• Bulletin of the Korean Chemical Society
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• v.33 no.9
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• pp.2971-2975
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• 2012

Second-order rate constants $k_N$ have been measured spectrophotometrically for nucleophilic substitution reactions of t-butyl 4-pyridyl carbonate 8 with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 8 is linear with ${\beta}_{nuc}$ = 0.84. The ${\beta}_{nuc}$ value obtained for the reactions of 8 is much larger than that reported for the corresponding reactions of t-butyl 2-pyridyl carbonate 6 (i.e., ${\beta}_{nuc}$ = 0.44), which was proposed to proceed through a forced concerted mechanism. Thus, the aminolysis of 8 has been concluded to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate $T^{\pm}$, in which expulsion of the leaving-group from $T^{\pm}$ occurs at the rate-determining step (RDS). In contrast, aminolysis of benzyl 4-pyridyl carbonate 7 has been reported to proceed through two intermediates, $T^{\pm}$ and its deprotonated form $T^-$ on the basis of the fact that the plots of pseudo-first-order rate constant $k_{obsd}$ vs. amine concentration curve upward. The current study has demonstrated convincingly that the nature of the leaving and nonleaving groups governs the reaction mechanism. The contrasting reaction mechanisms have been rationalized in terms of an intramolecular H-bonding interaction, steric acceleration, and steric inhibition.

• Journal of the Korean Ceramic Society
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• v.34 no.1
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• pp.95-101
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• 1997

Using aluminum powder with average particle size of 22.1 $\mu$m, aluminum compact made by Pressureless Powder Packing Method showed 52% green density. The activation energy of aluminum oxidation was cal-culated from the weight change of TG, and it was varied in the range of 16~64 kJ/mol. It was found from the variation of the activation energy and the observation of the microstructure that oxidation was de-pendent on the destruction of oxide film and the melt-out of aluminum. Aluminum compact was reaction-bonded at 1000~140$0^{\circ}C$ for 4~60hrs, and oxidation was dependent on temperature rather than time. Reac-tion-bonded aluminum oxide at 140$0^{\circ}C$ for 60hrs showed 92% oxidation percent. It was sintered at 1$600^{\circ}C$ for 15hrs and the sintered body showed 62% relative density.

• Journal of the Korean Chemical Society
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• v.38 no.3
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• pp.241-245
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• 1994

The oxidative addition reaction has been employed to synthesize heteropolynuclear compounds containing Si-M bonding interaction between the silicon atom of silatrane, pentacoordinate silicon derivative with transannular Si-N dative bond, and the main group element. The reaction of $SnBr_2 with 1-bromosilatrane(1a) in acetonitrile gives the mixture of yellow(2a) and white(2b) solids which were isolated and charaterized by ^1H-NMR, ^{29}Si-NMR, ^{119}Sn-NMR and Mass spectroscopy. The yellow compound was characterized as 1-tribromotinsilatrane which had Si-Sn bonding interaction. The reaction of SnBr2 with 1-bromo-3,7,10-trimethylsilatrane(1b) in methanol gives the Sn(Ⅳ) complex, N[CH_2CH(CH_3)O]_3SiSnBr_3(CH_3OH)_2(3),$ which was characterized by various means.

• Korean Journal of Materials Research
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• v.15 no.10
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• pp.662-666
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• 2005

Solid solutions of $(Zr/Ti)O_2$ were prepared in powder form by the coprecipitation technique. After mixing with carbon or exposing to nitrogen gas at elevated temperature, titanium cations selectively diffused out from the oxide compound to form titanium carbide (TiC) or titanium nitride (TiN), respectively. TiN formed strong interfacial contacts between the oxide grains. In contrast, TiC formed as small crystallites on oxide grains but did not bind the matrix grains together. TiN therefore played a role in strengthening the interparticle bonding, but TiC weakened the bonding between grains. Partial diffusion of titanium cations also led to nanolayered structure being formed between the oxide grains, which provided weak interfacial layers that fractured in a step-wise fashion.

• Korean Journal of Materials Research
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• v.13 no.3
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• pp.150-154
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• 2003

Amorphous carbon nitride films were deposited on Si(001) substrates by a plasma enhanced chemical vapor deposition technique (PECVD) using $CH_4$and $N_2$as reaction gases. The growth and film properties were investigated while the gas ratio and the working pressure were changed systematically. At 1 Torr working pressure, an increase in the $N_2$partial pressure results in a significant increase of the deposition rate as well as an apparent presence of C ≡N bonding, while little affecting the microstructure and amorphus nature of the films. In the case of changing the working pressure at a fixed $N_2$partial pressure of 98%, a film grown at a medium pressure of $1${\times}$10^{-2}$ Torr shows the most prominent C=N bonding nature and photoluminescent property.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2006.11a
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• pp.170-171
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• 2006

The chemical shift of SiOC film was observed according to the flow rate ratio. SiOC film has the broad main band of $880{\sim}1190cm^{-1}$ and the sharp Si-$CH_3$ bond at $1252cm^{-1}$, and the infrared spectra in the Si-O-C bond moved to low frequency according to the increasing of an oxygen flow rate. The chemical shift affected the carbon content in the SiOC film, and the decreasing of carbon atoms elongated the C-H bonding length, relatively. The main bond without the sharp Si-$CH_3$ bond at $1252cm^{-1}$ consisted of Si-C, C-O and Si-O bonds, and became the bonding structure of the Si-O-C bond.

• Proceedings of the KWS Conference
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• 2002.10a
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• pp.65-69
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• 2002

An Al film deposited on the Kovar alloy substrate was anodically-bonded to the borosilicate glass, and the bond interfaces was closely investigated by transmission electron microscopy. Al oxide was found to form a layer ~l0 nm thick at the bond interface, and fibrous structure of the same oxide was found to grow epitaxially in the glass from the oxide layer. The fibrous structure grew with the bonding time. The mechanism of the formation of this fibrous structure is proposed on the basis of the migration of Al ions under the electric field. Penetration of Al into glass beyond the interfacial Al oxide was not detected. The comparison of the amount of excess oxygen ions generated in the alkali depletion layer with that incorporated in the Al oxide suggests that the growth of the alkali-ion depletion layer is controlled by the consumption of excess oxygen to form the interfacial Al oxide.

• Journal of Welding and Joining
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• v.21 no.2
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• pp.64-69
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• 2003

The bonding phenomena and mechanical property of duplex stainless steel during brazing have been investigated. The UNS32550 was used for base metal, and the MBF50 was used for insert metal. Brazing was carried out under the various conditions (brazing temperature : 1473K, 1498K, holding time : 0∼1.8ks). There were various microconstituents in the bonded interlayer because of reaction between liquid insert metal and base metal. In the early stage of brazing, BN is formed in the bonded interlayer and base metal near the bonded layer. Cr made is formed in the bonded interlayer. The amount of BN and Cr nitrides decrease with the increase of bonding temperature and holding time. Superior shear strength of 550MPa is obtained by restraining the formation of nitrides. (Received January 17, 2003)

• 한국생물공학회:학술대회논문집
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• 2000.11a
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• pp.644-647
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• 2000

The properties of hydrogen bonding between poly(2-ethyl-2-oxazoline)[PEOx] and poly(acrylic acid)[PAA] were investigated. PEOx and PAA formed stable complex and precipitated due to hydrogen bonding between hydrogen of PAA and oxygen of PEOx in acidic condition(below pH 4.3). Optimum reaction ratio of PEOx and PAA was determined as mass ratio of 1:1.5 for applications in aqueous two phase system. The mixtures of the polymers formed aqueous two phase system with dextran solution after the breakage of hydrogen bondings. This properties can be used for the recovery of valuable products.

• Journal of the Semiconductor & Display Technology
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• v.7 no.1
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• pp.41-45
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• 2008

We studied the electrical characteristics of low-k SiOCR interlayer dielectric(ILD) films fabricated by plasma enhanced chemical vapor deposition (PECVD). The precursor bis-trimethylsilylmethane (BTMSM) was introduced into the reaction chamber with the various flow rates. The absorption intensities of Si-O-$CH_x$, bonding group and Si-$CH_x$, bonding group changed synchronously for the variation of precursor flow rate, but the intensity of Si-O-Si(C) responded asynchronously with the $CH_x$, combined bonds. The SiOCH films revealed ultra low dielectric constant around 2.1(1) and reduced further below 2.0 by heat treatments.