• Journal of Adhesion and Interface
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• v.7 no.4
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• pp.32-38
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• 2006

A series of organic-inorganic hybrids, PCL/EP/$SiO_2$, involving epoxy resin and triethoxysilane-terminated polycaprolactone elastomer (PCL-TESi) were prepared via polymerization of diglycidyl ether of bisphenol A (DGEBA) with amine curing agent KB-2 and sol-gel process of PCL-TESi. The curing reactions were started from the initially homogeneous mixture of DGEBA, KB-2 and the PCL-TESi. The organicinorganic hybrids containing up to 4.95% (wt) of $SiO_2$ were obtained and characterized by FT-IR, transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA). It was experimentally shown that the swelling property in toluene, morphologies and thermal properties of the resulting hybrids were quite dependent on the contents of $SiO_2$. The crosslink network density decreases with increasing of the PCL-TESi. And in TEM, the phase separated morphology of these hybrids was found, which resulted from the coagulation of Si-O-Si networks resulting from $-Si(OC_2H_5)_3$ of PCL-TESi self-curing by hydrolytic silanol condensation, with the advancement of the curing reaction in the modified epoxy resin systems. Meanwhile, the change of the $SiO_2$ content made the morphologies changed from aggregated particles of Si-O-Si in the hybrid to nanocluster of interconnected Si-O-Si particles, then to aggregated Si-O-Si dispersing in the continuous cured epoxy phase again, and last to co-continuous interpenetrating network. The glass transition behavior of the hybrid material was cooperative motion of large chain segments, which were hindered by the inorganic Si-O-Si network. And in TG analysis, the characteristic temperature at 5% of weight loss was evidently increased from $120.5^{\circ}C$ of pure cured epoxy to $277.6^{\circ}C$ of 3.84% (wt) of $SiO_2$ modified epoxy due to the existence of Si-O-Si when PCL-TESi was added in the hybrid.

• Proceedings of the Korean Vacuum Society Conference
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• 1994.02a
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• pp.50-50
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• 1994

Half-metallic Heusler alloys (NiMnSb, ppdMnSb, pptMnSb) have attracted much attention due to their unique electronic and magnetic structures. Sppin-ppolarized band structure calculation ppredicts metallic behavior for the majority sppin states and semiconductor behavior for the minority sppin states. We have studied the electronic structures of these half-metallic Heusler alloys by core-level pphotoemission sppectroscoppy of Mn 2pp and 3s XppS sppectra. We found large intensities of Mn 2pp satellites and 3s exchange spplitting comppared with other metal Mn-alloys. These satellite structure can be understood by applying Anderson imppurity model. This fact supports the calculated sppin pprojected ppartial density of states which suggests that the valence electrons be highly sppin ppolarized near Fermi level and that the electrons involved with charge-transfer be mainly minority sppin ones which have semiconducting band structure. The trend of charge transfer energies Δ from ligands (Sb 5pp) to Mn 3d, obtained from our model fitting, is consistent with that calculated from sppin pprojected ppartial density of state. Also the trend of d-d electron correlation energies U calculated from Mn Auger line L3 VV by Mg $K\alpha$ source is comppatible with that resulted from our model fitting. We fitted the Mn 3s curve in the same way as for insulating Mn comppounds by using the same pparameters calculated from Mn 2pp curve fitting exceppt for the Coulomb interaction energy Q between core hole and d-electrons. The 3s sppectra were analyzed by combing the charge transfer model and a simpple model taking into account the configuration mixing effect due to the intra-shell correlation. We found that the exchange interaction between 3s hole and 3d electrons is mainly respponsible for the satellite of Mn 3s sppectra. This is consistent with the neutron scattering data, which suggests local 3d magnetic moment. We find that the XppS analysis results of Mn 2pp and 3s satellite structures of half-metallic Heusler alloys are very similar to those of insulating transition metal comppounds.

• Journal of the Korean Institute of Telematics and Electronics
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• v.25 no.11
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• pp.1294-1303
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• 1988

Electron and hole traps in semi-insulating GaAs with activation energies ({\Delta}E_r) ranging from 0.16 $\pm$ 0.01 to 0.98 $\pm$ 0.01 eV, have been detected and characterized by photo-induced current transient measurements. SI undoped GaAs has fewer deep levels than SI GaAs: Cr. The thermal capture cross section and density of the traps have been estimated and some of the centers have been related to native defects. In particular, the activation energy of the compensating Cr, and "0" levels in semi-insulating GaAs were accurately measured. The transient measurements were complemented by Hall measurements at T > 300K and photocurrent spectra measurements. The transition energies for the deep compensating levels obtained by the analyses of data from these measurements, when compared with those from the transient measurements, indicate negligible lattice-coupling of these centers. Analysis of the transport data also indicates that neutral impurity scattering plays a significant role in semi-insulating materials at high temperatures.

• Bulletin of the Korean Chemical Society
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• v.26 no.4
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• pp.641-644
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• 2005

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)\;to\;{\beta}$-cyanostilbenes ($YC_6H_4CH=C(CN)C_6H_4$Y’) have been studied in acetonitrile at 30.0 oC. A greater degree of N-$C_{\alpha}$ bond formation (larger ${\beta}_X$) is obtained with a stronger electron-withdrawing substituent in either ${\alpha}-\;(\delta\sigma_Y\;{\gt}\;0)\;or\;{\beta}-ring\;(\delta\sigma_{Y'}\;{\gt}$ 0). A stronger charge development is observed in the TS on $C_{\beta}\;(\rho_{Y'}$= 1.06 for X=Y=H) rather than on $C_{\alpha}\;(\rho_{Y}$ = 0.62 for X=Y’H) indicating the lag in the resonance development into the activating group (CN) on $C_{\beta}$ in the transition state. Similarly, the magnitude of $\rho$$_{XY'}$(−0.72) is greater than $\rho_{XY}$ (−0.66) due to a stronger interaction of the nucleophile with $\beta$-ring than $\alpha$-ring. The positive sign of $\rho_{YY'}$correctly reflects $\pi$ bond cleavage between the two rings in the TS. Relatively large kinetic isotope effects ($k_H/k_D\;{\geq}$ 2.0) involving deuterated nucleophiles ($XC_6H_4CH_2ND_2$) suggest a four-membered cyclic TS in which concurrent N-C$_{\alpha}$ and H(D)-C$_{\beta}$ bond formation occurs.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3635-3640
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• 2013

We prepared Ni and Pd-modified $TiO_2@SiO_2$ core-shell nanostructures and then analyzed them by scanning electron microscopy, optical microscopy, X-ray diffraction crystallography, FT-IR and UV-Visible absorption spectroscopy. In addition, their CO oxidation performance was tested by temperature-programmed mass spectrometry. The CO oxidation activity showed an order of Ni-$TiO_2@SiO_2$ ($900^{\circ}C$) < Ni-$TiO_2@SiO_2$ ($90^{\circ}C$) < Ni-$TiO_2@SiO_2$ ($450^{\circ}C$) in the first CO oxidation run, and greatly improved activity in the same order in the second run. The $T_{10%}$ (the temperature at 10% CO conversion) corresponds to the CO oxidation rate of $2.8{\times}10^{-5}$ molCO $g{_{cat}}^{-1}s^{-1}$. For Ni-$TiO_2@SiO_2$ ($450^{\circ}C$), the $T_{10%}$ was observed at $365^{\circ}C$ in the first run and at $335^{\circ}C$ in the second run. For the Pd-$TiO_2@SiO_2$ ($450^{\circ}C$), the $T_{10%}$ was observed at a much lower temperature of $263^{\circ}C$ in the first CO oxidation run, and at $247^{\circ}C$ in the second run. The CO oxidation activities of transition metal modified $TiO_2@SiO_2$ core-shell nanostructures presented herein provide new insights that will be useful in developing catalysts for various environments.

• Nuclear Engineering and Technology
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• v.52 no.6
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• pp.1222-1230
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• 2020

The corrosion rates of the reactor pressure vessel materials of SA508 Grade 3 were measured using a weight loss method in aerated boric acid solutions to simulate the evaporation of leaked PWR primary water in an ambient environment. The corrosion behavior and products were examined using X-ray diffraction and electron microscopy. SA508 showed typical general corrosion characteristics. The corrosion rate increased steadily as the boron concentration was increased. As the immersion time elapsed, the corrosion rate slowly or rapidly decreased according to the oxidation reaction of iron. The corrosion rate showed a complicated pattern depending on the temperature; it increased gradually and then rapidly decreased again when reaching a certain transition temperature. The corrosion products of SA508 were found to be FeO(OH), Fe₂O₃, and Fe₃O₄. As the boron concentration decreased and the temperature was increased, the formation of Fe₃O₄ was more favorable as compared to the formation of FeO(OH) and Fe₂O₃. Consequently, the changes of the corrosion rate and behavior were closely related to the oxidation reaction of iron on the surface. The corrosive damage to SA508 appears to be most severe when the oxidation reaction is such that Fe₂O₃ forms as a corrosion product.

• Membrane and Water Treatment
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• v.1 no.3
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• pp.215-230
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• 2010

Poly(vinylidene fluoride-co-hexafluoropropylene), PVDF-HFP, hollow fiber membranes were prepared by the dry/wet spinning technique using different polyethylene glycol (PEG) concentrations as non-solvent additive in the dope solution. Two different PEG concentrations (3 and 5 wt.%). The morphology and structural characteristics of the hollow fiber membranes were studied by means of optical microscopy, scanning electron microscopy, atomic force microscopy (AFM) and void volume fraction. The experimental permeate flux and the salt (NaCl) rejection factor were determined using direct contact membrane distillation (DCMD) process. An increase of the PEG content in the spinning solution resulted in a faster coagulation of the PVDF-HFP copolymer and a transition of the cross-section internal layer structure from a sponge-type structure to a finger-type structure. Pore size, nodule size and roughness parameters of both the internal and external hollow fiber surfaces were determined by AFM. It was observed that both the pore size and roughness of the internal surface of the hollow fibers enhanced with increasing the PEG concentration, whereas no change was observed at the outer surface. The void volume fraction increased with the increase of the PEG content in the spinning solution resulting in a higher DCMD flux and a smaller salt rejection factor.

• Advances in materials Research
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• v.1 no.4
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• pp.299-310
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• 2012

This article describes the synthesis of a novel N-substituted pyrrole monomer containing an azobenzene group. The 2-[N-ethyl-N-[4-[(4-nitrophenyl) azo]-phenyl] amino] ethyl-3-chloropropionate (RedII) compound was synthesized via reaction of 4-nitro-4'-[N-ethyl-N-(2-hydroxyethyl)-amino] azobenzene (RedI) and 3-chloropropionic acid. RedII was reacted with the potassium salt of pyrrole then 2-[N-ethyl-N-[4-[(nitro phenyl) azo] phenyl] amino] ethyl-N-pyrrolyl propionate (Py-RedII) was prepared. Chemical polymerization of Py-RedII and copolymerization of Py-RedII with pyrrole carried out using $FeCl_3$. Poly (2-[N-ethyl-N-[4-[(nitro phenyl) azo] phenyl] amino] ethyl-N-pyrrolyl propionate) (PPy-RedII) was characterized by UV, IR, $^1HNMR$, $^{13}CNMR$ spectroscopies. Electropolymerization of Py-RedII and electroco-polymerization of Py-RedII and pyrrole were studied using conventional three electrodes system, Ag/AgCl reference electrode, platinum counter electrode and GC disk working electrode. Scanning electron microscopy (SEM), thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC) were used for thermal and rheological studies. The TGA curve of PPy-RedII demonstrated a high thermal stability up to 200°C and its DSC thermogram showed two endothermic peaks at 88 and $122^{\circ}C$. The glass transition temperature of the polymer was found to be above the room temperature. Electrical conductivities of PPy-RedII and it's copolymer with pyrrole (PPy-RedII-co-Py) were studied by the four-probe method and produced conductivities of $7.5{\times}10^{-4}$ and $6.5{\times}10^{-3}Scm^{-1}$, respectively.

• Bulletin of the Korean Chemical Society
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• v.25 no.5
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• pp.639-646
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• 2004

Metal treated activated carbons are prepared using various metals. Adsorption behaviors, morphologies, as well as antibacterial effects of metal treated samples are compared before and after solvent washing. Adsorption isotherms are used to characterize the porous structure of metal treated activated carbons before and after the solvent washing with acetone or ethyl alcohol. From these data, it is noticed that the changes in physicochemical properties of metal treated activated carbons depend on the solvents employed. Similar results are observed from BET data obtained from nitrogen adsorption isotherms. From scanning electron microscopy (SEM) studies, the changes in shape and size of metal particles are observed after the samples are washed with solvents. These changes result in different blocking effects, which, in turn, affect the adsorption behavior of metal treated activated carbons. X-ray diffraction (XRD) patterns of the samples treated with different metals are different each other. High intense sharp peaks attributed to metals are observed from silver treated samples, while the peaks are not observed from copper treated samples. To compare thermodynamic behavior of metal treated activated carbons washed with different type of solvents, differential scanning calorimetric (DSC) analysis is carried out. The analysis shows similar endothermic curves for all of the samples. Finally, antibacterial effects of metal treated activated carbon against Escherichia coli are discussed. Comparing the effects among the metals employed, highest effects are obtained from Cd, while lowest effects are obtained from Cu. Antibacterial activity becomes higher with the increase of the amount of metals treated, Optimum concentrations of metals to treat activated carbons, obtained from a shake flask test, are known to be 0.4, 0.1, and 0.6 moles for Ag, Cd, and Cu, respectively.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2081-2085
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• 2014

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of phenyl 2- pyridyl carbonate (6) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot for the reaction of 6 is linear with ${\beta}_{nuc}$ = 0.54, which is typical for reactions reported previously to proceed through a concerted mechanism. Substrate 6 is over $10^3$ times more reactive than 2-pyridyl benzoate (5), although the reactions of 6 and 5 proceed through the same mechanism. A combination of steric hindrance, inductive effect and resonance contribution is responsible for the kinetic results. The reactions of 6 and 5 proceed through a cyclic transition state (TS) in which H-bonding interactions increase the nucleofugality of the leaving group (i.e., 2-pyridiniumoxide). The enhanced nucleofugality forces the reactions of 6 and 5 to proceed through a concerted mechanism. In contrast, the corresponding reaction of 4-nitrophenyl 2-pyridyl carbonate (7) proceeds through a stepwise mechanism with quantitative liberation of 4-nitrophenoxide ion as the leaving group, indicating that replacement of the 4-nitrophenoxy group in 7 by the PhO group in 6 changes the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as the leaving group (i.e., from 4-nitrophenoxide to 2-pyridiniumoxide). The strong electron-withdrawing ability of the 4-nitrophenoxy group in 7 inhibits formation of a H-bonded cyclic TS. The presence or absence of a H-bonded cyclic TS governs the reaction mechanism (i.e., a concerted or stepwise mechanism) as well as the leaving group (i.e., 2-pyridiniumoxide or 4-nitrophenoxide).