• Journal of the Korean Chemical Society
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• v.44 no.2
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• pp.95-101
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• 2000

Macroacyclic transition metal complexes such as $Cu(H_2L[A]).H_2O$, $Cu(H_2L[B]).H_2O$, CuFe(L[A]($NO_3$).$4H_2O$, CuFe(L[B])($NO_3$).$4H_2O$, [$CuGd(H_2L[A])(NO_3)_2](NO_3).2CH_3OH$, [CuGd($H_2L$[B])($NO_3)_2$]($NO_3).2CH_3OH were prepared from the corresponding hexadentate compartmental ligands, $H_4L[A]$ and $H_4L[B]$, which were obtained by the condensation of 2-hydroxy-3-hydroxymethy1-5-methyIbenzaldehyde(HHNNB) and ethylenediamine or l,3-diaminopropane. Ln-macrocyclic([20]DOTA) complexes,[Ln([20]DOTA)($NO_3)(H_2O)$]($NO_3$)2.$xH_2O${Ln(III)=Pr, Sm, Gd, Dy, which had been synthesized from 2,6-diformyl-p-cresol(DFPC), was placed in methanol for 2 days, and [Ln([20] DOTA)($NO_3)(CH_3OH)]^{2+}$ was formed The equilibrium constants (k) for the substitution of coordinated $CH_3OH$ in the Ln-[20]DOTA complexes by various bidentate auxiliary ligands, $L_a$(=o-phenylenediamine,1,10-phenanthroline, ethylenediamine,oxalicacid, malonic acid, acethylacetone) were determined by spectroscopic method at $25^{\circ}C$ and 0.1M $NaClO_4$.The pKa of auxiliary ligands is in the order of o-phenylenediamine < 1,10-phenanthroline < ethylene-diamine, oxalic acid < malonic acid < acethylacetone. However, the equilibrium constant(K) has shown thetrend of ethyleneiamine < 1,10-phenanthroline < o-phenylenediamine, acethylacetone < malonic acid < oxalic acid.

• Journal of the Korean Electrochemical Society
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• v.8 no.4
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• pp.172-176
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• 2005

Recently, many researches on the high-voltage 5 V class cathode material have focused on $LiNi_{0.5}Mn_{1.5}O_4$, where $Mn^{3+}$ in the existing $LiMn_2O_4 (Li[Mn^{3+}][Mn^{4+}]O_4)$ is replaced by $Ni^{2+}(Li[Ni^{2+}]_{0.5}[Mn^{4+}]_{1.5}O_4)$ in order to utilize $Ni^{2+}/Ni^{4+}$ redox reaction in the 5V region. The partial substitution of Mn in $LiMn_2O_4$ for other transition metal element, $LiM_yMn_{1-y}O_4$(M=Cr, Al, Ni, Fe, Co, Cu, Ga etc) is known as a good solution to overcome the problems associated with $LiMn_2O_4$ like the gradual capacity fading. In this study, we synthesized $LiNi_{0.5}Mn_{1.5}O_4$ through a mechanochemical process and investigated its morphological, crystallographic and electrochemical characteristics. The results showed that 4 V peaks had been found in the cyclic volammograms of the synthesized powders due to the existence of $Mn^{3+}$ from the incomplete substitution of $Ni^{2+}$ for $Mn^{3+}$ implying that the mechanochemical activation alone was not good enough to synthesize an exact stoichiometric compound of $LiNi_{0.5}Mn_{1.5}O_4$. The synthetic condition of mechanochemical process, such as type of starting materials, ball-mill and calcination condition was optimized for the best electrochemical performance.

• Korean Chemical Engineering Research
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• v.49 no.2
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• pp.168-174
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• 2011

Various La-based perovskite catalysts were prepared by a Pechini method, and they were applied to the low-temperature oxidation of odor compounds exhausted from waste food treatment process for effective deodorization. Quantitative and qualitative analyses of exhausted gas were conducted to measure the amount of major odor compounds with respect to operation time. A standard odor sample composed of major odor compounds was then prepared for use as a feed for oxidation reaction system. Various transition metal(M)-substituted La-based perovskite catalysts ($LaMO_{3}$: M=Cr, Mn, Fe, Co, and Ni) were prepared and applied to the oxidation of odor compounds in order to investigate the $LaNiO_3$ catalyst showed the best catalytic performance. Pt-substituted perovskite catalysts ($LaNi_{1-x}Pt_{x}O_{3}$: x=0, 0.03, 0.1, and 0.3) were then prepared for enhancing the catalytic performance. It was found that $LaNi_{0.9}Pt_{0.1}O_{3}$ catalyst served as the most efficient catalyst. Supported perovskite catalysts ($XLaNi_{0.9}Pt_{0.1}O_{3}/Al_{2}O_{3}$: X=perovskite content(wt%), 0, 10, 20, 30, 40, 50, and 100) were finally applied for the purpose of maximizing the catalytic performance of perovskite catalyst in the low-temperature oxidation reaction. Catalytic performance of $XLaNi_{0.9}Pt_{0.1}O_{3}/Al_{2}O_{3}$ catalysts showed a volcano-shaped curve with respect to perovskite content. Among the catalysts tested, $20LaNi_{0.9}Pt_{0.1}O_{3}$/$Al_{2}O_{3}$ catalyst exhibited the highest conversion of odor compounds of 88.7% at $180^{\circ}C$.

• Journal of the Korean Electrochemical Society
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• v.19 no.3
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• pp.80-86
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• 2016

High Ni content layered oxide materials for the positive electrode in lithium-ion batteries have high specific capacity. However, their poor electrochemical and thermal stability at elevated temperature restrict the practical use. A small amount of $Al_2O_3$ was added to the mixture of transition metal hydroxide and lithium hydroxide. The $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ was simultaneously doped and coated with $Al_2O_3$ during heat-treatment. Electrochemical characteristics of modified $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ were evaluated by the galvanostatic cycling and the LSTA(linear sweep thermmametry) at the constant voltage conditions. The nano-sized $Al_2O_3$ added materials show better cycle performance at elevated temperature than that of micro-sized $Al_2O_3$. As the added amount of nano-$Al_2O_3$ increased, the thermal stability of electrode also enhanced, but the use of 2.5 mol% Al showed the best high temperature performance.

• Journal of Life Science
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• v.20 no.2
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• pp.281-291
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• 2010

We investigated the antioxidant effects of hederagenin 3-O-b-D-glucopyranosyl($1{\rightarrow}3$)-a-L-rhamnopyranosyl($1{\rightarrow}2$)-a-L-arabinopyranoside (HDL) isolated from root bark of Ulmus davidiana on the activity of enzymes related to reactive oxygen species (ROS) in human osteosarcoma U2OS cells. Cobalt chloride ($CoCl_2$), a transition metal, was used as an inducer of oxidative stress, generating hydrogen peroxide ($H_2O_2$) via increasing xanthine oxidase (XO) activity. The increased levels of $H_2O_2$, XO, ferritin, and ferritin iron by $CoCl_2$ were diminished effectively by co-treatment with HDL in U2OS cells. Furthermore, decreased levels of antioxidant enzymes such as superoxide dismutase (SOD), catalase (CAT) by $CoCl_2$ were highly increased by co-treatment with HDL in U2OS cells; however, the levels of glutathione peroxidase (GPx) did not change. The increased contents of TBARS related to lipid peroxidation were significantly reduced by HDL in U2OS cells. The concentration of GSH changed in a pattern that went against regulated TBARS by $CoCl_2$ and HDL. We examined the expression of p53, $p21^{CIP1/WAF1}$, and $p27^{KIP1}$ proteins related to oxidative stress and cell cycle regulation. As a result, the expression of $p27^{KIP1}$ modulated by $CoCl_2$ was not changed by HDL. However, the expression of p53 and $p21^{CIP1/WAF}$ increased by $CoCl_2$ was reduced by HDL in U2OS cells. Together with alteration of p53 and $p21^{CIP1/WAF1}$ proteins, the accumulated cells at G1 phase by $CoCl_2$ was decreased by HDL in U2OS cells. Our data suggests that HDL inhibits $CoCl_2$-generated ROS in U2OS cells, providing potentially new antioxidant compounds that are isolated from natural products.

• Economic and Environmental Geology
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• v.2 no.3
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• pp.1-25
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• 1969

In considering the mining industry, it is necessary to study the production, consumption and price of ore and metals in every country of the world in order to determine the trend of the industry in the present and for the future. This study is necessary especially for exporting domestically produced are which is in excess of domestic consumption and for importing are, or metal where local production does not meet domestic demand. It will be treated of Au, Ag, Cu, Pb, Zn, W, Mo, which are the most important non-ferrous metals, and which greatly affect the mining industry of Korea. The presentation will concern itself only with the free world. About 1, 200 ton of gold are produced annually with little fluctiation in recent years. Most of the gold produced is consumed by advanced countries for industrial uses as well as for producing precious objects. The U.S.A. expends yearly about four times its domestic production and Japan about three times its domestic production for industry and arts. Because of the instability of the currency of the U.S.A., England and France, recently, the price of gold has been $ 41-42 per ounce, whereas the official price is $35.00 per ounce. It will be expected that the official price will be raised in the near future. As for silver, about 6,500 tons are produced annually with no special fluctuation change in recent years. However, the annual consumption is about 14,000 ton, so the supply and demand is extremely unbalanced. The shortage is made up by the sale of the U.S. treasury's reserve stock and the reclaiminig of silver from coins and other scrap. As the Treasury'S reserves will be exhausted in a year or two, the price of silver which is $1. 64 per ounce, will go up drastically in about a year. As for copper, 5,257,000 ton's were mined in 1966. It's production is being increased about 5% annually. However, consumption exceeds production by about 100,000 ton a year. The recent Foreign refinery copper price in the U.S.A is $ 60 per pound. The supply of copper being insufficient to meet international demands, the price will go up and with no prospect of being lowered in the near future even with the slight annual increase in production. About 2,100,000 to 2,200,000 tons of lead are produced annually. Consumption exceeds production by about 50,000-60,000 tons annually. The current price of lead in New York is $ 155 per pound. As the supply of lead is internationally stable, It will be believed that there will be no significant change in its price in the near future. In 1967, 3,926,000 tons of Zinc were produced. There is annual increase of 4-7% in production. The annual consumption exceeds production by 100,000 to 200,000 tons. The current zinc price in the St. Louis market inthe U.S.A. is $ 145 per pound. Even though its supply is stable and sufficient world wide, the consumption rate will increase at a faster pace than before; hence, the price will slowly go up. Tungsten mines yield about 11,000 tons a year. Its production has been relatively constant in the past few years. The amount of its consumption increases slowly world wide, but in the free world· there has been a slight annual decrease. However, since Red China has not been exporting their tungsten to other countries for several months, the price on the London market of S.T.U. of $Wo_3$ has increased to $ 44~46. Should Red China begin to export actively again the price will drop to $ 40~42. In 1967, 56,000 tons of Molybdenum were produced. Production exceeds consumption by 200,000 -30,000 tons annually. The current price in the U.S.A. is $ 1.72 per Mo pound. Since the rate of production in the U.S.A. is on the increase with large amounts of ore reserve, the price of molubdenum should not go up.

• The Journal of the Korea Contents Association
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• v.8 no.11
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• pp.210-216
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• 2008

In this study, image comparisons were carried out using a MRI contrast medium which was derived by mixing a polyaminocarboxylic ligand and a gadolinium (III) transition metal which is paramagnetic and has good neutron absorbing capabilities with Gd-DTPA which is currently being used widely in the clinical setting. By using a 1.0T (Harmony, SIEMENS) MR equipment, phantoms of which 100cc of saline was diluted with a diethylenetriaminetriacetic acid derivative and Gd-DTPA were imaged. The amount of diethylenetriaminetriacetic acid and Gd-DTPA which was diluted into the 100cc of saline was 0.05mmol/L, 0.1mmol/L, 0.15mmol/L, 0.2mmol/L, 0.3mmol/L, 0.5mmol/L, 1.0mmol/L, 2.0mmol/L, 3.0mmol/L and 4.9mmol/L respectively. Head coils were used and while fixing the SE pulse sequence and image variable (as TE is 14ms, 1NEX with a 256x201 matrix), the signal intensity and simple contrast ratios according to changing concentrations and TR were compared with various TR at 300ms, 400ms, 500ms, 600ms, 700ms, 800ms, 900ms, 1000ms, 1200ms, 1400ms and 1600ms. According to the comparison results of the signal intensity of the image based on changes in contrast medium concentrations and TR, the differences in signal intensity between the two contrast mediums were found to be small at $1.0{\sim}2.0mmol/L$ when the highest signal intensity was achieved. However, at concentrations of 1.0mmol/L or less, the signal intensity was markedly higher in the Diethylenetriaminetriacetic acid derivative than in the Gd-DTPA complex. It was also found that the differences in the signal intensities demonstrated by the concentrations of the contrast mediums were affected by the TR. Accordingly, the efficacy of the Diethylenetriaminetriacetic acid derivative was shown to be better than the Gd-DTPA and also possible to get the optimum image quality by the use of an appropriate TR with appropriate concentrations of contrast medium.

• Journal of The Korean Astronomical Society
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• v.12 no.1
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• pp.41-70
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• 1979

From $B\ddot{o}hm$-Vitense's atmospheric model calculations, the relations, [$T_e$, (B-V)] and [B.C, (B-V)] with respect to heavy element abundance were obtained. Using these relations and evolutionary model calculations of Rood, and Sweigart and Gross, analytic expressions for some physical parameters relating to the C-M diagrams of globular clusters were derived, and they were applied to 21 globular clusters with observed transition periods of RR Lyrae variables. More than 20 different parameters were examined for each globular cluster. The derived ranges of some basic parameters are as follows; $Y=0.21{\sim}0.33,\;Z=1.5{\times}10^{-4}{\sim}4.5{\times}10^{-3},\;age,\;t=9.5{\sim}19{\times}10^9$ years, mass for red giants, $m_{RG}=0.74m_{\odot}{\sim}0.91m_{\odot}$, mass for RR Lyrae stars, $m_{RR}=0.59m_{\odot}{\sim}0.75m_{\odot}$, the visual magnitude difference between the turnoff point and the horizontal branch (HB), ${\Delta}V_{to}=3.1{\sim}3.4(<{\Delta}V_{to}>=3.32)$, the color of the blue edge of RR Lyrae gap, $(B-V)_{BE}=0.17{\sim}0.21=(<(B-V)_{BE}>=0.18),\;[\frac{m}{L}]_{RR}=-1.7{\sim}-1.9$, mass difference of $m_{RR}$ relative to $m_{RG},(m_{RG}-m_{RR})/m_{RG}=0.0{\sim}0.39$. It was found that the ranges of derived parameters agree reasonably well with the observed ones and those estimated by others. Some important results obtained herein can be summarized as follows; (i) There are considerable variations in the initial helium abundance and in age of globular clusters. (ii) The radial gradient of heavy element abundance does exist for globular clusters as shown by Janes for field stars and open clusters. (iii) The helium abundance seems to have been increased with age by massive star evolution after a considerable amount (Y>0.2) of helium had been attained by the Big-Bang nucleosynthesis, but there is not seen a radial gradient of helium abundance. (iv) A considerable amount of heavy elements ($Z{\sim}10{-3}$) might have been formed in the inner halo ($r_{GC}$<10 kpc) from the earliest galactic co1lapse, and then the heavy element abundance has been slowly enriched towards the galactic center and disk, establishing the radial gradient of heavy element abundance. (v) The final galactic disk formation might have taken much longer by about a half of the galactic age than the halo formation, supporting a slow, inhomogeneous co1lapse model of Larson. (vi) Of the three principal parameters controlling the morphology of C-M diagrams, it was found that the first parameter is heavy clement abundance, the second age and the third helium abundance. (vii) The globular clusters can be divided into three different groups, AI, BI and CII according to Z, Y an d age as well as Dickens' HB types. BI group clusters of HB types 4 and 5 like M 3 and NGC 7006 are the oldest and have the lowest helium abundance of the three groups. And also they appear in the inner halo. On the other hand, the youngest AI clusters have the highest Z and Y, and appear in the innermost halo region and in the disk. (viii) From the result of the clean separations of the clusters into three groups, a three dimensional classification with three parameters, Z, Y and age is prsented. (ix) The anomalous C-M diagrams can be expalined in terms of the three principal parameters. That is, the anomaly of NGC 362 and NGC 7006 is accounted for by the smaller age of the order of $1{\sim}2{\times}10^9$ years rather than by the helium abundance difference, compared with M 3. (x) The difference in two Oosterhoff types I and II can be explained in terms of the mean mass difference of RR Lyrae variables rather than in terms of the helium abundance difference as suggested by Stobie. The mean mass of the variables in Oosterhoff type I clusters is smaller by $0.074m_{\odot}$ which is exactly consistent with Rood's estimate. Since it was found that the mean mass of RR Lyrae stars increases with decreasing Z, the two Oosterhoff types can be explained substantially by the metal abundance difference; the type II has Z<$3.4{\times}10^{-4}$, and the type I has higher Z than the type II.

• Journal of the Korean Magnetics Society
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• v.16 no.1
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• pp.23-27
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• 2006

By substituting Mn or Cr for Co in inverse spinel $CoFe_2O_4,\;Mn_xCo_{1-x}Fe_2O_4\;and\;Cr_xCo_{1-x}Fe_2O_4$ and thin films were prepared by sol-gel method and their structural and magnetic properties were investigated. X-ray diffraction indicates that the cubic lattice constant increase for the Mn substitution while it hardly changes for the Cr substitution. Substitution of $Mn^{2+}$ for octahedral $Co^{2+}$ sites can explain the increase of lattice constant in $Mn_xCo_{1-x}Fe_2O_4$. On the other hand, Substitution of $Cr^{3+}$ for octahedral $Co^{2+}$ and subsequent reduction of $Fe^{3+}$ ion into $Fe^{2+}$ are expected to happen. Mossbauer spectroscopy measurements on $Cr_xCo_{1-x}Fe_2P_4$ indicate the existence of tetrahedral $Fe^{2+}$ ions that are created through reduction of tetrahedral $Fe^{3+}$ ions in order to compensate charge imbalance happened by $Cr^{3+}$ substitution for octahedral $Co^{2+}$ sites. On the other hand, no $Fe^{2+}$ ions were detected by Mossbauer spectroscopy for $Mn_xCo_{1-x}Fe_2O_4$. A migration of $Fe^{3+}$ ions from octahedral to tetrahedral sites In $Mn_xCo_{1-x}Fe_2O_4$ was detected by Mossbauer spectroscopy for x>0.47. Vibrating sample magnetometry measurements on the samples at room temperature revealed that the saturation magnetization increases by Mn and Cr substitution for certain range of x, qualitatively explainable in terms of the comparison of spin magnetic moment among the related transition-metal ions.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.239-240
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• 2008

As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.