• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.261-272
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• 1992

Tetradentate Schiff base Cobalt(II)(3MeOSED)$(H_2O)_2$ complexe was synthesized and allowed to react with dry oxygen to form oxygen adducts of Cobalt(III) complexes such as ${\mu}$-peroxo type [Co(III)(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$in DMF and DMSO or superoxo type [Co(III)(3MeOSED)(Py)]$O_2$ in pyridine. The oxygen adducted complex was investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMF (-DMSO,-Py) as supporting electrolyte solution. As a result the reduction reaction process occurred to four steps including prewave Of $O_2^-$in 1 : 1 oxygen adducted superoxo type [Co(III)(3MeOSED)(Py)]$O_2$complex and three steps not including prewave of $O_2^-$ in 1 : 2 oxygen adducted ${\mu}$-peroxo type [Co(III)-(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$. A superoxo type [Co(III)(3MeOSED)(L)]$O_2\;(L: CH_3OH)$ was generated with oxygen in methanol. Selectively oxidized hydrazobenzene $(H_2AB)$ to trans-azobenzene(t-AB) and the rate constant k for oxidation reaction of the following equation is $(2.96 {\pm} 0.2)$${\times}$ $10^{-1}$M/sec. $H_2AB$ + Co (II)(3MeOSED)$(L_2)+O_2\;{\rightleftarrow^K}$ [Co(III)(3MeOSED)(L)]$O_2{\cdot}H_2AB{\longrightarrow^K}$ Co(II(3MeOSED)$(L)_2$+t-AB+$H_2O_2 $.

• Korean Journal of Materials Research
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• v.5 no.8
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• pp.1013-1019
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• 1995

The thin plate of Co-Ni-P was deposited on the polyester film by the electroless plating method. Through present experiments, deposition rates and metal compositions of the plates were determined according to compositions of solution, pH and temperature. Also, magnetic properties of plates were examined according to metal compositions. Considering magnetic properties and deposition rates of electroless plating, the best condition was obtained as pH of 8.5 and 90℃. It was observed that metal compositions were evidently varied by the pH of solutions and the concentration of complex agents. However. they were not affected by other factors. At the optimum condition, the composition of the plate was Co(78%), Ni(16%), and P(6%). Also, it was found that the coercive force was 370 Oe, and squareness was 0.65 at this condition. Magnetic properties (hard or soft) of thin plates were determined by metal compositions. Therefore. the plate became soft magnetic plate as the composition of nickel increased over 30 per cents. The crystal structure of the soft magnetic plate was found to be amorphous in which it was strongly oriented to the (111)phahe of nickel. On the ohter hand, the hard magnetic place was found to be hcp crystalline of α-cobalt which was oriented to the (101)phase of cobalt and the (100)phase of cobalt.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.225-231
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• 1989

The heterogeneous rate constants for the electrochemical reduction by $trans-[Co(en)_2X_2](ClO_4)_n$(where X is cyanide, nitrite, ammonia, and isothiocyanate) at mercury and glassy carbon electrode were investigated by cyclic voltammetry, DC polarography, and by using rotating disk electrode. The good linear relationship was obtained between the activation energy of reduction and absorption wave number of complexes on glassy carbon electrode. At mercury electrode, $NO_2^-$ ligated complex showed the large deviation from the linear relationship. The difference in the value of rate constants for $NO_2^-$ ligated complex between mercury and glassy carbon electrode was about three order of magnitude which was much larger than the other complexes. It was suggested that $NO_^-$ ligated complex was reduced by inner-sphere mechanism on mercury electrode from the larger value of activation energy and entropy on mercury than carbon electrode.

• Journal of the Korean Chemical Society
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• v.31 no.1
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• pp.37-44
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• 1987

The rates of solvolysis of $cis-[Co(en)_2Cl_2]^+$ complex have been investigated using spectrophotometric method at various pressures up to 1500 bar in several binary-aqueous mixtures(water-methyl alcohol, water-acetone, water-isopropyl alcohol and water-ethylene glycol). The activation volumes obtained from the pressure effect on rate constants were 1.13∼4.44 cm3mole-1 for methyl alcohol, 1.13∼3.59$cm^3mole^{-1}$ for acetone, 0.82∼3.44$cm^3mole^{-1}$ for isopropyl alcohol and 1.13∼2.68cm3mole-1 for ethylene glycol. In case of water-methyl alcohol, in addition to, the rates of solvolysis of this complex were determined in the presence of Fe(Ⅱ) ion and the activation volumes were -0.56∼1.59cm3mole$^{-1}$. The rates of solvolysis of this complex were analyzed by comparing with the results obtained from activation volumes and free energy cycle.

• Journal of the Korean Chemical Society
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• v.14 no.1
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• pp.91-96
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• 1970

Formation of the complexes of manganese, zinc and cobaltous ions with citrate ions in aqueous, ethanol-water (20% by volume) and acetone-water (20% by volume) solutions was studied at room temperature by the equilibrium exchange technique. The pH of the solutions was controlled to 7.0-7.4, and the ionic strength of the solutions was kept at approximately 0.10. The results of the present study indicated that both $Mn^{++}\;and\;Zn^{++}$ formed one to one citrate-compexes, [M Cit]$^-$, in all the solvent systems examined, and that $Co^{++}$ formed one to one citrate-complex in aqueous solution but formed both one to one citrate-complex, [Co Cit]$^-$, and one to two citrate-complex, $[Co\;Cit_2]^{4-}$, in the mixed solvent systems mentioned above. It was also observed that the citrate-complexes of the transition metals examined were more stable in the mixed solvent systems than in water.

• Journal of the Korean Chemical Society
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• v.25 no.5
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• pp.306-310
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• 1981

Induced circular dichroism spectra of racemic cobalt(III) complexes for $[Co(en)_3]^{3+},\;[Co(tn_)3]^{3+},\;cis-[Co(NH_3)(en)_2]^{3+},\;[Co({\beta}-ala)(en)2_]^{2+},\;[Co(gly)(en)_2]^{2+}\;and\;[Co(acac)(en)_2]^{2+}$ were measured when they were dissolved in aqueous d-tartrate2- solution at room temperature. Only a single negative CD spectrum was observed for all the complexes above in visible region(400∼500nm). It was interpreted that these CD bands were attributed to the difference in interaction between ${\Lambda}$-and ${\Delta}$-enantiomers with d-tartrate$^{2-}$. Namely, when d-tartrate$^{2-}$ was added to ${\Lambda}$-enantiomer and ${\Delta}$-enantiomer, it caused ${\Lambda}$-enantiomer to change greatly and ${\Delta}$-enantiomer to change only slightly; combined the results proved induced circular dichroism. The enantiomer for which the eluent has a stronger affinity should be eluted faster in ion-exchange column chromatography. It is possible to predict the elution order of chromatography from the sign of the induced CD if stronger interaction of chiral anion with the complex leads to greater change in the natural CD spectrum of the complex. The elution order was in complete agreement with the prediction from the sign of the induced CD spectrum for all the measured complexes.

• Journal of the Korean Chemical Society
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• v.37 no.10
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• pp.881-887
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• 1993

A cobalt(II) ion-selective carbon-paste electrode (CPE) was constructed with ${\iota}$-sparteine. Cobalt(II) ion in aqueous solution was chemically deposited through the complexation with ${\iota}$-sparteine onto the CPE. The surface of CPEs were characterized by cyclic voltammetry and differential pulse voltammetry in an acetate buffer solution, separately. Exposure of the CPEs to an acid solution could regenerate surface to reuse it for the deposition. In more than 5 deposition / measurement / regeneration cycles, the response was reproducible and linear up to $5.0{\times}10^{-6}$M with linear sweep voltammetry. The peaks at 0.17V / 0.27V were correspond to the redox of Co(II)-SP complex deposited on CPE. The anodic peak of which appeared after scan over the cathodic peak of 0.17 V to more negative scan. In case of using the differencial pulse voltammetry (DPV), we have obtained the linear response $2.0{\times}10^{-7}$M with relative standard deviation ${\pm}5.6%$. The detection limit was $1.0{times}10^{-7}$M for 20 minutes of the deposition. We have also investigated the interference effect of various metal ions, which are expected to form the complex with the ligand on the electrode.

• Bulletin of the Korean Chemical Society
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• v.33 no.9
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• pp.2917-2924
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• 2012

Four novel metal-organic complexes $[Cd_2(IP)_2(TBZ)_2(H_2O)_2]{\cdot}(H_2O)$ (1), $[Zn_4(IP)_4(TBZ)_4]{\cdot}2(H_2O)$ (2), $[Zn_2(BTC)(TBZ)_2(CO_2H)]$ (3), [Co(PDC)(TBZ)] (4) (where IP = isophthalate; TBZ = thiabendazole; BTC = 1,3,5-benzenetricarboxylate; PDC = pyridine-3,4-dicarboxylate) have been prepared and characterized by IR spectrum, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. X-ray structure analysis reveals that 1, 2, and 3 are one-dimensional chain polymers, while 4 is a two-dimensional network polymer. The TBZ acts as a typical chelating ligand coordinated to the metal center in all complexes. The 1D chain architecture of 1 is constructed from isophthalates and cadmium atoms. A simultaneous presence of chelating, monodentate and bidentate coordination modes of IP ligands is observed in complex 2. In complex 3, the 16-membered rings are alternately arranged forming an infinite 1D double-chain structure. The 2D skeleton of 4 is formed by cobalt ions as nodes and PDC dianions as spacers, through coordination bonds. The hydrogen bonds and ${\pi}-{\pi}$ stacking play important roles in affecting the final structure where complexes 1 and 3 have 2D supramolecular networks, while complexes 2 and 4 have 3D supramolecular architectures.

• Economic and Environmental Geology
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• v.46 no.3
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• pp.257-266
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• 2013

The geology of Sinaola state consists of Precambrian metamorphic rocks(Sonobari Complex), two Paleozoic units(lower non-differentiated metamorphic rocks and upper Carboniferous sedimentary rocks), five Mesozoic units(metavolcanic, clastic, and calcareous rocks), Cenozoic volcanic rocks, and Quaternary clastic sediments and volcanic flows. The Sinaola state is potentially rich in metallic mineral resources with lower degree of non-metallic mineral resources. They are related to a variety of geological environments and are mainly physiographically located on the Sierra Madre Occidental. Mainly known mineral deposits are of gold and silver followed by zinc, lead, copper and some iron. The state also has deposits of molybdenum, tungsten and bismuth that have been occasionally exploited. There is a reference of nickel and cobalt mineralization, but these deposits have been exploited only at a small scale.

• Proceedings of the Korean Powder Metallurgy Institute Conference
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• 1997.10a
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• pp.7-7
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• 1997

During sintering of very porous green bodies, as obtained by compaction of hard powders - such as tungsten carbide or ceramics - or by injection moulding, important shrinkage occurs. Due to heterogeneous green density field, gravity effects, friction on the support, thermal gradients, etc., this shrinkage is often non-uniform, which' may induce significant shape changes. As the ratio of compact dimension to powder size is very high, the mechanics of continuum is relevant to model such phenomena. Thus numerical techniques, such as the finite element method can be used to simulate the sintering process and predict the final shape of the sintered part. Such type of simulation has much been developed in the last decade firstly for hot isostatic pressing and next for die compaction. Finite element modelling has been recently applied to free sintering. The simulation of sintering should be based on constitutive equations describing the thermo-mechanical behaviour of the material under any state of stress and any temperature which may arise within the sintering body. These equations can be drawn either from experimental data or from micromechanical models. The experiments usually consist in free sintering and sinter-forging tests. Indeed applying more complex loading conditions at high temperature under controlled atmosphere is delicate. Micromechanical models describe the constitutive behaviour of aggregates of spheres from the deformation of two-sphere contact either by viscous flow or grain boundary diffusion. Such models are not able to describe complex microstructure and mechanisms as observed in real materials but they can give some basic information on the formulation of constitutive equations. Practically both experimental and theoretical approaches can be coupled to identify the constitutive equations. Such procedure has been performed for modelling the sintering of compacts obtained by die pressing of a mixture of tungsten carbide and cobalt powders. The constitutive behaviour of this material during sintering has been described by a linear viscous constitutive model, whose functions have been fitted from results of free sintering and sinter-forging experiments. This model has next been introduced in ABAQUS finite element code to simulate the sintering of heterogeneous green compacts of various geometries at constant temperature. Examples of simulations are shown and compared with experiments.