• Advances in Energy Research
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• v.5 no.1
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• pp.13-29
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• 2017

The roles of Na, Mn, W and silica, and the synergistic effects between each metal in the $MnNa_2WO_4/SiO_2$ catalyst have been investigated for oxidative coupling of methane (OCM). The crystallisation of amorphous silica during calcination at $900^{\circ}C$ was promoted primarily by Na, but Mn and W also facilitated this process. The interaction between Na and Mn tended to increase the extent of conversion of $Mn_3O_4$ to $Mn_2O_3$. The formation of $Na_2WO_4$ was dependent on the order in which Na and W were introduced to the catalyst. The impregnation of W before Na resulted in the formation of $Na_2WO_4$, but this did not occur when the impregnation order was reversed. $MnWO_4$ formed in all cases where Mn and W were introduced into the silica support, regardless of the impregnation order; however, the formation of $MnWO_4$ was inhibited in the presence of Na. Of the prepared samples in which a single metal oxide was introduced to silica, only $Mn/SiO_2$ showed OCM activity with significant oxygen conversion, thus demonstrating the important role that Mn plays in promoting oxygen transfer in the reaction. The impregnation order of W and Na is critical for catalyst performance. The active site, which involves a combination of Na-Si-W-O, can be formed in situ when distorted $WO_4^{2-}$ interacts with silica during the crystallisation process facilitated by Na. This can only occur if the impregnation of W occurs before Na addition, or if the two components are introduced simultaneously.

• Korean Journal of Materials Research
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• v.13 no.2
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• pp.120-125
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• 2003

A low melting borosilicate glass frit was used as an adhesion promoter, which enables $MnWO_4$to be sintered with in a reasonable sintering temperature range ($800∼1000^{\circ}C$). The glass was evaluated for glass transition temperature ($Τ_{g}$ X) and thermal expansion coefficient($\alpha$). Mechanical property (Vickers hardness), grain growth, the comparison of lattice parameter and pore distribution of sintered $MnWO_4$ with the frit were methodically discussed. As sintering temperature increased, a typical liquid phase sintering showed the rapid grain growth and high densification of X$MnWO_4$grain, improvement of hardness (until $920^{\circ}C$) and different pore size distribution. Resistance of sintered $MnWO_4$varied from 450k$\Omega$ to 8.8M$\Omega$ under the measuring humidify ranging from 30 to 90%. Thus, the results will contribute to the application of glass frit containing sensor materials and their future use.

• Journal of the Korean Magnetic Resonance Society
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• v.22 no.4
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• pp.107-114
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• 2018

In this exploration, the nuclear magnetic resonance of the $^{207}Pb$ nucleus in $PbWO_4:Mn^{2+}$ and $PbWO_4:Dy^{3+}$ Single Crystals using FT-NMR spectrometer is investigated. The line width of the resonance line for the $^{207}Pb$ nucleus decreases as temperature increases due to motional narrowing. The chemical shift of $^{207}Pb$ NMR spectra also increases as temperature decreases for both crystals. The spinlattice relaxation times $T_1$ of $^{39}K$ nucleus were calculated as a function of temperature (180 K~400 K). The $T_1$ of $^{207}Pb$ nucleus decreases as temperature increases. The dominant relaxation mechanism at the studied temperature range can be deduced as the Raman process, which is the coupling between lattice vibrations and the nuclear spins. This deduction is substantiated by the fact that the nuclear spin-lattice relaxation rate $1/T_1$ of the $^{207}Pb$ nucleus in $PbWO_4:Mn^{2+}$ and $PbWO_4:Dy^{3+}$ single crystal is proportional to $T^2$, or temperature squared. The activation energies for the $^{207}Pb$ nucleus in $PbWO_4:Mn^{2+}$ and $PbWO_4:Dy^{3+}$ single crystals are $E_a=49{\pm}1meV$ and $E_a=47{\pm}2meV$, respectively.

• Proceedings of the Materials Research Society of Korea Conference
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• 2002.05a
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• pp.154-154
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• 2002

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.392.1-392.1
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• 2016

Nowadays, research interest in developing the wearable devices are growing remarkably. Portable consumer electronic systems are becoming lightweight, flexible and even wearable. In fact, wearable electronics require energy storage device with thin, foldable, stretchable and conformable properties. Accordingly, developing the flexible energy storage devices with desirable abilities has become the main focus of research area. Among various energy storage devices, supercapacitors have been considered as an attractive next generation energy storage device owing to their advantageous properties of high power density, rapid charge-discharge rate, long-cycle life and high safety. The energy being stored in pseudocapacitors is relatively higher compared to the electrochemical double-layer capacitors, which is due to the continuous redox reactions generated in the electrode materials of pseudocapacitors. Generally, transition metal oxides/hydroxide (such as $Co_3O_4$, $Ni(OH)_2$, $NiFe_2O_4$, $MnO_2$, $CoWO_4$, $NiWO_4$, etc.) with controlled nanostructures (NSs) are used as electrode materials to improve energy storage properties in pseudocapacitors. Therefore, different growth methods have been used to synthesize these NSs. Of various growth methods, electrochemical deposition is considered to be a simple and low-cost method to facilely integrate the various NSs on conductive electrodes. Herein, we synthesized amorphous $NiWO_4$ NSs on cost-effective conductive textiles by a facile electrochemical deposition. The as-grown amorphous $NiWO_4$ NSs served as a flexible and efficient electrode for energy storage applications.

• Proceedings of the Korea Association of Crystal Growth Conference
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• 1996.06b
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• pp.219-222
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• 1996

수열법은 밀폐용기중에서 10$0^{\circ}C$이상의 가열, 가압된 수용액이 반응에 관여하는 것으로써, 수정, CaCO3, AlPO4, GaPO4 등과 같은 단결정의 육성 뿐만 아니라 균일분산계로부터 균일한 결정성의 미립자 합성에도 폭넓게 이용되고 있다. 세라믹분말의 합성에 있어서, 이 방법은 특히 형상, 입자크기의 제어가 용이할 뿐만 아니라 고상법, 졸-겔법, 공침법에서와 같은 열처리, 분쇄과정이 필요없기 때문에 고순도의 초미립자를 얻을 수 있는 장점이 있다. 근년 미국, 일본에서는 수열법을 이용한 유전, 압전체 등 세라믹분말의 일부가 공업적인 규모로 대량 생산되고 있다. 그러나 이에 대한 국내 기술은 아직 초기단계에 이르고 있는 실정이다. 따라서 본 연구실에서는 수열법에 의한 단결정 육성 (예; 자수정, CaCO3, AlPO4, GaPO4, KTP, Emerald 등), 박막제조 (예; GaP, PbTiO3, BaTiO3 등), 정제 (고령토, 장석, 도석 등), 원석처리 (진주, 인공 emerald, 비취 등) 그리고 각종 세라믹분말의 합성 등과 같은 다양한 기반기술의 축적과 동시에 공업화에 대응한 수열장치를 위하여 반응용기의 대형화, 엄밀한 밀폐방식, 실용적인 수열조건 등을 개발해 오고 있다. 본 발표에서는 현재까지의 연구개발 내용 중에서 결정성 미립자에 관련한 세라믹분말의 합성에 대한 일부의 결과들을 보고한다. 일반적으로 수열장치는 전기로, 반응용기, 온도 및 압력제어계 등을 기본으로 하고 있으며 시판용의 대부분이 교반기가 부착된 수직형 (vertical type)이다. 이와 같은 방식에 있어서는 엄밀한 밀폐가 곤란, 반응온도의 한계성 (25$0^{\circ}C$ 이하), 증진율의 한계성 (소량생산) 등과 같은 점이 있기 때문에 본 연구실에서는 개폐식 전기로내에 엄밀한 밀폐가 가능한 수평식(horizontal type)의 반응용기를 채택한 뒤 이를 회전 또는 시이소(seesaw)식으로 움직일 수 있도록 하여 연속공정화, 온도구배의 자율조절 그리고 보다 저온에서도 인위적인 이온의 확산을 효율적으로 유도할 수 있도록 하였다. 이와 같은 방식은 기존의 방식과 비교하여 반응용기 내에 응집현상과 미반응물이 존재하지 않으며 또한 단분산으로 결정성 미립자를 대량적으로 얻을 수 있는 장점이 있었다. 다음은 이상과 같이 본 연구실에서 자체 개발한 수열장치를 이용하여 PbTiO3, (Pb,La)TiO3Mn, BaTiO3, ZnSiO4:Mn, CaWO4 등과 같은 세라믹분말에 대한 합성 실험의 결과이다. 압전성, 초전성이 우수한 PbTiO3 및 (Pb,La)TiO3:Mn 분말의 수열합성은 PbO, TiO2, La2O3 등의 분말을 출발원료로 하여 합성도도 25$0^{\circ}C$부근의 알카리성 용액중에서 결정성 PbTiO3 및 (Pb,La)TiO3:Mn 미립자를 단상으로 얻었으며 입자의 형상 및 크기는 합성온도와 수열용매의 종류에 의존하였다. 유전체로서 폭넓게 응용되고 있는 BaTiO3 분말은 Ba(OH)2.8H2O, TiO2와 같은 최적의 출발원료를 선택함으로써 15$0^{\circ}C$ 부근의 저온영역에서도 용이하게 합성할 수 있었다. 특히 본 연구에서는 수용성인 Ba(OH)2.8H2O를 사용함으로써 host-guest적인 반응을 유도시키는데 있어 물의 가장 실용적이고 효과적인 수열용매임도 알았다. ZnSiO4:Mn, CaWO4, MgWO4와 같은 형광체 분말은 공업적으로 고상반응 또는 습식법에 의해 얻어지고 있으나 이들 방법에 있어서는 분쇄공정으로 인한 형광특성의 저하와 같은 문제점이 있다. 따라서 본 연구에서는 수열법을 이용하여 이들 화합물의 합성을 시도하였으며 그 결과 합성온도 30$0^{\circ}C$ 부근의 알칼리성 용액중에서 수열적으로 얻어짐을 알았다. 여기서의 합성분말을 이용하여 실제 조명램프로 제조한 결과 녹색, 청색 발광용 형광체로서 우수한 형광특성을 나타내었다. 천연에서 소량 산출되고 있는 고가의 (Li,Al)MnO2(OH)2:Co 분말은 도자기의 전사지용 청색안료로써 이용되고 있다. 본 연구실에서는 LiOH.H2O, Al(OH)3, MnO2 등의 분말을 출발원료로 하고 24$0^{\circ}C$ 온도 부근 그리고 물을 수열용매로 하여 천연산에 필적하는 (Li,Al)MnO2(OH)2:Co 분말을 인공적으로 합성하였다.

• Proceedings of the Korean Magnestics Society Conference
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• 2008.12a
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• pp.111.2-111.2
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• 2008

• Applied Chemistry for Engineering
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• v.5 no.2
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• pp.327-336
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• 1994

The synergistic effects in mechanical mixture catalysts of Mo-V-O and metal oxide were investigated for the selective oxidation of acrolein. The metal oxides used are $SnO_2$, ${\alpha}-Sb_2O_4$, $WO_3$, ${\alpha}-Al_2O_3$, CuO, $MnO_2$, $Cu_2O$, MgO, CoO, and ZnO. Mechanical mixtures of Mo-V-O plus $SnO_2$ or ${\alpha}-Sb_2O_4$ had resulted in higher conversion of acrolein and higher yield of acrylic acid than Mo-V-O. The origin of the synergy is attributed to the cooperation of Mo-V-O and $SnO_2$ or ${\alpha}-Sb_2O_4$, in which $SnO_2$ or ${\alpha}-Sb_2O_4$ forms dissociated oxygens at their oxygen vacancies and transports them to Mo-V-O. $Cu_2O$, MgO, CuO, and $MnO_2$, increased conversion of acrolein but decreased yield of acrylic acid. CoO and ZnO inhibited the catalytic performance of Mo-V-O. The different role of these metal oxides is explained in terms of their oxidation-reduction properties.

• Economic and Environmental Geology
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• v.12 no.4
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• pp.181-195
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• 1979

The Nambu orebodies of the Okbang tungsten mine are hosted in the Precambrian amphibolite and Weonnam formation. These orebodies can be classified into two types; The scheelite-bearing ore vein occurring in the amphibolite (the Nambu 1, 2 adits) and tungsten-bearing quartz vein along the contact between the amphibolite and the Weonnam formation (the Young-ho, -1, -2, -3 levels). The scheelite-bearing ore vein in the amphilbolite is discontinuous, narrow, and highly irregular in geometry, occurring only within the amphibolite with which of the vein is graduational. Based on these feature of the mode of occurrence, the origin of this ore type might be attributed to a potential segregation of tungsten ore fluid in situ from hornblenditic basic magma of the host rock. Tungsten-bearing quartz vein, however, is considered to have deposited along the N30-60E trending fractures as a later hypothermal vein after the hornblendite was emplaced. The principal ore mineral is scheelite with minor amount of wolframite, and the gangue minerals are quartz, and small amounts of fluorite, pyrrhotite, chalcopyrite and calcite. Fluid inclusion study of minerals from the Nambu orebody reveals that the fluids in fluorite of the scheelite-bearning ore vein attained a temperature range of $208{\sim}256^{\circ}C$ and those in quartz from the tungsten-bearing quartz vein a temperature range of $220{\sim}357^{\circ}C$. The real formation temperatures can be somewhat higher than filling temperatures, if pressure correction is made. Chemical analysis of 8 amphibolitc samples on major and some trace elements indicate that the amphibolite is igneous origin. On a Niggli diagram (al-alk)versus c, the analytical values are plotted on an igneous field, and on a Niggli diagram mg versus c they follow a karroo igneous trend line. According to the Ba, Cr, and Ni versus Niggli mg plots suggested by Leake (1964), Okbang amphibolite fall outside a pelitic field and compare favorably with his plots form ortho-amphibolites. Analitical values of $MoO_3$ of 8 samples of scheelite minerals from the Nambu orebody indicate that the tungsten-bearing quartz vein (type n) of Nambu orebody shows a range from 1. 69% to 4.38% which is higher than 0.94%~3.25% $MoO_3$ for the scheelite-bearing ore vein (type I). This fact indicates that the type II was deposited in a lower $fO_2/higher$ $fO_2$ environment and under lower temperature than the type I. Analysis of major components $WO_3$, MnO, and FeO of 6 samples of wolframite from the type II veins revealed that they contain 73.35~76.2% $WO_3$, 7.94~11.63% MnO, and 10.53~14.82% FeO. MnO/FeO ratios of wolframite shows the range of 0.85~1.17 which suggests a slightly higher temperature type of deposits than other major tungsten deposits in the country.

• Analytical Science and Technology
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• v.10 no.6
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• pp.439-444
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• 1997

Twelve kinds (1set) standard materials of chemical ingredients of lead zirconate titanate[$Pb(ZrTi)O_3$] have been developed in order to determine fast and accurate measurement of X-ray fluorescence spectrometry. Especially, we used diluted(ahout sixteen times) filling compound($Li_2B_4O_7/LiBO_2=4/1$) to consider removal effect of matrix, storage convenience, and homogenous characteristics. As a result from the four different laboratories, we obtained extremly good agreement about the standard curve on twelve standard materials which containing eleven elements, PbO, $ZrO_2$, $TiO_2$, SrO, $WO_3$, $La_2O_3$, $Cr_2O_3$, MgO, $Nb_2O_5$, and $MnO_2$. The correlation factor of standard curve was over 0.998. However, ZnO has relatively low correlation factor, 0.977, because the concentration was 10ppm lower than other original materials. This analysis reveals that ZnO has shown the poor linearity as well as low fluorescence intensity. In present work, XRF standard materials are useful for determining a rapid and accurate results for major and minor elements concentration among PZT.