• Title/Summary/Keyword: secondary bonding

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Kinetic Isotope Effects Involving Deuterated Benzylamine Nucleophiles

  • Lee, Ik-Choon;Koh, Han-Joong;Sohn, Dong-Sook;Lee, Byung-Choon
    • Bulletin of the Korean Chemical Society
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    • v.12 no.1
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    • pp.101-103
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    • 1991
  • The kinetic isotope effects (KIE) are determined for the reactions of benzyl benzenesulfonates (BBS), ethyl benzenesulfonates (EBS) and phenacyl benzensulfonates (PAB) with deuterated benzylamine nucleophiles. The inverse secondary ${\alpha}$-deuterium KIE observed were somewhat smaller than those for the corresponding reactions with aniline nucleophiles. The primary $KIE_s$ obtained with PAB were slightly greater than those for the corresponding reactions with anilines, which suggested that the inverse secondary KIE is decreased due to a relatively earlier transition state for bond-making with little change in the hydrogen bonding strength to the carbonyl oxygen.

Manufacturing of an All Composite Unmanned Aerial Vehicle (전기체 복합재 무인항공기 제작)

  • 김동민;허명규;강공진
    • Proceedings of the Korean Society For Composite Materials Conference
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    • 2002.05a
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    • pp.163-166
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    • 2002
  • For the development of an all composite unmanned aerial vehicle (UAV), manufacturing consideration in design phase, works for composite parts fabrication, subassembly and final assembly are summarized. In design phase, to maximize the advantage of composite material, manufacturing processes such as cocuring, cobonding and secondary bonding are introduced. For the curing of designed parts, composite tools are designed and manufactured. Assembly jigs are designed to satisfy dimensional tolerance of the structure. Inspection criteria are established and applied to the manufacturing. Technical data about inspection items and methods are summarized as manufacturing specifications for the mass production of the UAV structure.

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Kinetics and Reaction Mechanism of Aminolyses of Benzyl 2-Pyridyl Carbonate and t-Butyl 2-Pyridyl Carbonate: Effect of Nonleaving Group on Reactivity and Reaction Mechanism

  • Kang, Ji-Sun;Lee, Jae-In;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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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.

Aminolysis of Benzyl 4-Pyridyl Carbonate in Acetonitrile: Effect of Modification of Leaving Group from 2-Pyridyloxide to 4-Pyridyloxide on Reactivity and Reaction Mechanism

  • Bae, Ae-Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2719-2723
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    • 2012
  • A kinetic study is reported for nucleophilic substitution reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in MeCN. The plot of pseudo-first-order rate constant ($k_{obsd}$) vs. [amine] curves upward, which is typical for reactions reported previously to proceed through a stepwise mechanism with two intermediates (i.e., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). Dissection of $k_{obsd}$ into the second- and third-order rate constants (i.e., $Kk_2$ and $Kk_3$, respectively) reveals that $Kk_3$ is significantly larger than $Kk_2$, indicating that the reactions proceed mainly through the deprotonation pathway (i.e., the $k_3$ process) in a high [amine] region. This contrasts to the recent report that the corresponding aminolysis of benzyl 2-pyridyl carbonate 5 proceeds through a forced concerted mechanism. An intramolecular H-bonding interaction was suggested to force the reactions of 5 to proceed through a concerted mechanism, since it could accelerate the rate of leaving-group expulsion (i.e., an increase in $k_2$). However, such H-bonding interaction, which could increase $k_2$, is structurally impossible for the reactions of 6. Thus, presence or absence of an intramolecular H-bonding interaction has been suggested to be responsible for the contrasting reaction mechanisms (i.e., a forced concerted mechanism for the reaction of 5 vs. a stepwise mechanism with $T^{\pm}$ and $T^-$ as intermediates for that of 6).

The Efficient Detection Algorithm of Various CR signals using Channel Bonding in TV White Space (TV White Space에서 채널 본딩된 다양한 CR 시스템의 효율적인 검출 알고리즘)

  • Lim, Sun-Min;Jung, Hoi-Yoon;Jeong, Byung-Jang
    • The Journal of Korean Institute of Communications and Information Sciences
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    • v.36 no.5A
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    • pp.536-542
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    • 2011
  • For efficient utilization of spectrum resources in TV white space after DTV transition, FCC allowed usage of the spectrum for CR system. The CR system is required to cognize channel usage state for utilizing the unused spectrum in TV white space which coexists various primary and secondary systems. In the meantime, as a demand for high throughput communication had been increased recently, CR systems also consider to adopt channel bonding technology, thus spectrum sensing for channel bonded system is essentially required. In this paper, we propose a novel spectrum sensing algorithm for channel bonding system using a single channel receiver. For IEEE 802.l1af signal, the proposed algorithm provide detection probability of 90% with false alarm probability 10% at SNR -18dB for single channel system and at SNR -7dB for 8 channel bonded system, respectively. Utilizing the proposed scheme, we can detect channel bonded signal using only a single receiver, therefore system overhead for spectrum sensing can be reduced significantly.

Effect of modifying the thickness of the plate at the level of the overlap length in the presence of bonding defects on the strength of an adhesive joint

  • Attout Boualem;Sidi Mohamed Medjdoub;Madani Kouider;Kaddouri Nadia;Elajrami Mohamed;Belhouari Mohamed;Amin Houari;Salah Amroune;R.D.S.G. Campilho
    • Advances in aircraft and spacecraft science
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    • v.11 no.1
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    • pp.83-103
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    • 2024
  • Adhesive bonding is currently widely used in many industrial fields, particularly in the aeronautics sector. Despite its advantages over mechanical joints such as riveting and welding, adhesive bonding is mostly used for secondary structures due to its low peel strength; especially if it is simultaneously exposed to temperature and humidity; and often presence of bonding defects. In fact, during joint preparation, several types of defects can be introduced into the adhesive layer such as air bubbles, cavities, or cracks, which induce stress concentrations potentially leading to premature failure. Indeed, the presence of defects in the adhesive joint has a significant effect on adhesive stresses, which emphasizes the need for a good surface treatment. The research in this field is aimed at minimizing the stresses in the adhesive joint at its free edges by geometric modifications of the ovelapping part and/or by changing the nature of the substrates. In this study, the finite element method is used to describe the mechanical behavior of bonded joints. Thus, a three-dimensional model is made to analyze the effect of defects in the adhesive joint at areas of high stress concentrations. The analysis consists of estimating the different stresses in an adhesive joint between two 2024-T3 aluminum plates. Two types of single lap joints(SLJ) were analyzed: a standard SLJ and another modified by removing 0.2 mm of material from the thickness of one plate along the overlap length, taking into account several factors such as the applied load, shape, size and position of the defect. The obtained results clearly show that the presence of a bonding defect significantly affects stresses in the adhesive joint, which become important if the joint is subjected to a higher applied load. On the other hand, the geometric modification made to the plate considerably reduces the various stresses in the adhesive joint even in the presence of a bonding defect.

Strength of Composit Single-lap Bonded Joints with Different Saltwater Moisture Contents (서로 다른 수분율을 갖도록 염수환경에 노출된 복합재 접착체결부의 강도)

  • Yang, Hyeon-Jeong;Jeong, Mun-Gyu;Kweon, Jin-Hwe;Choi, Jin-Ho
    • Composites Research
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    • v.24 no.4
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    • pp.48-54
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    • 2011
  • The effect of moisture contents by salt water on the strength of composite single-lap bonded joints is investigated. The specimens were manufactured in an autoclave by secondary bonding and immersed in the 3.5% salt water of $71^{\circ}C$ for different durations to get various moisture contents; 0, 0.2, 0.5, 1.0, and 2.0%(saturation). A total of 80 joint specimens were tested for 5 different moisture contents and 2 temperature environments. Test results show that while the joint strengths after the saturation of moisture decrease compared to those of dry ones, the strengths of the pre-saturated joint up to 1.0% of moisture content increase in both room and elevated temperature conditions. It is also shown that the strengths of joints tested in elevated temperature are slightly higher than the strength in room temperature by 2-5% until the moisture content reaches 1 %. In contrast, the high temperature strength of the saturated joint is about 5% lower than the room temperature strength.

Strength of Composite Single-Lap Bonded Joints with Various Manufacturing Processes for Aircraft Application (항공용 복합재 단일겹침 접착 체결부의 제작공정에 따른 강도 연구)

  • Song, Min-Gyu;Kweon, Jin-Hwe;Choi, Jin-Ho;Kim, Hyo-Jin;Song, Min-Hwan;Shin, Sang-Joon
    • Journal of the Korean Society for Aeronautical & Space Sciences
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    • v.37 no.8
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    • pp.751-758
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    • 2009
  • Failure strengths of composite single-lap adhesive joints were investigated with various parameters such as manufacturing method, overlap length and adherend thickness. A total of 335 single-lap joint specimens were tested under tension. Specimens were fabricated with 4 different manufacturing processes; cocuring without and with adhesive, secondary bonding and co-bonding. Each manufacturing process has 5 different overlap lengths and 4 different thicknesses, respectively. As expected, failure strength is higher in thicker adherend joints and lower in larger overlap length specimens. Interesting result is that the secondary bonded joints show the higher strength than the cobonded and cocured joints with adhesive, and give close or even higher strength compared with non-adhesive cocured case.

Silver Colloidal Effects on Excited-State Structure and Intramolecular Charge Transfer of p-N,N-dimethylaminobenzoic Acid Aqueous Cyclodextrin Solutions

  • Choe, Jeong Gwan;Kim, Yang Hui;Yun, Min Jung;Lee, Seung Jun;Kim, Gwan;Jeong, Sae Chae
    • Bulletin of the Korean Chemical Society
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    • v.22 no.2
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    • pp.219-227
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    • 2001
  • The silver colloidal effects on the excited-state structure and intramolecular charge transfer (ICT) of p-N,N-dimethylaminobenzoic acid (DMABA) in aqueous cyclodextrin (CD) solutions have been investigated by UV-VIS absorption, steady-state and time-resolved fluorescence, and transient Raman spectroscopy. As the concentration of silver colloids increases, the ratio of the ICT emission to the normal emission (Ia /Ib) of DMABA in the aqueous $\alpha-CD$ solutions are greatly decreased while the Ia /Ib values in the aqueous B-CD solutions are significantly enhanced. It is also noteworthy that the ICT emission maxima are red-shifted by 15-40 nm upon addition of silver colloids, implying that DMABA encapsulated in $\alpha-CD$ or B-CD cavity is exposed to more polar environment. The transient resonance Raman spectra of DMABA in silver colloidal solutions demonstrate that DMABA in the excited-state is desorbed from silver colloidal surfaces as demonstrated by the disappearance of νs (CO2-)(1380 cm-1 ) with appearance of ν(C-OH)(1280 cm -1) band, respectively. Thus, in the aqueous B-CD solutions the carboxylic acid group of DMABA in the excited-state can be readily hydrogen-bonded with the secondary hydroxyl group of B-CD while in aqueous and $\alpha-CD$ solutions the carboxylic acid group of DMABA has the hydrogen-bonding interaction with water. Consequently, in the aqueous B-CD solutions the enhancement of the Ia /Ia value arises from the intermolecular hydrogen-bonding interaction between DMABA and the secondary hydroxyl group of B-CD as well as the lower polarity of the rim of the B-CD cavity compared to bulk water. This is also supported by the increase of the association constant for DMABA/ B-CD complex in the presence of silver colloids.

Photovoltaic performance evaluation of the bonded single crystalline silicon solar cell on composite specimens under mechanical loading (기계적 하중 하에서 복합재료 시험편에 접착된 단결정 실리콘태양전지의 성능평가)

  • Kim, Jong-Cheon;Choi, Ik-Hyeon;Kim, Dae-Hyun;Jeong, Seong-Kyun
    • Composites Research
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    • v.24 no.6
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    • pp.56-63
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    • 2011
  • The objective of this study is to investigate appropriate bonding methods of solar cells in order to apply solar cells, which have been receiving particular attention as a renewable energy due to fossil energy depletion and environment issues, to composite structures. Back-contact solar cells with approximately 24.2% energy conversion efficiency were used in this study. Since silicon-based solar cells are mechanically fragile, the secondary-bonding methods using adhesive were examined in this study. The experiment was conducted with three kinds of bonding materials such as EVA film, Resin film and elastic adhesive. The performance of solar cells for three types of adhesives under mechanical loading on test specimens is conducted. In addition, the measuring equipment was designed to evaluate the performance of the solar cells under mechanical loading in real time and the fracture characteristics depending on bonding materials were evaluated. The reason decreasing solar cells efficiency were analyzed and considered by Fractography. The results show that the solar cell performance is largely affected by bonding techniques. Moreover, the bonding method using elastic adhesive shows best solar cell efficiency.