• Title/Summary/Keyword: Non-bridging oxygen

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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.

Probing Atomic Structure of Quarternary Aluminosilicate Glasses using Solid-state NMR (다성분계 현무암질 비정질 규산염의 원자 구조에 대한 고상핵자기 공명 분광분석연구)

  • Park, Sun-Young;Lee, Sung-Keun
    • Journal of the Mineralogical Society of Korea
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    • v.22 no.4
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    • pp.343-352
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    • 2009
  • High-resolution Solid-state NMR provides element specific and quantitative information and also resolves, otherwise overlapping atomic configurations in multi-component non-crystalline silicates. Here we report the preliminary results on the effect of composition on the structure of CMAS (CaO-MgO-$Al_2O_3-SiO_2$) silicate glasses, as a model system for basaltic magmas, using the high-resolution 1D and 2D solid-state NMR. The $^{27}Al$ MAS NMR spectra for the CMAS silicate glasses show that four-coordinated Al is predominant, demonstrating that $Al^{3+}$ is network forming cation. The peak position moves toward lower frequency about 4.7 ppm with increasing $X_{MgO}$ due to an increase in $Q^4$(4Si) fraction with increasing Si content, indicating that Al are surrounded only by bridging oxygen. $^{17}O$ MAS NMR spectra for $CaAl_2SiO_6$ and $CaMgSi_2O_6$ glasses qualitatively suggest that NBO fraction in the former is smaller than that in $CaMgSi_2O_6$ glasses. As $^{17}O$ 3QMAS NMR spectrum of model quaternary aluminosilicate glass resolved distinct bridging and non-bridging oxygen environments, atomic structure for natural magmas can also be potentially probed using high-resolution 3QMAS NMR.

Chemical Bonding State of Sulfur in Oxysulfide Glasses

  • Asahi, Taro;Miura, Yoshinari;Nanba, Tokuro;Yamashita, Hiroshi
    • The Korean Journal of Ceramics
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    • v.5 no.2
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    • pp.178-182
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    • 1999
  • Simple binary $Na_2S-SiO_2$ oxysulfide glasses were prepared by a conventional melt-quench method in order to investigate the role of sulfur in glass structure and the electronic state. By X-ray photoelectron spectroscopy(XPS) measurement, S2p binding energy of the glass was observed at approximately 161eV which was close to that of ionic $S^{2-}$. The coordinating state around silicon atoms were investigated by ${29}^Si$ MAS-NMR measurement. The chemical shift observed from NMR supported that sulfur atom was joined to a silicon atom by substituting for an oxygen atom and was present as a non-bridging sulfide ion in low alkali content. On the other hand, it could be presumed that a portion of sulfur anions existed in an isolated state from the glass-network frame at high alkali content. The state of these sulfurs was also studied by Raman spectroscopy in detail.

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Structure and Electrical Properties of Li2O-TiO2-P2O5/ Glasses (Li2O-TiO2-P2O5계 유리의 구조와 전기적 성질)

  • 윤기현;곽만석;이용근
    • Journal of the Korean Ceramic Society
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    • v.40 no.2
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    • pp.178-183
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    • 2003
  • Electrical conductivity of$50Li_2O-xTiO_2-(50-x)P_2O_5$ glasses has been studied with an increase of the intermediate$TiO_2$content. Thermal properties were observed from TG-DTA measurement and the variation of glass structure was investigated by FT-IR. The density and glass transition temperature increased with an increase of the $TiO_2$ content. These results were attributed to the fact that bond strengthening was occurred because of the formation of P-O-Ti cross linkages in the glass. The ionic conductivity increased with $TiO_2$ content and a maximum value, $1.2{imes}10^{-6}$S/cm showed at x=20. The ionic conductivity showed a large increasement as a result that the pyrophosphate group become the predominant structural unit. This result can explain that Li ions mobility increased as a number of non-bridging oxygen on phosphate units increased.

Structure and thermal properties of $SnO_2-B_2O_3-P_2O_5$ glasses ($SnO_2-P_2O_5-B_2O_3$ 유리구조 및 열적 특성)

  • An, Yong-Tae;Choi, Byung-Hyun;Ji, Mi-Jung;Ko, Young-Soo;Kim, Hyung-Sun
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.06a
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    • pp.91-91
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    • 2008
  • $SnO_2-B_2O_3-P_2O_5$ system were prepared by melt-quenching technique in the compositional series containing 50, 55 aod 60mol.% of $SnO_2$. A large glass-forming region was found at the phosphate side of the ternary system with homogeneous glasses containing up to 5-25mol.% of $B_2O_3$. For these glasses, thermal expansion coeffient($\alpha$), glass transition temperature(Tg), and glass softening temperature(Ts), were determined. The values a decrease with increasing $B_2O_3$ content, while Tg and Ts increased. The reason for the observed changes is local structure of the glasses. Local structure of the glasses was investigated by Raman and FT-IR measurements, suggesting that the number of bridging oxygens decreased whereas the non-bridging oxygen concentration increased with increasing $SnO_2$ content in the glasses.

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Structure and Thermal Properties of SnO2-(1-x)P2O5-xB2O3 Glasses (SnO2-(1-x)P2O5-xB2O3 유리의 열적, 구조적 특성)

  • An, Yong-Tae;Choi, Byung-Hyun;Ji, Mi-Jung;Chang, Woo-Suk;Bae, Hyun;Hwang, Hae-Jin
    • Journal of the Korean Ceramic Society
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    • v.47 no.2
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    • pp.117-121
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    • 2010
  • $SnO_2-(1-x)P_2O_5-xB_2O_3$ glass system were prepared by melt-quenching technique in the compositional series containing 50, 55 and 60 mol% of $SnO_2$. Local structure of the glasses was investigated by Raman and FT-IR measurements. A large glass-forming region was found at the phosphate side of the ternary system with homogeneous glasses containing up to 5~25 mol% of $B_2O_3$. According as content of $B_2O_3$ increases, theraml expansion coefficient of glass decreased but transition temperature and softening temperature increased. Because these phenomenon changed local structure of glass. According as content of $B_2O_3$ increases, quantity of bridging oxygen increased. Also, according as content of $SnO_2$ increases, confirmed that quantity of non-bridging oxygen increases.

A study on the crystallization processing of photosensitive glass by FT-IR and FT-Raman spectroscopy (FT-IR과 FT-Raman 분광계를 이용한 광민감유리의 결정화 과정에 관한 연구)

  • 이명원;강원호
    • Electrical & Electronic Materials
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    • v.10 no.3
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    • pp.284-288
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    • 1997
  • FT-IR and FT-Raman spectra were measured for 15Li$_{2}$O.3Al$_{2}$O$_{3}$.78SiO$_{2}$. 4K$_{2}$O glass system after UV irradiations. Optimum UV irradiation time of Li$_{2}$O.SiO$_{2}$ crystalline phase was 60 seconds and crystalline phase of Li$_{2}$O.SiO$_{2}$ was leached out on 5% HF. 977 cm$^{1}$ band of FT-Raman spectra can be attributed to two-non bridging oxygen in unit cell for 1 hour and optimum crystallization was confirmed for 3 hrs, 630.deg. C.

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Structural Modification of Alkali Tellurite Binary Glass System and Its Characterization

  • Lee, Kyu-Ho;Kim, Tae-Ho;Kim, Young-Seok;Jung, Young-Joon;Na, Young-Hoon;Ryu, Bong-Ki
    • Korean Journal of Materials Research
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    • v.18 no.5
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    • pp.235-240
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    • 2008
  • This paper presents results and observations obtained from a study of the optical and thermal properties of alkali tellurite depending on the composition. Fourier transform infrared (FT-IR) spectra showed evidence of chemical modification from $TeO_4$ trigonal bipyramids (tbp) to $TeO_3$ trigonal pyramids (tp) in tellurite glasses. The optical band gaps of the different glass samples calculated using Tauc's method were found to range from 3.5-3.8 eV. The glass transition temperature (Tg) and glass stability (${\Delta}T$) of alkali tellurite glasses were investigated, as $M_2O$ [M: Li, Na, K] amounted to 25 mol%, through the use of differential thermal analysis (DTA). The coefficient of thermal expansion (CTE) was measured in a thermo mechanical analysis (TMA) with a slow heating rate after the glass samples were annealed. The results confirm that the optical band gap of alkali tellurite glasses depends on the Te-O-Te structural relaxation related to the ratio of bridging/non bridging oxygen (BO/NBO). In contrast, the thermal properties are related to the ionic field strength of the Te-O-M and M-O-M bonds, and the Te-O-Te breakage depends on the ratio of BO/NBO.

Effect of Al2O3 on the Structure and Properties of Bioglass (생체 유리의 구조 및 물성에 미치는 Al2O3의 영향)

  • 노종남;황진명;김철영
    • Journal of the Korean Ceramic Society
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    • v.26 no.6
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    • pp.811-819
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    • 1989
  • There have been many studies on the biological phenomena of Bioglasses, which nay be used as implant materials in human body. However, not many works on the Bioglass compositions have been reported. In the present study, the effect of Al2O3 substitution for SiO2 in Bioglass of Na2O-CaO-P2O5-SiO2 system on its structure and properties was examined. Infrared and Raman spectroscopic studies for the glass structural analysis, differential thermal analysis and X-ray diffraction analysis for crystallization of the glass were perfomed. Several physical properties, such as thermal expansion coefficient, softening point, microhardness and reaction phenomena, were also measured. The major crystalline phase, after heat treatment of the glasses, was Na2Ca2(SiO2)3 and the crystal was transformed into other phase with increased substitution of Al2O3. The added Al2O3 reduced non-bridging oxygen in glass structure and thermal expansion coefficient, but increased glass density, sofening point and microhardness. When the glasses are reacted in Tris-buffer solution, the substituted Al2O3 inhibited the formation of hydroxyapatite on the Bioglas surface, and no hydroxyapatite was formed for the sample which contained more than 6wt.% of Al2O3 even if they were reacted for 600 hours.

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Structural, Optical, and Chemical Properties of Cadmium Phosphate Glasses

  • Chung, Jae-Yeop;Kim, Jong-Hwan;Choi, Su-Yeon;Park, Hyun-Joon;Hwang, Moon-Kyung;Jeong, Yoon-Ki;Ryu, Bong-Ki
    • Journal of the Korean Ceramic Society
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    • v.52 no.2
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    • pp.128-132
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    • 2015
  • In this study, we prepared cadmium phosphate glasses with various compositions, given by $xCdO-(100-x)P_2O_5$ (x = 10-55 mol%), and analyzed their Fourier transform infrared spectra, dissolution rate, thermal expansion coefficient, glass transition temperature, glass softening temperature, and optical band gap. We found that the thermal expansion coefficient and dissolution rate increased while the glass transition temperature and glass softening temperature decreased with increasing CdO content. These results suggest that CdO acts as a network modifier in binary phosphate glass and weakens its structure.