KR100609068B1 - Apparatus for electrodepositing thin film and the method for electrodepositing low Nickel base permalloy thin film using the same apparatus - Google Patents

Abstract

The present invention relates to a thin plate manufacturing apparatus by electrodeposition by stirring using a water level difference and a method for producing permalloy alloy thin plates used as soft magnetic materials by electrodeposition using the apparatus.

The present invention is an auxiliary bath or drum-type negative electrode and the positive electrode and the positive electrode is installed in the interior of the electrolytic cell to be spaced apart from the bottom of the electrolytic cell, the electrolyte is accommodated and the bottom of the electrolytic cell is installed; It provides a device for producing a thin plate by electrodeposition, characterized in that the current device is provided between the cathode and the electrolyte circulator unit is installed in the space formed by the electrolytic bath and the auxiliary bath.

In another aspect, the present invention is a method for producing a low nickel-based permalloy alloy plate, containing an electrolyte so that the sub-bath or drum-type negative electrode is partially immersed in the electrolytic cell, the electrolyte circulating unit transfers the electrolyte from the pool on one side to the pool on the other side By forming a flow of the electrolyte between the positive electrode and the negative electrode to form an alloy thin plate on the negative electrode provides a method for producing a low nickel-based permalloy alloy thin plate, the uniform thickness by such an apparatus and method Can produce low nickel-based permalloy alloy sheet materials.

Electrolyzer, Alloy Sheet, Cathode, Plating, Electrodeposition

Description

Apparatus for electrodepositing thin film and the method for electrodepositing low Nickel base permalloy thin film using the same apparatus}

Figure 1a is a schematic diagram of a manufacturing apparatus of a thin plate by electrodeposition of the present invention,

1B is a cross-sectional view taken along the line D-D 'of FIG. 1A;

Figure 2 is a schematic view of a manufacturing apparatus of another embodiment of the apparatus for manufacturing a thin plate by electrodeposition of the present invention,

3 is a computer simulation diagram of laminar flow generated in a flow path due to a water level difference according to an embodiment of the present invention;

4 is a computer simulation diagram of laminar flow generated in a flow path due to a level difference according to another embodiment of the present invention.

<Description of the symbols for the main parts of the drawings>

1 cathode 2 current device 3 anode

4: electrolyte solution 6: pump 8: electrolytic cell

9: auxiliary bath 10: electrolyte circulator 21: drum type negative electrode

22: arcuate anode 23: anode support 31: sheet

32: roll 33: coiler

A, B: Pool C: Euro

The present invention relates to a thin plate manufacturing apparatus by electrodeposition by stirring using a water level difference and a method for producing permalloy alloy thin plates used as soft magnetic materials by electrodeposition using the apparatus.

The basic principles of electrodeposition are well known in the art, as disclosed in Edison, U.S. Patent No. 1,417,464, which is a patent for copper plate manufacturing by electrodeposition, and U.S. Patent No. 1,543,861, McCord.

  In general, the metal foil is formed on the surface of the negative electrode by a device configured to flow a current between the negative electrode and the positive electrode at least partially submerged in the electrolyte, and the metal foil electrodeposited on the negative electrode surface is peeled off to become a product. At this time, the distance between the cathode and the fixed anode should be kept constant to produce a homogeneous sheet material.

  US Patent No. 3,652,442 to the Powers et al. (Invention: Electrodeposition Device with Means for Stirring Electrolyte Solution in Laminar Flow) has a triangular cross section and has sharp edges in the anteroposterior direction and a relatively sharp edge upwards. An electrolytic cell is provided with a paddle for agitation, and US Pat. No. 3,505,547 to Ambrosia et al., US Patent No. 3,716,464 to Kovac et al. It is described.

  However, the above patents are a method in which the stirring of the solution is performed by a paddle of a specific shape, and is limited to the preparation of high nickel-based permalloy having a Fe-80 wt% Ni composition.

In order to solve the above problems, the inventors of the present invention have developed a groundbreaking device different from the existing device, and, unlike the existing device for producing a thin film including an alloy foil, uses a new water level difference device. It is an object of the present invention to provide an apparatus of the present invention, and in particular, an apparatus capable of producing permalloy alloy by stirring, unlike an apparatus for producing a high nickel-based permalloy alloy by electrodeposition.

  Another object of the present invention to provide a method for producing a low nickel-based permalloy alloy thin plate having a uniform composition and thickness using the above-described device.

In order to achieve the above technical problem, the present invention includes an electrolytic cell in which an electrolyte is accommodated and an anode is installed at an inner bottom thereof, and an auxiliary is installed inside the electrolytic cell so as to be spaced apart from a bottom of the electrolytic cell and installed at a position opposite to the anode. Provided is a device for producing a thin plate by electrodeposition, characterized in that consisting of a molten metal, a current device provided between the anode and the cathode, and an electrolyte solution circulator installed in the space formed by the electrolytic cell and the auxiliary bath.

In addition, the present invention is an electrolytic cell containing the electrolyte is installed in the inner bottom of the electrolytic cell and the electrolytic cell spaced apart from the bottom of the electrolytic cell and the rotatable drum-type negative electrode and the current device is installed between the anode and the cathode and the It provides an apparatus for producing a thin plate by electrodeposition, characterized in that consisting of an electrolytic solution circulator unit installed in the space formed by the electrolytic cell and the drum-type negative electrode and a thin plate manufacturing unit to separate the thin plate from the drum-type negative electrode continuously. do.

In another aspect, the present invention is a method for producing a low nickel-based permalloy alloy plate, containing an electrolyte so that the sub-bath or drum-type negative electrode is partially immersed in the electrolytic cell, the electrolyte circulating unit transfers the electrolyte from the pool on one side to the pool on the other side It provides a method for producing a low nickel-based permalloy alloy thin plate by electrodeposition, characterized in that to form a flow of the electrolyte between the positive electrode and the negative electrode to form an alloy thin plate on the negative electrode.

EMBODIMENT OF THE INVENTION Hereinafter, the apparatus of this invention is demonstrated with reference to drawings.

1A is a schematic view of the apparatus for producing a thin plate by electrodeposition of the present invention, and FIG. 1B is a side cross-sectional schematic view of the apparatus for manufacturing a thin plate by electrodeposition of the present invention.

As shown in FIG. 1A, an electrolytic solution 8 is accommodated and an electrolytic cell 8 in which an anode 3 is installed at an inner bottom thereof and spaced apart from a bottom of the electrolytic cell 8 is installed inside the electrolytic cell 8. The auxiliary bath 9 in which the negative electrode 1 is installed at a position opposite to the positive electrode 3, the current device 2 provided between the positive electrode 3 and the negative electrode 1, the electrolytic cell 8, and the The auxiliary bath 9 is provided in both spaces formed by the electrolyte circulator 10 for circulating the electrolyte.

As shown in FIG. 1B, the auxiliary bath 1 is close to the electrolytic cell 8 on the side, and the electrolyte solution 4 does not flow out.

The negative electrode 1 is surface treated to have an appropriate surface roughness, and the positive electrode 3 is formed to a length corresponding to the negative electrode, and a constant distance, for example, 3 to 40 mm, on any side of the surface of the negative electrode 1 Keep them spaced apart. The separation distance can be adjusted by the position of the auxiliary bath (9).

A current device (2) capable of arbitrarily adjusting the current density is installed between the cathode (1) and the anode (3), and the current is supplied between the cathode (1) and the anode (3) using the current device (2). Let it flow In other words, a current flows through the negative electrode 1 connected to the negative electrode of the power supply and the positive electrode 3 connected to the positive electrode of the power supply.

In addition, the electrolyte circulator 10 may include a pump 6, a suction pipe 5 for sucking the electrolyte, and a discharge pipe 7 for discharging the electrolyte, and are corrosion-resistant materials that are not corroded by the electrolyte 4. It is preferably formed with a non-conductor or acid resistant pump that is not well electrodeposition plating.

2 is a schematic view of a manufacturing apparatus of another embodiment of the apparatus for manufacturing a thin plate by electrodeposition according to the present invention. Components common to those in FIG. 1A use the same reference numerals.

FIG. 2 is a view showing an apparatus for continuously producing a thin plate using the rotating drum type cathode 21. The apparatus using the drum type negative electrode 21 has the same principle as the device using the auxiliary bath 9 of FIG. 1A, but the shape of the negative electrode and the positive electrode is different, and the drum type negative electrode 21 replaces the auxiliary bath 9. In addition, the anode may be provided with an arcuate anode 22 in accordance with the shape of the drum type cathode 21, and an anode support 23 supporting the arcuate anode 22 may be installed. Then, the electrodeposited layer formed on the drum type cathode 21 is peeled to produce a thin plate 31, and a thin plate manufacturing unit 30 formed of a roll 32 and a winding coiler 33 for guiding the thin plate 31 is added. This allows continuous operation. The material of the drum type negative electrode 21 is the same as that of the negative electrode 1 of FIG. 1A.

Hereinafter, the operation of the apparatus of the present invention will be described in detail.

When the auxiliary bath 9 or the drum type negative electrode 21 is installed inside the electrolytic cell 8 and the electrolyte solution 4 is placed therein, the electrolytic cell 8 is formed by the auxiliary bath 9 or the drum type negative electrode 21. Two pools A and B are formed on the left and right. Between the two pools, the pump 6 sucks the electrolyte solution through the suction pipe 5 through the suction pipe 5 and discharges the electrolyte solution through the discharge pipe 7 into the A pool, thereby creating a level difference between the two pools. At this time, a flow path C is formed between the bottom of the electrolytic cell 8 and the bottom of the auxiliary bath 9 due to the level difference, and the electrolyte flows from the pool A to the pool B low in the water level in the flow path C. Laminar flow is generated.

At this time, when the cathode and the anode are energized, a metal thin plate is electrodeposited on the surface of the negative electrode 1 or the drum type cathode 21 to form, for example, a low nickel-based permalloy alloy thin layer. The thickness of the electrodeposition layer can be adjusted by the amount of current flowing through the current device and the energization time.

In the case of the embodiment of FIG. 1A, the electrodeposited metal plated layer having a predetermined thickness formed on the surface of the cathode 1 is peeled off from the surface of the cathode 1 to produce a metal sheet, and in the case of the embodiment of FIG. 2, a drum type. The thin plate 25 can be continuously manufactured while peeling off the thin plate 25 from the cathode 21 and wound by the coiler 26.

Hereinafter, a case of manufacturing a low nickel-based permalloy, ie, a Fe-Ni alloy thin plate having a Ni component of 36 to 55% by weight, by the apparatus for manufacturing an electrodeposited thin plate according to the present invention described above will be described.

The electrodeposition thin plate apparatus of the present invention described above may be used for the production of all metal thin plates, but is particularly effective for the production of low nickel-based permalloy alloy thin plates of 36 to 55% by weight of nickel.

That is, in the method of manufacturing a low nickel-based permalloy alloy plate, the electrolyte solution 4 is contained so that the auxiliary bath 1 or the drum type cathode 21 is partially immersed in the electrolytic cell 8, and the electrolyte solution circulator 10 By transferring the electrolyte from the pool (B) on one side to the pool (A) on the other side to form a flow of electrolyte between the positive electrode and the negative electrode can be produced a low nickel-based permalloy alloy thin plate on the negative electrode.

In order to manufacture the low nickel-based permalloy alloy thin plate, the electrodeposition layer electrodeposited and plated on the cathode should be easily peeled off. For this purpose, the conditions of the electrodeposition process must be reasonable, and the material and surface condition (surface roughness) of the cathode may be It is an important factor. If any one of the above conditions is unsuitable, the low-nickel permalloy alloy thin layer electrodeposited and plated on the surface of the negative electrode is not easily peeled off or too easily peeled from the surface of the negative electrode so that the low-nickel-based permalloy alloy thin plate of desired thickness Cannot be formed.

The material and surface condition (surface roughness) of the negative electrode directly affect the adhesion with the low nickel-based permalloy alloy thin layer electrodeposited and plated on the surface of the negative electrode, and thus the low nickel-based permalloy alloy thin layer electrodeposited and plated on the negative electrode surface. In order to easily peel off, a metal material of a high corrosion resistance material which hardly reacts with the electrolyte (not corroded by the electrolyte) is used as the cathode material, and the surface roughness may vary depending on the alloy composition.

For this purpose, it is suitable to use stainless steel, which is a metal material having high corrosion resistance to electrolyte and excellent electrical conductivity, for example, stainless steel, titanium, or titanium alloy of JIS standard SUS 300 series, and the surface of the cathode is 0.3 μm. Have more surface roughness

As described above, when the current flows between the cathode 1 and the anode 3 by an electric current device and electrodeposits the low nickel-based permalloy alloy thin layer on the surface of the cathode 1, the cathode 1 is electrolyzed. Hydrogen is generated. In this way, if the hydrogen generated from the cathode 1 is not removed quickly, the electrodeposited low nickel permalloy alloy thin layer is stained, and if not severely, electrodeposition plating is not performed.

Therefore, in the present invention, the electrolyte solution 4 is stirred, thereby causing a laminar flow due to the level difference in order to remove hydrogen generated in the negative electrode 1. This level difference is generated by the electrolyte circulation device 10, and the level difference can be adjusted by the capacity of the pump. And the velocity of laminar flow is determined by this level difference.

3A is a conceptual diagram when two pools are made using the auxiliary bath and water level difference is given. 3B and 3C are computer simulations of the shape of the laminar flow generated at the portion into which the electrolyte flows into the flow passage and the portion of the electrolyte flow out from the flow passage.

4A is a conceptual diagram when two pools are made using a drum type negative electrode and the water level difference is given. 4B and 4C are computer simulations of the shape of the laminar flow occurring at the portion into which the electrolyte flows into the flow passage and the portion of the electrolyte flowing out of the flow passage.

The electrolytic solution used in the electrodeposition manufacturing process of low nickel-based permalloy alloy thin plates is composed of 100 to 120 g / l of nickel chloride (Nickel Chloride), 12 to 50 g / l of iron sulfate and boric acid. 20 to 30 g / l, 0.2 to 0.4 g / l sodium lauryl sulfate, 3.2 to 9.9 g / l sodium saccharin, 25 to 39 g / l sodium chloride (NaCl) and sodium citrate (Na Citrate) solution containing 3.5 to 7.0 g / l. At this time, the acidity of the electrolyte is adjusted to pH 1.5 to 3.0.

The reason for numerical limitation of the composition of the above-mentioned electrolyte solution is as follows.

1) Nickel chloride: 100 ~ 120g / ℓ and Iron Sulfate 12 ~ 50g / ℓ

The above composition determines the composition of the low nickel permalloy alloy thin plate, and if the upper limit of the lower limit of the lower limit is exceeded, no appropriate component can be obtained.

2) Boric acid: 20 ~ 30g / ℓ

Boric acid regulates the acidity of the electrolyte, and it is difficult to control the composition at less than 20. When boric acid is more than 30, the boric acid causes a complicated problem such as severe energy loss and iron oxidation at the time of melting.

3) Sodium Lauryl Sulfate 0.2 ~ 0.4g / L

Sodium lauryl sulfate is a surfactant is difficult to remove the hydrogen below 0.2, and if more than 0.4 there is a large amount of foaming is difficult to work.

4) Sodium saccharin: 3.2 ~ 9.9g / ℓ

Saccharin sodium is a stress-relaxing agent, which causes a lot of stresses below 3.2, making it difficult to manufacture alloy thin plates, and when it exceeds 9.9, it adversely affects the physical properties of the alloy thin plates.

5) Sodium Chloride: 25 ~ 39g / ℓ

If the sodium chloride is less than 25, the thickness distribution of the alloy thin plate is not uniform, and if it exceeds 39, it causes a complex problem such that the energy loss is severe and the iron is oxidized at the time of melting.

6) Sodium Citrate: 3.5 ~ 7.0g / ℓ

Sodium citrate is less than 3.5, the thickness distribution of the alloy thin plate is not uniform, and exceeds 7.0 causes a complex problem, such as a strong energy loss to melt and the oxidation of iron at the time it takes to melt.

7) Acidity: pH 1.5 ~ 3.0

If the acidity is less than 1.5, electrodeposition is not properly performed, and if it exceeds 3.0, the acidity is severely changed so that sodium hydroxide or sulfonic acid must be added to control the acidity.

The electrolyte of the composition changes in its composition as the electrodeposition process proceeds, and the electrolyte may be replenished according to a general method to maintain the constant composition.

It was confirmed that the electrodeposition plating of the low nickel-based permalloy alloy thin layer on the surface of the negative electrode in the electrodeposition process was well maintained at a temperature of 20 to 80 ° C., preferably 45 ° C. or higher during the electrodeposition process. At this time, when the temperature range during the electrodeposition process exceeds 80 ℃, the waste of the electrolyte solution due to evaporation is severe and the composition of the electrolyte solution is highly likely to change, making it difficult to form a low nickel-based permalloy alloy thin layer having a desired composition. If less than a high stress on the alloy thin layer it is difficult to manufacture the alloy thin plate.

On the other hand, the positive electrode which is provided opposite the negative electrode is disposed so that the distance between the surface of the negative electrode and the positive electrode is always maintained at about 3 to 40 mm, preferably 10 mm on either side of the negative electrode and the positive electrode of the negative electrode in the electrodeposition process It was confirmed that the electrodeposition plating of the low nickel-based permalloy alloy thin layer on the surface is well performed, but the flow rate is difficult to control the flow rate even if the water level difference is less than 3mm, and the flow path is higher than 40mm, it is difficult to increase the flow rate.

On the other hand, the current density (㎃ / cm ² ) flowing by the current device 2 is 80 to 150, which is advantageous for electrodeposition plating of the low nickel-based permalloy alloy thin layer on the surface of the cathode. At this time, the current density and the electrodeposition speed have a proportional relationship. In the range of the current density, the electrodeposition speed (µm / min) can be increased within the range of 1.2 to 2.25 as the current density increases, and thus electrodeposition is performed. It was possible to reduce the plating time and to produce a low Ni-based permalloy alloy sheet having excellent characteristics. When the current density is out of the range, that is, when the current density is less than 80 mA / cm 2, the electrodeposition rate is too slow, and thus the productivity drops. When the current density exceeds 150 mA / cm 2, hydrogen generation is excessive. Electrodeposition does not work well.

EMBODIMENT OF THE INVENTION Hereinafter, the Example of this invention is described in detail.

(Example 1)

109 g / l nickel chloride, 35 g / l iron sulfate, 25 g / l boric acid, 0.2 g / l sodium lauryl sulfate, 7.2 g / l sodium saccharin, 30 g / l sodium chloride and sodium citrate The electrolytic solution 8 containing 5.0 g / l and the acidity adjusted to pH 2.5 is filled in the electrolytic cell 8, and the temperature of the electrolytic solution 4 is maintained at approximately 65 deg.

Subsidiary bath (9) with cathode (1) of 50mm in width and 500mm in length, made of SUS 316 steel, was placed so that the gap between the electrolytic bath (8) was 6mm and the flow path was created. do. A flow rate of 120 cm / s due to the difference in water levels and an electrolyte temperature of 65 ° C. could produce a Fe-37 wt% Ni alloy thin plate.

Table 1 shows the thickness and composition of the Fe-Ni alloy thin plate according to the current density and electrodeposition speed optimized according to the present embodiment.

According to the above embodiment, the possibility of manufacturing a low nickel-based permalloy alloy thin plate, an alloy component having a desired composition ratio, that is, 37 wt% of Fe, 63 wt% of Fe, and appropriateness of the applied current density range could be confirmed. It is in the same range of composition as the Fe-36 wt% Ni alloy known as an invar alloy whose coefficient of thermal expansion is close to zero.

(Example 2)

Width and diameter of the drum type cathode 21: 1000 mm and 100 mm

Current density: 100 mA / cm ²

Thickness of Manufactured Continuous Thin Plate: 13㎜

It contains 109 g / l nickel chloride, 25 g / l iron sulfate, 25 g / l boric acid, 0.2 g / l sodium lauryl sulfate, 7.2 g / l sodium saccharin, 30 g / l sodium chloride and 5.0 g / l sodium citrate At the same time, the electrolytic solution 4 whose acidity is adjusted to pH 2.5 is filled in the electrolytic furnace 8 and the temperature of the electrolytic solution 4 is maintained at approximately 45 ° C.

The drum-shaped negative electrode 21 having a width of 100 mm and a diameter of 1000 mm manufactured using SUS 316 steel is rotatably supported by a supporting roller, and the length of the drum-type negative electrode 21 does not come into contact with the electrolyte solution. The drum type negative electrode 21 is immersed in the electrolyte solution 4. Using the electrolyte circulator 10, the water level difference between the two pools was 140 mm and the electrolyte temperature was 45 ° C. to produce Fe-50 wt% Ni alloy thin plates as shown in Table 2 below.

According to the present invention by using the principle of stirring with a laminar flow using a water level difference instead of the conventional stirring method, it is possible to provide an efficient electrodeposition apparatus without a special stirring device, that is, a low nickel-based permalloy having a uniform thickness and uniform composition, that is It is possible to easily and efficiently provide a Fe-Ni alloy sheet having a composition of Ni of 36 to 55 wt%.

Claims (7)

An electrolytic cell in which an electrolyte is accommodated and an anode is installed on an inner bottom thereof; An auxiliary bath installed inside the electrolytic cell so as to be spaced apart from the bottom of the electrolytic cell and having a negative electrode installed at a position opposite to the positive electrode; A current device provided between the anode and the cathode; An electrolyte solution circulation unit installed in a space formed by the electrolytic cell and the auxiliary bath; Apparatus for producing a thin plate by electrodeposition, characterized in that consisting of. delete delete delete delete The electrolyte is contained in the electrolytic cell so that the auxiliary bath or drum type cathode is partially submerged, and the electrolyte is transferred from the pool on one side to the pool on the other side by the electrolyte circulation device to form a flow of electrolyte between the anode and the cathode to form an alloy thin plate on the cathode. In the method for producing a low nickel-based permalloy alloy thin plate by electrodeposition to form; The composition of the electrolyte is Nickel Chloride 100 ~ 120g / L, Iron Sulfate 12 ~ 50g / L, Boric Acid 20 ~ 30g / L, Sodium Lauryl Sulfate 0.2 ~ 0.4g / l, sodium saccharin (Na Saccharin) 3.2 ~ 9.9g / l, sodium chloride (NaCl) 25 ~ 39g / l and sodium citrate (Na Citrate) 3.5 ~ 7.0g / l, the acidity of the electrolyte is pH 1.5 ˜3.0, wherein the temperature of the electrolyte is maintained at 20 to 80 ° C. to produce a Fe-36 to 55% by weight Ni alloy thin plate. The electrodeposition rate is within the range of 1.2 ~ 2.25 ㎛ / min in the range of the current density of 80 ~ 150 ㎃ / ㎠ A method for producing a low nickel-based permalloy alloy thin plate by electrodeposition.

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