KR102065221B1 - Apparatus for preparing alloy foil and alloy foil prepared using the same - Google Patents

Abstract

The present invention is an electrolytic cell containing an electrolyte; A drum type negative electrode which is partially immersed in the electrolytic cell and rotates; A positive electrode immersed in the electrolytic cell and disposed to be spaced apart from each other along a circumference of the negative electrode; And a liquid supply part immersed in the electrolytic cell and disposed between the anodes to supply an electrolyte solution, wherein the flow rate control member is formed on at least one side of the upper end of the anode. According to the present invention, the front face difference of the alloy foil can be controlled to 0.1 wt% or less, thereby preventing the occurrence of curl in a subsequent step.

Description

Alloy foil manufacturing apparatus and alloy foil manufactured using the same {APPARATUS FOR PREPARING ALLOY FOIL AND ALLOY FOIL PREPARED USING THE SAME}

The present invention relates to an alloy foil manufacturing apparatus and an alloy foil produced using the same.

Plating takes place for various purposes. The plating system and method are determined according to the purpose of use and cost. To date, many plating systems such as copper, nickel, gold, silver, tin, chromium, lead, and zinc have been developed and used.

Iron and its alloys are also one of the plating systems where much research is being done. There are two major researches on iron plating. One is the research of replacing nickel or chromium with relatively inexpensive iron, and the other is developing products with specific properties through alloy plating with other elements. Examples are Fe-Ni, Fe-Zn, Fe-Cr-Ni, Fe-P, Fe-B, Fe-C, Fe-C-B and the like.

Iron-nickel-based alloys are one of the fields where much research has recently been made. Although iron-nickel alloys are expensive, they are used in various fields due to their excellent physical properties. Among them, permalloy of Fe-80Ni (wt%) has excellent magnetic properties, and Invar alloy of Fe-36Ni (wt%) has a very low coefficient of thermal expansion.

Invar alloys have been found in Guillaume in 1897 and won the Nobel Prize in 1920. Invar alloys also lead to the development of various alloys through methods such as the addition of nickel alloys and the addition of third alloying elements, such as cobalt, to expand their application.

As described above, there are many methods for manufacturing iron-nickel alloys applied to various fields, but the method currently used is a traditional cold rolling method. In the case of using the cold rolling method, the alloy has to go through complicated processes such as melting, forging, hot rolling, heat treatment, cold rolling, and heat treatment, and the rolling process requires a large-scale facility and a very high energy consumption.

In addition, in the production of thin film materials, rolling and heat treatment must be repeated, and as the thickness becomes thinner, the process becomes more complicated, and the production cost increases exponentially. Falls. In order to overcome such limitations of the conventional manufacturing method, a lot of researches have recently been made on the production of iron-nickel alloy thin films by electroforming.

The variation in the width, length and thickness direction of the alloy foil made through electroforming is larger than that of the rolling method. Among these, the difference between the front and back sides, i.e., the difference between the components of the front and back surfaces, can be cited as a simple example of the component variation in the thickness direction of the foil. When the component measured on one side of the foil is different from the value measured on the other side, it can be called a component deviation before. This tends to occur in the foil made by electroforming. This component deviation means that there are variations on both sides in physical properties such as strength on both sides and coefficient of thermal expansion.

When the foil is heat-treated at a temperature of about 300, which is relatively low in diffusion of metal atoms, curling occurs in the foil as shown in FIG. If the curl exceeds a certain level, the process of foil handling or coating becomes impossible and the product loses its value. Therefore, in order to remove the curl after such heat treatment, it is necessary to control the front face difference to near zero.

The present invention is to provide a device for removing the component variation of the curl of the alloy foil produced using a drum-type negative electrode and the front and back causing it, and thus the alloy foil in which the front and back difference is controlled to 0.1% by weight or less.

According to an aspect of the present invention, an electrolytic cell in which an electrolyte is accommodated; A drum type negative electrode which is partially immersed in the electrolytic cell and rotates; A positive electrode immersed in the electrolytic cell and disposed to be spaced apart from each other along a circumference of the negative electrode; And a liquid supply part immersed in the electrolytic cell and disposed between the anodes to supply an electrolyte solution, wherein the flow rate control member is formed on at least one side of the upper end of the anode.

The height of the flow control member may be obtained according to the following formula.

[Equation 1]

H = 35.6 Ⅹ (A-B)

(Where H is the height of the flow regulating member, A is the nickel content of the solution surface, and B is the nickel content of the drum surface.)

The height of the flow control member may be 100mm or less.

The material of the flow rate control member may be at least one selected from polyvinylchloride (PVC), polypropylene (PP), polyethylene (PE), polycarbonate (PC), and polytetrafluoroethylene (PTFE).

The flow rate of the anode region in which the flow regulating member is formed may be 70% or more (excluding 100%) of the region in which the flow regulating member is not formed.

The alloy foil may be an iron-nickel alloy foil.

According to another aspect of the present invention, there is provided an alloy foil produced by the above method.

The front side difference of the alloy foil may be 0.1% by weight or less.

According to the present invention, the front face difference of the alloy foil can be controlled to 0.1 wt% or less, thereby preventing the occurrence of curl in a subsequent step.

1 illustrates curls generated when heat-treating a foil having a large front side difference.
2 is a schematic diagram of an electroforming apparatus including a conventional drum type cathode.
Figure 3 schematically shows the metal ion concentration in the cathode when the electrodeposition is made.
4 schematically shows an alloy foil device according to one embodiment of the invention.
Figure 5 shows the change of the front side difference according to the height of the flow control member.
6 and 7 show changes in the components of the electrodeposition layer according to the plating liquid supply flow rate.
8 shows the change of components of the electrodeposition layer according to the plating liquid supply flow rate.
Figure 9 shows a photograph after the heat treatment of the alloy foil prepared according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to various examples. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

The present invention relates to an alloy foil manufacturing apparatus and an alloy foil produced using the same.

2 is a schematic diagram of a commonly used electroforming system. Referring to FIG. 2, the iron-nickel alloy foil 1 through electroforming or electroforming can be produced according to the following.

The electrolyte is supplied through the liquid supply part 14 to a gap surrounded by a rotating cylindrical drum type cathode 12 provided in the electrolytic cell 11 and a pair of arc-shaped insoluble anodes 13 opposed thereto. At this time, by applying an electric current, the iron-nickel alloy is electrodeposited on the surface of the negative electrode drum, and the iron-nickel alloy foil 1 is manufactured by winding it.

There are various reasons for the variation in the thickness direction of the iron-nickel alloy foil 1 produced by the above electroforming method. In the case of manufacturing the metal foil using the drum type electroforming apparatus of FIG. 3, the electrolyte is supplied from the lowermost end of the drum 12, and the supplied electrolyte is supplied through the flow path between the surface of the drum 12 and the anode 13. It is discharged by moving upwards. In this process, electrodeposition of the metal starts from the left drum surface 16-1 of FIG. 3 and electrodeposition of the metal is terminated on the opposite drum surface 16-2.

When an alloy foil is manufactured using the rotating drum as a cathode as described above, two surfaces of the foil have different physical properties. For example, in the case of roughness, the roughness of the drum surface attached to the drum is the same as that of the drum, but in the case of the solution surface in contact with the solution, the composition of the foil, the type and amount of the additive, the temperature, the pH, It is determined by the influence of many variables such as flow rate.

In the case of the components focused in the present invention, the components of the drum side and the solution side may be different. The composition of the foil may be affected by the type and condition of the cathode where electrodeposition is performed. In the case of the drum surface, electrodeposition is usually performed in a drum made of titanium or stainless steel, whereas in the case of the solution surface, electrodeposition is performed from the middle of the product. Component differences may occur. In addition, the difference between the gap between the left and the right, the flow (stirring), the temperature, etc. with respect to the plating liquid supply nozzle of FIG. 1 may cause a front surface difference.

Figure 3 schematically shows the metal ion concentration at the cathode when the electrodeposition is made. In the cathode, metal ions are consumed because electrode ions are electrodeposited, and these ions are supplied near the cathode surface through convection and diffusion. The metal ion concentration (C _a ) of the cathode surface is determined by the speed of the two ion supply processes and the consumption rate of the cathode.

The flow rate supplied from the electroforming apparatus is a contributing factor. As the flow rate increases, the supply of each metal ion becomes smooth, and the C _a of each ion increases. The concentration and proportion of metal ions in alloy plating are the most influential variables that determine the composition of the plated product. That is, the flow rate supplied to the plating cell affects the composition of the product by affecting the metal ion concentration on the surface of the cathode.

Accordingly, the present inventors have realized that the difference between the front and rear surfaces can be reduced by controlling the flow rate in the region where the drum surface and the solution surface are electrodeposited, and have completed the present invention. FIG. 4 schematically shows an alloy foil device according to an embodiment of the present invention. Hereinafter, the present invention will be described in more detail with reference to FIG. 4.

According to an aspect of the present invention, an electrolytic cell 11 in which an electrolyte is accommodated; A drum type negative electrode 12 which is partially immersed in the electrolytic cell and rotates; An anode (13) immersed in the electrolytic cell and spaced apart from each other along a circumference of the cathode; And a liquid supply unit 14 which is immersed in the electrolytic cell and disposed between the anodes to supply an electrolyte solution, and a flow rate adjusting member 10 is formed on at least one side of the upper end of the anode. do.

In the alloy foil manufacturing apparatus of the present invention, a flow rate adjusting member is formed on at least one side of the upper end of the anode. The flow regulating member serves to make a kind of dam in the area where the overflow of the plating liquid occurs, thereby varying the water level of both sides. If the flow rate control member is installed to increase the water level, the water pressure is increased to reduce the flow rate of the side on which the flow rate control member is installed. By adjusting the height of the flow rate adjusting member, the flow rate difference between both sides may be adjustable, which means that the front side difference of the foil to be manufactured can be controlled.

The height of the flow regulating member can be obtained according to the following equation.

[Equation 1]

H = 35.6 Ⅹ (A-B)

(Where H is the height of the flow control member, A is the nickel content of the solution surface, and B is the nickel content of the drum surface.) FIG. 5 shows the change of the front and rear difference according to the height of the flow control member. Referring to FIG. 5, the front surface difference (difference between the nickel content of the solution surface and the nickel content of the drum surface) is -0.0281 Ⅹ (height of the flow regulating member) +58.31, so that the height of the flow regulating member (H ) Can be derived from the relationship of 35.6 Ⅹ before.

On the other hand, Figure 6 shows the component change of the electrodeposition layer according to the plating liquid supply flow rate. As described above, since the height of the flow regulating member is derived from the relationship between 35.6 kPa (difference between the nickel content of the solution surface and the nickel content of the drum surface), the nickel content in the electrodeposited layer is -0.078 kPa. Can be.

The height of the flow control member may be 100mm or less (excluding 0) of the height of the flow control member, more preferably 20 to 60mm. In particular, the height of the flow rate control member derived according to Equation 1 described above is more preferably 30 to 40mm.

In addition, the flow rate of the positive electrode region in which the flow rate regulating member is formed may be 70% or more, that is, 70 to 100% of the flow rate of the region where the flow rate regulating member is not provided. As shown in Fig. 7, it can be seen that the relationship of component) = (flow rate) *-0.2229 + 51.7 holds. That is, the relationship of (flow rate) = (component) * -4.49 +232 is established. This means that the flow rate variation of 4.5 m ³ / h is required to compensate for the 1% component difference, which is about 15% due to the flow rate difference, and thus 30% on both sides when 2 Ni wt% of front face difference occurs. It can be seen that the flow rate difference is required.

The flow control member is preferably made of a non-conductive material, but is not particularly limited, for example, PVC (Polyvinylchloride), PP (Polypropylene), PE (Polyethylene), PC (Polycarbonate) and PTFE (Polytetrafluoroethylene) It may be formed of one or more selected from.

Since the positive voltage is applied to the anode, when a material such as iron is used, the phenomenon of oxidizing and melting occurs. However, you may consider using expensive metals such as Titanium or Hastelloy, which have good corrosion resistance. It is preferable to use one or more selected from

On the other hand, the alloy foil manufacturing apparatus of the present invention can be used without limitation, preferably can be used to manufacture the iron-nickel alloy foil. Hereinafter, the present invention will be described in more detail by exemplifying the production of iron-nickel alloy foils.

Iron-nickel alloy plating in order during the manufacture of the foil by about 50 wt% Ni the Ni ^{2 +} ions in a concentration higher than Fe ^{2 +} ions are used in the plating solution. Although nickel is a rarer metal than iron, it is due to an abnormal codeposition that makes electrode deposition easier.

Ni ^{2 +} ions is more than lot in the plating liquid, because the amount of the two ion consumed in the cathode is similar to the Fe ^{2 +} is the supply yohage i.e., strong convection and diffusion of large ions than Ni ^{2 +.} Accordingly, when a strong stirring or high flow rate plating solution is supplied, the iron content of the product is high and the nickel content is low.

In order to confirm this, the case of experiment by adjusting the rpm of the rotating stirrer by the beaker scale is shown in FIG. In addition, in the case of using the manufacturing equipment equipped with a flow rate control member as the present invention, the nickel content is increased when the flow rate is lowered, which is shown in FIG. Therefore, in the case of iron-nickel alloy electroforming, if there is a difference in the components of the solution side and the drum side, it can be seen that the nickel content can be increased by lowering the flow rate and flow rate in the region with low nickel content.

As described above, the alloy foil manufactured using the apparatus for producing an alloy foil according to the present invention has a front side difference of 0.1 wt% or less, and thus prevents occurrence of curl in a subsequent process.

Example

Hereinafter, an Example is given and this invention is demonstrated more concretely. The following examples are intended to illustrate the present invention in more detail, and the present invention is not limited thereto.

Example

An alloy foil manufacturing apparatus including a rotating drum-type cathode, a cathode surrounding the anode, a nozzle disposed between the anode to supply an electrolyte, and a winding unit for winding the formed foil was prepared, and an iron-nickel alloy foil was manufactured using the same.

As the electrolyte, a solution containing 12 g / L iron ions, 40 g / L nickel ions, 20 g / L sodium, and 3 g / L boron was used. The electrolyte was supplied at a flow rate of 35 m ³ / hr under the condition that the pH of the electrolyte solution was 2.0, the temperature was 57, and the current density was 30 A / dm ² . The thickness of the produced iron-nickel alloy foil was 20 μm.

First, the components of the drum surface and the solution surface of the foil prepared without installing the flow control member were measured using an X-ray Fluorescence Spectrometer (XRF), respectively. As a result, the solution side was 46.3 Ni wt% and the drum side was 45.7 Ni wt%.

This means that the nickel content of the solution side is 1.6 Ni wt% higher than the drum side. Nickel content in iron-nickel alloy foils affects the coefficient of thermal expansion (CTE) and strength.

This affects the expansion rate of both surfaces at the time of heat treatment, resulting in a phenomenon (curl) in which the foil bends toward the Ni component. As described above, when the foil having high Ni content in the solution surface was heat-treated at 300, it can be seen that horizontal curl of 11 mm occurred.

Since the component of the drum side is lower than that of the solution side, the flow control member made of PVC is installed on the side of the drum to make the flow rate relatively low. On the other hand, the flow control member was manufactured detachably replaceable during production. 5 shows the front surface difference (solution surface component-drum surface component) when the flow rate control members of various heights are installed.

As can be seen in Figure 5, but the front side difference more than 1 Ni wt% occurred, it was possible to make this close to 0 by installing a flow control member of 60mm on the drum surface side. In the case of heat treatment of this product that the difference is close to zero before the front surface is shown in Figure 9 it can be seen that the curl does not occur.

Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and variations can be made without departing from the technical spirit of the present invention described in the claims. It will be obvious to those of ordinary skill in the field.

Claims (8)

An electrolytic cell in which an electrolyte is accommodated;
A drum type negative electrode which is partially immersed in the electrolytic cell and rotates;
A positive electrode immersed in the electrolytic cell and disposed to be spaced apart from each other along a circumference of the negative electrode; And
And a liquid supply part immersed in the electrolytic cell and disposed between the anodes to supply an electrolyte solution.
At least one side of the anode is an alloy foil manufacturing apparatus is formed with a flow rate control member.
The method of claim 1,
Alloy foil manufacturing apparatus, characterized in that the height of the flow regulating member is obtained according to the following formula.
[Equation 1]
H = 35.6 Ⅹ (AB)
(Where H is the height of the flow regulating member, A is the nickel content (wt%) of the solution side, and B is the nickel content ((wt%)) of the drum face.)
The method of claim 1,
Alloy foil manufacturing apparatus, characterized in that the height of the flow control member is 100mm or less (excluding 0).
The method of claim 1,
The material of the flow control member is an alloy foil manufacturing apparatus, characterized in that at least one selected from PVC (Polyvinylchloride), PP (Polypropylene), PE (Polyethylene), PC (Polycarbonate) and PTFE (Polytetrafluoroethylene).
The method of claim 1,
The flow rate of the positive electrode region in which the flow rate control member is formed is 70% or more of the region where the flow rate control member is not formed.
The method of claim 1,
Alloy foil manufacturing apparatus, characterized in that the alloy foil is iron-nickel alloy foil.
An alloy foil produced by using the alloy foil manufacturing apparatus according to any one of claims 1 to 6.
The method of claim 7, wherein
Alloy foil, characterized in that the front side difference of the alloy foil is 0.1% by weight or less.

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