• Title/Summary/Keyword: CaO-$ZrO_2$

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Petrochemistry and Environmental Geochemistry of Shale and Coal from the Daedong Supergroup, Chungnam Coal Field, Korea (충남탄전, 대동누층군의 셰일과 탄질암에 관한 암석화학 및 환경지구화학적 특성)

  • Lee, Chan Hee;Lee, Hyun Koo;Kim, Kyoung-Woong
    • Economic and Environmental Geology
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    • v.30 no.5
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    • pp.417-431
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    • 1997
  • Characteristics of sedimentary rocks and enrichment of toxic elements in shale and coal from the Chungnam coal field were investigated based upon geochemistry of major, trace and rare earth elements. Shale and coal of the area are interbedded along the Traissic to the Jurassic Daedong Supergroup, which can be subdivided into grey shale, black shale and coal. The coal had been mined, however all the mines are abandonded due to the economic problems. The shale and coal are characterized by relatively low contents of $SiO_2$, and $Al_2O_3$ and high levels of loss-on-ignition (LOI), CaO and $Na_2O$ in comparison with the North American Shale Composite (NASC). Light rare earth elements (La, Ce, Yb and Lu) are highly enriched with the coal. Ratios of $Al_2O_3/Na_2O$ and $K_2O/Na_2O$ in shale and coal range from 30.0 to 351.8 and from 4.2 to 106.8, which have partly negative correlations against $SiO_2/Al_2O_3$ (1.24 to 6.06), respectively. Those are suggested that controls of mineral compositions in shale and coal can be due to substitution and migration of those elements by diagenesis and metamorphism. Shale and coal of the area may be deposited in terrestrial basin deduced from high C/S (39 to 895) and variable composition of organic carbon (0.39 to 18.40 wt.%) and low contents of reduced sulfur (0.01 to 0.05 wt.%). These shale and coal were originated from the high grade metamorphic and/or igneous rocks, and the rare earth elements of those rocks are slightly influenced with diagenesis and metamorphism on the basis of $Al_2O_3$ versus La, La against Ce, Zr versus Yb, the ratios of La/Ce (0.38 to 0.85) and Th/U (3.6 to 14.6). Characteristics of trace and rare earth elements as Co/Th (0.07 to 0.86), La/Sc (0.31 to 11.05), Se/Th (0.28 to 1.06), V/Ni (1.14 to 3.97), Cr/V (1.4 to 28.3), Ni/Co (2.12 to 8.00) and Zr/Hf (22.6~45.1) in the shale and coal argue for inefficient mixing of the simple source lithologies during sedimentation. These rocks also show much variation in $La_N/Yb_N$ (1.36 to 21.68), Th/Yb (3.5 to 20.0) and La/Th (0.31 to 7.89), and their origin is explained by derivation from a mixture of mainly acidic igneous and metamorphic rocks. Average concentrations in the shale and coal are As=7.2 and 7.5, Ba=913 and 974, Cr=500 and 145, Cu=20 and 26, Ni=38 and 35, Pb=30 and 36, and Zn=77 and 92 ppm, respectively, which are similar to those in the NASC. Average enrichment indices for major elements in the shale (0.79) and coal (0.77) are lower than those in the NASC. In addition, average enrichment index for rare earth elements in coal (2.39) is enriched rather than the shale (1.55). On the basis of the NASC, concentrations of minor and/or environmental toxic elements in the shale and coal were depleted of all the elements examined, excepting Cr, Pb, Rb and Th. Average enrichment indices of trace and/or potentially toxic elements (As, Cr, Cu, Ni, Pb, U and Zn) are 1.23 to 1.24 for shale and 1.06 to 1.22 for coal, respectively.

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Temporal variation of magma chemistry in association with extinction of spreading, the fossil Antarctic-Phoenix Ridge, Drake Passage, Antarctica

  • Choe, Won-Hie;Lee, Jong-Ik;Lee, Mi-Jung;Hur, Soon-Do;Jin, Young-Keun
    • 한국지구과학회:학술대회논문집
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    • 2005.09a
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    • pp.136-141
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    • 2005
  • The K Ar ages, whole rock geochemistry and Sr Nd Pb isotopes have been determined for the submarine basalts dredged from the P2 and P3 segments of the Antarctic-Phoenix Ridge (APR), Drake Passage, Antarctica, for better understanding on temporal variation of magma chemistry in association with extinction of seafloor spreading. The fossilized APR is distant from the known hot spots, and consists of older N-MORB prior to extinction of spreading and younger E-MORB after extinction. The older N-MORB (3.5-6.4 Ma) occur in the southeast flank of the P3 segment (PR3) and the younger E-MORB (1.4-3.1 Ma) comprise a huge seamount at the P3 segment (SPR) and a big volcanic edifice at the P2 segment (PR2). The N-type PR3 basalts have higher Mg#, K/Ba, and CaO/Al2O3 and lower Zr/Y, Sr, and Na8.0 with slight enrichment in incompatible elements and almost flat REE patterns. The E-type SPR and PR2 basalts are highly enriched in incompatible elements and LREE. The extinction of spreading occurring at 3.3 Ma seems to have led to a temporal magma oversupply with E-MORB signatures. Geochemical signatures such as Ba/TiO2, Ba/La, and Sm/La suggest heterogeneity of upper mantle and formation of E-MORB by higher contribution of enriched materials to mantle melting, compared to N-MORB environment. E-MORB magmas beneath the APR seem to have been produced by low melting degree (up to 1% or more) at deeper low-temperature regime, where metasomatized veins consisting of pyroxenites have preferentially participated in the melting. The occurrence of E-MORB at the APR is a good example to better understand what kinds of magmatism would occur in association with extinction of spreading.

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Capping Intercrystalline Defects of Polycrystalline UiO-66 Membranes by Polydimethylsiloxane Coating (폴리다이메틸실록산 코팅을 통한 다결정성 UiO-66 분리막의 비선택적 결정립계 결함 캡핑)

  • Ik Ji Kim;Hyuk Taek Kwon
    • Clean Technology
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    • v.29 no.1
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    • pp.71-75
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    • 2023
  • In general, the presence of non-selective intercrystalline (grain boundary) defects in polycrystalline metal-organic framework (MOF) or zeolite membranes, which are known to be ca. 1 nm in size, causes lower membrane performance (selectivity) than the intrinsically expected. In this study we show that applying a thin polymeric coating of polydimethylsiloxane (PDMS) on a polycrystalline MOF membrane is effective to cap the non-selective intercrystalline defects and therefore improve membrane performance. To demonstrate the concept, first, polycrystalline UiO-66, one of Zr-based MOFs, membranes were prepared by an in-situ solvothermal growth. By controlling membrane growth condition with respect to growth temperature, we were able to obtain polycrystalline UiO-66 membranes at 150 ℃ with intercrystalline defects of which the quantity is not significant, so it can be plugged by the suggested PDMS deposition. Second, their performances were compared before and after the PDMS deposition. As expected, the PDMS deposition ended up with a noticeable increase in CO2/N2 ideal selectivity from 6 to 14, indicating successful intercrystalline defect plugging. However, the enhancement in CO2/N2 selectivity was accompanied by a significant reduction in CO2 permeance from 5700 to 33 GPU because the PDMS deposition not only plugs defects but also forms a continuous coating on membrane surface, adding an additional transport resistance.

Mineralogy and Chemical Composition of the Residual Soils (Hwangto) from South Korea (우리 나라 황토(풍화토)의 구성광물 및 화학성분)

  • 황진연;장명익;김준식;조원모;안병석;강수원
    • Journal of the Mineralogical Society of Korea
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    • v.13 no.3
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    • pp.147-163
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    • 2000
  • The mineralogy and chemical composition of reddish to brownish yellow residual soils, so called "Hwangto" have been examined according to representative host rocks. The result of the study indicates that Hwangto consists of 40-80% clay minerals and various minerals such as quartz, feldspar, hornblende, goethite, and gibbsite. Clay minerals include kaolinite, halloysite, illite, hydroxy interlayered vermiculite (HIV), mica/vermiculite interstratifield mineral and chlorite. The mineralogical constituents and contents of Hwangto were different depending on the types of host rocks. Moreover, the Jurassic granitic rocks contain relatively more kaolin minerals, whereas the Cretaceous granitic rocks contain more HIV and illite. In addition, reddish Hwangto contains relatively more kaolinite and HIV, and yellowish Hwangto contains more illite and halloysite. It is suggested that feldspars and micas of host rocks were chemically weathered into illite, halloysite, illite/vermiculite interstratified minerals, and HIV, and finally into kaolinite. Compared with their host rocks, the major chemical compositions of Hwangto tend to contain more $Al_2O_3,\;Fe_2O_3,\;H_2O$ in amount and less Ca, Mg, and Na. Hwangto contains relatively high amount of trace elements, P, S, Zr, Sr, Ba, Rb, and Ce including considerable amount of Li, V, Cr, Zn, Co, Ni, Cu, Y, Nb, La, Nd, Pb, Th in excess of 10 ppm. Relatively high amount of most trace elements were detected in the Hwangto. The major and minor chemical compositions of the Hwangto were different depending on the types of host rocks. However, their difference was in the similar range compared with the compositions of host rocks.

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Chemical Speciations of Elements in the Fe-Mn Crusts by Sequential Extraction (단계별 추출법을 이용한 망간각 구성 원소의 존재 형태)

  • Kim, Jong-Uk;Moon, Jai-Woon;Chi, Sang-Bum;Ko, Young-Tak;Lee, Hyun-Bok
    • Ocean and Polar Research
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    • v.26 no.2
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    • pp.231-243
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    • 2004
  • Sequential extraction was carried out on twenty two subsamples of three ferromanganese crusts from three seamounts (Lemkein, Lomilik, and Litakpooki) near the Marshall Islands in the western Pacific. The extraction was designed to fractionate Fe-Mn crust forming elements into low defined groups: (1) exchangeable and carbornate, (2) Mn-oxide, (3) Fe-oxyhyd.oxide, and (4) residual fraction. X-ray diffraction result shows that target material were well removed by each extraction step except for CFA in phosphatized crusts generation. According to chemical analysis of each leachate, most of elements in the Fe-Mn crusts are bound with two major phases. Mn, Ba, Co, Ni, Zn, (Fe, Sr, Cu, and V) are strongly bounded with Mn-oxide $({\delta}-MnO_2)$ phase, whereas Fe, Ti, Zr, Mo, Pb, Al, Cu,(V, P, and Zn) show chemical affinity with Fe-oxyhydroxide phase. This result indicates that significant amount of Al, Ti, and Zr can not be explained by detrital origin. Ca, Mg, K, and Sr mainly occur as exchangeable elements and/or carbonate phase. Outermost layer 1 and inner layer 2 which are both young crusts generations are similar in chemical speciations of elements. However, some of Fe-oxyhydroxide bounded elements (Pb, Y, Mo, Ba, Al, and V) in phosphatized innermost layer 3 are released during phosphatization and incorporated into phosphate (Pb, Y, Mo, and Ba) or Mn-oxide phase (Al and V). Our sequential extraction results reveal that chemical speciations of elements in the hydrogenetic crusts are more or less different from interelemental relationship calculated by statistical method based on bulk chemistry.

Effect of Additives on the Densification and Electrical Properties of Ce0.8Gd0.2O2-δ Ceramics (Ceria의 소결과 전기전도도에 미치는 첨가제의 영향)

  • Yoo, Kyung-Bin;Oh, Eun-Ju;Choi, Gyeong-Man
    • Journal of the Korean Ceramic Society
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    • v.42 no.12 s.283
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    • pp.816-820
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    • 2005
  • The doped-ceria is a strong candidate material for an intermediate temperature SOFC. However, the mechanical strength and the magnitude of electrical conductivity need to be increased at low sintering temperature. In this study, to improve both properties, $1at\% $ of Mg, Ca, Cr, Fe, Co, Ni, Cu, Ga, and Zr were added to the GDC20 ($20at\%$ Gd-doped Ceria) and sintered at $1350^{\circ}C$ that is $250^{\circ}C$ lower than $1600^{\circ}C$. With addition, the relative density of the sintered sample increased. Fe, Co, Ni, Cu, Ga doped-GDC20 showed high relative density over $92\%$. Among them, Ga doped-GDC20 showed the most improved sinterability. The conductivity of doped­GDC20 increased by $\~10$ times at $300\~700^{\circ}C$.

Study on Engineering Barrier Role in Nuclear Waste Disposal

  • Hua, Zhang;Jianwen, Yang;Baojun, Li;Shanggeng, Luo
    • Proceedings of the Korean Radioactive Waste Society Conference
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    • 2004.02a
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    • pp.73-82
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    • 2004
  • This paper studies the leaching behaviors of pyrochlore-rich synroc incorporated 46.8wt% simulated actinides waste under the five simulated geological disposal media, which included the bentonite, granite, granite + ferroferric oxide, granite + cement, bentonite + ferroferric oxide, respectively. The mass loss rates reached to equilibrium after 182 day and was 10-7 g/$\textrm{mm}^2{\cdot}d$. That suggests the mass loss rate of pyrochlore-rich synroc, loaded 46.8wt% actinides waste, was very low. The surfaces of the leached specimens were analyzed by XRD, SEM/EDS. The experimental results show that the pyrochlore-rich synroc samples in the systems, which contained bentonite and cement, have two new phases formed on the leached specimens surface at $90^{\circ}C$ for 728d; The bentonite and cement can retard the elements leaching; $Fe_3O_4$ can speed the elements leaching; Expect for Ti ion depleted on the sample surface, other ion, such as U, Zr, AI, Ca, were in equable states and Ba ion was enriched during test time, which indicated the simulated disposal media have good ability to retard the leaching behavior of the pyrochlore-rich synroc.

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Effect of a Series Connection of a Bi-Electrolyte Hydrogen Sensor in a Leak Detector

  • Han, Hyeuk Jin;Park, Chong Ook;Hong, Youngkyu;Kim, Jong Suk;Yang, Jeong Woo;Kim, Yoon Seo
    • Journal of Sensor Science and Technology
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    • v.24 no.1
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    • pp.6-9
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    • 2015
  • Conventional leak detectors are widely based on helium gas sensors. However, the usage of hydrogen sensors in leak detectors has increased because of the high prices of helium leak detectors and the dearth in the supply of helium gas. In this study, a hydrogen leak detector was developed using solid-state hydrogen sensors. The hydrogen sensors are based on Park-Rapp probes with heterojunctions made by oxygen-ion conducting Yttria-stabilized zirconia and proton-conducting In-doped $CaZrO_3$. The hydrogen sensors were used for determining the potential difference between air and air balanced 5 ppm of $H_2$. Even though the Park-Rapp probe shows an excellent selectivity for hydrogen, the sensitivity of the sensor was low because of the low concentration of hydrogen, and the oxygen on the surface of the sensor. In order to increase the sensitivity of the sensor, the sensors were connected in series by Pt wires to increase the potential difference. The sensors were tested at temperatures ranging from $500-600^{\circ}C$.

Evaluation of Properties and Fabrication of Tubular Supports Segmented-in-Series Solid Oxide Fuel Cell (SOFC) (세그먼트 SOFC 관형 세라믹 지지체의 제작 및 특성 평가)

  • Yun, Ui-Jin;Lee, Jong-Won;Lee, Seung-Bok;Lim, Tak-Hyoung;Park, Seok-Joo;Song, Rak-Hyun;Shin, Dong-Ryul;Han, Kyoo-Seung
    • Transactions of the Korean hydrogen and new energy society
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    • v.21 no.3
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    • pp.214-219
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    • 2010
  • In this study, we fabricated tubular ceramic support for segmented-in-series solid oxide fuel cell (SOFC) by using CSZ(CaO-stabilized $ZrO_2$) as main material and activated carbon as pore former. Thermal expansion properties of ceramic support with different amounts of activated carbon were analyzed by using dilatometer to decide a suitable sintering temperature. The tubular ceramic supports with different amounts of activated carbon (5, 10, 15wt.%) were fabricated by the extrusion technique. After sintering at $1100^{\circ}C$ and $1400^{\circ}C$ for 5h., cross section and surface morphology of tubular ceramic support were analyzed by using SEM image. Also, the porosity, mechanical property, gas permeability of tubular ceramic supports was measured. Based on these results, we established the suitable fabrication technique of tubular ceramic support for segmented-in-series SOFC.

Element Mobility during the Weathering of Granitic Gneiss in the Yoogoo Area, Korea. (유구지역 화강암질 편마암의 풍화작용에 따른 원소의 거동)

  • 이석훈;김수진
    • Journal of the Mineralogical Society of Korea
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    • v.14 no.1
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    • pp.39-51
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    • 2001
  • 공주군 유구면 일대의 화강암질 편마암의 풍화작용에 따른 원소의 거동과 pH와 이차광물과의 관계를 XRF, ICP-AES, ICP-MS를 이용한 원소분석결과를 통하여 검토하였다. 이 지역의 암석은 pH6 내외의 산성환경, 침철석, 아나타제와 같은 다양한 이차광물을 생성하면서 심각한 화학조성의 변화를 초래했다. 주원소의 화학조성을 이용한 풍화지수는 토양층에서 79~88로 모암 중의 사장석이 용해되고 흑운모가 변질되어 캐올리광물의 생성이 활발한 방향으로 풍화작용이 진행되었다. 지표층으로 가면서 Al에 대한 주 원소의 거동은 Si, Ca, Na, K, P가 감소하고 Fe, Ti, Mn이 증가하는 경향을 보이며 pH가 낮은 풍화단면에서 주 원소의 변화량이 더 크다. 이 풍화대에서 Mg은 거의 일정하다. Li, As 모든 전이원소는 pH가 감소함에 따라 증가하며 특히 이들 원소는 Fe의 함량과 비례해서 증가해 침철석과 공침하였거나 표면에 흡착되어 있는 것으로 보인다. Ga은 Fe와 비례하기는 하지만 변화량은 전 풍화단면에서 일정하다. Zr, Mo, Sn, Cd은 pH에 변화에 상관없이 일정한 반면에 Rb, Sr, Ba, Y, Pb, Th, U 등은 감소하는 경향을 보인다. 특히 Rb 과 Sr은 Ca에 비례해서 감소한다. 희토류원소는 전 풍화단면에서 감소하는 경향을 보이는데 $Al_2$$O_3$에 대한 상대적인 변화량을 보면 경희토류원소는 사프롤라이트(saprolite)하부와 상부에서 부화되어 있고 중부 사프롤라이트와 토양층에서 감소하는 반면에 중희토류원소는 사프롤라이트 하부와 상부에서 감소하고 중부사프롤라이트 및 토양층에서 부화되는 경향을 보인다. 전반적으로 희토류원소의 원자번호가 클수록 손실율이 커진다. 이 풍화단면에서 원소의 거동은 각 풍화층의 pH와 생성된 이차광물의 조성에 지배를 받았다.

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