• 제목/요약/키워드: O-O bond formation

검색결과 138건 처리시간 0.025초

Chemical Reactivity of Ti+ within Water, Dimethyl Ether, and Methanol Clusters

  • Koo, Young-Mi;An, Hyung-Joon;Yoo, Seoung-Kyo;Jung, Kwang-Woo
    • Bulletin of the Korean Chemical Society
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    • 제24권2호
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    • pp.197-204
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    • 2003
  • The intracluster ion-molecule reactions of $Ti^+(H_2O)_n,\;Ti^+(CH_3OCH_3)_n,\;and\;Ti^+(CH_3OD)_n$ complexes produced by the mixing of the laser-vaporized plasma and the pulsed supersonic beam were studied using a reflectron time-of-flight mass spectrometer. The reactions of $Ti^+$ with water clusters were dominated by the dehydrogenation reaction, which produces $TiO^+(H_2O)_n$ clusters. The mass spectra resulting from the reactions of $Ti^+\;with\;CH_3OCH_3$ clusters exhibit a major sequence of $Ti^+(OCH_3)_m(CH_3OCH_3)_n$ cluster ions, which is attributed to the insertion of $Ti^+$ ion into C-O bond of $CH_3OCH_3$ followed by $CH_3$ elimination. The prevalence of $Ti^+(OCH_3)_m(CH_3OD)_n$ ions in the reaction of $Ti^+\;with\;CH_3OD$ clusters suggests that D elimination via O-D bond insertion is the preferred decomposition pathway. In addition, the results indicate that consecutive insertion reactions by the $Ti^+$ ion occur for up to three precursor molecules. Thus, examination of $Ti^+$ insertion into three different molecules establishes the reactivity order: O-H > C-O > C-H. The experiments additionally show that the chemical reactivity of heterocluster ions is greatly influenced by cluster size and argon stagnation pressure. The reaction energetics and formation mechanisms of the observed heterocluster ions are also discussed.

Fabrication of Mullite-Bonded Porous SiC Using Ti3AlC2 MAX Phase

  • Septiadi, Arifin;Yoon, Dang-Hyok
    • 한국세라믹학회지
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    • 제56권2호
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    • pp.191-196
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    • 2019
  • This study assessed the feasibility of a Ti3AlC2 MAX phase as an Al-source for the formation of a mullite bond in the fabrication of porous SiC tubes with high strength. The as-received Ti3AlC2 was partially oxidized at 1200℃ for 30 min before using to minimize the abrupt volume expansion caused by oxidation during sintering. Thermal treatment at 1100-1400℃ for 3 h in air led to the formation of Al2O3 by the decomposition of Ti3AlC2, which reacted further with oxidation-derived SiO2 on the SiC surface to form a mullite phase. The fabricated porous SiC tubes with a relative density of 48 - 62 % exhibited mechanical strengths of 80 - 200 MPa, which were much higher than those with the Al2O3 filler material. The high mechanical strength of the Ti3AlC2-added porous SiC was explained by the rigid mullite neck formation along with the retained Ti3AlC2 with good mechanical properties.

산업부산물을 첨가한 MgO 기반 모르타르의 기초물성 및 수화특성에 관한 연구 (Fundamental Properties and Hydration Characteristics of Mortar Based on MgO Added Industrial By-products)

  • 홍성걸;김도영;이동식
    • 콘크리트학회논문집
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    • 제25권5호
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    • pp.565-572
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    • 2013
  • CBPC(chemically-bonded phosphate ceramic) 바인더는 사소 MgO와 인산의 강력한 산-염기 반응을 이용한 초속경 보수재료로서, 시멘트와는 달리 CaO의 함량을 10% 이하로 줄인 재료이다. 이번 실험에서는 CBPC 바인더에 천연광물 및 산업부산물로 이뤄진 6가지 충전재들을 첨가하고 물리적 성능 및 수화 반응을 관찰하였다. 실리카퓸을 첨가한시편이 압축강도 및 동탄성계수가 상대적으로 높았고, 특히 장기강도 면에서 뚜렷한 증가율을 보였다. 또한 XRD 분석을 통해 실리카퓸을 첨가한 시편에서 마그네슘의 수화물인 M-S-H gel and $MgCO_3$ 피크를 관찰 할 수 있었다. 칼슘 성분이 다량 포함된 충전재를 넣은 시편의 경우 강도 및 내구성 면에서 좋지 않은 결과를 낳은 것으로 보아, 칼슘과 마그네슘 수화물은 서로 화학적으로 결합하지 않으므로 섞지 않는 것이 좋다는 결론을 도출했다. 결과적으로 MgO를 기반으로 하는 모르타르에는 순수하게 실리카 성분으로만 이루어진 실리카 흄과 같은 충전재가 알맞은 것으로 나타났다.

Emulsion Properties of Pseudo-Ceramide PC104/Water/Polyoxyethylene Cholesteryl Ether and Polyoxyethylene Cetyl Ether Mixtures.

  • Kim, Do-Hoon;Oh, Seong-Geun;Lee, Young-Jin;Kim, Youn-Joon;Kim, Han-Kon;Kang, Hak-Hee
    • 대한화장품학회:학술대회논문집
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    • 대한화장품학회 2003년도 IFSCC Conference Proceeding Book II
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    • pp.330-342
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    • 2003
  • The formation of emulsions and micelles in water/ceramide PC104/CholE $O_{20}$/C$_{16}$E $O_{20}$ and water/ceramide PC104/CholE $O_{20}$ mixtures was investigated through the phase behavior studies. The phase diagrams showed the existence of micelle and emulsion regions in both systems. The mixed surfactant system (CholE $O_{20}$/C$_{16}$E $O_{20}$) showed the wider micellar and emulsion regions than the single surfactant system (CholE $O_{20}$). From FT-IR measurements, it was found that the polyoxyethylene (POE) groups of surfactants formed the hydrogen bonds with amido carbonyl group in ceramide PC104. This result indicated that the hydrophilic part (EO) of surfactants could stabilize the lamellar structure and emulsion of ceramide PC104. The mixed surfactant system (CholE $O_{20}$/C$_{16}$E $O_{20}$) resulted in the smaller emulsion droplet size due to the effect of curvature at the interface, thus further increasing emulsion stability. With the penetration of $C_{16}$E $O_{20}$into the interfacial layer of surfactants in emulsion, the curvature of the interface might be altered for the formation of smaller emulsion droplets. The mixed surfactant system could incorporate up to 4 wt. % of ceramide PC104 into emulsion more than single surfactant system.ystem.m.

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TiO2 나노 입자를 이용한 상온건조용 항균 코팅 (Formation of Antibacterial Film dried at Room Temperature using nano-sized TiO2 Particle)

  • 최영진;김동규;김인수
    • 대한금속재료학회지
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    • 제48권5호
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    • pp.401-409
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    • 2010
  • This study was performed to develop an antibacterial film that can be dried at room temperature. A nanosized TiO$_2$ particle-dispersed solution was prepared by the hydrothermal treatment of peroxo-titanic acid at 160${^{\circ}C}$ for 4h. The binder was synthesized through the hydrolysis and condensation reactions of TEOS (10cc) and GPTS (3.5cc) in the mixture of H$_2$O (30cc) and EtOH (30cc). The synthesized binder was mixed with 0.1 M of TiO$_2$ solution in a volume ratio of binder/TiO$_2$ solution=0.25~0.5. The glass substrate was coated after using the dip coating method, which was then followed by drying for over 2h at room temperature. Although the TiO$_2$ particles did not chemically-bond to the binder, the coating layer strongly adhered to the substrate and displayed good antibacterial properties.

Epitaxial growth of yttrium-stabilized HfO$_2$ high-k gate dielectric thin films on Si

  • Dai, J.Y.;Lee, P.F.;Wong, K.H.;Chan, H.L.W.;Choy, C.L.
    • E2M - 전기 전자와 첨단 소재
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    • 제16권9호
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    • pp.63.2-64
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    • 2003
  • Epitaxial yttrium-stabilized HfO$_2$ thin films were deposited on p-type (100) Si substrates by pulsed laser deposition at a relatively lower substrate temperature of 550. Transmission electron microscopy observation revealed a fixed orientation relationship between the epitaxial film and Si; that is, (100)Si.(100)HfO$_2$ and [001]Si/[001]HfO$_2$. The film/Si interface is not atomically flat, suggesting possible interfacial reaction and diffusion, X-ray photoelectron spectrum analysis also revealed the interfacial reaction and diffusion evidenced by Hf silicate and Hf-Si bond formation at the interface. The epitaxial growth of the yttrium stabilized HfO$_2$ thin film on bare Si is via a direct growth mechanism without involoving the reaction between Hf atoms and SiO$_2$ layer. High-frequency capacitance-voltage measurement on an as-grown 40-A yttrium-stabilized HfO$_2$ epitaxial film yielded an dielectric constant of about 14 and equivalent oxide thickness to SiO$_2$ of 12 A. The leakage current density is 7.0${\times}$ 10e-2 A/$\textrm{cm}^2$ at 1V gate bias voltage.

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Cu/CeO2 촉매의 구조적 특성이 일산화탄소 저온 산화반응에 미치는 영향 연구 (A Study on the Influence of the Structural Characteristics of Cu/CeO2 Catalyst on the Low-Temperature Oxidation of Carbon Monoxide)

  • 김민수;최경륜;김세원;홍성창
    • 청정기술
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    • 제26권4호
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    • pp.286-292
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    • 2020
  • 본 연구는 Cu/CeO2-X 촉매의 저온 CO 산화 활성에 미치는 영향을 촉매의 구조적 특성, 반응 특성을 통해 확인하였다. 사용된 촉매는 습윤 함침법으로 제조되었으며, 각기 다른 소성온도(300~600 ℃)에서 형성된 CeO2 (지지체)를 이용하여 Cu (활성금속)를 담지함으로써 Cu/CeO2-X 촉매를 제조하였다. 제조된 Cu/CeO2-X 촉매는 저온 CO 산화 활성을 평가하였다. 125 ℃에서 Cu/CeO2_300 촉매는 90% 이상의 활성을 나타냈으며, CeO2의 소성온도가 증가됨에 따라 활성이 점차 감소하여, Cu/CeO2_600 촉매는 65%를 나타냈다. 다음으로 촉매의 물리/화학적 특성을 Raman, BET, XRD, H2-TPR, XPS 분석으로 확인하였다. XPS 분석 결과, CeO2-X의 소성온도가 낮을 수록 불안정한 Ce3+ 종(비 화학양론 종) 비율이 증가하였다. 증가된 Ce3+종은 Cu와 결합함으로 써 치환결합을 형성하였으며 Raman 분석의 CeO2 peak 변화와 H2-TPR 분석의 치환결합 구조의 환원 peak를 통해 확인하였다. 결과적으로 Cu와 CeO2의 치환 결합 형성은 촉매의 redox 특성 및 저온 CO 산화 활성을 증진시켰다고 판단된다.

카르보닐탄소원자의 친핵성 치환반응 (제9보). 이성분 혼합용매에서 2-염화테노일 및 2-염화퓨로일의 가용매분해반응 (Nucleophilic Substitution at a Carbonyl Carbon Atom (IX). Solvolysis of 2-Furoyl Chloride and 2-Thenoyl Chloride in Binary Mixtures)

  • 손진언;윤상기;이익춘
    • 대한화학회지
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    • 제23권6호
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    • pp.339-348
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    • 1979
  • 물-메탄올, 물-에탄올, 물-아세트니틜, 물-아세톤 및 아세트니트릴-메탄올의 2성분 혼합용매에서 2-염화테노일 및 2-염화퓨로일의 가용매분해 반응을 속도론적으로 연구하였다. 반응 속도는 반양성자성 용매에서 보다 양성자성 용매에서 더 빨랐으며 이것은 양성자성용매의 수소결합능력이 이탈기의 결합의 파괴를 돕기 때문이다. 그러나 아세트니트릴-메탄올 혼합용매에서는 특수용매화가 일어나며, 메탄올 몰분율 0.8부근에서 최대속도를 나타낸다. 또한 이 반응은 염화벤조일보다 느리며 그 속도 순서는 염화벤조일 > 2-염화테노일 > 2-염화퓨로일이며 이 중에서 퓨란고리의 전자흡인성이 제일 강함으로 전이상태에서 결합의 파괴가 어려워져서 반응속도가 늦어지는 것이다. 반응메카니즘은 전이상태에서 결합의 파괴가 결합의 형성보다 많이 진행된 dissociative $S_N2$ 반응이기는 하나 2-염화테노일은 물 함량이 많은 부분에서는 $S_N1$ 성겨기 꽤 크고 $S_N2$ 성격이 약화된다.

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Reactions of 4-Nitrophenyl 2-Thiophenecarboxylates with R2NH/R2NH2+ in 20 mol % DMSO (aq). Effects of 5-Thienyl Substituent and Base Strength

  • Pyun, Sang Yong;Cho, Bong Rae
    • Bulletin of the Korean Chemical Society
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    • 제34권7호
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    • pp.2036-2040
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    • 2013
  • Reactions of 4-nitrophenyl 2-thiophenecarboxylate (1a-e) with $R_2NH/R_2NH{_2}^+$ in 20 mol % DMSO (aq) have been studied kinetically. The $2^{nd}$ order kinetics, ${\beta}_{nuc}$ = 0.88-0.98, and linear Hammett and Yukawa-Tsuno plots observed for these reactions indicate an addition-elimination mechanism in which the $2^{nd}$ step is rate limiting. The ${\beta}_{nuc}$ value increased with a stronger electron-withdrawing 5-thienyl substituent, the Hammett plots are linear except for X = MeO, and Yukawa-Tsuno plots are linear with ${\rho}$ = 0.79-1.32 and r = 0.28-0.93, respectively. The ${\rho}$ value increased and r value decreased with a stronger nucleophile, indicating an increase in the electron density at the C=O bond and a decrease in the resonance demand. These results have been interpreted with enhanced N-C bond formation in the transition state with the reactivity increase.

Kinetics and Mechanism of the Pyridinolysis of Methyl Phenyl Phosphinic Chloride in Acetonitrile

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.1945-1950
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    • 2011
  • The pyridinolysis of methyl phenyl phosphinic chloride is investigated kinetically in acetonitrile at -20.0 $^{\circ}C$. The Hammett and Br${\o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave downwards with a break point at X = H, and unusual positive ${\rho}_X$ (= 2.94) and negative ${\beta}_X$ (= -0.48) values are obtained for the strongly basic nucleophiles. A stepwise mechanism with a rate-limiting step change from bond breaking for the weakly basic pyridines to bond formation for the strongly basic pyridines is proposed on the basis of biphasic concave downward Hammett and Br${\o}$nsted plots. Unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are rationalized by the isokinetic relationship. The pyridinolyses and anilinolyses of four $R_1R_2$P(=O)Cl-type substrates, dimethyl, diethyl, methyl phenyl, and diphenyl phosphinic chlorides in acetonitrile are compared to obtain systematic information on phosphoryl transfer reaction mechanism. The combination of the two ligands, Me and Ph, shows unexpected kinetic results for both the anilinolysis and pyridinolysis: greatest magnitude of $k_H/k_D$ (= 2.10) involving deuterated anilines $[XC_6H_4NH_2(D_2)]$ for the anilinolysis, and exceptionally fast rate and biphasic concave downward free energy correlation for the pyridinolysis.