• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.3-15
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• 1992

Electronic structures and reactivities of the chromium, molybdenum, and tungsten carbene complexes, $(CO)_5Cr=CCHCH_2(XCH_3)\;,\;(CO)_5Mo=CCHCH_2(XCH_3)\;, and\;(CO)_5W=CCHCH_2(XCH_3)$, are studied by means of Extended Huckel calculations. The origin of the M=Ccarbene double bond is clarified from the diagram of the orbital correlation with the fragment orbitals. The ${\sigma}$ bond of the M=Ccarbene double bond is formed by the electron transfer interaction from the HOMO of the carbene to the LUMO of the $(CO)_5M$. The ${\pi}$ bond is formed through the back-transfer of electrons from one of the degenerated d${\pi}$ orbitals to the LUMO of the carbene. The polarization of charge of the M=Ccarbene bond is calculated to be M=Ccarbene for Mo, and W carbenes. The chemical and physical properties of these complexes are resulted from an appreciable positive charge on the carbene carbon. The electrophilic reactivity of the carbene carbon is not charge controlled, but is controlled by the frontier orbital, LUMO.

• Journal of the Korean Magnetics Society
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• v.16 no.3
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• pp.168-172
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• 2006

We studied the magnetic and the related electronic properties of Ni-doped rutile $TiO_{2-{\delta}}$ films (including oxygen deficiency $\delta$) prepared using a sol-gel method. A room-temperature ferromagnetism was observed in the $TiO_{2-{\delta}}$ : Ni films with the saturation magnetization ($M_S$) decreasing with increasing Ni doping and remaining constant above 6 at% Ni doping. The observed ferromagnetism below 6 at% Ni doping is interpreted as due to magnetic polaron formed by a trapped electron in oxygen vacancy and magnetic impurity ions around it. For small Ni doping, $M_S$ up to $3.7{\mu}B/Ni$ was obtained. The ferromagnetism for Ni doping above 6 at% is interpreted as due to the existence of Ni clusters that can explain the p-n conductivity transition observed by Hall effect measurements.

• Korean Journal of Materials Research
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• v.8 no.12
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• pp.1099-1109
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• 1998

To investigate the effect of V and Sb on the corrosion behavior of Zr- based alloys, corrosion tests were performed on 6 kinds of Zr alloys in an autoclave at $360^{\circ}C$ for 100 days. The transition of the corrosion rate occurred in the sample containing 0.1wt.%V after 10 days but did not occur in the samples containing 0.2wt.%V and 0.4wt.%V. The corrosion resistance of V containing alloys increased with increasing V contents from 0.1 to 0.4wt.% and the alloys containing 0.4wt.%V showed the best corrosion resistance. In the ternary alloys containing 0.1wt.%Sb and 0.4wt.%Sb, the corrosion rate increased significantly from the short exposure time. It was observed that the optimal Sb content for corrosion resistance was 0.2wt.%. The size and volume fraction of precipitates increased with increasing V and Sb contents. The superior corrosion resistance was observed in the Zr alloy having precipitate size of 0.11-0.13$\mu\textrm{m}$. From the result of corrosion behavior and the obserbation of precipitates, the optimal size of the precipitate appear to control the electron conduction in the cathodic reaction and play an important role in maintaining a stable oxide microstructure.

• Korean Journal of Food Science and Technology
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• v.29 no.3
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• pp.516-521
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• 1997

Effect of amylose content on the physical properties of resistant starches (RS) from autoclaved maize starches (with starch:water=1:3.5, at $121^{\circ}C$) which were repeated up to 4 times heating-cooling cycles, were investigated by water uptake, scanning electron microscope (SEM) and differential scanning calorimetry (DSC). Amylose content of waxy maize starch (Amioca), common maize starch (PFP), high amylose starch(Amaizo, Amylomaize VII) were 0%, 29%, 50%, and 72%, respectively. Yield of RS increased as amylose content increased. Water uptake of all kinds of native starch was higher than that of RS, but lower than that of autoclaved starch. By SEM, RS showed some small particles on surface but the size of particles was different with amylose content. Single endothermic transition peak exhibited at $40{\sim}70^{\circ}C$ in autoclaved Amioca and PFP (crystalline melting of amylopectin) and at $132{\sim}169^{\circ}C$ in autoclaved Amaizo and Amylomaize VII(crystalline melting of amylose) by DSC. RS from all kinds of autoclaved starches except Amioca showed single endothermic peak over $155^{\circ}C$ but the enthalpy was not related to amylose content.

• Journal of Adhesion and Interface
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• v.17 no.1
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• pp.7-14
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• 2016

Epoxy composites with concentrations of 5-70 wt% of silica particles were prepared in order to improve mechanical property and poor thermal stability. The mechanical and thermal properties were investigated and compared to the corresponding properties of neat epoxy composite. Furthermore, the effects of silane compound treatment on silica particles were observed by the experimental results of the tensile strength, glass transition temperature, and thermal stability of epoxy composite. Tensile strength of epoxy composites was measured by universal testing machine (UTM) and after that, the structure and morphology analysis of epoxy nanocomposites were analyzed by field emission scanning electron microscope (FE-SEM) and energy dispersive spectroscopy (EDS). The increased solid content of CA0030 particle improved the tensile strength of epoxy/ modified composites to give 30-50 MPa. The thermal expansion coefficients (CTE) of neat epoxy resin and epoxy/silica composites measured with a thermomechanical analyzer (TMA) showed that the incorporation of silica particles was helpful to reduce the CTE of neat epoxy resin.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.29 no.3
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• pp.186-191
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• 2016

The effects of $Eu^{3+}$ doping on the structural, morphological, and optical properties of $MgMoO_4:Dy^{3+},Eu^{3+}$ phosphors prepared by solid-state reaction technique were investigated. XRD patterns exhibited that all the synthesized phosphors showed a monoclinic system with a dominant (220) diffraction peak, irrespective of the content of $Eu^{3+}$ ions. The surface morphology of $MgMoO_4:Dy^{3+},Eu^{3+}$ phosphors was studied using scanning electron microscopy and the grains showed a tendency to agglomerate as the content of $Eu^{3+}$ ions increased. The excitation spectra of the phosphor powders were composed of a strong charge transfer band centered at 294 nm in the range of 230~340 nm and two intense peaks at 354 and 389 nm, respectively, arising from the $^6H_{15/2}{\rightarrow}^6P_{7/2}$ and $^6H_{15/2}{\rightarrow}^4M_{21/2}$ transitions of $Dy^{3+}$ ions. The emission spectra of the $Mg_{0.85}MoO_4$:10 mol% $Dy^{3+}$ phosphors without incorporating $Eu^{3+}$ ions revealed a strong yellow band centered at 573 nm resulting from the $^4F_{9/2}{\rightarrow}^6H_{13/2}$ transition of $Dy^{3+}$. As the content of $Eu^{3+}$ was increased, the intensity of the yellow emission was gradually decreased, while that of red emission band located at 614 nm began to appear, approached a maximum value at 10 mol%, and then decreased at 15 mol% of $Eu^{3+}$. These results indicated that white light emission could be achieved by controlling the contents of the $Dy^{3+}$ and $Eu^{3+}$ ions incorporated into the $MgMoO_4$ host crystal.

• Journal of the Korean Chemical Society
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• v.55 no.2
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• pp.177-182
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• 2011

A diketo-type ligand was synthesized by the Knoevenagel condensation reaction of thiophene-2-aldehyde with acetylacetone, subsequently its transition metal complexes with Cu(II), Ni(II), and Co(II) chlorides were also prepared. All the complexes were characterized by various physico-chemical methods. The molar conductivity data reveals ionic nature for the complexes. The electronic spectrum and the EPR values suggest square planar geometry for the Cu(II) ion. Interaction of the Cu(II) complex with CTDNA (calf thymus DNA) was studied by absorption spectral method and cyclic voltammetry. The $k_{obs}$ values versus [DNA] gave a linear plot suggesting psuedo-first order reaction kinetics. The cyclic voltammogram of the Cu(II) complex reveals a quasi-reversible wave attributed to Cu(II)/Cu(I) redox couple for one electron transfer with $E_{1/2}$ values -0.240 V and -0.194 V. respectively. On addition of CTDNA, there is a shift in the $E_{1/2}$ values 168 mV and 18 mV respectively and decrease in Ep values. The shift in $E_{1/2}$ values in the presence of CTDNA suggests strong binding of Cu(II) complex to the CTDNA.

• Clean Technology
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• v.18 no.4
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• pp.366-372
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• 2012

Three acrylic copolymers containing tris(8-hydroxyquinoline) aluminum (AlQ3) pendant group (25 wt%), acrylateco-HEMA-$AlQ_3$ (25 wt%), were successfully synthesized by free radical polymerization from acrylates [methyl methacrylate (MMA), acrylonitrile (AN) or 2-hydroxyethyl methacrylate (HEMA)] with HEMA functionalized with AlQ3 pendant groups (HEMA-p-$AlQ_3$). The glass transition temperatures ($T_g$) of MMA-co-HEMA-p-$AlQ_3$ (copolymer 1), AN-co-HEMA-p-$AlQ_3$ (copolymer 2) and HEMA-co-HEMA-p-$AlQ_3$ (copolymer 3) were found to be 158, 150 and $126^{\circ}C$, respectively. They have good thermal stability: a very desirable feature for the stability of OLEDs. Their solubility, thermal properties, UV-visible absorption and photoluminescence behaviors were investigated. They were found to be soluble in various organic solvents such as tetrahydrofuran (THF), dimethylformamide (DMF), toluene and chloroform. It was also found that the UV-visible absorption and photoluminescence behaviors of these copolymers were similar to those of pristine $AlQ_3$. Green organic light-emitting diodes (OLEDs) have also been fabricated using these copolymers as light emission/electron transport components obtained easily by spin coating, and their current density voltage (J-V) curves were compared. The OLED device of the copolymer 3 had the lowest turn-on voltage of about 2 V compared to other copolymer types devices.

• Journal of the Korean Chemical Society
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• v.18 no.4
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• pp.223-238
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• 1974

CNDO/2 MO theoretical studies and kinetic studies of halide exchange reactions for alkylchloroformates have been carried out in order to investigate structure-reactivity relationship of alkylchloroformates. From the result of energetics, it was concluded that the most stable configuration of alkylchloroformate is that in which alkyl group and chlorine are trans to each other, and that the hindered rotation about the bond between the carbonyl carbon and alkoxy-oxygen bond is attributed to the ${\pi}-$electron delocalization. It has been found that the large charge separation is due to -M effect of carbonyl and alkoxy oxygens and-I effect of chlorine. The order of rates in solvents studied was $(CH_3)_2 > CO > CH_3CN{\gg}MeOH.$$I^->Br^->Cl^-$ in protic solvent, and of Cl^->Br^- >I^-$ in dipolar aprotic solvents. Alkyl group contribution has the decreasing order of $CH_3-> C_2H-{\gg}i-C_3H_7-.$ The solvent effect has been interpreted on the basis of initial and final state contribution. A transition state model has been suggested, and it has been proposed that the most favorable mechanism is the addition-elimination. From the results of activation parameters and electronic properties, an energy profile has been proposed. Structural factors determining reactivities of alkylchloroformates have been shown to be charge, energy level of ${\alpha}^*LUMO$ to C-Cl bond and ${\alpha}^{\ast} $antibonding strength with respect to C-Cl bond in this MO. Charge and polarizability of nucleophile, and the interaction of these effects with solvent structures are also found to be important.

• Korean Journal of Materials Research
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• v.13 no.8
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• pp.519-523
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• 2003

We report the synthesis of cubic spinel $ZnCo_2$$O_4$thin films and the tunability of the conduction type by control of the oxygen partial pressure ratio. Zinc cobalt oxide films were grown on$ SiO_2$(200 nm)/Si substrates by reactive magnetron sputtering method using Zn and Co metal targets in a mixed Ar/$O_2$atmosphere. We found from X-ray diffraction measurements that the crystal structure of the zinc cobalt oxide films grown under an oxygen-rich condition (the $O_2$/Ar partial pressure ratio of 9/1) changes from wurtzite-type $Zn_{1-x}$ $Co_{X}$O to spinel-type $ZnCo_2$$O_4$with the increase of the Co/Zn sputtering ratio,$ D_{co}$ $D_{zn}$ . We noted that the above structural change accompanied by the variation of the majority electrical conduction type from n-type (electrons) to p-type (holes). For a fixed $D_{co}$ $D_{zn}$ / of 2.0 yielding homogeneous spinel-type $_2$O$ZnCo_4$films, the type of the majority carriers also varied, depending on the$ O_2$/Ar partial pressure ratio: p-type for an $O_2$-rich and n-type for an Ar-rich atmosphere. The maximum electron and hole concentrations for the Zn $Co_2$ $O_4$films were found to be 1.37${\times}$10$^{20}$ c $m^{-3}$ and 2.41${\times}$10$^{20}$ c $m^{-3}$ , respectively, with a mobility of about 0.2 $\textrm{cm}^2$/Vs and a high conductivity of about 1.8 Ω/$cm^{-1}$ /.