KR20040108038A - Electroplating apparatus for controlling metal ions concentration in the electrolyte and method used by the apparatus - Google Patents

Abstract

PURPOSE: To provide an electroplating apparatus and method for substantially lowering manufacturing cost by constantly controlling concentration of metal ions in plating solution, an electroplating apparatus and method for easily electroplating a multicomponent alloy, and a product uniformly electroplated with the multicomponent alloy. CONSTITUTION: The electroplating apparatus(100) comprises a plating pot(110) including a plating solution, anode(120) and cathode(130) contacted with the plating solution(170) in the plating pot, and a power source(140) electrically connected to the anode and the cathode so that an electric current passes through the anode and the cathode, wherein the anode is consisted of one or more of soluble metal electrodes to be plated(122,123), and an insoluble electrode(121), wherein the apparatus further comprises a soluble metal electrode moving means(150) connected to the one or more of soluble metal electrodes composing the anode to move the one or more of soluble metal electrodes to the outside of the plating solution during electroplating, and an adjustment means(160) for adjusting time in which the one or more of soluble metal electrodes are used as the anode during electroplating by controlling the moving means, wherein the moving means is consisted of cylinder and air pipe, wherein in the electrodes composing the anode, the soluble metal electrodes and the insoluble electrode are selectively repeatedly used as the anode during electroplating, and wherein the soluble metal electrodes are nickel and iron, and the insoluble electrode is platinum.

Description

Electroplating apparatus for controlling metal ions concentration in the electrolyte and method used by the apparatus}

The present invention relates to an electroplating method and apparatus, and more particularly, to an alloy plated by maintaining a constant metal ion concentration forming the plated film in the process of plating the plated body with a plated film including at least one metal. The present invention relates to a plating method for controlling the concentration of metal ions contained in the plating solution so as to produce a uniform content, and an apparatus used in the method.

In general, important factors affecting the surface condition and composition quality of the plating products include the temperature, concentration of the plating solution, the amount of current given, and the surface shape of the cathode, but among these, the concentration of the metal ion to be plated in the plating solution is most important. .

For example, a method of using an insoluble electrode or a soluble electrode is known to produce a permalloy plated product, which is an alloy of nickel and iron, by electroplating.

When the insoluble electrode is used in the conventional apparatus for manufacturing a permalloy or nickel-iron alloy plating product, the iron and nickel ions in the plating solution are gradually decreased because iron and nickel ions in the solution are precipitated in stainless steel. When nickel electrode is used, iron and nickel ions in the plating solution are dissolved 100%, but only about 90% of iron and nickel ions are deposited on the surface of the stainless steel of the cathode depending on the current efficiency. As the plating process progresses due to the accumulation of iron and nickel ions in the solution, the iron and nickel ions continuously increase in the plating solution.

Therefore, in the case of plating permalloy alloy by depositing iron and nickel on the negative electrode stainless steel using an insoluble anode, the plating solution component is regularly measured at least once per plating bath whenever the work is performed to maintain the plating solution composition. When the iron and nickel ions concentration in the plating solution was different from the standard concentration, a certain solution was discharged and a permalloy metal solution was added to the plating solution to maintain the iron and nickel ion concentrations within the management standard. This is the same even when using a soluble anode.

Therefore, in the case of producing mass-produced plated products industrially by controlling the concentration of metal ions in such a conventional plating solution, the amount of metal ions added to the plating bath in the ionic state is added to the plating bath in order to uniformly control the metal ion concentration. Since it has to be, it has a problem of causing an increase in manufacturing cost.

In order to solve the above problems, an object of the present invention is to provide an electroplating apparatus and an electroplating method which can be controlled to maintain a constant concentration of the metal ion to be plated in the plating solution.

In addition, an object of the present invention is to provide an electroplating apparatus and an electroplating method capable of significantly lowering the manufacturing cost since the concentration of metal ions to be plated in the plating solution is controlled by a mechanical method.

In addition, an object of the present invention is to provide an electroplating apparatus and an electroplating method which can be easily plated with a plural alloy.

It is another object of the present invention to provide a product uniformly plated with a plural alloy.

1 is a schematic view for explaining the configuration of an electroplating apparatus according to a preferred embodiment of the present invention and controlling the concentration of metal ions to be plated in the plating solution in the apparatus.

<Description of Symbols for Major Parts of Drawings>

100: electroplating apparatus 110: plating bath

120 anode 121 insoluble electrode

122, 123: soluble metal electrode 130: cathode

140: power source 141: rectifier

150: soluble metal electrode moving means 160: adjusting means

170: plating solution

In order to achieve the above object, the present invention provides a plating bath containing a plating solution, an anode and a cathode in contact with the plating solution of the plating bath as an embodiment, and the current and the anode and cathode In an electroplating apparatus comprising a power source electrically connected with an anode and a cathode so as to pass through, the anode provides an electroplating apparatus, characterized in that it comprises one or more soluble plated metal electrodes and an insoluble electrode.

According to an embodiment of the present invention, the one or more soluble metal electrodes constituting the anode are connected to one or more soluble metal electrodes to move the one or more soluble metal electrodes to the outside of the plating solution during electroplating, and the one or more means are controlled by the movement means. It provides an electroplating apparatus characterized in that it further comprises a control means for controlling the time that the above soluble metal electrode is used as the anode during electroplating.

The present invention provides an electroplating apparatus, characterized in that the moving means is composed of a cylinder and an air pipe.

The present invention provides an electroplating apparatus, in which the soluble metal electrode and the insoluble electrode are selectively used as an anode during electroplating among the electrodes constituting the anode.

The present invention provides an electroplating apparatus according to one embodiment, wherein the soluble metal electrodes are nickel and iron, and the insoluble electrode is platinum.

In another embodiment, the present invention is to contact the substrate to be plated with the plating solution of the plating bath; In the electroplating method comprising applying a sufficient current density to the plating bath to deposit a metal on the substrate, the metal ions to be plated in the plating solution by selectively using an insoluble electrode and a soluble plated metal electrode as an anode It provides an electroplating method characterized by adjusting the concentration.

In one embodiment, the present invention provides an electroplating method, wherein the soluble metal electrode is at least one.

In one embodiment, the present invention provides an electroplating method, characterized in that it is repeatedly used in the order of any one of the soluble metal electrode, the insoluble electrode, and the other of the soluble metal electrode as the anode during the electroplating.

The present invention provides an electroplated product, characterized in that the metal plated on the product as a multi-element alloy.

The present invention provides an electroplating product, characterized in that the multi-element alloy is an iron-nickel alloy.

Hereinafter, with reference to the accompanying drawings will be described in detail the present invention.

1 is a schematic view for explaining the configuration of an electroplating apparatus according to a preferred embodiment of the present invention, as shown in FIG. 1, the electroplating apparatus 100 of the present invention is a plating bath including a plating solution 170 A cathode 120 made of a plated body on 110 and one or more soluble metal electrodes 122 and 123 and an insoluble electrode 121 to be plated may include a plating solution of the plating bath 110. A power source 140 electrically connected to the anode 120 and the cathode 130 is provided to contact the 170 and to pass through the anode 120 and the cathode 130.

The power source may be connected to the rectifier 141 so that the current density applied to the plating bath 110 is constant. In addition, the electroplating apparatus 100 further includes a soluble metal electrode moving means 150 to adjust the concentration of metal ions to be plated in the plating solution 170.

One or more soluble metal electrodes 122, 123 .. by the soluble metal electrode moving means 150 are repeatedly moved out of the plating solution 170 at regular time intervals to dissolve in the plating solution 170. In order to block the reaction and remove the difference between the amount of the soluble metal electrodes 122 and 123 .. dissolved and plated, plating is performed by using only the insoluble electrode 121 as the anode, and the soluble metal is again soluble after a certain time. By contacting the metal electrodes 122, 123, ... with the plating solution 170, the concentration of metal ions in the plating solution 170 is kept constant.

Here, the soluble metal electrode moving means 150 and the soluble metal electrodes 122, 123, .. are connected using a connection structure of a known configuration, and the soluble metal electrode moving means 150 is the at least one soluble metal electrode. (122, 123, ...) is composed of air pipes and cylinders, in particular pneumatic cylinders are connected to the air pressure, it is electrically connected to the power source 140, the electrical movement is controlled through an electric motor or the like. May be

In addition, the electroplating apparatus 100 of the present invention outputs a signal for controlling the soluble metal electrode moving means 150 to determine the time when the one or more soluble metal electrodes 122, 123, ... is used as an anode during electroplating. The adjusting means 160 is a control device of a known configuration including an operation unit and a processing unit, and automatically adjusts the soluble metal electrode moving means (according to the information input by the operation unit). 150 is repeatedly controlled to maintain a constant concentration of soluble metal ions in the plating solution 170 until the plating is completed.

Next, referring to the apparatus of FIG. 1 to control the concentration of the soluble metal ions in the plating solution in more detail, the anode 120 is an insoluble electrode 121, a soluble metal electrode 1 122, and a soluble metal, respectively. The electrode 2 (123), the soluble metal electrode 1 122 and the soluble metal electrode 2 (123) are each connected to a pneumatic cylinder, each of the pneumatic cylinder is connected to the air pipe. Since the pneumatic cylinder is controlled by the operation of the adjusting means 160, once the electroplating apparatus 100 is operated, the pneumatic cylinder connected to the soluble metal electrode 1 122 is operated according to a time 1 preset to the adjusting means. Thus, the soluble metal electrode 1 is positioned outside the plating solution 170, and only the soluble metal ion 2 is formed because the soluble metal electrode 2 123 acts as an anode for the set time 1.

When the set time 1 passes, the pneumatic cylinder is controlled by the adjusting means 160 to move the soluble metal electrode 2 to the outside of the plating solution 170, and the solubility is increased by the time 2 set in the adjusting means 160. The metal electrodes 1 122 and 2 123 are both located outside the plating solution 170 such that the insoluble electrode 121 serves as an anode. This process may be time-dependent, depending on the nature of the soluble metal ions 2, and in some cases may be unnecessary.

When the set time 2 passes, the pneumatic cylinder is controlled by the adjusting means 160 again so that the soluble metal electrode 1 outside the plating solution 170 moves to contact the plating solution 170. Since the soluble metal electrode 1 122 serves as an anode for a time 3 set at 160, only the soluble metal ion 1 is formed.

After the set time 3, the pneumatic cylinder is controlled by the adjusting means 160 so that the soluble metal electrode 1 is moved out of the plating solution 170, and the solubility is increased by the time 4 set in the adjusting means 160. The metal electrodes 1 122 and 2 123 are both located outside the plating solution 170 such that the insoluble electrode 121 acts as an anode again. This process is also controlled by the characteristics of the soluble metal ions 1, and in some cases may be unnecessary.

As such, the control means 160 repeatedly controls the soluble metal electrodes 122 and 123 and the insoluble electrode 121 to act as the anode 120 according to the set time, and repeatedly controls the plating solution until the end of plating. The concentration of the soluble metal ions in the 170 may be kept constant, and the one or more soluble metal ions may be deposited on the cathode 130 to form a plated film made of a poly-based alloy.

In this case, the timing and time of using the insoluble electrode 121 as the anode 120 may vary depending on the characteristics of the metal ions constituting the soluble metal electrodes 122 and 123. Here, the insoluble electrode is used as the anode for a predetermined time. For example, in the case of nickel-iron alloy plating, since the iron concentration in the plating solution is small, iron ions are precipitated by diffusion control, so that the iron content of the plating layer is sensitively changed, and the hydrogen is generated at the cathode. The plating efficiency may not be 100% due to the gas reaction according to the hydrogen evolution reaction, so that the plating solution 170 maintains the concentration of the plating solution 170 because unplated metal ions remain in the plating solution 170. .

Hereinafter, in the electroplating apparatus 100, iron and nickel are used as the soluble metal electrodes 122 and 123 of the anode 120, platinum is used as the insoluble electrode 121, and stainless steel is used as the cathode 130. The theoretical basis for the above description will be described through the process of plating the stainless steel with a nickel-iron alloy using steel.

The anodic reaction and the cathode reaction occurring in the anode 120 and the cathode 130 are as follows.

^{(Anode) Fe → Fe 2+ + 2e -} ------------ (1)

^{Ni → Ni 2+ + 2e - ------------} (2)

(Negative ^{electrode) Fe 2+ + 2e - → Fe} ------------ (3)

^{Ni 2+ + 2e - → Ni ------------} (4)

As shown in equations (1) and (2), an anode dissolution reaction occurs in the iron and nickel electrodes of the anode 120, in which iron and nickel lose two electrons and ionize, and are represented in equations (3) and (4). As described above, in the stainless steel which is the cathode 130, iron and nickel ions receive two electrons and precipitate as metal iron and nickel.

One ampere, the unit of current, is the strength of the current when one coulomb charge flows for one second. In addition, the electricity amount of 1 Faraday is the amount of electricity required to deposit 1 gr equivalent of metal (1 mol of iron = 1 mol = 55.845 gr, 1 mol of nickel = 58.693 gr for nickel), that is, 96,485.4 coulombs.

Therefore, the amount of iron and nickel dissolved in the anode when the current flows for t hours (seconds) is expressed as follows.

M = I × t × A / (n × F)

M: Iron or nickel electrode dissolved amount A: Atomic weight of iron or nickel

I: strength of current F: Faraday constant

n: valence

When the plating efficiency is 90%, the amount W of iron and nickel ions deposited in the stainless steel in the plating solution 170 is as follows.

W = 0.9 I × t × A / (n × F), W: Iron in the solution, nickel ion

Therefore, the time when the insoluble anode 121 is used as the anode to adjust the amount of iron, nickel ion (M) dissolved in the cathode 130 stainless steel and the amount of nickel ion (M) and the management target concentration is as follows. same.

T _Pt = T-W _re / W _th × T

T _Pt : Total time of insoluble platinum electrode used as anode

T: Total Plating Time

W _re : actual plating amount W _th : theoretical plating amount

According to the plating efficiency of the plural alloys to be plated as described above, the time for which the one or more soluble metal electrodes 122 and 123 and the insoluble electrode 121 are used as an anode in the adjusting means 160 may be set in advance. That is, the time is calculated to correct the plating solution concentration difference in consideration of the difference between the plating solution concentration management standard value and the measured value so that the ion concentration of the plating solution 170 is kept constant. It is used to calibrate the ion concentration in solution.

Experimental Example 1

In order to evaluate the effectiveness of the configuration and operation of the electroplating apparatus 100 according to the present invention, the experiment was performed using the conditions required for the preparation of permalloy alloy of 80% iron 20% nickel as follows.

First, iron and nickel concentrations of the plating cell in which plating was performed using stainless steel as a cathode were maintained at 0.3 g / L and 13.2 g / L, respectively.

At this time, the plating cell capacity of the plating cell was 2.5 L, and the adjusting means 160 was immersed in the solution for a controlled time in the iron electrode 102 and the nickel electrode 104 to control the concentration of the solution uniformly. Plating experiments were conducted for a certain period of time, and the current density was fixed at 0.135 mA / cm ³ and the plating area was 9 cm ² .

First, in the first step, the iron electrode and the nickel electrode are positively adjusted in the adjusting means 160 by calculating the consumption amount of the iron electrode and the nickel electrode, which are soluble anodes, based on the plating amount and the permalloy composition (Fe _{19.5 ± 0.5} Ni _{80.5 ± 0.5} ). Set the time to act as.

In the second step, after the platinum electrode is fixed in the solution, the iron electrode and the nickel electrode are connected to the pneumatic cylinder to blow air into the air pipe, and the iron electrode and the nickel electrode are immersed in the solution.

In the third step, when a current is applied to the positive electrode and the negative electrode, and at the same time, the control means is operated, the pneumatic cylinder connected to the iron electrode is lowered by the injected air and used as the positive electrode for the time set in the control means. Since it is controlled, the nickel electrode is located outside the plating solution so that only the iron electrode participates in the plating.

In the fourth step, both the iron electrode and the nickel electrode are pushed up by the pneumatic cylinder, and only the platinum electrode is used as the anode to participate in the plating. After the plating time of the insoluble platinum electrode set in the adjusting means, the nickel electrode is plated. Once inside, only the nickel electrode participates in the plating as an anode for a time set in the adjusting means.

In the fifth step, the nickel electrode participating in the plating for a predetermined time goes out of the solution, and at the same time, the nickel electrode is stimulated by the sensor attached to the pneumatic cylinder connected to the nickel electrode, and the iron electrode enters into the solution again. A series of processes up to 5 steps were precisely controlled through the same process until the end of the electric permalloy plating time, the results are shown in Table 1.

Permalloy plating test results by the electroplating apparatus and method of the present invention. 2 hours plating result 6 hours plating result Iron electrode Nickel electrode Iron electrode Nickel electrode Current density (A / cm ² ) 0.015 Plating area (cm ² ) 9 Molten amount (g) 0.05068 0.21196 0.15618 0.63353 Total dissolved amount (iron + nickel, g) 0.26264 0.78971 Plated amount (g) 0.26337 0.78993 Plating time (sec) 1100 4700 3300 14100

It can be seen from Table 1 that the plated with the composition of Fe _19.3 Ni _80.7 is suitable for electro-nickel-iron alloy plating. Fe _19.77 Ni is plated in the proportion of _80.23 plated case iron, nickel ion amount to be deposited on the metal ions and the cathode of stainless steel is dissolved in a soluble anode can seen that the same control of the present invention is very useful in the mass production system It can be seen.

The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by any person having ordinary skill in the art without departing from the gist of the present invention claimed in the claims. Of course, such changes will fall within the scope of the claims.

As described above, the electroplating apparatus and the electroplating method according to the present invention has the following effects.

First, according to the electroplating apparatus and the electroplating method of the present invention, the concentration of the metal ions to be plated in the plating solution can be kept constant.

In addition, according to the electroplating apparatus and the electroplating method of the present invention, since the concentration of the metal ions to be plated in the plating solution is controlled by a mechanical method, the manufacturing cost can be significantly reduced.

In addition, the electroplating apparatus and the electroplating method of the present invention can be easily plated with a multi-element alloy.

In addition, according to the electroplating apparatus and the electroplating method of the present invention it is possible to mass-produce products uniformly plated with a multi-element alloy efficiently and inexpensively.

Claims (11)

A plating bath including a plating solution, an anode and a cathode in contact with the plating solution of the plating bath, and a power source electrically connected to the anode and the cathode to allow current to pass through the cathode and the cathode. In an electroplating apparatus, the anode is an electroplating apparatus, characterized in that it is composed of at least one soluble plated metal electrode and an insoluble electrode. The method of claim 1, wherein the at least one soluble metal electrode moving means and the moving means connected to at least one soluble metal electrode constituting the anode to move the at least one soluble metal electrode out of the plating solution during electroplating An electroplating apparatus, characterized in that it further comprises a control means for adjusting the time the metal electrode is used as the anode during electroplating. 3. An electroplating apparatus according to claim 2, wherein the moving means comprises a cylinder and an air pipe. The electroplating apparatus of claim 1, wherein the electrodes constituting the anode are used as an anode during electroplating by repeatedly repeating the soluble metal electrode and the insoluble electrode. 2. The electroplating apparatus of claim 1, wherein the soluble metal electrodes are nickel and iron, and the insoluble electrode is platinum. Contacting the substrate to be plated with a plating solution of a plating bath; In the electroplating method comprising applying a sufficient current density to the plating bath to deposit a metal on the substrate, the metal ions to be plated in the plating solution by selectively using an insoluble electrode and a soluble plated metal electrode as an anode Electroplating method characterized by adjusting the concentration. 7. The electroplating method of claim 6, wherein the soluble metal electrode is one or more. The electroplating method of claim 7, wherein the electroplating is repeated as an anode in order of any one of the soluble metal electrodes, the insoluble electrode, and the other of the soluble metal electrodes. An electroplating product manufactured by the apparatus and method of any one of claims 1 to 8. 10. The electroplating product of claim 9, wherein the metal plated on the product is a multi-element alloy. The electroplating product of claim 10, wherein the metal plated on the product is an iron-nickel alloy.