• Corrosion Science and Technology
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• v.15 no.3
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• pp.120-124
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• 2016

The effect of alloying element Ca (0, 1, and 2 wt%) on corrosion resistance and bioactivity of the as-received and anodized surface of rolled plate AM60 alloys was investigated. A plasma electrolytic oxidation (PEO) was carried out to form anodic oxide film in $0.5mol\;dm^{-3}\;Na_3PO_4$ solution. The corrosion behavior was studied by polarization measurements while the in vitro bioactivity was tested by soaking the specimens in Simulated Body Fluid (1.5xSBF). Optical micrograph and elemental analysis of the substrate surfaces indicated that the number of intermetallic particles increased with Ca content in the alloys owing to the formation of a new phase $Al_2Ca$. The corrosion resistance of AM60 specimens improved only slightly by alloying with 2 wt% Ca which was attributed to the reticular distribution of $Al_2Ca$ phase existed in the alloy that might became barrier for corrosion propagation across grain boundaries. Corrosion resistance of the three alloys was significantly improved by coating the substrates with anodic oxide film formed by PEO. The film mainly composed of magnesium phosphate with thickness in the range $30-40{\mu}m$. The heat resistant phase of $Al_2Ca$ was believed to retard the plasma discharge during anodization and, hence, decreased the film thickness of Ca-containing alloys. The highest apatite forming ability in 1.5xSBF was observed for AM60-1Ca specimens (both substrate and anodized) that exhibited more degradation than the other two alloys as indicated by surface observation. The increase of surface roughness and the degree of supersaturation of 1.5xSBF due to dissolution of Mg ions from the substrate surface or the release of film compounds from the anodized surface are important factors to enhance deposition of Ca-P compound on the specimen surfaces.

• Journal of the Korean Ceramic Society
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• v.41 no.12 s.271
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• pp.900-906
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• 2004

Solid oxide fuel cells have a limitation in their low-temperature application due to the low ionic conductivity of electrolyte materials and difficulties in thin film formation on porous gas diffusion layer. These problems can be solved by improvement of ionic conductivity through controlled nanostructure of electrolyte and adopting nanoporous electrodes as substrates which have homogeneous submicron pore size and highly flattened surface. In this study, ultra-thin oxide films having submicron thickness without gas leakage are deposited on nanoporous substrates. By oxidation of metal thin films deposited onto nanoporous anodic alumina substrates with pore size of $20nm{\sim}200nm$ using dc-magnetron sputtering at room temperature, ultra-thin and dense ionic conducting oxide films with submicron thickness are realized. The specific material properties of the thin films including gas permeation, grain/gran boundaries formation, change of crystalline structure/microstructure by phase transition are investigated for optimization of ultra thin film deposition process.

• Applied Chemistry for Engineering
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• v.9 no.7
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• pp.998-1003
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• 1998

$BaTiO_3$ thin film was electrochemically deposited on Ti electrode in a 0.4 M $Ba(OH)_2$ solution of $85^{\circ}C$ using a current pulse waveform. Both $BaTiO_3$ crystallinity and faradaic efficiency for the film formation were enhanced with the increase of cathodic current density and pulse time. Based on the surface analysis and electrochemical studies, it was suggested that, during cathodic pulsed, the surface pH increase due to the reduction of $H_2O$ accelerates the structural changes of Ti oxides which were formed during anodic cycle. Prior to experiments, Ti oxides were intentionally grown in 0.1 M $H_2SO_4$ solution and the effect of initial oxide film thickness on the $BaTiO_3$ film formation was investigated. The migration of $Ti^{+4}$ ions through the oxide film was retarded with the increase of film thickness and it was observed that the crystallization of $BaTiO_3$ was only limited to the defect area of surface oxides.

• Journal of the Korean institute of surface engineering
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• v.52 no.4
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• pp.203-210
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• 2019

In this work, anodizing behavior of 6xxx series aluminum alloys was studied under constant current density and constant voltage conditions in 20% sulfuric acid solution by V-t curves, I-t curves, thickness measurement, observations of surface appearance and cross-sectional observation of anodizing films. The film growth rate of the anodizing films on Al6063, Al6061 and Al6082 obtained at 20 V were $0.63{\mu}m/min$. $0.46{\mu}m/min$ and $0.38{\mu}m/min$, respectively. Time to the initiation of imperfections at the oxide/substrate interface under constant current condition was shortened and colors of anodizing films became darker with the amount of alloying elements in 6xxx series aluminum alloys. Based upon the experimental results obtained in this work, it is concluded that maximum anodizing film thickness without interfacial defects is reduced with increasing amount of alloying elements and brighter anodizing films can be obtained by decreasing amount of alloying elements in the aluminum alloys.

• Corrosion Science and Technology
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• v.15 no.6
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• pp.265-270
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• 2016

The ellipso-microscopic observation of a titanium surface undergoing anodization in $0.05mol\;dm^{-3}$ of $H_2SO_4$ was conducted. During irradiation by ultra-violet (UV) light with a wavelength of 325 nm, the titanium surface allowed for the flow of a photo-induced current and showed up as a bright, patch-like image on an ellipso-microscopic view. The brightness and patch-pattern in the image changed with flowing photo-induced current. The changes in the brightness and the image corresponded to the formation and/or degradation of titanium oxide due to the photo-electrochemical reaction of the oxide. An in situ monitoring using the ellipso-microscope revealed that the film change was dependent on the irradiation light power, by UV-light increases the anodic current and results in the initiation of pitting at lower potentials as compared with the non-irradiated condition.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2016.11a
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• pp.115.2-115.2
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• 2016

Al alloys are being used widely for automobile, aerospace and mechanical components because of their high strength ratio to weight. However, still they suffer from abrasion or corrosion owing to insufficient resistances to friction or mechanical impact and chemical attack. Plasma electrolytic oxidation (PEO) method is one of the promising surface treatment methods for Al alloys which can render better hardness than aluminum anodic oxide (AAO) films prepared by conventional anodizing method in acidic solutions. In this presentation, some basic nature of PEO film formation and growth process on Al alloys will be presented based on the experimental results obtained and discussed in view of dielectric breakdown and reformation and the role of various anions in film breakdown and reformation of PEO films.

• Journal of the Semiconductor & Display Technology
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• v.20 no.1
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• pp.37-41
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• 2021

We report on the formation of anodic aluminum oxide (AAO) film using sulfuric acid containing cerium salt. When the temperature of the sulfuric acid containing cerium salt changes from 5 ℃ to 20 ℃, the current density and the thickness growth rate increase. The surface morphology of the AAO film change according to the temperature of the electrolytes. And that affected the breakdown voltage and the plasma etch rate. The breakdown voltage per unit thickness was the highest at 15 ℃, and the plasma etch rate was the lowest at 10 ℃ at 2.80 ㎛/h.

• 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.

• The Journal of Korean Academy of Prosthodontics
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• v.43 no.6
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• pp.751-763
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• 2005

Statement of problem. To improve a direct implant fixation to the bone, various strategies have been developed focusing on the surface of materials. The surface quality of the implant depends on the chemical, physical, mechanical and topographical properties of the surface. The different properties will interact with each other and a change in thickness of the oxide layer may also result in a change in surface energy, the surface topography and surface, chemical composition. However, there is limited the comprehensive study with regard to changed surface and biologic behavior of osteoblast by anodization. Purpose of study. The aim of this study was to analyze the characteristics of an oxide layer formed and to evaluate the cellular biologic behaviors on titanium by anodic oxidation (anodization) by cellular proliferation, differentiation, ECM formation and gene expression. And the phospholipase activity was measured on the anodized surface as preliminary study to understand how surface properties of Ti implant are transduced into downstream cellular events. Methods and Materials. The surface of a commercially pure titanium(Grade 2) was modified by anodic oxidation. The group 1 samples had a machined surface and other three experimental specimens were anodized under a constant voltage of 270 V(Group 2), 350 V(Group 3), and 450 V(Group 4). The specimen characteristics were inspected using the following five categories; the surface morphology, the surface roughness, the thickness of oxide layer, the crystallinity, and the chemical composition of the oxide layer. Cell numbers were taken as a marker for cell proliferation. While the expression of alkaline phosphatase and Runx2 (Cbfa1) was used as early differentiation marker for osteoblast. The type I collagen production was determined, which constitutes the main structural protein of the extracellular matrix. Phospholipase $A_2$ and D activity were detected. Results. (1) The anodized titanium had a porous oxide layer, and there was increase in both the size and number of pores with increasing anodizing voltage. (2) With increasing voltage, the surface roughness and thickness of the oxide film increased significantly (p<0.01), the $TiO_2$phase changed from anatase to rutile. During the anodic oxidization, Ca and P ions were more incorporated into the oxide layer. (3) The in vitro cell responses of the specimen were also dependant on the oxidation conditions. With increasing voltage, the ALP activity, type I collagen production, and Cbfa 1 gene expression increased significantly (p<0.01), while the cell proliferation decreased. (4) In preliminary study on the relation of surface property and phospholipase, PLD activity was increased but $PLA_2$ activity did not changed according to applied voltage. Conclusion. The anodized titanium shows improved surface characteristics than the machined titanium. The surface properties acquired by anodization appear to give rise more mature osteoblast characteristics and might result in increased bone growth, and contribute to the achievement of a tight fixation. The precise mechanism of surface property signaling is not known, may be related to phospholipase D.

• The Journal of Korean Academy of Prosthodontics
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• v.45 no.1
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• pp.85-97
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• 2007

Statement of problem: Recently, anodic oxidation of cp-titanium is a popular method for treatment of titanium implant surfaces. It is a relatively easy process, and the thickness, structure, composition, and the microstructure of the oxide layer can be variably modified. Moreover the biological properties of the oxide layer can be controlled. Purpose: In this study, the roughness, microstructure, crystal structure of the variously treated groups (current, voltage, frequency, electrolyte, thermal treatment) were evaluated. And the specimens were soaked in simulated body fluid (SBF) to evaluate the effects of the surface characteristics and the oxide layers on the bioactivity of the specimens which were directly related to bone formation and integration. Materials and methods: Surface treatments consisted of either anodization or anodization followed thermal treatment. Specimens were divided into seven groups, depending on their anodizing treatment conditions: constant current mode (350V for group 2), constant voltage mode (155V for group 3), 60 Hz pulse series (230V for group 4, 300V for group 5), and 1000 Hz pulse series (400V for group 6, 460V for group 7). Non-treated native surfaces were used as controls (group 1). In addition, for the purpose of evaluating the effects of thermal treatment, each group was heat treated by elevating the temperature by $5^{\circ}C$ per minute until $600^{\circ}C$ for 1 hour, and then bench cured. Using scanning electron microscope (SEM), porous oxide layers were observed on treated surfaces. The crystal structures and phases of titania were identified by thin-film x-ray diffractmeter (TF-XRD). Atomic force microscope (AFM) was used for roughness measurement (Sa, Sq). To evaluate bioactivity of modified titanium surfaces, each group was soaked in SBF for 168 hours (1 week), and then changed surface characteristics were analyzed by SEM and TF-XRD. Results: On basis of our findings, we concluded the following results. 1. Most groups showed morphologically porous structures. Except group 2, all groups showed fine to coarse convex structures, and the groups with superior quantity of oxide products showed superior morphology. 2. As a result of combined anodization and thermal treatment, there were no effects on composition of crystalline structure. But, heat treatment influenced the quantity of formation of the oxide products (rutile / anatase). 3. Roughness decreased in the order of groups 7,5,2,3,6,4,1 and there was statistical difference between group 7 and the others (p<0.05), but group 7 did not show any bioactivity within a week. 4. In groups that implanted ions (Ca/P) on the oxide layer through current and voltage control, showed superior morphology, and oxide products, but did not express any bioactivity within a week. 5. In group 3, the oxide layer was uniformly organized with rutile, with almost no titanium peak. And there were abnormally more [101] orientations of rutile crystalline structure, and bonelike apatite formation could be seen around these crystalline structures. Conclusion: As a result of control of various factors in anodization (current, voltage, frequency, electrolytes, thermal treatment), the surface morphology, micro-porosity, the 2nd phase formation, crystalline structure, thickness of the oxide layer could be modified. And even more, the bioactivity of the specimens in vitro could be induced. Thus anodic oxidation can be considered as an excellent surface treatment method that will able to not only control the physical properties but enhance the biological characteristics of the oxide layer. Furthermore, it is recommended in near future animal research to prove these results.