High-temperature structure of K2O–TeO2 glasses

Akagi, Ryuichi; Handa, Keita; Ohtori, Norikazu; Hannon, Alex C.; Tatsumisago, Masahiro; Umesaki, Norimasa

doi:10.1016/s0022-3093(99)00392-0

Cited by 44 publications

(31 citation statements)

References 14 publications

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“…The peak at about 460 cm −1 is attributed to the bending and stretching vibrations of the Te-O-Te or O-Te-O linkages. 11,12 In the high-frequency region, the Raman spectra had two Raman bands at around 670 and 770 cm −1 . These bands are ascribed to the stretching mode of the TeO 3 trigonal pyramid (tp) units containing terminal Te-O bonds such as Te O and Te-O − with non-bridging oxygen atoms (NBO), the stretching mode of TeO 4 trigonal bipyramid (tbp) units with bridging oxygen atoms (BO) and the bending mode of Te-O-Te or O-Te-O linkages, respectively.…”

Section: Xrd Resultsmentioning

confidence: 99%

“…10 The relationship between glass structure and the added alkali metal ion concentration has been studied by means of Raman spectroscopy, high-temperature XRD, X-ray radial distribution function, and XAFS. 11,12 However, the nature and morphologies of crystalline structures based on the potassium-tellurite (TeO 2 -K 2 O) glasses has not yet been established.…”

Section: Introductionmentioning

confidence: 99%

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Microstructural characterization and crystallization kinetics of (1−x)TeO2–xK2O (x=0.05, 0.10, 0.15, 0.20mol) glasses

Öveçoğlu

Kabalcı

et al. 2007

Journal of the European Ceramic Society

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Section: Xrd Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Microstructural characterization and crystallization kinetics of (1−x)TeO2–xK2O (x=0.05, 0.10, 0.15, 0.20mol) glasses

Öveçoğlu

Kabalcı

et al. 2007

Journal of the European Ceramic Society

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“…The oxygen atoms involved in bridging between TeO4 units occur at axial and equatorial positions 31,33 . Adding modifier components to provide glassforming compositions causes disruption of the network with the appearance of TeO3 2-units containing non-bridging oxygens that are coordinated to the modifier cations 34 . The TeO3 2-groups adopt a distorted tetrahedral geometry with the lone pair forming one apex.…”

Section: Discussionmentioning

confidence: 99%

Structural studies of Bi2O3-Nb2O5-TeO2 glasses

Wilding

Delaizir

Benmore

et al. 2016

Journal of Non-Crystalline Solids

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Bi2O3-Nb2O5-TeO2 glasses show unusual annealing behavior with appearance of spherulites within the matrix glass structure for the Bi0.5Nb0.5Te3O8 composition. The textures resemble those found previously among polyamorphic Al2O3-Y2O3 glasses containing metastably co-existing high-and lowdensity phases produced during quenching. However the spherulites produced within the Bi2O3-Nb2O5-TeO2 glass are crystalline and can be identified as an "anti-glass" phase related to -Bi2Te4O11. We used high energy synchrotron X-ray diffraction data to study structures of binary and ternary glasses quenched from liquids within the Bi2O3-Nb2O5-TeO2 system. These reveal a glassy network based on interconnected TeO4 and TeO3 units that is related to TeO2 crystalline materials but with larger Te...Te separations due to the presence of TeO3 groups and non-bridging oxygens linked to modifier (Bi 3+ , Nb 5+ ) cations. Analysis of the viscosity-temperature relations indicates that the glassforming liquids are "fragile" and there no evidence for a LLPT occurring in the supercooled liquid. The glasses obtained by quenching likely correspond to a high-density amorphous (HDA) state. Subsequent annealing above Tg shows mainly evidence for crystallization of the "anti-glass" tellurite phase. However, some evidence may exist for simultaneous formation of nanoscale amorphous spherultites that could correspond to the LDA polyamorph. The quenching and annealing behavior of Bi2O3-Nb2O5-TeO2 supercooled liquids and glasses is compared with similar materials in the Al2O3-Y2O3 system.

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“…Analytical techniques including X-ray diffraction (XRD) (Brady, 1956(Brady, , 1957Dimitriev et al, 1987), neutron diffraction (Neov et al, 1979), Fourier transform infrared (FTIR) spectroscopy (Dimitriev et al, 1987;Heo et al, 1992), Raman spectroscopy (Khatir et al, 1993;Duverger et al, 1997;Dimitriev et al, 1983;Kashchieva, 1984;Sekiya et al, 1994a;Chowdari and Kumari, 1999;Murugan et al, 2005Murugan et al, , 2006Sekiya et al, 1994b), 125 Te-based nuclear magnetic resonance (NMR) (Sakida et al, 2001;Sakida et al, 1999a, b), extended Xray absorption fine structure (Shimizugawa et al, 1995;Yamamoto et al, 1994), and Mössbauer spectroscopy (Nishida et al, 1990) have been used to determine the various structural configurations present in tellurite glasses. Observations of tellurite structural units have been discussed in the literature as they are affected by oxide additives including alkalis (Rao and Bhat, 2001;Bhat et al, 2004;Arnaudov et al, 1982;Akagi et al, 1999), alkaline earths (Arnaudov et al, 1982), and transition metals (Arnaudov et al, 1982;Kozhukharov et al, 1986;Bürger et al, 1992).…”

Section: Tellurite Glass Structural Configurationsmentioning

confidence: 99%

“…When modifiers, intermediates, and other additives are introduced into the tellurite network, the tbp1 structural units are no longer constrained, extending the Te-O interatomic bonds (Akagi et al, 1999;Neov et al, 1978). Consequently, additives stabilize the vitreous state (Arnaudov and Dimitriev, 2001).…”

Section: Alternative Electrochemical Salt Waste Forms Summary Of Fy/mentioning

confidence: 99%

Alternative Electrochemical Salt Waste Forms, Summary of FY/CY2011 Results

Riley¹,

McCloy²,

Crum³

et al. 2011

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SUMMARYThe Fuel Cycle Research and Development Program, sponsored by the U.S. Department of Energy Office of Nuclear Energy, is currently investigating alternative waste forms for wastes generated from the reprocessing of nuclear fuel. One such waste results from an electrochemical separations process, called the "Echem" process, in molten KCl-LiCl salt as a spent salt containing alkali, alkaline earth, lanthanide halides and a small quantities of actinide halides where the primary anion is chloride with small quantities of iodide. Pacific Northwest National Laboratory (PNNL) is investigating two candidate waste forms for the Echem spent-salt, high-halide minerals (i.e., sodalite and cancrinite) and tellurite (TeO 2 )-based glasses. Both of these candidates showed promise in FY2009 and FY2010 with a simplified nonradioactive simulant of the Echem waste. Further testing was performed on these waste forms in the fiscal (FY) and calendar (CY) year of 2011 to investigate the possibility of their use in a sustainable fuel cycle. This report summarizes the results of FY/CY2011 efforts.The chemical durability results for the tellurite glasses in FY2010 revealed a wide variety of waste form performance in these materials. The most promising glass studied was a lead-tellurite glass formulation with the Echem salt simulant. This glass showed very good chemical durability with a normalized release for sodium of 0.478 g/m 2 following a seven-day leaching test. With this in mind, the following studies were undertaken in FY/CY2011 to further investigate and optimize this type of glass as a potential waste form: 1) Expanded study on lead-tellurite glasses. The lead-tellurite glass system was further investigated in FY/CY2011 to determine the waste-loading limits and assess the tellurium-oxygen bonding structure as a function of waste loading with Raman spectroscopy and X-ray diffraction. Te-O bonding in tellurite glasses is quite complex; at least eight different structures have been presented in the literature and typically include α-TeO 4 , β-TeO 4 , TeO 3+1 , and TeO 3 structures (the α/β notation denotes the way that the TeO 4 species bond to one another, and the number after the "O" denotes the number of oxygens bonded to the central Te atom in that species). We also investigated some of the other waste-form related properties of the lead-tellurite glasses, such as the thermal diffusivity, glass transition temperature, crystallization temperature, melting temperature, and mass loss as a function of temperature. The structural investigation revealed that the medium-range order in the glass decreased and the tellurite network was depolymerized as the waste fraction was increased. It was apparent that glass-network breaking was predominantly caused by the additions of the waste cations and that the presence of chloride may have actually caused some repolymerization of the network by scavenging alkali and preventing it from acting as a network modifier. At the highest waste loadings, the glass became phaseseparated, resulting...

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High-temperature structure of K2O–TeO2 glasses

Cited by 44 publications

References 14 publications

Microstructural characterization and crystallization kinetics of (1−x)TeO2–xK2O (x=0.05, 0.10, 0.15, 0.20mol) glasses

Microstructural characterization and crystallization kinetics of (1−x)TeO2–xK2O (x=0.05, 0.10, 0.15, 0.20mol) glasses

Structural studies of Bi2O3-Nb2O5-TeO2 glasses

Alternative Electrochemical Salt Waste Forms, Summary of FY/CY2011 Results

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