KR100426857B1 - A CONTROL METHOD OF SULPHURIC ACID ION IN Cr ELECTROLYTIC SOLUTION - Google Patents
A CONTROL METHOD OF SULPHURIC ACID ION IN Cr ELECTROLYTIC SOLUTION Download PDFInfo
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- KR100426857B1 KR100426857B1 KR10-1999-0036074A KR19990036074A KR100426857B1 KR 100426857 B1 KR100426857 B1 KR 100426857B1 KR 19990036074 A KR19990036074 A KR 19990036074A KR 100426857 B1 KR100426857 B1 KR 100426857B1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
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Abstract
본 발명은 전기도금 후처리 설비인 전해크롬 용액의 농도를 제어하는 방법에 관한 것으로서, PCS(3)에서 전해크롬 용액중 황산이온(SO4 2-)의 현장 최적 조업조건의 기준농도(목표농도)를 미리 설정하는 단계와; 온라인 분석기(2)로 전해크롬용액 순환탱크(1) 내 황산이온(SO4 2-)의 농도를 분석하여 분석농도로 결정하는 단계; 상기 PCS(3)에서 목표농도와 분석농도의 비교로 H2SO4투입량을 계산하여 메터링펌프(4 )의 펌핑시간을 결정하는 단계 및 ; 결정된 펌핑시간동안 PCS(3) 내 DCS(Distribu tive Control System)가 상기 메터링펌프(4)를 동작시켜 황산 저장탱크(14) 내의 황산을 전해크롬용액 순환탱크(1)로 투입하는 단계로 이루어져 전기도금설비의 전해크롬 용액중 황산이온의 농도를 자동으로 조절할 수 있으므로 황산이온의 농도불균일에 따르는 표면색상 불균일, 크롬부착량 불균일 등을 방지하고, 황산의 투입량이 정확하게 되어 제품의 품질을 향상시킬 수 있을 뿐만 아니라 작업자가 직접 황산을 투입하는데 따르는 안전사고의 위험을 예방할 수 있는 장점이 있는 것이다.The present invention relates to a method for controlling the concentration of an electrolytic chromium solution, which is an electroplating aftertreatment facility, and the reference concentration (target concentration) of the site optimum operating conditions of sulfate ions (SO 4 2- ) in the electrolytic chromium solution in PCS (3). Presetting; Analyzing the concentration of sulfate ions (SO 4 2- ) in the electrolytic chromium solution circulation tank (1) by using an on-line analyzer (2) to determine the analytical concentration; Determining the pumping time of the metering pump (4) by calculating the H 2 SO 4 dose by comparing the target concentration with the analytical concentration in the PCS (3); Distributive Control System (DCS) in the PCS 3 operates the metering pump 4 during the determined pumping time to inject sulfuric acid in the sulfuric acid storage tank 14 into the electrolytic chromium solution circulation tank 1. Since the concentration of sulfate ion in the electrolytic chromium solution of electroplating equipment can be adjusted automatically, it is possible to prevent surface color unevenness and chromium adhesion amount unevenness due to the concentration unevenness of sulfate ion, and improve the quality of product by precisely adding sulfuric acid. In addition, there is an advantage that can prevent the risk of safety accidents that the operator directly put sulfuric acid.
Description
본 발명은 전기도금 후처리 설비인 전해크롬용액의 농도를 제어하는 방법에 관한 것으로서, 보다 상세하게는 전해크롬 작업중 용액내 황산이온(SO4 2-) 농도의 불균일에 의해 제품의 표면색상 불균일, 크롬부착량 불균일등을 유발하는 문제를 해결하기 위해 용액내 황산이온(SO4 2-) 농도를 일정하게 유지시켜 주는 전기도금 후처리 전해크롬 용액중 황산이온의 농도를 제어하는 방법에 관한 것이다.The present invention relates to a method for controlling the concentration of an electrolytic chromium solution, which is an electroplating aftertreatment facility, and more particularly, due to the nonuniformity of the concentration of sulfate ion (SO 4 2- ) in the solution during electrolytic chromium operation. The present invention relates to a method of controlling the concentration of sulfate ion in an electroplating post-treatment electrolytic chromium solution to maintain a constant concentration of sulfate ion (SO 4 2- ) in a solution to solve the problem of uneven chromium deposition.
일반적으로 전기도금의 후처리인 전해크롬 작업은 도 2에 도시한 바와 같이 전해액이 담겨져 있는 순환탱크에서 용액이 펌핑되어 전해크롬 도금조에 공급되고 도금조 내에서 이온상태의 크롬이 전기적인 힘에 의해서 강판 표면에 부착되는 구조를 갖고 있는 작업이다. 이러한 전해크롬 과정에서 표면색상이나 부착량에 민감한 반응을 갖고 있는 주요소는 용액중 황산이온(SO4 2-) 농도이고, 황산이온( SO4 2-) 농도의 불균일에 의해 제품표면의 백색도, 황색도, 표면얼룩등이 좌우되며 크롬 밀착성에도 영향을 미친다. 이러한 이유에 의해서 작업중 용액내 황산이온(SO4 2-)의 농도를 관리하게 되는데 일반적으로 현재까지는 작업중 공정시험분석의 4시간 주기로 용액을 샘플링(Sampling)하여 시험분석 의뢰하고 그 결과에 따라서 기준관리농도 대비 증감을 판단하여 농도를 조정하는데, 농도 조정시는 보충액인 H2SO4를 순환탱크에 투입하도록 되어 있다.In general, electrolytic chromium work, which is a post-treatment of electroplating, is supplied to an electrolytic chromium plating bath by pumping a solution from a circulation tank containing electrolyte as shown in FIG. It is the work which has a structure attached to the steel plate surface. In this electrolytic chromium process, the main element that has a sensitive reaction on surface color or adhesion amount is sulfate ion (SO 4 2- ) concentration in solution, and the whiteness and yellowness of the product surface due to the nonuniformity of sulfate ion (SO 4 2- ) concentration. , Surface stains, etc. are affected, and also affect chrome adhesion. For this reason, the concentration of sulfate ion (SO 4 2- ) in the solution during the operation is controlled. In general, the solution is sampled at 4 hour intervals during the process test analysis and commissioned for test analysis according to the result. The concentration is adjusted based on the increase and decrease of the concentration. When the concentration is adjusted, H 2 SO 4 , a supplementary liquid, is added to the circulation tank.
이러한 종래 전해크롬 용액중 황산이온의 농도를 제어하는 과정에서 발생되는 문제점은 다음과 같다.Problems occurring in the process of controlling the concentration of sulfate ions in the conventional electrolytic chromium solution are as follows.
첫째 4시간 주기의 용액분석결과에 의존하기 때문에 작업중 표면문제 발생시 이에 대한 빠른 대응이 어려워 제품불량이 야기되고, 둘째 보충액 투입시 투입량을 작업자가 매번 계산하여야 하기 때문에 계산에러 등을 유발시킬수 있을 뿐만 아니라 셋째 투입액이 H2SO4인 위험물임에도 불구하고 작업자가 직접 투입함으로써 안전위험이 수반되며 투입량도 부정확 하여 용액 조정의 정확성이 문제가 된다.As it depends on the solution analysis result of the first 4 hour cycle, it is difficult to respond quickly to surface problems during operation, which leads to product defects. Secondly, it is possible to cause calculation errors because the operator has to calculate the input amount every time the supplement is added. Third, even though the input liquid is H 2 SO 4 , it is a safety hazard by the operator directly, and the input amount is inaccurate. Therefore, the accuracy of solution adjustment is a problem.
본 발명은 상기한 실정을 감안하여 종래 전해크롬 용액의 농도 제어방법이 갖는 복합적인 문제점들을 해결하고자 발명한 것으로서, 전해크롬 용액내 황산이온 (SO4 2-) 농도에 대한 데이터를 온라인(On-Line) 분석기로 부터 얻어서 이를 컴퓨터를 이용 투입량을 계산하여 자동으로 투입함으로써 황산이온(SO4 2-) 농도를 제어하는 전기도금 후처리 전해크롬 용액중 황산이온의 농도를 제어하는 방법을 제공함에 그 목적이 있다.The present invention has been invented to solve the complex problems of the conventional method for controlling the concentration of the electrolytic chromium solution in view of the above situation, and the online data on the concentration of sulfate ion (SO 4 2- ) in the electrolytic chromium solution are online (On- Line) This method provides a method to control the concentration of sulfate ion in electroplating after-treatment electrolytic chromium solution that controls the concentration of sulfate ion (SO 4 2- ) by automatically calculating the input amount from the analyzer and using the computer. There is a purpose.
도 1은 전해크롬 용액중 황산이온(SO4 2-) 농도 자동제어 시스템의 구성도,1 is a block diagram of a system for automatically controlling the concentration of sulfate ions (SO 4 2- ) in an electrolytic chromium solution,
도 2는 본 발명에 따른 자동펌프와 황산 저장탱크 및 스위치 판넬의 상세도,Figure 2 is a detailed view of the automatic pump and sulfuric acid storage tank and the switch panel according to the present invention,
도 3은 본 발명의 제이시스템 제어신호 및 계산처리동작의 순서도이다.3 is a flowchart of the J-system control signal and calculation processing operation of the present invention.
< 도면의 주요부분에 대한 부호설명 ><Explanation of Signs of Major Parts of Drawings>
1 : 전해크롬용액 순환탱크 2 : 온라인 분석기1: electrolytic chromium solution circulation tank 2: on-line analyzer
3 : PCS 4 : 메터링펌프3: PCS 4: metering pump
5 : 중앙 운전실 6 : 릴레이5: central cab 6: relay
7 : 스위치 판넬 8 : 신호수신용 카드7: switch panel 8: signal receiving card
9 : 신호전송용 카드 10 : 지하 터미널박스9: signal transmission card 10: underground terminal box
11 : 터미널박스 12 : 신호케이블11: terminal box 12: signal cable
13 : 펌프 파워케이블 14 : 황산 저장탱크13 pump power cable 14 sulfuric acid storage tank
15 : 황산투입용 호스15: sulfuric acid injection hose
상기한 목적을 달성하기 위한 본 발명 전기도금 후처리 전해크롬 용액중 황산이온의 농도를 제어하는 방법은 전해크롬용액 순환탱크(1)와 온라인 분석기(2 ), PCS(3), 메터링펌프(4), 중앙 운전실(5), 릴레이(6), 스위치 판넬(7), 신호수신용카드(8), 신호전송용 카드(9), 지하 터미널박스(10), 터미널박스(11), 신호케이블 (12), 펌프 파워케이블(13), 황산 저장탱크(14) 및 황산투입용 호스(15)를 구비한 구성으로 PCS(3)에서 전해크롬 용액중 황산이온(SO4 2-)의 현장 최적 조업조건의 기준농도(목표농도)를 미리 설정하는 단계와; 온라인 분석기(2)로 전해크롬용액 순환탱크(1) 내 황산이온(SO4 2-)의 농도를 분석하여 분석농도로 결정하는 단계; 상기 PCS(3)에서 목표농도와 분석농도의 비교로 H2SO4투입량을 계산하여 메터링펌프(4 )의 펌핑시간을 결정하는 단계 및 ; 결정된 펌핑시간동안 PCS(3) 내 DCS(Distribut ive Control System)가 상기 메터링펌프(4)를 동작시켜 황산 저장탱크(14) 내의 황산을 전해크롬용액 순환탱크(1)로 투입하는 단계로 이루어져 전해크롬 용액중 황산이온의 농도를 자동으로 제어하는 것을 특징으로 한다.The method for controlling the concentration of sulfate ion in the electroplating post-treatment electrolytic chromium solution of the present invention for achieving the above object is the electrolytic chromium solution circulation tank (1) and online analyzer (2), PCS (3), metering pump ( 4), central cab (5), relay (6), switch panel (7), signal receiving card (8), signal transmission card (9), underground terminal box (10), terminal box (11), signal cable (12), pump power cable (13), sulfuric acid storage tank (14) and sulfuric acid injection hose (15), PCS (3) in the field optimization of sulfate ion (SO 4 2- ) in the electrolytic chromium solution Setting a reference concentration (target concentration) of the operating conditions in advance; Analyzing the concentration of sulfate ions (SO 4 2- ) in the electrolytic chromium solution circulation tank (1) by using an on-line analyzer (2) to determine the analytical concentration; Determining the pumping time of the metering pump (4) by calculating the H 2 SO 4 dose by comparing the target concentration with the analytical concentration in the PCS (3); Distributing Control System (DCS) in PCS (3) operates the metering pump (4) to determine the sulfuric acid in the sulfuric acid storage tank (14) into the electrolytic chromium solution circulation tank (1) during the determined pumping time. It is characterized by automatically controlling the concentration of sulfate ion in the electrolytic chromium solution.
이하 첨부도면을 참조하여 본 발명 전기도금 후처리 전해크롬 용액중 황산이온의 농도를 제어하는 방법을 상세하게 설명한다.Hereinafter, a method of controlling the concentration of sulfate ion in the electroplating post-treatment electrolytic chromium solution of the present invention will be described in detail with reference to the accompanying drawings.
도 1은 전해크롬 용액중 황산이온(SO4 2-) 농도 자동제어 시스템의 구성도로서, 전해액이 담겨져 있는 전해크롬용액 순환탱크(1)에서 펌핑(Pumping)된 용액이 미량원소 분석기인 온라인 분석기(2)에 공급되고, 이 온라인 분석기(2)에서 40분 주기로 용액중 황산이온(SO4 2-) 농도의 분석결과를 공정제어 시스템인 PCS(3; Process Control System)의 해당제어 로직으로 전송한다.1 is a schematic diagram of a system for automatically controlling the concentration of sulfate ions (SO 4 2- ) in an electrolytic chromium solution. The online analyzer is a trace element analyzer in which the solution pumped in the electrolytic chromium solution circulation tank 1 containing the electrolyte solution is a trace element analyzer. (2), the on-line analyzer (2) transmits the analysis result of the concentration of sulfate ion (SO 4 2- ) in solution to the corresponding control logic of the process control system (PCS) (3) every 40 minutes. do.
상기 PCS(3)에는 용액중 황산이온(SO4 2-)의 현장 최적 조업조건인 기준 설정 값이 미리 설정되어 있어서 수신된 온라인 분석기(2)의 데이터와 비교하여 기준 설정값 보다 농도가 낮을때는 기준값으로 농도를 맞추기 위해 보충액인 H2SO4의 투입량을 계산하게 된다. 투입량이 계산되면 현장에 설치한 자동 투입장치에 있는 메터링펌프( 4 ; Metering Pump)의 기동시간을 초 단위로 계산하고 이를 신호화 하여 중앙 운전실(5) 내 컴퓨터시스템에 내장된 현장 펌프를 직접 가동시키는 시스템인 DCS(Distributive Control System)에 전송하고, DCS는 입출력신호 변환장치를 이용하여 릴레이(6; Relay)를 작동시킨다. 이 릴레이(6)의 동작에 따라 신호전송라인 을 통하여 현장 메터링펌프(4)에 신호가 전달되어 메터링펌프(4)가 기동되는데 PCS(3)에서 계산된 H2SO4투입량에 해당되는 시간만큼 메터링펌프(4)가 동작하게 된다.The PCS 3 is preset with a reference setting value, which is an on-site optimum operating condition of the sulfate ion (SO 4 2- ) in the solution, and when the concentration is lower than the reference setting value compared with the data of the received online analyzer (2). To adjust the concentration to the reference value, the dose of H 2 SO 4 supplement is calculated. When the input amount is calculated, the starting time of the metering pump (4; metering pump) in the automatic input device installed in the field is calculated in seconds, and signaled, so that the on-site pump built in the computer system in the central cab 5 can be directly It transmits to DCS (Distributive Control System) which is an operating system, and DCS operates a relay 6 using an input / output signal converter. According to the operation of the relay 6, a signal is transmitted to the field metering pump 4 through the signal transmission line, and the metering pump 4 is started, which corresponds to the H 2 SO 4 input amount calculated by the PCS 3. The metering pump 4 is operated for a time.
메터링펌프(4)가 기동되면 황산 저장탱크(14) 내의 H2SO4가 펌핑되어 황산투입용 호스(15 ;Teflone Hose)(보호 파이프 안에 설치)를 통하여 전해크롬용액 순환탱크(1)로 자동투입되어 목표농도를 맞추게 되어 있다. 이러한 운전은 상황에 따라 운전자가 선택적으로 할 수도 있다.When the metering pump 4 is started, H 2 SO 4 in the sulfuric acid storage tank 14 is pumped to the electrolytic chromium solution circulation tank 1 through a sulfuric acid input hose 15 (installed in a protective pipe). It is automatically injected to meet the target concentration. Such driving may be selectively performed by the driver depending on the situation.
도 2는 본 발명에 따른 자동펌프와 황산 저장탱크 및 스위치 판넬의 상세도로서, 스위치 판넬(7;Switch Panel)에 Auto, Off, Man 모드를 두어 풀오토(Full Auto)의 경우 오토모드(Auto Mode)로 운전하고, 용액농도의 임의조정이 필요할때는맨모드(Man Mode)로 두어 작업자가 임의로 H2SO4를 투입할 수 있도록 하였다. 또한 이러한 작업은 중앙 운전실(5)에서 리모콘으로 운전이 가능하도록 DCS 운전화면내에 기능을 추가하여 구성 하였다.Figure 2 is a detailed view of the automatic pump and sulfuric acid storage tank and the switch panel according to the present invention, the switch panel (7; Switch Panel) to put the Auto, Off, Man mode in full auto (Auto mode in case of Full Auto) Mode), and when it is necessary to arbitrarily adjust the concentration of the solution, it is left in the man mode (Man Mode) so that an operator can input H 2 SO 4 arbitrarily. In addition, this operation was configured by adding a function in the DCS operation screen to enable operation with a remote control in the central cab (5).
상기 중앙 운전실(5)내 DCS 운전화면에는 운전모드 선택기능과 PCS(3)에서 설정된 펌프의 기동시간 및 기동되고 있는 상황을 모니터링(Monitoring)할 수 있는 수단을 마련하였다. 또한 피드포워드(Feed Forward) 개념의 농도제어를 위해 일정량 만큼 일정주기로 H2SO4가 투입되도록 하는 펌핑시간의 설정상태가 DCS 화면내에 모니터링 되도록 하였다.In the DCS operation screen in the central cab 5, an operation mode selection function and a means for monitoring the starting time of the pump set in the PCS 3 and the status of being started are provided. In addition, to control the concentration of feed forward concept, the setting state of pumping time to input H 2 SO 4 at a certain period by a certain amount is monitored in DCS screen.
도 3은 본 발명의 제이시스템 제어신호 및 계산처리동작의 순서도로서, PCS(3)에서 전해크롬 용액중 황산이온(SO4 2-)의 현장 최적 조업조건의 기준농도(목표농도)를 미리 설정하게 되며, 이러한 기준농도는 제품의 표면사양 및 제품의 특징에 따라 기준농도인 목표농도를 변경할 수 있고, 도 3에 나타낸 상수(9.5405)는 투입하려는 H2SO4의 농도에 따라 달라지게 된다. 이어 온라인 분석기(2)로 전해크롬용액 순환탱크(1) 내 황산이온(SO4 2-)의 농도를 분석하여 분석농도로 결정한 후 상기 PCS(3)에서 목표농도와 분석농도의 비교로 H2SO4투입량을 계산하여 메터링펌프(4)의 펌핑시간을 결정한다. 다음에는 결정된 펌핑시간동안 PCS(3) 내 DCS(Distribut ive Control System)가 상기 메터링펌프(4)를 동작시켜 황산 저장탱크(14) 내의 황산을 전해크롬용액 순환탱크(1)로 투입하게 된다. 이때 메터링펌프(4)의 토출량(설정값)은 0∼1200㎖/min 범위에서 임의로 조정할 수 있다.3 is a flowchart of the J-system control signal and calculation processing operation of the present invention, in which the reference concentration (target concentration) of the site optimum operating conditions of the sulfate ion (SO 4 2- ) in the electrolytic chromium solution in PCS 3 is preset. The reference concentration may be changed according to the surface specification of the product and the characteristics of the product. The target concentration, which is the reference concentration, may be changed, and the constant (9.5405) shown in FIG. 3 may vary depending on the concentration of H 2 SO 4 to be introduced. An online analyzer (2) to a sulfuric acid electrolytic chromium ion solution circulating tank (1) after determining by analysis of the concentration by analyzing the concentration of (SO 4 2-), a comparison of the target concentration and the concentration analysis in the PCS (3) H 2 The pumping time of the metering pump 4 is determined by calculating the SO 4 dose. Next, a DCS (Distributive Control System) in the PCS 3 operates the metering pump 4 to inject sulfuric acid in the sulfuric acid storage tank 14 into the electrolytic chromium solution circulation tank 1 during the determined pumping time. . At this time, the discharge amount (set value) of the metering pump 4 can be arbitrarily adjusted in the range of 0-1200 ml / min.
상기한 바와 같이 본 발명은 전기도금설비의 전해크롬 용액중 황산이온의 농도를 자동으로 조절할 수 있으므로 황산투입량 계산의 수작업에 따른 에러의 우려없이 황산이온의 농도불균일에 따르는 표면색상 불균일, 크롬부착량 불균일 등을 방지하고, 황산의 투입량이 정확하게 되어 제품의 품질을 향상시킬 수 있을 뿐만 아니라 황산을 작업자가 직접 투입하지 않게 되므로 안전사고의 위험을 예방할 수 있는 장점이 있다.As described above, the present invention can automatically adjust the concentration of sulfate ions in the electrolytic chromium solution of the electroplating equipment, so that the surface color unevenness and chromium deposition amount uneven due to the concentration unevenness of sulfate ions without fear of error due to manual calculation of sulfuric acid input amount. It is possible to prevent the back, and the amount of sulfuric acid is precisely to improve the quality of the product as well as to prevent the risk of safety accidents because the operator does not directly input sulfuric acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101048041B1 (en) | 2011-02-22 | 2011-07-13 | 주식회사 삼원알텍 | Apparatus for auto input of sulfuric acid for anodizing treatment apparatus of metal |
| KR101564407B1 (en) | 2013-11-26 | 2015-10-29 | 주식회사 포스코 | Electroplating solution control system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58211644A (en) * | 1982-06-03 | 1983-12-09 | Nippon Steel Corp | Automatic control method and apparatus for concentration of fluoride in plating bath for electrolytic chromic acid treated steel plate |
| KR970048434A (en) * | 1995-12-29 | 1997-07-29 | 김종진 | Automatic Measurement and Control of Alkali Concentration in Degreasing Process Using Ion-Selective Electrode |
| KR970059316A (en) * | 1996-01-31 | 1997-08-12 | 에모토 간지 | Concentration Control Method of Plating Solution Component in Continuous Electroplating |
| KR20000000227U (en) * | 1998-06-05 | 2000-01-15 | 이구택 | Sulfuric acid concentration automatic control device of electrolytic chromium solution |
-
1999
- 1999-08-28 KR KR10-1999-0036074A patent/KR100426857B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58211644A (en) * | 1982-06-03 | 1983-12-09 | Nippon Steel Corp | Automatic control method and apparatus for concentration of fluoride in plating bath for electrolytic chromic acid treated steel plate |
| KR970048434A (en) * | 1995-12-29 | 1997-07-29 | 김종진 | Automatic Measurement and Control of Alkali Concentration in Degreasing Process Using Ion-Selective Electrode |
| KR970059316A (en) * | 1996-01-31 | 1997-08-12 | 에모토 간지 | Concentration Control Method of Plating Solution Component in Continuous Electroplating |
| KR20000000227U (en) * | 1998-06-05 | 2000-01-15 | 이구택 | Sulfuric acid concentration automatic control device of electrolytic chromium solution |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101048041B1 (en) | 2011-02-22 | 2011-07-13 | 주식회사 삼원알텍 | Apparatus for auto input of sulfuric acid for anodizing treatment apparatus of metal |
| KR101564407B1 (en) | 2013-11-26 | 2015-10-29 | 주식회사 포스코 | Electroplating solution control system |
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| KR20010019590A (en) | 2001-03-15 |
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