• Proceedings of the Korean Institute of Building Construction Conference
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• 2022.04a
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• pp.172-173
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• 2022

Rough stones of aggregates used as concrete aggregates for 6 regions in Korea were sampled and the reactivity of alkali aggregates was analyzed using chemical analysis method and mortar rod method.

• Journal of the Korean Ceramic Society
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• v.49 no.4
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• pp.337-341
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• 2012

Mechanochemical processing (MCP) involves several high-energy collisions of powder particles with the milling media and results in the increased reactivity/sinterability of powder. The present paper shows results of mechanochemical processing (MCP) of silicon nitride powder mixture with the relevant sintering additives. The effects of MCP were studied by structural changes of powder particles themselves as well as by the resulting sintering/densification ability. It has been found that MCP significantly enhances reactivity and sinterability of the resultant material: silicon nitride ceramics could be pressureless sintered at $1500^{\circ}C$. Nevertheless, a degree of a silicon nitride crystal lattice and powder particle destruction (amorphization) as detected by XRD studies, is limited by the specific threshold. If that value is crossed then particle's surface damage effects are prevailing thus severe evaporation overdominates mass transport at elevated temperature. It is discussed that the cross-solid interaction between particles of various chemical composition, triggered by many different factors during mechanochemical processing, including a short-range diffusion in silicon nitride particles after collisions with other types of particles plays more important role in enhanced reactivity of tested compositions than amorphization of the crystal lattice itself. Controlled deagglomeration of $Si_3N_4$ particles during the course of high-energy milling was also considered.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1547-1550
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• 2012

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of benzyl 2-pyridyl carbonate $\mathbf{3}$ and $t$-butyl 2-pyridyl carbonate $\mathbf{3}$ with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Substrate $\mathbf{4}$ is much less reactive than $\mathbf{3}$ and the steric hindrance exerted by the bulky $t$-Bu group in $\mathbf{4}$ has been attributed to its decreased reactivity. The Br${\o}$nsted-type plots for the reactions of $\mathbf{3}$ and $\mathbf{4}$ are linear with ${\beta}_{nuc}=0.57$ and 0.45, respectively. Thus, the reactions have been concluded to proceed through a concerted mechanism, although the current reactions were expected to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate $T^{\pm}$. It has been proposed that the rate of leaving-group expulsion is accelerated by the intramolecular H-bonding interaction in $T^{\pm}$ and the "push" provided by the RO group through the resonance interaction. Thus, the enhanced nucleofugality forces the reactions to proceed through a concerted mechanism. The reactivity-selectivity principle (RSP) is not applicable to the current reaction systems, since the reaction of the less reactive $\mathbf{4}$ results in a smaller ${\beta}_{nuc}$ than that of the more reactive $\mathbf{3}$. Steric hindrance exerted by the bulky $t$-Bu group in $\mathbf{4}$ has been suggested to be responsible for the failure of the RSP.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.519-523
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• 2012

A kinetic study is reported on nucleophilic displacement reactions of benzyl 2-pyridyl carbonate 6 with alkalimetal ethoxides, EtOM (M = Li, Na, and K), in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of pseudo-firstorder rate constant $k_{obsd}$ vs. [EtOM] curve upward, a typical phenomenon reported previously for alkaline ethanolysis of esters in which alkali-metal ions behave as a Lewis-acid catalyst. The kobsd value for the reaction of 6 with a fixed EtOK concentration decreases rapidly upon addition of 18-crown-6-ether (18C6), a complexing agent for $K^+$ ion up to [18C6]/[EtOK] = 1.0 and then remains constant thereafter, indicating that the catalytic effect exerted by K+ ion disappears in the presence of excess 18C6. The reactivity of EtOM towards 6 increases in the order $EtO^-$ < EtOLi < EtONa < EtOK, which is contrasting to the reactivity order reported for the corresponding reactions of 2-pyridyl benzoate 4, i.e., $EtO^-$ < EtOK < EtONa < EtOLi. Besides, 6 is 1.7 and 3.5 times more reactive than 4 towards dissociated $EtO^-$ and ion-paired EtOK, respectively. The reactivity difference and the contrasting metal-ion selectivity are discussed in terms of electronic effects and transition-state structures.

• Journal of the Korean Chemical Society
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• v.9 no.1
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• pp.1-7
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• 1965

Reaction of monochloroacetic acid with zinc in presence of toluene, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, and dioxane solvents showed the solvent effect in order of dimethylformamide, dioxane, dimethyl sulfoxide, toluene, acetonitrile, and tetrahydrofuran. The increasing reactivity of the reagents was observed in order of the polarity and hydrophilicity of the solvent. The same reaction of ethyl monochloroacetate in the same series of solvents showed also the solvent effect, but the difference was not large as compared to that of the acid. The reaction of the acid, ester, zinc, and carbonyl precursors such as benzaldehyde and 4-heptanone gave the Reformatsky reaction product in the case of the aldehyde, but the reactivity with 4-heptanone was slight. The yield of the product was varied by the method of addition of reagents. The best yield observed in case of the acid reaction was 38.5% of the hydroxy acid and 0.8g of the salt in presence of acetonitrile and in case of the ester reaction 19.3% of ethyl cinnamate and 21.6% of polymer. The variation of the reactivity of reagents due to the reaction temperature was observed in case of carbonyl reaction. The result was discussed in terms of the solvent effect and the procedures were described.

• Journal of the Korean Society of Industry Convergence
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• v.7 no.1
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• pp.107-113
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• 2004

Several transition metal complexes, [$M(L)X_2$](M=Pd(II), Ni(II); X=CI, Br) are prepared with aminophosphine ligands such as 1,2-bis{(diphenylphosphino)amino}ethane{$Ph_2PNHCH_2CH_2NHPPh_2$}($L_1$), 1,2-bis{(diphenylphosphino)amino}propane{$Ph_2PNHCH(CH_3)CH_2NHPPh_2$}($L_2$), trans-1,2-bis{(diphenylphosphino)amino}cyclohexane{$Ph_2PNHC_6H_{10}NHPPh_2$}($L_3$) and 1,2-bis{(diphenylphosphino)amino}benzene{$Ph_2PNHC_6H_4NHPPh_2$}($L_4$). The properties of these complexes are characterized by optical spectroscopic methods including UV/vis spectroscopy, CD, IR, $^1H$- and $^{31}P-NMR$ together with conductometer and elemental analysis. All complexes are stable under atmospheric environment. Catalytic reactivity for C-C coupling between [$M(L)X_2$] and Grignard reagents(RMgX; R=phenyl, propyl, buthyl) by thermolysis were investigated utilizing GC/mass, $^1H$- and $^{13}C-NMR$. When mol scale is 1:20 at [$Pd(L)Cl_2$] and Grignard reagents, the high catalytic activity for C-C coupling is apparent. The [$M(L)X_2$](X=Cl, Br) complexes which have strong bond at M-P exhibit high yields for C-C coupling reactions. When the central metal ion is Pd(II), the high catalytic activity for C-C coupling is apparent. The complex coordinated with Br shows higher catalytic activity for C-C coupling reactions compared to Cl.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.93-97
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl X-substituted-2-methylbenzoates (5a-e) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The Hammett plots for the aminolysis of 5a-e are nonlinear, e.g., substrates possessing an electron-donating group (EDG) in the benzoyl moiety deviate negatively from the linear line composed of substrates bearing no EDG. In contrast, the Yukawa-Tsuno plots for the same reactions exhibit excellent linear correlations with ${\rho}_X$ = 0.30-0.59 and r = 0.90-1.15, indicating that the nonlinear Hammett plots are caused by stabilization of the substrates possessing an EDG through resonance interactions but are not due to a change in the rate-determining step (RDS). The Br${\phi}$nsted-type plots are linear with ${\beta}_{nuc}$ = 0.66-0.82. Thus, the aminolysis of 5a-e has been suggested to proceed through a stepwise mechanism in which departure of the leaving group occurs at the RDS. The ${\rho}_X$ and ${\beta}_{nuc}$ values for the aminolysis of 5a-e increase as the reactivity of the substrates and amines increases, indicating that the reactivity-selectivity principle is not applicable to the current reactions.

• Korean Chemical Engineering Research
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• v.44 no.4
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• pp.356-362
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• 2006

The $SO_2$ reduction using CO and $H_2$ over Sn-Zr based catalysts was performed in this study. Sn-Zr based catalysts with Sn/Zr molar ratio (0/1, 1/4, 1/1, 2/1, 3/1, 1/0) were prepared by the precipitation and co-precipitation method. The effect of the temperature on the reaction characteristics of the $SO_2$ reduction with a reducing agent such as $H_2$ and CO was investigated under the conditions of space velocity of $10,000ml/g_{-cat.}h$, $([CO(or\;H_2)]/[SO_2])$ of 2.0. As a result, the activity of Sn-Zr based catalysts were higher than $SnO_2$ and $ZrO_2$. The reactivity for the $SO_2$ reduction with CO was higher than that with $H_2$, and sulfur yield in the $SO_2$ reduction by $H_2$ was higher than that by CO. The reactivity for the $SO_2$ reduction with $H_2$ was increased with the reaction temperature regardless of Sn-Zr based catalyst with a Sn/Zr molar ratio. $SnO_2-ZrO_2$ (Sn/Zr=1/4) had highest activity at $550^{\circ}C$, in the $SO_2$ reduction with $H_2$ and $SO_2$ conversion of 94.4％ and sulfur yield of 66.4％ were obtained at $550^{\circ}C$. On the other hand, in the $SO_2$ reduction by CO, the reactivity was decreased with the increase over $325^{\circ}C$. At the optimal temperature of $325^{\circ}C$, $SO_2$ conversion and sulfur yield were about 100％ and 99.5％, respectively, in the $SO_2$ reduction over $SnO_2-ZrO_2$ (Sn/Zr=3/1). Also, the $SO_2$ reduction using syngas with $CO/H_2$ ratio over $SnO_2-ZrO_2$ (Sn/Zr=2/1) was performed in order to investigate the application possibility of the simulated coal gas as the reductant in DSRP. As a result, the reactivity of the $SO_2$ reduction using syngas with $CO/H_2$ ratio was increased with increasing the CO content of syngas. Therefore, it could be known that DSRP using the simulated coal gas over Sn-Zr based catalyst is possible to be realized in IGCC system

• Journal of the Korean Ceramic Society
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• v.53 no.3
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• pp.317-324
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• 2016

Continued miniaturization and increasingly exact requirements for thin film deposition in the semiconductor industry is driving the search for new effective, efficient, selective precursors and processes. The requirements of defect-free, conformal films, and precise thickness control have focused attention on atomic layer deposition (ALD). ALD precursors so far have been developed through a trial-and-error experimental approach, leveraging the expertise and tribal knowledge of individual research groups. Precursors can show significant variation in performance, depending on specific choice of co-reactant, deposition stage, and processing conditions. The chemical design space for reactive thin film precursors is enormous and there is urgent need for the development of computational approaches to help identify new ligand-metal architectures and functional co-reactants that deliver the required surface activity for next-generation thin-film deposition processes. In this paper we discuss quantum mechanical simulation (e.g. density functional theory, DFT) applied to ALD precursor reactivity and state-of-the-art automated screening approaches to assist experimental efforts leading toward optimized precursors for next-generation ALD processes.

• Journal of the Korean Chemical Society
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• v.58 no.3
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• pp.289-296
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• 2014

Electrochemical copolymerization of o-chlorophenol (oCP) with o-hydroxyphenol (oHP) was carried out in aqueous $H_2SO_4$ by using cyclic voltammetry (CV) technique. In addition, CV was used to evaluate the differences in electrochemical characteristics of the copolymer in comparison with the corresponding homopolymers, poly(o-chlorophenol) (PoCP) and poly(o-hydroxyphenol) (PoHP). The variation of peak currents with respect to sweep rates was compared between copolymer and homopolymers, PoCP and PoHP, films. Further support for copolymer characterization was obtained by recording UV-visible, IR spectra and elemental analysis. The mechanism of the electrochemical polymerization has been discussed. The monomer reactivity ratios ($r_1$ and $r_2$) were calculated using Fineman-R$\ddot{o}$ss method and was found to be 0.4 and 1.3 repetitivelly and the copolymer structure is a block structure and more rich in oHP units.