• 한국재료학회지
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• 제14권9호
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• pp.607-613
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• 2004

This study was to investigate the surface properties of electrochemically oxidized Ti-6Al-7Nb alloy by anodic spark discharge technique. Anodizing was performed at current density 30 $mA/cm^2$ up to 300 V in electrolyte solutions containing $DL-{\alpha}$-glycerophosphate disodium salt hydrate($DL-{\alpha}$-GP) and calcium acetate (CA). Hydrothermal treatment was done at $300^{\circ}C$ for 2 hrs to produce a thin outermost layer of hydroxyapatite (HA). The bioactivity was evaluated from HA formation on the surfaces in a Hanks' solution with pH 7.4 at $36.5^{\circ}C$ for 30 days. The size of micropores and the thickness of oxide film increased and complicated multilayer by increasing the spark forming voltage. Needle-like HA crystals were observed on anodic oxide film after the hydrothermal treatment at $300^{\circ}C$ for 2 hrs. When increasing $DL-{\alpha}$-GP in electrolyte composition, the precipitated HA crystals showed the shape of thick and shorter rod. However, when increasing CA, the more fine needle shape HA crystals were appeared. The bioactivity in Hanks' solution was accelerated when the oxide films composed with strong anatase peak with presence of rutile peak. The increase of amount of Ca and P was observed in groups having bioactivity in Hanks' solution. The Ca/P ratio of the precipitated HA layer was equivalent to that of HA crystal and it was closer to 1.67 as increasing the immersion time in Hanks' solution.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2016년도 추계학술대회 논문집
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• pp.152-152
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• 2016

Anodizing is a technology to generate thicker and high-quality films than natural oxide films by treating metals via electrochemical methods. It is a technique to develop metals for various uses, and extensive research on the commercial use has been performed for a long time. Aluminum anodic oxide (AAO) is generate oxide films, whose sizes and characteristics depending on the types of electrolytes, voltages, temperatures and time. Electrochemical manufacturing method of nano structure is an efficient technology in terms of cost reduction, high productivity and complicated shapes, which receives the spotlight in diverse areas. The sulfuric acid was used as an anodizing electrolyte, controlling its temperature to $10^{\circ}C$. The anode was 5083 Al alloy with dimension of $5(t){\times}20{\times}20mm$ while the cathode was the platinum. The distance between the anode and the cathode was maintained at 3 cm. Agitation was introduced by magnetic stirrer at 300 rpm to prevent localized temperature rise that hinders stable growth of oxide layer. In order to observe surface characteristics with applied current density, the electrolyte temperature, concentration was maintained at constant condition for $10^{\circ}C$, 10 vol.%, respectively. To prevent hindrance of stable growth of oxide layer due to local temperature increase during the experiment, stirring was maintained at constant rate. In addition, using galvanostatic method, it was maintained at current density of $10{\sim}30mA/cm^2$ for 40 minutes. The cavitation experiment was carried out with an ultrasonic vibratory apparatus using piezo-electric effect with modified ASTM-G32. The peak-to-peak amplitude was $30{\mu}m$ and the distance between the horn tip and specimen was 1 mm. The specimen after the experiment was cleaned in an ultrasonic, dried in a vacuum oven for more than 24 hours, and weighed with an electric balance. The surface damage morphology was observed with 3D analysis microscope. As a result of the investigation, differences were observed surface hardness and anti-cavitation characteristics depending on the development of oxide film with applied current density.

• 대한치과보철학회지
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• 제45권1호
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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.

• 한국표면공학회지
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• 제51권1호
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• pp.21-26
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• 2018

The $Cu_2(btc)_3$ metal-organic frameworks (MOF) coated anodic aluminum oxide (AAO) membrane was successfully prepared by layer-by-layer technique using hand spray method. It was confirmed that the $Cu_2(btc)_3$ layer, which has the pore sized in 2-3 nm, on surface of AAO exhibited the polycrystalline thin film structure by XRD analysis. More than 100 repetitive spray cycles were required to obtain more robust and thick MOFs on AAO and it was possible to uniformly coat both the top and bottom surfaces of the AAO. It should be noted that the MOFs also could be coated on surface of pores resulting in reduce the size of pore from 52 nm to 32 nm.

• 한국정보통신학회:학술대회논문집
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• 한국해양정보통신학회 2010년도 춘계학술대회
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• pp.814-817
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• 2010

다공성 알루미나 나노틀은 2단계의 양극산화 과정에 의해 세공의 직경이 균일하며, 배열이 규칙적이며 나노틀에 완벽하게 수직으로 배향되어 있다. 게다가 세공의 직경과 세공간의 간격은 양극산화시 전압과 전해질등을 바꾸어 주면 쉽게 조절할 수 있다. 금속을 세공내에 전기 화학적으로 탐지하면 각 세공 내에 규칙적인 직경의 금속 나노선이 생성된다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2003년도 추계학술발표강연 및 논문개요집
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• pp.128-128
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• 2003

Electrochromism (EC) is defined as a phenomenon in which a change in color takes place in the presence of an applied voltage. Because of their low power consumption, high coloration efficiency, EC devices have a variety of potential applications in smart windows, mirror, and optical switching devices. An EC devices generally consist of a transparent conducting layer, electrochromic cathodic and anodic coloring materials and an ion conducting electrolyte. EC has been widely studied in transition metal oxides(e.g., WO$_3$, NiO, V$_2$O$\sub$5/) Among these materials, WO$_3$ is a most interesting material for cathodic coloration materials due to its lush coloration efficiency (CE), large dynamic range, cyclic reversibility, and low cost material. WO$_3$ films have been prepared by a variety of methods including vacuum evaporation, chemical vapor deposition, electrodeposition process, sol-gel synthesis, sputtering, and laser ablation. Sol-gel process is widely used for oxide film at low temperature in atmosphere and requires lower capital investment to deposit large area coating compared to vacuum deposition process.

• 한국진공학회지
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• 제15권1호
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• pp.97-102
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• 2006

양극 산화된 알루미나 (anodized aluminum oxide : AAO)는 균일하고 일정한 크기의 나노기공 패턴을 지니고 있다. AAO를 이온빔 나노 patterning을 위한 이온조사 시 마스크로서 이용하기 위해 AAO 나노 기공을 통과하는 이온빔의 투과율(AAO에 입사한 이온에 대한 투과이온의 양의 비)을 측정하였다. Al bulk foil을 양극 산화하여 두께가 $4{\mu}m$이고 종횡비(두께와 기공의 지름의 비)가 각각 200:1, 100:1 인 AAO를 Goniometer에 부착하여 500 keV의 $O^{2+}$ 이온빔에 대해 나노기공을 정렬시킨 후, 기울임 각에 따른 투과율을 측정한 결과, 종횡비가 200:1, 100:1 일 때 투과율은 각각 약 $10^{-8},\;10^{-4}$로 거의 이온빔이 투과하지 못하였다. 반면에 $SiO_2$ 위에 증착된 Al 박막으로 양극산화하여 종횡비가 5:1인 AAO의 이온빔 투과율은 0.67로 투과율이 현저히 향상되었다. 높은 종횡비를 갖는 AAO의 경우에는 범과 AAO 기공의 정렬이 쉽지 않은데다 알루미나의 비전도성으로 인한 charge-up 현상으로 인해 이온빔이 극히 투과하기 어렵기 때문이다. 실제로 80 keV의 Co 음이온을 종횡비 5:1인 AAO에 조사시킨 후에는 AAO 나노기공과 동일한 크기의 나노 구조체가 형성됨을 주사전자현미경(scanning electron microscopy: SEM) 관찰을 통하여 확인하였다.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2017년도 춘계학술대회 논문집
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• pp.77-77
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• 2017

Titanium and its alloys offer attractive properties in a variety of applications. These are widely used for the field of biomedical implants because of its good biocompatibility and high corrosion resistance. Titanium anodizing is often used in the metal finishing of products, especially those can be used in the medical devices with dense oxide surface. Based on SAE/AMS (Society of Automotive Engineers/Aerospace Material Specification) 2488D, it has the specification for industrial titanium anodizing that have three different types of titanium anodization as following: Type I is used as a coating for elevated temperature forming; Type II is used as an anti-galling coating without additional lubrication or as a pre-treatment for improving adherence of film lubricants; Type III is used as a treatment to produce a spectrum of surface colours on titanium. In this study, we have focused on Type II anodization for the medical (dental and orthopedic) application, the anodized surface was modified with gray color under alkaline electrolyte. The surface characteristics were analyzed with Focused Ion Beam (FIB), Scanning Electron Microscopy (SEM), surface roughness, Vickers hardness, three point bending test, biocompatibility, and corrosion (potentiodynamic) test. The Ti-6Al-4V alloy was used for specimen, the anodizing procedure was conducted in alkaline solution (NaOH based, pH>13). Applied voltage was range between 20 V to 40 V until the ampere to be zero. As results, the surface characteristics of anodic oxide layer were analyzed with SEM, the dissecting layer was fabricated with FIB method prior to analyze surface. The surface roughness was measured by arithmetic mean deviation of the roughness profile (Ra). The Vickers hardness was obtained with Vickers hardness tester, indentation was repeated for 5 times on each sample, and the three point bending property was verified by yield load values. In order to determine the corrosion resistance for the corrosion rate, the potentiodynamic test was performed for each specimen. The biological safety assessment was analyzed by cytotoxic and pyrogen test. Through FIB feature of anodic surfaces, the thickness of oxide layer was 1.1 um. The surface roughness, Vickers hardness, bending yield, and corrosion resistance of the anodized specimen were shown higher value than those of non-treated specimen. Also we could verify that there was no significant issues from cytotoxicity and pyrogen test.

• 한국표면공학회지
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• 제51권2호
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• pp.87-94
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• 2018

Various sealing techniques were applied to the anodized 5083 aluminum alloy for marine environment to reduce corrosion and cavitation erosion damage. Electrochemical experiments and cavitation erosion tests were conducted to evaluate the corrosion resistance and cavitation resistance of the anodic oxide film treated with sealing in natural seawater solution. Then, damaged surface morphology was analyzed by scanning electron microscope(SEM) and 3D microscope. As the results of the electrochemical experiments, it was observed that the surface damage of all the experimental conditions in the anodic polarization experiment was locally grown by the combination of crack and corrosion damage. In the Tafel analysis, the corrosion resistance of all sealing treatment conditions was improved compared to the anodizing. On the other hand, cavitation erosion tests showed that the anodizing and all the sealing treatment conditions generated local pit damage by cavitation erosion attack and grew to crater damage in the observation of damaged surface by SEM. Also, the weight loss and the surface damage depth measured with the experiment time presented that most of the sealing treatment conditions showed better cavitation erosion resistance than the anodizing, and they had an incubation period at the beginning of the experiment.

• 대한화학회지
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• 제57권5호
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• pp.547-553
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• 2013

전해연마를 한 지르코늄(Zr)을 가지고 $F^-$ 이온이 함유된 무기 전해질과 유기 전해질에서 2 단계 양극산화를 진행하여 산화 지르코늄($ZrO_2$) 나노 다공성 산화막을 제조하였다. 2 단계 양극산화를 진행하면서 무기 전해질에서보다 유기 전해질에서 만들어진 지르코늄 산화막이 보다 균일한 나노 다공성 산화막을 가지게 되었다. 나노 다공성 산화막의 크기와 구조는 FE-SEM(field emission scanning electron microscopy), XRD(X-ray diffraction), EDS(energy dispersive spectroscopy)를 이용하여 특성을 분석하였고 형광스펙트럼을 측정하여 $ZrO_2$ 나노 다공성 산화막의 형광성을 알아보았다.