• Bulletin of the Korean Chemical Society
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• v.11 no.1
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• pp.49-54
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• 1990

The gas-phase thermolysis reactions of ${\alpha}$- and ${\beta}$-methylated ethyl formates, Y = $CH-X-CHR_1CH_2R_2$ where X = Y = O or S and $R_1\;=\;R_2$ = H or $CH_3$, are investigated theoretically using the AM1 method. The experimental reactivity order is reproduced correctly by AM1 in all cases. The thermolysis proceeds through a six-membered cyclic transition state conforming to a retro-ene reaction, which can be conveniently interpreted using the frontier orbital theory of three-species interactions. The methyl group substituted at $C_{\alpha}\;or\;C_{\beta}$ is shown to elevate the ${\pi}$-HOMO of the donor fragment (Y = C) and depress the ${\sigma}^{\ast}$-LUMO of the acceptor fragment ($C_{\beta}$-H), increasing the nucleophilicity of Y toward ${\beta}$-hydrogen which in turn increases the reactivity. The two bond breaking processes of the $C_{\alpha}$-X and $C_{\beta}$-H bonds are concerted but not synchronous so that the reaction takes place in two stages as Taylor suggested. The initial cleavage of $C_{\alpha}$-X is of little importance but the subsequent scission of $C_{\beta}$-H occurs in a rate determining stage.

• Applied Chemistry for Engineering
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• v.30 no.6
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• pp.673-680
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• 2019

GAP or GAP-co-BO based energetic thermoplastic elastomers (ETPEs) were synthesized by changing the hard segment content percent in the range of 30~45% by 5% difference. Thermal and mechanical properties of GAP-co-BO based ETPEs were compared to those of GAP based ETPEs. FT-IR results showed that the capability of forming hydrogen bond increases with increasing the hard segment content in GAP/GAP-co-BO based ETPE, and also the GAP-co-BO based ETPEs are stronger than GAP based ETPEs in the hydrogen bond formation. DSC and DMA results showed that the glass transition temperature (T_g) of GAP based ETPEs increased with the increment of the hard segment content, while the T_g of GAP-co-BO based ETPEs was maintained even the hard segment content increased. The storage modulus at room temperature of the GAP-co-BO based ETPEs was higher than that of the GAP based ETPEs. This was due to the strong phase separation behavior of the hard and soft segment of GAP-co-BO based ETPEs, which further resulted in the stronger breaking strength and lower tensile elongation at break point for GAP-co-BO based ETPE than the GAP based one.

• The Journal of Korean Academy of Prosthodontics
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• v.39 no.3
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• pp.260-272
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• 2001

All-ceramic restorations have had a more limited life expectancy than metal ceramic restorations because of their low strength. Their relatively lower strength and resistance to fracture have restricted the use of all-ceramic crowns to anterior applications where occlusal loads are lower. But there has been increasing interest in all-ceramic restorations because patients are primarily concerned with improved esthetics. Many efforts have been made to in prove the mechanical properties of dental ceramics. This study was designed to elucidate the influence of the luting agent on the strength of the Empress 2 crown (staining technique) cemented on human teeth. Seventy extracted human permanent molar teeth were chosen. Teeth were prepared for Empress 2 crowns with milling machine on a surveyor. A dental bur was placed in the mandrel that was positioned so that the long axis of the bur was perpendicular to the surveyor base. Dimensions of the Empress 2 crown preparation were $6^{\circ}$ taper on each side, $1.5{\pm}0.1mm$ shoulder margin, and 4mm crown height. The luting cements used in this study were as follow: 1. Uncemented 2. Zinc phosphate cements (Confi-Dental) 3. Conventional glass ionomer cement : Fuji 1 (GC) 4. Resin-modified glass ionomer cements : Fuji plus (GC) 5. Adhesive cements : Panavia F (Kuralay), Variolink II (Vivadent), Choice (Bisco). Fracture test using Instron. The crowns were loaded in compressive force to evaluate the effect of these cements on the breaking strength of these all-ceramic crowns. A steel ball with a diameter of 4mm was placed on the occlusal surface and load was applied to the steel ball by a cylindrical bolt with a crosshead speed of 0.5mm per minute until fracture occurred. The fractured surface was examined using Scanning Electron Microscopic Image (SEM) to discover the correlation between fracture strength and bonding capacity. Within the limitation of this in vitro study design, the results were as follows : 1. fomentations significantly increased the fracture resistance of Empress ceramic crowns compared to control. Uncemented (206.9 N): ZPC (812.9 N): Fuji 1 (879.5 N): Fuji Plus (937.7 N): Choice (1105.4 N): Variolink II (1221.1 N): Panavia F (1445.2 N). 2. Resin luting agent, treated by a silane bond enhancing agents, yielded a significant increase in fracture resistance. In some of the Panavia F group, a fracture extended into dentin. 3. According to SEM images of fractured Empress crowns, the stronger the bond at both interfaces(crown and die), the more fracture strength was acquired.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3947-3951
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• 2011

The nucleophilic substitution reactions of Y-aryl ethyl chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Me. The substituents of X = 4-CN and 4-Ac show great positive deviations from both the Hammett and Bronsted plots. The Hammett plots for substituent Y variations in the substrates exhibit biphasic concave upwards with a minimum point at Y = H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are all in spite of the biphasic free energy correlations for both substituent X and Y variations, since the ${\rho}_X$values with both the strongly and weakly basic pyridines are almost constant. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed where the distance between X and Y does not vary from the intermediate to the second transition state. A frontside attack is proposed with the strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values and a backside attack is proposed with the weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$. The positive deviations of the two strong ${\pi}$-acceptor parasubstituents, X = 4-Ac and 4-CN, from both the Hammett and Bronsted plots are rationalized by the great extents of bond formation and breaking.

• Journal of Korea Technical Association of The Pulp and Paper Industry
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• v.38 no.4 s.117
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• pp.17-23
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• 2006

Paper has fibers and fines network structure and it is strongly affected by interface bond-ing between fibers. Paper structural properties can be determined depending on the inter-fiber bonding. Fines play an important role in Campbell and consolidation effect through wet pressing and drying operations. The fines are essential for the formation of bonds between fibers and for the improvement of strength properties of papers. Since the fines are components of the pulp, there are always two factors to be considered: the quality and quantity of the fines. The quality of fines might be a potential variable to give a more accurate picture of the papermaking potential of the pulp. The object of this study is to investigate the effect of different types of pulp fines on the properties of paper and to access the potential of fines for controlling the bulk of paper. Refined Sw-BKP, Hw-BKP and BCTMP fines were used to investigate the fines effect. Wet-web strength, breaking length, scattering coefficient, and hydrodynamic specific volume, and drying shrinkage were measured. According to the results, chemical and morphological compositions of fines do not strongly affect to wet-web forming by their similar Campbell effect, but strongly affect to drying operation which forms hydrogen bonding among fiber-fines-fiber matrixes. Paper bulk should be controlled by the extent of hydrogen bonding between fibers during drying operation.

• Proceedings of the KOSOMBE Conference
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• v.1997 no.05
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• pp.35-38
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• 1997

The interfacial bonding energy between laser surface treated HA layer and Ti alloy substrate was investigated using a mechanical push-out tester. The initial slope of shear-stress and reduced displacement curves, maximum interfacial bond strength and bonding energy were calculated from results of the push-out test. The calculated initial slpoes are 38 MPa for the Ti alloy(A), 65 MPa for the sandblast finished specimen(B), 95 MPa for the HA plasma spray coated specimen and 49 MPa for the laser surface treated specimen(D). The maximum interfacial bonding strength are 3 MPa for the A, 19 MPa for the B, 20 MPa for the C, 10 MPa for the D. The interfacial bonding energies are $3.3\times10^{-9}J/mm^2$ for the A, $15.5\times10^{-9}J/mm^2$ for the B, $15.6\times10^{-9}J/mm^2$ for the C and $18.3\times10^{-9}J/mm^2$ for the D. Microscopic observation shows that the breaking of the laser treated specimen had been occured through the boundary between HA layer and polymer resin, but the untreated specimen had been occured through the inside of HA coating layer.

• Journal of the Korean Chemical Society
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• v.17 no.3
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• pp.154-162
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• 1973

The rates and activation parameters for the halide $(Cl^{-}, Br^{-}, I^{-})$TeX> exchange reactions of substituted benzenesulfonyl-chloride, $XC_6H_4SO_2Cl$(X:p-MeO, H, p-Cl, p-Br, p-NO$_2l$) in dry acetone at two temperatures have been determined. It was found that the ion-pair of metal halide,$M^{+}X^{-}$, have negligible reactivity compared to free halide ions. It was also found that the nucleophilic order is $Cl^{-}>Br^{-}>I^{-}$for electron-donating substituent, and $Cl^{-}>I^{-}>Br^{-}$ for electron-withdrawing substituents. These results and convex nature of the Hammett plot are interpreted in the light of simple $S_N2$mechanism with the bond breaking becoming important for compounds with the electron withdra-wing substituents.

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.40-46
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• 1986

Rate constants for the solvolysis of o-methylbenzyl chloride were determined at 30$^{\circ}$ and 40$^{\circ}$C in aqueous ethanol mixtures under various pressures up to 1600 bar. From the rate constants, the activation parameters ${\Delta}V^{\neq}$, ${\Delta}{\beta}^{\neq}$, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and${\Delta}G^{\neq}$ were evaluated. The values exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of electrostriction. To examine the reaction mechanism by Laidler and Eyring equation, we compared the rate constants with the dielectric constants of aqueous ethanol and the number of water molecule participated in the transition state. It was concluded that solvolytic reaction proceeds via $S_N$1 mechanism.

• Journal of the Society of Cosmetic Scientists of Korea
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• v.42 no.3
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• pp.279-284
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• 2016

In this study, facial hair weakening ability of urea and anti-oxidants for shaving was investigated. The hair weakening ability and cross-section increase of hair depends on concentration of urea. The results showed that urea affects swelling of hair and this is related to the hair weakening ability. Anti-oxidants showed outstanding weakening ability despite of their low concentrations by breaking disulfide bond in facial hair. To evaluate the suitability of urea and anti-oxidants for facial cosmetic products, in vitro safety tests were proceeded. The results showed that urea and glutathione were safe for face. As a result, urea and glutathione were safe and outstanding as hair weakening agent for cosmetic shaving products.

• Journal of the Korean Chemical Society
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• v.35 no.1
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• pp.64-69
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• 1991

Kinetics of the reaction of p-methylphenacyl arenesulfonates with pyridine in acetonitrile were investigated by an electric conductivity method at 1∼2000 bars and 35∼55$^{\circ}C$. The rates of these reactions were increased with raising pressures and temperatures. The activation enthalpy(${\Delta}H^{\neq}$), entropy(${\Delta}S^{\neq}$) and activation volume(${\Delta}V^{\neq}$) of the reaction were obtained with the rate constants. Activation volume and entropy were both negative valued, and activation enthalpy was positive. The acteivation parameters (${\Delta}V^{\neq}$ and ${\Delta}S^{\neq}$) were decreased with increasing pressure. From all of the above results, it was found that this reaction proceeds on the S$_N$2 in which C${\cdots}$O bond breaking is more advanced as pressure increases.