• 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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• 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>.

• 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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• 제47권1호
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• pp.39-47
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• 2014

The peculiar feature of cathodic protection in seawater has the capability to form mineral calcareous deposits such as magnesium and calcium on metal surfaces. It is assumed that $OH^-$ ions are generated close to the metal surface as a result of cathodic protection and generated $OH^-$ ions increases the pH of the metal/seawater interface outlined as the following formulae. (1) $O_2+2H_2O+4e{\rightarrow}4OH^-$, or (2) $2H_2O+2e{\rightarrow}H_2+2OH^-$. And high pH causes precipitation of $Mg(OH)_2$ and $CaCO_3$ in accordance with the following formulae. (1) $Mg^{2+}+2OH^-{\rightarrow}Mg(OH)_2$, (2) $Ca^{2+}+CO{_3}^{2-}{\rightarrow}CaCO_3$. The focus of this study was to increase the amount of $CO{_3}^{2-}$ with the injection of $CO_2$ gas to the solution for accelerating process of the following formulae. (1) $H_2O+CO_2{\rightarrow}H_2CO_3$, (2) $HCO^{3-}{\rightarrow}{H^+}+CO{_3}^{2-}$. Electrodeposit films were formed by an electro-deposition technique on steel substrates in solutions of both natural seawater and natural seawater dissolved $CO_2$ gas with different current densities, over different time periods. The contents of films were investigated by scanning electron microscopy(SEM) and X-ray diffraction(XRD). The adhesion and corrosion resistance of the coating films were evaluated by anodic polarization. From an experimental result, only $CaCO_3$ were found in solution where injected $CO_2$ gas regardless of current density. In case of injecting the $CO_2$ gas, weight gain of electrodeposits films hugely increased and it had appropriate physical properties.