• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2016년도 추계학술대회 논문집
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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.

• 한국표면공학회지
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• 제50권5호
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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.

• 한국표면공학회지
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• 제54권5호
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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.

• 한국주조공학회지
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• 제29권5호
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• pp.233-237
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• 2009

The effect of electrolyte on mechanical and corrosion properties of AZ91 magnesium alloy by plasma electrolytic oxidation (PEO) method was investigated. The coating layers formed in the silicate and the aluminate electrolytes showed porous structures. The small pores were randomly distributed on the coatings formed in aluminate electrolyte while the coatings formed in silicate electrolyte showed much bigger pores. In the aluminate electrolyte, the coatings were composed of Mg, MgO and $MgAl_2O_4$, whereas Mg, MgO, $MgAl_2O_4$ and $Mg_2SiO_4$ were identified in the coatings formed in silicate electrolyte. The hardness of coatings in the silicate electrolyte was higher than that of coating grown in the aluminate electrolyte. The AZ91 alloy coated in the silicate electrolyte had higher tensile strength and elongation than that coated in the aluminate electrolyte. In addition, the coatings formed in the silicate electrolyte showed much better corrosion resistance compared to the coatings formed in the aluminate electrolyte.

• 한국표면공학회지
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• 제51권6호
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• pp.344-353
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• 2018

Plasma electrolytic oxidation of Ti-25Ta-xHf alloy in electrolyte containing Ca and P for dental implants was investigated using various experimental techniques. Ti-25Ta-xHf (x=0 and 15 wt.%) alloys were manufactured in an arc-melting vacuum furnace. Micropores were formed in PEO films on Ti-25Ta-xHf alloys in 0.15 M calcium acetate monohydrate + 0.02 M calcium glycerophosphate at 240 V, 270 V and 300 V for 3 min, respectively. The microstructure of Ti-25Ta-xHf alloys changed from (${\alpha}^{\prime}+{\alpha}^{{\prime}{\prime}}$) phase to (${\alpha}^{{\prime}{\prime}}+{\beta}$) phase by addition of Hf. As the applied potential increased, the number of pore and the area ratio of occupied by micro-pore decreased, whereas the pore size increased. The anatase phase increase as the applied potential increased. Also, the crystallite size of anatase-$TiO_2$ can be controlled by applied voltage.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2017년도 춘계학술대회 논문집
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• pp.79-79
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• 2017

Metallic biomaterials have been mainly used for the fabrication of medical devices for the replacement of hard tissue such as artificial hip joints, bone plates, and dental implants. Because they are very reliable on the viewpoint of mechanical performance. This trend is expected to continue. Especially, Ti and Ti alloys are bioinert. So, they do not chemically bond to the bone, whereas they physically bond with bone tissue. For their poor surface biocompatibility, the surface of Ti alloys has to be modified to improve the surface osteoinductivity. Recently, ceramic-like coatings on titanium, produced by plasma electrolytic oxidation (PEO), have been developed with calciumand phosphorus-enriched surfaces. A lso included the influences of coatings, which can accelerate healing and cell integration, as well as improve tribological properties. However, the adhesions of these coatings to the Ti surface need to be improved for clinical use. Particularly Silicon (Si) has been found to be essential for normal bone, cartilage growth and development. This hydroxyapatite, modified with the inclusion of small concentrations of silicon has been demonstrating to improve the osteoblast proliferation and the bone extracellular matrix production. Strontium-containing hydroxyapatite (Sr-HA) was designed as a filling material to improve the biocompatibility of bone cement. In vitro, the presence of strontium in the coating enhances osteoblast activity and differentiation, whereas it inhibits osteoclast production and proliferation. The objective of this work was to study Morphology of bone-like apatite formation on Sr and Si-doped hydroxyapatite surface of Ti-6Al-4V alloy after plasma electrolytic oxidation. Anodized alloys was prepared at 270V~300V voltages with various concentrations of Si and Sr ions. Bone-like apatite formation was carried out in SBF solution. The morphology of PEO, phase and composition of oxide surface of Ti-6Al-4V alloys were examined by FE-SEM, EDS, and XRD.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2016년도 추계학술대회 논문집
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• pp.120-120
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• 2016

Ti-6Al-4V alloy have been used for dental implant because of its excellent biocompatibility, corrosion resistance, and mechanical properties. However, the integration of such implant in bone was not in good condition to achieve improved osseointergraiton. For solving this problem, calcium phosphate (CaP) has been applied as coating materials on Ti alloy implants for hard tissue applications because its chemical similarity to the inorganic component of human bone, capability of conducting bone formation and strong affinity to the surrounding bone tissue. Various metallic elements, such as strontium (Sr), magnesium (Mg), zinc (Zn), sodium (Na), silicon (Si), silver (Ag), and yttrium (Y) are known to play an important role in the bone formation and also affect bone mineral characteristics, such as crystallinity, degradation behavior, and mechanical properties. Especially, Zn is essential for the growth of the human and Zn coating has a major impact on the improvement of corrosion resistance. Plasma electrolytic oxidation (PEO) is a promising technology to produce porous and firmly adherent inorganic Zn containing $TiO_2(Zn-TiO_2)$coatings on Ti surface, and the a mount of Zn introduced in to the coatings can be optimized by altering the electrolyte composition. In this study, corrosion behavior of Ti-6Al-4V alloy after plasma electrolytic oxidation in solutions containing Ca, P and Zn were studied by scanning electron microscopy (SEM), AC impedance, and potentiodynamic polarization test. A series of $Zn-TiO_2$ coatings are produced on Ti dental implant using PEO, with the substitution degree, respectively, at 0, 5, 10 and 20%. The potentiodynamic polarization and AC impedance tests for corrosion behaviors were carried out in 0.9% NaCl solution at similar body temperature using a potentiostat with a scan rate of 1.67mV/s and potential range from -1500mV to +2000mV. Also, AC impedance was performed at frequencies ranging from 10MHz to 100kHz for corrosion resistance.

• 대한금속재료학회지
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• 제48권9호
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• pp.813-818
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• 2010

In current automobile and electronic industries, the use of magnesium alloys where both energy and weight saving are attainable is increasing. Despite their light weight, there has been an inherent drawback arising from the surface vulnerable to be oxidized with ease, specifically under corrosive environments. To protect magnesium alloy from corrosion, the present work deals with the electrochemical response of the oxide layer on magnesium alloy specimen prepared by plasma electrolytic oxidation (PEO) method in an electrolyte with zirconia powder. Surface observation using scanning electron microscopy evidences that a number of zirconia particles are effectively incorporated into oxide layer. From the results of potentio-dynamic tests in 3.5 wt% NaCl solution, the PEO-treated sample containing zirconia particles shows better corrosion properties than that without zirconia, which is the result of zirconia incorporation into the coating layer. Corrosion resistance is also measured by utilizing salt spray tests for 120 hrs.

• 한국세라믹학회지
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• 제50권2호
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• pp.108-115
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• 2013

Oxide coatings were prepared on Al-1050 substrates by an environment-friendly plasma electrolytic oxidation (PEO) process using an electrolytic solution of $Na_2SiO_3$ (8 g/L) and NaOH (3 g/L). The effects of three different duty cycles (20%, 40%, and 60%) and frequencies (50 Hz, 200 Hz, and 800 Hz) on the structure and micro-hardness of the oxide coatings were investigated. XRD analysis revealed that the oxides were mainly composed of ${\alpha}-Al_2O_3$, ${\gamma}-Al_2O_3$, and mullite. The proportion of each crystalline phase depended on various electrical parameters, such as duty cycle and frequency. SEM images indicated that the oxide coatings formed at a 60% duty cycle exhibited relatively coarser surfaces with larger pore sizes and sintering particles. However, the oxides prepared at a 20% duty cycle showed relatively smooth surfaces. The PEO treatment also resulted in a strong adhesion between the oxide coating and the substrate. The oxide coatings were found to improve the micro-hardness with the increase of duty cycle. The structural and physical properties of the oxide coatings were affected by the duty cycles.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2018년도 춘계학술대회 논문집
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• pp.74-74
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• 2018

Ti-6Al-4V alloys have been widely used as orthopedic materials because of their excellent corrosion resistance and mechanical properties. However, it does not bind directly to the bone, so it requires a surface modification. This problem can be solved by nanotube and micropore formation. Plasma electrolytic oxidation (PEO) treatment for micropore, which combines high-voltage spark and electrochemical oxidation, is a new way of forming a ceramic coating on light metals such as titanium and its alloys. This method has excellent reproducibility and can easily control the shape and size of the Ti alloy. In this study, formation of bioactive surface by PEO-treatment after $2^{nd}$ ATO technique of Ti-6Al-4V alloy was invesgated by various instrument. Nanotube oxide surface structure was formed on the surface by anodic oxidation treatment in 0.8 wt.% NaF and 1M $H_3PO_4$ electrolytes. After nanotube formation, nanotube layer was removed by ultrasonic cleaning. PEO-treatment was carried out at 280V for 3 minutes in the electrolytic solution containing the bioactive substance (Mg, Zn, Mn, Sr, and Si). The surface of Ti-6Al-4V alloy was observed by field emission scanning electron microscopy (FE-SEM, S-4800 Hitachi, Japan). An energy dispersive X-ray spectrometer (EDS, Inca program, Oxford, UK) was used to analyze the spectra of physiologically active Si, Mn, Mg, Zn, and Sr ions. The PEO film formed on the Ti-6Al-4V alloy surface was characterized using an X-ray diffractometer (TF-XRD, X'pert Philips, Netherlands). It is confirmed that bioactive ions play an essential role in the normal bone growth and metabolism of the human skeletal tissues.