• Title/Summary/Keyword: Low-temperature synthesis

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Facile synthesis of nanostructured n-type SiGe alloys with enhanced thermoelectric performance using rapid solidification employing melt spinning followed by spark plasma sintering

  • Vishwakarma, Avinash;Bathula, Sivaiah;Chauhan, Nagendra S.;Bhardwaj, Ruchi;Gahtori, Bhasker;Srivastava, Avanish K.;Dhar, Ajay
    • Current Applied Physics
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    • v.18 no.12
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    • pp.1540-1545
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    • 2018
  • SiGe alloy is widely used thermoelectric materials for high temperature thermoelectric generator applications. However, its high thermoelectric performance has been thus far realized only in alloys synthesized employing mechanical alloying techniques, which are time-consuming and employ several materials processing steps. In the current study, for the first time, we report an enhanced thermoelectric figure-of-merit (ZT) ~ 1.1 at $900^{\circ}C$ in ntype $Si_{80}Ge_{20}$ nano-alloys, synthesized using a facile and up-scalable methodology consisting of rapid solidification at high optimized cooling rate ${\sim}3.4{\times}10^7K/s$, employing melt spinning followed by spark plasma sintering of the resulting nano-crystalline melt-spun ribbons. This enhancement in ZT > 20% over its bulk counterpart, owes its origin to the nano-crystalline microstructure formed at high cooling rates, which results in crystallite size ~7 nm leading to high density of grain boundaries, which scatter heat-carrying phonons. This abundant scattering resulted in a very low thermal conductivity ${\sim}2.1Wm^{-1}K^{-1}$, which corresponds to ~50% reduction over its bulk counterpart and is amongst the lowest reported thus far in n-type SiGe alloys. The synthesized samples were characterized using X-ray diffraction, scanning electron microscopy and transmission electron microscopy, based on which the enhancement in their thermoelectric performance has been discussed.

Thermal and Rheological Characterizations of Polycarbosilane Precursor by Solvent Treatment (폴리카보실란 전구체의 용매 처리에 따른 열적 및 유변학적 특성 분석)

  • Song, Yeeun;Joo, Young Jun;Shin, Dong Geun;Cho, Kwang Youn;Lee, Doojin
    • Composites Research
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    • v.35 no.1
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    • pp.23-30
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    • 2022
  • Polycarbosilane(PCS) is an important precursor for melt-spinning the silicon carbide(SiC) fibers and manufacturing ceramics. The PCS is a metal-organic polymer precursor capable of producing continuous SiC fibers having excellent performance such as high-temperature resistance and oxidation resistance. The SiC fibers are manufactured through melt-spinning, stabilization, and heat treatment processes using the PCS manufactured by synthesis, purification, and control of the molecular structure. In this paper, we analyzed the effect of purification of unreacted substances and low molecular weight through solvent treatment of PCS and the effect of heat treatment at various temperatures change the polymerization and network rearrangement of PCS. Especially, we investigated the complex viscosity and structural arrangement of PCS precursors according to solvent treatment and heat treatment through the rheological properties.

Extremophiles as a Source of Unique Enzymes for Biotechnological Applications

  • Antranikian G.
    • Proceedings of the Microbiological Society of Korea Conference
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    • 2001.11a
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    • pp.39-45
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    • 2001
  • Extremophiles are unique microorganisms that are adapted to survive in ecological niches such as high or low temperatures, extremes of pH, high salt concentrations and high pressure. These unusual microorganisms have unique biochemical features which can be exploited for use in the biotechnological industries. Due to the high biodiversity of extremophilic archaea and bacteria and their existence in various biotopes a variety of biocatalysts with different physicochemical properties have been discovered. The extreme molecular stability of their enzymes, membranes and the synthesis of unique organic compounds and polymers make extremophiles interesting candidates for basic and applied research. Some of the enzymes from extremophiles, especially hyperthermophilic marine microorganisms (growth above $85^{\circ}C$), have already been purified in our laboratory. These include the enzyme systems from Pyrococcus, Pyrodictium, Thermococcus and Thermotoga sp. that are involved in polysacharide modification and protein bioconversion. Only recently, the genome of the thermoalkaliphilic strain. Anaerobranca gottschalkii has been completely sequenced providing a unique resource of novel biocatalysts that are active at high temperature and pH. The gene encoding the branching enzyme from this organism was cloned and expressed in a mesophilic host and finally characterized. A novel glucoamylase was purified from an aerobic archaeon which shows optimal activity at $90^{\circ}C$ and pH 2.0. This thermoacidophilic archaeon Picrophilus oshimae grows optimally at pH 0.7 and $60^{\circ}C$. Furthermore, we were able to detect thermoactive proteases from two anaerobic isolates which are able to hydrolyze feather keratin completely at $80^{\circ}C$ forming amino acids and peptides. In addition, new marine psychrophilic isolates will be presented that are able to secrete enzymes such as lipases, proteases and amylases possessing high activity below the freezing point of water.

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Sesquiterpenoids Bioconversion Analysis by Wood Rot Fungi

  • Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu;Kim, Myungkil
    • 한국균학회소식:학술대회논문집
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    • 2016.05a
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    • pp.19-20
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    • 2016
  • Sesquiterpenoids are defined as $C_{15}$ compounds derived from farnesyl pyrophosphate (FPP), and their complex structures are found in the tissue of many diverse plants (Degenhardt et al. 2009). FPP's long chain length and additional double bond enables its conversion to a huge range of mono-, di-, and tri-cyclic structures. A number of cyclic sesquiterpenes with alcohol, aldehyde, and ketone derivatives have key biological and medicinal properties (Fraga 1999). Fungi, such as the wood-rotting Polyporus brumalis, are excellent sources of pharmaceutically interesting natural products such as sesquiterpenoids. In this study, we investigated the biosynthesis of P. brumalis sesquiterpenoids on modified medium. Fungal suspensions of 11 white rot species were inoculated in modified medium containing $C_6H_{12}O_6$, $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ for 20 days. Cultivation was stopped by solvent extraction via separation of the mycelium. The metabolites were identified as follows: propionic acid (1), mevalonic acid lactone (2), ${\beta}$-eudesmane (3), and ${\beta}$-eudesmol (4), respectively (Figure 1). The main peaks of ${\beta}$-eudesmane and ${\beta}$-eudesmol, which were indicative of sesquiterpene structures, were consistently detected for 5, 7, 12, and 15 days These results demonstrated the existence of terpene metabolism in the mycelium of P. brumalis. Polyporus spp. are known to generate flavor components such as methyl 2,4-dihydroxy-3,6-dimethyl benzoate; 2-hydroxy-4-methoxy-6-methyl benzoic acid; 3-hydroxy-5-methyl phenol; and 3-methoxy-2,5-dimethyl phenol in submerged cultures (Hoffmann and Esser 1978). Drimanes of sesquiterpenes were reported as metabolites from P. arcularius and shown to exhibit antimicrobial activity against Gram-positive bacteria such as Staphylococcus aureus (Fleck et al. 1996). The main metabolites of P. brumalis, ${\beta}$-Eudesmol and ${\beta}$-eudesmane, were categorized as eudesmane-type sesquiterpene structures. The eudesmane skeleton could be biosynthesized from FPP-derived IPP, and approximately 1,000 structures have been identified in plants as essential oils. The biosynthesis of eudesmol from P. brumalis may thus be an important tool for the production of useful natural compounds as presumed from its identified potent bioactivity in plants. Essential oils comprising eudesmane-type sesquiterpenoids have been previously and extensively researched (Wu et al. 2006). ${\beta}$-Eudesmol is a well-known and important eudesmane alcohol with an anticholinergic effect in the vascular endothelium (Tsuneki et al. 2005). Additionally, recent studies demonstrated that ${\beta}$-eudesmol acts as a channel blocker for nicotinic acetylcholine receptors at the neuromuscular junction, and it can inhibit angiogenesis in vitro and in vivo by blocking the mitogen-activated protein kinase (MAPK) signaling pathway (Seo et al. 2011). Variation of nutrients was conducted to determine an optimum condition for the biosynthesis of sesquiterpenes by P. brumalis. Genes encoding terpene synthases, which are crucial to the terpene synthesis pathway, generally respond to environmental factors such as pH, temperature, and available nutrients (Hoffmeister and Keller 2007, Yu and Keller 2005). Calvo et al. described the effect of major nutrients, carbon and nitrogen, on the synthesis of secondary metabolites (Calvo et al. 2002). P. brumalis did not prefer to synthesize sesquiterpenes under all growth conditions. Results of differences in metabolites observed in P. brumalis grown in PDB and modified medium highlighted the potential effect inorganic sources such as $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ on sesquiterpene synthesis. ${\beta}$-eudesmol was apparent during cultivation except for when P. brumalis was grown on $MgSO_4$-free medium. These results demonstrated that $MgSO_4$ can specifically control the biosynthesis of ${\beta}$-eudesmol. Magnesium has been reported as a cofactor that binds to sesquiterpene synthase (Agger et al. 2008). Specifically, the $Mg^{2+}$ ions bind to two conserved metal-binding motifs. These metal ions complex to the substrate pyrophosphate, thereby promoting the ionization of the leaving groups of FPP and resulting in the generation of a highly reactive allylic cation. Effect of magnesium source on the sesquiterpene biosynthesis was also identified via analysis of the concentration of total carbohydrates. Our current study offered further insight that fungal sesquiterpene biosynthesis can be controlled by nutrients. To profile the metabolites of P. brumalis, the cultures were extracted based on the growth curve. Despite metabolites produced during mycelia growth, there was difficulty in detecting significant changes in metabolite production, especially those at low concentrations. These compounds may be of interest in understanding their synthetic mechanisms in P. brumalis. The synthesis of terpene compounds began during the growth phase at day 9. Sesquiterpene synthesis occurred after growth was complete. At day 9, drimenol, farnesol, and mevalonic lactone (or mevalonic acid lactone) were identified. Mevalonic acid lactone is the precursor of the mevalonic pathway, and particularly, it is a precursor for a number of biologically important lipids, including cholesterol hormones (Buckley et al. 2002). Farnesol is the precursor of sesquiterpenoids. Drimenol compounds, bi-cyclic-sesquiterpene alcohols, can be synthesized from trans-trans farnesol via cyclization and rearrangement (Polovinka et al. 1994). They have also been identified in the basidiomycota Lentinus lepideus as secondary metabolites. After 12 days in the growth phase, ${\beta}$-elemene caryophyllene, ${\delta}$-cadiene, and eudesmane were detected with ${\beta}$-eudesmol. The data showed the synthesis of sesquiterpene hydrocarbons with bi-cyclic structures. These compounds can be synthesized from FPP by cyclization. Cyclic terpenoids are synthesized through the formation of a carbon skeleton from linear precursors by terpene cyclase, which is followed by chemical modification by oxidation, reduction, methylation, etc. Sesquiterpene cyclase is a key branch-point enzyme that catalyzes the complex intermolecular cyclization of the linear prenyl diphosphate into cyclic hydrocarbons (Toyomasu et al. 2007). After 20 days in stationary phase, the oxygenated structures eudesmol, elemol, and caryophyllene oxide were detected. Thus, after growth, sesquiterpenes were identified. Per these results, we showed that terpene metabolism in wood-rotting fungi occurs in the stationary phase. We also showed that such metabolism can be controlled by magnesium supplementation in the growth medium. In conclusion, we identified P. brumalis as a wood-rotting fungus that can produce sesquiterpenes. To mechanistically understand eudesmane-type sesquiterpene biosynthesis in P. brumalis, further research into the genes regulating the dynamics of such biosynthesis is warranted.

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Synthesis and Characterization of Pyridinium Dinitramide Salt (피리디니움 디나이트라아마이드염의 합성과 특성연구)

  • Kim, Wooram;Kwon, Younja;Jo, Youngmin
    • Applied Chemistry for Engineering
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    • v.27 no.4
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    • pp.397-401
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    • 2016
  • A new solid oxidizer, pyridinium dinitramide (Py-DN) is a low toxic energetic material which can be utilized as a HPGP (high performance green propellant). In this work, Py-DN was synthesized using various starting materials including potassium sulfamate, pyridine hydrochloride, strong nitric acid and sulfuric acid. Physical and chemical properties of the Py-DN were characterized using UV-Vis, FT-IR and a thermal analyzer and their properties were compared to those of previously prepared salts including ammonium dinitramide[ADN, $NH_4N(NO_2)_2$] and guanidine dinitramide[GDN, $NH_2C(NH_2)NH_2N(NO_2)_2$] in our lab. Endothermic and exothermic decomposition temperatures of Py-DN were $77.4^{\circ}C$ and $144.7^{\circ}C$, respectively. The combustion caloric value was 1739 J/g, which is thermally more sensitive than that of conventional dinitramides. It may enable to lower the decomposition temperature, which can reduce preheating temperature required for satellite thruster applications.

Hydrothermal Synthesis and Structural Characterization of x mol% Calcia-Stabilized ZrO2 Nanopowders (x mol% 칼시아-안정화 지르코니아 나노분말의 수열합성 및 구조적 특성평가)

  • Ryu, Je-Hyeok;Moon, Jung-In;Park, Yeon-Kyung;Nguyen, Tuan Dung;Song, Jeong-Hwan;Kim, Taik-Nam
    • Korean Journal of Materials Research
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    • v.22 no.5
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    • pp.220-226
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    • 2012
  • Pure zirconia and $x$ mol% calcia partially stabilized zirconia ($x$ = 1.5, 3, and 8) nanopowders were synthesized by hydrothermal method with various reaction temperatures for 24 hrs. The precipitated precursor of pure zirconia and $x$ mol% calcia doped zirconia was prepared by adding $NH_4OH$ to starting solutions; resulting sample was then put into an autoclave reactor. The optimal experimental conditions, such as reaction temperatures and times and amounts of stabilizer CaO, were carefully studied. The synthesized $ZrO_2$ and $x$ mol% CaO-$ZrO_2$ ($x$ = 1.5, 3, and 8) powders were characterized by XRD, SEM, TG-DTA, and Raman spectroscopy. When the hydrothermal temperature was as low as $160^{\circ}C$, pure $ZrO_2$ and $x$ mol% CaO-$ZrO_2$ ($x$ = 1.5 and 3) powders were identified as a mixture of monoclinic and tetragonal phases. However, a stable tetragonal phase of zirconia was observed in the 8 mol% calcia doped zirconia nanopowder at hydrothermal temperature above $160^{\circ}C$. To observe the phase transition, the 3 mol% CaO-$ZrO_2$ and 8 mol% CaO-$ZrO_2$ nanopowders were heat treated from 600 to $1000^{\circ}C$ for 2h. The 3 mol% CaO-$ZrO_2$ heat treated at above $1000^{\circ}C$ was found to undergo a complete phase transition from mixture phase to monoclinic phase. However, the 8 mol% calcia doped zirconia appeared in the stable tetragonal phase after heat treatment. The result of this study therefore should be considered as the preparation of 8 mol% CaO-$ZrO_2$ nanopowders via the hydrothermal method.

Synthesis of Tungsten Doped Vanadium Dioxide and Its Thermochromic Property Studies (텅스텐이 도핑된 바나듐 산화물의 합성 및 열전이 특성 연구)

  • Hwang, Kyung-Jun;Jo, Cho Won;Yoo, Jung Whan
    • Applied Chemistry for Engineering
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    • v.24 no.1
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    • pp.44-48
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    • 2013
  • In this work, we have prepared tungsten doped vanadium oxide ($W-VO_2$) particles with a low phase transition temperature. $W-VO_2$ particles were synthesized via thermolysis method using vanadyl (IV) sulfate and ammonium bicarbonate as precursors. The structure and thermochromic property of synthesized $W-VO_2$ particles were investigated by FE-SEM, EDS, XRD, XPS, and DSC analysis. The prepared $W-VO_2$ showed a nearly platy morphology, which indicates that the tungsten was successfully doped in the crystal lattices of $VO_2$. $W-VO_2$ nanoparticles with the size of 60 nm exhibited a monoclinic crystal structure and its chemical composition and surface state were also likely to be close to that of $VO_2$. In addition, the phase transition temperature of $W-VO_2$ was $38.5^{\circ}C$, which was approximately $29.2^{\circ}C$ lower than that of pure $VO_2$ ($67.7^{\circ}C$), indicating that the prepared sample had a good reversible thermochromic stability.

Synthesis of indium hydroxide powders by a precipitation method (침전법을 이용한 Indium hydroxide 분말의 합성 연구)

  • Choi, Eun-Kyoung;Lee, Won-Jun;Han, Kyu-Sung;Kim, Ung-Soo;Kim, Jin-Ho;Hwang, Kwang-Teak;Kim, Jong-Young;Hwang, Hae-Jin;Shim, Kwang-Bo;Cho, Woo-Seok
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.27 no.3
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    • pp.122-129
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    • 2017
  • For the production of a high-density ITO target, $In_2O_3$ powders with a small particle size and low agglomeration should be synthesized. The purpose of this study is to control the size and shape of the Indium hydroxide precursor which affects the properties of the $In_2O_3$ powder. As a starting raw material, Indium metal was dissolved in a Nitric acid ($HNO_3$) solution. The effect of concentration, pH, and temperature on the properties of Indium hydroxide was investigated using ammonium hydroxide as a precipitant. Crystallite size of each sample was analyzed by X-ray diffraction and the shape and the size of the powder was analyzed by transmission electron microscopy. As a result, the particle size of Indium hydroxide was increased with increase in the concentration of $In(NO_3)_3$ and the particle size and shape of the Indium hydroxide remained unchanged with increase in the pH of the solution. The particle size increased with increase in the precipitation temperature during precipitation.

A Development and Validation of Cosmetic Container Based on L-Ascorbic Acid Oxidation Property (L-Ascorbic Acid의 산화특성에 따른 화장품 용기 개발 및 유효성 분석)

  • Yoon, Sungwook
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.39 no.2
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    • pp.149-158
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    • 2013
  • L-ascorbic acid, the representative antioxidants, has a great effect on skin whitening, collagen synthesis, and anti-aging, but has low oxidative stability during storage. Therefore, in this study, thermal and oxidation properties of L-ascorbic acid under various storage conditions (powder, aqueous phase, changes of temperature, UV-irradiation, and inflow of external air etc.) were investigated. And the storage stability of ingredient was validated in the double-spaced pouch by analysing oxidation properties under each storage conditions (powder phase and blended with essence). In oder to analyze the thermal properties, TGA, DSC, and FT-IR analysis were carried out and UV-visible spectrophotometer & redox titration were used in parallel for oxidation property analyses. From the result of experiment, L-ascorbic acid was oxidized fast when it contained lots of metallic ion, hydroxy ion in aqueous solution under high temperature, UV-irradiation & inflow external air, whereas it was not oxidized for a long time when it was stored as pure powder although it has same condition as heating up, UV-irradiation & inflow external air. Based on this result, retention period of cosmetics which is using L-ascorbic acid, less stable material in oxidation can be innovatively increased when using double-spaced pouch that is designed and produced for separating storage of active ingredients.

Fabrication and Electrical Properties of High Tc $A_{2}B_{2}O_{7}$ Piezoelectric Ceramics Using the Powders Prepared by the Chemical Coprecipitation Method (화학적공침법에 의한 $A_{2}B_{2}O_{7}$ 고온압전세라믹스의 제작과 전기적 특성)

  • Son, Chang-Heon;Jeon, Sang-Jae;Nam, Hyo-Duk
    • Journal of Sensor Science and Technology
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    • v.6 no.4
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    • pp.316-327
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    • 1997
  • Polycrystalline $Sr_{2}Nb_{2}O_{7}$ and $La_{2}Ti_{2}O_{7}$ ceramics with very high Curie temperatures were synthesized by the chemical coprecipitation method (CCP). The powders synthesized were identified by XRD and their sintering behavior and physical properties were studied. The grain-orientation and electrical properties of sintered ceramics were investigated as a function of firing temperature. Single phase could be obtained by CCP method at temperature lower than that of the conventional method by 100 - $150^{\circ}C$. Strontium niobate, $Sr_{2}Nb_{2}O_{7}$, powder was Prepared by CCP method at temperatures as low as $800^{\circ}C$ via intermediate phase of $Sr_{5}Nb_{4}O_{15}$ formed at $700^{\circ}C$. The resulting CCP-derived powder was observed to have finer and more uniform particle size distribution than those obtained through the conventional or the molten salt synthesis method. Sintering of CCP-derived $Sr_{2}Nb_{2}O_{7}$ powder at $1500^{\circ}C$ yielded a highly dense ceramics with 97% theoretical density. Very high grain-orientation developed along the (0k0) direction was observed by SEM, which resulted in anisotropic dielectric properties of the sintered samples, with the dielectric constant values approaching those for single crystal.

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