• Title/Summary/Keyword: 비정질 규산염

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Effect of Boron Content on Atomic Structure of Boron-bearing Multicomponent Oxide Glasses: A View from Solid-state NMR (비정질 소듐 보레이트와 붕소를 함유한 다성분계 규산염 용융체의 붕소의 함량에 따른 원자 구조에 대한 고상 핵자기 공명 분광분석 연구)

  • Lee, A Chim;Lee, Sung Keun
    • Journal of the Mineralogical Society of Korea
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    • v.29 no.3
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    • pp.155-165
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    • 2016
  • Understanding the effect of boron content on atomic structures of boron-bearing multicomponent silicate melts is essential to reveal the atomistic origins of diverse geochemical processes involving silica-rich magmas, such as explosive volcanic eruption. The detailed atomic environments around B and Al in boron-bearing complex aluminosilicate glasses yield atomistic insights into reactivity of nuclear waste glasses in contact with aqueous solutions. We report experimental results on the effect of boron content on the atomic structures of sodium borate glasses and boron-bearing multicomponent silicate melts [malinkoite ($NaBSiO_4$)-nepheline ($NaAlSiO_4$) pseudo-binary glasses] using the high-resolution solid-state NMR ($^{11}B$ and $^{27}Al$). The $^{11}B$ MAS NMR spectra of sodium borate glasses show that three-coodrinated boron ($^{[3]}B$) increases with increasing $B_2O_3$ content. While the spectra imply that the fraction of non-ring species decreases with decreasing boron content, peak position of the species is expected to vary with Na content. Therefore, the quantitative estimation of the fractions of the ring/non-ring species remains to be explored. The $^{11}B$ MAS NMR spectra of the glasses in the malinkoite-nepheline join show that four-coordinated boron ($^{[4]}B$) increases as $X_{Ma}$ [$=NaBSiO_4/(NaBSiO_4+NaAlSiO_4)$] increases while $^{[3]}B$ decreases. $^{27}Al$ MAS NMR spectra of the multicomponent glasses confirm that four-coordinated aluminum ($^{[4]}Al$) is dominant. It is also observed that a drastic decrease in the peak widths (full-width at half-maximum, FWHM) of $^{[4]}Al$ with an addition of boron ($X_{Ma}=0.25$) in nepheline glasses. This indicates a decrease in structural and topological disorder around $^{[4]}Al$ in the glasses with increasing boron content. The quantitative atomic environments around boron of both binary and multicomponent glasses were estimated from the simulation results of $^{11}B$ MAS NMR spectra, revealing complex-nonlinear variation of boron topology with varying composition. The current results can be potentially used to account for the structural origins of the change in macroscopic properties of boron-bearing oxide melts with varying boron content.

알칼리-골재팽창을 최소화시키는 포틀랜드 제올라이트 시멘트

  • 한국양회공업협회
    • Cement
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    • s.108
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    • pp.57-60
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    • 1987
  • 이 논문에서는 통상의 포졸란 대신에 제올라이트 물질 즉, 화산 응회암을 적절히 분쇄한 후 혼합해서 만든 시멘트의 특성 변화에 대해 논하였다. 이러한 치환이 알칼리-골재 팽창 반응을 최소화시키고 장기강도를 향상시키는 장점이 있다는 사실도 밝혀냈다. 특히 제올라이트를 미리 열처리해서 첨가했을 때 이러한 팽창감소 효과가 현저하다는 것도 발견하였다. 강도증진 효과는 포졸란 유리상의 활성도에 비해 제올라이트 광물의 활성도가 높기 때문으로 해석되며 팽창의 감소는 비정질 수화 규산염이 먼저 알칼리와 반응을 하는 성질이 있기 때문으로 판단된다.

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A Solid-State NMR Study of Coordination Transformation in Amorphous Aluminum Oxide: Implication for Crystallization of Magma Ocean (고상 NMR을 이용한 비정질 알루미나의 상전이 연구: 마그마 바다 구성 용융체의 결정화 과정의 의의)

  • Ryu, Saebom;Lee, Sung Keun
    • Journal of the Mineralogical Society of Korea
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    • v.25 no.4
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    • pp.283-293
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    • 2012
  • In order to have better insights into the chemical differentiation of Earth from its magma ocean phase to the current stratified structure, detailed information of crystallization kinetics of silicate melts consisting of the magma ocean is essential. The structural transitions in oxide glasses and melts upon crystallization provide improved prospects for a systematic and quantitative understanding of the crystallization processes. Here, we report the $^{27}Al$ 3QMAS NMR spectra for sol-gel synthesized $Al_2O_3$ glass with varying temperature and annealing time. The NMR spectra for the amorphous $Al_2O_3$ show well-resolved Al coordination environments, characterized with mostly $^{[4,5]}Al$ and a minor fraction of $^{[6]}Al$. The fraction of $^{[5]}Al$ in the alumina phase decreases with increasing annealing time at constant temperature. The NMR results of $Al_2O_3$ phases also imply that multiple processes (e.g., crystallization and/or changes in structural disorder within glasses) could involve upon its phase transition. The current results and method can be useful to understand crystallization kinetics of diverse natural and multi-component silicate glasses and melts. The potential result may yield atomic-level understanding of Earth's chemical evolution and differentiation from the magma ocean.

Oxygen Sites in Quaternary Ca-Na Aluminosilicate Classes : O-17 Solid-State NMR Study (사성분계 비정질 Ca-Na 알루미노규산염의 산소주변의 원자구조 : O-17 고상핵자기 공명분광학분석)

  • Sung, So-Young;Lee, Sung-Keun
    • Journal of the Mineralogical Society of Korea
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    • v.19 no.4 s.50
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    • pp.347-353
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    • 2006
  • The atomic-nano scale structures of multi-component aluminosilicate glasses have not been well understood in spite of its implications fur dynamics and generation of magma in the natural system due to lack of suitable spectroscopic and scattering experiments. Here, we report O-17 MAS and isotropic projection of 3QMAS NMR spectra for quaternary Na-Ca silicate glasses $[(CaO)_x(Na_2O)_{1-x}]\;(A1_2O_3)_{0.5}(SiO_2)_6,\;CNAS)$ at 14.1 Tesla where atomic configurations around bridging oxygen (Si-O-Si, Si-O-Al) and non bridging oxygen (Na-O-Si, Ca-O-Si, (Na, Ca)-O-Si) are partially resolved. With increasing Na content, the fraction of Na-O-Si increases while those for bridging oxygens remain constant. The Na/Ca ratio apparently affects the peak widths of bridging oxygen peaks (e.g., Si-O-Si)) and thus the topological entropy as well as chemical shifts of the bridging oxygen peaks, implying that both BOs and NBOs are strongly interacting with network modifying cations The effect of cation field strength on the degree of Al-avoidance was also discussed.

Mineralogical Evolution of Non-Andic Soils, Jeju Island (제주도 Non-Andic 토양의 광물학적 진화)

  • 하대호;유장한;문희수;이규호;송윤구
    • Economic and Environmental Geology
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    • v.35 no.6
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    • pp.491-508
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    • 2002
  • While about 80% of Jeju soils are classified as Andisols, the soils derived from volcanic ash in Dangsanbong are not Andisols. There is a significant difference of precipitation in localities of Jeju island. The study area is characterized by the lowest amount of annual rainfall in Jeju Island, and by the layered silicates as dominant solid phase in clay fraction. The purpose of this study was to characterize the mineralogy of the non-Andie soils in detail, especially hydroxy-interlayered silicates. Two major soil horizons are recognized in the soil profile developed in the Dangsanbong area, which can be designated as A and C. The soil pH($H_{2}0$), ranges from 6.6 to 7.3 increasing with depth, is higher than that of typical Andisols(pH<6.0). While the pH(NaF), ranges from 9.49 to 9.81, indicates that significant amount of amorphous phases might be present as exchanging complexes. It is estimated to about 1.542.88 wt% by using chemical selective dissolution. The organic content of surface horizon is about 2 wt%. This soil are composed of quartz, feldspar and olivine as major constituents with minor of silicate clays. Quartz is frequently observed in A and distinctly decreases in its amount with depth, while olivine is dominant phase in C and rarely observed in A. In the <0.2$\mu\textrm{m}$ size fraction, smectite and kaolinite/smectite interstratification are dominant with minor of illite. The amounts of smectite decrease with depth, while the amounts of kaolinite/smecite interstratification increase with depth, which indicates the trend of mineral transformation with increasing the degree of weathering. The proportion of kaolinite in kaolinite/smectite interstratification is about 85%, and is not changed significantly through the profile. In the 2-0.2$\mu\textrm{m}$size fraction, vermiculite, smectite, illite and kaolinite are major components with minor of chlorite. Most of chlorite are interstratified with smectite. Chlorite which is not interstratified with smectite occurs only in surface horizon. The proportion of the chlorite in the chlorite/smectite interstratification is 59-70(%) and increases with depth. Hydroxy-interlayered vermiculite(HIV) with hydroxy-Fe/AI in their interlayers occurs in both A and C horizon. The amounts of hydroxy-Fe/AI decrease with depth. Hydroxy-interlayered smectite(HIS) of which interlayers might be composed of hydroxy-Mg/Al occurs only in C horizon. As the results of mineralogical investigation for the soil profile in the study area, clay minerals might be changed and evolved through the following weathering sequences: 1) Smectite Kaolinite, HIS, Vermiculite, 2) Vermiculite HIV Chlorite.

Atomic Structure of Dissolved Carbon in Enstatite: Raman Spectroscopy and Quantum Chemical Calculations of NMR Chemical Shift (라만 분광분석과 NMR 화학 이동 양자 계산을 이용한 엔스테타이트에 용해된 탄소의 원자 환경 연구)

  • Kim, Eun-Jeong;Lee, Sung-Keun
    • Journal of the Mineralogical Society of Korea
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    • v.24 no.4
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    • pp.289-300
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    • 2011
  • Atomistic origins of carbon solubility into silicates are essential to understand the effect of carbon on the properties of silicates and evolution of the Earth system through igneous and volcanic processes. Here, we investigate the atomic structure and NMR properties of dissolved carbon in enstatite using Raman spectroscopy and quantum chemical calculations. Raman spectrum for enstatite synthesized with 2.4. wt% of amorphous carbon at 1.5 GPa and $1,400^{\circ}C$ shows vibrational modes of enstatite, but does not show any vibrational modes of $CO_2$ or ${CO_3}^{2-}$. The result indicates low solubility of carbon into enstatite at a given pressure and temperature conditions. Because $^{13}C$ NMR chemical shift is sensitive to local atomic structure around carbon and we calculated $^{13}C$ NMR chemical shielding tensors for C substituted enstatite cluster as well as molecular $CO_2$ using quantum chemical calculations to give insights into $^{13}C$ NMR chemical shifts of carbon in enstatite. The result shows that $^{13}C$ NMR chemical shift of $CO_2$ is 125 ppm, consistent with previous studies. Calculated $^{13}C$ NMR chemical shift of C is ~254 ppm. The current calculation will alllow us to assign potential $^{13}C$ NMR spectra for the enstatite dissolved with carbon and thus may be useful in exploring the atomic environment of carbon.

Synthesis of zeolite A from serpentine (사문석으로부터 제올라이트 A의 합성)

  • 김동진;정헌생;이재천;김인회;이자현
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.10 no.1
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    • pp.73-79
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    • 2000
  • Highly porous amorphous silica obtained from a serpentine mineral by hydrochloric acid treatment was used to produce a zeolite A through the hydrothermal reaction under atmospheric pressure. An optimum synthesis condition of the zeolite A was achieved at $80^{\circ}C$ for two hours with a mole ratio of $Na_2O/SiO_2$1.5. Additionally, it was found that a hydroxysodalite zeolite was formed under the experimental conditions over the reaction temperature of $80^{\circ}C$ and the reaction time of 120 minutes even though the crystallization of zeolite proceeds rapidly as the reaction temperature and the alkalinity becomes higher.

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Supergene Alteration of Basaltic Ash in Udo Tuff Cone, Jeju Island (제주도 우도 현무암질 화산재의 표성 변질작용)

  • Jeong, Gi-Young
    • Journal of the Mineralogical Society of Korea
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    • v.23 no.2
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    • pp.141-150
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    • 2010
  • Basaltic ash of Udo tuff cone, Jeju Island, was almost fresh across strata, but significantly altered toward surface by supergene process. The supergene alteration of the Udo tuff was examined by using X-ray diffraction, scanning and transmission electron microscopy, and electron microprobe analysis for elucidating the alteration process of basaltic ash in terrestrial environments. Fresh ash particles were composed of glass matrix, plagioclase, olivine, and pyroxene. The glass matrix was selectively replaced inward by colloform alteration rinds of Fe-Ti-rich amorphous silicate nanogranules and smectite, often leaving glass core at the center of larger ash particles. Some of the dissolved species released from the altered ash particle precipitated as fine honycomb aggregates of smectite on the pore walls, contributing to the cementation and lithification of volcanic ash.

A Study of Copper Production Techniques at the Archaeological Site in Gwanbukri, Buyeo in the 6th and 7th Centuries (6~7C 부여 관북리 유적의 동 생산기법 연구)

  • Lee, Ga Young;Cho, Nam Chul
    • Journal of Conservation Science
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    • v.36 no.3
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    • pp.162-177
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    • 2020
  • Research was conducted to characterize the copper production and smelting process with 11 copper smelting by-products (copper slag and copper crucible) excavated from the NA and LA areas at the Gwanbuk-ri archeological site in Buyeo. Scanning electron microscopy-energy dispersive spectroscopy, wavelength dispersive X-ray fluorescence, X-ray diffraction, and Raman microspectroscopy were employed in the analysis. The research results reveal that the copper slag from Gwanbuk-ri contained silicate oxide, magnetite, fayalite, and delafossite, which are typical characteristics of crucible slag and refined slag. The outward appearance and microstructure of the slag were grouped as follows: 1. glassy matrix + Cu prill, 2. glassy matrix + Cu prill + magnetite, 3. silicate mineral matrix + Cu prill, 4. crystalline (delafossite and magnetite) + amorphous (Cu prill), 5. magnetite + fayalite, and 6. slag from slag. The copper slags from Guanbuk-ri were found to contain residues of impurities such as SiO2, Al2O3, CaO, SO4, P2O5, Ag2O, and Sb2O3 in their microstructure, and, in some cases, it was confirmed that copper, tin and lead are alloys. These results indicate that refining of intermediate copper(including impurities) and refining of alloys of copper(including impurities) - tin and refining of copper(including impurities) - tin - lead took place during the copper production process at Gwanbuk-ri, Buyeo.