe _a Si _b B _c M _d (I);

The iron-based amorphous alloy of the present application has a chemical composition expression of Fe _a Si _b B _c M _d , wherein M is an unavoidable impurity element, wherein the atomic ratios of a, b, and c are respectively: 81.0 ≤ a ≤ 83.0, 0.5 ≤ b ≤ 4.5, 12.5 ≤ c ≤ 16.0; the rest is d, d ≤ 0.4. The invention makes the iron-based amorphous alloy have better comprehensive magnetic properties by adding the above elements and defining the atomic percentage thereof.

Specifically, the Fe element in the iron-based amorphous alloy is a ferromagnetic element, which is a main source of magnetic properties of the iron-based amorphous alloy, and the high Fe content makes the iron-based amorphous alloy have an important guarantee of high saturation magnetic induction strength. The atomic percentage of Fe in the present application is 81.0 to 83.0. In the embodiment, the atomic percentage of Fe is 81.3 to 82.8. More specifically, the atomic percentage of Fe is 81.5 to 82.5. More specifically, the atomic percentage of the Fe is 81.3, 81.45, 81.5, 81.7, 81.85, 82.05, 82.30, 82.42, 82.5, 82.6, 82.65, 82.80 or 82.9. The content of Fe exceeding 83.0 leads to a decrease in the amorphous forming ability of the alloy, an increase in the antegrade difficulty and a production cost, and industrial production is difficult to achieve.

The Si element and the B element as amorphous forming elements are necessary conditions for the alloy system to form amorphous under industrial production conditions. In the present application, the content of Si is 0.5 to 4.5, and in the embodiment, the content of Si is 2.5 to 4.2, and more specifically, the content of Si is 2.75, 2.8, 2.85, 3.02, 3.1, 3.3, 3.5, 3.7, 3.8, 3.95, 4.0, 4.12, 4.2, 4.28, 4.3, 4.45 or 4.5. Si atom A percentage of less than 0.5 results in a decrease in the ability to form amorphous and a decrease in the magnetic properties of the strip. In the present application, the content of B is from 12.5 to 16.0. In a specific embodiment, the content of B is 13.0 ≤ c ≤ 15.5. In a specific embodiment, the content of B is 13.7 ≤ c ≤ 14.7; In a specific embodiment, the content of B is 13.2, 13.3, 13.5, 13.8, 13.9, 14.0, 14.1, 14.2, 14.5, 14.8, 14.9, 15.1, 15.2 or 15.5. When the atomic percentage of B is greater than 16.0, the alloy composition deviates from the eutectic point, and the amorphous forming ability of the alloy is lowered.

M is an impurity element, and the content thereof is of course as low as possible. Therefore, the content of M in the present application is not particularly limited as long as it is ≤ 0.4.

In some embodiments, in the amorphous iron-based alloy, a=81.5, 2.5≤b≤4.5, 14.0≤c≤16.0; in some embodiments, in the iron-based amorphous alloy, a = 82, 3.0 ≤ b ≤ 4.0, 14.0 ≤ c ≤ 15.0; in some embodiments, in the iron-based amorphous alloy, 82.3 ≤ a ≤ 82.8, 2.5 ≤ b ≤ 4.5, 13.0 ≤ c ≤ 15.0 .

Therefore, the composition and content of the iron-based amorphous alloy of the present application form a high-saturation magnetic induction-strength iron-based amorphous alloy from a reasonable combination of improving magnetic induction, improving amorphous forming ability, and reducing preparation difficulty.

The preparation method of the iron-based amorphous alloy described in the present application comprises the following steps:

According to the atomic percentage of the iron-based amorphous alloy of the formula Fe _a Si _b B _c , the raw material after the compounding is smelted, and the melted molten metal is heated and kept warm, and then subjected to single-roll quenching to obtain an iron-based amorphous alloy strip. .

In the process of preparing an iron-based amorphous alloy, the present application employs the technical means conventional in the art to prepare an iron-based amorphous alloy of the specific composition of the present application. For the preparation process thereof regarding the process of compounding and smelting, the specific operation means of the present application are not specifically described. In the smelting process, the smelting temperature is 1300 to 1600 ° C and the time is 80 to 130 min. After the smelting, in the present application, the melted molten metal is heated and maintained, and then subjected to single-roll quenching to obtain an iron-based amorphous alloy strip. The temperature for the temperature rise is preferably from 1,350 to 1,550 ° C, and the time for the heat retention is preferably from 90 to 120 minutes. The single-roll quenching spray belt temperature is 1350~1450 ° C, and the cooling roll linear speed is 20-30 m/s. After a single roll quenching, the present invention obtains an iron-based amorphous alloy strip which is completely amorphous, has a critical thickness of at least 45 μm, and has a good toughness of the strip, and is folded 180 degrees continuously. The amorphous forming ability (GFA) of an alloy refers to the size of an amorphous alloy that can be obtained under certain preparation conditions. The larger the size, the stronger the amorphous forming ability. For amorphous ribbons, the critical thickness is an important indicator for evaluating its amorphous forming ability. Large, amorphous forming ability is stronger. For the purposes of the present invention, the critical thickness is at least 45 μm, which has a considerable margin of preparation for the industrial production of the product, reducing the requirements for cooling equipment during its industrialization. For the application of amorphous strip, ductile and brittleness is an important application index. Because the strip needs to be sheared in the next application, if the strip is brittle, it will lead to more debris during the shearing process. Seriously affect the shaping of the core and the assembly of the transformer. The strip of the invention has good toughness, can be folded 180 degrees continuously, and no fragments are generated during the subsequent shearing process.

The iron-based amorphous alloy strip prepared by the present application has a thickness of 23 to 32 μm and a width of 100 to 300 mm. For amorphous strips, strip thickness is one of the important parameters affecting the core loss, which is also the main factor for amorphous strips superior to silicon steel sheets in terms of no-load loss. The core loss of soft magnetic materials mainly consists of three parts: hysteresis loss, eddy current loss and residual loss. The thickness of the thickness directly affects the eddy current loss. For the magnetic material, eddy current will appear at the magnetic domain wall, and the eddy current will generate a magnetic flux opposite to the magnetic flux generated by the external magnetic field at each moment. The more the reverse action is applied to the inside of the material, the magnetic induction and magnetic field strength are severely uneven along the sample cross section. This is why soft magnetic materials are made into thin strips - reducing the effects of eddy currents. However, for amorphous ribbons, the thinner the better, the thinner the strip will increase the wear of the cutter during the subsequent processing of the core, increasing the number of strips, and thus increasing the cost of the core. Considering the above two aspects comprehensively, the present application prepares an iron-based amorphous alloy strip having a thickness of 23 to 32 μm by the selection of a preparation process. At present, the width of the strip commonly used on the market is 142 mm, 170 mm, 213 mm, and the wider the width of the strip, the more difficult it is to prepare.

The present application heat-treats after obtaining an iron-based amorphous alloy strip having a temperature of 300 to 360 ° C, a holding time of 60 to 120 min, and a magnetic field strength of 800 to 1400 A/m. Influencing factors of magnetic properties of amorphous and nanocrystalline soft magnetic materials In addition to the composition of the alloy itself, the heat treatment process is also a key factor. In general, the annealing process can eliminate the stress of the amorphous magnetic material, reduce the coercive force, increase the magnetic permeability, and obtain excellent magnetic properties. For the iron-based amorphous strip, the heat treatment process mainly includes three parameters: the holding temperature, the holding time and the magnetic field strength. First, the holding temperature must be lower than the crystallization temperature. Once higher than the crystallization temperature, the amorphous ribbon is crystallized and the magnetic properties are drastically deteriorated. The alloy of the present invention has a crystallization temperature of less than 500 °C. Under the premise of lower than the crystallization temperature, the suitable temperature range of insulation is a guarantee for the excellent magnetic properties of the amorphous ribbon. The research of the present application shows that the relationship between the core loss of the strip, the excitation power and the holding temperature of the heat treatment is that as the holding temperature is increased, the two parameters have a tendency to decrease first and then increase, that is, for the present invention, When the holding temperature is less than 300 ° C or greater than 360 At °C, performance deterioration occurs, and acceptable magnetic properties can be obtained between 300 and 360 °C. Secondly, for the holding time, the principle is similar to the holding temperature, and there is a suitable time interval, and the holding time is too short or too long to achieve the optimal performance of the present invention. Finally, a suitable magnetic field strength is a necessary guarantee for the magnetization of the material. The main reason for magnetic field annealing of amorphous materials is that the fixed direction, fixed intensity magnetic field promotes the magnetic domain deflection of the material toward the magnetic field, reduces the magnetic anisotropy of the material, and optimizes the soft magnetic properties. For the present invention, when the magnetic field strength is less than 800 A/m, the magnetization process of the material is incomplete and the best effect cannot be achieved. When the magnetic field strength is >1400 A/m, the material is completely magnetized, and the magnetic properties are not increased due to the magnetic field strength. Large and optimized, it will increase the difficulty and cost of the heat treatment process.

The core loss P ≤ 0.1800 W/kg of the iron-based amorphous ribbon after annealing in the present invention, the excitation power Pe ≤ 0.2200 VA / kg, and the coercive force Hc ≤ 4 A / m. Coercivity is an important indicator for evaluating the properties of soft magnetic materials. The smaller the coercivity, the better the soft magnetic properties. For amorphous strips used in the distribution transformer industry, the parameters for evaluating their magnetic properties mainly include two parameters: core loss and excitation power. The smaller these two parameters, the better the performance of the subsequent core and transformer. Therefore, the iron-based amorphous alloy prepared by the present application can be applied to a core material of a transformer, an engine, and a generator.

In order to further understand the present invention, the iron-based amorphous alloy provided by the present invention and the preparation method thereof will be described in detail below with reference to the examples, and the scope of protection of the present invention is not limited by the following examples.

According to the alloy composition of Fe _a Si _b B _cd M _f , the metal raw material is remelted by using an intermediate frequency smelting furnace (melting temperature is 1300-1600 ° C, holding time is 80-130 min), and the molten steel is discharged to the intermediate frequency after the smelting is completed. Bottom furnace, after heating and sedation (heating to 1350 ~ 1550 ° C, holding 90 ~ 120min), using a single roll quenching (spray temperature of 1350 ~ 1450 ° C, cooling roller line speed of 20 ~ 30m / s) An iron-based amorphous broadband having a width of 142 mm and a thickness of 23 to 28 μm was prepared. Table 1 lists the alloy composition, saturation magnetic induction value (Bs), excitation power (Pe) and core loss (P) of the inventive examples and comparative examples; wherein Examples 1 to 15 are Examples of the present invention, Comparative Example 16, 17 is the comparative example.

Table 1 Magnetic performance data sheets of the examples and comparative examples of the present invention

Remarks: The annular sample is used for heat treatment: inner diameter 50.5mm, outer diameter 52.5～54.5mm, test condition: 1.35T/50Hz. The heat treatment temperature in the present application is 300 to 360 ° C, the holding time is 60 to 120 minutes, and the magnetic field strength is 800 to 1400 A/m.

It can be seen from the above embodiments that the iron-based amorphous alloy of the embodiment of the present invention can obtain a good saturation magnetic induction intensity, and the value is not less than 1.62 T, which exceeds the conventional iron of the conventional magnetic transformer with a saturation magnetic induction of 1.56 T. Amorphous material (Comparative Example 16). The improvement of the saturation magnetic induction strength can further optimize the design of the transformer core, reduce the volume of the transformer, and reduce the cost. Can also be seen from Table 2. It can be seen that the alloy composition according to the example of the present invention has good magnetic properties. Under the condition of 50 Hz and 1.35 T, the excitation power of the iron core after heat treatment is ≤0.2200 VA/kg, and the core loss is ≤0.1800 W/kg. The use requirements were met compared to conventional amorphous materials (Comparative Example 16).

2 is a graph showing the relationship between the magnetic properties and the heat treatment temperature of the exemplary embodiment of the present invention and the comparative example. The curve in FIG. 2(a) is the relationship between the excitation power and the heat treatment temperature of the embodiment 2, and the curve is the embodiment 10. The relationship between the excitation power and the heat treatment temperature, and the curve ▲ is the relationship between the excitation power of Example 15 and the heat treatment temperature.

The curve is the relationship between the excitation power of Comparative Example 16 and the heat treatment temperature. The curve in Fig. 2(b) is the relationship between the core loss and the heat treatment temperature of Example 2, and the curve is the core loss and heat treatment of Example 10. The relationship between the temperature and the ▲ curve is the relationship between the core loss and the heat treatment temperature of Example 15.

The curve is the relationship between the core loss of Comparative Example 16 and the heat treatment temperature; as can be seen from Fig. 2, the alloy of the present invention has stable magnetic properties at a temperature of at least 20 ° C in a wide temperature range, that is, the excitation power (Pe) and The core loss (P) fluctuates within ±0.01. Compared with the conventional 1.56T amorphous ribbon, the optimum heat treatment temperature is at least 20 °C, which can reduce the temperature control requirements of the heat treatment equipment, increase the service life of the heat treatment equipment, and indirectly reduce the cost of the heat treatment process.

3 is a comparison diagram of loss curves of a typical invention example and a comparative example of 50 Hz. The curve in FIG. 3 is the loss curve of the embodiment 2, the curve is the loss curve of the embodiment 10, and the curve is the embodiment 15. Loss curve,

The curve is the iron loss curve of Comparative Example 16; as can be seen from Figure 3, the alloy of the present invention has better performance advantages in comparison with conventional iron-based amorphous materials under higher working magnetic density conditions, that is, the alloy of the present invention. The core and transformer prepared from the iron-based amorphous material prepared by the component can be operated under higher working magnetic density conditions.

The above description of the embodiments is merely to assist in understanding the method of the present invention and its core idea. It should be noted that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention.

The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but It is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

An iron-based amorphous alloy as shown in formula (I),

Fe a Si b B c M d (I);

Where a, b, c and d respectively represent the atomic content of the corresponding component; 81.0 ≤ a ≤ 83.0, 0.5 ≤ b ≤ 4.5, 12.5 ≤ c ≤ 16.0, d ≤ 0.4, a + b + c + d = 100 ; M is an impurity element.
The iron-based amorphous alloy according to claim 1, wherein the iron-based amorphous alloy has a saturation magnetic induction of ≥ 1.62T.
The iron-based amorphous alloy according to claim 1, wherein the atomic percentage of Fe is 81.3 ≤ a ≤ 82.8.
The iron-based amorphous alloy according to claim 1, wherein the atomic percentage of Fe is 81.5 ≤ a ≤ 82.5.
The iron-based amorphous alloy according to claim 1, wherein said Si has an atomic percentage of 2.5 ≤ b ≤ 4.2.
The iron-based amorphous alloy according to claim 1, wherein said B has an atomic percentage of 13.0 ≤ c ≤ 15.5.
The iron-based amorphous alloy according to claim 1, wherein said B has an atomic percentage of 13.7 ≤ c ≤ 14.7.
The iron-based amorphous alloy according to claim 1, wherein in the iron-based amorphous alloy, a = 81.5, 2.5 ≤ b ≤ 4.5, and 14.0 ≤ c ≤ 16.0.
The iron-based amorphous alloy according to claim 1, wherein in the iron-based amorphous alloy, a = 82, 3.0 ≤ b ≤ 4.0, and 14.0 ≤ c ≤ 15.0.
The iron-based amorphous alloy according to claim 1, wherein in the iron-based amorphous alloy, 82.3 ≤ a ≤ 82.8, 2.5 ≤ b ≤ 4.5, and 13.0 ≤ c ≤ 15.0.
The iron-based amorphous alloy according to any one of claims 1 to 10, wherein the iron-based amorphous alloy according to any one of claims 1 to 10 is prepared into a strip, and then a longitudinal magnetic field is applied. The heat treatment is performed to obtain a strip after the heat treatment; the heat treatment temperature is 300 to 360 ° C, the heat retention time is 60 to 120 min, and the magnetic field strength is 800 to 1400 m/A.
The iron-based amorphous alloy according to claim 11, wherein after said heat treatment The core loss of the strip is ≤0.1800W/kg, the excitation power is ≤0.2200VA/kg, and the coercive force is ≤4A/m.