• Title/Summary/Keyword: Stoichiometry

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Spark plasma sintering of UO2 fuel composite with Gd2O3 integral fuel burnable absorber

  • Papynov, E.K.;Shichalin, O.O.;Belov, A.A.;Portnyagin, A.S.;Buravlev, I.Yu;Mayorov, V.Yu;Sukhorada, A.E.;Gridasova, E.A.;Nomerovskiy, A.D.;Glavinskaya, V.O.;Tananaev, I.G.;Sergienko, V.I.
    • Nuclear Engineering and Technology
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    • v.52 no.8
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    • pp.1756-1763
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    • 2020
  • The paper studies spark plasma sintering (SPS) of industrially used UO2-based fuel containing integral fuel burnable absorber (IFBA) of neutrons Gd2O3. Densification dynamics of pristine UO2 powder and the one added with 2 and 8 wt% of Gd2O3 under ultrasonication in liquid has been studied under SPS conditions at 1050, 1250, and 1450 ℃. Effect of sintering temperature on phase composition as well as on O/U stoichiometry has been investigated for UO2 SPS ceramics. Sintering of uranium dioxide added with Gd2O3 yields solid solution (U,Gd)O2, which is isostructural to UO2. SEM with EDX and metallography were implemented to analyze the microstructure of the obtained UO2 ceramics and composite UO2-Gd2O3 one, particularly, open porosity, defects, and Gd2O3 distribution were studied. Microhardness, compressive strength and density were shown to reduce after addition of Gd2O3. Obtained results prove the hypothesis on formation of stable pores in the system of UO2-Gd2O3 due to Kirkendall effect that reduces sintering efficiency. The paper expands fundamental knowledge on pros and cons of fuel fabrication with IFBA using SPS technology.

A study of defect structures in $LiNbO_{3}$ single crystals by optical absorptions (광흡수에 의한 $LiNbO_{3}$ 단결정의 결함 구조 연구)

  • 김상수
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.6 no.3
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    • pp.327-340
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    • 1996
  • In this study, a series of $LiNbO_{3}$ crystals with different [Li]/[Nb] ratios, congruent $LiNbO_{3}$ crystals with doped Mg and with Mg and codoped with Mn were grown by the Czocharalski method. These were investigated by UV and IR spectrophotometry. Stoichiometry dependences of the UV absorption edge and the $OH^{-}$ absorption spectra were studied with different [Li]/[Nb] ratios. The position of the UV absorption edge adn the shape and peak point of the $OH^{-}$ absorption spectra changed monotonously upto a critical concentration of Mg ions. The mechanism of the incorporation of Mg ions changes at this concentration. The decomposition of the $OH^{-}$ absorption spectra using a Gaussian lineshape function showed that in Li-deficient crystals the absorption spectra consist of five components in contrast to more or less perfect stoichiometric crystals which reveal to three components. On the basis of these results, the intrinsic and the extrinsic defect structure models in $LiNbO_{3}$ crystals were examined. The behaviour of $\nu$ (OH) reflects the defect structure and supports the Li-site vacancy model as the intrinsic defect structure model and the corresponding extrinsic defect model. A brief discussion is also given of the behaviour of $\nu$ (OH) in $LiNbO_{3}$ crystals simultaneously doped with several kinds of impurity.

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The Preparation of Bi-2223 Superconducting Powder and Tape by Emulsion Drying Method (에멀젼 건조법에 의한 Bi-2223 초전도 분말과 테이프 제조)

  • 장중철;이응상;이희균;홍계원
    • Journal of the Korean Ceramic Society
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    • v.34 no.2
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    • pp.115-122
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    • 1997
  • The powder preparation by using emulsion drying method, one of the chemical powder fabrication methods has the advantages; easy to control the chemical stoichiometry and to fabricate homogeneously fine particles. In the present study, the initial morphology and size distribution of the powder fabricated by using emulsion dry-ing method were controlled and were improved the homogeneity. By carefully controlling the mixing ratio of oil phase and aqueous solution and surfactant of preventing emulsion separation, the Bi(Pb)-Sr-Ca-Cu-O su-perconducting powders were prepared. The properties of the superconducting powder fabricated by this method and the microstructures and superconducting properties of the pelletized samples were investigated. The microstructures and electric properties of the tapes prepared by oxide powder-in-tube method were in-vestigated. The fabricated powder was spherical with less than 1$\mu$m but most of them was agglomerated with 2~5$\mu$m in size. The critical temperature of the pelletized sample annealed at 84$0^{\circ}C$ for 72 hours in oxygen par-tial pressure of 1/13atm in Ar atmosphere was 108K. And the critical current of the first and second annealed tapes in air prepared by oxide powder-in-tube process were 0.4A and 1.5A, respectively.

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Triclinic Na3.12Co2.44(P2O7)2 as a High Redox Potential Cathode Material for Na-Ion Batteries

  • Ha, Kwang-Ho;Kwon, Mi-Sook;Lee, Kyu Tae
    • Journal of Electrochemical Science and Technology
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    • v.11 no.2
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    • pp.187-194
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    • 2020
  • Two types of sodium cobalt pyrophosphates, triclinic Na3.12Co2.44(P2O7)2 and orthorhombic Na2CoP2O7, are compared as high-voltage cathode materials for Na-ion batteries. Na2CoP2O7 shows no electrochemical activity, delivering negligible capacity. In contrast, Na3.12Co2.44(P2O7)2 exhibits good electrochemical performance, such as high redox potential at ca. 4.3 V (vs. Na/Na+) and stable capacity retention over 50 cycles, although Na3.12Co2.44(P2O7)2 delivered approximately 40 mA h g-1. This is attributed to the fact that Na2CoP2O7 (~3.1 Å) has smaller diffusion channel size than Na3.12Co2.44(P2O7)2 (~4.2 Å). Moreover, the electrochemical performance of Na3.12Co2.44(P2O7)2 is examined using Na cells and Li cells. The overpotential of Na cells is smaller than that of Li cells. This is due to the fact that Na3.12Co2.44(P2O7)2 has a smaller charge transfer resistance and higher diffusivity for Na+ ions than Li+ ions. This implies that the large channel size of Na3.12Co2.44(P2O7)2 is more appropriate for Na+ ions than Li+ ions. Therefore, Na3.12Co2.44(P2O7)2 is considered a promising high-voltage cathode material for Na-ion batteries, if new electrolytes, which are stable above 4.5 V vs. Na/Na+, are introduced.

Numerical Modeling of Current Density and Water Behavior at a Designated Cross Section of the Gas Diffusion Layer in a Proton Exchange Membrane Fuel Cell (고분자전해질 연료전지의 동작압력에 대한 가스 확산층의 위치 별 전류밀도 및 수분거동에 대한 수치해석)

  • Kang, Sin-Jo;Kim, Young-Bae
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.36 no.2
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    • pp.161-170
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    • 2012
  • There are many factors to consider when attempting to improve the efficiency of fuel cell operation, such as the operation temperature, humidity, stoichiometry, operation pressure, geometric features, etc. In this paper, the effects of the operation pressure were investigated to find the current density and water saturation behavior on a cross section designated by the design geometry. A two-dimensional geometric model was established with a gas channel that can provide $H_2$ to the anode and $O_2$ and water vapor to the cathode gas diffusion layer (GDL). The results from this numerical modeling revealed that higher operation pressures would produce a higher current density than lower ones, and the water saturation behavior was different at operation pressures of 2 atm and 3 atm in the cathode GDL. In particular, the water saturation ratios are higher directly below the collector than in other areas. In addition, this paper presents the dependence of the velocity behavior in the cathode on pressure changes, and the velocity fluctuations through the GDL are higher in the output area than in inlet area. This conclusion will be utilized to design more efficient fuel cell modeling of real fuel cell operation.

Seawater N/P ratio of the East Sea (동해 해수의 질소:인의 비)

  • LEE, TONGSUP;RHO, TAE-KEUN
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.20 no.4
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    • pp.199-205
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    • 2015
  • Nitrogen and phosphorus are the limiting elements for growth of phytoplankton, which is a major primary producer of marine ecosystem. Incidentally the stoichiometry of N/P of ocean waters, measured by the (nitrate + nitrite)/phosphate ratio converges to a constant of 16. This characteristic ratio has been used widely for the understanding the ecosystem dynamics and biogeochemical cycles in the ocean. In the East Sea, several key papers were issued in recent years regarding the climate change and its impact on ecosystem dynamic and biogeochemical cycles using N/P ratio because the East Sea is a "miniature ocean" having her own meridional overturning circulation with the appropriate responding time and excellent accessibility. However, cited N/P values are different by authors that we tried to propose a single representative value by reanalyzing the historical nutrient data. We present N/P of the East Sea as $12.7{\pm}0.1$ for the year 2000. The ratio reveals a remarkable consistency for waters exceeding 300m depth (below the seasonal thermocline). We recommend to use this value in the future studies and hope to minimize confusion for understanding ecosystem response and biogeochemical cycles in relation to future climate change until new N/P value is established from future studies.

Enhanced Antimicrobial Activities and Physicochemical Characteristics of Isoliquiritigenin Encapsulated in Hydroxypropyl-β-Cyclodextrin (아이소리퀴리티게닌을 담지한 2-하이드록시프로필-베타사이클로덱스트린의 물리화학적 특성 및 항균활성 연구)

  • Kim, Hae Soo;Im, Na Ri;Park, Soo Nam
    • Applied Chemistry for Engineering
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    • v.26 no.6
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    • pp.719-724
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    • 2015
  • Isoliquiritigenin (ILG) is a hydrophobic component in licorice and has a variety of pharmaceutical and biological activities. In this study, we prepared an isoliquiritigenin-hydroxypropyl-${\beta}$-cyclodextrin (ILG/HP-${\beta}$-CD) complex by freeze-drying method to enhance its water solubility. The complex was characterized by phase solubility studies, DSC, SEM, and 1H NMR. Antimicrobial activities against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) were evaluated by broth dilution method. The results showed that the stoichiometry of ILG/HP-${\beta}$-CD complex was 1 : 1. The antimicrobial activity of ILG/HP-${\beta}$-CD complex was higher than that of using free ILG against S. aureus and E. coli. Therefore, we suggest that ILG/HP-${\beta}$-CD complex may be used as a natural antiseptic and could potentially replace synthetic preservatives in cosmetic and food industries.

PEMOCVD of Ti(C,N) Thin Films on D2 Steel and Si(100) Substrates at Low Growth Temperatures

  • Kim, Myung-Chan;Heo, Cheol-Ho;Boo, Jin-Hyo;Cho,Yong-Ki;Han, Jeon-Geon
    • Proceedings of the Korean Vacuum Society Conference
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    • 1999.07a
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    • pp.211-211
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    • 1999
  • Titanium nitride (TiN) thin films have useful properties including high hardness, good electrical conductivity, high melting point, and chemical inertness. The applications have included wear-resistant hard coatings on machine tools and bearings, decorative coating making use of the golden color, thermal control coatings for widows, and erosion resistant coatings for spacecraft plasma probes. For all these applications as feature sizes shrink and aspect ratios grow, the issue of good step coverage becomes increasingly important. It is therefore essential to manufacture conformal coatings of TiN. The growth of TiN thin films by chemical vapor deposition (CVD) is of great interest for achieving conformal deposition. The most widely used precursor for TiN is TiCl4 and NH3. However, chlorine impurity in the as-grown films and relatively high deposition temperature (>$600^{\circ}C$) are considered major drawbacks from actual device fabrication. To overcome these problems, recently, MOCVD processes including plasma assisted have been suggested. In this study, therefore, we have doposited Ti(C, N) thin films on Si(100) and D2 steel substrates in the temperature range of 150-30$0^{\circ}C$ using tetrakis diethylamido titanium (TDEAT) and titanium isopropoxide (TIP) by pulsed DC plamsa enhanced metal-organic chemical vapor deposition (PEMOCVD) method. Polycrystalline Ti(C, N) thin films were successfully grown on either D2 steel or Si(100) surfaces at temperature as low as 15$0^{\circ}C$. Compositions of the as-grown films were determined with XPS and RBS. From XPS analysis, thin films of Ti(C, N) with low oxygen concentration were obtained. RBS data were also confirmed the changes of stoichiometry and microhardness of our films. Radical formation and ionization behaviors in plasma are analyzed by optical emission spectroscopy (OES) at various pulsed bias and gases conditions. H2 and He+H2 gases are used as carrier gases to compare plasma parameter and the effect of N2 and NH3 gases as reactive gas is also evaluated in reduction of C content of the films. In this study, we fond that He and H2 mixture gas is very effective in enhancing ionization of radicals, especially N resulting is high hardness. The higher hardness of film is obtained to be ca. 1700 HK 0.01 but it depends on gas species and bias voltage. The proper process is evident for H and N2 gas atmosphere and bias voltage of 600V. However, NH3 gas highly reduces formation of CN radical, thereby decreasing C content of Ti(C, N) thin films in a great deal. Compared to PVD TiN films, the Ti(C, N) film grown by PEMOCVD has very good conformability; the step coverage exceeds 85% with an aspect ratio of more than 3.

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Growth of SiC Oxidation Protective Coating Layers on graphite substrates Using Single Source Precursors

  • Kim, Myung-Chan;Heo, Cheol-Ho;Park, Jin-Hyo;Park, Seung-Jun;Han, Jeon-Geon
    • Proceedings of the Korean Vacuum Society Conference
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    • 1999.07a
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    • pp.122-122
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    • 1999
  • Graphite with its advantages of high thermal conductivity, low thermal expansion coefficient, and low elasticity, has been widely used as a structural material for high temperature. However, graphite can easily react with oxygen at even low temperature as 40$0^{\circ}C$, resulting in CO2 formation. In order to apply the graphite to high temperature structural material, therefore, it is necessary to improve its oxidation resistive property. Silicon Carbide (SiC) is a semiconductor material for high-temperature, radiation-resistant, and high power/high frequency electronic devices due to its excellent properties. Conventional chemical vapor deposited SiC films has also been widely used as a coating materials for structural applications because of its outstanding properties such as high thermal conductivity, high microhardness, good chemical resistant for oxidation. Therefore, SiC with similar thermal expansion coefficient as graphite is recently considered to be a g행 candidate material for protective coating operating at high temperature, corrosive, and high-wear environments. Due to large lattice mismatch (~50%), however, it was very difficult to grow thick SiC layer on graphite surface. In theis study, we have deposited thick SiC thin films on graphite substrates at temperature range of 700-85$0^{\circ}C$ using single molecular precursors by both thermal MOCVD and PEMOCVD methods for oxidation protection wear and tribological coating . Two organosilicon compounds such as diethylmethylsilane (EDMS), (Et)2SiH(CH3), and hexamethyldisilane (HMDS),(CH3)Si-Si(CH3)3, were utilized as single source precursors, and hydrogen and Ar were used as a bubbler and carrier gas. Polycrystalline cubic SiC protective layers in [110] direction were successfully grown on graphite substrates at temperature as low as 80$0^{\circ}C$ from HMDS by PEMOCVD. In the case of thermal MOCVD, on the other hand, only amorphous SiC layers were obtained with either HMDS or DMS at 85$0^{\circ}C$. We compared the difference of crystal quality and physical properties of the PEMOCVD was highly effective process in improving the characteristics of the a SiC protective layers grown by thermal MOCVD and PEMOCVD method and confirmed that PEMOCVD was highly effective process in improving the characteristics of the SiC layer properties compared to those grown by thermal MOCVD. The as-grown samples were characterized in situ with OES and RGA and ex situ with XRD, XPS, and SEM. The mechanical and oxidation-resistant properties have been checked. The optimum SiC film was obtained at 85$0^{\circ}C$ and RF power of 200W. The maximum deposition rate and microhardness are 2$mu extrm{m}$/h and 4,336kg/mm2 Hv, respectively. The hardness was strongly influenced with the stoichiometry of SiC protective layers.

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Ni0.5Zn0.4Cu0.1Fe2O4 Complex Ferrite Nanoparticles Synthesized by Chemical Coprecipitation Predicted by Thermodynamic Modeling

  • Kang, Bo-Sun;Park, Joo-Seok;Ahn, Jong-Pil;Kim, Kwang-Hyun;Tae, Ki-Sik;Lee, Hyun-Ju;Kim, Do-Kyung
    • Journal of the Korean Ceramic Society
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    • v.50 no.3
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    • pp.231-237
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    • 2013
  • Thermodynamic modeling of the $Ni_{0.5}Zn_{0.4}Cu_{0.1}Fe_2O_4$ complex ferrite system has been adopted as a rational approach to establish routes to better synthesis conditions for pure phase $Ni_{0.5}Zn_{0.4}Cu_{0.1}Fe_2O_4$ complex ferrite. Quantitative analysis of the different reaction equilibria involved in the precipitation of $Ni_{0.5}Zn_{0.4}Cu_{0.1}Fe_2O_4$ from aqueous solutions has been used to determine the optimum synthesis conditions. The spinel ferrites, such as magnetite and substitutes for magnetite, with the general formula $MFe_2O_4$, where M= $Fe^{2+}$, $Co^{2+}$, and $Ni^{2+}$ are prepared by coprecipitation of $Fe^{3+}$ and $M^{2+}$ ions with a stoichiometry of $M^{2+}/Fe^{3+}$= 0.5. The average particle size of the as synthesized $Ni_{0.5}Zn_{0.4}Cu_{0.1}Fe_2O_4$, measured by transmission electron microscopy (TEM), is 14.2 nm, with a standard deviation of 3.5 nm the size when calculated using X-ray diffraction (XRD) is 16 nm. When $Ni_{0.5}Zn_{0.4}Cu_{0.1}Fe_2O_4$ ferrite is annealed at elevated temperature, larger grains are formed by the necking and mass transport between the $Ni_{0.5}Zn_{0.4}Cu_{0.1}Fe_2O_4$ ferrite nanoparticles. Thus, the grain sizes of the $Ni_{0.5}Zn_{0.4}Cu_{0.1}Fe_2O_4$ gradually increase as heat treatment temperature increases. Based on the results of Thermogravimetric Analysis (TGA) and Differential Scanning Calorimeter (DSC) analysis, it is found that the hydroxyl groups on the surface of the as synthesized ferrite nanoparticles finally decompose to $Ni_{0.5}Zn_{0.4}Cu_{0.1}Fe_2O_4$ crystal with heat treatment. The results of XRD and TEM confirmed the nanoscale dimensions and spinel structure of the samples.