• Journal of Powder Materials
• /
• 제18권4호
• /
• pp.359-364
• /
• 2011

Zr-Ti alloy powders were successfully synthesized by magnesium thermal reduction of metal chlorides. The evaporated and mixed gasses of $ZrCl_4+TiCl_4$ were injected to liquid magnesium and the chloride components were reduced by magnesium leading to the formation of $MgCl_2$. The released Zr and Ti atoms were then condensed to particle forms inside the mixture of liquid magnesium and magnesium chloride, which could be dissolved fully in post process by 1~5% HCl solution at room temperature. By the fraction-control of individually injected $ZrCl_4$ and $TiCl_4$ gasses, the final compositions of produced alloy powders were changed in the ranges of Zr-0 wt.%~20 wt.%Ti and their purity and particle size were about 99.4% and the level of several micrometers, respectively.

• Journal of Powder Materials
• /
• 제11권4호
• /
• pp.322-327
• /
• 2004

Ultrafine titanium carbide particles were synthesized by the reaction of liquid-magnesium and vaporized TiCl$_{4}$+C$_{x}$Cl$_{4}$(x = 1 and 2) solution. Fine titanium carbide particles with about 50 nm were successfully produced by combining Ti and C atoms released by chloride reduction of magnesium, and vacuum was then used to remove the residual phases of MgCl$_{2}$ and excess Mg. Small amounts of impurities such as O, Fe, Mg and Cl were detected in the product, but such problem can be solved by more precise process control. The lattice parameter of the product was 0.43267 nm, near the standard value. With respect to the reaction kinetics, the activation energy for the reactions of TiCl$_{4}$+C$_{2}$Cl$_{4}$and Mg was found to 69 kJ/mole, which was about half value against the use of TiCl$_{4}$+CCl$_{4}$, and such higher reactivity of the former contributed to increase the stoichiometry until the level of TiC$_{0.96}$ and decrease the free carbon content below 0.3 wt.%.

• Journal of the Korean Chemical Society
• /
• 제11권2호
• /
• pp.45-50
• /
• 1967

Radio thin layer chromatography of organic halogen compounds by neutron irradiation technique was investigated for the purpose of identifying and separating the mixture of halogen compounds. It was found that various halides, organic acids, and aldehyde gave a distinct developing peak both in cases of individual compound and a mixture of two or three components when the samples were developed by solvent methanol. But poly chlorinated compounds and aromatic or alicyclic chlorides gave more than one component peak when the sample was developed after neutron irradiation. Rf value of each compound was distinct and reproducible. The procedures were described and validity of the present method is discussed.

• Journal of the Korean Chemical Society
• /
• 제27권1호
• /
• pp.1-8
• /
• 1983

Solvent effects on nucleophilic substitution reaction of naphthalene sulfonyl chlorides with pyridine in protic and aprotic solvent have been studied by means of conductometry. Results showed that the rate constants increased with dielectric constants for protic solvents, while they decreased with dielectric constants for aprotic solvents, except for acetonitrile which has a higher dielectric constant but had also greater rate constant. The rate constants were shown to be more susceptible to polarity-polarizability parameter, , than to hydrogen bond donor acidity parameter, ${\alpha}$, indicating that the pulling effect of hydrogen bonding solvent.

• Bulletin of the Korean Chemical Society
• /
• 제32권9호
• /
• pp.3239-3244
• /
• 2011

Dinuclear Ni(II)-thiophene halides, which contain linear bridging thienylenes, trans,trans-[$(PR_3)_2$(X)Ni-Y-Ni(X)$(PR_3)_2$] {X = Cl, Br; $H_2Y$ = 5,5'-dichloro-2,2'-bithiophene ($H_2bth$); $H_2tth$ = 5,5"-dichloro-2,2':5',2''-terthiophene ($H_2tth$)} were prepared by the oxidative addition of dihalobithiophene ($H_2bth$) or dihaloterthiophene ($H_2tth$) to [$Ni(COD)_2$] in the presence of tertiary phosphines. Subsequent reactions of $NaN_3$ with the dinuclear Ni(II)-thiophene chlorides gave the corresponding Ni(II)-azido complexes, trans,trans-[$(PR_3)_2(N_3)$Ni-Y-Ni$(N_3)(PR_3)_2$], whose reactivity toward trimethylsilyl pseudohalides such as trimethylsilyl isothiocyanates and cyanides was investigated. In addition, the reaction of trans-[$BrNi(PEt_3)_2-C_4H_2S-C_4H_2S$-CHO], a thienyl Ni(II) complex containing a terminal aldehyde group, with phosphonium ylide was examined.

• Applied Chemistry for Engineering
• /
• 제5권6호
• /
• pp.1078-1091
• /
• 1994

Thermodynamic calculations have been made from existing literature data to show that it is reasonable to expect to recover metal chlorides from the chlorination of metal sulfides with chlorine gas. The reactions between 12 metal sulfides, such as, $Ag_2S$, $As_2S_3$, CdS, CuS, $Cu_2S$, FeS, HgS, $MoS_2$, $Ni_3S_2$, PbS, $Sb_2S_3$ and chlorine gas were investigated by means of thermogravimetric method. The theorical calculation and the experimental investigation showed that chlorination of sulfide is a better alternative process for the extraction metallurgical process of sulfide ores.

• Proceedings of the Korea Concrete Institute Conference
• /
• 한국콘크리트학회 2010년도 춘계 학술대회 제22권1호
• /
• pp.467-468
• /
• 2010

Over the past few decades, considerable numbers of studies on the durability of concrete have been carried out extensively. The majority of these researches have been performed on sound uncracked concrete, although most of in-situ concrete structures have more or less micro-cracks. It is only recent approach that the attention has shifted towards the influence of cracks and crack width on the penetration of chloride into concrete. The penetration of chlorides into concrete through the cracks can make a significant harmful effect on reinforcement corrosion. Author of this study examined the effect of cracks on chloride penetration by short term experiment. However, it is necessary to accomplish the effect by long term experiment to get reliable goal. In this study, the long term and short term experiments were carried out. This can be useful for establishing new species model of chloride penetration through cracks in concrete.

• International Journal of Concrete Structures and Materials
• /
• 제2권2호
• /
• pp.137-143
• /
• 2008

In recent years, much research work has been performed on durability design and long-term performance of concrete structures in marine environments. In particular, the development of new procedures for probability-based durability design has been shown to provide a more realistic basis for the analysis. This approach has been successfully applied to several new concrete structures, where requirements for a more controlled durability and service life have been specified. For reinforced concrete structures in a marine environment, it is commonly assumed that the dominant degradation mechanism is the corrosion of the reinforcement due to the presence of chlorides. The design approach is based on the verification of durability limit states, examples of which are: depassivation of reinforcement, cracking and spalling due to corrosion, and collapse due to cross section loss of reinforcement. With this design approach the probability of failure can be determined as a function of time. In the present paper, a probability-based durability performance analysis is used in order to demonstrate the importance of the durability design approach of concrete structures in marine environments. In addition, the sensitivity of the various durability parameters affecting and controlling the durability of concrete structures in a marine environment is studied. Results show that the potential of this approach to assist durability design decisions making process is great. Based the crucial information generated, it is possible to prolong the service life of structures while simultaneously optimizing the final design solution.

• Bulletin of the Korean Chemical Society
• /
• 제32권12호
• /
• pp.4361-4365
• /
• 2011

The nucleophilic substitution reactions of bis(N,N-dimethylamino) phosphinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The magnitudes of ${\rho}_X$ (= -6.42) and ${\beta}_X$ (= 2.27) values are exceptionally great. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.69-0.96). A concerted $S_N2$ mechanism involving a backside attack is proposed on the basis of secondary inverse DKIEs and the variation trend of the $k_H/k_D$ values with X. The anilinolyses of six phosphinic chlorides in MeCN are briefly reviewed by means of DKIEs, steric effects of the two ligands, positive charge of the reaction center phosphorus atom, and selectivity parameters to obtain systematic information on phosphoryl transfer reaction mechanism.

• Bulletin of the Korean Chemical Society
• /
• 제32권7호
• /
• pp.2413-2417
• /
• 2011

The specific rates of solvolysis of 1- naphthyl chloroformate (1-NaphOCOCl, 1) and 2-naphthyl chloroformate (2-NaphOCOCl, 2) have been determined in a wide range of solvents at 2.0 and 10.0$^{\circ}C$. These give a satisfactory correlation over the full range of solvents when the extended (two-term) Grunwald-Winstein equation is applied. The sensitivities (l and m-values) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) are similar to those reported previously for solvolysis of phenyl chloroformate, which has been suggested to proceed through an addition-elimination mechanism with the addition step being rate determining. For four representative solvents, studies were made at several temperatures and activation parameters determined. These observations were also compared with those previously reported for phenyl chloroformates and naphthoyl chlorides.