KR102371572B1 - A method of manufacturing the cube-on-face texture using diffusion and an electrical steel sheet produced thereby - Google Patents

Abstract

The present invention relates to a method for manufacturing a cube-on-face texture using diffusion and an electrical steel sheet manufactured thereby. To this end, there is provided a heat treatment step in which a metal plate composed of iron (Fe) or an iron-based alloy in contact with silicon (Si) or a silicon compound on a plane perpendicular to a normal direction (ND) is thermally treated in an ideal region where austenite (γ) and ferrite (α) are mixed or in a region where the austenite (γ) phase is stable. According to this, a very high Si fraction can be secured by a simple method, and at the same time, texture having a {100} plane on the surface can be produced with a very high fraction.

Description

A method of manufacturing the cube-on-face texture using diffusion and an electrical steel sheet produced thereby}

The present invention relates to a method for manufacturing a cube-on-face texture using diffusion and an electrical steel sheet manufactured through the same.

Electrical steel sheet is mainly used in electrical equipment such as motors and transformers, unlike other metal materials used for structural steel, tools, and exterior plates, and plays a role in increasing efficiency. In particular, in order to manufacture high-efficiency motors or high-efficiency transformers, it is essential to manufacture electrical steel sheets with high magnetic flux density and minimal iron loss.

The electrical steel sheet is divided into a grain-oriented electrical steel sheet used in stationary machines such as a transformer and a non-oriented electrical steel sheet used in a rotating machine such as a motor.

The grain-oriented electrical steel sheet is an electrical steel sheet including a Goss texture. Goss Texture is a {110}<001> texture ({110}<001> texture) having a {100} plane parallel to the rolling direction and a <001> magnetic direction parallel to the rolling direction. means to be Grain-oriented electrical steel sheet manufacturing process is generally hot rolling, preliminary annealing (a process of improving magnetic properties by removing rust formed on the surface of hot rolled material through a scale breaker and hydrochloric acid tank and improving cold rolling properties through heat treatment), cold rolling ( In order to secure the thickness and material suitable for the application, the process is carried out at a normal reduction ratio of 40% to 90%), decarburization annealing (a process in which carbon is removed from the material and MgO coating is carried out), high temperature annealing, flattening annealing, insulation coating stage (electrical In order to improve workability and minimize eddy current loss proportional to the thickness of the steel sheet when processing and laminating the steel sheet and using it as an iron core), an insulating coating solution is applied to the top and bottom of the steel sheet). An electrical steel sheet including a cube-on-face texture can also be used as a grain-oriented electrical steel sheet in special cases.

Non-oriented electrical steel sheet (Non-oriented) is an electrical steel sheet including a cube-on-face texture (Cube-on-face texture) or a random texture (Random texture). The cube-on-face texture has a {100} plane parallel to a plane perpendicular to the ND and has a uniform distribution of {100} in the rotational direction. That is, the cube-on-face texture is a texture in which the magnetic direction parallel to the normal direction of the grain <100> direction, and the {100} plane, which is easy to magnetize for RD, TD, is uniformly distributed ({100}<0vw> texture) This means that it is formed. The random texture means that a texture having a magnetic direction in a random direction with respect to RD, ND, and TD is formed. In general, the non-oriented electrical steel sheet manufacturing process may include hot rolling, preliminary annealing, cold rolling, final annealing, and insulating coating steps.

However, in the conventional method, the plane perpendicular to the ND (Normal Direction) of the electrical steel sheet is parallel to the {100} plane of the crystal grains of the electrical steel sheet, and the direction of the crystal grains is RD (Rolling Direction) and TD (Transverse Direction). It is very difficult to make a random cube-on-face texture, and there is a problem that most of the random textures are generated. Korean Patent Publication No. 10-2017-0072278 of JFE Steel, Korean Patent No. 10-1722702 of POSCO Co., Ltd., and Korean Patent No. 10-0797895 such as Seong Jin-kyung, which are existing prior documents, also show that non-oriented electrical steel sheet with low iron loss and excellent magnetism is manufactured. Although it has a purpose, in the manufacturing method in the prior literature, only the differences with respect to the type and composition ratio of the components contained in the steel sheet are presented, and the manufacturing method for increasing the generation rate of the cube-on-face texture is not disclosed. .

Also, in Tomida (1995), austenite (γ) phase transformation from austenite (γ) to ferrite (α) occurs on the surface of the electrical steel sheet by vaporizing Mn at a stable high temperature and 10 ^-3 Pa level in a high vacuum atmosphere. Although it is suggested that a rotated cube texture with {100} clustered on one side is generated, it is different from the formation of a cube-on-face texture having a {100} plane parallel to the plane perpendicular to the ND. It was very difficult to apply to the mass production process of electrical steel sheet because the distance was long and long-term heat treatment in high vacuum and high temperature was required.

Also, J.K. Sung (2011) suggests the formation of a {100}<0vw> cube-on-face texture as the phase transformation from austenite (γ) to ferrite (α) occurs by continuous cooling, but There was a problem limited to the composition of pure iron and Fe-1wt%Si and it was very difficult to apply it to the mass production process of electrical steel sheet because heat treatment at high temperature was required for a long time.

Also, Y.K. In Ahn (2020), when the phase transformation from austenite (γ) to ferrite (α) occurs by continuous cooling, stress is applied to the surface of the electrical steel sheet to reduce the nucleation barrier on the surface and induce surface nucleation. Although the formation of a {100}<0vw> cube-on-face texture by The formation of a tissue (cube-on-face texture) was suggested, and there was a problem in that no results of more than 2 wt% Si were presented.

As described above, in the existing prior literature, the non-oriented electrical steel sheet generates a texture by causing surface nucleation by generating a phase transformation from austenite (γ) to ferrite (α) through heat treatment in a fixed composition, high vacuum Phase transformation from austenite (γ) to ferrite (α) occurs through Mn vaporizing in the state of being austenite (γ) to ferrite (α) by generating a textured structure by causing surface nucleation or by heat treatment It is suggested to create a cube-on-face texture by using a method of generating a texture by causing surface nucleation through the application of stress in the An efficient electrical steel sheet manufacturing method in which the fraction of cube-on-face texture having parallel {100} planes is improved while the Si fraction is improved to exceed 2 wt% has not been proposed.

Korean Patent Laid-Open Patent No. 10-2017-0072278, Non-oriented electrical steel sheet and manufacturing method of non-oriented electrical steel sheet, JFE Steel Republic of Korea Patent Registration 10-1722702, Non-oriented electrical steel sheet and its manufacturing method, POSCO Co., Ltd. Republic of Korea Patent 10-0797895, surface (100) surface forming method, manufacturing method of non-oriented electrical steel sheet using the same and non-oriented electrical steel sheet manufactured using the same, Jinkyung Sung, Cube Steel Co., Ltd., Jiyoon Sung, Hyunmin Sung

Toshiro Tomida, Takashi Tanaka, Developmentof (100) Texture in Silicon Steel Sheets by Removal of Manganeseand Decarbunzatron, ISIJ International. Vol. 35 (1995). No. 5, pp. 548-556 J.K. Sung, D.N. Lee, D. H. Wang and Y. M. Koo, Efficient Generation of Cube-on-Face Crystallographic Texture in Iron and its Alloys, ISIJ Int. 51 (2011) 284-290. Yong-Keun Ahn, Soo-Bin Kwon, Yong-Kwon Jeong, Ji-Ung Cho, Tae-Young Kim, Nong-Moon Hwang. Fabrication of cube-on-face textured Fe-1wt%Si and Fe-2wt%Si-1wt%Ni electrical steel using surface nucleation during γ→α phase transformation. Materials Characterization 170 (2020), 110724.

An object of the present invention relates to a novel approach to surface nucleation through phase transformation, wherein the fraction of cube-on-face texture having a {100} plane parallel to a plane perpendicular to ND is {100}<0vw> cube-on-face texture manufacturing method using diffusion of a ferrite stabilizing element at a temperature at which austenite (γ) is stable, and at the same time the Si fraction is improved to more than 2wt%Si It is to provide an electric steel sheet.

Hereinafter, specific means for achieving the object of the present invention will be described.

It is an object of the present invention, for a metal plate composed of iron (Fe) or an iron-based alloy, the ND ( A heat treatment step of heat treatment by contacting silicon (Si) or a silicon compound on a surface perpendicular to the Normal Direction); including, wherein the silicon particles of the silicon or the silicon compound in contact with the metal plate are diffused to at least a part of the surface, and the at least part of the surface is austenite (γ) by the silicon particles diffused into the metal plate. ) to ferrite (α), the cube-on-face texture having a {100} plane parallel to the plane is formed, characterized in that the cube-on-face texture production using diffusion This can be achieved by providing a method.

In addition, the silicon or the silicon compound in contact with the metal plate may be characterized in that it comprises at least one of a silicon wafer, a silane-based gas, and silicon chloride.

In addition, the specific element in contact with the metal plate may be characterized in that it means silicon (Si).

In addition, the specific element in contact with the metal plate may include a silicon wafer, and the compound may include at least one of a silane-based gas and silicon chloride.

In addition, the cube-on-face texture formed may be characterized in that the 50% or more fraction on the surface of the metal plate material.

In addition, the cube-on-face texture formed may be characterized in that the fraction of 35% or more on the surface of the metal plate material.

In addition, the formed cube-on-face texture may be characterized in that it has a {100} plane parallel to the plane within an error range of ±15 degrees or less.

In addition, the specific element in contact with the metal plate may be characterized in that it includes at least one of ferrite (ferrite) stabilizing element.

Another object of the present invention, austenite (γ) and ferrite (α) is a metal plate composed of iron (Fe) or iron-based alloy in contact with silicon (Si) or a silicon compound on a surface perpendicular to ND (Normal Direction) a heat treatment step of heat-treating in a mixed abnormal region or in a region in which the austenite (γ) phase is stable; including, wherein the silicon particles of the silicon or the silicon compound in contact with the metal plate are diffused to at least a part of the surface, and the at least part of the surface is austenite (γ) by the silicon particles diffused into the metal plate. ) to ferrite (α), the cube-on-face texture having a {100} plane parallel to the plane is formed, characterized in that the cube-on-face texture production using diffusion This can be achieved by providing a method.

Another object of the present invention, austenite (γ) and ferrite (α) is a metal plate composed of iron (Fe) or iron-based alloy in contact with silicon (Si) or a silicon compound on a surface perpendicular to ND (Normal Direction) Non-directional electricity manufactured so that a cube-on-face texture having a {100} plane parallel to the plane is formed by heat treatment in a mixed abnormal region or a region in which the austenite (γ) phase is stable It can be achieved by providing a steel plate.

Another object of the present invention is the ND of the metal plate in an ideal region in which austenite (γ) and ferrite (α) are mixed or in a region in which the austenite (γ) phase is stable for a metal plate composed of iron (Fe) or an iron-based alloy (Normal Direction) is heat-treated by contacting silicon (Si) or a silicon compound on a surface perpendicular to the surface, so that a cube-on-face texture having a {100} surface parallel to the surface is formed This can be achieved by providing a non-oriented electrical steel sheet.

In addition, the contact of the specific element or the compound of the specific element may be characterized by vapor deposition or coating.

In addition, the contact of the specific element or the compound of the specific element is made before the heat treatment step, and the heat treatment in the heat treatment step may be characterized by batch annealing.

As described above, according to the present invention, there are the following effects.

First, according to the cube-on-face texture and electrical steel sheet manufacturing method according to an embodiment of the present invention, a very high Si fraction can be secured by a simple method, and at the same time, the texture having a {100} plane on the surface is reduced to a very high fraction. There are effects that can be created. Prior documents such as Patent Document 0003 suggest that a cube-on-face texture is formed only in pure Fe or Fe-1wt%Si composition. According to the method of the prior literature, it is difficult to manufacture a non-oriented electrical steel sheet having a high fraction of Si while including a cube-on-face texture of a high fraction.

Second, according to the cube-on-face texture and the electrical steel sheet manufacturing method according to an embodiment of the present invention, the magnetic direction diversity of the texture having the {100} plane parallel to the ND of the metal plate can be secured. It works.

Third, according to the cube-on-face texture and the method for manufacturing an electrical steel sheet according to an embodiment of the present invention, it is possible to manufacture a oriented/non-oriented electrical steel sheet with excellent magnetic properties in a state in which restrictions on atmosphere control are significantly reduced. It has the effect of being easy to apply to the mass production line of non-oriented electrical steel sheet.

Fourth, according to the method for manufacturing a cube-on-face texture and an electrical steel sheet according to an embodiment of the present invention, there is an effect of being able to generate a cube-on-face texture of a very high fraction only by heat treatment in a relatively short period of time.

Fifth, according to the method for manufacturing a cube-on-face texture using diffusion according to an embodiment of the present invention, since a deposition process or a coating process can be applied and the heat treatment time can be configured to be relatively short, continuous for mass production of electrical steel sheet There is an effect that can be applied to the process.

Sixth, according to the method for manufacturing a cube-on-face texture using diffusion according to an embodiment of the present invention, batch annealing can be applied and heat treatment even in a narrow space compared to continuous annealing heat treatment when mass-producing electrical steel sheets including a cube-on-face texture possible, resulting in a reduction in facility investment cost.

The following drawings attached to this specification illustrate preferred embodiments of the present invention, and serve to further understand the technical spirit of the present invention together with the detailed description of the present invention, so the present invention is limited only to the matters described in such drawings should not be interpreted as
1 is a flow chart showing a cube-on-face texture manufacturing method using diffusion;
2 is a graph showing the phase balance of iron (Fe) according to temperature and pressure (Fe phase diagram, Baohua Zhang, AIP Advances 4, 017128 (2014)),
3 is a schematic diagram illustrating performing a heat treatment step (S10) in a state in which a silicon wafer is in contact with at least one surface of a metal plate according to an embodiment of the present invention;
4 is a schematic diagram showing that the heat treatment step (S10) is performed while silicon is deposited on a metal plate according to an embodiment of the present invention;
5 is a schematic diagram showing a silicon diffusion step according to an embodiment of the present invention;
6 is a schematic diagram and a photograph showing the specimen of Example 1;
7 is a graph showing the heat treatment of Example 1;
8 is an EBSD result of Example 1;
9 is an XRF analysis result of Example 1;
10 is a schematic diagram showing the loading of the metal plate specimen and the silicon wafer of Example 2;
11 is a graph showing the heat treatment step of Example 2;
12 is a photograph showing a metal plate specimen and a silicon wafer after the heat treatment of Example 2;
13 and 14 are EBSD results of Example 2,
15 is a cross section (IQ map) analysis result of Example 2;
16 is a cross section (IPF map) analysis result of Example 2;
17 is a cross section (Line EDS) analysis result of Example 2,
18 is an EBSD result of a metal plate specimen after the heat treatment step (S10) of Example 3;
19 is an EBSD result of a metal plate specimen after the silicon diffusion step (S20) and the phase transformation step (S30) of Example 3;
20 is an EBSD result of a metal plate specimen after the phase transformation step (S30) of Example 4;
21, 22, and 23 are EBSD results after the heat treatment step (S10) of the metal plate specimen of 1.00 wt% Si of Comparative Example 1,
24, 25 and 26 are EBSD results after the heat treatment step (S10) of the metal plate specimen of 2.00 wt% Si of Comparative Example 1,
27 is an EBSD result after the phase transformation from the γ phase to the α phase by a change in temperature through heat treatment on the 1.00 wt% Si metal plate specimen of Comparative Example 2;
28 is a vapor deposition (Vapor Deposition) method on a metal plate specimen of 1.00 wt% Si in the α-phase region of Comparative Example 3, at least one surface of the plane perpendicular to the ND (Normal Direction) of the metal plate in contact with silicon particles. Showing the EBSD results after silicon diffusion as a method of
29 is a graph showing DSC analysis of Fe-1wt%Si;
30 is a view showing the component analysis results of a metal plate specimen of an example of Si diffusion by temperature;
31, 32, and 33 show the EBSD results of Si diffusion examples by temperature;
34 is a photograph showing after heat treatment at 900° C. for 2 hours of a metal plate specimen of 1.00 wt% Si of Comparative Example in α phase;
35 shows the EBSD results of a comparative example on α;
Figure 36 shows the Si wt% of the comparative example in the α phase,
37 depicts the EBSD analysis of the cube on face upper bound tissue fraction example.
38 is a schematic diagram illustrating a continuous process using a deposition process of a cube-on-face texture manufacturing method using diffusion according to an embodiment of the present invention;
39 is a schematic diagram showing a continuous process (continuous process using a coating process) without using a deposition process of the cube-on-face texture manufacturing method using diffusion according to an embodiment of the present invention;
40 is a schematic diagram illustrating a continuous process using diffusion after deposition (or coating) of a method for manufacturing a cube-on-face texture using diffusion according to an embodiment of the present invention;
41 is a schematic diagram illustrating a batch process using batch annealing in a method for manufacturing a cube-on-face texture using diffusion according to an embodiment of the present invention.

Hereinafter, embodiments in which those skilled in the art can easily practice the present invention will be described in detail with reference to the accompanying drawings. However, in the detailed description of the operating principle of the preferred embodiment of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, the same reference numerals are used throughout the drawings for parts having similar functions and functions. In addition, the inclusion of specific components does not exclude other components unless otherwise stated, but means that other components may be further included.

Cube-on-face texture manufacturing method using diffusion

1 is a flowchart illustrating a method for manufacturing a cube-on-face texture using diffusion. As shown in FIG. 1 , the method for manufacturing a cube-on-face texture according to an embodiment of the present invention may include a heat treatment step S10 , a silicon diffusion step S20 , and a phase transformation step S30 .

The heat treatment step (S10) is a heat treatment step of heat-treating a metal plate made of iron or an iron-based alloy in an ideal region in which austenite (γ) and ferrite (α) are mixed or in a region in which the austenite (γ) phase is stable, before the heat treatment Alternatively, silicon (Si) particles or a silicon compound on a surface perpendicular to the ND (Normal Direction) may be configured to contact the metal plate. Hereinafter, for convenience of explanation, a heat treatment step of heat-treating a metal sheet in a region in which the austenite (γ) phase is stable has been described, but the scope of the present invention is a heat treatment in an abnormal region in which austenite (γ) and ferrite (α) are mixed. includes steps.

2 is a graph showing the phase equilibrium of iron (Fe) according to temperature and pressure (Fe phase diagram, Baohua Zhang, AIP Advances 4, 017128 (2014)). As shown in FIG. 2 , iron (Fe) or an iron-based alloy may exhibit various solid states, including atomic arrangement structures of austenite (γ) and ferrite (α), depending on temperature, pressure, and composition. The region in which the austenite (γ) phase is stable with respect to a metal sheet composed of iron or an iron-based alloy means a state in which the atomic arrangement structure of iron or iron-based alloy forms a face-centered cubic lattice (FCC). In addition, the region in which the ferrite (α) phase is stable with respect to a metal plate made of iron or iron-based alloy means a state in which the atomic arrangement structure of iron or iron-based alloy forms a body-centered cubic lattice (BCC). For a metal sheet composed of iron or an iron-based alloy, the ideal region in which austenite (γ) and ferrite (α) are mixed means a boundary section of phase transformation.

The temperature and pressure conditions of the heat treatment step (S10) are an ideal region or austenite in which austenite (γ) and ferrite (α) are mixed with respect to the composition (type and content of component elements included in the metal plate) of the metal plate. (γ) means a temperature condition and pressure condition in a region where the phase is stable, and is variable depending on the type and content of component elements included in the metal plate.

According to an embodiment of the present invention, the method of configuring the metal plate in a state in which it is in contact with silicon or a silicon compound is a silicon wafer (Si Wafer) or solid state on at least one surface of the planes perpendicular to the ND (Normal Direction) of the metal plate. It may be configured such that the heat treatment step (S10) is performed in a state in which the silicon compound is in contact. FIG. 3 is a schematic diagram illustrating performing a heat treatment step (S10) in a state in which a silicon wafer is in contact with at least one surface of a metal plate according to an embodiment of the present invention. As shown in FIG. 3, according to an embodiment of the present invention, (a) before heat treatment by a heater, a metal sheet in contact with silicon is charged into the chamber in a state in which silicon is in contact with the metal sheet outside the chamber, and the heat treatment step ( S10) may be performed, or (b) the heat treatment step S10 may be performed in a state in which the silicon-contacted metal plate is placed inside the chamber. The atmosphere of the chamber may be composed of a reducing atmosphere such as H ₂ gas.

Alternatively, the method for configuring the metal plate according to another embodiment of the present invention to be in contact with silicon or a silicon compound is a vapor deposition method using silicon particles on at least one surface of the planes perpendicular to the ND (Normal Direction) of the metal plate. is configured so that the heat treatment step (S10) is performed in a contact state, or at least one of the surfaces perpendicular to the ND (Normal Direction) of the metal plate by a vapor deposition method after the heat treatment step (S10) On at least one surface The silicon particles may be configured to be in contact. For example, when chemical vapor deposition (CVD) is used, a gaseous silicon compound such as a silane-based gas (Si _n H _2n+2 ) or silicon chloride may be used. 4 is a schematic diagram illustrating that silicon is deposited on a metal plate and the heat treatment step (S10) is performed at the same time according to an embodiment of the present invention. As shown in Figure 4, according to another embodiment of the present invention, the metal plate is charged into the chamber and heat treatment is performed by the heater, while silicon is deposited on the metal plate by vapor deposition inside the chamber, so that the heat treatment step (S10) is performed. It may be configured to be so, and the atmosphere of the chamber may be composed of a reducing atmosphere such as H ₂ gas. That is, the scope of the present invention includes both the metal plate material configured to be in contact with silicon or a silicon compound outside and inside the chamber.

According to the above, when chemical vapor deposition is used, the surface of the metal plate can be uniformly coated with silicon, the formation of a silicon diffusion layer can be selected, high-vacuum is not required, and surface cleaning and post-treatment are easy. is generated In particular, when using a silane-based gas, there are problems such as corrosion of the vapor deposition device by other gaseous silicon compounds, volatilization of metal plates by halogen compounds, carbon deposition and formation of silicon dioxide, etc. An effect is produced in which problems are reduced.

In addition, the scope of the present invention as a method for configuring the metal sheet according to another embodiment of the present invention to be in contact with silicon or a silicon compound is by generating a volatile silicon compound by a reaction between solids and gas in a chamber. Pack cementation method in which silicon or a silicon compound is brought into contact with the metal plate, by depositing silicon thickly at a temperature at which silicon does not diffuse on the metal plate to form a film, and then inducing phase transformation through rapid heat treatment to form a cube-on-face texture. Silicon film method, silicon powder, silicon compound powder, or powder coating method in which silicon or silicon compound is in contact with a metal plate by applying a slurry of silicon powder or powder to a metal plate, a silicon-containing gel on the surface of a metal plate by using a sol precursor containing silicon The surface perpendicular to the ND (Normal Direction) of the metal plate by the sol-gel method to form It may include a method of contacting a silicone or a silicone compound to the.

Silicon diffusion step (S20) is a silicon (Si) or silicon compound in contact with the metal plate under the condition that the metal plate is heat treated in an ideal region in which austenite (γ) and ferrite (α) are mixed or in a region in which the austenite (γ) phase is stable. This is a step in which silicon (Si) of the austenite (γ) phase is diffused on at least a portion of the surface of the metal plate.

In the silicon diffusion according to an embodiment of the present invention, the heat treatment step (S10) and the silicon diffusion step (S20) in a state in which a silicon wafer or a silicon compound in a solid state is in contact with at least one surface of a metal plate is performed so that the silicon of the silicon wafer or silicon compound is diffused on the surface of the metal plate. Alternatively, according to another embodiment of the present invention, silicon diffusion when silicon is in contact with a metal plate by a vapor deposition method is performed before step S10, after step S10, or simultaneously with step S10 on the surface of the metal plate. Silicon is formed, and the formed silicon may be configured to diffuse on the surface of the metal plate.

5 is a schematic diagram illustrating a silicon diffusion step according to an embodiment of the present invention. As shown in Figure 5, the silicon diffusion step (S20) according to an embodiment of the present invention is a silicon or silicon compound (silicon wafer, silicon in contact with at least some of the surfaces perpendicular to the ND (Normal Direction) of the metal plate material. In the form of particles, silicon film, etc.), the silicon particles are diffused in the direction of the γ-Fe metal plate to form a silicon diffusion layer.

The mechanism of silicon diffusion for a metal plate according to an embodiment of the present invention may include interdiffusion, vacancy diffusion, interstitial diffusion, and the like, and determine the origin of silicon diffusion. When classified as a basis, lattice diffusion or grain boundary diffusion may be included. Prior literature Yunker, M.L., Van Orman, J.A. (2007) Interdiffusion of solid iron and nickel at high pressure. According to Earth and Planetary Science Letters, 254, 203-213, the diffusion pattern for fcc metal containing γ-Fe with a grain size of 100 μm or more showed that lattice diffusion was dominant at relatively high pressure. there is.

The following equation is a calculation formula based on Fick's second law of diffusion for the concentration of silicon diffusion due to non-steady-state diffusion.

In the above equation, C(x,t) means the silicon diffusion depth x and the silicon diffusion concentration for time t on the surface of the metal plate. C ₀ is the concentration of Si contained in the metal plate material, C _s is the Si source means the Si concentration of silicon or a silicon compound. erf is the error function, erfc is the complementary error function (referential error function, 餘誤差函數), and D is the diffusion coefficient. The following equation is a calculation equation for the diffusion coefficient D.

In the above equation, D is a diffusion coefficient, D ₀ is a constant, R is a gas constant, T is an absolute temperature, and H ^* (P) is an activation enthalpy. Since H ^* (P) = E ^* +PV ^* , the activation enthalpy is linearly proportional to the pressure, and according to Equation 2, it can be confirmed that the diffusion coefficient of silicon diffusion is inversely proportional to the pressure and proportional to the temperature. In the silicon diffusion step (S20) according to an embodiment of the present invention, the depth of the silicon diffusion layer and the silicon concentration diffused in the metal plate can be adjusted by adjusting the temperature and pressure conditions of the chamber based on Equations 1 and 2 there is.

The phase transformation step (S30) is a step in which at least a portion of the surface of the metal plate is phase transformed by silicon diffused on the surface of the metal plate to change from austenite (γ) to ferrite (α) phase, and the surface of the metal plate by S30 α-Fe nuclei having a {100} plane parallel to the Cube-on-texture ({100}<0vw> texture), which is parallel to the ND of the metal plate and has no orientation with respect to RD and TD, is generated. The place where the nucleation barrier of the α phase is lowest on the surface becomes a triple junction, and the place where the nucleation barrier is the lowest in the bulk except for the surface becomes a quadruple junction. Accordingly, according to an embodiment of the present invention, nucleation of α-Fe having a {100} plane parallel to the surface of the metal plate is mainly generated on the surface of the metal plate, which is a cube-on-face set on the surface of the metal plate. It forms a cube-on-face texture.

With respect to the phase transformation according to an embodiment of the present invention, the phase transformation step (S30) may be performed from the γ phase to the α phase through Si diffusion in the γ phase or an ideal region in which the γ phase and the α phase are mixed, which is the Si diffusion As a phase transformation caused by a change in composition through (diffusion), a high silicon fraction appears in the region where silicon is diffused, confirming Si diffusion.

According to the phase transformation step (S30) according to an embodiment of the present invention as described above, in the process of the phase transformation of Fe crystal grains on the surface of the metal plate from γ to α phase, the {100} plane of α-Fe crystal grains is on the metal plate surface. Cube-on-face arranged in parallel and having <100> evenly distributed in RD and TD perpendicular to ND (a state where <100>, which is easy to magnetize in the rotational direction of the metal plate, is uniformly distributed and there is no anisotropy) The effect that the cube-on-face texture is generated above a certain level is generated.

Preferably, the fraction of {100}<0vw> cube-on-face texture generated on the surface of the metal plate according to an embodiment of the present invention may be 50% or more, and the angular error may be generated within ±15 degrees.

More preferably, the fraction of {100}<0vw> cube-on-face texture generated on the surface of the metal plate according to an embodiment of the present invention may be 35% or more, and an angular error of ±15 degrees may be generated.

Also, preferably, according to an embodiment of the present invention, the surface silicon (Si) fraction of the metal sheet having the {100}<0vw> cube-on-face texture formed on the surface may be 2 wt% or more.

More preferably, the surface silicon (Si) fraction of the metal sheet having the {100}<0vw> cube-on-face texture formed on the surface according to an embodiment of the present invention may be 3 wt% or more.

As described above, according to an embodiment of the present invention, it is possible to secure a high silicon (Si) fraction while creating a cube-on-face texture on the surface of a metal plate made of iron or an iron-based alloy. The effect that there is will occur. When the silicon fraction is improved, the iron loss of the electrical steel sheet is reduced and the magnetic flux density is improved, so it can be seen that the higher the silicon fraction is, the better the electrical steel sheet. It mainly produces electrical steel sheets. According to prior documents such as Patent Document 0003, it is difficult to manufacture an electrical steel sheet (especially non-oriented) having a high Si fraction.

In addition, according to an embodiment of the present invention, since γ→α phase transformation is caused by diffusion, it is possible to manufacture electrical steel sheets with excellent magnetic properties (especially non-oriented electrical steel sheets) in a state in which restrictions on atmosphere control are significantly reduced. A disengagement effect occurs. In particular, this can lead to cost savings in mass production.

In addition, according to an embodiment of the present invention, n-step heat treatment or elaborate n-th furnace cooling is not required, thereby simplifying the process and reducing costs.

[Example 1]

In Example 1, Fe-1%Si metal plate specimens were prepared in wt%. Example 1 was made in a H ₂ environment (99.9999%, 1000 sccm, 6N). 6 is a schematic diagram and a photograph showing the specimen of Example 1. As shown in FIG. 6 , in Example 1, the heat treatment step (S10) was performed in a state in which the silicon wafer was in contact with the surface of the metal plate specimen.

7 is a graph showing the heat treatment of Example 1. 7, in Example 1, the temperature was raised to 950 °C at 10 °C/min and maintained for 5 minutes, then the temperature was raised to 1100 °C, and heat treatment was performed at 1100 °C for 5 minutes by heat treatment. Thereafter, the first cooling was performed to 950° C. (cooled at -1.2° C./min). The secondary furnace was cooled at 950°C at a faster cooling rate. Example 1 became the γ phase in the 1100° C. heat treatment step (S10), and the phase transformation step (S30) was performed to the α phase by the change of the composition through silicon diffusion (S20).

8 shows the EBSD results of Example 1. FIG. As shown in Figure 8, it can be confirmed that a fairly high fraction (81.9%) of {100}<0vw> Cube-on-face texture is formed on the surface of the metal plate specimen, and the grain size It can be confirmed that is 446 μm.

9 shows the XRF analysis result of Example 1. As shown in FIG. 9 , according to the XRF analysis result, a {100}<0vw> cube-on-face texture of a fairly high fraction (81.9%) was formed on the surface of the metal plate specimen at the same time , it can be seen that the Si content of 1 wt% increased to 10.25 wt%. That is, it is possible to secure a very high Si fraction, which is an effect that occurs when an embodiment of the present invention is applied, and at the same time, a cube-on-face texture having a {100} plane parallel to the surface is very The effect that can be created with a high fraction and the effect of generating a very high fraction of {100}<0vw> cube-on-face texture with only a relatively short heat treatment will be confirmed in Example 1 can

[Example 2]

In Example 2, in wt%, C: <0.003%, Si: 0.96%, Mn: 0.045%, P: 0.005%, S: <0.003%, Al: <0.003%, Ti: 0.0005%, N: 0.0012% , Ni: A metal plate specimen (thickness of 350 μm) composed of 0% and the remaining Fe and other unavoidable impurities was prepared. Example 2 was made in an H ₂ environment (6N) at a flow rate of 1000 sccm. 10 is a schematic view showing the loading of the metal plate specimen and the silicon wafer of Example 2. As shown in FIG. 10 , in Example 2, S10, S20 and S30 were performed by contacting a silicon wafer (thickness of 650 μm) on the upper surface of the metal plate specimen.

11 is a graph showing the heat treatment step of Example 2. 11 , in Example 2, heat treatment was performed at 1100° C. for 2 minutes, 4 minutes, 7.5 minutes, 15 minutes, 30 minutes, and 60 minutes, respectively, and the heat treatment was performed after heat treatment. Example 1 became the γ phase in the heat treatment step (S10), and the phase transformation step (S30) was performed to the α phase by the change of the composition through silicon diffusion (S20).

12 is a photograph showing a metal plate specimen and a silicon wafer after heat treatment of Example 2. Referring to FIG. As shown in FIG. 12 , it can be confirmed that the weight increase of the metal plate specimen after the heat treatment of Example 2 occurred. At 1100°C for 2 minutes, heat treatment 0.02 g, 4 minutes heat treatment 0.04 g, 7.5 minutes heat treatment 0.05 g, 15 minutes heat treatment 0.09 g, 30 minutes heat treatment 0.15 g, 60 minutes heat treatment 0.15 A weight gain in g occurred.

13 and 14 show the EBSD results of Example 2. 13 and 14, in Example 2, the cube-on-face texture having a {100} plane parallel to the surface of the metal sheet on the surface of the metal sheet to which the silicon wafer is touched is dominant regardless of the heat treatment time. ) can be checked. {100}<0vw> cube-on-face texture with a fraction of 77.9% and a grain size of 107 μm on the surface of the metal sheet specimen when heat treated at 1100° C. for 2 minutes, 58.8% fraction and {100}<0vw> cube-on-face texture with a grain size of 147 μm, 86.9% fraction when heat treated for 7.5 minutes and a {100}<0vw> cube-on-face texture with a grain size of 230 μm (Cube-on-face texture) -on-face texture), when heat treated for 15 minutes, {100}<0vw> cube-on-face texture with 55.9% fraction and grain size of 274μm, 63.7% fraction and grain size when heat treated for 30 minutes {100}<0vw> cube-on-face texture with a size of 351 μm, a {100}<0vw> cube-on-face texture with a grain size of 367 μm and a 74.6% fraction when heat treated for 60 minutes -on-face texture) was formed.

15 shows a cross section (IQ map) analysis result of Example 2. 16 shows the cross section (IPF map) analysis result of Example 2. Figure 17 shows the cross section (Line EDS) analysis results of Example 2. As shown in FIGS. 15, 16, and 17 , it can be seen that as the heat treatment time increases, the depth in which Si is diffused in the metal plate specimen increases. {100}<0vw> cube-on-face texture with a depth of 125 μm and a silicon content of 8.79 wt% Si from the surface of the metal plate specimen when heat treated at 1100° C. for 2 minutes, depth 179 μm when heat treated for 4 minutes and {100}<0vw> cube-on-face texture with a silicon content of 10.10wt%Si, a {100}<0vw> cube with a depth of 288μm and a silicon content of 9.67wt%Si when heat treated for 7.5 minutes Cube-on-face texture, {100}<0vw> Cube-on-face texture with a depth of 382 μm and a silicon content of 9.60 wt% Si when annealed for 15 minutes, 30 minutes {100}<0vw> Cube-on-face texture with a depth of 476 μm and a silicon content of 11.03 wt% Si when heat treated, { with a depth of 507 μm and a silicon content of 11.38 wt% Si when heat treated for 60 minutes 100}<0vw> It can be seen that a cube-on-face texture is formed.

[Example 3]

In Example 3, EBSD analysis was performed for each step of the 1.00 wt% Si metal plate specimen. In Example 3, a silicon wafer (thickness 650 μm) was brought into contact with the upper surface of the metal plate specimen, and a heat treatment step (S10), a silicon diffusion step (S20), and a phase transformation step (S30) were performed between 1000°C and 1100°C.

18 shows the EBSD results of the metal plate specimen after the heat treatment step (S10) of Example 3. As shown in FIG. 18 , in the metal plate specimen of the heat treatment step S10 of Example 3, a significant portion was a γ-fiber texture, and a {100}<0vw> cube-on-face texture was hardly formed. Considering that the composition of Si is 0.91 wt%, the result of FIG. 18 shows that the phase transformation by Si diffusion is not induced, and since the phase transformation by the change in the composition does not occur due to Si diffusion, nucleation from the surface was not induced. It can be seen that this is a derived result.

19 shows the EBSD results of the metal plate specimen after the silicon diffusion step (S20) and the phase transformation step (S30) of Example 3; As shown in FIG. 19, in the metal plate specimen after the silicon diffusion step (S20) and the phase transformation step (S30) of Example 3, since the Si composition increased to 10.98 wt% Si, it can be confirmed that Si diffusion proceeded. According to these points, it can be confirmed that the metal plate specimen was phase-transformed to the α-phase by the change of the composition through Si diffusion in the γ-phase.

Therefore, according to Example 3, it can be confirmed that the γ phase was obtained in the heat treatment step (S10), and the phase transformation step (S30) proceeded to the α phase by a change in the composition through silicon diffusion (S20).

[Example 4]

In Example 4, EBSD analysis was performed after step S30 of a metal plate specimen of 1.00 wt% Si. In Example 4, a heat treatment step (S10), silicon diffusion as a method of contacting silicon particles on at least one surface of the surfaces perpendicular to the ND (Normal Direction) of the metal plate by a silane gas vapor deposition (Vapor Deposition) method on a metal plate specimen A step (S20) and a phase transformation step (S30) were performed.

20 shows the EBSD results of the metal plate specimen after the phase transformation step (S30) of Example 4. As shown in Fig. 20, in the metal plate specimen after the phase transformation step (S30) of Example 4, the Si composition was 9.82 wt% Si, and phase transformation from γ to α phase by the change of the composition through silicon diffusion (S20) It can be confirmed that this has occurred, and it can be seen that the fraction of the cube-on-face texture reaches 39.0%. Therefore, according to Example 4, it can be confirmed that the heat treatment step (S10), the silicon diffusion step (S20) and the phase transformation step (S30) of the present invention can be implemented by the vapor deposition method.

[Comparative Example 1]

In Comparative Example 1, a heat treatment step (S10) was performed on a metal plate specimen of 1.00 wt% Si or 2.00 wt% Si, and EBSD analysis was performed.

21, 22, and 23 show the EBSD results after the heat treatment step (S10) of the 1.00 wt% Si metal plate specimen of Comparative Example 1, and FIGS. 24, 25 and 26 are the 2.00 wt% Si metal of Comparative Example 1. The EBSD results after the heat treatment step (S10) of the plate specimen are shown. As shown in FIGS. 21 to 27 , it can be confirmed that the cube-on-face texture is not generated only by the heat treatment step ( S10 ).

[Comparative Example 2]

In Comparative Example 2, a metal plate specimen of 1.00 wt% Si was subjected to a phase transformation from a γ phase to an α phase by a change in temperature through heat treatment, and EBSD analysis was performed.

27 shows the EBSD results after the phase transformation from the γ phase to the α phase by the change of temperature through heat treatment on the 1.00 wt% Si metal plate specimen of Comparative Example 2. FIG. As shown in FIG. 27, when the phase transformation from the γ phase to the α phase caused by a change in temperature through heat treatment on a 1.00 wt% Si metal plate specimen proceeds, a random texture is formed, {100 }<0vw> It can be seen that Cube-on-face texture is not generated.

[Comparative Example 3]

In Comparative Example 3, silicon particles were brought into contact with at least one surface of the surfaces perpendicular to the ND (Normal Direction) of the metal plate by a silane gas vapor deposition method on a metal plate specimen of 1.00 wt% Si in the α phase region. Silicon diffusion was carried out as a method and EBSD analysis was performed.

28 is a vapor deposition (Vapor Deposition) method on a metal plate specimen of 1.00 wt% Si in the α-phase region of Comparative Example 3 Contacting silicon particles on at least one surface of the planes perpendicular to the ND (Normal Direction) of the metal plate. It shows the EBSD results after silicon diffusion was carried out in the following manner. 28, silicon particles on at least one surface of the surfaces perpendicular to the ND (Normal Direction) of the metal plate by a vapor deposition method on a metal plate specimen of 1.00 wt% Si in the α-phase region. When silicon diffusion proceeds by a contact method, only the Si fraction of the metal sheet increases and {100}<0vw> Cube-on-face texture is not significantly generated (Cube-on-face texture) This 4.1% generation) can be seen. Unlike the present invention, in Comparative Example 3, since the metal plate is in the α-phase region during silicon diffusion, the phase transformation from the γ-phase to the α-phase caused by the change in the composition does not occur despite the silicon diffusion.

[Example of Si diffusion by temperature]

In this example, component analysis was performed for each specific temperature of a metal plate specimen of 1.00 wt% Si in each step according to an embodiment of the present invention. Specifically, in this example, a silicon wafer (thickness 650 μm) was brought into contact with the upper surface of the metal plate specimen, and the heat treatment step (S10), the silicon diffusion step (S20) and the phase transformation step (S30) were performed at 1100° C., 1000° C., Component analysis was performed at 1050°C and 1100°C. 29 is a graph showing DSC analysis of Fe-1 wt%Si. As shown in FIG. 29, in the case of Fe-1wt%Si, a phase transformation occurs due to a temperature change from an α phase to a γ phase from around 999°C. When the α phase or α phase and γ phase are mixed, it can be considered close to the ideal region, and in the case of 1050°C and 1100°C, it is judged to be close to the γ phase.

30 is a view showing the component analysis results of the metal plate specimen of the Si diffusion example for each temperature. As shown in FIG. 30 , it was determined that Si diffusion did not proceed as 0.91 wt% Si under the 1000°C condition, and it was confirmed that Si diffusion was gradually made under the 1050°C condition, and 14.4 wt% at 1100°C condition. As Si, it can be confirmed that Si diffusion has sufficiently progressed.

31, 32, and 33 show EBSD results of Si diffusion examples according to temperature. As shown in FIG. 31 , when heat treatment was performed at 1000° C. for 5 minutes, {100}<0vw> cube-on-face texture showed a 0.02% fraction on the surface of the metal plate specimen, which hardly appeared. , and the grain size was confirmed to be 123 μm. It can be confirmed that a strong γ-phase fiber texture is formed under the conditions of FIG. 31 . As shown in Figure 32, under the 1050 ℃ condition, {100} <0vw> cube-on-face texture on the surface of the metal plate specimen showed a 67.1% fraction, the grain size was confirmed to be 311 μm became As shown in FIG. 34, under the condition of 1100° C., {100}<0vw> cube-on-face texture on the surface of the metal plate specimen exhibited an 81.9% fraction, and the grain size was confirmed to be 446 μm. became

According to the results of FIGS. 31, 32, and 33, {100}<0vw> Cube-on-face texture as the metal plate specimen is phase-transformed to α-phase by a change in composition through Si diffusion from γ-phase You can check that this has been created. Therefore, according to the example of diffusion of Si by temperature, it can be confirmed once again that the phase transformation step (S30) proceeded to the α phase due to the change in the composition through the silicon diffusion (S20) and the γ phase in the heat treatment step (S10).

[Comparative example on α phase]

In relation to the generation of the {100}<0vw> cube-on-face texture in the α phase, component analysis was performed after heat treatment at 900° C. of a metal sheet specimen of 1.00 wt% Si. As shown in FIG. 29, in the case of Fe-1wt%Si, a phase transformation occurs due to a temperature change from α to γ phase from around 999° C., so it is judged close to the α phase in the case of 900° C. in this example. .

34 is a photograph showing a metal sheet specimen of 1.00 wt% Si of Comparative Example in α phase after heat treatment at 900° C. for 2 hours, FIG. 35 is an EBSD result of a comparative example in α phase, and FIG. 36 is a comparison in α phase. Examples of Si wt% are shown. 34, 35 and 36, in the absence of Si diffusion in the α phase, a strong γ fiber texture was formed, and {100}<0vw> Cube-on-face texture was hardly generated. can confirm that it is not.

A comparative example in the case of Si diffusion in the α phase can be explained through Comparative Example 3 above, and as described in Comparative Example 3, when there is Si diffusion in the α phase, only the Si fraction of the metal plate increases and {100} <0vw> It can be seen that the cube-on-face texture is not significantly generated (4.1% of the cube-on-face texture is generated).

[Example of upper limit of cube on face texture fraction]

According to an embodiment of the present invention, the upper limit of the fraction of {100}<0vw> cube-on-face texture generated on the surface of the metal plate may be close to 100% depending on conditions. In this example, Fe-2%Si-1wt%Ni metal plate specimens were prepared in wt%. In this embodiment, the heat treatment step (S10) was performed in a state in which the silicon wafer was in contact with the surface of the metal plate specimen.

Figure 37 depicts the EBSD analysis of the cube on face texture fraction upper bound example. As shown in FIG. 37 , when each step according to an embodiment of the present invention is performed on the specimen of the cube-on-face texture fraction upper limit embodiment, 96.8% of {100}<0vw> cube-on-face texture It can be seen that the fraction appears. As shown in FIG. 37 , it can be confirmed that the upper limit of the fraction of {100}<0vw> cube-on-face texture generated on the surface of the metal plate may be close to 100% depending on conditions.

However, it is known that cold rolling is not possible industrially for about 6.5% Si or more because the elongation of the electrical steel sheet is rapidly reduced due to the addition of Si. The upper limit of the fraction of {100}<0vw> cube-on-face texture generated on the surface of the electrical steel sheet may not be significant.

[Example of mass production process]

38 is a schematic diagram illustrating a continuous process using a deposition process of a method for manufacturing a cube-on-face texture using diffusion according to an embodiment of the present invention. 38, in the continuous process using the deposition process of the cube-on-face texture manufacturing method using diffusion according to an embodiment of the present invention, the metal plate is charged into the annealing chamber and the austenite (γ) phase is at a stable temperature. A heat treatment step (S10) proceeds, silicon is deposited on the surface of the metal plate by a deposition process inside the chamber in the austenite (γ) phase state, and the silicon is diffused to the surface of the metal plate (silicon diffusion (S20)), silicon At least a portion of the metal plate material undergoes phase transformation (phase transformation step (S30)) into the ferrite (α) phase due to the change in composition due to diffusion. At this time, in the continuous process using the deposition process of the cube-on-face texture manufacturing method using diffusion according to an embodiment of the present invention, the deposition process is PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), ALD (Atomic Layer Deposition) ) and the like may be used. When the PVD process is used, a deposition method such as thermal evaporation, e-beam evaporation, or sputtering may be applied. If the CVD process is used, hot wall CVD or cold wall CVD depending on the temperature of the substrate and the reactor wall, Atmosphere Pressure CVD or Low Pressure CVD depending on the temperature inside the reactor, Thermal CVD, Plasma Enhanced CVD, or Plasma Enhanced CVD depending on the activation energy supply method Photo CVD, depending on the reaction temperature High Temp. CVD or Low Temp. Depending on the type of CVD or deposition film, a deposition method such as dielectric CVD or poly and metal CVD may be applied.

As such, the cube-on-face texture manufacturing method using diffusion according to an embodiment of the present invention can be applied to a deposition process and the heat treatment time can be configured to be relatively short, so it can be applied to a continuous process for mass production of electrical steel sheet. A possible effect occurs. The conventional cube-on-face texture manufacturing method disclosed in the prior literature had a problem in that it was difficult to apply to a continuous process for mass production of electrical steel sheets. For example, in the case of Tomida (1995), {100}<0vw> is far from the formation of a cube-on-face texture, and long-term heat treatment in high vacuum and high temperature is required, so electrical steel sheet There was a problem that was very difficult to apply to the mass production process. Also, J.K. In Sung (2011), there was a problem limited to the composition of pure iron and Fe-1wt%Si, and it was very difficult to apply it to the mass production process of electrical steel sheet because heat treatment at high temperature was required for a long time. Also, Y.K. Ahn (2020) suggests the formation of a {100}<0vw> cube-on-face texture only up to the result of the Fe-2wt%Si-1wt%Ni composition, and results in excess of 2wt%Si There was a problem that was not suggested, and there was a limitation that stress should be generated on the surface of the metal sheet during heat treatment, so it was difficult to apply it to the continuous process for mass production of electrical steel sheet. In particular, among the prior literature, Y.K. Ahn (2020) has a problem that is far from the above deposition process because there is a limitation to generate stress on the surface of the metal plate during heat treatment.

39 is a schematic diagram illustrating a continuous process (continuous process using a coating process) without using a deposition process of the method for manufacturing a cube-on-face texture using diffusion according to an embodiment of the present invention. As shown in Figure 39, the continuous process (continuous process using the coating process) without using the deposition process of the cube-on-face texture manufacturing method using diffusion according to an embodiment of the present invention, the metal plate material is charged into the annealing chamber and the austenite (γ) phase is subjected to a heat treatment step (S10) at a stable temperature. It is coated so that silicon is diffused to the surface of the metal plate (silicon diffusion (S20)), and at least a part of the metal plate is phase transformation (phase transformation step (S30)) to ferrite (α) by a change in composition due to silicon diffusion do.

As such, the cube-on-face texture manufacturing method using diffusion according to an embodiment of the present invention performs silicon coating with a coating process such as a hot dip plating process, an electrolytic plating process, or a powder contact process even when it is difficult to apply a deposition process. Since the continuous process can be applied and the heat treatment time can be configured to be relatively short, there is an effect that can be applied to the continuous process for mass production of electrical steel sheet. In particular, in the prior literature, Y.K. In Ahn (2020), there is a problem that is far from the above coating process because there is a limitation to generate stress on the surface of the metal plate during heat treatment.

40 is a schematic diagram illustrating a continuous process using diffusion after deposition (or coating) of a method for manufacturing a cube-on-face texture using diffusion according to an embodiment of the present invention. As shown in FIG. 40, the continuous process using diffusion after deposition (or coating) of the method for manufacturing a cube-on-face texture using diffusion according to an embodiment of the present invention is a variation of the continuous process shown in FIGS. 38 and 39 For example, a metal plate is first charged into the deposition chamber (or coating chamber), and a deposition process such as PVD, CVD, or ALD (when a coating chamber is applied, a coating process such as a hot dip plating process, an electrolytic plating process, or a powder contact process) It is applied before the heat treatment step (S10) and silicon coating is performed on the surface of the metal plate, after which the metal plate is charged into the annealing chamber and the heat treatment step (S10) is performed at a temperature at which the austenite (γ) phase is stable, austenite (γ) In the phase state, silicon donated (or pre-coated) on the surface of the metal plate by the previous deposition process (or coating process) is diffused to the surface of the metal plate (silicon diffusion (S20)), and changes in composition due to silicon diffusion By this, at least a portion of the metal plate is subjected to a phase transformation (phase transformation step (S30)) into the ferrite (α) phase.

According to the continuous process using diffusion after deposition (or coating) of the cube-on-face texture manufacturing method using diffusion according to an embodiment of the present invention, the deposition chamber (or coating chamber) and the annealing chamber are separated in the continuous process. Therefore, the effect of further improving the efficiency of silicon deposition (or coating) is generated.

41 is a schematic diagram illustrating a batch process using batch annealing in a method for manufacturing a cube-on-face texture using diffusion according to an embodiment of the present invention. As shown in FIG. 41, the process using batch annealing of the cube-on-face texture manufacturing method using diffusion according to an embodiment of the present invention is a modification of the continuous process shown in FIG. or coating chamber), and a deposition process such as PVD, CVD or ALD (if a coating chamber is applied, a coating process such as a hot dip plating process, an electrolytic plating process, or a powder contact process) is applied before the heat treatment step (S10) Silicon coating is performed on the surface of the metal plate, and then the metal plate is charged into the batch annealing chamber for batch-type heat treatment, and the austenite (γ) phase heat treatment step (S10) is performed at a stable temperature, and the austenite (γ) phase state In the preceding deposition process (or coating process), silicon donated (or pre-coated) on the surface of the metal plate is diffused to the surface of the metal plate (silicon diffusion (S20)). At least a portion of the plate material is to undergo a phase transformation (phase transformation step (S30)) into the ferrite (α) phase.

According to the batch annealing process of the cube-on-face texture manufacturing method using diffusion according to an embodiment of the present invention, the deposition chamber (or coating chamber) and the annealing chamber can be separated within the process, so silicon deposition An effect that can further improve the efficiency of (or coating) is generated. In addition, since the heat treatment is performed in a batch manner, heat treatment can be performed even in a narrow space, thereby reducing the facility investment cost.

The existing cube-on-face texture manufacturing method disclosed in the prior literature had a problem in that it was difficult to apply to the above batch process. For example, in the case of Tomida (1995), it was very difficult to apply Mn vaporization in a high vacuum and high temperature to a batch process. Also, J.K. Sung (2011) had a problem in that it was difficult to apply to a batch process because it required long-term heat treatment at high temperature. Also, Y.K. In Ahn (2020), there is a limitation that stress must be generated on the surface of the metal sheet during heat treatment, so it is difficult to apply it to the batch process.

With respect to the environment, it has been described as an H ₂ environment for convenience of description, but the scope of the present invention is not limited to the H ₂ environment. The scope of the present invention may include an inert gas including a hydrogen environment, a reducing atmosphere such as a reducing active gas, or a vacuum atmosphere.

With respect to silicon diffusion, although it has been described based on Si for convenience of description, ferrite stabilizing elements such as Al, Mo, Cr, Ti, P, V, and W may also be included in the scope of the present invention.

As described above, those skilled in the art to which the present invention pertains will be able to understand that the present invention may be embodied in other specific forms without changing the technical spirit or essential features thereof. Therefore, it should be understood that the above-described embodiments are illustrative in all respects and not restrictive. The scope of the present invention is indicated by the following claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be construed as being included in the scope of the present invention.

The features and advantages described herein are not all inclusive, and many additional features and advantages will become apparent to those skilled in the art, particularly upon consideration of the drawings, the specification, and the claims. Moreover, it should be noted that the language used herein has been selected primarily for readability and teaching purposes, and may not be selected to delineate or limit the subject matter of the present invention.

The foregoing description of embodiments of the invention has been presented for purposes of illustration. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Those skilled in the art will appreciate that many modifications and variations are possible in light of the above disclosure.

Therefore, the scope of the present invention is not limited by the detailed description, but by any claims of the application based thereon. Accordingly, the disclosure of the embodiments of the present invention is illustrative, and does not limit the scope of the present invention as set forth in the following claims.

Claims (24)

A heat treatment step of heat-treating a metal sheet including an iron-based alloy containing 0.96 wt% Si to 2 wt% Si into an ideal region in which austenite (γ) and ferrite (α) are mixed or austenite (γ) phase is stable;
A contact step of contacting a specific element or a compound of the specific element to a surface perpendicular to the ND (Normal Direction) of the metal plate before or after the heat treatment step; and
a phase transformation step in which particles of the specific element or compound are diffused to the surface, and a part of the surface is phase transformed from austenite (γ) to ferrite (α) by the diffusion;
including,
The specific element includes Si,
After the phase transformation step, characterized in that the cube-on-face texture (cube-on-face texture) having a {100} plane parallel to the plane is formed on the part of the plane,
A method for manufacturing a cube-on-face texture using diffusion.
delete delete According to claim 1,
The cube-on-face texture formed is characterized in that the fraction is greater than or equal to 35% and less than or equal to 96.8% on the surface of the metal plate,
A method for manufacturing a cube-on-face texture using diffusion.
The method of claim 1,
The cube-on-face texture formed is characterized in that it has a {100} plane parallel to the plane within an error range of ±15 degrees or less,
A method for manufacturing a cube-on-face texture using diffusion.
delete According to claim 1,
The contact of the specific element or the compound of the specific element is characterized in that by vapor deposition or coating,
A method for manufacturing a cube-on-face texture using diffusion.
According to claim 1,
The contact of the specific element or the compound of the specific element is made before the heat treatment step,
The heat treatment of the heat treatment step is characterized in that by batch annealing,
A method for manufacturing a cube-on-face texture using diffusion.
A method for manufacturing an electrical steel sheet, comprising:
A heat treatment step of heat-treating a metal sheet comprising an iron-based alloy containing 0.96 wt% Si to 2 wt% Si in an ideal region in which austenite (γ) and ferrite (α) are mixed or austenite (γ) phase is stable;
A contact step of contacting a specific element or a compound of the specific element to a surface perpendicular to the ND (Normal Direction) of the metal plate before or after the heat treatment step; and
a phase transformation step in which particles of the specific element or compound are diffused to the surface, and a part of the surface is phase transformed from austenite (γ) to ferrite (α) by the diffusion;
including,
The specific element includes Si,
After the phase transformation step, characterized in that the electrical steel sheet is manufactured in which a cube-on-face texture having a {100} plane parallel to the plane is formed on the part of the plane,
A method for manufacturing an electrical steel sheet using diffusion.
delete delete 10. The method of claim 9,
The cube-on-face texture formed is characterized in that the fraction is greater than or equal to 35% and less than or equal to 96.8% on the surface of the metal plate,
A method for manufacturing an electrical steel sheet using diffusion.
10. The method of claim 9,
The cube-on-face texture formed is characterized in that it has a {100} plane parallel to the plane within an error range of ±15 degrees or less,
A method for manufacturing an electrical steel sheet using diffusion.
delete 10. The method of claim 9,
The contact of the specific element or the compound of the specific element is characterized in that by vapor deposition or coating,
A method for manufacturing an electrical steel sheet using diffusion.
10. The method of claim 9,
The contact of the specific element or the compound of the specific element is made before the heat treatment step,
The heat treatment of the heat treatment step is characterized in that by batch annealing,
A method for manufacturing an electrical steel sheet using diffusion.
A metal sheet comprising an iron-based alloy containing 0.96 wt% Si to 2 wt% Si is heat-treated in an ideal region in which austenite (γ) and ferrite (α) are mixed or in a region in which the austenite (γ) phase is stable, and By contacting a specific element or a compound of the specific element to the surface perpendicular to the ND (Normal Direction) of the metal sheet before or after or after, the particles of the specific element or the compound are diffused to the surface, and by the diffusion A part of the face is phase transformed from austenite (γ) to ferrite (α), the specific element contains Si, and after the phase transformation, the cube on the part of the face has a {100} face parallel to the face An electrical steel sheet manufactured to form a cube-on-face texture.
delete delete 18. The method of claim 17,
The cube-on-face texture formed is characterized in that the fraction is greater than or equal to 35% and less than or equal to 96.8% on the surface of the metal plate,
electric steel plate.
18. The method of claim 17,
The cube-on-face texture formed is characterized in that it has a {100} plane parallel to the plane within an error range of ±15 degrees or less,
electric steel plate.
delete 18. The method of claim 17,
The contact of the specific element or the compound of the specific element is characterized in that by vapor deposition or coating,
electric steel plate.
18. The method of claim 17,
The contact of the specific element or the compound of the specific element is made before the heat treatment,
The heat treatment is characterized in that by batch annealing,
electric steel plate.

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