• Applied Chemistry for Engineering
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• v.17 no.3
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• pp.235-242
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• 2006

Liquid phase alkylation of biphenyl (BP) was studied over large pore zeolites. Selective formation of the least bulky products, 4,4'-diisopropylbiphenyl (4,4'-DIPB) occurred only in the isopropylation of BP over some large pore molecular sieves. H-mordenites (MOR) gave the highest selectivity among them. The dealumination of MOR enhanced catalytic activity and the selectivity of 4,4'-DIPB because of the decrease of coke-deposition. Non-selective catalysis occurs on external acid sites over MOR with the low $SiO_2/Al_2O_3$ ratio because severe coke-deposition deactivates the acid sites inside the pores by blocking pore openings. The selectivity of DIPB isomers was changed with reaction temperature. Selective formation of 4,4'-DIPB was observed at moderate temperatures such as $250^{\circ}C$, whereas the decrease of the selectivity of 4,4'-DIPB occurred at higher temperatures as $300^{\circ}C$. However, 4,4'-DIPB was almost exclusive isomer in the encapsulated DIPB isomers inside the pores even at high temperatures. These decreases of the selectivity of 4,4'-DIPB are due to the isomerization of 4,4'-DIPB on the external acid sites. Some 12-membered molecular sieves, such as SSZ-24, MAPO-5 (M:Mg, Zn, Si), SSZ-31, and ZSM-12, which have straight channels, gave 4,4'-DIPB with moderate to high selectivity; however; SSZ-55, SSZ-42, and MAPO-36 (M: Mg, Zn) gave lower selectivity because of cages in 12-membered one dimensional channels. Three dimensional H-Y and Beta zeolites also yield 4,4'-DIPB in low yield because of their wide circumstances for the isopropylation of BP. The increasing the size of alkylating agent enhanced the shape-selective alkylaiton even for the zeolites, such as UTD-1. The ethylation of BP to ethylbiphenyls (EBPs) and diethylbiphenyls (DEBPs) over MOR was non-selective. The ethylation of BP to EBPs was controlled kinetically. However, there was difference in reactivity of EBPs and DEBPs for their further ethylation. 4-EBP was ethylated preferentially among the isomers, although the formation of 4,4'-DEBP was less selective. The least bulky 4-EBP and 4,4'-DEBP have the highest reactivity among EBPs and DEBPs for the ethylation to polyethylbiphenyls (PEBPs). These results show that the environments of MOR pores are too loose for shape selective formation of the least bulky isomers, 4-EBP and 4,4'-DEBP in the ethylation of BP, and that MOR pores have enough space for the further ethylation of 4,4'-DEBP.

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.77-82
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• 2011

A new high performance liquid chromatograpgy (HPLC) stationary phase that possesses an internal carbonyl functional group is synthesized by heterogeneous "graft from" method. This new stationary phase, poly (vinyl octadecanoate) grafted silica (Sil-2) is then characterized by different physico-chemical methods such as diffuse reflectance infrared fourier transform, suspension state $^1H$ NMR, solid state $^{13}C$ CP/MAS NMR, $^{29}Si$ CP/MAS NMR, elemental analysis and thermogravimetric analysis. Chromatographic properties of Sil-2 were evaluated under reversed phase condition by separating polycyclic aromatic hydrocarbons (PAHs) and comparing the chromatographic results with those on polymeric as well as monomeric octadecylated silica stationary phases.

• Bulletin of the Korean Chemical Society
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• v.25 no.12
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• pp.1917-1923
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• 2004

Although the proteolytic activity of the Cu(II) complex of cyclen (Cyc) is greatly enhanced upon attachment to a cross-linked polystyrene (PS), the Cu(II)Cyc-containing PS derivatives reported previously hydrolyzed only a very limited number of proteins. The PS-based artificial metalloproteases can overcome thermal, mechanical, and chemical instabilities of natural proteases, but the narrow substrate selectivity of the artificial metalloproteases limits their industrial application. In the present study, artificial metalloproteases exhibiting broad substrate selectivity were synthesized by attaching Cu(II)Cyc to a PS derivative using linkers with various structures in an attempt to facilitate the interaction of various protein substrates with the PS surface. The new artificial metalloproteases hydrolyzed all of the four protein substrates (albumin, myoglobin, ${\gamma}$-globulin, and lysozyme) examined, manifesting $k_{cat}/K_m$ values of 28-1500 $h_{-1}M_{-1}$ at 50 $^{\circ}C$. The improvement in substrate selectivity is attributed to steric and/or polar interaction between the bound protein and the PS surface as well as the hydrophobicity of the microenvironment of the catalytic centers.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2410-2414
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of Y-substituted-phenyl picolinates (7a-7h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Comparison of the kinetic results with those reported previously for the corresponding reactions of Y-substituted-phenyl benzoates (1a-1f) reveals that 7a-7h are significantly more reactive than 1a-1f. The Br${\o}$nsted-type plot for the aminolysis of 4-nitrophenyl picolinate (7a) is linear with ${\beta}_{nuc}=0.78$, which is typical for reactions proceeding through a stepwise mechanism with expulsion of the leaving group being the rate-determining step. The Br${\o}$nsted-type plots for the piperidinolysis of 7a-7h and 1a-1f are also linear with ${\beta}_{lg}=-1.04$ and -1.39, respectively, indicating that the more reactive 7a-7h are less selective than the less reactive 1a-1f to the leaving-group basicity. One might suggest that the enhanced reactivity of 7a-7h is due to the inductive effect exerted by the electronegative N atom in the picolinyl moiety, while the decreased selectivity of the more reactive substrates is in accord with the reactivity-selectivity principle. However, the nature of intermediate (e.g., a stabilized cyclic intermediate through the intramolecular H-bonding interaction for the reactions of 7a-7h, which is structurally not possible for the reactions of 1a-1f) is also responsible for the enhanced reactivity with a decreased selectivity.

• Membrane Journal
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• v.9 no.2
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• pp.107-113
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• 1999

Alcohol concentration via pervaporation process was performed by using commercial PDMS(polydimethylsiloxane) composite membrane and plasma treated PP(polypropylene) membranes. Effects of operating parameters of pcrvaporation process were examined. With the increase of butanol concentration in the feed, flux and selectivity increased due to the greater affinity of butanol with PDMS than that of water. As the operating temperature increased, free volume as well as the solubilities and diffusivities of alcohol and water increased to result in the greater flux and less selectivity of the membrane. As solubility parameter difference between alcohol and PDMS membrane decreased, high flux and good selectivity were obtained. When PP membrane was plasma treated with methanol, it has 6 times greater flux than PDMS membrane with equivalent separation factor. With the increase of plasma treatment time, flux and selectivity were enhanced. However, excess treatment time caused pore blocking to result in the flux decrease.

• Nuclear Engineering and Technology
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• v.55 no.2
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• pp.640-647
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• 2023

Material corrosion in nuclear power plant (NPP) is not controlled only by amine injection but also by ion exchange (IX) which is the best option to remove trace Na⁺. This study was conducted to understand the Na⁺ leakage characteristics of IX beds packed with ethanolamine-form (ETAH-form) and hydrogen-form (H-form) resins in the simulated water-steam cycle in terms of intrinsic behaviors of four kinds of cation-exchange resins through ASTM test and Vanselow mass action modeling. Na⁺ was inappreciably escaped throughout the channel created in resin layer. Na⁺ leakage from IX bed was non-linearly raised because of its decreasing selectivity with increasing Na⁺ capture and with increasing the fraction of ETAH-form resin. Na⁺ did not reach the breakthrough earlier than ETAH⁺ and NH₄⁺ due to the increased selectivity of Na⁺ to the cation-exchange resin (H⁺ < ETAH⁺ < NH₄⁺ ≪ Na⁺) at the feed composition. Na⁺ leakage from the resin bed filled with small particles was decreased due to the enhanced dynamic IX processes, regardless of its low selectivity. Thus, the particle size is a predominant factor among intrinsic properties of IX resin to reduce Na⁺ leakage from the condensate polishing plant (CPP) in NPPs.

• ETRI Journal
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• v.24 no.3
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• pp.211-220
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• 2002

This study characterizes an oxide etching process in a magnetically enhanced reactive ion etching (MERIE) reactor with a $CHF_3/CF_4$ gas chemistry. We use a statistical $2^{4-1}$ experimental design plus one center point to characterize the relationships between the process factors and etch responses. The factors that we varied in the design include RF power, pressure, and gas composition, and the modeled etch responses were the etch rate, etch selectivity to TiN, and uniformity. The developed models produced 3D response plots. Etching of $SiO_2$ mainly depends on F density and ion bombardment. $SiO_2$ etch selectivity to TiN sensitively depends on the F density in the plasma and the effects of ion bombardment. The process conditions for a high etch selectivity are a 0.3 to 0.5 $CF_4$ flow ratio and a -600 V to -650 V DC bias voltage according to the process pressure in our experiment. Etching uniformity was improved with an increase in the $CF_4$ flow ratio in the gas mixture, an increase in the source power, and a higher pressure. Our characterization of via etching in a $CHF_3/CF_4$ MERIE using neural networks was successful, economical, and effective. The results provide highly valuable information about etching mechanisms and optimum etching conditions.

• Journal of the Korean institute of surface engineering
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• v.49 no.3
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• pp.286-300
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• 2016

Pd-Ag alloy membranes have attracted a great deal of attention for their use in hydrogen purification and separation due to their high theoretical permeability, infinite selectivity and chemical compatibility with hydro-carbon containing gas streams. For commercial application, Pd-based membranes for hydrogen purification and separation need not only a high perm-selectivity but also a stable long-term durability. However, it has been difficult to fabricate thin, dense Pd-Ag alloy membranes on a porous stainless steel metal support with surface pores free and a stable diffusion barrier for preventing metallic diffusion from the porous stainless steel support. In this study, thin Pd-Ag alloy membranes were prepared by advanced Pd/Ag/Pd/Ag/Pd multi-layer sputter deposition on the modified porous stainless steel support using rough polishing/$ZrO_2$ powder filling and micro-polishing surface treatment, and following Ag up-filling heat treatment. Because the modified Pd-Ag alloy membranes using rough polishing/$ZrO_2$ powder filling method demonstrate high hydrogen permeability as well as diffusion barrier efficiency, it leads to the performance improvement in hydrogen perm-selectivity. Our membranes, therefore, are expected to be applicable to industrial fields for hydrogen purification and separation owing to enhanced functionality, durability and metal support/Pd alloy film integration.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.11 no.6
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• pp.447-452
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• 1998

The selective dry etching of GaAs to Al\ulcornerGa\ulcornerAs using $BCI_3/SF_6$ gas mixture in electron cyclotron resonance(ECR) plasma is investigated. A selectivity of GaAs to AlGaAs of more than 100 and maximum etch rate of GaAs are obtained at a gas ratio $SF_6/BCI_3+SF_6$ of 25%. We verified the formation of $AlF_3$ on $Al_{0.25}Ga_{0.75}As$from the Auger spectra which enhanced the etch selectivity. In order to investigate surface damage of AlGaAs caused by ECR plasma, we performed a low temperature photoluminescence(PL) measurement as a function of RF power. As the RF power. As the RF power increases, the PL intensity decreases monotonically from 50 to 100 Wand then repidly decreases until 250 W. This behavior is due to surface damage by plasma treatment. This dry etching technique using $BCI_3/SF_6$ gas mixture in ECR plasma is suitable for gate recess formation on the GaAs based pseudomorphic high electron mobility transistor(PHEMT)

• Transactions on Electrical and Electronic Materials
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• v.11 no.3
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• pp.116-119
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• 2010

The etching characteristics of zinc oxide (ZnO) were investigated, including the etch rate and the selectivity of ZnO in a $Cl_2/BCl_3$/Ar plasma. It was found that the ZnO etch rate, the RF power, and the gas pressure showed non-monotonic behaviors with an increasing Cl2 fraction in the $Cl_2/BCl_3$/Ar plasma, a gas mixture of $Cl_2$(3 sccm)/$BCl_3$(16 sccm)/Ar (4 sccm) resulted in a maximum ZnO etch rate of 53 nm/min and a maximum etch selectivity of 0.89 for ZnO/$SiO_2$. We used atomic force microscopy to determine the roughness of the surface. Based on these data, the ion-assisted chemical reaction was proposed as the main etch mechanism for the plasmas. Due to the relatively low volatility of the by-products formed during etching with $Cl_2/BCl_3$/Ar plasma, ion bombardment and physical sputtering were required to obtain the high ZnO etch rate. The chemical states of the etched surfaces were investigated using X-ray photoelectron spectroscopy (XPS). This data suggested that the ZnO etch mechanism was due to ion enhanced chemical etching.