• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3218-3222
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• 2013

The aminolyses, anilinolysis and pyridinolysis, of bis(2-oxo-3-oxazolidinyl) phosphinic chloride (1) have been kinetically investigated in acetonitrile at 55.0 and $35.0^{\circ}C$, respectively. For the reactions of 1 with substituted anilines and deuterated anilines, a concerted SN2 mechanism is proposed based on the selectivity parameters and activation parameters. The deuterium kinetic isotope effects ($k_H/k_D$) invariably increase from secondary inverse to primary normal as the aniline becomes more basic, rationalized by the transition state variation from a backside to a frontside attack. For the pyridinolysis of 1, the authors propose a stepwise mechanism with a rate-limiting step change from bond breaking for more basic pyridines to bond formation for less basic pyridines based on the selectivity parameters and activation parameters. Biphasic concave upward free energy relationship with X is ascribed to a change in the attacking direction of the nucleophile from a frontside attack with more basic pyridines to a backside attack with less basic pyridines.

• Journal of the Korean Applied Science and Technology
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• v.6 no.1
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• pp.67-73
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• 1989

The adsorptions of 2-(dimethylalkylammonio)propanoates with straight chain alkyl group having from 12 to 16 carbon atoms on the liquid-air interface were decreased while lowering the surface tensions at critical micelle concentrations. In micellization, the standard free energy changes per methylene in alkyl group were found to make same contribution to the micelle formation of corresponding C-alkylcarboxybetaines, and the standard enthalpy and entropy changes were studied within the range of temperature from 30 to $50^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• v.28 no.2
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• pp.188-192
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• 2007

In this work, the effects of chemical treatment of polyimide films were studied by FT-IR, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angles. The adhesion characteristics of the films were also investigated in the peel strengths of polyimide/aluminum films. The increases of surface functional groups of KOH-treated polyimide films were greatly correlated with the polar component of surface free energy. The peel strength of polyimides to metal substrate was also greatly enhanced by increasing the KOH treatment time, which can be attributed to the formation of polar functional groups on the polyimide surfaces, resulting in enhancement of the work of adhesion between polymer film and metal plate.

• Journal of IKEEE
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• v.21 no.3
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• pp.297-308
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• 2017

By using electron beam evaporation under appropriate conditions, we obtained graphene intercalated sheets on Si(111) with an average crystallite size less than 11nm. The formation of such nanocrystalline graphene was found as a time-dependent function of carbon deposition at a substrate temperature of $1000^{\circ}C$. The structural and electronic properties as well as the surface morphology of such produced materials have been confirmed by reflection high energy electron diffraction, Auger electron spectroscopy, X-ray photoemission spectroscopy, Raman spectroscopy, scanning electron microscopy, atomic force microscopy and scanning tunneling microscopy.

• Applied Microscopy
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• v.44 no.4
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• pp.133-137
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• 2014

We suggest a facile transmission electron microscopy (TEM) specimen preparation method for the direct (polymer-free) transfer of layer-area graphene from Cu substrates to a TEM grid. The standard (polymer-based) method and direct transfer method were by TEM, high-resolution TEM, and energy dispersive X-ray spectroscopy (EDS). The folds and crystalline particles were formed in a graphene specimen by the standard method, while the graphene specimen by the direct method with a new etchant solution exhibited clean and full coverage of the graphene surface, which reduced several wet chemical steps and accompanying mechanical stresses and avoided formation of the oxide metal.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3947-3951
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• 2011

The nucleophilic substitution reactions of Y-aryl ethyl chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Me. The substituents of X = 4-CN and 4-Ac show great positive deviations from both the Hammett and Bronsted plots. The Hammett plots for substituent Y variations in the substrates exhibit biphasic concave upwards with a minimum point at Y = H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are all in spite of the biphasic free energy correlations for both substituent X and Y variations, since the ${\rho}_X$values with both the strongly and weakly basic pyridines are almost constant. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed where the distance between X and Y does not vary from the intermediate to the second transition state. A frontside attack is proposed with the strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values and a backside attack is proposed with the weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$. The positive deviations of the two strong ${\pi}$-acceptor parasubstituents, X = 4-Ac and 4-CN, from both the Hammett and Bronsted plots are rationalized by the great extents of bond formation and breaking.

• Journal of the Microelectronics and Packaging Society
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• v.15 no.1
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• pp.33-37
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• 2008

A noticeable amount of Kirkendall voids formed at the Sn-3.5Ag solder joint with electroplated Cu, and that became even more significant when an additive was added to Cu electroplating bath. With SPS, a large amount of voids formed at the $Cu/Cu_3Sn$ interface of the solder joint during thermal aging at $150^{\circ}C$. The in-situ AES analysis of fractured joints revealed S segregation on the void surface. Only Cu, Sn, and S peaks were detected at the fractured $Cu/Cu_3Sn$ interfaces, and the S peak decreased rapidly with AES depth profiling. The segregation of S at the $Cu/Cu_3Sn$ interface lowered interface energy and thereby reduced the free energy barrier for the Kirkendall void nucleation. The drop impact test revealed that the electrodeposited Cu film with SPS degraded drastically with aging time. Fracture occurred at the $Cu/Cu_3Sn$ interface where a lot of voids existed. Therefore, voids occupied at the $Cu/Cu_3Sn$ interface are shown to seriously degrade drop reliability of solder joints.

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.837-845
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• 2002

Based on ab initio calculations at the MP2(FULL)/6-31+G**//RHF/6-31G** level, we compare the energetic and mechanistic features of a model reaction for catalytic action of Δ?-3-ketosteroid isomerase (KSL,E.C.5.3,3.1) with those of a corresponding nonenzymatic reaction in aqueous solution. The results show that the two catalytic acid residues,Tyr14 and Asp99, can lower the free energy of activation by 8.6kcal/mol, which is in good agreement with the experimentally predicted~9 kcal/mol,contribution of electrophilic catalyses to the whole enzymatic rate enhancement. The dienolate intermediate formed by proton transfer from the substrate carbon acid to the catalytic base residue (Asp38) ins predicted to be stabilized by 12.0 kcal/mol in the enzymatic reaction, making its formation thermodynamically favorable. It has been argued that enzymes catalyzing the reactions of carbon acids should resolve the thermodynamic problem of stabilizing the enolate intermediate as well as the kinetic porblem of lowering the free energy of activation for porton abstraction. We find that KSI can successfully overcome the thermodynamic difficulty ingerent in the nonenzymatic reaction through the electrophilic catalyses of the two acid residues. Owing to the stabilization of dienolate intermediate, the reketonization step could influence the overall reaction rate more significantly in the KSI- catalyzed reaction than in the nonenzymatic reaction, further supporting the previous experimental findings. However, the electrophilic catalyses alone cannot account for the whole catalygic capability (12-13 kcal/mol), confiming the earlier experimental implications for the invement of additional catalytic components. The present computational study indicates clearly how catalytic residues of KSI resolve the fundamental problems associated with the entropic penalty for forming the rate-limiting transition state and its destabilization in the bulk solvation environment.

• Korean Journal of Materials Research
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• v.12 no.7
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• pp.550-554
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• 2002

The effect of Mn on cavitation erosion resistance and the sliding wear resistance of Fe-base hardfacing NewAlloy was investigated. Mn is known to decrease stacking fault energy and enhance the formation of $\varepsilon$-martensite. Cavitation erosion resistance for 50 hours and sliding wear resistance for 100 cycles were evaluated by weight loss. Fe-base hardfacing NewAlloy showed more excellent cavitation erosion resistance than Mn-added NewAlloys. $\Upsilon-\alpha$' phase transformation that can enhance erosion resistance by matrix hardening occurred in every specimens. But, only in Mn free Fe-base hardfacing NewAlloy, the hardened matrix could repress the propagation of cracks that was initialed at the matrix-carbides interfaces more effectively than Mn-added NewAlloy The Mn free Fe-base hardfacing NewAlloy showed better sliding wear resistance than Mn-added alloys. Mn-addition up to 5wt.% couldn't increase the sliding wear and cavitation erosion resistance of Fe-base hardfacing alloy because it didn't make $\Upsilon\to\varepsilon$ martensite phase transformation. Therefore, it is considered that the cavitation erosion and the sliding wear resistance can be improved due to $\Upsilon\to\varepsilon$ martensite phase transformation when Mn is added more than 5wt.% in Fe-base hardfacing alloys.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.1 no.1
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• pp.51-59
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• 1991

Early stage of GaAs nucleation on Si substrate was theoretically studied by computer simulation. Compared to the constant ledge interaction energy in conventional nucleation theory, functional behavior of ledge-ledge interaction resulted in small size clusters depending on the cluster size and shape. Among various kinds of clusters, the multilayer pyramidal shape GaAs cluster requires smallest excess free energy due to the formation of Ga(111) facet planes. There this result suggests that the defects involved in GaAs/Si are originated from the early stage nucleation.