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The Effect of Calcination Temperature on the Performance of Ni-Ce0.8Zr0.2O2 Catalysts for Steam Reforming of Methane under Severe Conditions (가혹한 조건의 SRM 반응에서 Ni-Ce0.8Zr0.2O2 촉매의 소성온도에 따른 영향)

  • Jang, Won-Jun;Jeong, Dae-Woon;Shim, Jae-Oh;Roh, Hyun-Seog
    • Journal of Hydrogen and New Energy
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    • v.23 no.3
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    • pp.213-218
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    • 2012
  • Steam reforming of methane (SRM) is the primary method to produce hydrogen. Commercial Ni-based catalysts have been optimized for SRM with excess steam ($H_2O/CH_4$ > 2.5) at high temperatures (> $700^{\circ}C$). However, commercial catalysts are not suitable under severe conditions such as stoichiometric steam over methane ratio ($H_2O/CH_4$ = 1.0) and low temperature ($600^{\circ}C$). In this study, 15wt.% Ni catalysts supported on $Ce_{0.8}Zr_{0.2}O_2$ were prepared at various calcination temperatures for SRM at a very high gas hourly space velocity (GHSV) of $621,704h^{-1}$. The calcination temperature was systematically varied to optimize 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst at a $H_2O/CH_4$ ratio of 1.0 and at $600^{\circ}C$. 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst calcined at $500^{\circ}C$ exhibited the highest $CH_4$ conversion as well as stability with time on stream. Also, 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst calcined at $500^{\circ}C$ showed the highest $H_2$ yield (58%) and CO yield (21%) among the catalysts. This is due to complex NiO species, which have relatively strong metal to support interaction (SMSI).

Competitive Adsorption of Multi-species of Heavy Metals onto Sandy Clay Loam and Clay Soils (사질식양토와 식토에서 중금속 이온의 다중 경쟁 흡착)

  • Chung, Doug Y.;Noh, Hyun-Hee
    • Korean Journal of Soil Science and Fertilizer
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    • v.38 no.5
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    • pp.238-246
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    • 2005
  • We conducted this investigation to observe competitive adsorption phenomena among the heavy metals onto the available sorption sites of soil particle surfaces in sandy clay loam and clay soil collected from Nonsan city, Chungnam and Yoosung, Daejeon in Korea, respectively. Polluted and contaminated soils can often contain more than one heavy metal species, resulting in competition for available sorption sites among heavy metals in soils due to complex competitive ion exchange and specific sorption mechanism. And the adsorption characteristics of the heavy metals were reported that the selectivity for the sorption sites was closely related with electropotential and electro negativity carried by the heavy metals. The heavy metals were treated as single, binary and ternary systems as bulk solution phase. Adsorption in multi-element system was different from single-element system as Cr, Pb and Cd. The adsorption isotherms showed the adsorption was increased with increasing equilibrium concentrations. For binary and ternary systems, the amount of adsorption at the same equilibrium concentration was influenced by the concentration of individual ionic species and valence carried by the respective heavy metal. Also we found that the adsorption isotherms of Cd and Pb selected in this experiment were closely related with electronegativity and ionic potential regardless number of heavy metals in solution, while the adsorption of Cr carried higher valance and lower electro negativity than Cd and Pb was higher than those of Cd and Pb, indicating that adsorption of Cr was influenced by ionic potential than by electronegativity. Therefore adsorption in multi-element system could be influenced by electronegativity and ionic potential and valance for the same valance metals and different valance, respectively. But it still needs further investigation with respect to ionic strength and activity in multi-element system to verify sorption characteristics and reaction processes of Cr, especially for ternary system in soils.

Sol-gel deposited TiInO thin-films transistor with Ti effect

  • Kim, Jung-Hye;Son, Dae-Ho;Kim, Dae-Hwan;Kang, Jin-Kyu;Ha, Ki-Ryong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.200-200
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    • 2010
  • In recent times, metal oxide semiconductors thin films transistor (TFT), such as zinc and indium based oxide TFTs, have attracted considerable attention because of their several advantageous electrical and optical properties. There are many deposition methods for fabrication of ZnO-based materials such as chemical vapor deposition, RF/DC sputtering and pulsed laser deposition. However, these vacuum process require expensive equipment and result in high manufacturing costs. Also, the methods is difficult to fabricate various multicomponent oxide semiconductor. Recently, several groups report solution processed metal oxide TFTs for low cost and non vacuum process. In this study, we have newly developed solution-processed TFTs based on Ti-related multi-component transparent oxide, i. e., InTiO as the active layer. We propose new multicomponent oxide, Titanium indium oxide(TiInO), to fabricate the high performance TFT through the sol-gel method. We investigated the influence of relative compositions of Ti on the electrical properties. Indium nitrate hydrate [$In(NO^3).xH_2O$] and Titanium isobutoxide [$C_{16}H_{36}O_4Ti$] were dissolved in acetylacetone. Then monoethanolamine (MEA) and acetic acid ($CH_3COOH$) were added to the solution. The molar concentration of indium was kept as 0.1 mol concentration and the amount of Ti was varied according to weighting percent (0, 5, 10%). The complex solutions become clear and homogeneous after stirring for 24 hours. Heavily boron (p+) doped Si wafer with 100nm thermally grown $SiO_2$ serve as the gate and gate dielectric of the TFT, respectively. TiInO thin films were deposited using the sol-gel solution by the spin-coating method. After coating, the films annealed in a tube furnace at $500^{\circ}C$ for 1hour under oxygen ambient. The 5% Ti-doped InO TFT had a field-effect mobility $1.15cm^2/V{\cdot}S$, a threshold voltage of 4.73 V, an on/off current ratio grater than $10^7$, and a subthreshold slop of 0.49 V/dec. The 10% Ti-doped InO TFT had a field-effect mobility $1.03\;cm^2/V{\cdot}S$, a threshold voltage of 1.87 V, an on/off current ration grater than $10^7$, and a subthreshold slop of 0.67 V/dec.

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Selective Synthesis of Acetonitrile via Direct Amination of Ethanol Over Ni/SiO2-Al2O3 Mixed Oxide Catalysts (Ni/SiO2-Al2O3 복합 산화물 촉매 상에서 에탄올의 직접 아민화 반응에 의한 선택적 아세토니트릴 합성)

  • Kim, Hanna;Shin, Chae-Ho
    • Korean Chemical Engineering Research
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    • v.59 no.2
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    • pp.281-295
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    • 2021
  • In this study, the direct amination of ethanol was performed over impregnated Ni on SiO2-Al2O3 mixed oxide catalysts prepared by varying Si/(Si + Al) molar ratio to 30 mol%. To characterize the physico-chemical properties of the catalysts used, X-ray diffraction (XRD), N2-physisorption, temperature-programmed desorption of iso-propyl alcohol (IPA-TPD), temperature-programmed desorption of ethanol (EtOH-TPD), temperature-programmed reduction with H2 (H2-TPR), H2-chemisorption and transmission electron microscopy (TEM) were used. The acidic property was continuously increased until Si/(Si + Al) = 30 mol% in SiO2-Al2O3 mixed oxides used. The dispersion of Ni metal and surface area, acid characteristics of the supported Ni catalyst have a complex effect on the catalytic reaction activity. The low reduction temperature of nickel oxide and acidic properties were beneficial to the formation of acetonitrile. In terms of conversion of ethanol, Ni/SiO2-Al2O3 catalyst with a molar ratio of 10 mol% Si/(Si+Al) showed the highest activity and a volcanic curve based on it. The tendency of results were consistent in the metal dispersion and catalytic activity.

Au-Ag-bearing Ore Mineralization at the Geochang Hydrothermal Vein Deposit (거창 열수 맥상광상의 함 금-은 광화작용)

  • Hong, Seok Jin;Lee, Sunjin;Choi, Sang-Hoon
    • Economic and Environmental Geology
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    • v.55 no.2
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    • pp.171-181
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    • 2022
  • The Geochang Au-Ag deposit is located within the Yeongnam Massif. Within the area a number of hydrothermal quartz and calcite veins were formed by narrow open-space filling of parallel and subparallel fractures in the granitic gneiss and/or gneissic granite. Mineral paragenesis can be divided into two stages (stage I, ore-bearing quartz vein; stage II, barren calcite vein) by major tectonic fracturing. Stage I, at which the precipitation of major ore minerals occurred, is further divided into three substages (early, middle and late) with paragenetic time based on minor fractures and discernible mineral assemblages: early, marked by deposition of pyrite with minor pyrrhotite and arsenopyrite; middle, characterized by introduction of electrum and base-metal sulfides with minor sulfosalts; late, marked by hematite with base-metal sulfides. Fluid inclusion data show that stage I ore mineralization was deposited between initial high temperatures (≥380℃ ) and later lower temperatures (≤210℃ ) from H2O-CO2-NaCl fluids with salinities between 7.0 to 0.7 equiv. wt. % NaCl of Geochang hydrothermal system. The relationship between salinity and homogenization temperature indicates a complex history of boiling, fluid unmixing (CO2 effervescence), cooling and dilution via influx of cooler, more dilute meteoric waters over the temperature range ≥380℃ to ≤210℃. Changes in stage I vein mineralogy reflect decreasing temperature and fugacity of sulfur by evolution of the Geochang hydrothermal system with increasing paragenetic time. The Geochang deposit may represents a mesothermal gold-silver deposit.

Room Temperature Imprint Lithography for Surface Patterning of Al Foils and Plates (알루미늄 박 및 플레이트 표면 미세 패터닝을 위한 상온 임프린팅 기술)

  • Tae Wan Park;Seungmin Kim;Eun Bin Kang;Woon Ik Park
    • Journal of the Microelectronics and Packaging Society
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    • v.30 no.2
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    • pp.65-70
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    • 2023
  • Nanoimprint lithography (NIL) has attracted much attention due to its process simplicity, excellent patternability, process scalability, high productivity, and low processing cost for pattern formation. However, the pattern size that can be implemented on metal materials through conventional NIL technologies is generally limited to the micro level. Here, we introduce a novel hard imprint lithography method, extreme-pressure imprint lithography (EPIL), for the direct nano-to-microscale pattern formation on the surfaces of metal substrates with various thicknesses. The EPIL process allows reliable nanoscopic patterning on diverse surfaces, such as polymers, metals, and ceramics, without the use of ultraviolet (UV) light, laser, imprint resist, or electrical pulse. Micro/nano molds fabricated by laser micromachining and conventional photolithography are utilized for the nanopatterning of Al substrates through precise plastic deformation by applying high load or pressure at room temperature. We demonstrate micro/nanoscale pattern formation on the Al substrates with various thicknesses from 20 ㎛ to 100 mm. Moreover, we also show how to obtain controllable pattern structures on the surface of metallic materials via the versatile EPIL technique. We expect that this imprint lithography-based new approach will be applied to other emerging nanofabrication methods for various device applications with complex geometries on the surface of metallic materials.

Synthesis of new N2O2 tetradentate ligands and the substituent effect on the stability constants of the transition metal complexes (새로운 산소-질소(N2O2)계 네 자리 리간드의 합성과 전이금속 착물 안정도상수에 대한 치환기 효과)

  • Kim, Sun Deuk;Jin, Gyoung Rok
    • Analytical Science and Technology
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    • v.19 no.2
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    • pp.131-141
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    • 2006
  • Hydrobromic acid salt of a $N_2O_2$ tetradentate ligand, N,N'-bis(2-hydroxybenzyl)-ethylene-diamine ($H-BHE{\cdot}2HBr$) was synthesized. $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ and $CH_3O-BHE{\cdot}2HBr$ having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of $H-BHE{\cdot}2HBr$ were also synthesized. $Nap-BHE{\cdot}2HBr$ having naphthalen-2-ol instead of the phenol group was also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and the order of the calculated overall proton dissociation constants (${\log}{\beta}_p$) of each ligand was Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE. The order showed a similar trend to that of Hammett substituent constants(${\sigma}_P$). The order of the stability constants (${\log}K_{ML}$) was CO(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order in their stability constants (${\log}K_{ML}$) of each transition metal complex agreed well with that of the overall proton dissociation constants (${\log}{\beta}_p$).

Antibody Functionalized UiO-66-(COOH)2 Amplified Surface Plasmon Resonance Analysis Method for fM Oxytocin (펨토몰 농도의 옥시토신 검출을 위한 항체 기능성 UiO-66-(COOH)2 증폭형 표면 플라즈몬 공명 분석법 개발)

  • Myungseob Lee;Ha-Young Nam;Su Yeon Park;Sung Hwa Jhung;Hye Jin Lee
    • Applied Chemistry for Engineering
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    • v.35 no.4
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    • pp.335-340
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    • 2024
  • In this paper, we synthesized organic and inorganic hybrid materials to introduce antibody functionality to UIO-66 and incorporated them into a surface plasmon resonance (SPR) assay to enhance the sensitivity of detecting small molecules such as oxytocin. A biological marker peptide called oxytocin may help in the diagnosis of heart failure, Alzheimer's disease, and cancer. To detect oxytocin at concentrations as low as a few femtomole (fM), we developed a surface sandwich assay utilizing a pair of oxytocin-specific antibodies for enhancing selectivity and one of metal organic frameworks [e.g., UiO-66-(COOH)2] possessing high porosity and surface-area as a signal amplifier. Initially, real-time SPR assays were used to confirm that each selected oxytocin-specific antibody binds strongly to oxytocin and to different binding sites on oxytocin. One of these antibodies (e.g., anti-OXT[OTI5G4]) was immobilized on the surface of a thin gold chip. Upon sequential injecting of oxytocin and the other antibody (e.g., anti-OXT[4G11]) conjugated to UiO-66-(COOH)2 onto the surface to form the surface sandwich complex of anti-OXT[OTI5G4]/oxytocin/UiO-66-(COOH)2-anti-OXT[4G11]), SPR changes, which varied with oxytocin concentration, were then measured in real time. The results demonstrated that sensitivity was amplified by over a million-fold compared to assays without UiO-66-(COOH)2, enabling oxytocin detection down to approximately 10 fM.

Effect of Transition Metal Ion on the Reaction of Benzylbromide with Grignard Reagent (Grignard 시약과 브로모벤질과의 반응에서 첨가전이 금속이온의 영향 연구)

  • Jack C. Kim;Young-Sim Koh;Ung-Chan Yoon;Min-Sook Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.2
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    • pp.228-236
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    • 1993
  • The effect of ferric ion on the reaction of CH_3$MgI with benzylbromide was investigated by determining the product ratio between cross-coupling product, ethylbenzene (A) and homocoupling product, bibenzyl (B) in the presence of ferric ion. When CH_3$MgI prepared with pure magnesium was used, the ratio of A to B was 22 to 78 and with reagent grade magnesium, the ratio became 33 to 67 indicating that metallic impurities in magnesium affect the reaction mechanism to lead less homocoupling product, B. The ratio changes became significant when ferric chloride was added in the reaction mixture in catalytic amounts and the ratio of A to B reached to 80 to 20 at maximum. The reaction in the presence of ferric ion seems to follow mainly an ionic mechanism which involves iron-benzyl bromide ${\pi}$-complex formation. The complex formation is expected to be able to enhance ionic attack of CH_3$MgI on benzyl carbon to give more A.

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State of the Art of the Cyclic Plasticity Models of Structural Steel (구조용 강재의 반복소성모델 분석 연구)

  • Lee, Eun Taik
    • Journal of Korean Society of Steel Construction
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    • v.14 no.6
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    • pp.735-746
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    • 2002
  • The task of plastic theory is twofold: first, to set up relationships between stress and strain that adequately describe the observed plastic deformation of metals, and second, to develop techniques for using these relationships in studying of the mechanics of metal forming processes, and the anlaysis and design of structures. One of the major problems in the theory of plasticity is to describe the behavior of work-hardening materials in the plastic range for complex loading histories. This can be achieved by formulating constitutive laws either in the integral or differential forms. To adequately predict the response of steel members during cyclic loading, the hardening rule must account for the features of cyclic stress-strain behavior. Neithe of the basic isotropic and kinematic hardening rules is suitable for describing cyclic streess-strain behavior, although a kinematic hardening rule describes the nearly linear portions of the stabilized hystersis loops. There is also a limited expansion of the yield surface as predicted by the isotropic hardening rule. Strong ground motions or wind gusts affect the complex and nonproportional loading histories in the inelastic behavior of structues rather than the proportional loading. Nonproportional loading is defined as externally applied forces on the structure, with variable ratios during the entire loading history. This also includes the rate of time-dependency of the loads. For nonproportional loading histories, unloading may take place along a chord instead of the radius of the load surface. In such cases, the shape of the stress-strain curve has to be determined experimentally for all non-radial loading conditions. The plasticity models including two surface models ae surveyed based on a yield surface and a bound surface that represent a state of maximum stress. This paper is concerned with the improvement of a plasticity models of the two-surface type for structural steel. This is follwed by an overview of plasticity models on structural steel. Finally the need for further research is identified.