• The Journal of Korean Academy of Prosthodontics
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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.

• Journal of Korean Society of Environmental Engineers
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• 제22권4호
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• pp.765-773
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• 2000

The degradation of humic acid using $TiO_2$ coatings was studied, $TiO_2$ coatings were prepared by dip-coating method. Sol solutions for coating were prepared by mixing the gel, which can be produced by the reaction of $TiOCl_2$ and $NH_4OH$ solution, and hydrogen peroxide solution, and hydrolysis of titanium tetraisopropoxide (TTIP). It was shown from XRD that coatings from sol aged at $100^{\circ}C$ for 18h with titanium peroxo solution were crystallized to anatase in the range of temperatures of $25^{\circ}C$ to $500^{\circ}C$. In contrast, those coated from TTIP were crystallized to anatase at temperature above $400^{\circ}C$. So the sols originated from $TiCl_4$ can be applied for not only on the heat-resistance substrates but on the plastic substrates. Thickness and the quality of the films were dependent on the withdrawing speed, the concentration of sol, and the number of coating. The films showed various interference colors depending on the thickness of them. In the case that the films coated 2 times at withdrawing speed of 2.5cm per minute by 0.2M sol, the films had a transparent light blue color with thickness of around 50nm. It was known from the result of photo-degradation by $TiO_2$ coatings using humic acid that the removal efficiency of $COD_{cr}$ was over 85% after illumination of $UV/H_2O_2$ for 40min. and that of UV/VIS absorbable materials was over 95%.

• Applied Chemistry for Engineering
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• 제22권6호
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• pp.685-690
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• 2011

In this study, a solvothermal reaction to prepare nanocrystalline titania was carried out using $TiCl_4$ and mixed solvents of alcohol and water. The effects of the type and the composition of alcohol on the crystal structure and agglomeration of final $TiO_2$ products were investigated. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) as well as scanning electron microscopy (SEM). In the solvothermal reaction using the n-butanol solutions with different volume ratios of n-butanol/water (100/0, 75/25, 50/50, 25/75, 0/100), the extent of agglomeration of obtained rutile $TiO_2$ was found to change with the volume ratio of n-butanol/water, and the n-butanol/water ratio of 75/25 revealed the best result for the preparation of well-dispersed nanocrystalline $TiO_2$ powders. The crystal phase of $TiO_2$ prepared through the solvothermal reaction changed with the type of alcohol in solvent (alcohol/water = 75/25). $TiO_2$ products obtained with the aqueous solutions of methanol, ethanol and isopropanol have an anatase phase, while that with n-butanol has a rutile phase. The results showed that, in the solvothermal reaction using both $TiCl_4$ as a starting material and the alcohol-water mixed solvents without any other additive, the enhancement of dispersion and control of crystal structure of $TiO_2$ products can be feasible by simply varying the composition and type of alcohol in the mixed solvents.

• Applied Chemistry for Engineering
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• 제21권1호
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• pp.29-33
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• 2010

In this study, boron, carbon, nitrogen and fluorine co-doped $TiO_{2}$ photocatalysts using tetraethylammonium tetrafluoroborate (TEATFB) have been prepared by different heat treatment temperatures to decrease the band gap. To explore the visible light photocatalytic activity of the novel low‐zband gap $TiO_{2}$ photocatalyst, the removal of two dyes was investigated, namely, acridine orange and rhodamine B. XRD patterns demonstrate that the samples calcined at temperatures up to $800^{\circ}C$ clearly show anatase peaks. The XPS results show that all the doped samples contain N, C, B and F elements and the doped $TiO_{2}$ shows the shift in the band gap transition down to 2.98 eV as UV-DRS results. In these UV-Vis results, photocatalytic activity of the doped $TiO_{2}$ is 1.61 times better than undoped $TiO_{2}$. Specially, excellent photoactivity results were obtained in the case of samples treated at $700^{\circ}C$.

• Korean Chemical Engineering Research
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• 제51권2호
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• pp.163-170
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• 2013

Selective catalytic reduction of $NO_x$ by $NH_3$ ($NH_3$-SCR) over $V_2O_5/TiO_2$-based catalysts is recently reported to be an anthropogenic emitter of $N_2O$ that is a global warming gas with a global warming potential of 310. Therefore, this review will get a touch on significance of some parameters regarding $N_2O$ formation in the $deNO_xing$ reaction for fossil fuels-fired power plants applications. The $N_2O$ production in $NH_3$-SCR reaction with such catalysts occurs via side reactions between $NO_x$ and $NH_3$ in addition to $NH_3$ oxidation, and the extent of these undesired reactions depends strongly on the loadings of $V_2O_5$ as a primary active component and the promoter as a secondary one ($WO_3$ and $MoO_3$) in the SCR catalysts, the feed and operating variables such as reaction temperature, $NO_2/NO_x$ ratio, oxygen concentration, gas hourly space velocity, water content and thermal excursion, and the physical and chemical histories of the catalysts on site. Although all these parameters are associated with the $N_2O$ formation in $deNO_xing$ reaction, details of some of them have been discussed and a better way of suppressing the $N_2O$ production in commercial SCR plants has been proposed.

• Nuclear Engineering and Technology
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• 제28권5호
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• pp.458-466
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• 1996

The effects of dopants on the modification of microstructure of UO$_2$ and UO$_2$-4wt%CeO$_2$ sintered pellets have been studied in hydrogen and $CO_2$/CO mixture atmospheres by using $Ta_2O_5$, TiO$_2$ and $Nb_2O_5$ as sintering additives. The dopant were added as oxide powders and homogenized by attrition milling. The mixed powders were pressed, and then sintered in hydrogen at 1$700^{\circ}C$ , or in oxidizing atmosphere using Controlled $CO_2$/CO mixtures at 125$0^{\circ}C$. Both density and microstructure of UO$_2$ are modified by the addition of dopants in reducing atmosphere. The sintered density is increased with $Ta_2O_5$ addition up to 0.33wt% and subsequently decreased with higher content of the additive. The effect on the densification and the gain growth are apparent with the addition of 0.24wt% $Nb_2O_5$. With 0.lwt% titania and 0.6wt% $Ta_2O_5$, the sintered density is decreased, but the grain size is increased. In oxidizing atmosphere, the grain sizes for UO$_2$ doped with the above additives are smaller than that for pure UO$_2$. The grain size of Ta or Nb-doped UO$_2$ is decreased with increasing $CO_2$/CO ratio, but that of pure UO$_2$or T-doped UO$_2$ is increased. A large portion of second phases is observed in UO$_2$ doped with 0.lwt% TiO$_2$ sintered in hydrogen atmosphere, while, in $CO_2$/CO atmospheres, the second phases or dopant agglomerates are not observed. For UO$_2$-4wt%CeO$_2$ mixed oxide, the effect of additives on the gain growth is not so much as that for the pure UO$_2$. This is attributed to the formation of clusters by dopant cations and Ce ions, so that the additives contribute to a lesser exent to the grain growth for the mixed oxide.

• Journal of Korean Society of Environmental Engineers
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• 제22권3호
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• pp.511-521
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• 2000

Investigation was carried out lean burn de-NOx properties of Pt-$TiO_2$ bifunctional catalyst by propylene in order to get the high de-NOx activity and the wide temperature window under coexistence of $SO_2$ and $H_2O$. Only noncatalyst and carrier catalyst themselves had NOx conversion activity at high temperature over $400^{\circ}C$. NOx conversion activity of catalysts exchanged copper ion resulted in Cu-$TiO_2$>Cu-ZSM-5>Cu-$Al_2O_3$>CU-YZ>Cu-AZ. Catalysts impregnated with platinum based on titania gave the results of high NOx conversion activity at low temperature. $250^{\circ}C$. Bifunctional catalysts based on Pt-$TiO_2$ showed high NOx conversion activity both at a low zone of $300^{\circ}C$ and a high zone of $500^{\circ}C$. Pt-$TiO_2$/$Al_2O_3$ catalyst gave the highest NOx conversion activity at a low temperature zone. and Pt-$TiO_2$/$Mn_2O_3$(21) catalyst gave the highest NOx conversion activity at a high temperature zone. Under the coexistence of $SO_2$ and $H_2O$. NOx conversion activities of 0.55wt%Pt-$TiO_2$/5wt%Cu-ZSM-5 catalyst was high both at a low and high temperature zone, and increased depending on oxygen concentration. 0.55wt%Pt-$TiO_2$/5wt%Cu-ZSM-5 catalyst showed the best correlation between de-NOx activities and the propyl ere conversion rates to CO on the log function.

• Journal of the Microelectronics and Packaging Society
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• 제22권2호
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• pp.21-26
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• 2015

Mesoporous ceramic materials were applied in various fields such as adsorbent and gas sensor because of low thermal conductivity and high specific surface area properties. This structure could be divided into open-pore structure and closed-pore structure. Although closed-pore structure mesoporous ceramic materials have higher mechanical property than open-pore structure, it has a restriction on the application because the increase of specific surface area is limited. So, in this work, specific surface area of closed-pore structure $TiO_2$ was increased by anneal time. As increased annealing time, crystallization and grain growth of $TiO_2$ skeleton structured material in mesoporous structure induced a collapse and agglomeration of pores. Through this pore structural change, pore connectivity and specific surface area could be enhanced. After anneal for 24 hrs, porosity was decreased from 36.3% to 34.1%, but specific surface area was increased from $48m^2/g$ to $156m^2/g$. CO gas sensitivity was also increased by about 7.4 times due to an increase of specific surface area.

• Journal of Environmental Science International
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• 제14권2호
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• pp.221-230
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• 2005

Catalytic wet oxidation of trichloroethylene (TCE) in water has been conducted using $TiO_2-supported$ cobalt oxides at $36^{\circ}C$ with a weight hourly space velocity of $7,500\;h^{-1}.\;5\%\;CoO_x/TiO_2$, prepared by using an incipient wetness technique, might be the most promising catalyst for the wet oxidation although it exhibited a transient behavior in time on-stream activity. Not only could the bare support be inactive for the wet decomposition reaction, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. XPS spectra of both fresh and used Co surfaces gave different surface spectral features for each $CoO_x,\;Co\;2P_{3/2}$ binding energy for Co species in the fresh catalyst appeared at 781.3 eV, which is very similar to the chemical states of $CoTiO_x$ such as $CO_2TiO_4\;and\;CoTiO_3$. The used catalyst exhibited a 780.3-eV main peak with a satellite structure at 795.8 eV. Based on XPS spectra of reference Co compound, the TCE-exposed Co surfaces could be assigned to be in the form of mainly $Co_3O_4$. XRD patterns for $5\%\;CoO_x/TiO_2$ catalyst indicated that the phase structure of Co species in the catalyst even before reaction is quite comparable to the diffraction lines of external $Co_3O_4$ standard. A model structure of $CoO_x$ present predominantly on titania surfaces would be $Co_3O_4$, encapsulated in thin-film $CoTiO_x$ species consisting of $Co_2TiO_4$ and $CoTiO_3$, which may be active for the decomposition of TCE in a flow of water.

• Journal of the Korean Ceramic Society
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• 제39권5호
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• pp.438-445
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• 2002

In this study, the glass frit of $PbO-TiO-2-SiO_2-BaO-ZnO-Al_2O-3-CaO-B_2O_3-Bi_2O_3-MgO$ system was manufactured. The glass was melted at $1,400{\circ}C$, quenched and attrition-milled. The glass frit powder was pressed and fired for 2h at the range of $750~1,000{\circ}C$. The crystallization of glass frit began at about $750{\circ}$ and at low temperature, the main crystal phases were hexagonal celsian($BaAl_2Si_2O_8$) and alumina. As the firing temperature increased, the crystal phases of monoclinic celsian, zinc aluminate, zinc silicate, calcium titanium silicate and titania appeared. And the increase of firing temperature led to transformation of hexagonal celsian to monoclinic. The only glass frit containing 15wt% PbO had the crystal phase of solid solution of $PbTiO_3-CaTiO_3$. At the frequency of 1 MHz, the dielectric constant of glass frit crystallized was in the range of 11~16 and the dielectric loss less than 0.020. But the glass frit containing 15wt% PbO had the dielectric constant of 17~26 and loss of 0.010~0.015 because of crystal phase of solid solution of $PbTiO_3-CaTiO_3$.