WO2019124791A1

WO2019124791A1 - Apparatus for manufacturing alloy foil and alloy foil manufactured using same

Info

Publication number: WO2019124791A1
Application number: PCT/KR2018/014806
Authority: WO
Inventors: 양홍석; 이재곤; 정관호; 김홍준; 김현태; 김종권; 홍재화
Original assignee: 주식회사 포스코
Priority date: 2017-12-22
Filing date: 2018-11-28
Publication date: 2019-06-27
Also published as: KR102065221B1; KR20190076466A

Abstract

The present invention relates to an apparatus for manufacturing an alloy foil, comprising: an electrolytic bath containing an electrolyte; a drum type cathode that is rotated while being partially immersed in the electrolytic bath; a plurality of anodes immersed in the electrolytic bath and arranged along the periphery of the cathode so as to be spaced apart from each other; and a electrolyte supply unit immersed in the electrolytic bath and disposed between the anodes to supply an electrolyte, wherein a flow rate regulating member is formed on at least one side of the upper ends of the anodes. According to the present invention, it is possible to control a difference between a front surface and a rear surface of the alloy foil to 0.1 wt% or less, thereby preventing generation of curls in subsequent processes.

Description

Alloy foil manufacturing apparatus and alloy foil manufactured using the same

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

Plating is done for various purposes. Many plating systems such as copper, nickel, gold, silver, tin, chrome, lead, and zinc have been developed and used until now depending on the purpose and cost of the plating system and method.

Iron and its alloys are also one of the most studied alloys. There are two major researches on iron plating. One is the relatively low cost alternative to nickel and chromium, and the other is the development of products with specific properties through alloy plating with other elements. Fe-Ni, Fe-Zn, Fe-Cr-Ni, Fe-P, Fe-B, Fe-C and Fe-C-B.

Iron-nickel alloys are one of the areas where many researches have been conducted recently. Iron-nickel-based alloys are used in many fields with excellent physical properties despite their high cost. Among them, permalloy of Fe-80Ni (wt%) has excellent magnetic properties and Fe-36Ni (wt%) Invar alloy has very low coefficient of thermal expansion.

Invar alloy has been widely used in precision machinery and semiconductor materials since Guillaume was found in 1897 and received the Nobel Prize in 1920. In addition, the invar alloy has been linked to the development of various alloys by changing the content of nickel and adding a third alloy element such as cobalt, and the application range of the alloy is being widened.

There are various methods of manufacturing iron-nickel alloys applicable to various fields as described above, but the main method currently used is conventional cold rolling. When the cold rolling method is used, complicated processes such as melting, forging, hot rolling, heat treatment, cold rolling and heat treatment of alloys must be performed. Rolling is a process requiring large scale equipment and consuming a great amount of energy.

In addition, when producing a thin film material, it is necessary to repeat the process of rolling and heat treatment. As the thickness becomes thinner, the process becomes complicated and the production cost rises exponentially. Falls. In order to overcome the limitations of the conventional manufacturing method, there have been many studies on the production of iron-nickel alloy thin films by electroforming (electroforming).

The width, length and thickness direction component of the alloy foil made by electroforming is larger than that of the rolling process. Among them, the component difference in the thickness direction of the foil creates a difference in electric field, that is, a difference in the component of the front surface. When the component measured on one side of the foil differs from the value measured on the other side, it can be called the component deviation of the former, and this deviation tends to occur in foils made by electroforming. This component deviation means that there are variations on both sides of the physical properties such as strength and thermal expansion coefficient on both sides.

When the foil is subjected to heat treatment at a relatively low temperature of about 300 캜 at which metal atoms are not diffused, a curl is generated in the foil as shown in Fig. 1 due to the deviation of both sides. If the curl exceeds a certain level, the process of foil handling or coating becomes impossible and the value of the product is lost. Therefore, in order to eliminate the curl after such heat treatment, it is necessary to control the difference of the electric potential close to zero.

The present invention provides an apparatus for removing curl of an alloy foil manufactured by using a drum type negative electrode and a front surface of a front surface of the alloy foil, and an alloy foil having a front side difference of 0.1 wt% or less.

According to an aspect of the present invention, there is provided an electrolytic cell comprising: an electrolytic bath containing an electrolytic solution; A drum type negative electrode partially immersed in the electrolytic bath and rotated; A cathode immersed in the electrolytic cell and arranged along a periphery of the cathode, the plurality of electrodes being spaced apart from each other; And a liquid supply part immersed in the electrolytic bath and disposed between the anode and the electrolyte to supply an electrolytic solution, wherein a flow rate regulating 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.

[Formula 1]

H = 35.6 X (A-B)

(Where H is the height of the flow rate control 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 100 mm or less.

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

The flow rate of the anode region where the flow rate regulating member is formed may be 70% or more of the region where the flow rate 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 difference in electric field of the alloy foil may be 0.1 wt% or less.

According to the present invention, it is possible to control the electric field difference of the alloy foil to 0.1 wt% or less, thereby preventing the generation of curl in the subsequent process.

Fig. 1 shows the curl which occurs when the foil having the difference in electric field is heat-treated.

2 is a schematic view of an electroforming apparatus including a conventional drum-shaped negative electrode

Figure 3 schematically shows the metal ion concentration at the cathode when electrodeposition is carried out.

4 schematically shows an alloy foil apparatus according to an embodiment of the present invention.

Fig. 5 shows the change in the difference of the electric field depending on the height of the flow control member.

6 and 7 show changes in the composition of the electrodeposited layer depending on the flow rate of the plating liquid supplied.

8 shows changes in the composition of the electrodeposited layer depending on the supply amount of the plating liquid.

9 is a photograph of the alloy foil manufactured according to the present invention after heat treatment.

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

The present invention relates to an apparatus for producing an alloy foil and an alloy foil manufactured using the same.

2 is a schematic view of a commonly used electroforming system; Referring to Fig. 2, the iron-nickel alloy foil 1 through electroforming or electroforming can be manufactured as follows.

The electrolytic solution is supplied through the liquid-permeable portion 14 into the gap surrounded by the rotating drum-shaped negative electrode 12 provided in the electrolytic bath 11 and the pair of arc-shaped insoluble anodes 13 opposed thereto. At this time, an iron-nickel alloy foil (1) is produced by electrodepositing an iron-nickel alloy on the surface of the negative electrode drum by energizing the current and winding it.

There are various reasons why the compositional deviation in the thickness direction of the iron-nickel alloy foil 1 produced by the electroforming method as described above occurs. 3, the electrolytic solution is supplied from the lowermost end of the drum 12, and the supplied electrolytic solution is supplied to the electrolytic bath through the channel between the surface of the drum 12 and the anode 13 And then discharged. In this process, the electrodeposition of the metal starts from the left drum surface (position 16-1) in Fig. 3, and the electrodeposition of the metal at the opposite side of the drum surface (position 16-2) is terminated.

When the alloy foil is manufactured using the rotating drum as the negative electrode, the 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 contacting with the solution, the composition of the foil, the kind and amount of additives, Flow rate, and other variables.

In the present invention, components of the solution surface may be different from those of the drum surface. The components of the foil are affected by the type and state of the cathode on which the electrodeposition occurs. In the case of the drum surface, the electrodeposition is usually carried out on a drum made of titanium or stainless steel. On the other hand, This can lead to component differences. Also, if there is a gap between the left and right gaps, flow (stirring), temperature, etc., around the plating liquid supply nozzle of FIG. 1, a difference may occur.

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

Flow rate supplied by the electroforming apparatus becomes higher the flow rate as a factor causing the convection when desired supply of the respective metal ion C _a of each ion is high. The concentration and proportion of metal ions in alloy plating are the most influential variables determining the composition of the plating product. That is, the flow rate supplied to the plating cell affects the composition of the product by influencing the metal ion concentration on the surface of the cathode.

Therefore, the inventors of the present invention focused on the fact that controlling the flow rate of the drum surface and the region where the solution surface is electrodeposited can reduce the difference in the electric field, and have completed the present invention. FIG. 4 is a schematic view of an alloy foil apparatus according to an embodiment of the present invention, and the present invention will be described in detail with reference to FIG.

According to an aspect of the present invention, there is provided an electrolytic cell comprising: an electrolytic bath (11) containing an electrolytic solution; A drum type negative electrode 12 partially immersed in the electrolytic bath and rotated; A positive electrode (13) immersed in the electrolytic cell and arranged along a periphery of the negative electrode so as to be spaced apart from each other; And a liquid supply portion (14) immersed in the electrolytic bath and disposed between the positive and negative electrodes to supply an electrolytic solution, wherein a flow regulating member (10) is formed on at least one side of the upper end of the positive electrode do.

In the apparatus for producing an alloy foil of the present invention, a flow rate regulating member is formed on at least one side of the upper end of the anode. The flow rate controlling member plays a role of making a kind of dam in an area where overflow of the plating liquid occurs, thereby making the water level on both sides different. When the flow rate regulating member is installed and the water level is increased, the water pressure is increased and the flow rate on the side where the flow rate regulating member is installed decreases. By adjusting the height of the flow control member, the flow rate difference between the two sides can be adjusted, which means that the difference in the front of the foil can be controlled.

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

[Formula 1]

H = 35.6 X (A-B)

(Where H is the height of the flow rate control member, A is the nickel content of the solution surface, and B is the nickel content of the drum surface). (Difference in nickel content between the solution surface and the drum surface) is -0.0281 X (height of the flow control member) +58.31, the height H of the flow control member ) Is 35.6 x D, it can be derived from the relationship of the difference.

On the other hand, FIG. 6 shows changes in the composition of the electrodeposited layer depending on the supply amount of the plating liquid. As described above, the height of the flow control member is derived from the relationship of 35.6 χ (difference between the nickel content on the solution surface and the nickel content on the drum surface), so that the nickel content in the electrodeposited layer is -0.078 x .

The height of the flow rate regulating member may be 100 mm or less (excluding 0), more preferably 20 to 60 mm, in height of the flow rate regulating member. In particular, it is more preferable that the height of the flow rate adjusting member derived from Equation 1 described above is 30 to 40 mm.

In addition, the flow rate of the anode 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 installed. (Flow) * - 0.2229 + 51.7, as shown in Fig. 7, is established. That is, the relationship (flow rate) = (component) * - 4.49 + 232 holds. This means that a flow rate variation of 4.5 m ³ / h is required to compensate for the component difference of 1%, which is about 15% due to the difference in flow rate. Therefore, if the difference is 2 Ni wt% The flow rate difference between the two is required.

The flow rate controlling member is preferably made of a nonconductive material. The flow rate controlling member may be made of, for example, PVC, polypropylene, polyethylene, polycarbonate and PTFE, And the like.

Since a positive voltage is applied to the positive electrode, when a material such as iron is used, a phenomenon occurs in which the material is oxidized and melted. However, in consideration of time and cost, it is possible to use an expensive metal such as titanium or Hastelloy which has good corrosion resistance. However, considering time and cost, it is possible to use PVC, Polypropylene, PE, Polycarbonate, ) Is preferably used.

On the other hand, the apparatus for producing an alloy foil of the present invention can be used without limitation, but can be preferably used for producing an iron-nickel alloy foil. Hereinafter, the present invention will be described in more detail with reference to the production of an iron-nickel alloy foil.

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. Nickel is a more rare metal than iron, but it is due to abnormal codeposition that the deposition of iron is easier. This is because the abnormal alloy corresponds to abnormal codeposition.

Compared to Ni ² ⁺ ions in the plating solution, Fe ² ⁺ consumes more ions than Ni ² ⁺ , ie, strong convection and diffusion, because the amount consumed at the cathode is similar for the two ions. As a result, when a strong agitation or high flow rate plating solution is supplied, the iron content of the product is increased and the nickel content is decreased.

FIG. 8 shows an experiment in which the rpm of the rotating agitator is adjusted by the beaker scale to confirm this. Also, when the manufacturing facility equipped with the flow rate control member is used as in the present invention, the nickel content is increased when the supplied flow rate is lowered, as shown in FIG. Therefore, in the case of iron-nickel alloy electroforming, it can be seen that when there is a difference in the composition of the solution surface and the drum surface, the nickel content can be increased by lowering the flow and flow rate in the nickel content region.

As described above, the alloy foil manufactured using the apparatus for producing an alloy foil according to the present invention has a difference in electric field difference of less than 0.1% by weight, so that the generation of curl in the subsequent process can be prevented.

실시예Example

Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are intended to further illustrate the present invention and are not intended to limit the present invention.

Example

An alloy foil manufacturing apparatus comprising a rotating drum negative electrode, an anode surrounding the rotating drum negative electrode, a nozzle disposed between the anode and the anode, and a winding portion winding the formed foil are prepared and an iron-nickel alloy foil is manufactured using the apparatus.

A solution containing 12 g / L of iron ion, 40 g / L of nickel ion, 20 g / L of sodium and 3 g / L of boron was used as the electrolytic solution. The electrolytic solution was supplied at a flow rate of 35 m ³ / hr at a pH of 2.0, a temperature of 57 ° C and a current density of 30 A / dm ² . The thickness of the produced iron-nickel alloy foil was 20 탆.

First, the components of the drum surface and the solution surface of the foil manufactured without the flow rate controlling member were measured by using an X-ray fluorescence spectrometer (XRF). As a result, the solution surface was 46.3 Ni wt% and the drum surface was 45.7 Ni wt%.

This means that the nickel content on the solution side is 1.6 Ni wt% higher than the drum surface. In an iron-nickel alloy foil, the nickel component affects the coefficient of thermal expansion (CTE) and strength.

This affects the expansion ratio of both sides during the heat treatment, resulting in a phenomenon in which the foil bends toward the higher Ni component (curl). As described above, it can be seen from FIG. 1 that when the foil having a high Ni content on the solution surface is heat-treated at 300 ° C, 11 ㎜ of horizontal curl is generated.

Since the component of the drum surface is lower than the component of the solution surface, a flow regulating member made of PVC is provided on the drum side to relatively lower the flow rate. On the other hand, the flow rate control member was manufactured as a detachable type that can be replaced during production. FIG. 5 shows the difference in surface area (solution surface component-drum surface component) when flow adjusting members having various heights were provided.

As can be seen from FIG. 5, a difference of more than 1 Ni wt% occurred, but if a flow control member of 60 mm was installed on the drum side, it could be made close to zero. FIG. 9 shows that the heat-treated product of the present invention, which has a car of 0 in the case of electric discharge, has no curl.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be obvious to those of ordinary skill in the art.

Claims

An electrolytic bath containing an electrolytic solution;

A drum type negative electrode partially immersed in the electrolytic bath and rotated;

A cathode immersed in the electrolytic cell and arranged along a periphery of the cathode, the plurality of electrodes being spaced apart from each other; And

And a liquid-supply unit immersed in the electrolytic bath and disposed between the positive electrodes to supply an electrolytic solution,

And a flow rate regulating member is formed on at least one side of the upper end of the positive electrode.
The method according to claim 1,

Wherein the height of the flow control member is obtained according to the following formula.

[Formula 1]

H = 35.6 X (A-B)

(Where H is the height of the flow control member, A is the nickel content (wt%) on the solution surface, and B is the nickel content ((wt%)) on the drum surface.
The method according to claim 1,

Wherein the flow control member has a height of 100 mm or less (excluding 0).
The method according to claim 1,

Wherein the flow control member is made of at least one material selected from the group consisting of polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE), polycarbonate (PC), and polytetrafluoroethylene (PTFE).
The method according to claim 1,

Wherein the flow rate of the anode region in which the flow rate regulating member is formed is 70% or more of the region in which the flow rate regulating member is not formed.
The method according to claim 1,

Wherein the alloy foil is an iron-nickel alloy foil.
An alloy foil produced by using the apparatus for producing an alloy foil according to any one of claims 1 to 6.
8. The method of claim 7,

Wherein the difference in electric field of the alloy foil is 0.1 wt% or less.