• Corrosion Science and Technology
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• 제11권1호
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• pp.29-36
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• 2012

The resistance spot welding of high strength steel degrades the weldability because of its high strength with rich chemical composition and coating layer to protect from corrosion. During the each resistance welding process the electrodes tip reacts with coating layer, then subsequently deteriorates and shorten electrode life. In this study, the Al-coated HPF (Hot Press Forming) steels and Zn-coated TRIP steels were used to investigate the electrode life for resistance spot welding. Experimental results show that the reactivity of Al-coating on HPF steels to electrode tip surface behaviors different from the conventional Zn-coated high strength steels. The electrode tip diameter and nugget size in electrode life test of Al-coated HPF steels are observed to be constant with respect to weld numbers. For Al-coated HPF steels, the hard aluminum oxide layer being formed during high temperature heat treatment process reduces reactivity with copper electrode during the resistance welding process. Eventually, the electrode life in resistance spot welding of Al-coated HPF steels has the advantage over the galvanized steel sheets.

• 한국분말재료학회지
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• 제26권3호
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• pp.220-224
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• 2019

The aluminum (Al)/copper oxide (CuO) complex is known as the most promising material for thermite reactions, releasing a high heat and pressure through ignition or thermal heating. To improve the reaction rate and wettability for handling safety, nanosized primary particles are applied on Al/CuO composite for energetic materials in explosives or propellants. Herein, graphene oxide (GO) is adopted for the Al/CuO composites as the functional supporting materials, preventing a phase-separation between solvent and composites, leading to a significantly enhanced reactivity. The characterizations of Al/CuO decorated on GO(Al/CuO/GO) are performed through scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectroscopy mapping analysis. Moreover, the functional bridging between Al/CuO and GO is suggested by identifying the chemical bonding with GO in X-ray photoelectron spectroscopy analysis. The reactivity of Al/CuO/GO composites is evaluated by comparing the maximum pressure and rate of the pressure increase of Al/CuO and Al/CuO/GO. The composites with a specific concentration of GO (10 wt%) demonstrate a well-dispersed mixture in hexane solution without phase separation.

• Safety and Health at Work
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• 제11권4호
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• pp.500-508
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• 2020

Background: Research on the status of many chemicals used in the semiconductor industry is needed. The purpose of this study was to describe the overall status of chemical use in the semiconductor industry in Korea and to examine it from a health perspective. Methods: Data on the status of chemical use and safety data sheets at 11 of 12 major semiconductor workplaces in Korea were collected. The number of chemical products and chemical constituents, quantities of chemicals, and trade secret ingredients used, as well as the health hazards were examined. Results: On average, 210 chemical products and 135 chemical constituents were used at the surveyed workplaces. Among all chemical products, 33% (range: 16-56%) contained at least one trade secret ingredient. Most of the trade secret ingredients were used in the photolithography process. Several carcinogens, including sulfuric acid, chromic acid, ethylene oxide, crystalline silica, potassium dichromate, and formaldehyde were also used. Only 29% (39 of 135) of the chemical constituents had occupational exposure limits, and more than 60% had no National Fire Protection Association health, safety, and reactivity ratings. Based on the aforementioned results, this study revealed the following. First, many chemical products and constituents are being used in the semiconductor industry and many products contained trade secret ingredients. Second, many products contained significant amounts of carcinogenic, mutagenic, and reproductive toxicant materials. Conclusion: We conclude that protecting workers in the semiconductor industry against harm from chemical substances will be difficult, due to widespread use of trade secret ingredients and a lack of hazard information. The findings of the status of chemical use and the health and safety risks in semiconductor industry will contribute to epidemiological studies, safe workplace, and worker health protection.

• Bulletin of the Korean Chemical Society
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• 제33권5호
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• pp.1551-1555
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• 2012

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of benzyl 2-pyridyl carbonate $\mathbf{7}$ and $t$-butyl 2-pyridyl carbonate $\mathbf{8}$ with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. Substrate $\mathbf{8}$ is less reactive than $\mathbf{7}$. Steric hindrance exerted by the bulky $t$-Bu group of $\mathbf{8}$ has been suggested to be responsible for the decreased reactivity. The Br${\o}$nsted-type plots for the reactions of $\mathbf{7}$ and $\mathbf{8}$ are linear with ${\beta}_{nuc}=0.49$ and 0.44, respectively, which is typical for reactions reported previously to proceed through a concerted mechanism. Aminolyses of $\mathbf{7}$ and $\mathbf{8}$ were expected to proceed through a zwitterionic tetrahedral intermediate $T^{\pm}$, which would be stabilized through an intramolecular H-bonding interaction. However, the kinetic results suggest that the reactions proceed through a concerted mechanism. The H-bonding interaction in $T^{\pm}$ has been suggested to accelerate the rate of leaving-group expulsion from $T^{\pm}$. Another factor that might accelerate expulsion of the leaving group is the "push" provided by the RO group in $T^{\pm}$ through resonance interactions. Thus, it has been concluded that the enhanced nucleofugality through the H-bonding interaction and the "push" provided by the RO group forces the reactions to proceed through a concerted mechanism.

• Bulletin of the Korean Chemical Society
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• 제32권spc8호
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• pp.2955-2959
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• 2011

Second-order rate constants for nucleophilic substitution reactions of 2,4-dinitrophenyl benzenesulfonate 1a with a series of alicyclic secondary amines in MeCN have been measured spectrophotometrically and compared with those reported previously for the corresponding reactions performed in aqueous medium to investigate the effect of medium on reactivity and reaction mechanism. The amines employed in this study are found to be more reactive in the aprotic solvent than in $H_2O$. The reactions of 1a in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.58, which contrasts to the curved Br${\o}$nsted-type plot reported previously for the corresponding reactions performed in the aqueous medium (i.e., ${\beta}_2$ = 0.86 and ${\beta}_1$ = 0.38). Accordingly, it has been concluded that the reaction mechanism changes from a stepwise mechanism to a concerted pathway upon changing the medium from $H_2O$ to MeCN. Reactions of Y-substituted phenyl benzenesulfonates 1a-c with piperidine in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{lg}$ = -1.31, indicating that expulsion of the leaving group is significantly more advanced than bond formation in the transition state. The trigonal bipyramidal intermediate ($TBPy^{\pm}$) proposed previously for the reactions in $H_2O$ would be highly unstable in MeCN due to strong repulsion between the negative charge in $TBPy^{\pm}$ and the negative dipole end of MeCN. Thus, destabilization of $TBPy^{\pm}$ in MeCN has been concluded to change the reaction mechanism from a stepwise mechanism to a concerted pathway.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3253-3257
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• 2012

Second-order rate constants for the reactions of phenyl Y-substituted-phenyl carbonates 5a-g with Z-substituted-phenoxides ($k_{Z-PhO^-}$) have been measured spectrophotometrically in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. 4-Nitrophenyl phenyl carbonate (5e) is up to 235 times more reactive than 4-nitrophenyl benzoate (4e). The Br$\o$nsted-type plot for the reactions of 5e with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.54$, which is typical for reactions reported previously to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for the reactions of 5a-f with 4-chlorophenoxide exhibit highly scattered points. In contrast, the Yukawa-Tsuno plot results in an excellent linear correlation with ${\rho}_Y=1.51$ and r = 0.52, indicating that the leaving-group departure occurs at the rate-determining step (RDS). A stepwise mechanism, in which leaving-group departure occurs at RDS, has been excluded since the incoming 4-$ClPhO^-$ is more basic and a poorer nucleofuge than the leaving Y-substituted-phenoxides. Thus, the reaction has been concluded to proceed through a concerted mechanism. Our study has shown that the modification of the nonleaving group from benzoyl to phenyloxycarbonyl causes a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as an increase in the reactivity.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1915-1919
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• 2010

Second-order rate constants $(k_N)$ have been measured for reactions of 2,4-dinitrophenyl phenyl carbonate (2) with a series of pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ and compared with the $k_N$ values reported for the corresponding reactions of 2,4-dinitrophenyl benzoate (1) to investigate the effect of nonleaving group on reactivity and mechanism. The reactions of 2 result in larger $k_N$ values than those of 1. The Br${\o}$nsted-type plot for the reactions of 2 exhibits a downward curvature (i.e., ${\beta}2$ = 0.84 and ${\beta}1$ = 0.16), which is typical for reactions reported to proceed through a stepwise mechanism with a change in rate-determining step. The $pK_a$ at the center of the Br${\o}$nsted curvature, defined as $pK_a{^{\circ}}$, has been found to be 8.5 and 9.5 for the reactions of 2 and 1, respectively. Dissection of $k_N$ into the microscopic rate constants (e.g., $k_1$ and $k_2/k_{-1}$ ratio) has revealed that the reactions of 2 result in larger k1 values than those of 1, indicating that PhO behaves as a stronger electron-withdrawing group than Ph. However, the $k_2/k_{-1}$ ratio has been found to be independent of the electronic nature of Ph and PhO.

• Bulletin of the Korean Chemical Society
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• 제35권5호
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• pp.1506-1510
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• 2014

A kinetic study on nucleophilic substitution reaction of 5-nitro-8-quinolyl picolinate (6) with alkali-metal ethoxides (EtOM; M = K, Na, and Li) in anhydrous ethanol is reported. The plot of $k_{obsd}$ vs. [EtOM] curves upward in the absence of crown ethers but is linear with significantly decreased reactivity in the presence of crown ethers. 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 significantly more reactive than the dissociated $EtO^-$ (e.g., $k_{EtOM}/k_{EtO^-}$ = 33.4-141). This indicates that the reaction of 6 is catalyzed by $M^+$ ions in the order $Na^+$ > $Li^+$ > $K^+$ and the catalytic effect disappears in the presence of a proper crown ether. Picolinate ester 6 is much more reactive and is more strongly catalyzed by $M^+$ ions than 5-nitro-8-quinolyl benzoate (5). It has been concluded that $M^+$ ions catalyze the reaction of 6 by increasing electrophilicity of the reaction center through a cyclic transition state, which is structurally not possible for the reaction of 5.

• 대한화학회지
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• 제26권6호
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• pp.421-426
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• 1982

자유 라디칼 개시제에 의한 인산디에틸이소프로페닐(DEIPA)과 초산비닐(VAc) 및 아크릴로니트릴(An)의 혼성중합 연구를 행하여 단위체 반응성비를 얻었다. 개시제로는 과산화벤조일을 사용하였으며 중합온도는 $60^{\cric}C$이었다. 단위체 반응성비는${\gamma}_1$(VAc) = 1.56, ${\gamma}_2$(DEIPA) = 0.44: ${\gamma}_1$(AN) = 15.2, ${\gamma}_2$(DEIPA) = 0.031이었다. 이 값으로부터 DEIPA의 Alfrey-Price 상수 Q=0.015, e=0.39 및 Q=0.014, e=0.34를 얻었으며${\alpha}$ 위치에 있는 메틸기가 반응성을 감소시킴을 알았다. 공중합체중 DEIPA의 함량이 증가함에 따라 공중합체의 고유점성도 및 수평균 분자량이 감소함도 알았다.

• 폴리머
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• 제30권4호
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• pp.326-331
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• 2006

대표적인 고내열 POF(plastic optical fiber)의 재료로 사용되는 MMA(methyl methacrylate)/IPMI(N-isopropyl maleimide) 공중합체는 단량체 간의 반응성이 매우 차이가 나므로 $(r_1/r_2=1.72:0.17)$, 중합체의 조성분포가 불균일하게 되어 물성을 저하시키는 원인으로 작용한다. 본 논문에서는 MMA/IPMI 공중합에 스티렌을 도입하여, IPMI의 반응성을 증가시켜 중합체의 조성 분포를 좀 더 균일하게 개선하였으며, 전환율도 약 $1.5{\sim}2$배 정도로 증가시키는 결과를 얻을 수 있었다. 합성된 MMA/IPMI/St 삼원공중합체의 경우 굴절률은 MMA/IPMI 공중합체보다 증가하였으며 이는 주로 스티렌의 함량과 관련되는 것으로 나타났다.