• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.20 no.1
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• pp.43-63
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• 2022

The aim of this review is to communicate some essential knowledge of the underlying mechanism of the corrosion of structural containment alloys during molten salt reactor operation in the context of prospective online monitoring in future MSR installations. The formation of metal halide species and the progression of their concentration in the molten salt do reflect containment corrosion, tracing the depletion of alloying metals at the alloy salt interface will assure safe conditions during reactor operation. Even though the progress of alloying metal halides concentrations in the molten salt do strongly understate actual corrosion rates, their prospective 1^st order kinetics followed by near-linearly increase is attributed to homogeneous matrix corrosion. The service life of the structural containment alloy is derived from homogeneous matrix corrosion and near-surface void formation but less so from intergranular cracking (IGC) and pitting corrosion. Online monitoring of corrosion species is of particular interest for molten chloride systems since besides the expected formation of chromium chloride species CrCl₂ and CrCl₃, other metal chloride species such as FeCl₂, FeCl₃, MoCl₂, MnCl₂ and NiCl₂ will form, depending on the selected structural alloy. The metal chloride concentrations should follow, after an incubation period of about 10,000 hours, a linear projection with a positive slope and a steady increase of < 1 ppm per day. During the incubation period, metal concentration show 1^st order kinetics and increasing linearly with time^1/2. Ideally, a linear increase reflects homogeneous matrix corrosion, while a sharp increase in the metal chloride concentration could set a warning flag for potential material failure within the projected service life, e.g. as result of intergranular cracking or pitting corrosion. Continuous monitoring of metal chloride concentrations can therefore provide direct information about the mechanism of the ongoing corrosion scenario and offer valuable information for a timely warning of prospective material failure.

• Bulletin of the Korean Chemical Society
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• v.29 no.10
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• pp.1905-1910
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• 2008

The reaction of 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.0$0^{1.18}.0^{7.12}$]docosane ($L^1$) with formaldehyde in warm methanol yielded 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.$1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^7$) containing one 1,3-diazacyclohexane subunit. In methanol, $L^7$ readily reacts with $Cu^{2+}$ ion to form [$CuL^7(H_2O)$]$^{2+}$ which is extremely inert against methanolysis. In the solution containing $Ni^{2+}$ ion, however, $L^7$ reacts with methanol to yield [$NiL^3$]$^{2+}$ ($L^3$ = 2-(methoxymethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.$0^{1.18}.0^{7.12}$]- docosane), in which one N-$CH_2OCH_3$ pendant arm is appended. The copper(II) complex [$CuL^7(H_2O)$]- $(ClO_4)_2{\cdot}3H_2O\;(I{\cdot}3H_2O)$ has a severely distorted trigonal bipyramidal coordination geometry with a 4-5- 6-5 chelate ring sequence. The crystal structure of [$NiL^3$]$(PF_6)_2{\cdot}2H_2O$ (IIb) shows that the N-$CH_2OCH_3$ pendant arm is not coordinated to the metal ion in the solid state. In various solvents (S), however, the nickel(II) complex exists as a mixture of [$NiL^3$(S)]$^{2+}$, in which the N-$CH_2OCH_3$ group as well as S is coordinated to the metal ion, and [$NiL^3$]^{2+}.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.418-429
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• 2011

Novel chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), ruthenium(III), and zirconyl(II) complexes of $N^1,N^2$-bis(3-((3-hydroxynaphthalen-2-yl)methylene-amino)propyl)phthalamide ($H_4L$, 1) have been synthesized and characterized by elemental, physical, and spectral analyses. The spectral data showed that the ligand behaves as either neutral tridentate ligand as in complexes 2-5 with the general formula $[H_4LMX_2(H_2O)]{\cdot}nH_2O$ (M=Cu(II), Ni(II), Co(II), X = Cl or $NO_3$), neutral hexadentate ligand as in complexes 10-12 with the general formula $[H_4LM_2Cl_6]{\cdot}nH_2O$ (M=Fe(III), Cr(III) or Ru(III)), or dibasic hexadentate ligand as in complexes 6-9 with the general formula $[H_2LM_2Cl_2(H_2O)_4]{\cdot}nH_2O$ (M = Cu(II), Ni(II), Co(II) or Mn(II), and 13 with general formula $[H_4L(ZrO)_2Cl_2]{\cdot}8H_2O$. Molar conductance in DMF solution indicated the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complexes 2, 5, and 6 showed $g_{\parallel}$ >g> $g_e$, indicating distorted octahedral structure and the presence of the unpaired electron in the $N^1,N^2$ orbital with significant covalent bond character. For the dimeric copper(II) complex $[H_2LCu_2Cl_2(H_2O)_4]{\cdot}3H_2O$ (6), the distance between the two copper centers was calculated using field zero splitting parameter for the parallel component that was estimated from the ESR spectrum. The antibacterial and antifungal activities of the compounds showed that, some of metal complexes exhibited a greater inhibitory effect than standard drug as tetracycline (bacteria) and Amphotricene B (fungi).

• Microbiology and Biotechnology Letters
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• v.16 no.6
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• pp.494-498
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• 1988

The optimum conditions for glucoamylase production, and ethanol productivity of the transformant TSD-14 were investigated as compared with the parental strains. The properties of TSD-14 were comparatively similar to the donor S. diastaticus IFO 1046 as regards the conditions of glucoamylase production and ethanol productivity. The soluble starch was the most effective carbon source for the glucoamylase production. While inorganic nitrogen sources did not prompt cell growth and enzyme production, the organic nitrogen sources generally enhanced both cell growth and glucoamylase production. The metal salts such as FeSO$_4$, MgSO$_4$, MnCl$_2$, and NiSO$_4$were favorable to the enzyme production. And the optium temperature and initial pH for glucoamylase production were 3$0^{\circ}C$ and 5. The transformant TSD-14 produced 8.3%(v/v) ethanol from 15% sucrose medium, 4.8%(v/v) ethanol from 15% soluble starch medium, and 7.5%(v/v) ethanol from 15% liquefied potato starch medium. The corresponding fermentation efficiency were 84% , 45% and 70%, respectively.

• Journal of the Korean Chemical Society
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• v.47 no.6
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• pp.569-577
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• 2003

Ligands, Br-PEMP, Cl-PEMP and $CH_3O-PEMP$ having Br, Cl and $CH_3O$ substituents at 5-position of the $N_2O$ tridentate ligand, 2-[(2-pyridine-2-ethylamio)-methyl]-phenol (H-PEMP) containing pyridine and phenol were synthesized. Another ligand, Naph-PEMP having pyridine and 2-hydroxy-1-naphthalene was also synthesized. The ligands were characterized using elemental analysis, UV-visible, IR, $^1H\;NMR\;and\;^{13}C$ NMR spectroscopy and mass analysis. The potentiometric titration study in aqueous solution revealed that the proton dissociation of the ligands occurred in three steps and the order of overall proton dissociation constants (log${\beta}$) was $CH_3O-PEMP$ > Naph-PEMP > H-PEMP > Cl-PEMP > Br-PEMP. The order of stability constants (logML and log$ML_2$) of their transition metal complexes was Co(II) < Ni(II) < Cu(II) > Zn(II). The order in their stability constants values of each transition metal complex agreed well with that in overall proton dissociation constant value of the ligands.

• Analytical Science and Technology
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• v.19 no.2
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• pp.131-141
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• 2006

Hydrobromic acid salt of a $N_2O_2$ tetradentate ligand, N,N'-bis(2-hydroxybenzyl)-ethylene-diamine ($H-BHE{\cdot}2HBr$) was synthesized. $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ and $CH_3O-BHE{\cdot}2HBr$ having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of $H-BHE{\cdot}2HBr$ were also synthesized. $Nap-BHE{\cdot}2HBr$ having naphthalen-2-ol instead of the phenol group was also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and the order of the calculated overall proton dissociation constants (${\log}{\beta}_p$) of each ligand was Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE. The order showed a similar trend to that of Hammett substituent constants(${\sigma}_P$). The order of the stability constants (${\log}K_{ML}$) was CO(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order in their stability constants (${\log}K_{ML}$) of each transition metal complex agreed well with that of the overall proton dissociation constants (${\log}{\beta}_p$).

• Journal of the Korean Vacuum Society
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• v.19 no.6
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• pp.475-482
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• 2010

Polycrystalline NiO thin films were deposited on glass substrate by RF magnetron sputtering using only Ar as a plasma sputter gas. based on the analysis of x-ray diffraction (XRD), NiO films had a polycrystalline cubic (NaCl type) structure. NiO thin films grown below and above $200^{\circ}C$ showed preferred orientation of (111) and (220) respectively. It showed colossal change in electrical resistivity as much a ${\sim}10^7$ order form an insulating state of $105\;{\Omega}cm$ below $200^{\circ}C$ to a conducting state of $10^{-2}{\sim}10^{-1}\;{\Omega}cm$ above $300^{\circ}C$ such a Mott metal-insulator transition (MIT) in polycrystalline.

• Journal of Korean Society for Atmospheric Environment
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• v.14 no.1
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• pp.11-23
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• 1998

The purpose of this study was to survey chemical distribution of inorganic elements and ions in the submicron particles, to characterize qualitatively emitting sources by factor analysis, and finally to reveal existing patterns in terms of chemical compounds by a stepwise multiple regression analysis. Total of 141 samples were collected by a cascade impactor from 1989 to1996. Fifteen chemical species (Al, Ba, Cd, K, Pb, Cu, Fe, Ni, $Cl^-, NO_3^-, SO_4^{2-}, K^+, Mg^{2+}, Ca^{2+}, and Na^+$) were characterized by AAS and IC. The study showed that average seasonal levels of submicron particulate matters $(d_p<0.43 \mum)$ were 18.7 $\mug/m^3$ in spring, 15.5 $\mug/m^3$ in summer, 15.7 $\mug/m^3$ in fall, and 24.5 $\mug/m^3$ in winter, respectively. All of the anion concentrations in the particle were highest in the winter season. By applying a factor analysis, 5 source patterns were qualitatively obtained, such as sulfate related source, nitrate related source, oil burning source, calcium related source, and coal combustion source. Finally, when applying a stepwise multiple regression analysis, the results clearly showed that $Na^+ and Ca^{2+}, K^+ and Ca^{2+}, NO_3^-$ and relative humidity, $Cl^-$ and ambient temperature, $Ca^{2+} and Cl^-, Mg^{2+} and SO_4^{2-}, Na^+ and NO_3^-, and Ca^{2+} and NO_3^-$, respectively, are negatively contributed to each other. As a result of those statistical analysis, we could suggest that some chemical compounds in the submicron particles such as$NaNO_3, MgSO_4, Ca(NO_3)_2, and CaCl_2$ may not exist on the filter as final composing products; however, other compounds may possibly exist in the form of $Mg(NO_3)_2, CaSO_4, Na_2SO_4, K_2SO_4, MgCl_2, NaCl, and KCl$. Thus, it must be necessary to identify differences between the results of above statistical analysis and of the real world by laboratory experiments.

• Journal of Korean Society for Atmospheric Environment
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• v.14 no.6
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• pp.631-642
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• 1998

Fall-out particles were collected by the modified British deposit gauges at 35 sampling sites in Suwon area from January to November, 1996. Twenty chemical species (Al. Ba, Cd, Cr, K, Pb, Sb, Zn, Cu, Fe, Ni, V, F-, Cl-, NO3-, 5042-, Na+, NH4+, Mg2+, and Ca2+) were analyzed by AAS and If. The purposes of this study were to estimate qualitatively various emission sources of the fell-out particle by applying multivariate statistical techniques such as factor analysis, multiple regression analysis, and discriminant analysis. During the study, outlier sites were determined by a z-score method. Cl-, Na+, Mg2+, and SO42- were highly correlated due to their common marine related source. Wind speed was the most influential factor for the deposition fluxes of the particle itself and all the chemical species as well. When applying the factor analysis, 8 source patterns were qualitatively obtained, such as marine source, soil source, oil burning source, Cr related source, tire source, Cd related source, agriculture source, and F- related source. As a result of the multiple regression analysis, we could suggest that some chemical compounds may possibly exist in the form of CaSO4, NaN03, NaCl, MgC12, (NH4)2SO4, NaF, and CaCl2 in the fall-out particles. Finally, spatial and seasonal classification study performed by a discriminant analysis showed th.at SO42-, Ca2+, Cl-, and Fe were dominant in the group of spatial pattern; however, SO42-, Cl-, Al, and V were in the group of seasonal pattern.

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.44-50
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• 1992

The ability to account for magnetic and spectra properties of complexes was investigated for the splitting of the degenerate d-orbitals and with nonaqueous solution by UV/vis-spectrophotometric method. The correlation of the magnetitude of 10Dq obtained from the spectra, the pairing energy, and the spin state of the complexes. The electrochemical behavior of complexes were investigated by the use of cyclic voltammetry in aprotic media. These reduction peak of $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$ and $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$ were irreversible one-electron processes at peak $E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$ and $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$ of these complexes vs. Ag/AgCl, but nickel complexes were not to be reducible.