• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2009-2014
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Journal of the Korean Chemical Society
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• v.57 no.3
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• pp.365-369
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• 2013

With the wide application of ASP (alkaline-surfactant-polymer) flooding, the scaling becomes more and more serious, which is harmful to the oilfield and environment. In order to investigate the effects of HPAM on calcium carbonate crystallization, the crystallization behaviors of $CaCO_3$ in HPAM (Hydrolyzed polyacrylamide) solutions were studied and the composition and morphology of $CaCO_3$ crystal were investigated in different concentrations of polyacrylamide solutions. The crystal forms and morphologies of $CaCO_3$ were characterized by Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy. The results show that the crystallization of $CaCO_3$ is strongly influenced by the HPAM. The paper analyzed the internal cause, and the results show: The reasons leading to the change of morphology are carboxyl groups in polyacrylamide molecule and $Ca^{2+}$ in solution form chelates by coordination bond. And the chelates are adsorbed on the calcium hydroxide surfaces of solid-liquid interfaces so as to change the formation rate of calcium carbonate crystal nucleus. The research provides a reliable basis for the mechanism research of the scaling problem in the oil extraction process of ASP flooding and the adoption of scale inhibition and scale inhibitor.

• Journal of Technologic Dentistry
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• v.35 no.4
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• pp.313-320
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• 2013

Purpose: The purpose of this study was to know the physical properties of UDMA dental composite resins containing two photosensitizers, PD, DA, as a photosensitizer instead of CQ. We want to know Remaining Double Bond(RDB) of UDMA unfilled resin and diametral tensile strength and flexural strength of composite resin containing PD and DA were compared with those of CQ, most widely used photosensitizer for dental composite resins. Methods: The RDB of UDMA studied by FT-IR spectroscopy increased with irradiation time. The composite resins were tested for their physical properties. The dental composite resins were made with UDMA as a monomer, silanized silica as filler, N,N-dimethylaminoethyl methacrylate (DAEM) as amine initiator, and one of the two kinds of new photosensitizers. Results: The relative RDB of UDMA was in the order: DA > CQ > PD but the physical properties of the composite resins show PD and DA with higher results compared with that containing CQ. The reason for the results is that PD and DA serve not only as a photosensitizer but also as a photo-crosslinking agent. Conclusion: PD and DA show as effective photosensizers, suitable for UDMA dental composite resin compare with a higher efficiency than CQ.

• Earthquakes and Structures
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• v.5 no.3
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• pp.321-341
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• 2013

This paper investigates earthquake response of reinforced concrete regular frames subjected to rebar corrosion. A typical four-story reinforced concrete frame is designed according to Turkish Earthquake Code in order to examine earthquake response. Then different levels of rebar corrosion scenarios are applied to this frame structure. The deteriorated conditions as a result of these scenarios are included loss in cross sectional area of rebar, loss of mechanical properties of rebar, loss in bond strength and variations in damage limits of concrete sections. The frame is evaluated using a nonlinear static analysis in its sound as well as deteriorated conditions. The rebar corrosion effect on the structural response is investigated by comparing the response of the frame in each scenario with respect to the sound condition of the frame. The results shows that the progressive deterioration of the frame over time cause serious reductions on the base shear and top displacement capacity and also structural ductility of the corroded frames. The propagation time, intensity, and extensity of rebar corrosion on the frame are important parameters governing the effect of rebar corrosion on earthquake response of the frame.

• Journal of Surface Science and Engineering
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• v.34 no.2
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• pp.161-168
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• 2001

A Thermal Barrier Coating (TBC) can play an important role in protecting parts from harmful environments at high temperatures such as oxidation, corrosion, and wear in order to improve the efficiency of aircraft engines by lowering the surface temperature of the turbine blade. The TBC can increase the life span of the product and improve the operating properties. Therefore, in this study the mechanical and thermal properties of the TBC such as oxidation, fatigue and shock at high temperatures were evaluated. A samples of a bond coat (CoNiCrAlY) produced by the High Velocity Oxygen Fuel (HVOF) and Low Pressure Plasma Spray (LPPS) method were used. The thickness of the HVOF coating layer was approximately $450\mu\textrm{m}$ to 500$\mu\textrm{m}$ and the hardness number of the coating layer was between 350Hv and 400Hv. The thickness of the LPPS coating was about 350$\mu\textrm{m}$ to 400$\mu\textrm{m}$ and the hardness number of the coating was about 370Hv to 420Hv. The X-ray diffraction analysis showed that CoNiCrAlY coating layer of the HVOF and LPPS was composed of the $\beta$and ${\gamma}$phase. After the high temperature oxidation test, the oxide scale with about l0$\mu\textrm{m}$ to 20$\mu\textrm{m}$ thickness appeared at the coating surface on the Al-depleted zone was observed under the oxide scale layer.

• 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.

• Bulletin of the Korean Chemical Society
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• v.19 no.7
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• pp.776-779
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• 1998

Second-order rate constants have been measured spectrophotometrically for the addition reaction of a series of alicyclic amines to 3-butyn-2-one to yield their respective enamines at 25.0 'C. The reactivity of the amines increases with increasing the basicity of the amines. However, the Bronsted-type plot obtained exhibits a downward curvature as the basicity of the amines increases, i.e. βnuc decreases from 0.3 for low basic amines (pKa < 9) and to 0.1 for highly basic amines (pKa > 9). Such a curvature in the Bronsted-type plot is clearly indicative of a change in the reaction mechanism or transition state structure. From the corresponding reactions run in D2O, the magnitude of kinetic isotope effect (KIE) has been calculated to be about 0.8 for highly basic amines and 1.21 for weakly basic amines. The difference in the magnitude of KIE also supports a change in the reaction mechanism or transition state structure upon changing the basicity of the amines. Furthermore, the small KIE clearly suggests that H+ transfer is not involved in the rate-determining step, i.e. the addition reaction is considered to proceed via a stepwise mechanism in which the attack of the amines to the acetylene is the rate-determining step. The curvature in the Bronsted-type plot has been attributed to a change in the degree of bond formation between the amine and the acetylene.

• Computers and Concrete
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• v.18 no.2
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• pp.267-278
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• 2016

In order to observe the internal damage of concrete in real time, we introduced acoustic emission nondestructive detecting technology into a series of fracture tests; the test results revealed the whole process that concrete undergoes when it sustains damage that leads to failure, according to the change rules of the acoustic emission parameters. The results showed that both the initiation and unstable loads can be accurately determined using the abrupt change of the acoustic emission rate curves and the turning point of the acoustic emission parameters' accumulative curves. The whole process, from damage to failure, includes five phases, beginning with damage, such as cracking, a stable crack growth process, a critical unstable stage, and unstable propagation. The brittle fracture characteristics of concrete change when steel bars are joined, because the steel bars and the concrete structure bond, which causes an increase in the acoustic emission signals within the fracture process of the reinforced concrete. The unstable propagation stage is also extended. Our research results provide a valid methodology and technical explanations, which can help researchers to monitor the cracking process of concrete structures, in real time, during actual projects.

• Journal of the Architectural Institute of Korea Structure & Construction
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• v.34 no.11
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• pp.3-10
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• 2018

Cladding that finishes the exterior of a building could enhance the value of the building, and shape control is an important factor. With the recent development of 3D printing, cementitious claddings were printed by 3D printer in China, U.S.A and elsewhere. On the other hand, the structural safety of the exterior panel should be examined, as casualties occur when the exterior panel fails due to typhoon or impact. Cement-based cladding is reinforced by wire mesh to improve safety. Introducing 3D printing composite system with polymer and cement, makes it possible to produce claddings fast and accurate. Prior to the development of 3D printing cementitious cladding, the major parameters influencing the optimal shape were identified based on structural performance. The wind load, joint, and bond behavior between polymer and cement were considered. Polymer laminate shape, order, and thickness were variables, and finite element analysis was performed.

• Bulletin of the Korean Chemical Society
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• v.15 no.2
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• pp.161-167
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates (3) with alkali metal ethoxides ($EtO^-M^+$) and butane-2,3-dione monoximates ($Ox^-M^+$) in ethanol at $25^{\circ}C$. The reactivity of the alkali metal ethoxides decreases in the order $EtO^-K^+> EtO^- > EtO^-Li^+$, indicating that $K^+$ ion behaves as a catalyst and $Li^+$ ion acts as an inhibitor for all the substrates studied. For the corresponding reactions of 3 with Ox^-M^+$, $Li^+$ ion also exhibits inhibitory effect for all the substrates, while, $K^+$ ion shows catalytic or inhibitory effects depending on the nature of substituents on the acyl and phenyl moieties. A study of substituent effect on rate has revealed that both EtO^- $and Ox^-$ systems have the same reaction mechanism. The different behavior shown by $K^+$ ion for the reaction of 3 with $EtO^-$ and $Ox^-$ would be attributed to a difference in charge polarization of S=O bond in the transition state between the two systems and/or a change in conformation of Ox^-K^+$.