• Journal of Advanced Marine Engineering and Technology
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• v.28 no.6
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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.

• Proceedings of the Korean Society of Marine Engineers Conference
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• 2005.11a
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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.

• Journal of the Korean institute of surface engineering
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• v.37 no.5
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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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• v.39 no.7
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• pp.779-785
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• 2015

Cathodic protection is recognized as the most cost-effective and technically appropriate corrosion prevention method for the submerged zone of offshore structures, ships, and deep-sea facilities. When cathodic protection is applied, the cathodic currents cause dissolved oxygen reduction, generating hydroxyl ions near the polarized surface that increase the interfacial pH and result in enhanced carbonate ion concentration and precipitation of an inorganic layer whose principal component is calcium carbonate. Depending on the potential, magnesium hydroxide can also precipitate. This mixed deposit is generally called "calcareous deposit." This layer functions as a barrier against the corrosive environment, leading to a decrease in current demand. Hence, the importance of calcareous deposits for the effective, efficient operation of marine cathodic protection systems is recognized by engineers and scientists concerned with cathodic protection in submerged marine environments. Calcareous deposit formation on a marine structure depends on the potential, current, pH, temperature, pressure, sea-water chemistry, flow, and time; deposit quality is significantly influenced by these factors. This study determines how calcareous deposits form in sea water, and assesses the interrelationship of formation conditions (such as the sea water temperature and surface condition of steel), deposited structure, and properties and the effectiveness of the cathodic protection.

• Journal of the Korean institute of surface engineering
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• v.47 no.1
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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.