KR20060002467A - Fabrication methods of high silicon-iron sheet by electrodeposition process for electrical applications - Google Patents

Abstract

The present invention relates to a method for manufacturing a high silicon steel sheet for an electronic device by a pre-plating method of plating a commercial silicon steel sheet or a pure iron sheet in a railway amount containing silicon (Si) particles and post-treatment. The method for manufacturing a high silicon steel sheet for an electronic device by the electroplating method according to the present invention includes a plating process (100) for plating a steel sheet containing a small amount of silicon (Si) in an iron sulfate plating solution (140), and the plating process (100). It is characterized in that it comprises a post-treatment process 200 for post-treatment of the rough steel plate 180, and the base metal 360 made of titanium (Ti) or stainless steel (SUS) to the iron chloride solution ( A first plating process 300 for plating in 340, a second plating process 400 for plating the pure iron thin plate 370 formed in the first plating process 300 with the iron sulfate solution 440, and the first plating process 300. It is characterized in that it comprises a post-treatment process 500 for post-processing the iron plate 480 through the two plating process (400). According to the present invention as described above, there is an advantage that mass production of a high silicon (Si) ultra-thin steel sheet at low cost.

Electric pole plating, railway gold, high silicon steel, soft magnetic material, material for electronic equipment

Description

Fabrication Methods of High Silicon-Iron Sheet by Electrodeposition Process for Electrical Applications}

1 is a schematic process conceptual view showing an embodiment of a method for manufacturing a high silicon steel sheet for an electronic device by the electroplating method according to the present invention.

Figure 2 is a schematic process conceptual view showing another embodiment of a high silicon steel sheet manufacturing method for electronic devices by the electroplating method according to the present invention.

3 is a schematic process flow diagram according to FIG. 1;

4 shows a schematic process flow diagram according to FIG. 2.

FIG. 5 is a scanning electron microscope (SEM) photograph of an iron (Fe) plated layer containing silicon (Si) particles formed on a pure iron sheet in an iron sulfate plating solution of a method for manufacturing a high silicon steel sheet for an electronic device according to the present invention.

6 is an energy dispersive spectroscopy (EDS) of an iron (Fe) plated layer containing silicon (Si) particles formed on a pure iron sheet in an iron sulfate plating solution of the method for manufacturing a high silicon steel sheet for electronic devices according to the present invention. ) Analysis.

Explanation of symbols on the main parts of the drawings

100. ..... Plating Process 120. ..... Bathtub

140,440. ..... 160 Iron Sulfate Solution

180,480. ..... Iron plate 220,520. ..... Rolling Equipment

240,540. ..... Annealing Equipment 260,560. ..... High Silicon Steel Sheet

300. ..... First Plating Process 320. ..... First Bathtub

340. ..... iron chloride solution 360. .....

362. ..... Shaft 370. ..... Pure Steel Sheet

380. ..... 1st Roller 400. ..... 2nd Plating Process

420. ..... The second bathtub 460. ..... The second roller

500. ..... Post-Processing

The present invention relates to a method for manufacturing a steel sheet for an electronic device, and more particularly, a high silicon for an electronic device by a pre-plating method of plating a commercial silicon steel sheet or a pure iron sheet in an iron (Fe) plating solution containing silicon (Si) particles and post-treatment. It relates to a steel sheet manufacturing method.

In general, iron loss of electrical steel sheet used as iron cores of various motors is divided into hysteresis loss and eddy current loss. The smaller the iron loss, the higher the energy efficiency of the electric equipment. Since hysteresis loss is proportional to the square of frequency and eddy current loss is proportional to frequency, iron loss is greatly influenced by eddy current loss when magnetizing electrical steel plate in high frequency region.

Since the eddy current loss is proportional to the square of the thickness of the steel sheet and inversely proportional to the electrical resistivity of the steel sheet, the eddy current loss can be reduced by reducing the thickness of the steel sheet or increasing the electrical resistivity of the steel sheet.

As a method of increasing the electrical resistivity of an electrical steel sheet, an alloy is formed by adding aluminum (Al), manganese (Mn), or silicon (Si) to a molten metal.

However, when a large amount of these elements is added, that is, silicon (Si) is about 4 wt%, and aluminum (Al) is about 3 wt% or more, the steel sheet exhibits very large brittleness, and thus cold rolling is impossible. In addition, when a large amount of manganese (Mn) is added as an alloying element, not only steel workability is degraded, but also manganese (Mn) oxides are formed, so that pickling properties are also reduced.

Therefore, the method of adding aluminum (Al), manganese (Mn), or silicon (Si) to a molten metal, and rolling it to obtain an electrical steel sheet having high electrical resistivity has not been industrially used.

The cold rolled electrical steel sheet containing a small amount of aluminum (Al), manganese (Mn) or silicon (Si) to a desired thickness, and then coated with a manganese (Mn) or silicon (Si) on the surface of the steel sheet and diffused to a high concentration alloy Methods of obtaining steel sheet have been proposed.

In Korean Patent Publication No. 10-0406391, a non-oriented electric having excellent high-frequency iron loss characteristics by electroplating manganese (Mn) on a cold rolled sheet, which is a conventional non-oriented electrical steel sheet, and then annealing the diffusion of manganese (Mn) into the steel sheet. A method of producing a steel sheet is proposed.

On the other hand, silicon (Si) is known to be difficult to plate on the metal surface by hot dip or electroplating.

In addition to the plating method, another method for coating silicon (Si) on an electrical steel sheet is a vapor phase chemical vapor deposition (CVD) in a 1200 ° C SiCl ₄ atmosphere proposed in Korean Patent Laid-Open Publication No. 2001-0006259. However, this method is uneconomical because it takes a long time to deposit silicon (Si), a bad working environment, and a difficult continuous process.

On the other hand, US Patent No. 5262039 in the iron chloride solution containing Fe-Si particles at the same time by coating the iron (Fe) and Fe-Si particles on the surface by using an electroplating method, a high concentration of silicon by diffusion treatment in an inert gas atmosphere at 1150 ℃ A method of obtaining a (Si) steel sheet is presented. However, this method has not been industrially used due to uneven growth of the iron (Fe) plating layer on the conductive Fe-Si particles.

Therefore, an object of the present invention for solving the above problems, the high silicon for electronic devices by the electroplating method of plating a commercial silicon steel sheet or a pure iron sheet in an iron (Fe) plating solution containing silicon (Si) particles and post-treatment It is to provide a steel sheet manufacturing method.

In order to achieve the above object, the method of manufacturing a high silicon steel sheet for an electronic device by the electroplating method of the present invention includes a plating process of plating a steel sheet containing a small amount of silicon (Si) in an iron sulfate plating solution, and the plating process. It is characterized in that it comprises a post-treatment process for post-treatment of the rough iron sheet.

The steel sheet is characterized by containing less than 3wt% silicon (Si).

In addition, the first plating process for plating a base metal consisting of titanium (Ti) or stainless steel (SUS) to the railway value, and the second plating process for plating the pure iron sheet formed in the first plating process in the iron sulfate solution; It is characterized in that it comprises a post-treatment process for the post-treatment of the iron plate passed through the second plating process.

The railway value in the first plating process is characterized in that the iron chloride solution.

The iron sulfate solution is characterized in that it contains silicon (Si) particles 5g / l ~ 300g / l and FeSO ₄ · 7H ₂ O 20g / l ~ 600g / l.

The post-treatment process is characterized in that at least one of cold rolling, diffusion heat treatment, stress relief heat treatment.

The cold rolling is characterized in that it is carried out at 350 ℃ or less.

In addition, the diffusion heat treatment is characterized in that it is carried out for 0.1 hours to 10 hours in a reducing atmosphere of 1000 ℃ ~ 1250 ℃.

According to the present invention as described above, there is an advantage that mass production of a high silicon (Si) ultra-thin steel sheet at low cost.

6.5wt% silicon steel [Fe-6.5wt% Si] has high permeability, low distortion, and high resistivity compared to the conventional 3wt% silicon steel sheet, so it has excellent high frequency characteristics, reduces noise, and consumes 30% of power consumption. It is a soft magnetic material that can reduce ~ 50%, and is widely used in many electronic components such as various motors, high speed generators, various transformers, reactors, automobile exhaust gas senses, shielding materials, inductors, and low noise filters.

In addition, the only commercially manufactured method of 6.5wt% silicon steel sheet was developed in Japanese steel pipe (NKK), and hot-rolled 3.5wt% silicon steel sheet to a target thickness and silicon (Si) through high temperature chemical vapor deposition technology. It is a method of obtaining a 6.5wt% silicon steel sheet by depositing on the surface and homogenizing through an annealing process.

However, this method is more economical because it has problems such as high manufacturing cost due to chemical vapor deposition process, limitation of product size, and longer time required for silicon (Si) to diffuse from surface to inside during annealing. Development of new manufacturing methods is needed.

Therefore, if the vacancy with iron (Fe) by using the non-conductive silicon (Si) particles to obtain an iron (Fe) plating layer containing an appropriate amount of silicon (Si) 6.5wt% high silicon steel sheet It is expected to be the best way to produce the.

Hereinafter, with reference to the accompanying drawings a preferred embodiment of a method for manufacturing a high silicon steel sheet for an electronic device by the electroplating method according to the present invention having the configuration as described above will be described in detail.

1 is a schematic process conceptual view showing an embodiment of a method for manufacturing a high silicon steel sheet for an electronic device according to the electroplating method according to the present invention, Figure 2 is a high silicon steel sheet for manufacturing an electronic device according to the electroplating method according to the present invention A schematic process conceptual diagram showing another embodiment of the method is shown and a schematic process flow diagram according to FIG. 1 is shown in FIG. 3.

4 shows a schematic process flow diagram according to FIG. 2, and FIG. 5 shows silicon (Si) particles formed on a pure iron sheet in an iron sulfate plating solution of a method for manufacturing a high silicon steel sheet for an electronic device by electroplating according to the present invention. The scanning electron microscope (SEM) photograph of the iron (Fe) plated layer is shown, Figure 6 is a silicon formed on a pure iron sheet in an iron sulfate plating solution of a method of manufacturing a high silicon steel sheet for electronic devices by the electroplating method according to the present invention The results of Energy Dispersive Spectroscopy (EDS) analysis of an iron (Fe) plated layer containing (Si) particles are shown.

As shown in these drawings, the method of manufacturing a high silicon steel sheet for an electronic device by the electroplating method can be largely carried out in two ways. In other words, in the first embodiment, a method of plating and post-treating a steel sheet containing a small amount of silicon (Si) in an iron sulfate solution is first performed, and in the second embodiment, a base metal is primarily plated in a railway amount (iron chloride solution). One pure iron thin plate may be carried out by post-treatment by secondary plating in an iron sulfate solution.

First, a method of manufacturing a high silicon steel sheet for an electronic device by the electroplating method according to the first embodiment is composed of two steps. That is, a plating process (100) for plating a steel sheet (commercial silicon steel sheet) containing a small amount (less than 3wt%) of silicon (Si) in the iron sulfate solution 140, and an iron thin plate that has undergone the plating process (100) ( 180 is divided into a post-processing process 200 for post-processing.

The plating process 100 is formed of a commercial silicon steel sheet containing silicon (Si) of 3wt% or less as described above in a substantially rectangular shape, and having a pair of rollers 160 on the left and right sides. 120).

The bath 120 as described above is filled with the iron sulfate solution 140, the iron sulfate solution 140 is FeSO ₄ · 7H ₂ O 20 ~ 600 g / l, silicon (Si) particles 5 ~ 300 g / l , Ethylene glycol (Ethylene glycol) 5 ~ 60 ml / l, Ascorbic acid 0.1 ~ 1 g / l, the temperature is 30 ~ 80 ℃, pH = 1 ~ 4 conditions.

The commercial silicon steel sheet, which proceeds to the next process by the rollers 160 provided in a pair of left and right upper and lower portions of the bath 120, has iron (Fe) having a component of 13 wt% silicon (Si) on both sides thereof. ) The plating layer is plated to a thickness of 7.3 μm to be formed of an iron thin plate 180.

In addition, the iron plate 180 subjected to the plating process 100 is subjected to a post-treatment process 200 to perform any one or more of cold rolling or diffusion heat treatment, stress relief heat treatment. Cold rolling in the post-treatment process 200 is carried out at a temperature of less than 350 ℃ in the rolling equipment 220, as shown in Figure 3, the diffusion heat treatment is 1000 ℃ ~ 1250 ℃ in the annealing (240) It will be carried out for 0.1 hours to 10 hours in the reducing component of the crisis.

When the plating process 100 and the post-treatment process 200 are performed in two steps, the high silicon steel sheet 260 for electronic devices containing 6.5 wt% of silicon (Si) is obtained.

Next, the method of manufacturing a high silicon steel sheet for an electronic device by the electroplating method according to the second embodiment is composed of three steps. That is, the first plating process 300 for plating the base metal 360 made of titanium (Ti) or stainless steel (SUS) in the iron chloride plating solution 340, and the pure iron sheet formed in the first plating process 300 A second plating process 400 for plating 370 in the iron sulfate solution 440 and a post-treatment process 500 for post-processing the iron thin plate 480 that have undergone the second plating process 400 are performed. .

The first plating process 300, the second plating process 400, and the post-treatment process 500 are performed as shown in the process flow diagram of FIG. 4. More specifically, the iron chloride solution 340 is partially filled in the first tub 320 having a substantially rectangular shape, and a roll-shaped base metal 360 composed of titanium (Ti) or stainless steel (SUS) is formed above the three tubular baths. Soak in about a minute.

The iron chloride solution 340 is composed of 375 g / l FeCl ₂ · 4H ₂ O, 170 g / l CaCl ₂ , 1 g / l Ascorbic acid, pH = 1.2, the temperature is 90 ℃, the current density is 4 A / dm ² condition.

Then, when rotated in the direction of the arrow around the axis 362 constituting the center of the base metal 360, iron (Fe) is plated on the surface of the base metal 360 to form a pure iron thin plate 370 do. When the pure iron thin plate 370 on the surface of the base metal 360 formed as described above is slowly removed from the base metal 360 rotating, a thin pure iron plate 370 of 0.005 to 0.5 mm can be obtained.

Then, the pure iron sheet 370 is secondarily plated in the iron sulfate plating solution 440 via the first roller 380 which rotates to guide the second plating process 400 to be described below. The second plating process 400 is formed in a shape of a substantially rectangular four-sided block and is formed in a second bath 420 provided with a pair of second rollers 460 on the left and right sides.

The iron sulfate solution 440 is filled in the second bath 420 as described above, and the iron sulfate solution 440 is FeSO ₄ · 7H ₂ O 20 to 600 g / l as in the plating process 100. , Silicon (Si) particles 5 ~ 300 g / l, ethylene glycol (Ethylene glycol) 5 ~ 60 ml / l, ascorbic acid 0.1 ~ 1 g / l, the temperature is 30 ~ 80 ℃, pH = 1 ~ It is a condition of 4.

The pure iron sheet 370, which proceeds to the next process by the second roller 460, which is provided in a pair of left and right upper and lower portions of the second bath 420, has 13 wt% of silicon (Si) on both sides thereof. A double iron sheet 480 is formed having a 7.3 μm thick plating layer with the components.

In addition, the iron plate 480 passed through the second plating process 400 is subjected to a post-treatment process 500 for performing any one or more of cold rolling or diffusion heat treatment and stress relief heat treatment. Cold rolling in the post-treatment process 500 is performed at a temperature of 350 ° C. or less in the rolling equipment 520, as shown in FIG. 4, and diffusion heat treatment is performed at 1000 ° C. to 1250 ° C. in the annealing equipment 540. It will be carried out for 0.1 hours to 10 hours in the reducing component of the crisis.

When the process up to the post-treatment process 500 is thus performed, a silicon silicon (Si) -containing high silicon steel sheet 560 for 6.5 wt% is obtained.

On the other hand, as shown in Figure 5 Looking at the scanning electron microscope (SEM) pictures of the iron plate (180,480) through the plating process 100 and the second plating process 400, the commercial silicon steel sheet and the pure iron sheet 370 It can be seen that the iron (Fe) -silicon (Si) particles are evenly distributed on both sides of the).

In addition, as shown in FIG. 6, when the plating layers of the iron thin plates 180 and 480 which have undergone the plating process 100 and the second plating process 400 are analyzed by EDS (Energy Dispersive Spectroscopy), silicon (Si) and iron ( Fe) is vacant.

The scope of the present invention is not limited to the above-exemplified embodiments, and many other modifications based on the present invention will be possible to those skilled in the art within the above technical scope.

As described in detail above, in the method for manufacturing a high silicon steel sheet for an electronic device by the electroplating method according to the present invention, a method of performing post-treatment by plating a steel sheet containing a small amount of silicon (Si) in an iron sulfate plating solution according to the first embodiment; In the second embodiment, a pure iron plate obtained by primarily plating a base metal composed of titanium (Ti) or stainless steel (SUS) in an iron chloride plating solution was secondly plated in an iron sulfate plating solution and then subjected to post-treatment.

Therefore, by dispersing and depositing silicon (Si) particles in the iron (Fe) plating layer, there is an effect of increasing the surface area of silicon (Si), which may contribute to diffusion, and shorten the heat treatment time due to the reduction of diffusion distance. There is an advantage to that.

And, since the plating layer is formed on both sides, the residual stress in the plating layer is reduced to increase the ductility, and the effect that cracks are not expected is expected.

In addition, since the plating layer is formed on both sides, there is an advantage that the plating speed can be twice as fast as that of single-side plating.

In addition, the iron (Fe) plated layer containing a large amount of silicon (Si) particles formed on both sides of the pure iron sheet is subjected to a cold rolling process before or after the heat treatment, so as to control the thickness of the high silicon steel sheet and to refine the grains or to compress the internal pores. This is expected to accelerate the diffusion of silicon.

Claims (8)

A plating process of plating a steel sheet containing a small amount of silicon (Si) in an iron sulfate solution; The method of manufacturing a high silicon steel sheet for an electronic device according to the electroplating method, characterized in that it comprises a post-treatment process for the post-treatment of the iron plate after the plating process. The method of claim 1, wherein the steel sheet contains silicon (Si) in an amount of 3 wt% or less. A first plating process of plating a base metal composed of titanium (Ti) or stainless steel (SUS) on a railway value; A second plating process of plating the pure iron sheet formed in the first plating process with an iron sulfate solution; A method of manufacturing a high silicon steel sheet for an electronic device by electroplating, characterized in that it comprises a post-treatment process of post-treatment of the iron plate passed through the second plating process. 4. The method of claim 3, wherein the railway value in the first plating process is an iron chloride solution. The electroplating method according to claim 1 or 3, wherein the iron sulfate plating solution contains 5 g / l to 300 g / l of silicon (Si) particles and 20 g / l to 600 g / l of FeSO ₄ · 7H ₂ O. Method for manufacturing high silicon steel sheet for electronic equipment by The method of claim 1 or 3, wherein the post-treatment is at least one of cold rolling, diffusion heat treatment, and stress relief heat treatment. The method of claim 6, wherein the cold rolling is carried out at 350 ° C or less. 7. The method of claim 6, wherein the diffusion heat treatment is performed for 0.1 hour to 10 hours in a reducing atmosphere of 1000 ° C to 1250 ° C.

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