• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2016.11a
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• pp.144-144
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• 2016

플라즈마 전해 산화법(Plasma electrolytic oxidation)에 의해 형성된 코팅층은 특유의 기공구조로 인해 부식 환경에 노출 시 부식액의 침투가 급속히 이루어지는 단점이 있다. 이를 극복하기 위한 방법으로 유기코팅, sol-gel법, 폴리머 코팅 등에 의해 기공을 봉공(sealing)하는 방법이 제안되고 있다. 본 연구에서는 Al 합금의 플라즈마 전해 산화 처리 후 질산 세륨 수용액(Cerium nitrate solution)에 의한 봉공 효과를 확인하고자 하였다. PEO 코팅을 위한 전해액은 2g/L의 KOH와 $2g/L\;Na_2SiO_3$를 증류수에 용해시켜 준비하였다. PEO 코팅층은 Al 시편을 전해액 내에 위치시켜 양극으로 하고 STS를 음극으로 하여 $0.1A/cm^2$의 펄스 정전류밀도(주파수: 100Hz, 듀티비: 20%)를 15분 동안 인가하여 형성시켰다. 봉공을 위한 실링액은 증류수에 $0.3g/L\;H_2O_2$와 $1g/L\;H_3BO_3$를 첨가하고, $Ce(NO_3)_3$를 농도 변수로 첨가하여 준비하였으며, PEO 코팅 처리된 시편을 실링액에 침지하여 실링액의 농도와 침지시간을 달리하여 봉공을 실시하였다. 제작된 PEO 코팅층에 대해 SEM, EDS, XRD를 이용한 표면분석을 실시하였으며, 내식성을 확인하고자 동전위분극시험을 실시하였다. 연구 결과, 세륨 실링 처리된 PEO 코팅 층에서 미량의 세륨 성분이 검출되었으나, 세륨계 화합물 생성에 의한 마이크로 크기의 기공의 폐쇄는 관찰되지 않았다. 또한, 전기화학적 특성 평가 결과 실링 처리된 PEO 코팅층의 경우 Al 모재에 비해 2차수 정도 감소된 부식전류밀도를 나타내었다. 이 같은 내식성의 향상은 세륨 성분에 의한 부식 억제 효과 때문으로 판단된다.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2016.11a
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• pp.198-198
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• 2016

An ideal orthopedic implant should provide an excellent bone-implant connection, less implant loosening and minimum adverse reactions. Commercial pure titanium (CP-Ti) and Ti alloys have been widely utilized for biomedical applications such as orthopedic and dental implants. However, being bioinert, the integration of such implant in bone was not in good condition to achieve improved osseointegraiton, there have been many efforts to modify the composition and topography of implant surface. These processes are generally classified as physical, chemical, and electrochemical methods. Plasma electrolytic oxidation (PEO) as an electrochemical route has been recently utilized to produce this kind of composite coatings. Mg ion plays a key role in bone metabolism, since it influences osteoblast and osteoclast activity. From previous studies, it has been found that Mg ions improve the bone formation on Ti alloys. PEO is a promising technology to produce porous and firmly adherent inorganic Mg containing $TiO_2$($Mg-TiO_2$ ) coatings on Ti surface, and the amount of Mg introduced into the coatings can be optimized by altering the electrolyte composition. In this study, a series of $Mg-TiO_2$ coatings are produced on Ti-6Al-4V ELI dental implant using PEO, with the substitution degree, respectively, at 0, 5, 10 and 20%. Based on the preliminary analysis of the coating structure, composition and morphology, a bone like apatite formation model is used to evaluate the in vitro biological responses at the bone-implant interface. The enhancement of the bone like apatite forming ability arises from $Mg-TiO_2$ surface, which has formed the reduction of the Mg ions. The promising results successfully demonstrate the immense potential of $Mg-TiO_2$ coatings in dental and biomaterials applications.

• Journal of the Korean institute of surface engineering
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• v.49 no.1
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• pp.46-53
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• 2016

The structure of plasma electrolytic oxidation (PEO) coatings was investigated as a function of NaOH concentration in 0.06 M $Na_2SiO_3$ + 0.06 M $Na_3PO_4$ solution by using SEM and epoxy replica method. The PEO film was formed on AZ31 Mg alloy by the application of anodic pulse current with 0.2 ms width and its formation behavior was studied by voltage-time curves during the formation of PEO films. It was found that the addition of NaOH into $PO_4{^{3-}}$ and $SiO_3{^{2-}}$ containing aqueous solution causes a decrease in the PEO film formation voltage, suggesting that dielectric breakdown of the PEO becomes easier with increasing $OH^-$ ion concentration in the solution. With increasing $OH^-$ ion concentration, thickness of the PEO film increased and surface roughness decreased. The size of pores formed in the PEO layer became smaller and the number of cracks in the PEO layer increased with increasing $OH^-$ ion concentration. Based on the experimental results obtained in the work, it is suggested that $OH^-$ ions in the solution can contribute not only to the dielectric breakdown but also to the formation of PEO films in the presence of $PO_4{^{3-}}$ and $SiO_3{^{2-}}$ ions in the solution.

• Journal of the Korean institute of surface engineering
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• v.50 no.5
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• pp.308-314
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• 2017

Anodic film formation behavior of AZ31 Mg alloy was studied as a function of NaOH concentration in 1 M $Na_2CO_3$ + 0.5 M $Na_2SiO_3$ solution under the application of a constant anodic current density, based on the analyses of voltage-time curves, surface appearances and morphologies of the anodically formed PEO (plasma electrolytic oxidation) films. The anodic film formation voltage and its fluctuations became largely lowered with increasing added NaOH concentration in the solution. Two different types of film defects, large size dark spots indented from the original surface and locally extruded white spots, were observed on the PEO-treated surface, depending on the concentration of added NaOH. The large size dark spots appeared only when added NaOH concentration is less than 0.2 M and they seem to result from the local detachments of porous PEO films. The white spots were observed to be very porous and locally extruded and their size became smaller with increasing added NaOH concentration. The white spot defects disappeared completely when more than 0.8 M NaOH is added in the solution. Concludingly it is suggested that the presence of enough concentration of $OH^-$ ions in the carbonate and silicate ion-containing electrolyte can prevent local thickening and/or detachment of the PEO films on the AZ31 Mg alloy surface and lower the PEO film formation voltage less than 70 V.

• Journal of the Korean institute of surface engineering
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• v.52 no.5
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• pp.265-274
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• 2019

Formation behavior of PEO (Plasma Electrolytic Oxidation) films on AZ31 Mg alloy was investigated under application of 310 Hz AC as a function of $Na_3PO_4$ concentration from 0.02 M to 0.2 M. Film formation voltage and in-situ observation of arcs generated on the specimen surface were recorded with time, and surface morphologies of the PEO films were investigated using optical microscopy, confocal scanning laser microscopy and scanning electron microscopy. PEO film formation voltage decreased linearly with increasing $Na_3PO_4$ concentration which is attributed to the increase of solution pH. PEO films were grown uniformly over the entire surface in $Na_3PO_4$ solutions between 0.05 M and 0.1 M. However, non-uniform PEO films with white spots were formed in $Na_3PO_4$ solutions containing more than 0.1 M. Thickness and roughness of PEO films on AZ31 Mg alloy increased linearly with increasing $Na_3PO_4$ concentration and their increasing rates appeared to be much higher under 1 M than above 1 M. The experimental results suggest that phosphate ions can contribute to the formation of PEO films but higher $Na_3PO_4$ concentration more than 1 M results in local damages of PEO films due to repeated generation of white arcs at the same surface site of AZ31 Mg alloy.

• Journal of the Korean institute of surface engineering
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• v.54 no.5
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• pp.238-247
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• 2021

PEO (plasma electrolytic oxidation) was applied to modify the surface of AZ31 magnesium alloy in this study. The mixed solution of sodium hydroxide (NaOH) and sodium silicate (Na₂SiO₃) was used as the electrolyte, and 0 - 0.05 g/L of Ca-GP (Glycerol Phosphate Calcium salt) was added in the electrolyte as an additive. PEO treatment was conducted at a current density of 30mA/cm² for 5 minutes using a DC power supply. The surface properties were identified by SEM, XRD and surface roughness analyses, and the corrosion resistance was evaluated by potentiodynamic polarization and immersion tests. In addition, the biocompatibility was evaluated by immersion test in SBF solution. As the concentration of Ca-GP was increased, the surface morphology was denser and more uniform, and the amount of Ca and the thickness of oxide layer increased. Only Mg peak was observed in XRD analysis due to very thin oxide layer. The corrosion resistance of PEO-treated samples increased with the concentration of Ca-GP in comparision with the untreated sample. In particular, the highest corrosion resistance was identified at the group of 0.04g Ca-GP through potentiodynamic polarization and immersion tests in saline solution (0.9 wt.%NaCl). During the immersion in saline solution, pH rapidly increased at the beginning of immersion period due to rapid corrosion, and then increase rate of pH decreased. However, the pH value in the SBF temporarily increased from 7.4 to 8.5 during the day, then decreased due to the inhibition of corrosion with HA(hydroxyapatite) formation.

• Journal of the Korean institute of surface engineering
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• v.52 no.3
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• pp.138-144
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• 2019

In this work, PEO (Plasma Electrolytic Oxidation) film formation behavior of Al6061 alloy was investigated as a function of applied current density of AC at 310 Hz in the range from $120mA/cm^2$ to $300mA/cm^2$ in 0.5 M $Na_2SiO_3$ solution. When applied current density is lower than a critical voltage of about $132mA/cm^2$, voltage reaches a steady-state values less than 120 V without generation of arcs and metallic color of the alloy surface remains. On the other hand, when applied current density exceeds about $132mA/cm^2$, voltage increases continuously with time and arcs are generated at more than 175 V, resulting in the formation of PEO films with grey colors. Two different types of arcs, large size and small number of arcs with orange color, and small size and large number of arcs with white color, were generated at the same time when the PEO film thickness exceeds about $50{\mu}m$, irrespective of applied current density. Formation efficiency of the PEO films was found to increase with increasing applied current density and the growth rate was obtained to be about $5{\mu}m/min$ at $300mA/cm^2$. It was also found that surface roughness of the PEO films with $70{\mu}m$ thickness is not dependent on the applied current density.

• Journal of the Korean institute of surface engineering
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• v.53 no.6
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• pp.351-359
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• 2020

Formation behavior and properties of PEO (Plasma Electrolytic Oxidation) film on AA2024 were investigated under application of pulsed current as a function of Na3PO4 concentration in 0.05 M Na2SiO3 solution by analyzing voltage-time behavior, in-situ observation of arc generation, observation of surface morphology and measurements of thickness and surface roughness. Arc generation voltage decreased with increasing Na3PO4 concentration. Color difference of PEO films between edge and inner part disappeared by addition of Na3PO4. It was also observed that size of nodules on PEO film decreased with increasing Na3PO4 concentration. Thickness of PEO films formed on AA2024 increased with increasing Na3PO4 concentration. Whereas, surface roughness of PEO films decreased with increasing Na3PO4 concentration up to 0.05 M of Na3PO4 which is attributed to the deceased size of nodules on the PEO films. However, the surface roughness increased with increasing Na3PO4 concentration more than 0.07 M of Na3PO4 which seems to be due to the formation of non-uniform PEO films with smooth surface and large size pores formed by orange-colored big arcs. The experimental results suggest that added sodium phosphate less than 0.2 M in an alkaline silicate solution can contribute to the formation of relatively thick and uniform thickness of PEO films under arc generation voltage lower than 300 V.

• Journal of the Korean institute of surface engineering
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• v.54 no.4
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• pp.184-193
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• 2021

This study demonstrates formation behavior and morphological changes of PEO (Plasma Electrolytic Oxidation) films on AZ91 Mg alloy as a function of pre-treatment time in 1 M HF solution at 25 ± 1 ℃. The electrochemical behavior and morphological changes of AZ91 Mg alloy in the pre-treatment solution were also investigated with pre-treatment time. The PEO films were formed on the pre-treated AZ91 Mg alloy specimen by the application of anodic current 100 mA/cm² of 300 Hz AC in 0.1 M NaOH + 0.4 M Na₂SiO₃ solution. Vigorous generation of hydrogen bubbles were observed upon immersion in the pre-treatment solution and its generation rate decreased with immersion time. It was also found that 𝛽-Mg₁₇Al₁₂ in AZ91 Mg alloy was dissolved and a protective thin film of MgF₂ was formed on the AZ91 Mg alloy surface during the pre-treatment process in the 1 M HF solution. PEO film did not grow on the AZ91 Mg alloy specimen when the surface was not pre-treated and irregular PEO films with nodular defects were formed for the specimens pre-treated up to 1 min. Uniform PEO films were formed when the AZ91 Mg alloy specimen was pre-treated more than 3 min. The growth rate of PEO films on AZ91 Mg alloy increased significantly with increasing pre-treatment time.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2011.05a
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• pp.158-159
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• 2011

In this work, The electrochemical behavior of CF/Al composite was investigated at constant current densities in aqueous solutions. The surface and cross section of PEO-treated CF/Al were observed using SEM, EDS and OM. The CF/Al composite contains carbon fibers of about 40 Vol.% with 5~7 um diameter and 100~150 um length. The carbon fibers appeared to b removed by anodic oxidation in sulfuric acid solution, leaving a carbon-fiber free zone in the surface region. Anodic oxide films were formed in the carbon-free region by plasma electrolytic oxidation(PEO) method in alkaline solutions.