• Title/Summary/Keyword: bonding mechanism

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PAN based-based copolymer membranes for dehydration of water/pyridine mixture (물/피리딘 혼합물 분리용 PAN계 공중합막)

  • 박춘호;남상용;이영무
    • Proceedings of the Membrane Society of Korea Conference
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    • 1998.10a
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    • pp.73-74
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    • 1998
  • 1. Introduction : We have researched to separate water effectively from aqueous pyridine solution. In our previous papers, we have proposed new separation mechanism, in-situ complex, which is different from solution-diffusion and accelerated transport by hydrogen bonding. We have adopted in-situ complex mechanism to membranes containing phosphoric acids as well as acrylic acid and sulfonic acid in copolymer for dehydration of pyridine.

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Kinetics and Reaction Mechanism of Aminolyses of Benzyl 2-Pyridyl Carbonate and t-Butyl 2-Pyridyl Carbonate in Acetonitrile

  • Bae, Ae-Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1547-1550
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    • 2012
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of benzyl 2-pyridyl carbonate $\mathbf{3}$ and $t$-butyl 2-pyridyl carbonate $\mathbf{3}$ with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Substrate $\mathbf{4}$ is much less reactive than $\mathbf{3}$ and the steric hindrance exerted by the bulky $t$-Bu group in $\mathbf{4}$ has been attributed to its decreased reactivity. The Br${\o}$nsted-type plots for the reactions of $\mathbf{3}$ and $\mathbf{4}$ are linear with ${\beta}_{nuc}=0.57$ and 0.45, respectively. Thus, the reactions have been concluded to proceed through a concerted mechanism, although the current reactions were expected to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate $T^{\pm}$. It has been proposed that the rate of leaving-group expulsion is accelerated by the intramolecular H-bonding interaction in $T^{\pm}$ and the "push" provided by the RO group through the resonance interaction. Thus, the enhanced nucleofugality forces the reactions to proceed through a concerted mechanism. The reactivity-selectivity principle (RSP) is not applicable to the current reaction systems, since the reaction of the less reactive $\mathbf{4}$ results in a smaller ${\beta}_{nuc}$ than that of the more reactive $\mathbf{3}$. Steric hindrance exerted by the bulky $t$-Bu group in $\mathbf{4}$ has been suggested to be responsible for the failure of the RSP.

The α-Effect and Mechanism of Reactions of Y-Substituted Phenyl Benzenesulfonates with Hydrogen Peroxide Ion

  • Im, Li-Ra;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2393-2397
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    • 2009
  • Second-order rate constants ($k_{HOO}$‒) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted phenyl benzenesulfonates (1a-g) with $HOO^-$ ion in $H_2O$ at $25.0\;{\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot is linear with ${\beta}_{lg}$ = ‒0.73. The Hammett plot correlated with with ${\sigma}^-$ constants results in much better linearity than ${\sigma}^o$ constants, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS) either in a stepwise mechanism or in a concerted pathway. However, a stepwise mechanism in which departure of the leaving group occurs in the RDS has been excluded since $HOO^-$ ion is more basic and a poorer leaving group than the leaving Y-substituted phenoxide ions. Thus, the reactions of 1a-g with $HOO^-$ ion have been concluded to proceed through a concerted mechanism. The $\alpha$-nucleophile $HOO^-$ ion is more reactive than its reference nucleophile $OH^-$ ion although the former is ca. 4 p$K_a$ units less basic than the latter (i.e., the $\alpha$-effect). TS stabilization through intramolecular H-bonding interaction has been suggested to be irresponsible for the $\alpha$-effect shown by $HOO^-$ ion, since the magnitude of the $\alpha$-effect is independent of the electronic nature of substituent Y in the leaving group. GS destabilization through desolvation of $HOO^-$ ion has been concluded to be responsible for the $\alpha$-effect found in the this study.

AE Characteristics for Fracture Mechanism of Al 7075/CFRP Hybrid Composite (Al 7075/CFRP Hybrid 복합재료의 파손특성에 대한 AE 특성 연구)

  • 이진경;이준현;송상헌;윤한기
    • Proceedings of the Korean Society For Composite Materials Conference
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    • 2001.05a
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    • pp.268-271
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    • 2001
  • When compared to other composite materials such as FRP and MMC, hybrid composite material is more attractive one due to the high specific strength and the resistance to fatigue. However, the fracture mechanism of hybrid composite material is extremely complicated because of the bonding structure of metals and FRP. Recently, nondestructive technique has been used to evaluate the fracture mechanism of these composite materials. In this study, AE technique has been used to clarify the fracture mechanism and the degree of damage for Al 7075/CFRP hybrid composite material. It was found that AE event, energy and amplitude among AE parameters were effective to evaluate fracture process of Al 7075/CFRP composite material. In addition, the relationship between the AE signal and the characteristics of failure surface using optical microscope was discussed.

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Design of Magneto-Rheological Clutch Coil Operation Unit using Electro Magnetic Field Analysis (전자기장 해석을 이용한 자기점성 유체 클러치 코일 작동부 설계)

  • Song, Jun-Han;Choi, Dook-Hwan;Chun, Chong-Keun;Kwon, Young-Chul;Lee, Tae-Haeng
    • Transactions of the Korean Society of Automotive Engineers
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    • v.17 no.3
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    • pp.22-28
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    • 2009
  • Recently, there has been an active study about smart fluid to control the vibration, in which MR fluid is evaluated as most efficient because it can generate different bonding forces based on the intensity of the external magnetic fields. This paper attempts to find a mechanism that, under limited conditions during a clutch production that uses such dynamic characteristic, defects the maximum intensity of electromagnetism. Using the finite element analysis program, we predicted a change within the bonding force of the MR fluid occurring inside the clutch when it is subjected to an increased electric current. In addition, we analyzed the change in the magnetic intensity when the coil comprising the coil control center is switched to multiple lines from the standard single line, to find a mechanism that can maximize the effect. Based on this analysis, we developed the clutch and tested its function, hoping to widen future MR fluid's range of application.

Lattice Oxygen Activation in NiFe (Oxy)hydroxide using Se (셀레늄을 활용한 니켈철 (옥시)수산화물의 격자 산소 활성화)

  • Jo, Seunghwan;Sohn, Jung Inn
    • Korean Journal of Materials Research
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    • v.32 no.8
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    • pp.339-344
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    • 2022
  • The lattice oxygen mechanism (LOM) is considered one of the promising approaches to overcome the sluggish oxygen evolution reaction (OER), bypassing -OOH* coordination with a high energetic barrier. Activated lattice oxygen can participate in the OER as a reactant and enables O*-O* coupling for direct O2 formation. However, such reaction kinetics inevitably include the generation of oxygen vacancies, which leads to structural degradation, and eventually shortens the lifetime of catalysts. Here, we demonstrate that Se incorporation significantly enhances OER performance and the stability of NiFe (oxy)hydroxide (NiFe) which follows the LOM pathway. In Se introduced NiFe (NiFeSe), Se forms not only metal-Se bonding but also Se-oxygen bonding by replacing oxygen sites and metal sites, respectively. As a result, transition metals show reduced valence states while oxygen shows less reduced valence states (O-/O22-) which is a clear evidence of lattice oxygen activation. By virtue of its electronic structure modulation, NiFeSe shows enhanced OER activity and long-term stability with robust active lattice oxygen compared to NiFe.

A Study on the Evaluation Method to Flexural-bonding Behavior of FRP-Rebar Concrete Member (FRP를 보강근으로 사용한 콘크리트 부재의 휨-부착 거동 평가방법에 관한 연구)

  • Choi, So-Yoeng;Choi, Myoung-Sung;Kim, Il-Sun;Yang, Eun-Ik
    • Journal of the Korea institute for structural maintenance and inspection
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    • v.25 no.5
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    • pp.149-156
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    • 2021
  • FRP has been proposed to replace the steel as a reinforcement in the concrete structures for addressing the corrosion issue. However, FRP-Rebar does not behave in the same manner as steel because the properties of FRP are different. For example, FRP-Rebar has a high tensile strength, low stiffness, and linear elastic behavior which results in a difference bonding mechanism to transfer the load between the reinforcement and the surrounding concrete. Therefore, bonding behavior between FRP-Rebar and concrete has to be investigated using the bonding test. So, Pull-out test has been used to estimate bond behavior because it is simple. However, the results of pull-out test have a difference with flexural-boding behavior of FRP-Rebar concrete member. So, it is needed to evaluate the real fleuxral-bonding behavior. In this study, the evaluation method to flexural-bonding behavior of FRP-Rebar concrete member was reviewed and compared. It was found that the most accurate evaluation method for the fleuxral-bonding behavior of FRP-Rebar concrete member was splice beam test, however, the size and length of specimen have to increase than other test method and the design and analysis of splice beam is complex. Meanwhile, characteristics of concrete could be reflected by using arched beam test, unlike hinged beam test which is based on the ignored change of moment arm length in equilibrium equation. However, the possibility of shear failure exists before the flexural-bonding failure occur.

Bonding Mechanism of Direct Copper to Glass Seal in an Evacuated Tube Solar Collector (태양열 집열기에 사용되는 구리-유리관 접합기구)

  • 김철영;남명식;곽희열
    • Journal of the Korean Ceramic Society
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    • v.38 no.11
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    • pp.1000-1007
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    • 2001
  • In an evacuated tube solar collector, the stable sealing of the heat pipe to the glass tube is important for the collector to use for a long period of time. The sealing of copper tube to the glass is quite difficult because of the large differences in the physical and chemical properties of the two materials. In this study, therefore, a proper copper oxide layer was induced to improve the chemical bonding of the two materials, and the oxidation state of copper and the interface between copper and glass were examined by XRD, SEM and EDS. Its bonding strength was also measured. Cu$_2$O was formed when the bare copper was heat-treated under 600$^{\circ}C$, while CuO oxide layer was formed above that temperature. The bonding state of CuO to the copper was very poor. The borate treatment of the copper, however, extend the stable forming of Cu$_2$O layer to 800$^{\circ}C$. Borosilicate glass tube was sealed to a copper tube by Housekeeper method only when the sealing part was covered with Cu$_2$O layer. The bonding strength at the interface was measured 354.4N, its thermal shock resistance was acceptable.

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