• Title/Summary/Keyword: Lattice Reduction

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One-step synthesis of dual-transition metal substitution on ionic liquid based N-doped mesoporous carbon for oxygen reduction reaction

  • Byambasuren, Ulziidelger;Jeon, Yukwon;Altansukh, Dorjgotov;Ji, Yunseong;Shul, Yong-Gun
    • Carbon letters
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    • v.17 no.1
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    • pp.53-64
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    • 2016
  • Nitrogen (N)-doped ordered mesoporous carbons (OMCs) with a dual transition metal system were synthesized as non-Pt catalysts for the ORR. The highly nitrogen doped OMCs were prepared by the precursor of ionic liquid (3-methyl-1-butylpyridine dicyanamide) for N/C species and a mesoporous silica template for the physical structure. Mostly, N-doped carbons are promoted by a single transition metal to improve catalytic activity for ORR in PEMFCs. In this study, our N-doped mesoporous carbons were promoted by the dual transition metals of iron and cobalt (Fe, Co), which were incorporated into the N-doped carbons lattice by subsequently heat treatments. All the prepared carbons were characterized by via transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). To evaluate the activities of synthesized doped carbons, linear sweep was recorded in an acidic solution to compare the ORR catalytic activities values for the use in the PEMFC system. The dual transition metal promotion improved the ORR activity compared with the single transition metal promotion, due to the increase in the quaternary nitrogen species from the structural change by the dual metals. The effect of different ratio of the dual metals into the N doped carbon were examined to evaluate the activities of the oxygen reduction reaction.

Methane Partial Oxidation Using Cu-ferrite (Cu-ferrite에 의한 메탄의 부분산화)

  • Woo, Sung-Woung;Kang, Kyoung-Soo;Kim, Chang-Hee;Park, Chu-Sik
    • Transactions of the Korean hydrogen and new energy society
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    • v.18 no.2
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    • pp.124-131
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    • 2007
  • Methane is partially oxidized to produce the syngas by the lattice oxygen of metal oxides in the absence of gaseous oxygen. The present work deals with ferrite including copper component, which does not chemisorb methane, to investigate the suppression of the carbon deposition during the reduction of metal oxides by methane. Iron-based oxides of $Cu_xFe_{3-x}O_4$(X=0.25, 0.5, 1.0) was synthesized by the co-precipitation method. Thermogravimetric Analysis(TGA) was used to observe the isothermal reduction behavior of $Cu_xFe_{3-x}O_4$ and $Fe_3O_4$ at $600-900^{\circ}C$ under methane atmosphere. The crystal structures of reduced specimens were characterized by X-rays powder diffraction(XRD) technique. From the analyses of TGA, it is concluded that the reduction kinetics of $CuFe_2O_4$ was the fastest among $Fe_3O_4$ and $Cu_xFe_{3-x}O_4$(X=0.25, 0.5, 1.0). The X-ray diffraction analyses indicated that $Cu_xFe_{3-x}O_4$ was decomposed to Cu and $Fe_3O_4$ phase at $600^{\circ}C$ and was reduced to Cu and Fe phase at $800^{\circ}C$. $Fe_3O_4$, which was reduced at $900^{\circ}C$, showed Fe, graphite and $Fe_3C$ phases. On the contrary, $Cu_xFe_{3-x}O_4$ does not show the graphite or $Fe_3C$ phases. This results infer that Cu component suppress the carbon deposition on Cu-ferrite.

Synthesis and Oxygen Reduction Reaction Characteristics of Multi-Walled Carbon Nanotubes Supported PtxM(1-x) (M = Co, Cu, Ni) Alloy Catalysts for Polymer Electrolyte Membrane Fuel Cell (다중벽 탄소 나노 튜브에 담지한 PtxM(1-x)(M = Co, Cu, Ni) 합금촉매의 제조 및 고분자 전해질 연료전지에서 산소환원 특성)

  • Jung, Dong-Won;Park, Soon;Ahn, Chi-Yeong;Choi, Seong-Ho;Kim, Jun-Bom
    • Korean Journal of Materials Research
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    • v.19 no.12
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    • pp.667-673
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    • 2009
  • The electrocatalytic characteristics of oxygen reduction reaction of the $PtxM_{(1-x)}$ (M = Co, Cu, Ni) supported on multi-walled carbon nanotubes (MWNTs) have been evaluated in a Polymer Electrolyte Membrane Fuel Cell (PEMFC). The $Pt_xM_{(1-x)}$/MWNTs catalysts with a Pt : M atomic ratio of about 3 : 1 were synthesized and applied to the cathode of PEMFC. The crystalline structure and morphology images of the $Pt_xM_{(1-x)}$ particles were characterized by X-ray diffraction and transmission electron microscopy, respectively. The results showed that the crystalline structure of the Pt alloy particles in Pt/MWNTs and $Pt_xM_{(1-x)}$/MWNTs catalysts are seen as FCC, and synthesized $Pt_xM_{(1-x)}$ crystals have lattice parameters smaller than the pure Pt crystal. According to the electrochemical surface area (ESA) calculated with cyclic voltammetry analysis, $Pt_{0.77}Co_{0.23}$/MWNTs catalyst has higher ESA than the other catalysts. The evaluation of a unit cell test using Pt/MWNTs or $Pt_xM_{(1-x)}$/MWNTs as the cathode catalysts demonstrated higher cell performance than did a commercial Pt/C catalyst. Among the MWNTs-supported Pt and $Pt_xM_{(1-x)}$ (M = Co, Cu, Ni) catalysts, the $Pt_{0.77}Co_{0.23}$/MWNTs shows the highest performance with the cathode catalyst of PEMFC because they had the largest ESA.

Synthesis and Characterization of Ni4Cr Nanofiber Electrocatalyst for Hydrogen Evolution Reaction (수소발생반응을 위한 Ni4Cr 나노 섬유 전기화학 촉매 합성 및 특성 분석)

  • Lee, Jeong Hun;Jang, Myeong Je;Park, Yoo Sei;Choi, Sung Mook;Kim, Yang Do;Lee, Kyu Hwan
    • Journal of the Korean institute of surface engineering
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    • v.50 no.5
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    • pp.322-331
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    • 2017
  • Hydrogen evolution reaction(HER) was studied over $Ni_4Cr$ nanofibers(NFs) prepared by electrospinning method and oxidation/reduction heat treatment for alkaline water electrolysis. The physicochemical and electrochemical properties such as average diameter, lattice parameter, HER activity of synthesized $Ni_4Cr$ NFs could be modified by proper electrospinning process condition and reduction temperature. It was shown that $Ni_4Cr$ NFs had average diameter from 151 to 273 nm. Also, it exhibited the overpotential between 0.419 V and 0.526 V at $1mA/cm^2$ and Tafel slope of -334.75 mV to -444.55 mV per decade in 1 M KOH solution. These results indicate that $Ni_4Cr$ NFs with reduction heat treatment at $600^{\circ}C$ show thinnest diameter and highest HER activity among the other catalysts.

Luminescence properties of InGaN/GaN green light-emitting diodes grown by using graded short-period superlattice structures

  • Cho, Il-Wook;Na, Hyeon Ji;Ryu, Mee-Yi;Kim, Jin Soo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.279.2-279.2
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    • 2016
  • InGaN/GaN multiple quantum wells (MQWs) have been attracted much attention as light-emitting diodes (LEDs) in the visible and UV regions. Particularly, quantum efficiency of green LEDs is decreased dramatically as approaching to the green wavelength (~500 nm). This low efficiency has been explained by quantum confined Stark effect (QCSE) induced by piezoelectric field caused from a large lattice mismatch between InGaN and GaN. To improve the quantum efficiency of green LED, several ways including epitaxial lateral overgrowth that reduces differences of lattice constant between GaN and sapphire substrates, and non-polar method that uses non- or semi-polar substrates to reduce QCSE were proposed. In this study, graded short-period InGaN/GaN superlattice (GSL) was grown below the 5-period InGaN/GaN MQWs. InGaN/GaN MQWs were grown on the patterned sapphire substrates by vertical-metal-organic chemical-vapor deposition system. Five-period InGaN/GaN MQWs without GSL structure (C-LED) were also grown to compare with an InGaN/GaN GSL sample. The luminescence properties of green InGaN/GaN LEDs have been investigated by using photoluminescence (PL) and time-resolved PL (TRPL) measurements. The PL intensities of the GSL sample measured at 10 and 300 K increase about 1.2 and 2 times, respectively, compared to those of the C-LED sample. Furthermore, the PL decay of the GSL sample measured at 10 and 300 K becomes faster and slower than that of the C-LED sample, respectively. By inserting the GSL structures, the difference of lattice constant between GaN and sapphire substrates is reduced, resulting that the overlap between electron and hole wave functions is increased due to the reduced piezoelectric field and the reduction in dislocation density. As a results, the GSL sample exhibits the increased PL intensity and faster PL decay compared with those for the C-LED sample. These PL and TRPL results indicate that the green emission of InGaN/GaN LEDs can be improved by inserting the GSL structures.

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Structural analysis and thermal expansion property of Cu doped LSM for SOFCs (Cu가 도핑된 LSM의 구조분석과 열팽창특성 연구)

  • Noh, Tai-Min;Ryu, Ji-Seung;Kim, Jin-Seong;Jeong, Cheol-Weon;Lee, Hee-Soo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.21 no.4
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    • pp.175-180
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    • 2011
  • The doping effect of Cu in the Sr-doped lanthan manganites (LSM) has been investigated in terms of structural analysis and thermal expansion coefficient (TEC). The $La_{0.8}Sr_{0.2}Mn_{1-x}Cu_xO_3$ ($0{\leq}x{\leq}0.3$) were prepared by solid state reaction method and their crystal structure and TEC were measured. A decrease in the lattice parameters and the TEC were observed with increase eu content, whereas they were decreased for x = 0.3. For $0{\leq}x{\leq}0.2$, the decrease of the lattice parameter and the TEC with increase Cu content were attributed to the reduction of ionic radius of Cu ions due to the presence of $Cu^{3+}$ ions. For x = 0.3, however, the increase was originated from the formation of oxygen vacancies due 10 the presence of $Cu^{2+}$ and $Mn^{4+}$.

Variations of the Electrochemical Properties of LiMn2O4 with the Calcining Temperature

  • Song, Myoung-Youp;Shon, Mi-suk
    • Journal of the Korean Ceramic Society
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    • v.39 no.6
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    • pp.523-527
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    • 2002
  • LiMn$_2$O$_4$ compounds were synthesized by calcining a mixture of LiOH and MnO$_2$(CMD) at 47$0^{\circ}C$ for 10 h and then calcining again at $650^{\circ}C$ to 90$0^{\circ}C$ fur 48 h in air with intermediate grinding. All the synthesized samples exhibited XRD patterns for the cubic spinel phase with a space group Fd3m. The lattice parameter increased gradually as the sintering temperature rose. The electrochemical cells were charged and discharged fur 20 cycles at a current density 300$\mu$A/$\textrm{cm}^2$ between 3.5 V and 4.3 V. The voltage vs. discharge capacity curves for all the samples showed two plateaus. The LiMn$_2$O$_4$ sample calcined at 90$0^{\circ}C$ had the largest first discharge capacity. This sample exhibited the best crystallinity, had relatively large lattice parameter and had relatively large particles with rectatively homogeneous size. All the samples showed good cycling performances. Among all the samples, the LiMn$_2$O$_4$ calcined at 85$0^{\circ}C$ had relatively large first discharge capacity and very good cycling performance. The addition of excess LiOH and the mixing in ethanol considered to help the formation of the more LiMn$_2$O$_4$ phase per unit weight sample and the more stable LiMn$_2$O$_4$phase. These led to the larger discharge capacities and the better cycling performances. The cyclic voltammograms fur the second cycle of the LiMn$_2$O$_4$ samples showed the oxidation and reduction peaks around 4.05 V and 4.18 V and around 4.08 V and 3.94 V, respectively. The larger first discharge capacity of the sample calcined at the higher temperature is related to the larger lattice parameter.

Proper Orthogonal Decomposition Based Intrusive Reduced Order Models to Accelerate Computational Speed of Dynamic Analyses of Structures Using Explicit Time Integration Methods (외연적 시간적분법 활용 동적 구조해석 속도 향상을 위한 적합직교분해 기반 침습적 차수축소모델 적용 연구)

  • Young Kwang Hwang;Myungil Kim
    • Journal of the Computational Structural Engineering Institute of Korea
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    • v.37 no.1
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    • pp.9-16
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    • 2024
  • Using the proper orthogonal decomposition (POD) based intrusive reduced order model (ROM), the total degrees of freedom of the structural system can be significantly reduced and the critical time step satisfying the conditional stability increases in the explicit time integrations. In this study, therefore, the changes in the critical time step in the explicit time integrations are investigated using both the POD-ROM and Voronoi-cell lattice model (VCLM). The snapshot matrix is composed of the data from the structural response under the arbitrary dynamic loads such as seismic excitation, from which the POD-ROM is constructed and the predictive capability is validated. The simulated results show that the significant reduction in the computational time can be achieved using the POD-ROM with sufficiently ensuring the numerical accuracy in the seismic analyses. In addition, the validations show that the POD based intrusive ROM is compatible with the Voronoi-cell lattice based explicit dynamic analyses. In the future study, the research results will be utilized as an elemental technology for the developments of the real-time predictive models or monitoring system involving the high-fidelity simulations of structural dynamics.

INTERGRANULAR CORROSION-RESISTANT STAINLESS STEEL BY GRAIN BOUNDARY ENGINEERING

  • Hiroyuki Kokawa;Masayuki Shimada;Wang, Zhan-Jie;Yutaka S. Sato
    • Proceedings of the KWS Conference
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    • 2002.10a
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    • pp.250-254
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    • 2002
  • Intergranular corrosion of austenitic stainless steels is a conventional and momentous problem during welding and high temperature use. One of the major reasons for such intergranular corrosion is so-called sensitization, i.e., chromium depletion due to chromium carbide precipitation at grain boundaries. Conventional methods for preventing sensitization of austenitic stainless steels include reduction of carbon content in the material, stabilization of carbon atoms as non-chromium carbides by the addition of titanium, niobium or zirconium, local solution-heat-treatment by laser beam, etc. These methods, however, are not without drawbacks. Recent grain boundary structure studies have demonstrated that grain boundary phenomena strongly depend on the crystallographic nature and atomic structure of the grain boundary, and that grain boundaries with coincidence site lattices are immune to intergranular corrosion. The concept of "grain boundary design and control", which involves a desirable grain boundary character distribution, has been developed as grain boundary engineering. The feasibility of grain boundary engineering has been demonstrated mainly by thermomechanical treatments. In the present study, a thermomechanical treatment was tried to improve the resistance to the sensitization by grain boundary engineering. A type 304 austenitic stainless steel was pre-strained and heat-treated, and then sensitized, varying the parameters (pre-strain, temperature, time, etc.) during the thermomechanical treatment. The grain boundary character distribution was examined by orientation imaging microscopy. The intergranular corrosion resistance was evaluated by electrochemical potentiokinetic reactivation and ferric sulfate-sulfuric acid tests. The sensitivity to intergranular corrosion was reduced by the thermomechanical treatment and indicated a minimum at a small roll-reduction. The frequency of coincidence-site-lattice boundaries indicated a maximum at a small strain. The ferric sulfate-sulfuric acid test showed much smaller corrosion rate in the thermomechanically-treated specimen than in the base material. An excellent intergranular corrosion resistance was obtained by a small strain annealing at a relatively low temperature for long time. The optimum parameters created a uniform distribution of a high frequency of coincidence site lattice boundaries in the specimen where corrosive random boundaries were isolated. The results suggest that the thermomechanical treatment can introduce low energy segments in the grain boundary network by annealing twins and can arrest the percolation of intergranular corrosion from the surface.

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Preparation of ZrC/SiC by Carbothermal Reduction of Zircon (지르콘의 탄소열환원에 의한 ZrC/SiC의 합성)

  • Park, Hong-Chae;Lee, Yoon-Bok;Lee, Cheol-Gyu;Oh, Ki-Dong
    • Applied Chemistry for Engineering
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    • v.5 no.6
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    • pp.1044-1055
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    • 1994
  • The preparation of ZrC/SiC mixed powders from $ZrSiO_4/C$ and $ZrSiO_4/Al/C$ systems was attempted in the temperature range below $1600^{\circ}C$ under Ar or $Ar/H_2$ gas flow(100-500ml/min). The formation mechanism and kinetics of ZrC/SiC were suggested and the resultant powders were characterized. In $ZrSiO_4/C$ system, ZrC and SiC were formed by competitive reaction of $ZrO_2(s)$ and SiO(g) with carbon at temperature higher than $1400^{\circ}C$. The apparent activation energy for the formation of ZrC was approximately 18.5kcal/mol($1400-1600^{\circ}C$). In $ZrSiO_4/Al/C$ system, ZrC was formed by reaction of ZrO(g) with Al(l, g) and carbon at temperature higher than $1200^{\circ}C$, and SiC was formed by reduction-carbonization of SiO(g) with Al(l, g) and carbon at temperature higher than $1300^{\circ}C$. The products obtained at $1600^{\circ}C$ for 5h consisted of ZrC with lattice constant of $4.679{\AA}$ and crystallite size of $640{\AA}$, and SiC with lattice constant of $4.135{\AA}$ and crystallize size of $500{\AA}$. And also, the mean particle size was about $21.8{\mu}m$.

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