• Bulletin of the Korean Chemical Society
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• v.19 no.12
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• pp.1334-1336
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• 1998

Kinetic studies are carried out on the reactions of 2-chloro-2-propen-1-yl arenesulfonates with anilines and N,N-dimethylanilines in acetonitrilile at 45.0 ℃. The 2-chloro substituent is found to deactive the allyl moiety with considerable decrease in the rates. The sign and magnitude of the cross-interaction constant (ρxz 0.3) and the inverse secondary kinetic isotope effect (kH/kD 0.92) support an SN2 mechanism with a relatively tight transition state. The possibility of an SN2' mechanism can be safely precluded based on the ρxz values observed.

• Bulletin of the Korean Chemical Society
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• v.16 no.7
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• pp.657-661
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• 1995

Kinetic studies are carried out on the reaction of S-phenyl dithiobenzoates with benzylamines in acetonitrile at 30.0 ℃. Small magnitude of ρX (βX) as well as ρZ (βZ) obtained suggests rate-limiting nucleophilic attack of the thiocarbonyl carbon. This is supported by the unusually small magnitude of ρXY and ρYZ, albeit their signs do not agree with those expected. Moreover, the inverse secondary kinetic isotope effects (kH/kD<1.0) involving deuterated benzylamine nucleophiles are also in line with the proposed mechanism.

• Korean Journal of Materials Research
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• v.24 no.2
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• pp.98-104
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• 2014

Vacuum kinetic spray(VKS) is a relatively advanced process for fabricating thin/thick and dense ceramic coatings via submicron-sized particle impact at room temperature. However, unfortunately, the particle velocity, which is an important value for investigating the deposition mechanism, has not been clarified yet. Thus, in this research, VKS average particle velocities were derived by numerical analysis method(CFD: computational fluid dynamics) connected with an experimental approach(SCM: slit cell method). When the process gas or powder particles are accelerated by a compressive force generated by gas pressure in kinetic spraying, a tensile force generated by the vacuum in the VKS system accelerates the process gas. As a result, the gas is able to reach supersonic speed even though only 0.6MPa gas pressure is used in VKS. In addition, small size powders can be accelerated up to supersonic velocity by means of the drag-force of the low pressure process gas flow. Furthermore, in this process, the increase of gas flow makes the drag-force stronger and gas distribution more homogenized in the pipe, by which the total particle average velocity becomes higher and the difference between max. and min. particle velocity decreases. Consequently, the control of particle size and gas flow rate are important factors in making the velocity of particles high enough for successful deposition in the VKS system.

• Bulletin of the Korean Chemical Society
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• v.32 no.5
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• pp.1539-1542
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• 2011

The aminolysis of O-methyl S-aryl thiocarbonates with benzylamines are studied in acetonitrile at -45.0$^{\circ}C$. The ${\beta}_X$(${\beta}_{nuc}$) values are in the range 0.62-0.80 with a negative cross-interaction constant, ${\rho}_{XZ}$ = -0.42, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles ($XC_6H_4CH_2ND_2$) are large, $k_H/k_D$ = 1.29-1.75, suggesting that the N-H(D) bond is partially broken in the transition state by forming a hydrogen-bonded four-center cyclic structure. The concerted mechanism is enforced by the strong push provided by the MeO group which enhances the nucleofugalities of both benzylamine and arenethiolate from the putative zwitterionic tetrahedral intermediate.

• Proceedings of the KSME Conference
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• 2004.11a
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• pp.1704-1709
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• 2004

New reduced chemical kinetic mechanism for prediction of autoignition process of HSDI diesel engine was investigated. For precise prediction of the ignition characteristics of diesel fuel, mechanism coefficients were fitted by the experimental results of ignition delay of diesel spray in a constant volume vessel. Ignition delay of diesel engine on various operation condition was calculated based on the new reduced chemical mechanism. The calculation results agreed well with experimental data.

• Journal of Mechanical Science and Technology
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• v.16 no.1
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• pp.102-108
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• 2002

Numerical simulations of 1, 2 dichloroethane(EDC) pyrolyisis are conducted to understand the process in the production of the vinyl chloride monomer (VCM) and by-products. A chemical kinetic mechanism Is developed, with the adopted scheme involving 44 gas-phase species and 260 elementary forward and backward reactions. Detailed sensitivity analyses and the rates of production analysis are performed on each of the reactions and the various species, respectively. The concentrations of EDC, VCM, and HCI predicted by this mechanism are in good agreement with those deduced from experiments of commercial and laboratory scale. The mechanism is found to accurately predict the EDC yield an(1 the production of by-products by varying the ranges of pyrolysis temperature, residence time, and pressure which impact on the pyrolysis of 1, 2 dichloroethane. The influence of reactions related to H atom on the relative sensitivity of EDC becomes important as the residence time increases. The pyrolysis of EDC mainly occurs through C$_2$H$_4$Cl$_2$+Cl=CH$_2$CICHI+HCI.

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.137-140
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• 2011

The aminolysis reactions of phenyl N-benzyl thiocarbamate with benzylamines in acetonitrile at $50.0^{\circ}C$ are investigated. The reactions are first order in both the amine and the substrate. Under amine excess, pseudo-first coefficient ($k_{obs}$) are obtained, plot of $k_{obs}$ vs free amine concentration are linear. The signs of ${\rho}_{XZ}$ (< 0) are consistent with concerted mechanism. Moreover, the variations of $\rho_X$ and $\rho_Z$ with respect to the sustituent in the substrate and large ${\rho}_{XZ}$ value indicate that the reactions proceed concerted mechanism. The normal kinetic isotope effects ($k_H/k_D$ = 1.3 ~ 1.5) involving deuterated benzylamine nucleophiles suggest a hydrogen-bonded, four-centered-type transition state. The activation parameters, ${\Delta}H^\ddagger$ and ${\Delta}S^\ddagger$, are consistent with this transition state structure.

• Polymer(Korea)
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• v.25 no.6
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• pp.866-875
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• 2001

In this work, thermal decomposition mechanism based on kinetic parameters and thermal stability of carbon fiber-reinforced carbon matrix composites (C/C composites), have been studied under high temperature oxidative conditions with addition of tetra-ethylorthosilicate (TEOS) as an oxidation inhibitor. Thermogravimetric analysis (TGA) was executed to evaluate the thermal decomposition mechanism and thermal stability of C/C composites in the temperature range of 30 ～ $850^{\circ}C$. As a result, the kinetic parameters of the composites impregnated with TEOS, i.e., activation energy for thermal decomposition ($E_d$), order of reaction (n) , and pre-exponential factor (A) were evaluated as 136 kJ/mol, 0, and 2.3$\times$$10^9s^{-1}$, respectively. Especially, the IPDT and $E_d$ of C/C composites impregnated with TEOS were improved largely compared with the composites impregnated without TEOS, due to the formation of $SiO_2$ on composite surfaces, resulting in interrupting the oxygen attack to carbon active site in the composites.

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3274-3278
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• 2012

The kinetic studies on the reactions of phenyl N-phenyl phosphoramidochloridate (8) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $60.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are huge secondary inverse ($k_H/k_D$ = 0.52-0.69). A concerted mechanism is proposed with a backside attack transition state (TS) on the basis of the secondary inverse DKIEs and the variation trends of the $k_H/k_D$ values with X. The degree of bond formation in the TS is really extensive taking into account the very small values of the DKIEs. The steric effects of the two ligands on the rates are extensively discussed for the aminolyses of the chlorophosphate-type substrates on the basis of the Taft equation.

• International Journal of Precision Engineering and Manufacturing
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• v.9 no.2
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• pp.11-17
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• 2008

Critical erosion kinetic energy models for radial/median cracks and lateral cracks in a workpiece are established in this study. We used experimental results to demonstrate that the fracture erosion resistance and erosion machining number could be used to evaluate the brittle fracture resistance and machinability of a workpiece. Erosion kinetic energy models were developed to predict brittle fracture and ductile shear, and a critical erosion kinetic energy model was developed to predict the transition from brittle fracture to ductile shear. These models were verified experimentally.