• 한국표면공학회지
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• 제52권2호
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• pp.103-110
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• 2019

As an anti-corrosion method in seawater, cathodic protection is widely recognized as the most effective and technically appropriate corrosion prevention methodology for marine structures against harsh corrosive environment. When applying the cathodic protection in seawater, the surface of the metal facilities the formation of compounds of $CaCO_3$ and $Mg(OH)_2$. These mixed compounds are generally called 'calcareous deposits'. This layer functions as a barrier against the corrosive environment and functions to further inhibit the corrosion process and then leading to a decrease in current demand for cathodic protection. However, calcareous deposit films are partially formed on the surface of the cathode and there are some difficulties to maintain both a corrosion resistance for a long period of time and a strong adhesion between deposits and base metal. In this study, the pulse electrodeposition process was applied to improve adhesion and corrosion resistance of the calcareous deposit films, and to solve the problem of hydrogen embrittlement at high current density. The uniform and compact calcareous deposit films were prepared by pulse electrodeposition process, and their properties were characterized using various surface analytical techniques together with electrochemical methods.

• Journal of Advanced Marine Engineering and Technology
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• 제28권6호
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• pp.1000-1009
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• 2004

The environment friendly calcareous deposit films were formed on steel plates by electrodeposition technique in natural seawater and synthetic solutions such as dissolved $\textrm{Mg}^{2+}$ and $\textrm{Ca}^{2+}$ ions at various potential conditions. The influence of potential conditions on composition ratio, structure and morphology of the electrodeposited films were investigated by scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS) and X-ray diffractor (XRD). Accordingly, this study was provided a better understanding of the composition between the growth of $\textrm{Mg(OH)}_2$ and that of $\textrm{CaCO}_3$ during the formation of calcareous deposit films on steel substrate under cathodically electrodeposition in synthetic and natural seawater. The results showed that the formation of good overall calcareous deposited film in seawater can be achieved by controlling the Ca/Mg ratio according to interfacial pH with the effective use of the electro deposition technique.

• 한국마린엔지니어링학회:학술대회논문집
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• 한국마린엔지니어링학회 2005년도 후기학술대회논문집
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• pp.196-197
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• 2005

Cathodic protection is one of the successful ways to prevent corrosion of steel structures in marine environments. The unique feature of cathodic protection in seawater is the formation of calcareous deposits on cathodic metal surface. The formation principles of calcareous deposit seawater had been known for a long time. That is, cathodic reduction reactions associated with cathodic protection in seawater generate $OH^-$ at the metal surface in accordance with the formular ; 1/2 $O_2$ + $H_2O$ + $2e^-$ $2OH^-$ and $2H_2O$ + $2e^-$ ${\rightarrow}$ $H_2$ + $2OH^-$. These reactions increase the pH at the metal / seawater interface. The high pH causes precipitation of $Mg(OH)_2$ and $CaCO_3$ in accordance with the formular ; $Mg^{2+}$ + $2(OH)^-$ ${\rightarrow}$ $Mg(OH)_2$ and $Ca^{2+}$ + $HCO_3^-$ + $OH^-$ ${\rightarrow}$ $H_2O$ + $CaCO_3$. These are typically the main compounds in calcareous deposits. It obviously has several advantages compared to the conventional coatings, since the environment-friendly calcareous deposit coating is formed by the elements($Mg^{2+}$, $Ca^{2+}$) naturally present in seawater. In this study, environmental friendly calcareous deposit films were prepared on steel plates by electro plating technic in natural seawater. The influence of current density on composition ratio, structure and morphology of the coated films were investigated by scanning electron microscopy formation process of calcareous deposits films in natural seawater. And we confirmed the properties of all the films can be improved greatly by controlling the material structure and morphology with effective use of the electroplating method in natural seawater.

• 한국표면공학회지
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• 제49권2호
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• pp.166-171
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• 2016

Cathodic protection is widely recognized as the most cost effective and technically appropriate corrosion prevention methodology for the port, offshore structures, ships. When applying the cathodic protection method to metal facilities in seawater, on the surface of the metal facilities a compound of calcium carbonate($CaCO_3$) or magnesium hydroxide($Mg(OH)_2$) films are formed by $Ca^{2+}$ and $Mg^{2+}$ ions among the many ionic components dissolving in the seawater. And calcareous deposit films such as $CaCO_3$ and $Mg(OH)_2$ etc. are formed by the surface of the steel product. These calcareous deposit film functions as a barrier against the corrosive environment, leading to a decrease in current demand. On the other hand, the general calcareous deposit film is a compound like ceramics. Therefore, there may be some problems such as weaker adhesive power and the longer time of film formation uniting with the base metal. In this study, we tried to determine and control the optimal condition through applying the principle of cathodic current process to form calcareous deposit film of uniform and compact on steel plate. The quantity of precipitates was analyzed, and both the morphology, component and crystal structure were analyzed as well through SEM, EDS and XRD. And based on the previous analysis, it was elucidated mechanism of calcareous deposit film formed in the sacrificial anode type (Al, Zn) and current density (1, 3, $5A/m^2$) conditions. In addition, the taping test was performed to evaluate the adhesion.

• 한국표면공학회지
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• 제50권6호
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• pp.531-535
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• 2017

Enormous amount of waste oyster-shell (OS) has a major disposal problem in coastal regions. OSs have attracted much attention for recycling, because these are mainly composed of calcium carbonate with rare impurities. In this study, we demonstrate the calcareous deposit films on steel plate by using OSs on the basic of cathodic protection technique. The composition of the OSs was analyzed by wavelength dispersive X-ray fluorescence spectrometer. Carbon dioxide gas was pumped into distilled water to make carbonic acid solution for dissolution of OS. The calcareous deposit was characterized by second electron microscope (SEM), energy dispersive X-ray analysis (EDX) and X-ray diffraction. Corrosion rates were estimated by measurements of anodic polarization and immersion test. It is confirmed that calcareous deposits on steel plate are formed under all condition of cathodic protection by using waste OS from the SEM and EDX results. Calcareous deposits on steel by OS provide good corrosion resistance by acting as a barrier to oxygen supply to the steel surface.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2003년도 춘계학술발표회 초록집
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• pp.30-30
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• 2003

• Journal of Advanced Marine Engineering and Technology
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• 제39권7호
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• pp.779-785
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• 2015

일반적으로 선박 및 해양구조물, 그리고 심해 설비의 가장 적절한 부식 방지법으로는 음극방식법이 널리 사용되고 있다. 해수 중에 이러한 음극방식법이 적용될 경우, 음극전류가 용존 해 있는 산소를 환원시킴으로써 음극분극 된 설비 표면에 수산화 이온을 다량 발생시키게 되고, 이로 인하여 계면에서의 pH는 증가하게 된다. 또한 탄산이온의 농도 역시 증가하게 되어, 바닷물 속에 용해되어 있는 마그네슘과 칼슘 이온들이 이들 수산화 이온 및 탄산 이온과 결합함으로써, 수산화마그네슘 및 탄산칼슘을 주성분으로 하는 무기물 층이 설비 표면에 석출하게 되는데 이렇게 형성된 피막을 일반적으로 "석회질 피막"이라고 한다. 이러한 무기물 층은 해수라는 부식환경에서 모재를 보호하는 물리적 장벽으로서의 역할을 함은 물론 음극방식을 할 때 요구되는 전류밀도를 감소시키는 역할을 하게 된다. 한편 이러한 해수 중에서의 석회질 피막의 형성은 전위, 전류, pH, 온도, 시간 등을 포함한 많은 변수들에 의해 변화하게 되는데, 이에 본 연구에서는 여러 가지 변수들 중 특히나 해수의 온도 및 시험편 표면 조건에 따른 무기물 층의 피막구조변화 및 특성변화를 살펴봄으로서 환경친화적인 코팅막의 개발에 대한 설계지침을 제공 할 수 있었다.

• 한국표면공학회지
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• 제37권5호
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• pp.253-262
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• 2004

Calcareous deposits are the consequence of pH increase of the electrolyte adjacent to metal surface affected by cathodic current in seawater. It obviously has several advantages over conventional coatings, since the calcareous deposit coating is formed from coating (Mg$^{2+}$, $Ca^{2+}$) naturally existing in seawater. In consideration of this respect, environment friendly calcareous deposit films were formed by an electro deposition technique on steel substrates submerged in 48$^{\circ}C$ natural seawater. And the influence of current density, coating time and attachment of steel mesh on composition ratio, structure and morphology of the electrodeposited films were investigated by Scanning Electron Microscopy(SEM), Energy Dispersive Spectroscopy(EDS) and X-Ray Diffractor(XRD), respectively. Accordingly, this study provides a better understanding of the composition between the growth of $Mg(OH)_2$ and $CaCO_3$ during the formation of electro deposit films on steel substrate under cathodically electrodeposition in $48^{\circ}C$ natural seawater. The Mg compositions, in general, are getting decreased regardless of current density but Ca compositions are getting increased as electrodeposition time runs. That is, $Mg(OH)_2$ compounds of brucite structure shaped as flat type is formed at the initial stage of electrodeposition, but CaCO$_3$ compounds of aragonite structure shaped as flower type is formed in large scale. Besides, $Mg(OH)_2$ compounds were much formed at 5 A/$\m^2$ environment condition compared to the 3 A/$\m^2$ and 4 A/$\m^2$ environment conditions. This is because that OH- which was comparatively largely generated at the metal surface is preferably combined with $Mg^{2+}$TEX>.

• 한국표면공학회지
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• 제46권1호
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• pp.1-8
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• 2013

Cathodic current on a metal tends to increase the $OH^-$ neighboring to the metal surface, especially during electro-deposition in seawater. The increased pH at metal/seawater interface results in precipitation of brucite crystal structure-$Mg(OH)_2$ as following formula; $Mg^{2+}+2OH^-{\rightarrow}Mg(OH)_2$, that is typical mechanism of the main calcareous deposits-compound in electro deposited coating films. In this study, the effects of anode and current density on deposition rate, composition structure and morphology of the deposited films were systematically investigated by scanning electron microscopy(SEM) and x-ray diffraction(XRD), respectively in order to overcome the problems such as deposition rate and a weak adhesion between deposit film and metal surface. The adhesion and corrosion resistance of the coating films were also evaluated by anodic polarization test. The electro-deposited film formed by using AZ31-Mg anode had the most appropriate physical properties. Weight gain of electro-deposit films increased with increasing cathodic current. Electro-deposit prepared at $5A/cm^2$ current density shows better adhesion than that formed at $8{\sim}10A/cm^2$.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2015년도 추계학술대회 논문집
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• pp.351-351
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• 2015

음극방식법은 피방식체에 외부전원을 인가하거나 보다 활성 금속을 전기적으로 연결하여 피방식체를 일정 전위까지 음극분극 되도록 하여 부식을 억제하는 방법이다. 해수 중 음극방식을 실시할 경우 생성되는 석회질 피막(Calcareous deposit)은 소요전류밀도 감소로 인한 희생양극의 수명연장 및 물리적 방호벽 역할을 한다. 그러나 일반적인 석회질 피막은 세라믹과 같은 화합물로써 밀착력이 매우 약하며, 적지 않은 피막 형성 시간이 소요된다. 따라서 본 연구에서는 해수 중 음극전류 프로세스를 응용하여 실제 강관의 해중부 및 간만대 영역까지 석회질 피막을 균일-치밀하게 형성시키기 위한 최적의 조건을 찾고자 하였다. 각 조건별로 제작된 석회질 피막은 SEM, EDS 및 XRD를 통해 막의 모폴로지, 조성원소 및 결정 구조를 분석하였으며, 이를 바탕으로 희생양극 종류(Al, Zn) 및 1, 3, $5mA/m^2$의 전류밀도 조건에서 부위-기간별 형성된 석회질 피막의 메커니즘을 해명하였다. 또한 밀착성과 내식특성을 평가하기 위해 테이핑 테스트, 침지-자연전위 거동을 분석 및 평가하였다.