• Journal of the Korean Chemical Society
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• v.33 no.4
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• pp.366-370
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• 1989

A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

• Journal of the Korean Chemical Society
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• v.33 no.4
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• pp.371-378
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• 1989

Kinetics of the substitution reaction of [pt[dien]X]$^+$(X = $Cl^-$, $Br^-$, $I^-$) with NO2- in aqueous solution were investigated by a spectrophotometric method at $20-35^{\circ}C$ and 1-1500 bars. The rates of these reactions were increased with raising temperature and pressure. The relative reactivities of replaceable ligands in [pt[dien]X]$^+$ follow the order ($Cl^-$ > $Br^-$ > $I^-$). Activation volumes (${\mid}{\Delta}V^{\neq}{\mid}$) were large negative values and decreased with raising temperature. First ($k_1$) and second($k_2$) order rate constants of these reactions were determined at $25^{\circ}C$ and both $k_1$ and $k_2$ were increased with raising pressure and activation volumes (${\Delta}{V_1}^{\neq}$, ${\Delta}{V_2}^{\neq}$) for the $k_1$ and $k_2$ path were large negative values respectively. The $k_1$ and $k_2$ of these reactions were determined at 1 bar and these values were increased with raising temperature. Activation parameters of $k_1$ and $k_2$ path were determined, therefore it can be inferred frp, these results that the substitution reactions of [pt[dien]X]$^+$ with ${NO_2}^-$ proceed through on associative (A) mechanism independent of a leaving groups and reaction paths.

• Progress in Medical Physics
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• v.12 no.1
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• pp.1-8
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• 2001

Diamond thin films were synthesized by a chemical vapor deposition (CVD). Raman spectrum showed the diamond line at 1332 $cm^{-1}$ / and x-ray diffraction pattern exhibited a strong (111) peak of diamond. The scanning electron microscopy analysis showed that the CVD diamond thin film was grown to be unepitaxial crystallites with pyramidal hillocks. A wavelength-resolved thermoluminescence (TL) of the CVD diamond thin film irradiated with X-rays showed one peak at 430 nm around 560 K. The glow curve of the CVD diamond thin film produced one dominant 560-K peak that was caused by first-order kinetics. Its activation energy and the escape frequency were calculated to be 0.92 ～ 1.05 eV and 1.34 $\times$ 10$^{7}$ sec$^{-1}$ , respectively. The emission spectrum at 560 K was split into 1.63-eV, 2.60-eV, and 3.07-eV emission bands which is known to be attribute to silicon-vacancy center, A center, and H3 center, respectively.

• Polymer(Korea)
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• v.30 no.1
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• pp.28-34
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• 2006

A series of methoxypoly(ethylene glycol) $(MPEG)-poly(\varepsilon-co-L-lactide)$ (PCLA) diblock copolymers were synthesized by ring-opening polymerization of a mixture of $\varepsilon-caprolactone$ and L-lactide with different ratios in the presence of $Sn(Oct)_2$. The characterization of MPEG-PCLA diblock copolymers were examined by $^1H-NMR$, GPC, DSC, and XRD. Kinetic study on ring-opening polymerization of monomer mixtures was carried out in various conditions such as a variation with polymerization time, amount of catalyst, and temperature. The highest conversion obtained in 1.2 ratic of initiator venn catalyst at $110\;^{\circ}C$. The biodegradable characterization of MPEG-PCLA diblock copolymers in aqueous solution was carried out by using GPC for $1\~14$ weeks. The biodegradability of MPEG-PCLA diblock copolymers increased as the L-lactide content of diblock copolymers increased. In conclusion, we confirmed the dependence of polymerization rate according to various conditions. In addition, we can control the biodegradability of MPEC-PCLA diblock copolymers by changing the ratio of PCL and PLA block segment.

• Polymer(Korea)
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• v.26 no.2
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• pp.218-226
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• 2002

For the preparation of high resilience polyurethane (PU) foams with polyether type cell openers which have different ethylene oxide (EO) content, molecular weight and chain structure, the influences of tell opener structure on the kinetics, rheology, structural stability, open cell content and mechanical properties of the obtained foam were investigated. It was observed that urea formation reaction was delayed with the increase of EO content and incorporation of ester linkage in cell opener molecule and was relatively independent on the molecular weight. With the rheological studies, the decreases of viscosity and storage modulus were confirmed for the increase of EO content and molecular weight, so that the resulted foam had low structural stability and high open cell content. The cell opener having ester linkage in molecule exhibited the lowest values of viscosity and storage modulus and the obtained foam has high open cell content. However, the structural stability increased due to the larger intermolecular interaction of ester linkage. The hardness, tensile strength, tear strength and elongation of foam were deteriorated with increase of EO content and molecular weight of tell opener. On the other hand, the cell opener having ester linkage in molecule improved the values of tensile strength, tear strength and elongation.

• Membrane Journal
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• v.27 no.5
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• pp.425-433
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• 2017

As the problems related to the environmental pollution such as carbon dioxide emission are emerging, the need for the renewable energy and environmentally friendly energy is getting intense. Fuel cells are eco-friendly energy generation devices that generate electrical energy and produce water as a sole by-product. Compared to the traditional proton exchange membrane fuel cell (PEMFC), anion exchange membrane alkaline fuel cell (AEMAFC) has a main advantage of possibility to use low cost metal catalysts due to its faster kinetics. The AEM, which conducts $OH^-$ ions, should possess high ion conductivity as well as high chemical stability at high pH conditions. We hereby introduce a crosslinked poly(2,6-dimethyl-1,4-phenylene oxide) having a spacer-type conducting group as novel AEM, and report a high ion conductivity ($67.9mScm^{-1}$ at $80^{\circ}C$) and mechanical properties (Young's modulus : 0.53 GPa) as well as chemical stability (6.8% IEC loss at $80^{\circ}C$ for 1,000 h,) for the developed membrane.

• Korean Chemical Engineering Research
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• v.43 no.6
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• pp.675-682
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• 2005

Al containing mesoporous molecular sieve (Al-MMS) was synthesized by hydrolysis of $H_2SiF_6$ and $Al(NO_3)_3{\cdot}9H_2O$. The material obtained was characterized by XRD, $N_2$-physisorption. The specific surface area was $981m^2/g$, and the average pore size was uniformity $39{\AA}$. It was confirmed that the acidity of Al-MMS was milder than that of zeolite Y based on the results of $NH_3$-TPD. Active materials, Pt and Pd, were loaded on Al-MMS in order to examine the feasibility of using Al-MMS as a catalyst support in the hydrogenation of aromatic compounds included in the residue oil of a naphtha cracker. The hydrogenation activity of PtPd/Al-MMS has been studied by following the kinetics of the hydrogenation of naphthalene, and by comparing the kinetic parameters obtained with Pt and Pd catalysts supported on the other mesoporous material support and commercial conventional support materials. PtPd/Al-MMS catalyst shows the highest activity of hydrogenation and sulfur resistance. The high activity of PtPd/Al-MMS was confirmed again in the hydrogenation of PGO (pyrolized gas oil), which is residue oil obtained from a naphtha cracker. Therefore, PtPd/Al-MMS can be applied to the hydrogenation of aromatic compounds included in the residue oil of a commercial naphtha cracker commericially.

• Korean Chemical Engineering Research
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• v.47 no.3
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• pp.292-302
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• 2009

The wet oxidation of phenol has been investigated at temperatures from 150 to $250^{\circ}C$ and oxygen partial pressures from 25.8 to 75.0 bar with initial pH of 1.0 to 12.0 and initial phenol concentration of 10 g/l. Chemical Oxygen Demand COD has bee measured to estimate the oxidation rate. Reaction intermediates have been identified and their concentration profiles have been determined using liquid chromatography. The destruction rate of phenol have shown the first-order kinetics with respect to phenol and the changes in COD during wet oxidation have been described well with the lumped model. The impact of various homogeneous catalysts, such as $Cu^{2+}$, $Fe^{2+}$, $Zn^{2+}$, $Co^{2+}$ and $Ce^{3+}$ ions, on the destruction rate of phenol and COD has also been studied. The homogeneous catalyst of $CuSO_4$ has been found to be the most effective for the destruction of phenol and COD during wet oxidations. The destruction rate of formic acid formed during wet oxidations of phenol have increased as increasing temperature and $CuSO_4$ concentration. The final concentrations of acetic acid which has been formed during wet oxidations and difficult to oxidize have increased with reaction temperature and with decrease in the catalyst load.

• Korean Chemical Engineering Research
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• v.47 no.3
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• pp.344-348
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• 2009

One-dimensional modeling was carried-out to predict the capacity loss of a lithium-ion polymer battery during cycling. The model not only accounted for electrochemical kinetics and ionic mass transfer in a battery cell, but also considered the parasitic reaction inducing the capacity loss. In order to validate the modeling, modeling results were compared with the measurement data of the cycling behaviors of the lithium-ion polymer batteries having nominal capacity of 5Ah from LG Chem. The cycling was performed under the protocol of the constant current discharge and the constant current and constant voltage charge. The discharge rate of 1C was used. The range of state of charge was between 1 and 0.2. The voltage was kept constant at 4.2 V until the charge current tapered to 50 mA. The retention capacity of the battery was measured with 1C and 5C discharge rates before the beginning of cycling and after every 100 cycles of cycling. The modeling results were in good agreement with the measurement data.

• Restorative Dentistry and Endodontics
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• v.35 no.3
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• pp.180-187
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• 2010

Since the introduction of restorative dental composites, their physical properties have been significantly improved. However, polymerization shrinkage is still a major drawback. Many efforts have been made to develop a low shrinking composite, and silorane-based composites have recently been introduced into the market. In addition, many different methods have been developed to measure the polymerization shrinkage. In this study, we developed a new method to measure the linear polymerization shrinkage of composites without direct contact to a specimen using a particle tracking method with computer vision. The shrinkage kinetics of a commercial silorane-based composite (P90) and two conventional methacrylate-based composites (Z250 and Z350) were investigated and compared. The results were as follows: 1. The linear shrinkage of composites was 0.33-1.41%. Shrinkage was lowest for the silorane-based (P90) composite, and highest for the flowable Z350 composite. 2. The new instrument was able to measure the true linear shrinkage of composites in real time without sensitivity to the specimen preparation and geometry.