• Title/Summary/Keyword: Thermal phase transition

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Variation in optical, dielectric and sintering behavior of nanocrystalline NdBa2NbO6

  • Mathai, Kumpamthanath Chacko;Vidya, Sukumariamma;Solomon, Sam;Thomas, Jijimon Kumpukattu
    • Advances in materials Research
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    • v.2 no.2
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    • pp.77-91
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    • 2013
  • High quality nanoparticles of neodymium barium niobium ($NdBa_2NbO_6$) perovskites have been synthesized using an auto ignition combustion technique for the first time. The nanoparticles thus obtained have been characterized by powder X-ray diffraction, thermo gravimetric analysis, differential thermal analysis, Fourier transform infrared spectroscopy, Raman spectroscopy and transmission electron microscopy. UV-Visible absorption and photoluminescence spectra of the samples are also recorded. The structural analysis shows that the nano powder is phase pure with the average particle size of 35 nm. The band gap determined for $NdBa_2NbO_6$ is 3.9 eV which corresponds to UV-radiation for optical inter band transition with a wavelength of 370nm. The nanopowder could be sintered to 96% of the theoretical density at $1325^{\circ}C$ for 2h. The ultrafine cuboidal nature of nanopowders with fewer degree of agglomeration improved the sinterability for compactness at relatively lower temperature and time. During the sintering process the wide band gap semiconducting behavior diminishes and the material turns to a high permittivity dielectric. The microstructure of the sintered surface was examined using scanning electron microscopy. The striking value of dielectric constant ${\varepsilon}_r=43$, loss factor tan ${\delta}=1.97{\times}10^{-4}$ and the observed band gap value make it suitable for many dielectric devices.

Study on self-diffusion transport phenomena during mercurous bromide (Hg2Br2) vapor processes (브로민화수은(I)(Hg2Br2) 증착공정에서 자체확산 연구)

  • Nam Il Kim;Geug Tae Kim
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.34 no.2
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    • pp.48-54
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    • 2024
  • During the Hg2Br2 physical vapor transport process with self-diffusion, it is concluded that for 10-3g0≤ g ≤ 1g0 the thermal buoyancy driven convection is dominant in the vapor phase; at the gravitational level of g = 10-4g0, the transition region from the convection to diffusion occurs; for 10-6g0 ≤ g ≤ 10-5g0, the diffusion mode is predominant. The total molar flux of Hg2Br2 decays exponentially with the decreasing of one tenth of gravitational magnitude. For 10℃ ≤ ΔT ≤ 50℃, the total molar flux increases linearly and directly with the temperature difference between the source and crystal regions.

Interpretation of Firing Temperature and Thermal Deformation of Roof Tiles from Ancient Tombs of Seokchon-dong in Seoul, Korea (서울 석촌동 고분군 출토 기와의 소성온도와 열변형 특성 해석)

  • Jin, Hong Ju;Jang, Sungyoon;Lee, Myeong Seong
    • Economic and Environmental Geology
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    • v.54 no.6
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    • pp.671-687
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    • 2021
  • This study investigated the firing temperature and thermal deformation process of roof tiles excavated from the connected stone-mound tomb in Seokchon-dong, Seoul, based on mineralogical and physical properties. A large number of roof tiles were excavated from the tomb site and some roof tiles were deformed by heat and were fired in uneven conditions. The colors of original roof tiles and their cores are mostly yellowish-brown, with high water absorption over 12%, containing fine-grained textures and some minerals such as quartz, feldspars, amphibole, and mica. It is estimated that the original roof tiles were fired below 900℃ in oxidation condition, showing loose matrices and mica layers by scanning electron microscopy. However, deformed roof tiles have the uneven surface color of reddish-brown and bluish-gray, and those cross-sections have sandwich structures in which dense reddish-brown surface and porous grey core coexist. They contained mullite and hercynite, so it was estimated to have been fired over 1,000℃, with 0.81~11% water absorption. In some samples, bloating pores by overfiring were observed, which means that they were fired at more than 1,200℃. In addition, the refirng experiments that the original roof tile was fired between 800℃ and 1,200℃ were carried out to investigate the physical and mineralogical properties of roof tiles compared to deformed ones. As a result, the water absorption decreased rapidly and the mineral phase started to change over 1,000℃. As the temperature gradually rises, the matrices are partially melted and recrystallized, resulting in similar thermal characteristics of deformed roof tiles. Therefore, the roof tiles from ancient tombs in Seokchon-dong seem to experience the secondary high temperature of 1,000 to 1,200℃ under uneven firing conditions, resulting in deformation characteristics such as shape transformation and mineral phase transition. It is considered to have been related to cremation rituals at the tombs of Seockchon-dong during the Baekje period.

Cobalt(II) Complex of 1,2-Bis(2,2'-bipyridyl-6-yl)ethane. Crystallization Process and Structural Analysis of Two Shapes of Crystals (1,2-비스(2,2'-디피리딜-6일)에탄의 코발트 착물. 두 가지 형태의 결정화 과정 및 구조 분석적 접근)

  • Park, Sung-Ho;Yoo, Kyung-Ho;Jung, Ok-Sang
    • Analytical Science and Technology
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    • v.12 no.5
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    • pp.421-427
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    • 1999
  • Two shapes of crystals have been isolated by the interdiffusion of $Co(NCS)_2$ dissolved in methanol with 1,2-bis(2,2'-bipyridyl-6-yl)ethane (bbpe) dissolved in chloroform. The two crystals have been elucidated as $trans-Co^{II}(NCS)_2(bbpe)$ and $trans-Co^{II}(NCS)_2(bbpe){\cdot}2CHCl_3$, by X-ray crystallography, elemental analysis, IR, and thermal analysis. The two molecular structures are very similar except for the absence or presence of chloroform solvate molecules. The bbpe ligand coordinates to the cobalt(II) ion in an open-ended tetradentate mode, resulting in discrete mononuclear cobalt(II) complex. The cobalt atom adopts a typical octahedral arrangement with six nitrogen donating atoms with two NCS groups in trans positions. A significant solid-to-solid phase transition occurs presumably due to the change of conformationally flexible bbpe ligand. The formation of both crystals oeeurs in a successive two-step process, the formation of $trans-Co^{II}(NCS)_2(bbpe)$ and its transformation into $trans-Co^{II}(NCS)_2(bbpe){\cdot}2CHCl_3$. The thermal stability and favorable formation of the solvate crystals may be ascribed to the interaction between S atom of NCS group and Cl of chloroform.

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Thermal stabilizing effect of Yb3+ Er3+ codoping into TiO2 powder prepared by sol-gel method and its upconversion characteristic (Yb3+ Er3+ ions 동시도핑에 의한 TiO2 분말의 열적 안정성 증가효과와 upconversion 특성 연구)

  • Eun, Jong-Won;Oh, Dong-Keun;Kim, Kwang-Jin;Hong, Tae-Ui;Jeong, Seong-Min;Choi, Bong-Geun;Shim, Kwang-Bo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.20 no.4
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    • pp.173-177
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    • 2010
  • Thermal stabilizing effect of $Yb^{3+},\;Er^{3+}$ codoping into $TiO_2$ powder prepared by sol-gel method and its upconversion characteristics were analyzed. The effect of $TiO_2:Yb^{3+},\;Er^{3+}$ ions on crystallinity and phase transition was studied by X-ray diffraction (XRD). The change of band-gap energy induced from Yb and Er codoping was analyzed by UV-Vis. The band-gap energy of $TiO_2$ have been slightly narrowed by $Yb^{3+},\;Er^{3+}$ codoping, which indicated that the $Yb^{3+},\;Er^{3+}$ ions can enhance the photo-catalytic property of $TiO_2$. green and red up-conversions of $Yb^{3+}$ and $Er^{3+}$ co-doped $Y_2O_3:Yb^{3+},\;Er^{3+}$ phosphor were analyzed by PL equipped with 980 nm laser.

Comparative analysis of two methods of laser induced boron isotopes separation

  • K.A., Lyakhov;Lee, H.J.
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.407-408
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    • 2011
  • Natural boron consists of two stable isotopes 10B and 11B with natural abundance of 18.8 atom percent of 10B and 81.2 atom percent of 11B. The thermal neutron absorption cross-section for 10B and 11B are 3837 barn and 0.005 barn respectively. 10B enriched specific compounds are used for control rods and as a reactor coolant additives. In this work 2 methods for boron enrichment were analysed: 1) Gas irradiation in static conditions. Dissociation occurs due to multiphoton absorption by specific isotopes in appropriately tuned laser field. IR shifted laser pulses are usually used in combination with increasing the laser intensity also improves selectivity up to some degree. In order to prevent recombination of dissociated molecules BCl3 is mixed with H2S 2) SILARC method. Advantages of this method: a) Gas cooling is helpful to split and shrink boron isotopes absorption bands. In order to achieve better selectivity BCl3 gas has to be substantially rarefied (~0.01%-5%) in mixture with carrier gas. b) Laser intensity is lower than in the first method. Some preliminary calculations of dissociation and recombination with carrier gas molecules energetics for both methods will be demonstrated Boron separation in SILARC method can be represented as multistage process: 1) Mixture of BCl3 with carrier gas is putted in reservoir 2) Gas overcooling due to expansion through Laval nozzle 3) IR multiphoton absorption by gas irradiated by specifically tuned laser field with subsequent gradual gas condensation in outlet chamber It is planned to develop software which includes these stages. This software will rely on the following available software based on quantum molecular dynamics in external quantized field: 1) WavePacket: Each particle is treated semiclassicaly based on Wigner transform method 2) Turbomole: It is based on local density methods like density of functional methods (DFT) and its improvement- coupled clusters approach (CC) to take into account quantum correlation. These models will be used to extract information concerning kinetic coefficients, and their dependence on applied external field. Information on radiative corrections to equation of state induced by laser field which take into account possible phase transition (or crossover?) can be also revealed. This mixed phase equation of state with quantum corrections will be further used in hydrodynamical simulations. Moreover results of these hydrodynamical simulations can be compared with results of CFD calculations. The first reasonable question to ask before starting the CFD simulations is whether turbulent effects are significant or not, and how to model turbulence? The questions of laser beam parameters and outlet chamber geometry which are most optimal to make all gas volume irradiated is also discussed. Relationship between enrichment factor and stagnation pressure and temperature based on experimental data is also reported.

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Thermotropic Liquid Crystalline Behaviors of 4-{4'-(nitrophenylazo)phenoxy}alkanoic Acids and 4-{4'-(nitrophenylazo)phenoxy}alkanoyl Chlorides (4-{4'-(니트로페닐아조)펜옥시}알칸 산들 그리고 4-{4'-(니트로페닐아조)펜옥시}알카노일 클로라이드들의 열방성 액정 거동)

  • Jeong, Seung Yong;Ma, Yung Dae
    • Applied Chemistry for Engineering
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    • v.19 no.5
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    • pp.504-511
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    • 2008
  • Two kinds of nitroazobenzene derivatives: 4-{4'-(nitrophenylazo)phenoxy}alkanoic acids (NAAn, n = 2~8, 10, number of methylene units in the alkyl chain) and 4-{4'-(nitrophenylazo)phenoxy}alkanoyl chlorides (NACn, n = 2~8, 10) were synthesized, and their thermotropic liquid crystalline behaviors were investigated. NAA6 formed an enantiotropic nematic phase, while the remainders, except NAA2, showed monotropic nematic phases. Isotropic-nematic transition temperature ($T_{iN}$) and change of entropy (${\Delta}S$) at $T_{iN}$ for both of NAAn and NACn varied by the change of n, and pronounced odd-even effects of n were also observed. However, the $T_{iN}$ and ${\Delta}S$ values of NAAn were much higher than those of NACn. This fact may be attributed to the hydrogen bonding between carboxyl groups. Thermal properties and degree of order in the mesophase and the magnitude of the odd-even effects of both NAAn and NACn were significantly different from those reported for 4-(alkoxy)-4'-nitroazobenzenes. It was discussed in terms of the differences in the molecular anisotropy and the temperature-dependent flexibility of the substituted groups.

A study on synthesis of $Li_{x}Mn_{2}O_{4}$ for asecondary battery with various $MnO_{2}$ structure (다양한 $MnO_{2}$ 구조에 따른 2차전지용 $Li_{x}Mn_{2}O_{4}$ 합성에 관한 연구)

  • 김익진;이영훈;이종호;이재한;장동환;이경희;고영신
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.6 no.4
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    • pp.600-608
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    • 1996
  • Specific structural properties of Li intercalation reaction into the spinel relatedmanganese dioxide, $Li_{x}Mn_{2}O_{4}(0.2{\leq}x{\leq}2.0)$, are investigated by X-ray diffractional and electrochemical studies of Li/1M $LiClO_{4}$-propylene carbonate solution/$Li_{x}Mn_{2}O_{4}$ cell. The effect of the chemical composition and the reaction temperature on electrochemical parameter of $Li_{x}Mn_{2}O_{4}$ are studied by the phenomena of phase-transition, analysis of crystal lattice, fine structure, and thermal analysis. Treatment of the spinel $Li_{x}Mn_{2}O_{4}$ with aqueous acid was found to result in conversiton of $Li_{x}Mn_{2}O_{4}$ to nearly pure $MnO_{2}$, as evidenced by a reduction in the lattice constant $a_{c}$ from 8.255 to $8.031\;{\AA}$. At a composition range of $0.2{\leq}x{\leq}0.6$ in $Li_{x}Mn_{2}O_{4}$ the reduction proceeded in a homogeneous phase, which was characterized by a constant voltage of 3.9~3.7 V together with a lattice constant of $8.255\;{\AA}$.

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Optical and Structural Analysis of BaSi2O2N2:Eu Green Phosphor for High-Color-Rendering Lighting (고연색 백색 광원용 BaSi2O2N2:Eu 형광체의 광학·구조 특성 분석)

  • Lee, Sunghoon;Kang, Taewook;Kang, Hyeonwoo;Jeong, Yongseok;Kim, Jongsu;Heo, Hoon
    • Korean Journal of Materials Research
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    • v.29 no.7
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    • pp.437-442
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    • 2019
  • Green $BaSi_2O_2N_2:0.02Eu^{2+}$ phosphor is synthesized through a two-step solid state reaction method. The first firing is for crystallization, and the second firing is for reduction of $Eu^{3+}$ into $Eu^{2+}$ and growth of crystal grains. By thermal analysis, the three-time endothermic reaction is confirmed: pyrolysis reaction of $BaCO_3$ at $900^{\circ}C$ and phase transitions at $1,300^{\circ}C$ and $1,400^{\circ}C$. By structural analysis, it is confirmed that single phase [$BaSi_2O_2N_2$] is obtained with Cmcm space group of orthorhombic structure. After the first firing the morphology is rod-like type and, after the second firing, the morphology becomes round. Our phosphor shows a green emission with a peak position of 495 nm and a peak width of 32 nm due to the $4f^65d^1{\rightarrow}4f^7$ transition of $Eu^{2+}$ ion. An LED package (chip size $5.6{\times}3.0mm$) is fabricated with a mixture of our green $BaSi_2O_2N_2$, and yellow $Y_3Al_5O_{12}$ and red $Sr_2Si_5N_8$ phosphors. The color rendering index (90) is higher than that of the mixture without our green phosphor (82), which indicates that this is an excellent green candidate for white LEDs with a deluxe color rendering index.

New Approaches for Overcoming Current Issues of Plasma Sputtering Process During Organic-electronics Device Fabrication: Plasma Damage Free and Room Temperature Process for High Quality Metal Oxide Thin Film

  • Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.100-101
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    • 2012
  • The plasma damage free and room temperature processedthin film deposition technology is essential for realization of various next generation organic microelectronic devices such as flexible AMOLED display, flexible OLED lighting, and organic photovoltaic cells because characteristics of fragile organic materials in the plasma process and low glass transition temperatures (Tg) of polymer substrate. In case of directly deposition of metal oxide thin films (including transparent conductive oxide (TCO) and amorphous oxide semiconductor (AOS)) on the organic layers, plasma damages against to the organic materials is fatal. This damage is believed to be originated mainly from high energy energetic particles during the sputtering process such as negative oxygen ions, reflected neutrals by reflection of plasma background gas at the target surface, sputtered atoms, bulk plasma ions, and secondary electrons. To solve this problem, we developed the NBAS (Neutral Beam Assisted Sputtering) process as a plasma damage free and room temperature processed sputtering technology. As a result, electro-optical properties of NBAS processed ITO thin film showed resistivity of $4.0{\times}10^{-4}{\Omega}{\cdot}m$ and high transmittance (>90% at 550 nm) with nano- crystalline structure at room temperature process. Furthermore, in the experiment result of directly deposition of TCO top anode on the inverted structure OLED cell, it is verified that NBAS TCO deposition process does not damages to the underlying organic layers. In case of deposition of transparent conductive oxide (TCO) thin film on the plastic polymer substrate, the room temperature processed sputtering coating of high quality TCO thin film is required. During the sputtering process with higher density plasma, the energetic particles contribute self supplying of activation & crystallization energy without any additional heating and post-annealing and forminga high quality TCO thin film. However, negative oxygen ions which generated from sputteringtarget surface by electron attachment are accelerated to high energy by induced cathode self-bias. Thus the high energy negative oxygen ions can lead to critical physical bombardment damages to forming oxide thin film and this effect does not recover in room temperature process without post thermal annealing. To salve the inherent limitation of plasma sputtering, we have been developed the Magnetic Field Shielded Sputtering (MFSS) process as the high quality oxide thin film deposition process at room temperature. The MFSS process is effectively eliminate or suppress the negative oxygen ions bombardment damage by the plasma limiter which composed permanent magnet array. As a result, electro-optical properties of MFSS processed ITO thin film (resistivity $3.9{\times}10^{-4}{\Omega}{\cdot}cm$, transmittance 95% at 550 nm) have approachedthose of a high temperature DC magnetron sputtering (DMS) ITO thin film were. Also, AOS (a-IGZO) TFTs fabricated by MFSS process without higher temperature post annealing showed very comparable electrical performance with those by DMS process with $400^{\circ}C$ post annealing. They are important to note that the bombardment of a negative oxygen ion which is accelerated by dc self-bias during rf sputtering could degrade the electrical performance of ITO electrodes and a-IGZO TFTs. Finally, we found that reduction of damage from the high energy negative oxygen ions bombardment drives improvement of crystalline structure in the ITO thin film and suppression of the sub-gab states in a-IGZO semiconductor thin film. For realization of organic flexible electronic devices based on plastic substrates, gas barrier coatings are required to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency flexible AMOLEDs needs an extremely low water vapor transition rate (WVTR) of $1{\times}10^{-6}gm^{-2}day^{-1}$. The key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required (under ${\sim}10^{-6}gm^{-2}day^{-1}$) is the suppression of nano-sized defect sites and gas diffusion pathways among the grain boundaries. For formation of high quality single inorganic gas barrier layer, we developed high density nano-structured Al2O3 single gas barrier layer usinga NBAS process. The NBAS process can continuously change crystalline structures from an amorphous phase to a nano- crystalline phase with various grain sizes in a single inorganic thin film. As a result, the water vapor transmission rates (WVTR) of the NBAS processed $Al_2O_3$ gas barrier film have improved order of magnitude compared with that of conventional $Al_2O_3$ layers made by the RF magnetron sputteringprocess under the same sputtering conditions; the WVTR of the NBAS processed $Al_2O_3$ gas barrier film was about $5{\times}10^{-6}g/m^2/day$ by just single layer.

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