• Bulletin of the Korean Chemical Society
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• v.34 no.5
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• pp.1525-1529
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• 2013

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2-pyridyl thionobenzoate (5b) with alkali-metal ethoxides (EtOM, $M^+=Li^+$, $Na^+$, $K^+$, and 18-crown-6-ether complexed $K^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. $[EtOM]_o$ curve upward regardless of the nature of the $M^+$ ions, while those of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ are linear with a positive intercept. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is more reactive than the dissociated $EtO^-$, and $M^+$ ions catalyze the reactions in the order $K^+$ < $Na^+$ < $Li^+$ < 18C6-complexed $K^+$. The plot of log $k_{EtOM}$ vs. $1/r_{Stokes}$ results in an excellent linear correlation, indicating that the reactions are catalyzed by the solvated $M^+$ ions but not by the bare $M^+$ ions. The reactions of 5b with EtOM have been concluded to proceed through a six-membered cyclic TS, in which the solvated $M^+$ ions increase the electrophilicity of the reaction center and the nucleofugality of the leaving group.

• Journal of the Korean Chemical Society
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• v.24 no.2
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• pp.115-120
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• 1980

A kinetic study of the methanolysis of t-butylbromide and benzoylchloride in methanol-acetonitrile mixtures is reported. First order rate constants for the methanolysis of t-butyl bromide show maximum at $X_{MeOH}$=0.75∼0.9 and 25∼$50^{\circ}C$. Apparent second order rate constants for the methanolysis of benzoylchloride also show maximum at $X_{MeOH}$= 0.6∼0.95 and 12∼$26^{\circ}C$. The maximum rate is ascribed to the solvent structure change; the addition of acetonitrile to methanol perturbs the methanol structure increasing the free methanol molecules available to stabilize the transition state for the methanolysis of t-butylbromide and benzoylchloride. It has been shown that methanol acts as nucleophilic and electrophilic catalyst upon methanolysis of t-butylbromide and as electrophilic catalyst upon methanolysis of benzoylchloride.

• Journal of the Korean Chemical Society
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• v.37 no.6
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• pp.555-561
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• 1993

Ultraviolet spectrophotometric investigation has been carried out on the system of iododestannylation iodine and tetramethyltin in methanol. The transient CT absorption spectrum can be observed and the subsequent disappearance of CT absorption spectrum was accompained by the cleavage of tetramethyltin with iodine. From there, the rate constants for the iododestannylation were determined at 10, 25 and 35$^{\circ}C$ up to 1600 bar and the reaction rates were increased with increasing temperature and pressure. From these rate constants, the values of the activation parameters (${\Delta}V^\neq,\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}\;and\;{\Delta}G^{\neq}$) were obtained. The activation volumes and activation compressibility coefficients were both negativity. The activation enthalpies were positive and activation entropies had large negative values. From these values discussed in terms of solvent structure variation of transition state and mechanism. From these results, it was found that the reaction is followed with $S_E2$ mechaenism and weakened $S_E2$ mechanism nature by increasing pressure.

• Structural Engineering and Mechanics
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• v.87 no.3
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• pp.221-229
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• 2023

Urbanization and industrialization have significantly increased the amount of solid waste produced in recent decades, posing considerable disposal problems and environmental burdens. The practice of waste utilization in concrete has gained popularity among construction practitioners and researchers for the efficient use of resources and the transition to the circular economy in construction. This study employed Lytag aggregate, an environmentally friendly pulverized fuel ash-based lightweight aggregate, as a substitute for natural coarse aggregate. At the same time, fly ash, an industrial by-product, was used as a partial substitute for cement. Concrete mix M20 was experimented with using fly ash and Lytag lightweight aggregate. The percentages of fly ash that make up the replacements were 5%, 10%, 15%, 20%, and 25%. The Compressive Strength (CS), Split Tensile Strength (STS), and deflection were discovered at these percentages after 56 days of testing. The concrete cube, cylinder, and beam specimens were examined in the explorations, as mentioned earlier. The results indicate that a 10% substitution of cement with fly ash and a replacement of coarse aggregate with Lytag lightweight aggregate produced concrete that performed well in terms of mechanical properties and deflection. The cementitious composites have varying characteristics as the environment changes. Therefore, understanding their mechanical properties are crucial for safety reasons. CS, STS, and deflection are the essential property of concrete. Machine learning (ML) approaches have been necessary to predict the CS of concrete. The Artificial Fish Swarm Optimization (AFSO), Particle Swarm Optimization (PSO), and Harmony Search (HS) algorithms were investigated for the prediction of outcomes. This work deftly explains the tremendous AFSO technique, which achieves the precise ideal values of the weights in the model to crown the mathematical modeling technique. This has been proved by the minimum, maximum, and sample median, and the first and third quartiles were used as the basis for a boxplot through the standardized method of showing the dataset. It graphically displays the quantitative value distribution of a field. The correlation matrix and confidence interval were represented graphically using the corrupt method.

• Journal of the Korean Magnetics Society
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• v.14 no.1
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• pp.38-44
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• 2004

The iron doped colossal magnetoresistance materials with La-Ba-Mn-O perovskites structure have been synthesized by chemical reaction of sol-gel methods. Their crystallographic and magnetic properties have been studied with x-ray diffraction, VSM, RBS, Mossbauer spectroscopy, and magnetoresistance measurements. The crystal structure of the La$\_$0.67/Ba$\_$0.33/Mn$\_$0.99/Fe$\_$0.01/ $O_3$ at room temperature was determined to be orthorhombic of Pnma. The lattice parameters a$\_$0/ and c$\_$0/ increased gradually, but b$\_$0/ deceased with increase of iron substitution. The magnetization and coercivity deceased, also the Curie temperature decreased from 360 K as x increased from 0.00 to 0.05. Magnetoresistence measurements were carried out, and the maximum MR ($\Delta$$\rho$/$\rho$(0)) was observed at 281 K, about 9.5 % in 10 kOe. The temperature of maximum resistance (R$\_$MAX/) decreased with increasing substitution of Fe ions and a semiconductor-metal transition temperature (T$\_$SC-M/) decreased too. This phenomena show that ferromagnetic transition temperature decreased by substituting Fe for Mn ions, it decreases double exchange interaction. This result accords with magnetic structure of neutron diffraction. Mossbauer spectra of La$\_$0.67/Ba$\_$0.33/Mn$\_$0.99/Fe$\_$0.01/ $O_3$were taken at various temperatures ranging from 15 to 350 K. With lowering temperature of the sample, two magnetic phases were increased and finally it showed the two sharp sextets of spectra at 15 K. The isomer shift at all temperature range is about 0.3 mm/s relative to Fe metal, which means that both Fe ions are Fe$\^$3+/ states.Fe$\^$3+/ states.

• Journal of the Korean Electrochemical Society
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• v.24 no.3
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• pp.52-64
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• 2021

The effect of Fe and BO₃ doping on structure, thermal, and electrical properties of Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y (x = 0.2, 0.5)-based glass and glass ceramics was investigated. In addition, their crystallization behavior during sintering and ionic conductivity were also investigated in terms of sintering temperature. FT-IR and XPS results indicated that Fe²⁺ and Fe³⁺ ions in Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y glass worked as a network modifier (FeO₆ octahedra) and also as a network former (FeO₄ tetrahedra). In the case of the glass with low substitution of BO₃, boron formed (PB)O₄ network structure, while boron preferred BO₃ triangles or B₃O₃ boroxol rings with increasing the BO₃ content owing to boic oxide anomaly, which can result in an increased non-bridging oxygen. The glass transition temperature (GTT) and crystallization temperature (CT) was lowered as the BO₃ substitution was increased, while Fe²⁺ lowered the GTT and raised the CT. The ionic conductivity of Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y glass ceramics were 8.85×10^-4 and 1.38×10^-4S/cm for x = 0.2 and 0.5, respectively. The oxidation state of doped Fe and boric oxide anomaly were due to the enhanced lithium ion conductivity of glass ceramics.

• Journal of the Korean Vacuum Society
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• v.15 no.5
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• pp.527-533
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• 2006

Spinel $LiNi_xMn_{2-x}O_4$ thin films were synthesized up to x = 0.9 by a sol-gel method employing spin-coating. The Ni-substituted films were found to maintain cubic structure at low x but to exhibit tetragonal structure for $x{\geq}0.6$. Such cubic-tetragonal phase transition indicates that $Ni^{3+}(d7)$ ions with low-spin $(t_{2g}^6,e_g^1)$ state occupy the octahedral sites of the compound, thus being subject to the Jahn-Teller distortion. By x-ray photoelectron spectroscopy both $Ni^{2+}$ and $Ni^{3+}$ ions were detected. Optical properties of the $LiNi_xMn_{2-x}O_4$ films were investigated by spectroscopic ellipsometry (SE) in the visible?ultraviolet range. The measured dielectric function spectra by SE mainly consist of broad absorption structures attributed to charge-transfer (CT) transitions, $O^{2-}(2p){\rightarrow}Mn^{4+}(3d)$ for 1.9 $(t_{2g})$ and $2.8{\sim}3.0$ eV $(e_g)$ structures and $O^{2-}(2p){\rightarrow}Mn^{3+}(3d)$ for 2.3 $(t_{2g})$ and $3.4{\sim}3.6$ eV $(e_g)$ structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as due to d-d crystal-field transitions within the octahedral $Mn^{3+}$ ion. The strengths of these absorption structures are reduced by the Ni substitution. Rapid reduction of the CT transition strength involving the eg states for x = 0.6 is attributed to the reduced wavefunction overlap between the $e_g$ and the $O^{2-}(2p)$ states due to the tetragonal extension of the lattice constant by the Jahn-Teller effect.

• 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.

• Asian-Australasian Journal of Animal Sciences
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• v.24 no.11
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• pp.1552-1559
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• 2011

Real time PCR was used in this study to determine the effect of triticale dried distillers grains with solubles (TDDGS) as a replacement for grain or barley silage in finishing diets on the presence of six classical ruminal bacterial species (Succinivibrio dextrinosolvens, Selenomonas ruminantium, Streptococcus bovis, Megasphaera elsdenii, Prevotella ruminicola and Fibrobacter succinogenes) within the rumen contents of feedlot cattle. This study was divided into a step-wise adaptation experiment (112 days) that examined the effects of adaptation to diets containing increasing levels of TDDGS up to 30% (n = 4), a short-term experiment comparing animals (n = 16) fed control, 20%, 25% or 30% TDDGS diets over 28 days, and a rapid transition experiment (56 days) where animals (n = 4) were rapidly switched from a diet containing 30% TDDGS to a barley-based diet with no TDDGS. It was found that feeding TDDGS as replacement for barley grain (control vs. 20% TDDGS) decreased 16S rRNA copy numbers of starch-fermenting S. ruminantium and S. bovis (p<0.001 and p = 0.04, respectively), but did not alter 16S rRNA copy numbers of the other rumen bacteria. Furthermore, feeding TDDGS as a replacement barley silage (20% vs. 25% and 30% TDDGS) increased 16S rRNA copy numbers of S. ruminantium, M. elsdenii and F. succinogenes (p<0.001; p = 0.03 and p<0.001, respectively), but decreased (p<0.001) the 16S rRNA copy number of P. ruminicola. Upon removal of 30% TDDGS and return to the control diet, 16S rRNA copy numbers of S. ruminantium, M. elsdenii and F. succinogenes decreased (p = 0.01; p = 0.03 and p = 0.01, respectively), but S. dextrinosolvens and S. bovis increased (p = 0.04 and p = 0.009, respectively). The results suggest that replacement of TDDGS for grain reduces 16S rRNA copy numbers of starch-fermenting bacteria, whereas substitution for barley silage increases 16S rRNA copy numbers of bacteria involved in fibre digestion and the metabolism of lactic acid. This outcome supports the contention that the fibre in TDDGS is highly fermentable.

• Korean Journal of Materials Research
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• v.21 no.5
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• pp.250-254
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• 2011

We have synthesized bluish-green, highly-efficient $BaSi_2O_2N_2:Eu^{2+}$ and $(Ba,Sr)Si_2O_2N_2:Eu^{2+}$ phosphors through a conventional solid state reaction method using metal carbonate, $Si_3N_4$, and $Eu_2O_3$ as raw materials. The X-ray diffraction (XRD) pattern of these phosphors revealed that a $BaSi_2O_2N_2$ single phase was obtained. The excitation and emission spectra showed typical broadband excitation and emission resulting from the 5d to 4f transition of $Eu^{2+}$. These phosphors absorb blue light at around 450 nm and emit bluish-green luminescence, with a peak wavelength at around 495 nm. From the results of an experiment involving Eu concentration quenching, the relative PL intensity was reduced dramatically for Eu = 0.033. A small substitution of Sr in place of Ba increased the relative emission intensity of the phosphor. We prepared several white LEDs through a combination of $BaSi_2O_2N_2:Eu^{2+}$, YAG:$Ce^{3+}$, and silicone resin with a blue InGaN-based LED. In the case of only the YAG:$Ce^{3+}$-converted LED, the color rendering index was 73.4 and the efficiency was 127 lm/W. In contrast, in the YAG:$Ce^{3+}$ and $BaSi_2O_2N_2:Eu^{2+}$-converted LED, two distinct emission bands from InGaN (450 nm) and the two phosphors (475-750 nm) are observed, and combine to give a spectrum that appears white to the naked eye. The range of the color rendering index and the efficiency were 79.7-81.2 and 117-128 lm/W, respectively. The increased values of the color rendering index indicate that the two phosphor-converted LEDs have improved bluish-green emission compared to the YAG:Ce-converted LED. As such, the $BaSi_2O_2N_2:Eu^{2+}$ phosphor is applicable to white high-rendered LEDs for solid state lighting.