• 제목/요약/키워드: bond mechanism

검색결과 463건 처리시간 0.024초

아세토니트릴-메탄올 혼합용매계에서 질산벤질과 아닐린의 친핵성 치환반응 (Kinetic Studies on the Nucleophilic Reactions of Substituted Benzylnitrates with Anilines in $CH_3CN-CH_3OH$)

  • 손창국;김왕기;이수정;양기열
    • 대한화학회지
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    • 제34권3호
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    • pp.227-231
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    • 1990
  • 50-100% $CH_3CN-CH_3OH$ 혼합용매계에서 파라-치환된 질산벤질과 아닐린과의 친핵성 치환반응에 대한 2차 속도상수를 전기전도도법으로 구하였다. 속도자료를 이용하여 Hammett ${\rho}_N$${\rho}_C$값, Bronsted $\beta$값 및 용매화 파라미터 계수들을 구하였으며 이들을 PES및 양자역학 모형에 적용하여 구조 변화를 논의하였다. 연구 결과 결합형성보다 결합절단이 비교적 많이 진행된 상태에서 치환기 변화에 따라 결합절단의 진척이 결합형성을 촉진하는 동시적 $S_N2$ 반응메카니즘으로 진행됨을 알았다.

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HF 전처리시 실리콘 기판의 초기접합 메카니즘에 관한 연구 (A study on pre-bonding mechanism of Si wafer at HF pre-treatment)

  • 강경두;박진성;이채봉;주병권;정귀상
    • 대한전기학회:학술대회논문집
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    • 대한전기학회 1999년도 하계학술대회 논문집 G
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    • pp.3313-3315
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    • 1999
  • Si direct bonding(SDB) technology is very attractive for both Si-on-insulator(SOI) electric devices and MEMS applications because of its stress free structure and stability. This paper presents on pre-bonding according to HF pre-treatment conditions in Si wafer direct bonding. The characteristics of bonded sample were measured under different bonding conditions of HF concentration, and applied pressure. The bonding strength was evaluated by tensile strength method. The bonded interface and the void were analyzed by using SEM and IR camera respectively. A bond characteristic on the interface was analyzed by using IT- IR. Si-F bonds on Si surface after HF pre-treatment are replaced by Si-OH during a DI water rinse. Consequently, hydrophobic wafer was bonded by hydrogen bonding of Si $OH{\cdots}(HOH{\cdots}HOH{\cdots}HOH){\cdots}OH-Si$. The bond strength depends on the HF pre-treatment condition before pre- bonding (Min:$2.4kgf/crn^2{\sim}Max:14.9kgf/crn^2$)

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Improvement of the cyclic response of RC columns with inadequate lap splices-Experimental and analytical investigation

  • Kalogeropoulos, George I.;Tsonos, Alexander-Dimitrios G.
    • Earthquakes and Structures
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    • 제16권3호
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    • pp.279-293
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    • 2019
  • The overall seismic performance of existing pre 1960-70s reinforced concrete (RC) structures is significantly affected by the inadequate length of columns' lap-spliced reinforcement. Due to this crucial structural deficiency, the cyclic response is dominated by premature bond - slip failure, strength and stiffness degradation, poor energy dissipation capacity and low ductility. Recent earthquakes worldwide highlighted the importance of improving the load transfer mechanism between lap-spliced bars, while it was clearly demonstrated that the failure of lap splices may result in a devastating effect on structural integrity. Extensive experimental and analytical research was carried out herein, to evaluate the effectiveness and reliability of strengthening techniques applied to RC columns with lap-spliced reinforcement and also accurately predict the columns' response during an earthquake. Ten large scale cantilever column subassemblages, representative of columns found in existing pre 1970s RC structures, were constructed and strengthened by steel or RC jacketing. The enhanced specimens were imposed to earthquake-type loading and their lateral response was evaluated with respect to the hysteresis of two original and two control subassemblages. The main variables examined were the lap splice length, the steel jacket width and the amount of additional confinement offered by the jackets. Moreover, an analytical formulation proposed by Tsonos (2007a, 2019) was modified appropriately and applied to the lap splice region, to calculate shear stress developed in the concrete and predict if yielding of reinforcement is achieved. The accuracy of the analytical method was checked against experimental results from both the literature and the experimental work included herein.

Optimal pressure and temperature for Cu-Cu direct bonding in three-dimensional packaging of stacked integrated circuits

  • Seunghyun Yum;June Won Hyun
    • 한국표면공학회지
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    • 제56권3호
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    • pp.180-184
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    • 2023
  • Scholars have proposed wafer-level bonding and three-dimensional (3D) stacked integrated circuit (IC) and have investigated Cu-Cu bonding to overcome the limitation of Moore's law. However, information about quantitative Cu-Cu direct-bonding conditions, such as temperature, pressure, and interfacial adhesion energy, is scant. This study determines the optimal temperature and pressure for Cu-Cu bonding by varying the bonding temperature to 100, 150, 200, 250, and 350 ℃ and pressure to 2,303 and 3,087 N/cm2. Various conditions and methods for surface treatment were performed to prevent oxidation of the surface of the sample and remove organic compounds in Cu direct bonding as variables of temperature and pressure. EDX experiments were conducted to confirm chemical information on the bonding characteristics between the substrate and Cu to confirm the bonding mechanism between the substrate and Cu. In addition, after the combination with the change of temperature and pressure variables, UTM measurement was performed to investigate the bond force between the substrate and Cu, and it was confirmed that the bond force increased proportionally as the temperature and pressure increased.

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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개선된 부착슬립 모델을 적용한 부분 CFST 기둥의 수치해석 (Numerical Approach for a Partial CFST Column using an Improved Bond-Slip Model)

  • 황주영;곽효경
    • 한국전산구조공학회논문집
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    • 제33권3호
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    • pp.153-158
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    • 2020
  • 본 논문에서는 부분 CFST (concrete-filled steel tube) 기둥에 대한 수치해석적 저항력 평가 방법에 대해 소개하고 있다. 기존 RC(reinforced concrete) 기둥에서 소성힌지가 발생할 것으로 예상되는 부분을 강관으로 보강함으로써 완전 CFST 기둥보다는 적은 재료를 사용하여 비슷한 휨 모멘트 저항력을 가지는 부분 CFST 기둥의 디자인 컨셉을 제시하였다. 부분 CFST 기둥에서 외부 강관과 내부 콘크리트 사이의 계면에서 거동을 수치해석적으로 모사하기 위해 개선된 부착슬립모델을 적용한 유한요소모델을 구축하고, 이중곡률 휨-압축시험결과와 비교를 통해 타당성을 검증하였다. 검증된 수치모델을 바탕으로 매개변수 연구를 통해서 P-M 상관도를 그려 단면 조건에 따른 최대 저항력을 평가하였다. 또한, 강관 두께별로 필요 보강길이를 산출하고, 보강 조건에 따른 부분 CFST 기둥에서의 파괴메커니즘을 분석하였다.

Anomalous Behavior of the Ethyl Group in the Aminolysis of S-Phenyl Acetate with Benzylamine in Acetonitrile

  • Lee, Ik-Choon;Lee, Hai-Whang;Lee, Byung-Choon;Choi, Jin-Heui
    • Bulletin of the Korean Chemical Society
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    • 제23권2호
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    • pp.201-204
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    • 2002
  • The rates of the aminolysis of S-phenyl substituted-acetate series $(RC(=O)SC_6H_4Z$, with R=Me, Et, i-Pr, t-Bu and Bn) with benzylamines $(XC_6H_4CH_2NH_2)$ are not correlated simply with the Taft's polar $({\sigma}^{\ast})$ and/or steric effect constants $(E_s)$ of the substituents due to abnormally enhanced rate of the substrate with R=Et. Furthermore, the cross-interaction constant, ${\rho}x_z$ , is the largest with R=Et. These anomalous behaviors can only be explained by invoking the vicinal bond $({\sigma})$-antibond $({\sigma}^{\ast})$ charge transfer interaction between C-$C{\alpha}$ and C-S bonds. In the tetrahedral zwitterionic intermediate, $T^{\pm}$ , formed with R=Et the vicinal ${\sigma}_{c-c}-{\sigma}^{\ast}_{c-s}$ delocalization is the strongest with an optimum antiperiplanar arrangement and a narrow energy gap, ${\Delta}{\varepsilon}={\varepsilon}_{{\sigma}^{\ast}}-{\varepsilon}_{\sigma}$. Due to this charge transfer interaction, the stability of the intermediate increases (with the concomitant increase in the equilibrium constant K (= $k_a/k_{-a}$)) and also the leaving ability of the thiophenolate leaving group increases (and hence $k_b$ increases) so that the overall rate, $k_n\;=\;Kk_b$, is strongly enhanced. Theoretical support is provided by the natural bond orbital (NBO) analyses at the B3LYP/6-31+$G^{\ast}$ level. The anomaly exhibited by R=Et attests to the stepwise reaction mechanism in which the leaving group departure is rate limiting.

소수성 파라메터를 적용한 알킬벤젠류의 역상컬럼내의 용출거동 예측 (Prediction of Retention Behavior of Alkyl Benzenes by Hydrophobicity Parameters in Reversed-Phase Column)

  • 이창영;박명용;이용문
    • 약학회지
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    • 제53권5호
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    • pp.281-285
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    • 2009
  • The retention of solutes in reversed-phase high-performance liquid chromatography depends on their hydrophobicity. Although the retention behaviors of alkyl benzenes have been reported so far, quite a few authors have mentioned the retention behavior of alkyl benzenes with plural hydrophobicity parameters. In this sense, we were interested in the retention behaviors of alkyl benzenes having benzene moiety and increasing alkyl chain. In this study, we therefore investigated the retention behavior of alkyl benzenes in reversed-phase high-performance liquid chromatography in order to obtain information concerning the effects of the aromatic moiety and the carbon chain on the retention mechanism by comparing their capacity factor (k') in relation to the carbon chain length. The eluent acetonitrile ($CH_3CN$) showed high selectivity on alkyl benzenes, showing the high difference of capacity factor (${\Delta}log\;k'$) between toluene and octyl benzene. Indeed, the ${\Delta}log\;k'$ of 80% $CH_3CN$ represented 1.42- and 4.25-times longer than 90% MeOH and 60% THF, respectively. The hydrophobicity parameters, van der Waals volume, bond constant, partition constant, $\pi$-energy effect and enthalpy were evaluated with the capacity factor (k') of alkyl benzenes eluted on 80% CH3CN, 90% MeOH and 60% THF, respectively. The best eluent for predicting retention behavior of alkyl benzenes was 90% MeOH ($R^2$ 0.999). The three parameters, van der Waals volume, bond constant and partition constant were well coincident to log k' by increasing alkyl benzenes. However, $\pi$-energy effect and enthalpy were severely disagreeable. Taken together, van der Waals volume, bond constant and partition constant were a reliable parameters to predict the retention behaviors of alkyl benzenes on reversed-phase column.

S-Phenyl-S-vinyl-N-p-tosylsulfilimine 유도체에 대한 Thioglycolic Acid의 친핵성 첨가반응에 관한 반응속도론적 연구 (Kinetic Studies on the Nucleophilic Addition of Thioglycolic Acid to S-Phenyl-S-vinyl-N-p-tosylsulfilimine Derivatives)

  • 김태린;한만소;편상용
    • 대한화학회지
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    • 제40권10호
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    • pp.663-669
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    • 1996
  • Vinylsulfilimine(VSI) 유도체($p-OCH_3$, H, p-Cl 및 p-Br)에 대한 thioglycolic acid의 친핵성 첨가반응속도를 자외선 분광법으로 측정하여 넓은 pH 범위에서 적용될 수 있는 속도식을 구하였다. pH에 따른 속도상수의 변화, general base 및 치환기 효과 등을 바탕으로 반응 메카니즘을 제안하였다. 즉 pH3.0 이하에서는 sulfilimine의 질소에 양성자가 먼저 첨가된 다음 중성 thioglycolic acid 분자가 탄소 이중결합에 첨가되고, pH 3.0-9.0 영역에서 thioglycolic acid의 중성분자와 음이온의 첨가가 경쟁적으로 일어나며, pH 9.0 이상에서는 황화 음이온이 첨가되는 전형적인 Michael type의 반응이 진행됨을 알았다.

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${\beta}$-Nitrostyrene 유도체에 대한 Thiourea의 친핵성 첨가반응에 관한 반응속도론적 연구 (Kinetic Studies on the Nucleophilic Addition of Thiourea to ${\beta}$-Nitrostyrene Derivatives)

  • 김태린;정연수;정명숙
    • 대한화학회지
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    • 제35권3호
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    • pp.268-274
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    • 1991
  • ${\beta}$-nitrostyrene 유도체(p-H, p-Cl, p-CH$_3$, p-OCH$_3$, p-NO$_2$)에 대한 thiourea의 친핵성 첨가반응속도를 자외선 분광분석법으로 측정하여 pH에 따르는 반응속도 상수의 변화, general base 및 치환기 효과등으로부터 넓은 pH 범위에서 실험치와 잘 일치하는 반응속도식을 구하였고, 실험사실에 잘 맞는 반응 메카니즘을 제안하였다. 즉, pH 9.00 이상에서의 반응속도는 hydroxide ion의 농도에 비례하는 sulfide anion이 첨가되는 전형적인 Michael type의 반응이 일어나며, pH 9.00 ~ 7.00에서는 thiourea의 중성분자와 그의 anion들이 경쟁적으로 첨가되며 pH 7.00 이하에서는 thiourea의 중성분자만이 첨가됨을 알았다.

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