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Sample records for alkali oxide glass

  1. Barium oxide, calcium oxide, magnesia, and alkali oxide free glass

    DOEpatents

    Lu, Peizhen Kathy; Mahapatra, Manoj Kumar

    2013-09-24

    A glass composition consisting essentially of about 10-45 mole percent of SrO; about 35-75 mole percent SiO.sub.2; one or more compounds from the group of compounds consisting of La.sub.2O.sub.3, Al.sub.2O.sub.3, B.sub.2O.sub.3, and Ni; the La.sub.2O.sub.3 less than about 20 mole percent; the Al.sub.2O.sub.3 less than about 25 mole percent; the B.sub.2O.sub.3 less than about 15 mole percent; and the Ni less than about 5 mole percent. Preferably, the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide. Preferably, the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack. The SOFC stack comprises a plurality of SOFCs connected by one or more interconnect and manifold materials and sealed by the glass. Preferably, each SOFC comprises an anode, a cathode, and a solid electrolyte.

  2. Mixed alkali effect on the spectroscopic properties of alkali-alkaline earth oxide borate glasses

    NASA Astrophysics Data System (ADS)

    Srinivas, G.; Ramesh, B.; Shareefuddin, Md.; Chary, M. N.; Sayanna, R.

    2016-05-01

    The mixed alkali and alkaline earth oxide borate glass with the composition xK2O - (25-x) Li2O-12.5BaO-12.5MgO-50B2O3 (x = 0, 5, 10, 15, 20 and 25mol %) and doped with 1mol% CuO were prepared by the melt quenching technique. From the optical absorption spectra the optical band gap, electronic polarizability(α02-), interaction parameter (A), theoretical and experimental optical basicity (Λ) values were evaluated. From the Electron Paramagnetic Resonance (EPR) spectral data the number of spins (N) and susceptibility (χ) were evaluated. The values of (α02-), and (Λ) increases with increasing of K2O content and electronic polarizability and interaction parameter show opposite behaviuor which may be due to the creation of non-bridging oxygens and expansion of borate network. The reciprocal of susceptibility (1/χ) and spin concentration (N) as a function of K2O content, varied nonlinearly which may be due to creation of non-bridging oxygens in the present glass system. This may be attributed to mixed alkali effect (MAE).

  3. Scaling behavior in the conductivity of alkali oxide glasses

    SciTech Connect

    Sidebottom, D.L.; Green, P.F.; Brow, R.K.

    1995-11-01

    Although the frequency dependent conductivity, {sigma}({omega}), of ion-containing glasses displays power law dispersion ({sigma}({omega}) {approx} {omega}{sup n}) that can usually be described by a master curve, several findings have suggested that this scaling fails at low temperatures as indicated by a temperature dependence of the scaling exponent, n. The authors investigate this behavior in the frequency range between 1 Hz and 10{sup 6} Hz for a different materials including alkali metaphosphate glasses and a polymer. They identify two distinct regimes of conductive behavior, {sigma}{sub {vert_bar}} and {sigma}{sub {parallel}}. The first, {sigma}{sub {vert_bar}}, is strongly temperature dependent and appears to obey a master curve representation. The second, {sigma}{sub {parallel}}, exhibits only a weak temperature dependence with a roughly linear frequency dependence. A strong depression of {sigma}{sub {vert_bar}} occurs for the mixed alkali case, but {sigma}{sub {parallel}} is unaffected and occurs at roughly the same location in all the alkali compositions studied. They propose that {sigma}{sub {parallel}} does not arise from cation motion, but rather originates from a second mechanisms likely involving small distortions of the underlying glassy matrix. This assignment of {sigma}{sub {parallel}} is further supported by the roughly universal location of {sigma}{sub {parallel}}, to within an order of magnitude, of a variety of materials, including a polymer electrolyte and a doped crystal. Since {sigma}{sub {vert_bar}}(T) and {sigma}{sub {parallel}}(T {approx} const.) are viewed as separate phenomena, the temperature dependence of the scaling exponent is shown to result merely from a superposition of these two contributions and does not indicate any intrinsic failure of the scaling property of {sigma}{sub {vert_bar}}.

  4. Alkali oxide containing mesoporous bioactive glasses: synthesis, characterization and in vitro bioactivity.

    PubMed

    Vaid, Chitra; Murugavel, Sevi

    2013-03-01

    We report, for the first time, the synthesis of sodium oxide containing mesoporous bioactive quaternary glasses and compared with two different mesoporous ternary silicate systems by modified sol-gel process. With the aid of three different glass systems, a systematic analysis has been made on phosphorous-bearing (P-bearing) and phosphorous-free (P-free) mesoporous bioactive glasses to investigate the role of phosphorus on in vitro bioactivity of various silicate glasses with constant alkali oxide content. The combined use of multiple analytical techniques XRD, FTIR, SEM, nitrogen adsorption/desorption analysis before and after soaking in the SBF solution allowed us to establish strong correlation between composition, pore structure and bioactivity. We find that the P-bearing mesoporous glasses show the rapid hydroxycarbonate apatite (HCA) crystallization than P-free mesoporous glasses independent of calcium content. The present study reveals that the presence of phosphorous jointly with calcium in the bioactive glass system significantly enhances the rate of apatite formation as well as crystallization of apatite phase. Additionally, we find that a glass with sodium orthophosphate rich phase enhances the solubility when immersed in SBF and further accelerate the kinetics of apatite formation. The influences of the chemical composition and their superior textural properties on bioactivity are explained in terms of the unique structure of mesoporous bioactive glasses.

  5. Mixed alkali effect in nonconventional alkali gallotitanate glasses

    SciTech Connect

    Miyaji, Fumiaki; Hasegawa, Shinya; Yoko, Toshinobu; Sakka, Sumio . Inst. for Chemical Research)

    1993-02-01

    The mixed alkali effect on electrical conductivity, that is, the reduction of conductivity due to alkali mixing, was observed in Na[sub 2]O-K[sub 2]O-Ga[sub 2]O[sub 3]-TiO[sub 2] glasses, which are nonconventional in the sense that glass-forming oxides defined by Zachariasen are not involved. The magnitude of the reduction in conductivity of the present glasses due to alkali mixing was similar to that of corresponding mixed alkali silicate and phosphate glasses. The activation energy for electrical conduction showed a maximum around the composition Na/(Na + K) = 0.5, where the conductivity was at a minimum.

  6. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: thermal cycle stability and chemical compatibility

    SciTech Connect

    Chou, Y. S.; Thomsen, Edwin C.; Williams, Riley T.; Choi, Jung-Pyung; Canfield, Nathan L.; Bonnett, Jeff F.; Stevenson, Jeffry W.; Shyam, Amit; Lara-Curzio, E.

    2011-03-01

    An alkali silicate glass (SCN-1) is currently being evaluated as a candidate sealing glass for solid oxide fuel (SOFC) applications. The glass containing ~17 mole% alkalis (K2O and Na2O) remains vitreous and compliant during SOFC operation, unlike conventional SOFC sealing glasses, which experience substantial devitrification after the sealing process. The non-crystallizing compliant sealing glass has lower glass transition and softening temperatures since the microstructure remains glassy without significant crystallite formation, and hence can relieve or reduce residual stresses and also has the potential for crack healing. Sealing approaches based on compliant glass will also need to satisfy all the mechanical, thermal, chemical, physical, and electrical requirements for SOFC applications, not only in bulk properties but also at sealing interfaces. In this first of a series of papers we will report the thermal cycle stability of the glass when sealed between two SOFC components, i.e., a NiO/YSZ anode supported YSZ bilayer and a coated ferritic stainless steel interconnect material. High temperature leak rates were monitored versus thermal cycles between 700-850oC using back pressures ranging from 0.2 psi to 1.0 psi. Isothermal stability was also evaluated in a dual environment consisting of flowing dilute H2 fuel versus ambient air. In addition, chemical compatibility at the alumina and YSZ interfaces was examined with scanning electron microscopy and energy dispersive spectroscopy. The results shed new light on the topic of SOFC glass seal development.

  7. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: the effect of protective alumina coating on electrical stability in dual environment

    SciTech Connect

    Chou, Y. S.; Choi, Jung-Pyung; Stevenson, Jeffry W.

    2012-12-01

    An alkali-containing silicate glass was recently proposed as a potential sealant for solid oxide fuel cells (SOFC). The glass contains appreciable amount of alkalis and retains its glassy microstructure at elevated temperatures over time. It is more compliant as compared to conventional glass-ceramics sealants and could potentially heal cracks during thermal cycling. In previous papers the thermal cycle stability, thermal stability and chemical compatibility were reported with yttria-stabilized zirconia (YSZ) electrolyte and YSZ-coated ferritic stainless steel interconnect. In this paper, we report the electrical stability of the compliant glass with aluminized AISI441 interconnect material under DC load in dual environment at 700-800oC. Apparent electrical resistivity was measured with a 4-point method for the glass sealed between two aluminized AISI441 metal coupons as well as plain AISI441 substrates. The results showed good electrical stability with the aluminized AISI441 substrate, while unstable behavior was observed for un-coated substrates. In addition, interfacial microstructure was examined with scanning electron microscopy and correlated with the measured resistivity results. Overall, the alumina coating demonstrated good chemical stability with the alkali-containing silicate sealing glass under DC loading.

  8. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: Combined stability in isothermal ageing and thermal cycling with YSZ coated ferritic stainless steels

    SciTech Connect

    Chou, Y. S.; Thomsen, Edwin C.; Choi, Jung-Pyung; Stevenson, Jeffry W.

    2012-01-01

    An alkali-containing silicate glass (SCN-1) is currently being evaluated as a candidate sealing glass for solid oxide fuel cell (SOFC) applications. The glass contains about 17 mole% alkalis (K+Na) and has low glass transition and softening temperatures. It remains vitreous and compliant around 750-800oC after sealing without substantial crystallization, as contrary to conventional glass-ceramic sealants, which experience rapid crystallization after the sealing process. The glassy nature and low characteristic temperatures can reduce residual stresses and result in the potential for crack healing. In a previous study, the glass was found to have good thermal cycle stability and was chemically compatible with YSZ coating during short term testing. In the current study, the compliant glass was further evaluated in a more realistic way in that the sealed glass couples were first isothermally aged for 1000h followed by thermal cycling. High temperature leakage was measured. The chemical compatibility was also investigated with powder mixtures at 700 and 800oC to enhance potential interfacial reaction. In addition, interfacial microstructure was examined with scanning electron microscopy and evaluated with regard to the leakage and chemical compatibility results.

  9. Alkali-lead-iron phosphate glass and associated method

    DOEpatents

    Boatner, Lynn A.; Sales, Brian C.; Franco, Sofia C. S.

    1994-01-01

    A glass composition and method of preparation utilizes a mixture consisting of phosphorus oxide within the range of about 40 to 49 molar percent, lead oxide within the range of about 10 to 25 molar percent, iron oxide within the range of about 10 to 17 molar percent and an alkali oxide within the range of about 23 to 30 molar percent. The glass resulting from the melting and subsequent solidifying of the mixture possesses a high degree of durability and a coefficient of thermal expansion as high as that of any of a number of metals. Such features render this glass highly desirable in glass-to-metal seal applications.

  10. Alkali-lead-iron phosphate glass and associated method

    DOEpatents

    Boatner, L.A.; Sales, B.C.; Franco, S.C.S.

    1994-03-29

    A glass composition and method of preparation utilizes a mixture consisting of phosphorus oxide within the range of about 40 to 49 molar percent, lead oxide within the range of about 10 to 25 molar percent, iron oxide within the range of about 10 to 17 molar percent and an alkali oxide within the range of about 23 to 30 molar percent. The glass resulting from the melting and subsequent solidifying of the mixture possesses a high degree of durability and a coefficient of thermal expansion as high as that of any of a number of metals. Such features render this glass highly desirable in glass-to-metal seal applications. 6 figures.

  11. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: Combined stability in isothermal ageing and thermal cycling with YSZ coated ferritic stainless steels

    NASA Astrophysics Data System (ADS)

    Chou, Yeong-Shyung; Thomsen, E. C.; Choi, J.-P.; Stevenson, J. W.

    2012-01-01

    An alkali silicate glass (SCN-1) is being evaluated as a candidate sealant for solid oxide fuel cell (SOFC) applications. The glass contains about 17 wt.% alkalis (K + Na) and has low glass transition and softening temperatures. It remains vitreous and compliant after sealing without substantial crystallization, as contrary to conventional glass-ceramic sealant. The glassy nature and low characteristic temperatures can reduce residual stresses and result in the potential for crack healing. In a previous study, the glass was found to have good thermal cycle stability and was chemically compatible with yttria stabilized zirconia (YSZ) coating during short term testing. In this study, the compliant glass was further evaluated in a more realistic way in that the sealed couples were first isothermally aged for 1000 h followed by thermal cycling. High temperature leakage was measured. Chemical compatibility was also investigated with powder mixtures to enhance potential interfacial reaction. In addition, interfacial microstructure was examined with scanning electron microscopy and evaluated with regard to the leakage and chemical compatibility results. Overall the compliant sealing glass showed desirable chemical compatibility with YSZ coated metallic interconnect of minimum reaction and hermetic behavior at 700-750 °C in dual environment.

  12. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: the effect of protective YSZ coating on electrical stability in dual environment

    SciTech Connect

    Chou, Y. S.; Thomsen, Edwin C.; Choi, Jung-Pyung; Stevenson, Jeffry W.

    2012-03-15

    Recently, compliant sealing glass has been proposed as a potential candidate sealant for solid oxide fuel cell (SOFC) applications. In a previous paper, the thermal stability and chemical compatibility were reported for a compliant alkali-containing silicate glass sealed between anode supported YSZ bi-layer and YSZ-coated stainless steel interconnect. In this paper, we will report the electrical stability of the compliant glass under a DC load and dual environment at 700-800 degrees C. Apparent electrical resistivity was measured with a 4-point method for the glass sealed between two plain SS441 metal coupons or YSZ-coated aluminized substrates. The results showed instability with plain SS441 at 800 degrees C, but stable behavior of increasing resistivity with time was observed with the YSZ coated SS441. In addition, results of interfacial microstructure analysis with scanning electron microscopy will be correlated with the measured resistivity results. Overall, the YSZ coating demonstrated chemically stability with the alkali-containing compliant silicate sealing glass under electrical field and dual environments.

  13. Apparatus enables accurate determination of alkali oxides in alkali metals

    NASA Technical Reports Server (NTRS)

    Dupraw, W. A.; Gahn, R. F.; Graab, J. W.; Maple, W. E.; Rosenblum, L.

    1966-01-01

    Evacuated apparatus determines the alkali oxide content of an alkali metal by separating the metal from the oxide by amalgamation with mercury. The apparatus prevents oxygen and moisture from inadvertently entering the system during the sampling and analytical procedure.

  14. Effect of alkali addition on DC conductivity and thermal properties of vanadium-bismo-borate glasses

    SciTech Connect

    Khasa, S. Dahiya, M. S.; Agarwal, A.

    2014-04-24

    The DC Conductivity and Differential Thermal Analysis of glasses with composition (30−x)Li{sub 2}O⋅xV{sub 2}O{sub 5}⋅20Bi{sub 2}O{sub 3}⋅50B{sub 2}O{sub 3}(x=15, 10, 5) has been carried out in order to study the effect of replacing the Transition Metal Oxide (TMO) with alkali oxide. A significant increase in the DC conductivity has been observed with increase in alkali content. Again the thermal measurements have shown the decrease in both glass transition temperature (T{sub g}) and crystallization temperature (T{sub x}). The Glass Stability (GS) and Glass Forming Ability (GFA) have also been calculated and these also were found to decrease with increase in alkali oxide content at the cost of TMO.

  15. Thermal history effects on electrical relaxation and conductivity for potassium silicate glass with low alkali concentrations

    NASA Technical Reports Server (NTRS)

    Angel, Paul W.; Hann, Raiford E.; Cooper, Alfred R.

    1993-01-01

    Electrical response measurements from 10 Hz to 100 kHz between 120 and 540 C were made on potassium-silicate glasses with alkali oxide contents of 2, 3, 5 and 10 mol percent. Low alkali content glasses were chosen in order to try to reduce the Coulombic interactions between alkali ions to the point that frozen structural effects from the glass could be observed. Conductivity and electrical relaxation responses for both annealed and quenched glasses of the same composition were compared. Lower DC conductivity (sigma(sub DC)) activation energies were measured for the quenched compared to the annealed glasses. The two glasses with the lowest alkali contents exhibited a non-Arrhenius concave up curvature in the log(sigma(sub DC)) against 1/T plots, which decreased upon quenching. A sharp decrease in sigma(sub DC) was observed for glasses containing K2O concentrations of 5 mol percent or less. The log modulus loss peak (M'') maximum frequency plots against 1/T all showed Arrhenius behavior for both annealed and quenched samples. The activation energies for these plots closely agreed with the sigma(sub DC) activation energies. A sharp increase in activation energy was observed for both series as the potassium oxide concentration decreased. Changes in the electrical response are attributed to structural effects due to different alkali concentrations. Differences between the annealed and quenched response are linked to a change in the distribution of activation energies (DAE).

  16. Infrared and Raman spectroscopic studies on alkali borate glasses: evidence of mixed alkali effect.

    PubMed

    Padmaja, G; Kistaiah, P

    2009-03-19

    A lithium-potassium-borate glass system containing manganese and iron cations has been thoroughly investigated in order to obtain information about the mixed alkali effect and the structural role of both the manganese and iron in such glass hosts. Mixed alkali borate glasses of the (30 - x)Li(2)O - xK(2)O - 10CdO/ZnO - 59B(2)O(3) (x = 0, 10, 15, 20, and 30) doped with 1MnO(2)/1Fe(2)O(3) system were prepared by a melt quench technique. The amorphous phase of the prepared glass samples was confirmed from their X-ray diffraction. The spectroscopic properties of glass samples were studied using infrared (IR) and Raman spectroscopic techniques. The density of all the prepared glasses was measured using Archimedes principle. Molar volumes were estimated from the density data. IR spectra of these glasses revealed a dramatic variation of three- and four-coordinated boron structures as a function of mixed alkali concentration. The vibrations due to Li-O, K-O, and MnO(4)/FeO(4) arrangements are consistent in all the compositions and show a nonlinear variation in the intensity with alkali content. Raman spectra of different alkali combinations with CdO and ZnO present drastic changes in the intensity of various Raman bands. The observation of disappearance and reappearance of IR and Raman bands as a function of various alkali concentrations is an important result pertaining to the mixed alkali effect in borate glasses. Acting as complementary spectroscopic techniques, both types of measurements, IR and Raman, revealed that the network structure of the studied glasses is mainly based on BO(3) and BO(4) units placed in different structural groups, the BO(3) units being dominant. The measured IR and Raman spectra of different glasses are used to clarify the optical properties of the present glasses correlating them with their structure and composition. PMID:19235995

  17. Electric field-induced softening of alkali silicate glasses

    SciTech Connect

    McLaren, C.; Heffner, W.; Jain, H.; Tessarollo, R.; Raj, R.

    2015-11-02

    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  18. Optical Properties of Tm(3+) Ions in Alkali Germanate Glass

    NASA Technical Reports Server (NTRS)

    Walsh, Brian M.; Barnes, Norman P.; Reichle, Donald J.; Jiang, Shibin

    2006-01-01

    Tm-doped alkali germanate glass is investigated for use as a laser material. Spectroscopic investigations of bulk Tm-doped germanate glass are reported for the absorption, emission and luminescence decay. Tm:germanate shows promise as a fiber laser when pumped with 0.792 m diodes because of low phonon energies. Spectroscopic analysis indicates low nonradiative quenching and pulsed laser performance studies confirm this prediction by showing a quantum efficiency of 1.69.

  19. Theory of corrosion of alkali-borosilicate glass

    SciTech Connect

    Clark, D.E.; Hench, L.L.

    1983-01-01

    The alkali-borosilicate (ABS) system provides the basis for a wide variety of commercially important products among which are the nuclear waste glasses. Although a large number of investigations have been undertaken in the last five years, the corrosion mechanisms of the ABS glasses have not been characterized nearly as well as for the soda-lime-silicate (NCS) glasses commonly used for containers. It is well known that the corrosion of the latter glasses involves ion exchange, network dissolution, and precipitation mechanisms resulting in the development of one of five types of surface films. In the present paper we compare the corrosion behavior to the ABS and NCS glasses and discuss our current understanding of ABS glass corrosion in terms of mechanisms, kinetics, surface film formation and thermodynamics.

  20. Optical response of alkali metal atoms confined in nanoporous glass

    SciTech Connect

    Burchianti, A; Marinelli, C; Mariotti, E; Bogi, A; Marmugi, L; Giomi, S; Maccari, M; Veronesi, S; Moi, L

    2014-03-28

    We study the influence of optical radiation on adsorption and desorption processes of alkali metal atoms confined in nanoporous glass matrices. Exposure of the sample to near-IR or visible light changes the atomic distribution inside the glass nanopores, forcing the entire system to evolve towards a different state. This effect, due to both atomic photodesorption and confinement, causes the growth and evaporation of metastable nanoparticles. It is shown that, by a proper choice of light characteristics and pore size, these processes can be controlled and tailored, thus opening new perspectives for fabrication of nanostructured surfaces. (nanoobjects)

  1. Synthesis and studies on microhardness of alkali zinc borate glasses

    SciTech Connect

    Subhashini, Bhattacharya, Soumalya Shashikala, H. D. Udayashankar, N. K.

    2014-04-24

    The mixed alkali effect on zinc borate glasses have been reported. The glass systems of nominal composition 10Zn+xLi{sub 2}O+yNa{sub 2}O+80B{sub 2}O{sub 3} (x = y = 0, 5, 10, 15 mol%) were prepared using standard melt quenching method. The structural, physical and mechanical properties of the samples have been studied using X-ray diffraction(XRD), density measurement and Vickers hardness measurement, respectively. A consistent increase in the density was observed, which explains the role of the modifiers (Li{sub 2}O and Na{sub 2}O) in the network modification of borate structure. The molar volume is decreasing linearly with the alkali concentration, which is attributed to the conversion of tetrahedral boron (BO{sub 4/2}){sup −} into (BO{sub 3/2}){sup −}. The microhardness studies reveals the anisotropy nature of the material. It further confirms that the samples belong to hard glass category.

  2. Alteration layer formation of Ca- and Zn-oxide bearing alkali borosilicate glasses for immobilisation of UK high level waste: A vapour hydration study

    NASA Astrophysics Data System (ADS)

    Cassingham, N. J.; Corkhill, C. L.; Stennett, M. C.; Hand, R. J.; Hyatt, N. C.

    2016-10-01

    The UK high level nuclear waste glass modified with CaO/ZnO was investigated using the vapour phase hydration test, performed at 200 °C, with the aim of understanding the impact of the modification on the chemical composition and microstructure of the alteration layer. Experiments were undertaken on non-modified and CaO/ZnO-modified base glass, with or without 25 wt% of simulant Magnox waste calcine. The modification resulted in a dramatic reduction in gel layer thickness and also a reduction in the reaction rate, from 3.4 ± 0.3 g m-2 d-1 without CaO/ZnO modification to 0.9 ± 0.1 g m-2 d-1 with CaO/ZnO. The precipitated phase assemblage for the CaO/ZnO-modified compositions was identified as hydrated Ca- and Zn-bearing silicate phases, which were absent from the non-modified counterpart. These results are in agreement with other recent studies showing the beneficial effects of ZnO additions on glass durability.

  3. Alkali oxide-tantalum oxide and alkali oxide-niobium oxide ionic conductors

    NASA Technical Reports Server (NTRS)

    Roth, R. S.; Parker, H. S.; Brower, W. S.; Minor, D.

    1974-01-01

    A search was made for new cationic conducting phases in alkali-tantalate and niobate systems. The phase equilibrium diagrams were constructed for the six binary systems Nb2O5-LiNbO3, Nb2O5-NaNbO3, Nb2O5-KNbO3, Ta2O5-NaTaO3, Ta2O5-LiTaO3, and Ta2O5-KTaO3. Various other binary and ternary systems were also examined. Pellets of nineteen phases were evaluated (by the sponsoring agency) by dielectric loss measurements. Attempts were made to grow large crystals of eight different phases. The system Ta2O5-KTaO3 contains at least three phases which showed peaks in dielectric loss vs. temperature. All three contain structures related to the tungsten bronzes with alkali ions in non-stoichiometric crystallographic positions.

  4. Alkali oxide-tantalum, niobium and antimony oxide ionic conductors

    NASA Technical Reports Server (NTRS)

    Roth, R. S.; Brower, W. S.; Parker, H. S.; Minor, D. B.; Waring, J. L.

    1975-01-01

    The phase equilibrium relations of four systems were investigated in detail. These consisted of sodium and potassium antimonates with antimony oxide and tantalum and niobium oxide with rubidium oxide as far as the ratio 4Rb2O:llB2O5 (B=Nb, Ta). The ternary system NaSbO3-Sb2O4-NaF was investigated extensively to determine the actual composition of the body centered cubic sodium antimonate. Various other binary and ternary oxide systems involving alkali oxides were examined in lesser detail. The phases synthesized were screened by ion exchange methods to determine mobility of the mobility of the alkali ion within the niobium, tantalum or antimony oxide (fluoride) structural framework. Five structure types warranted further investigation; these structure types are (1) hexagonal tungsten bronze (HTB), (2) pyrochlore, (3) the hybrid HTB-pyrochlore hexagonal ordered phases, (4) body centered cubic antimonates and (5) 2K2O:3Nb2O5. Although all of these phases exhibit good ion exchange properties only the pyrochlore was prepared with Na(+) ions as an equilibrium phase and as a low porosity ceramic. Sb(+3) in the channel interferes with ionic conductivity in this case, although relatively good ionic conductivity was found for the metastable Na(+) ion exchanged analogs of RbTa2O5F and KTaWO6 pyrochlore phases.

  5. Alkali-aggregate reactivity of typical siliceious glass and carbonate rocks in alkali-activated fly ash based geopolymers

    NASA Astrophysics Data System (ADS)

    Lu, Duyou; Liu, Yongdao; Zheng, Yanzeng; Xu, Zhongzi; Shen, Xiaodong

    2013-08-01

    For exploring the behaviour of alkali-aggregate reactivity (AAR) in alkali-activated geopolymeric materials and assessing the procedures for testing AAR in geopolymers, the expansion behaviour of fly ash based geopolymer mortars with pure silica glass and typical carbonate rocks were studied respectively by curing at various conditions, i.e. 23°C and 38°C with relative humidity over 95%, immersed in 1M NaOH solution at 80°C. Results show that, at various curing conditions, neither harmful ASR nor harmful ACR was observed in geopolymers with the criteria specified for OPC system. However, with the change of curing conditions, the geopolymer binder and reactive aggregates may experience different reaction processes leading to quite different dimensional changes, especially with additional alkalis and elevated temperatures. It suggests that high temperature with additional alkali for accelerating AAR in traditional OPC system may not appropriate for assessing the alkali-aggregate reactivity behaviour in geopolymers designed for normal conditions. On the other hand, it is hopeful to control the dimensional change of geopolymer mortar or concrete by selecting the type of aggregates and the appropriate curing conditions, thus changing the harmful AAR in OPC into beneficial AAR in geopolymers and other alkali-activated cementitious systems.

  6. Investigation of luminescence and spectroscopic properties of Nd3+ions in cadmium alkali borate glasses

    NASA Astrophysics Data System (ADS)

    Mohan, Shaweta; Thind, Kulwant Singh

    2016-07-01

    Neodymium doped cadmium alkali borate glasses having composition 20CdOsbnd 20R2Osbnd 59.5H3BO3sbnd 0.5Nd2O3; (R = Li, Na and K) were prepared by conventional melt-quenching technique. The amorphous nature of the glasses was confirmed by X-ray diffraction studies. The physical properties such as density, refractive index, molar volume, rare earth ion concentration etc. were determined. Optical absorption and fluorescence spectra were recorded. The Judd-Ofelt theory was applied on the optical absorption spectra of the glasses to evaluate the three phenomenological intensity parameters Ω2, Ω4 and Ω6. These parameters were in turn used to predict the radiative properties such as the radiative transition probability (A), radiative lifetime (τR) and branching ratio (βR) for the fluorescent levels of Nd3+ ion in the present glass series. The lasing efficiency of the prepared glasses has been characterized by the spectroscopic quality factor (Ω4/Ω6), the value of which is in the range of 0.2-1.5, typical for Nd3+ in different laser hosts. The variation of Ω2 with the change in alkali oxide has been attributed to the changes in the asymmetry of the ligand field at the rare earth ion site. The shift of the hypersensitive bands, study of the oscillator strengths and the variation of the spectral profile of the transition 4I9/2 → 4F7/2 + 4S3/2 indicate a maximum covalency of Ndsbnd O bond for glass with potassium ions. From the fluorescence spectra, peak wavelength (λp), effective line widths (Δλeff) and stimulated emission cross-section (σp) have been obtained for the three transitions 4F3/2 → 4I9/2,4F3/2 → 4I11/2 and4F3/2 → 4I13/2 of Nd3+ ion. The relatively high values of σp obtained for Nd3+ in present glass system suggest that these materials can be considered as suitable candidates for laser applications. The glass with potassium ions shows the highest value of the stimulated emission cross-section.

  7. Tellurite glass as a waste form for mixed alkali-chloride waste streams: Candidate materials selection and initial testing

    NASA Astrophysics Data System (ADS)

    Riley, Brian J.; Rieck, Bennett T.; McCloy, John S.; Crum, Jarrod V.; Sundaram, S. K.; Vienna, John D.

    2012-05-01

    Tellurite glasses have historically been shown to host large concentrations of halides. They are here considered for the first time as a waste form for immobilizing chloride wastes, such as may be generated in the proposed molten alkali salt electrochemical separations step in nuclear fuel reprocessing. Key properties of several tellurite glasses are determined to assess acceptability as a chloride waste form. TeO2 glasses with other oxides (PbO, Al2O3 + B2O3, WO3, P2O5, or ZnO) were fabricated with and without 10 mass% of a simulated (non-radioactive) mixed alkali, alkaline-earth, and rare earth chloride waste. Measured chemical durability is compared for the glasses, as determined by the product consistency test (PCT), a common standardized chemical durability test often used to validate borosilicate glass waste forms. The glass with the most promise as a waste form is the TeO2-PbO system, as it offers good halide retention, a low sodium release (by PCT) comparable with high-level waste silicate glass waste forms, and a high storage density.

  8. Communication: Dimensionality of the ionic conduction pathways in glass and the mixed-alkali effect.

    PubMed

    Novy, Melissa; Avila-Paredes, Hugo; Kim, Sangtae; Sen, Sabyasachi

    2015-12-28

    A revised empirical relationship between the power law exponent of ac conductivity dispersion and the dimensionality of the ionic conduction pathway is established on the basis of electrical impedance spectroscopic (EIS) measurements on crystalline ionic conductors. These results imply that the "universal" ac conductivity dispersion observed in glassy solids is associated with ionic transport along fractal pathways. EIS measurements on single-alkali glasses indicate that the dimensionality of this pathway D is ∼2.5, while in mixed-alkali glasses, D is lower and goes through a minimum value of ∼2.2 when the concentrations of the two alkalis become equal. D and σ display similar variation with alkali composition, thus suggesting a topological origin of the mixed-alkali effect.

  9. Communication: Dimensionality of the ionic conduction pathways in glass and the mixed-alkali effect.

    PubMed

    Novy, Melissa; Avila-Paredes, Hugo; Kim, Sangtae; Sen, Sabyasachi

    2015-12-28

    A revised empirical relationship between the power law exponent of ac conductivity dispersion and the dimensionality of the ionic conduction pathway is established on the basis of electrical impedance spectroscopic (EIS) measurements on crystalline ionic conductors. These results imply that the "universal" ac conductivity dispersion observed in glassy solids is associated with ionic transport along fractal pathways. EIS measurements on single-alkali glasses indicate that the dimensionality of this pathway D is ∼2.5, while in mixed-alkali glasses, D is lower and goes through a minimum value of ∼2.2 when the concentrations of the two alkalis become equal. D and σ display similar variation with alkali composition, thus suggesting a topological origin of the mixed-alkali effect. PMID:26723583

  10. ``Cooperativity blockage'' in the mixed alkali effect as revealed by molecular-dynamics simulations of alkali metasilicate glass

    NASA Astrophysics Data System (ADS)

    Habasaki, Junko; Ngai, K. L.; Hiwatari, Yasuaki

    2004-07-01

    The relaxation dynamics of a complex interacting system can be drastically changed when mixing with another component having different dynamics. In this work, we elucidate the effect of the less mobile guest ions on the dynamics of the more mobile host ions in mixed alkali glasses by molecular-dynamics (MD) simulations. One MD simulation was carried out on lithium metasilicate glass with the guest ions created by freezing some randomly chosen lithium ions at their initial locations at 700 K. A remarkable slowing down of the dynamics of the majority mobile Li ions was observed both in the self-part of the density-density correlation function, Fs(k,t), and in the mean-squared displacements. On the other hand, there is no significant change in the structure. The motion of the Li ions in the unadulterated Li metasilicate glass is dynamically heterogeneous. In the present work, the fast and slow ions were divided into two groups. The number of fast ions, which shows faster dynamics (Lévy flight) facilitated by cooperative jumps, decreases considerably when small amount of Li ions are frozen. Consequently there is a large overall reduction of the mobility of the Li ions. The result is also in accordance with the experimental finding in mixed alkali silicate glasses that the most dramatic reduction of ionic conductivity occurs in the dilute foreign alkali limit. Similar suppression of the cooperative jumps is observed in the MD simulation data of mixed alkali system, LiKSiO3. Naturally, the effect found here is appropriately described as "cooperativity blockage." Slowing down of the motion of Li ions also was observed when a small number of oxygen atoms chosen at random were frozen. The effect is smaller than the case of freezing some the Li ions, but it is not negligible. The cooperativity blockage is also implemented by confining the Li metasilicate glass inside two parallel walls formed by freezing Li ions in the same metasilicate glass. Molecular-dynamics simulations

  11. Role of glass structure in defining the chemical dissolution behavior, bioactivity and antioxidant properties of zinc and strontium co-doped alkali-free phosphosilicate glasses.

    PubMed

    Kapoor, Saurabh; Goel, Ashutosh; Tilocca, Antonio; Dhuna, Vikram; Bhatia, Gaurav; Dhuna, Kshitija; Ferreira, José M F

    2014-07-01

    We investigated the structure-property relationships in a series of alkali-free phosphosilicate glass compositions co-doped with Zn(2+) and Sr(2+). The emphasis was laid on understanding the structural role of Sr(2+) and Zn(2+) co-doping on the chemical dissolution behavior of glasses and its impact on their in vitro bioactivity. The structure of glasses was studied using molecular dynamics simulations in combination with solid state nuclear magnetic resonance spectroscopy. The relevant structural properties are then linked to the observed degradation behavior, in vitro bioactivity, osteoblast proliferation and oxidative stress levels. The apatite-forming ability of glasses has been investigated by X-ray diffraction, infrared spectroscopy and scanning electron microscopy-energy-dispersive spectroscopy after immersion of glass powders/bulk in simulated body fluid (SBF) for time durations varying between 1h and 14 days, while their chemical degradation has been studied in Tris-HCl in accordance with ISO 10993-14. All the glasses exhibit hydroxyapatite formation on their surface within 1-3h of their immersion in SBF. The cellular responses were observed in vitro on bulk glass samples using human osteosarcoma MG63 cell line. The dose-dependent cytoprotective effect of glasses with respect to the concentration of zinc and strontium released from the glasses is also discussed. PMID:24709542

  12. Role of glass structure in defining the chemical dissolution behavior, bioactivity and antioxidant properties of zinc and strontium co-doped alkali-free phosphosilicate glasses.

    PubMed

    Kapoor, Saurabh; Goel, Ashutosh; Tilocca, Antonio; Dhuna, Vikram; Bhatia, Gaurav; Dhuna, Kshitija; Ferreira, José M F

    2014-07-01

    We investigated the structure-property relationships in a series of alkali-free phosphosilicate glass compositions co-doped with Zn(2+) and Sr(2+). The emphasis was laid on understanding the structural role of Sr(2+) and Zn(2+) co-doping on the chemical dissolution behavior of glasses and its impact on their in vitro bioactivity. The structure of glasses was studied using molecular dynamics simulations in combination with solid state nuclear magnetic resonance spectroscopy. The relevant structural properties are then linked to the observed degradation behavior, in vitro bioactivity, osteoblast proliferation and oxidative stress levels. The apatite-forming ability of glasses has been investigated by X-ray diffraction, infrared spectroscopy and scanning electron microscopy-energy-dispersive spectroscopy after immersion of glass powders/bulk in simulated body fluid (SBF) for time durations varying between 1h and 14 days, while their chemical degradation has been studied in Tris-HCl in accordance with ISO 10993-14. All the glasses exhibit hydroxyapatite formation on their surface within 1-3h of their immersion in SBF. The cellular responses were observed in vitro on bulk glass samples using human osteosarcoma MG63 cell line. The dose-dependent cytoprotective effect of glasses with respect to the concentration of zinc and strontium released from the glasses is also discussed.

  13. The influence of alkali and alkaline earths on the working range for bioactive glasses.

    PubMed

    Brink, M

    1997-07-01

    Viscosity-temperature dependence has been investigated for glasses in a system where bioactive compositions are found. A glass is called bioactive when living bone can bond to it. In this work, high-temperature microscopy was used to determine viscosity-temperature behaviour for 40 glasses in the system Na2O-K2O-MgO-CaO-B2O3-P2O5-SiO2. The silica content in the glasses was 39-70 wt% % All glasses containing < 54 mol % SiO2 devitrified during the viscosity measurements. Generally, glasses that devitrified contained more alkali but less alkaline earths than glasses with a large working range. A working range is the temperature interval at which forming of a glass can take place. This temperature interval can, for bioactive glasses, be enlarged by decreasing the amount of alkali, especially Na2O, in the glass and by increasing the amount of alkaline earths, especially MgO. Optionally, B2O3 and P2O5 can be added to the glass. An enlarged working range is a prerequisite for an expanded medical use of bioactive glasses as e.g., sintered and blown products, and fibers. PMID:9212395

  14. PLUTONIUM SOLUBILITY IN HIGH-LEVEL WASTE ALKALI BOROSILICATE GLASS

    SciTech Connect

    Marra, J.; Crawford, C.; Fox, K.; Bibler, N.

    2011-01-04

    The solubility of plutonium in a Sludge Batch 6 (SB6) reference glass and the effect of incorporation of Pu in the glass on specific glass properties were evaluated. A Pu loading of 1 wt % in glass was studied. Prior to actual plutonium glass testing, surrogate testing (using Hf as a surrogate for Pu) was conducted to evaluate the homogeneity of significant quantities of Hf (Pu) in the glass, determine the most appropriate methods to evaluate homogeneity for Pu glass testing, and to evaluate the impact of Hf loading in the glass on select glass properties. Surrogate testing was conducted using Hf to represent between 0 and 1 wt % Pu in glass on an equivalent molar basis. A Pu loading of 1 wt % in glass translated to {approx}18 kg Pu per Defense Waste Processing Facility (DWPF) canister, or about 10X the current allowed limit per the Waste Acceptance Product Specifications (2500 g/m{sup 3} of glass or about 1700 g/canister) and about 30X the current allowable concentration based on the fissile material concentration limit referenced in the Yucca Mountain Project License Application (897 g/m{sup 3}3 of glass or about 600 g Pu/canister). Based on historical process throughput data, this level was considered to represent a reasonable upper bound for Pu loading based on the ability to provide Pu containing feed to the DWPF. The task elements included evaluating the distribution of Pu in the glass (e.g. homogeneity), evaluating crystallization within the glass, evaluating select glass properties (with surrogates), and evaluating durability using the Product Consistency Test -- Method A (PCT-A). The behavior of Pu in the melter was evaluated using paper studies and corresponding analyses of DWPF melter pour samples.The results of the testing indicated that at 1 wt % Pu in the glass, the Pu was homogeneously distributed and did not result in any formation of plutonium-containing crystalline phases as long as the glass was prepared under 'well-mixed' conditions. The

  15. Cation-network interactions in binary alkali metal borate glasses. A far-infrared study

    SciTech Connect

    Kamitsos, E.I.; Karakassides, M.A.; Chryssikos, G.D.

    1987-10-22

    The far-infrared spectra of compositions probing the glass-forming regions of all five binary alkali metal borate systems chi M/sub 2/O x (1 - chi)B/sub 2/O/sub 3/ (0 < chi less than or equal to 0.40, M = Na; and 0 < chi less than or equal to 0.35, M = K, Rb, Cs) have been measured and analyzed to systematically study the alkali metal cation-network interactions and their compositional dependence. Band deconvolution of the measured spectra showed the presence of two distinct distributions of alkali metal cation sites in Li, Na, and K glasses. Similar results have been obtained for rubidium and cesium borate glasses of compositions chi > 0.25. One distribution of cation sites has been observed for the lower alkali metal content Rb and Cs glasses. The fractions of cations in the two different network sites have also been evaluated. The squares of the frequencies of the cation-motion bands were found to vary linearly with composition, and exhibit kinks at chi similarly ordered 20, for all but the Cs glasses. This behavior was explained on the basis of the network structural changes known to occur at this composition.

  16. Modifier interaction and mixed-alkali effect in bond constraint theory applied to ternary alkali metaphosphate glasses

    NASA Astrophysics Data System (ADS)

    Poletto Rodrigues, Bruno; Deubener, Joachim; Wondraczek, Lothar

    2016-05-01

    Introducing an interaction parameter γ, we implement modifier interaction and the mixed-alkali effect into bond constraint theory, and apply this extension for simplistic property prediction on ternary phosphate glasses. The severity of the mixed alkali effect results from the interplay of two simultaneous contributions: Bond constraints on the modifier species soften or stiffen with decreasing or increasing γ, respectively. When the modifier size is not too dissimilar the decrease in γ reflects that the alkali ions can easily migrate between different sites, forcing the network to continuously re-accommodate for any subsequent distortions. With increasing size difference, migration becomes increasingly difficult without considerable network deformation. This holds even for smaller ions, where the sluggish dynamics of the larger constituent result in blocking of the fast ion movement, leading to the subsequent increase in γ. Beyond a certain size difference in the modifier pair, a value of γ exceeding unity may indicate the presence of steric hindrance due to the large surrounding modifiers impeding the phosphate network to re-accommodate deformation.

  17. Thorium and cerium chemical behaviour in ion-irradiated alkali-borosilicate glasses

    NASA Astrophysics Data System (ADS)

    Trocellier, P.; Haddi, A.; Poissonnet, S.; Bonnaillie, P.; Serruys, Y.

    2006-08-01

    Simple alkali-borosilicate glasses containing SiO2-B2O3-Li2O-Na2O and only one or two transition metal oxides (CeO2 and/or ThO2) have been synthesized by melting the stoichiometric powder mixture at 1100 °C in a platinum crucible. Thorium and cerium were used as chemical analogs of minor actinides (Pu and Am). Th is a purely tetravalent element, although Ce can be tetravalent or trivalent. Glass samples were submitted to aqueous leaching tests at 90 °C in deionised water for one week, with or without having previously been ion-irradiated. The irradiation experiments were conducted in the nuclear energy loss regime. Kr ions supplied by a 1 MV electrostatic Van de Graaff accelerator, were used to produce displacement cascades in the first hundreds of nanometers beneath the sample's surfaces. The leached samples were then characterized by scanning electron microscopy (SEM), electron microprobe analysis (EMA) and ion beam analytical (IBA) methods: Rutherford backscattering spectrometry and elastic recoil detection analysis (RBS and ERDA), proton-induced X-ray or gamma ray emission (PIXE and PIGE). Th and Ce are shown to be enriched in the near surface region of leached glasses due to the extremely low solubility of their hydroxides. The effect of surface damage on the chemical behaviour of Th and Ce is then detailed. The possibility for Ce(IV) to be reduced as Ce(III) during ion-irradiation just before leaching and its consequences on the relative solubility of corresponding chemical species is discussed in terms of hydroxide solubility thermodynamical equilibria.

  18. Classification of oxide glasses: A polarizability approach

    SciTech Connect

    Dimitrov, Vesselin; Komatsu, Takayuki . E-mail: komatsu@chem.nagaokaut.ac.jp

    2005-03-15

    A classification of binary oxide glasses has been proposed taking into account the values obtained on their refractive index-based oxide ion polarizability {alpha}{sub O2-}(n{sub 0}), optical basicity {lambda}(n{sub 0}), metallization criterion M(n{sub 0}), interaction parameter A(n{sub 0}), and ion's effective charges as well as O1s and metal binding energies determined by XPS. Four groups of oxide glasses have been established: glasses formed by two glass-forming acidic oxides; glasses formed by glass-forming acidic oxide and modifier's basic oxide; glasses formed by glass-forming acidic and conditional glass-forming basic oxide; glasses formed by two basic oxides. The role of electronic ion polarizability in chemical bonding of oxide glasses has been also estimated. Good agreement has been found with the previous results concerning classification of simple oxides. The results obtained probably provide good basis for prediction of type of bonding in oxide glasses on the basis of refractive index as well as for prediction of new nonlinear optical materials.

  19. Structure, biodegradation behavior and cytotoxicity of alkali-containing alkaline-earth phosphosilicate glasses.

    PubMed

    Kansal, Ishu; Reddy, AlluAmarnath; Muñoz, Francisco; Choi, Seong-Jun; Kim, Hae-Won; Tulyaganov, Dilshat U; Ferreira, José M F

    2014-11-01

    We report on the effect of sodium on the structure, chemical degradation and bioactivity of glasses in the CaO-MgO-SiO2-P2O5-CaF2 system. The (29)Si and (31)P magic angle spinning-nuclear magnetic resonance spectroscopy of melt-quenched glasses with varying Na2O/MgO ratios exhibit a silicate glass network with the dominance of Q(2)(Si) units and phosphorus mainly forming orthophosphate species. Sodium incorporation in the glasses did not induce a significant structural change in the silicate network, while it did influence the phosphate environment due to its lower ionic field strength in comparison with that of magnesium. The apatite forming ability of glasses has been investigated by immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1h and 7 days while their chemical degradation has been studied in Tris-HCl in accordance with ISO-10993-14. Increasing Na(+)/Mg(2+) ratio caused a decrease in the chemical durability of glasses and in the apatite forming ability especially during initial steps of interaction between glass and SBF solution. The cellular responses were observed in vitro on bulk glass samples using mouse-derived pre-osteoblastic MC3T3-E1 cell line. The preliminary study suggested that the increasing alkali-concentration in glasses led to cytotoxicity in the cell culture medium.

  20. Structure, biodegradation behavior and cytotoxicity of alkali-containing alkaline-earth phosphosilicate glasses.

    PubMed

    Kansal, Ishu; Reddy, AlluAmarnath; Muñoz, Francisco; Choi, Seong-Jun; Kim, Hae-Won; Tulyaganov, Dilshat U; Ferreira, José M F

    2014-11-01

    We report on the effect of sodium on the structure, chemical degradation and bioactivity of glasses in the CaO-MgO-SiO2-P2O5-CaF2 system. The (29)Si and (31)P magic angle spinning-nuclear magnetic resonance spectroscopy of melt-quenched glasses with varying Na2O/MgO ratios exhibit a silicate glass network with the dominance of Q(2)(Si) units and phosphorus mainly forming orthophosphate species. Sodium incorporation in the glasses did not induce a significant structural change in the silicate network, while it did influence the phosphate environment due to its lower ionic field strength in comparison with that of magnesium. The apatite forming ability of glasses has been investigated by immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1h and 7 days while their chemical degradation has been studied in Tris-HCl in accordance with ISO-10993-14. Increasing Na(+)/Mg(2+) ratio caused a decrease in the chemical durability of glasses and in the apatite forming ability especially during initial steps of interaction between glass and SBF solution. The cellular responses were observed in vitro on bulk glass samples using mouse-derived pre-osteoblastic MC3T3-E1 cell line. The preliminary study suggested that the increasing alkali-concentration in glasses led to cytotoxicity in the cell culture medium. PMID:25280692

  1. Alkali-silica reactivity of expanded glass granules in structure of lightweight concrete

    NASA Astrophysics Data System (ADS)

    Bumanis, G.; Bajare, D.; Locs, J.; Korjakins, A.

    2013-12-01

    Main component in the lightweight concrete, which provides its properties, is aggregate. A lot of investigations on alkali silica reaction (ASR) between cement and lightweight aggregates have been done with their results published in the academic literature. Whereas expanded glass granules, which is relatively new product in the market of building materials, has not been a frequent research object. Therefore lightweight granules made from waste glass and eight types of cement with different chemical and mineralogical composition were examined in this research. Expanded glass granules used in this research is commercially available material produced by Penostek. Lightweight concrete mixtures were prepared by using commercial chemical additives to improve workability of concrete. The aim of the study is to identify effect of cement composition to the ASR reaction which occurs between expanded glass granules and binder. Expanded glass granules mechanical and physical properties were determined. In addition, properties of fresh and hardened concrete were determined. The ASR test was processed according to RILEM AAR-2 testing recommendation. Tests with scanning electron microscope and microstructural investigations were performed for expanded glass granules and hardened concrete specimens before and after exposing them in alkali solution.

  2. Raman Analysis of Perrhenate and Pertechnetate in Alkali Salts and Borosilicate Glasses

    SciTech Connect

    Gassman, Paul L.; McCloy, John S.; Soderquist, Chuck Z.; Schweiger, Michael J.

    2014-01-03

    Sodium borosilicate glasses containing various concentrations of rhenium or technetium were fabricated, and their vibrational spectra studied using a Raman microscope. Spectra were interpreted with reference to new high resolution measurements of alkali pertechnetates and perrhenates NaReO4, KReO4, NaTcO4, and KTcO4. At low concentrations of ReO4- or TcO4-, glass spectra show weak peaks superimposed on a dominant spectrum of glass characteristic of silicate and borate network vibrations. At high concentrations, sharp peaks characteristic of crystal field splitting and C4h symmetry dominate the spectra of glasses, indicating alkali nearby tetrahedral Re or Tc. Often peaks indicative of both the K and Na pertechnetates/ perrhenates are evident in the Raman spectrum, with the latter being favored at high additions of the source chemical, since Na is more prevalent in the glass and ion exchange takes place. These results have significance to immobilization of nuclear waste containing radioactive 99Tc in glass for ultimate disposal.

  3. Alkali-free bioactive glasses for bone tissue engineering: a preliminary investigation.

    PubMed

    Goel, Ashutosh; Kapoor, Saurabh; Rajagopal, Raghu Raman; Pascual, Maria J; Kim, Hae-Won; Ferreira, José M F

    2012-01-01

    An alkali-free series of bioactive glasses has been designed and developed in the glass system CaO-MgO-SiO(2)-P(2)O(5)-CaF(2) along the diopside (CaMgSi(2)O(6))-fluorapatite (Ca(5)(PO(4))(3)F)-tricalcium phosphate (3CaO·P(2)O(5)) join. The silicate network in all the investigated glasses is predominantly coordinated in Q(2) (Si) units, while phosphorus tends to remain in an orthophosphate (Q(0)) environment. The in vitro bioactivity analysis of glasses has been made by immersion of glass powders in simulated body fluid (SBF) while chemical degradation has been studied in Tris-HCl in accordance with ISO-10993-14. Some of the investigated glasses exhibit hydroxyapatite formation on their surface within 1-12 h of their immersion in SBF solution. The sintering and crystallization kinetics of glasses has been investigated by differential thermal analysis and hot-stage microscopy, respectively while the crystalline phase evolution in resultant glass-ceramics has been studied in the temperature range of 800-900°C using powder X-ray diffraction and scanning electron microscopy. The alkaline phosphatase activity and osteogenic differentiation for glasses have been studied in vitro on sintered glass powder compacts using rat bone marrow mesenchymal stem cells. The as-designed glasses are ideal candidates for their potential applications in bone tissue engineering in the form of bioactive glasses as well as glass/glass-ceramic scaffolds.

  4. Mixed alkali effect in glasses containing MnO{sub 2}

    SciTech Connect

    Reddy, M. Sudhakara; Rajiv, Asha; Veeranna Gowda, V. C.; Chakradhar, R. P. S.; Reddy, C. Narayana

    2013-02-05

    Glass systems of the composition xLi{sub 2}O-(25-x)K{sub 2}O-70(0.4ZnO+0.6P{sub 2}O{sub 5})+5MnO{sub 2} (x = 4,8,12,16 and 20 mol %) have been prepared by melt quenching technique. The thermal and mechanical properties of the glasses have been evaluated as a function of mixed alkali content. Glass transition temperature and Vickers's hardness of the glasses show a pronounced deviation from linearity at 12 mol%Li{sub 2}O. Theoretically estimated elastic moduli of the glasses show small positive deviations from linearity. MAE in these properties has been attributed to the localized changes in the glass network. The absorption spectra of Mn{sup 2+} ions in these glasses showed strong broad absorption band at 514 nm corresponding to the transition {sup 6}A{sub 1g}(S){yields}{sup 4}T{sub 1g}(G), characteristic of manganese ions in octahedral symmetry. The fundamental absorption edge in UV region is used to study the optical transitions and electronic band structure. From UV absorption edge, optical band gap energies have been evaluated. Band gap energies of the glasses have exhibited MAE and shows minimum value for 12 mol%Li{sub 2}O glass.

  5. Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials

    DOE PAGES

    Boyle, Timothy J.; Neville, Michael L.; Sears, Jeremiah Matthew; Cramer, Roger

    2016-03-15

    In this study, a series of alkali metal yttrium neo-pentoxide ([AY(ONep)4]) compounds were developed as precursors to alkali yttrium oxide (AYO2) nanomaterials. The reaction of yttrium amide ([Y(NR2)3] where R=Si(CH3)3) with four equivalents of H-ONep followed by addition of [A(NR2)] (A=Li, Na, K) or Ao (Ao=Rb, Cs) led to the formation of a complex series of AnY(ONep)3+n species, crystallographically identified as [Y2Li3(μ3-ONep)(μ3-HONep)(μ-ONep)5(ONep)3(HONep)2] (1), [YNa2(μ3-ONep)4(ONep)]2 (2), {[Y2K3(μ3-ONep)3(μ-ONep)4(ONep)2(ηξ-tol)2][Y4K2(μ4-O)(μ3-ONep)8(ONep)4]•ηx-tol]} (3), [Y4K2(μ4-O)(μ3-ONep)8(ONep)4] (3a), [Y2Rb3(μ4-ONep)3(μ-ONep)6] (4), and [Y2Cs4(μ6-O)(μ3-ONep)6(μ3-HONep)2(ONep)2(ηx-tol)4]•tol (5). Compounds 1–5 were investigated as single source precursors to AYOx nanomaterials following solvothermal routes (pyridine, 185 °C for 24h). The final products after thermal processing weremore » found by powder X-ray diffraction experiments to be Y2O3 with variable sized particles based on transmission electron diffraction. Energy dispersive X-ray spectroscopy studies indicated that the heavier alkali metal species were present in the isolated nanomaterials.« less

  6. Alkali-free bioactive glasses for bone tissue engineering: A preliminary investigation

    SciTech Connect

    Goel, Ashutosh; Kapoor, Saurabh; Rajagopal, Raghu R.; Pascual, Maria J.; Kim, Hae-Won; Ferreira, Jose M.

    2011-08-25

    An alkali-free series of bioactive glasses has been designed and developed in the glass system CaO-MgO-SiO2-P2O5-CaF2 along diopside (CaMgSi2O6) – fluorapatite [Ca5(PO4)3F] – tricalcium phosphate (3CaO•P2O5) join. The silicate network in all the investigated glasses is predominantly coordinated in Q2 (Si) units while phosphorus tends to remain in orthophosphate (Q0) environment. The in vitro bioactivity analysis of glasses has been made by immersion of glass powders in simulated body fluid (SBF) while chemical degradation has been studied in Tris-HCl in accordance with ISO-10993-14. Some of the investigated glasses exhibit hydroxyapatite (HA) formation on their surface with in 1-12 h of their immersion in SBF solution. The sintering and crystallization kinetics of glasses has been investigated by differential thermal analysis (DTA) and hot-stage microscopy (HSM), respectively while the crystalline phase evolution in resultant glass-ceramics (GCs) has been studied in the temperature range of 800-900 oC using powder X-ray diffraction (XRD) and scanning electron microscope (SEM). The cell growth and osteogenic differentiation for glasses has been studied in vitro on sintered glass powder compacts using rat bone marrow mesenchymal stem cells. The as designed glasses are ideal candidates for their potential applications in bone tissue engineering in the form of bioactive glasses as well as glass/GC scaffolds.

  7. Coupled ion redistribution and electronic breakdown in low-alkali boroaluminosilicate glass

    SciTech Connect

    Choi, Doo Hyun; Randall, Clive Furman, Eugene Lanagan, Michael

    2015-08-28

    Dielectrics with high electrostatic energy storage must have exceptionally high dielectric breakdown strength at elevated temperatures. Another important consideration in designing a high performance dielectric is understanding the thickness and temperature dependence of breakdown strengths. Here, we develop a numerical model which assumes a coupled ionic redistribution and electronic breakdown is applied to predict the breakdown strength of low-alkali glass. The ionic charge transport of three likely charge carriers (Na{sup +}, H{sup +}/H{sub 3}O{sup +}, Ba{sup 2+}) was used to calculate the ionic depletion width in low-alkali boroaluminosilicate which can further be used for the breakdown modeling. This model predicts the breakdown strengths in the 10{sup 8}–10{sup 9 }V/m range and also accounts for the experimentally observed two distinct thickness dependent regions for breakdown. Moreover, the model successfully predicts the temperature dependent breakdown strength for low-alkali glass from room temperature up to 150 °C. This model showed that breakdown strengths were governed by minority charge carriers in the form of ionic transport (mostly sodium) in these glasses.

  8. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated sulfonated diphenyl oxide... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and...

  9. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkylated sulfonated diphenyl oxide... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and...

  10. Cation mass dependence of the nearly constant dielectric loss in alkali triborate glasses.

    PubMed

    Rivera, A; León, C; Varsamis, C P E; Chryssikos, G D; Ngai, K L; Roland, C M; Buckley, L J

    2002-03-25

    Electrical ac conductivity measurements on alkali triborate glasses ( M2O x 3B2O3, M = Li, Na, K, and Rb) were performed at temperatures down to 8 K and frequencies up to 1 GHz. All samples show a nearly constant dielectric loss (NCL), at the limit of high frequencies and/or low temperatures. The magnitude of the NCL is found to decrease as m(-1/3) with increasing alkali ion mass m. This quantitative result for the NCL, closely related to the mean-square displacement of ions, indicates that the origin of the NCL might be related to vibrational relaxation of the ions in the anharmonic potentials that cage them, and the cage is decaying very slowly with time. PMID:11909481

  11. Quantification of the boron speciation in alkali borosilicate glasses by electron energy loss spectroscopy

    PubMed Central

    Cheng, Shaodong; Yang, Guang; Zhao, Yanqi; Peng, MingYing; Skibsted, Jørgen; Yue, Yuanzheng

    2015-01-01

    Transmission electron microscopy and related analytical techniques have been widely used to study the microstructure of different materials. However, few research works have been performed in the field of glasses, possibly due to the electron-beam irradiation damage. In this paper, we have developed a method based on electron energy loss spectroscopy (EELS) data acquisition and analyses, which enables determination of the boron speciation in a series of ternary alkali borosilicate glasses with constant molar ratios. A script for the fast acquisition of EELS has been designed, from which the fraction of BO4 tetrahedra can be obtained by fitting the experimental data with linear combinations of the reference spectra. The BO4 fractions (N4) obtained by EELS are consistent with those from 11B MAS NMR spectra, suggesting that EELS can be an alternative and convenient way to determine the N4 fraction in glasses. In addition, the boron speciation of a CeO2 doped potassium borosilicate glass has been analyzed by using the time-resolved EELS spectra. The results clearly demonstrate that the BO4 to BO3 transformation induced by the electron beam irradiation can be efficiently suppressed by doping CeO2 to the borosilicate glasses. PMID:26643370

  12. Mechanical stiffening and thermal softening of superionic alkali metal oxides

    NASA Astrophysics Data System (ADS)

    Chaudhary, S.; Shriya, S.; Kumar, J.; Ameri, M.; Varshney, Dinesh

    2015-06-01

    The mechanical (pressure) and thermal (temperature) dependent nature of superionic cubic M2O (M = Li, Na, K, and Rb) alkali metal oxides is studied. The model Hamiltonian in ab initio theory include long-range Coulomb, charge transfer, covalency, van der Waals interaction and the short-range repulsive interaction upto second-neighbor ions. The second order elastic constants as functions of pressure discern increasing trend, while to that they decreases with enhanced temperature. From the knowledge of elastic constants, Pugh ratio, Poisson's ratio, heat capacity and thermal expansion coefficient are calculated. It is noticed that cubic M2O is brittle on applied pressure and temperature and mechanically stiffened as a consequence of bond compression and bond strengthening and thermally softened due to bond expansion and bond weakening due to lattice vibrations.

  13. A study of physical and optical absorption spectra of VO2+ ions in potassium and sodium oxide borate glasses

    NASA Astrophysics Data System (ADS)

    Srinivas, G.; Ramesh, B.; Kumar, J. Siva; Shareefuddin, Md.; Chary, M. N.; Sayanna, R.

    2016-05-01

    Spectroscopic and physical properties of V2O5 doped mixed alkali borate glasses are investigated. Borate glasses containing fixed concentrations of alkaline earth oxides (MgO and BaO) and alkali oxides (K2O and Na2O) were changes and are prepared by melt quenching technique. The values of ri, rp, Rm, αm molar volume and Λth increase and oxygen packing density, density and dopant ion concentration decrease with increasing of K2O content. As a result there shall be an increase in the disorder of the glass network. The optical band gap energies, Urbach energy, boron-boron separation,refractive index, dielectric constant, electronic polarizability and reflection loss values are varies nonlinearly with the K2O content which manifests the mixed alkali effect.

  14. Evaluation of alkali concentration in conditions relevant to oxygen/natural gas glass furnaces by laser-induced breakdown spectroscopy.

    SciTech Connect

    Walsh, Peter M.; Molina, Alejandro; Shaddix, Christopher R.; Blevins, Linda Gail; Sickafoose, Shane M.

    2005-01-01

    A number of industrial combustion systems are adopting oxygen-enhanced firing to improve heat transfer characteristics and reduce emissions. The exhaust gas from these systems is dominated by H2O and CO2 and therefore has substantially different gas properties from traditional combustion exhaust. In the past, laser-induced breakdown spectroscopy (LIBS) has been successfully used for the evaluation of alkali aerosol concentrations in air-based combustion systems. This paper presents results of LIBS measurements of alkali concentrations in a laboratory calibration setup and in an oxygen/natural gas container glass furnace. It shows how both gas conditions (composition and temperature) and the molecular form of the alkali species affect the LIBS signals. The paper proposes strategies for mitigating these effects in future applications of LIBS in oxygen-enhanced combustion systems.

  15. Process for preparing higher oxides of the alkali and alkaline earth metals

    NASA Technical Reports Server (NTRS)

    Sadhukhan, P.; Bell, A. (Inventor)

    1978-01-01

    High purity inorganic higher oxides of the alkali and alkaline earth metals are prepared by subjecting the hydroxide of the alkali and alkaline earth metal to a radio frequency discharge sustained in oxygen. The process is particulary adaptable to the production of high purity potassium superoxide by subjecting potassium hydroxide to glow discharge sustained in oxygen under the pressure of about 0.75 to 1.00 torr.

  16. Oxide glasses for mid-infrared lasers

    NASA Astrophysics Data System (ADS)

    Richards, Billy D. O.; Jha, Animesh; Jose, Gin; Jiang, Xin

    2011-06-01

    We present an overview of rare-earth doped heavy metal oxide and oxy-fluoride glasses which show promise as host materials for lasers operating in the 2-5 μm spectral region for medical, military and sensing applications. By engineering glass composition and purity, tellurite and germanate glasses can support transmission up to and beyond 5 μm and can have favourable thermal, mechanical and environmental stability compared to fluoride glasses. We discuss techniques for glass purification and water removal for enhanced infrared transmission. By comparing the material properties of the glass, and spectroscopic performance of selected rare-earth dopant ions we can identify promising compositions for fibre and bulk lasers in the mid-infrared. Tellurite glass has recently been demonstrated to be a suitable host material for efficient and compact lasers in the {2 μm spectral region in fibre and bulk form and the next challenge is to extend the operating range further into the infrared region where silica fibre is not sufficiently transparent, and provide an alternative to fluoride glass and fibre.

  17. Alkali aluminosilicate melts and glasses: structuring at the middle range order of amorphous matter

    NASA Astrophysics Data System (ADS)

    Le Losq, C.; neuville, D. R.

    2012-12-01

    Rheological properties of silicate melts govern both magma ascension from the mantle to the surface of the earth and volcanological eruptions styles and behaviours. It is well known that several parameters impact strongly these properties, such as for instance the temperature, pressure, chemical composition and volatiles concentration, finally influencing eruptive behaviour of volcanoes. In this work, we will focus on the Na2O-K2O-Al2O3-SiO2 system, which is of a prime importance because it deals with a non-negligible part of natural melts, like for instance the Vesuvius (Italy) or Erebus (Antartica) magmas. In an oncoming paper in Chemical Geology (Le Losq and Neuville, 2012), we have communicated results of the study of mixing Na-K in tectosilicate melts containing a high concentration of silica (≥75mol%). In the present communication, we will enlarge this first point of view to tectosilicate melts presenting a lower silica concentration. We will first present our viscosity data, and then the Adam and Gibbs theory that allows theoretically modelling Na-K mixing in aluminosilicate melts by using the so-called "mixed alkali effect". On the basis of the rheological results, the Na-K mixing cannot be explained with the ideal "mixed alkali effect", which involves random exchange of Na-K cationic pairs. To go further and as rheological properties are directly linked with structural properties, we will present our first results obtained by Raman and NMR spectroscopy. These last ones provide important structural pieces of information on the polymerization state of glasses and melts, and also on the environment of tetrahedrally coordinated cations. Rheological and structural results all highlight that Na and K are not randomly distributed in aluminosilicate glasses and melts networks. Na melts present a network with some channels and a non-random distribution of Al and Si. K networks are different. They also present a non-random distribution of Al and Si, but in two sub

  18. Heat conductivity of LiF-NaF-Al(PO{sub 3}){sub 3} mixed-alkali glasses

    SciTech Connect

    Il`in, A.A.; Pronkin, A.A.

    1995-03-01

    Described is the heat conductivity of LiF-NaF-Al(PO{sub 3}){sub 3} mixed-alkali phosphate glasses. The percentage of NaF was varied to measure the density, mean sound velocity, Debye temperature, thermal oscillation frequency, and heat conductivity coefficient at different molar fractions. Correlation between the heat conductivity and the Debye temperature show the same regularity of variation in these parameters as for most crystalline substances.

  19. Alkali Silicate Glass Coatings for Mitigating the Risks of Tin Whiskers

    NASA Astrophysics Data System (ADS)

    Hillman, Dave; Wilcoxon, Ross; Lower, Nate; Grossman, Dan

    2015-12-01

    Alkali silicate glass (ASG) coatings were investigated as a possible method for inhibiting tin whisker initiation and growth. The aqueous-based ASG formulations used in this study were deposited with equipment and conditions that are typical of those used to apply conventional conformal coatings. Processes for controlling ASG coating properties were developed, and a number of ASG-based coating combinations were applied to test components with pure tin surfaces. Coatings were applied both in a laboratory environment at Rockwell Collins and in a manufacturing environment at Plasma Ruggedized Solutions. Testing in elevated humidity/temperature environments and subsequent inspection of the test articles identified coating combinations that inhibited tin whisker growth as well as other material combinations that actually accelerated tin whisker growth. None of the coatings evaluated in this study, including conventional acrylic and Parylene conformal coatings, completely prevented the formation of tin whiskers. Two of the coatings were particularly effective at reducing the risks of whisker growth, albeit through different mechanisms. Parylene conformal coating almost, but not completely, eliminated whisker formation, and only a few tin whiskers were found on these surfaces during the study. A composite of ASG and alumina nanoparticles inhibited whisker formation to a lesser degree than Parylene, but did disrupt whisker growth mechanisms so as to inhibit the formation of long, and more dangerous, tin whiskers. Additional testing also demonstrated that the conformal coatings had relatively little effect on the dielectric loss of a stripline test structure operating at frequencies over 30 GHz.

  20. Removal of oxides from alkali metal melts by reductive titration to electrical resistance-change end points

    DOEpatents

    Tsang, Floris Y.

    1980-01-01

    Alkali metal oxides dissolved in alkali metal melts are reduced with soluble metals which are converted to insoluble oxides. The end points of the reduction is detected as an increase in electrical resistance across an alkali metal ion-conductive membrane interposed between the oxide-containing melt and a material capable of accepting the alkali metal ions from the membrane when a difference in electrical potential, of the appropriate polarity, is established across it. The resistance increase results from blocking of the membrane face by ions of the excess reductant metal, to which the membrane is essentially non-conductive.

  1. Solid oxide fuel cell having a glass composite seal

    SciTech Connect

    De Rose, Anthony J.; Mukerjee, Subhasish; Haltiner, Jr., Karl Jacob

    2013-04-16

    A solid oxide fuel cell stack having a plurality of cassettes and a glass composite seal disposed between the sealing surfaces of adjacent cassettes, thereby joining the cassettes and providing a hermetic seal therebetween. The glass composite seal includes an alkaline earth aluminosilicate (AEAS) glass disposed about a viscous glass such that the AEAS glass retains the viscous glass in a predetermined position between the first and second sealing surfaces. The AEAS glass provides geometric stability to the glass composite seal to maintain the proper distance between the adjacent cassettes while the viscous glass provides for a compliant and self-healing seal. The glass composite seal may include fibers, powders, and/or beads of zirconium oxide, aluminum oxide, yttria-stabilized zirconia (YSZ), or mixtures thereof, to enhance the desirable properties of the glass composite seal.

  2. Liquidus temperature and chemical durability of selected glasses to immobilize rare earth oxides waste

    NASA Astrophysics Data System (ADS)

    Mohd Fadzil, Syazwani; Hrma, Pavel; Schweiger, Michael J.; Riley, Brian J.

    2015-10-01

    Pyroprocessing is are processing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl-KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the glass matrix at high loadings. Crystallization that occurs in waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (TL): the International Simple Glass designed by the International Working Group, sodium borosilicate glass developed by Korea Hydro and Nuclear Power, and the lanthanide aluminoborosilicate (LABS) glass established in the United States. The LABS glass allows the highest waste loadings (over 50 mass% RE2O3) while possessing an acceptable chemical durability.

  3. High thermal neutron flux effects on structural and macroscopic properties of alkali-borosilicate glasses used as neutron guide substrate

    NASA Astrophysics Data System (ADS)

    Boffy, R.; Peuget, S.; Schweins, R.; Beaucour, J.; Bermejo, F. J.

    2016-05-01

    The behaviour of four alkali-borosilicate glasses under homogeneous thermal neutron irradiation has been studied. These materials are used for the manufacturing of neutron guides which are installed in most facilities as devices to transport neutrons from intense sources such as nuclear reactors or spallation sources up to scientific instruments. Several experimental techniques such as Raman, NMR, SANS and STEM have been employed in order to understand the rather different macroscopic behaviour under irradiation of materials that belong to a same glass family. The results have shown that the remarkable glass shrinking observed for neutron doses below 0.5 ·1018 n/cm2 critically depends upon the presence of domains where silicate and borate network do not mix.

  4. The mixed glass former effect in 0.35sodium oxide + 0.65[(x)boron trioxide + (1-x)phosphorus pentoxide] glasses

    NASA Astrophysics Data System (ADS)

    Christensen, Randilynn Beth

    Energy storage is a growing concern in an ever increasingly battery driven society. Development of safer, smaller, and longer lasting batteries is in demand. Ion conducting glasses are an important type of solid electrolyte that could be used to answer this need. Unfortunately, many known ion conducting glasses, such as binary lithium oxide glasses with conductivities in the 10-7--10-8 S/cm range, are not conductive enough for practical use. In order for ion conducting glasses to be used as a commercial solid electrolyte, a method of increasing the glasses' ionic conductivity must be found. While alkali mixed glass former glasses, such as Bi2O3+B2O3+LiO2 and Li2S+SiS2+GeS2, have shown increases in the alkali ion conductivity up to two orders of magnitude, the cause of this increase is unclear. This phenomena has become known as the Mixed Glass Former Effect (MGFE) and is defined by a non-linear, non-additive change in ionic conductivity. Although the MGFE has been observed in the literature, it has not been observed in all mixed glass former (MGF) glasses and has also been seen as a negative or positive effect. In this talk, I will review our comprehensive study of the physical properties, structure, and the effect of composition on MGF sodium borophosphate glasses. It is our hypothesis that changes in the short range order structures, caused by the mixing of the boron and phosphate networks, are responsible for the MGFE. I will show a strong correlation between physical properties and structural changes with changing glass former composition.

  5. Chemical durability of alkali-borosilicate glasses studied by analytical SEM, IBA, isotopic-tracing and SIMS

    NASA Astrophysics Data System (ADS)

    Trocellier, P.; Djanarthany, S.; Chêne, J.; Haddi, A.; Brass, A. M.; Poissonnet, S.; Farges, F.

    2005-10-01

    Simple and complex alkali-borosilicate glasses were submitted to aqueous corrosion at room temperature, 60 and 90 °C in solutions with pH ranging between 0 and 12. Analytical scanning electron microscopy (SEM), ion beam analysis (IBA) techniques, isotopic tracing and secondary ion mass-depth profiling (SIMS) have been used to investigate the variations of the surface composition of glass. In acidic medium, the glass surface is generally covered by a thick hydrated silica layer, mobile elements like Li, Na and B and transition elements (Fe, Zr, Mo, etc.) are strongly depleted. Near pH 7, relative enrichments of aluminium, iron and rare earths are shown together with strong Li, Na and B depletions. In basic medium, the glass surface exhibits relative enrichments of the major part of transition metals (from Cr to U) whereas mobile elements seem to be kept close to their nominal concentration level at the glass surface and Si is severely impoverished. Hydrogen incorporated at the glass surface after leaching is much more immobile in neutral and basic media than in acid medium.

  6. Liquidus temperature and chemical durability of selected glasses to immobilize rare earth oxides waste

    SciTech Connect

    Mohd Fadzil, Syazwani Binti; Hrma, Pavel R.; Schweiger, Michael J.; Riley, Brian J.

    2015-06-30

    Pyroprocessing is a reprocessing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl-KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the matrix at high loadings. Crystallization that occurs in waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (TL): the International Simple Glass designed by the International Working Group, sodium borosilicate glass developed by Korea Hydro and Nuclear Power, and the lanthanide aluminoborosilicate (LABS) glass established in the United States. The LABS glass allows the highest waste loadings (over 50 mass% RE2O3) while possessing an acceptable chemical durability.

  7. Cation effects in the oxidative coupling of methane on silica-supported binary alkali and alkaline earths

    SciTech Connect

    Voyatzis, R.; Moffat, J.B. )

    1993-07-01

    The oxidative coupling of methane has been investigated with a series of silica-supported binary oxide catalysts containing alkali or alkaline earths or combinations of the former and latter. The conversion of methane and the stability of the silica-supported binary alkali metal oxides were found to increase with decreasing cation mobility, while the selectivities and conversions observed with the binary alkaline earths increase with cation size. The selectivities and conversions of binary alkali/alkaline earths appear to depend upon the size of the alkali and alkaline earth cations, respectively. With small quantities of TCM (CCl[sub 4]) added continuously to the feedstream, catalysts containing small alkali and large alkaline earth cations produced the largest selectivities and conversions. 23 refs., 14 figs., 2 tabs.

  8. Theoretical study of the diatomic alkali and alkaline-earth oxides

    NASA Technical Reports Server (NTRS)

    Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

    1986-01-01

    Theoretical dissociation energies for the ground states of the alkali and alkaline earth oxides are presented that are believed to be accurate to 0.1 eV. The 2 Pi - 2 Sigma + separations for the alkali oxides are found to be more sensitive to basis set than to electron correlation. Predicted 2 Pi ground states for LiO and NaO and 2 Sigma + ground states for RbO and CsO are found to be in agreement with previous theoretical and experimental work. For KO, a 2 Sigma + state is found at both the numerical Hartree-Fock (NHF) level and at the singles plus doubles configuration interaction level using a Slater basis set that is within 0.02 eV of the NHF limit. It is found that an accurate balanced treatment of the two states requires correlating the electrons on both the metal and oxide ion.

  9. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, D.C.; Mailhe, C.C.; De Jonghe, L.C.

    1985-07-10

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  10. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, David C.; Mailhe, Catherine C.; De Jonghe, Lutgard C.

    1986-01-01

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  11. Element specificity of ortho-positronium annihilation for alkali-metal loaded SiO{sub 2} glasses

    SciTech Connect

    Sato, K.; Hatta, T.

    2015-03-07

    Momentum distributions associated with ortho-positronium (o-Ps) pick-off annihilation photon are often influenced by light elements, as, e.g., carbon, oxygen, and fluorine. This phenomenon, so-called element specificity of o-Ps pick-off annihilation, has been utilized for studying the elemental environment around the open spaces. To gain an insight into the element specificity of o-Ps pick-off annihilation, the chemical shift of oxygen 1s binding energy and the momentum distributions associated with o-Ps pick-off annihilation were systematically investigated for alkali-metal loaded SiO{sub 2} glasses by means of X-ray photoelectron spectroscopy and positron-age-momentum correlation spectroscopy, respectively. Alkali metals introduced into the open spaces surrounded by oxygen atoms cause charge transfer from alkali metals to oxygen atoms, leading to the lower chemical shift for the oxygen 1s binding energy. The momentum distribution of o-Ps localized into the open spaces is found to be closely correlated with the oxygen 1s chemical shift. This correlation with the deepest 1s energy level evidences that the element specificity of o-Ps originates from pick-off annihilation with orbital electrons, i.e., dominantly with oxygen 2p valence electrons and s electrons with lower probability.

  12. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

    1996-09-24

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M{sub x}Z{sub y}Mn{sub (1{minus}y)}O{sub 2}, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell. 11 figs.

  13. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

    1996-01-01

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

  14. ALKALI/ AKALINE-EARTH CONTENT EFFECTS ON PROPERTIES OF HIGH-ALUMINA NUCLEAR WASTE GLASSES

    SciTech Connect

    McCloy, John S.; Rodriguez, Carmen P.; Windisch, Charles F.; Leslie, Clifford J.; Schweiger, Michael J.; Riley, Brian J.; Vienna, John D.

    2010-10-01

    A series of high alumina (>20 mass %) borosilicate glasses have been made and characterized based on the assumption that the primary modifier cation field strength plays a significant role in mediating glass structure of nuclear waste glasses. Any crystallization upon quenching or after heat treatment at 950 °C for 24 hours was identified and quantified by X-ray diffraction. Particular note was take of any aluminosilicates formed, such as those in the nepheline group (MAlSiO4 where M=K, Na, Li), as these remove multiple glass-formers from the network upon crystallization. The relative roles of potassium, sodium, lithium, calcium, and magnesium on glass structure and crystallization in high alumina glasses were explored using Raman and infrared vibrational spectroscopy. Strong evidence was found for the importance of 4 membered rings in glasses with 10 mol % alkaline earths (Ca, Mg).

  15. Structure of Alkali Borate Glasses at High Pressure: B and Li K-Edge Inelastic X-Ray Scattering Study

    SciTech Connect

    Lee, Sung Keun; Eng, Peter J.; Mao, Ho-kwang; Meng, Yue; Shu, Jinfu

    2008-06-16

    We report the first in situ boron K-edge inelastic x-ray scattering (IXS) spectra for alkali borate glasses (Li{sub 2}B{sub 4}O{sub 7}) at high pressure up to 30 GPa where pressure-induced coordination transformation from three-coordinated to four-coordinated boron was directly probed. Coordination transformation (reversible upon decompression) begins around 5 GPa and the fraction of four-coordinated boron increases with pressure from about 50% (at 1 atm) to more than 95% (at 30 GPa) with multiple densification mechanisms, evidenced by three distinct pressure ranges for (d{sup [4]}B/dP){sub T}. The lithium K-edge IXS spectrum for Li-borate glasses at 5 GPa shows IXS features similar to that at 1 atm, suggesting that the Li environment does not change much with pressure up to 5 GPa. These results provide improved understanding of the structure of low-z glass at high pressure.

  16. Investigation of emulsified, acid and acid-alkali catalyzed mesoporous bioactive glass microspheres for bone regeneration and drug delivery.

    PubMed

    Miao, Guohou; Chen, Xiaofeng; Dong, Hua; Fang, Liming; Mao, Cong; Li, Yuli; Li, Zhengmao; Hu, Qing

    2013-10-01

    Acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were successfully synthesized via combination of sol-gel and water-in-oil (W/O) micro-emulsion methods. The structural, morphological and textural properties of mesoporous bioactive glass microspheres (MBGMs) were characterized by various techniques. Results show that both MBGMs-A and MBGMs-B exhibit regularly spherical shape but with different internal porous structures, i.e., a dense microstructure for MBGMs-A and internally porous structure for MBGMs-B. (29)Si NMR data reveal that MGBMs have low polymerization degree of silica network. The in vitro bioactivity tests indicate that the apatite formation rate of MBGMs-B was faster than that of MBGMs-A after soaking in simulated body fluid (SBF) solution. Furthermore, the two kinds of MBGMs have similar storage capacity of alendronate (AL), and the release behaviors of AL could be controlled due to their unique porous structure. In conclusion, the microspheres are shown to be promising candidates as bone-related drug carriers and filling materials of composite scaffold for bone repair.

  17. Investigation of emulsified, acid and acid-alkali catalyzed mesoporous bioactive glass microspheres for bone regeneration and drug delivery.

    PubMed

    Miao, Guohou; Chen, Xiaofeng; Dong, Hua; Fang, Liming; Mao, Cong; Li, Yuli; Li, Zhengmao; Hu, Qing

    2013-10-01

    Acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were successfully synthesized via combination of sol-gel and water-in-oil (W/O) micro-emulsion methods. The structural, morphological and textural properties of mesoporous bioactive glass microspheres (MBGMs) were characterized by various techniques. Results show that both MBGMs-A and MBGMs-B exhibit regularly spherical shape but with different internal porous structures, i.e., a dense microstructure for MBGMs-A and internally porous structure for MBGMs-B. (29)Si NMR data reveal that MGBMs have low polymerization degree of silica network. The in vitro bioactivity tests indicate that the apatite formation rate of MBGMs-B was faster than that of MBGMs-A after soaking in simulated body fluid (SBF) solution. Furthermore, the two kinds of MBGMs have similar storage capacity of alendronate (AL), and the release behaviors of AL could be controlled due to their unique porous structure. In conclusion, the microspheres are shown to be promising candidates as bone-related drug carriers and filling materials of composite scaffold for bone repair. PMID:23910338

  18. The Structural Role of Zr within Alkali Borosilicate Glasses for Nuclear Waste Immobilisation

    SciTech Connect

    A Connelly; N Hyatt; K Travis; R Hand; E Maddrell; R Short

    2011-12-31

    Zirconium is a key constituent element of High Level nuclear Waste (HLW) glasses, occurring both as a fission product and a fuel cladding component. As part of a wider research program aimed at optimizing the solubility of zirconium in HLW glasses, we have investigated the structural chemistry of zirconium in such materials using X-ray Absorption Spectroscopy (XAS). Zirconium K-edge XAS data were acquired from several inactive simulant and simplified waste glass compositions, including a specimen of blended Magnox/UO{sub 2} fuel waste glass. These data demonstrate that zirconium is immobilized as (octahedral) six-fold coordinate ZrO{sub 6} species in these glasses, with a Zr-O contact distance of 2.09 {angstrom}. The next nearest neighbors of the Zr species are Si at 3.42 {angstrom} and possibly Na at 3.44 {angstrom}, no next nearest neighbor Zr could be resolved.

  19. Determination of the valence band structure of an alkali phosphorus oxynitride glass: A synchrotron XPS study on LiPON

    NASA Astrophysics Data System (ADS)

    Schwöbel, André; Precht, Ruben; Motzko, Markus; Carrillo Solano, Mercedes A.; Calvet, Wolfram; Hausbrand, René; Jaegermann, Wolfram

    2014-12-01

    Lithium phosphorus oxynitride (LiPON) is a solid state electrolyte commonly used in thin film batteries (TFBs). Advanced TFBs face the issue of detrimental electrode-electrolyte interlayer formation, related to the electronic structure of the interface. In this contribution, we study the valence band structure of LiPON using resonant photoemission and synchrotron photoemission with variable excitation energies. The identification of different valence band features is done according to the known valence band features of meta- and orthophosphates. Additionally we compare our results with partial density of states simulations from literature. We find that the valence band structure is similar to the known metaphosphates with an additional contribution of nitrogen states at the top of the valence band. From the results we conclude that synchrotron X-ray photoemission (XPS) is a useful tool to study the valence band structure of nitridated alkali phosphate glasses.

  20. The development of a potassium-sulfide glass fiber cell and studies on impurities in alkali metal-sulfur cells

    NASA Technical Reports Server (NTRS)

    Tsang, F. Y.

    1977-01-01

    Potassium sulfur rechargeable cells, having as the electrolyte the thin walls of hollow glass fibers made from permeable glass, were developed. The cells had short lives, probably due to the construction materials and impurities in the potassium. The effect of the impurities in the analogous NA-S system was studied. Calcium, potassium, and NaOH/oxide impurities caused increased resistance or corrosion of the glass fibers. For long lived cell operation, the Na must contain less than 1 ppm Ca and less than a few ppm of hydroxide/oxide. Up to 150 ppm K can be tolerated. After purification of the Na anolyte, cell lifetimes in excess of 1000 deep charge-discharge cycles or over 8 months on continuous cycling at 10-30 percent depth of discharge were obtained.

  1. Ring distributions in alkali- and alkaline-earth aluminosilicate framework glasses- a raman spectroscopic study

    USGS Publications Warehouse

    Sharma, S.K.; Philpotts, J.A.; Matson, D.W.

    1985-01-01

    Raman spectra of crystalline polymorphs of a number of tectosilicate minerals having various sizes of smallest rings of TO4 tetrahedra (T = Si, Al) have been investigated to identify the bands that are sensitive indicators of the smallest rings in the network. The information obtained from the Raman spectra of tectosilicate minerals (e.g., SiO2 polymorphs, NaAlSi3O8 (Ab), NaAlSiO4 (Ne), KAlSi3O8 (Or), and KAlSi2O6 (Lc)) is used to interpret the Raman spectra of the isochemical glasses. It is shown that the frequency of the dominant ??s (TOT) band in the spectra of both crystals and glasses is related to the dominant size of TO4 rings in the structure. In agreement with previous X-ray RDF work, it is found that in the glasses of Ab and Jd (NaAlSi2O6) compositions, six-membered rings of TO4 tetrahedra predominate. The Raman spectrum of Or glass, however, indicates that clusters of intermixed four- and six-membered rings of TO4 tetrahedra, similar to those existing in crystalline leucite, are also present in the glass. Raman evidence indicates that four-membered rings of TO4 tetrahedra predominate in the glass of An composition. Similarly, the higher frequency of the ??s (TOT) band in the spectrum of Ne glass as compared with the frequency the ??s (TOT) band in the spectra of crystalline cargenieite and nephelite indicates either an admixture of the four- and six-membered rings or the puckering of six-membered rings in the glass structure. ?? 1985.

  2. Multilevel tunnelling systems and fractal clustering in the low-temperature mixed alkali-silicate glasses.

    PubMed

    Jug, Giancarlo; Paliienko, Maksym

    2013-01-01

    The thermal and dielectric anomalies of window-type glasses at low temperatures (T < 1 K) are rather successfully explained by the two-level systems (2LS) standard tunneling model (STM). However, the magnetic effects discovered in the multisilicate glasses in recent times, magnetic effects in the organic glasses, and also some older data from mixed (SiO₂)(1-x) (K₂O)(x) and (SiO₂)(1-x) (Na₂O)(x) glasses indicate the need for a suitable extension of the 2LS-STM. We show that--not only for the magnetic effects, but also for the mixed glasses in the absence of a field--the right extension of the 2LS-STM is provided by the (anomalous) multilevel tunnelling systems (ATS) proposed by one of us for multicomponent amorphous solids. Though a secondary type of TS, different from the standard 2LS, was invoked long ago already, we clarify their physical origin and mathematical description and show that their contribution considerably improves the agreement with the experimental data. In spite of dealing with low-temperature properties, our work impinges on the structure and statistical physics of glasses at all temperatures. PMID:23861652

  3. Multilevel tunnelling systems and fractal clustering in the low-temperature mixed alkali-silicate glasses.

    PubMed

    Jug, Giancarlo; Paliienko, Maksym

    2013-01-01

    The thermal and dielectric anomalies of window-type glasses at low temperatures (T < 1 K) are rather successfully explained by the two-level systems (2LS) standard tunneling model (STM). However, the magnetic effects discovered in the multisilicate glasses in recent times, magnetic effects in the organic glasses, and also some older data from mixed (SiO₂)(1-x) (K₂O)(x) and (SiO₂)(1-x) (Na₂O)(x) glasses indicate the need for a suitable extension of the 2LS-STM. We show that--not only for the magnetic effects, but also for the mixed glasses in the absence of a field--the right extension of the 2LS-STM is provided by the (anomalous) multilevel tunnelling systems (ATS) proposed by one of us for multicomponent amorphous solids. Though a secondary type of TS, different from the standard 2LS, was invoked long ago already, we clarify their physical origin and mathematical description and show that their contribution considerably improves the agreement with the experimental data. In spite of dealing with low-temperature properties, our work impinges on the structure and statistical physics of glasses at all temperatures.

  4. Glass Mica Composite Seals for Solid Oxide Fuel Cells

    SciTech Connect

    Chou, Y S.; Stevenson, Jeffry W.; Singh, Prabhakar

    2005-07-20

    A novel glass-mica composite seal was developed based on the previous concept of ''infiltrated'' mica seals for solid oxide fuel cells. A Ba-Al-Ca silicate sealing glass was mixed with mica flakes to form the glass-mica composite seals. The glass-mica composite seals were tested thermal cycle stability in terms of the high temperature leakage and compressive stresses. Post mortem analyses were used to characterize the fracture and leak path of the glass-mica composite seals.

  5. Structural investigation and electron paramagnetic resonance of vanadyl doped alkali niobium borate glasses.

    PubMed

    Agarwal, A; Sheoran, A; Sanghi, S; Bhatnagar, V; Gupta, S K; Arora, M

    2010-03-01

    Glasses with compositions xNb(2)O(5).(30-x)M(2)O.69B(2)O(3) (where M=Li, Na, K; x=0, 4, 8 mol%) doped with 1 mol% V(2)O(5) have been prepared using normal melt quench technique. The IR transmission spectra of the glasses have been studied over the range 400-4000 cm(-1). The changes caused by the addition of Nb(2)O(5) on the structure of these glasses have been reported. The electron paramagnetic resonance spectra of VO(2+) ions in these glasses have been recorded in X-band (9.14 GHz) at room temperature (300 K). The spin Hamiltonian parameters, dipolar hyperfine coupling parameter and Fermi contact interaction parameter have been calculated. It is observed that the resultant resonance spectra contain hyperfine structures (hfs) due to V(4+) ions which exist as VO(2+) ions in octahedral coordination with a tetragonal compression in the present glasses. The tetragonality of V(4+)O(6) complex decreases with increasing concentration of Nb(2)O(5). The 3d(xy) orbit contracts with increase in Nb(2)O(5):M(2)O ratio. Values of the theoretical optical basicity, Lambda(th), have also been reported.

  6. Optical glass surfaces polishing by cerium oxide particles

    NASA Astrophysics Data System (ADS)

    Bouzid, D.; Belkhie, N.; Aliouane, T.

    2012-02-01

    The use of powders in metallic oxides as means of grinding and polishing of the optical glass components have seen recently a large application in optical industry. In fact, cerium oxide abrasive is more used in the optical glass polishing. It is used as grains abrasive in suspension or fixed abrasive (pellets); these pellets are manufactured from a mixture made of cerium oxide abrasive and a organic binder. The cerium oxide used in the experiments is made by (Logitech USA) of 99 % purity, the average grain size of the particle is 300 nm, the density being 6,74 g /cm3 and the specific surface is 3,3042 m2/g. In this study, we are interested in the surfaces quality of the optical glass borosilicate crown (BK7) polished by particles in cerium oxide bounded by epoxy. The surfaces of the optical glass treated are characterized by the roughness, the flatness by using the microscope Zygo and the SEM.

  7. Silicate species of water glass and insights for alkali-activated green cement

    SciTech Connect

    Jansson, Helén; Bernin, Diana; Ramser, Kerstin

    2015-06-15

    Despite that sodium silicate solutions of high pH are commonly used in industrial applications, most investigations are focused on low to medium values of pH. Therefore we have investigated such solutions in a broad modulus range and up to high pH values (∼14) by use of infrared (IR) spectroscopy and silicon nuclear magnetic resonance ({sup 29}Si-NMR). The results show that the modulus dependent pH value leads to more or less charged species, which affects the configurations of the silicate units. This in turn, influences the alkali-activation process of low CO{sub 2} footprint cements, i.e. materials based on industrial waste or by-products.

  8. Silicate species of water glass and insights for alkali-activated green cement

    NASA Astrophysics Data System (ADS)

    Jansson, Helén; Bernin, Diana; Ramser, Kerstin

    2015-06-01

    Despite that sodium silicate solutions of high pH are commonly used in industrial applications, most investigations are focused on low to medium values of pH. Therefore we have investigated such solutions in a broad modulus range and up to high pH values (˜14) by use of infrared (IR) spectroscopy and silicon nuclear magnetic resonance (29Si-NMR). The results show that the modulus dependent pH value leads to more or less charged species, which affects the configurations of the silicate units. This in turn, influences the alkali-activation process of low CO2 footprint cements, i.e. materials based on industrial waste or by-products.

  9. Liquid Crystals and Glasses in Binary Systems from Sodium and Alkali-Earth Metal Butyrates

    NASA Astrophysics Data System (ADS)

    Mirnaya, T. A.; Bereznitski, Y. V.; Volkov, S. V.

    1996-07-01

    The temperature and composition ranges of liquid crystal and glass formation have been established for the binary mixtures of mesogenic sodium butyrate with non-mesogenic magnesium, calcium and strontium butyrates by means of differential thermal analysis and hot stage polarization microscopy. The formation of a vitreous optically anisotropic mesophase has been found for binaries of sodium butyrate with calcium and strontium butyrates.

  10. Glass material oxidation and dissolution system: Converting miscellaneous fissile materials to glass

    SciTech Connect

    Forsberg, C.W.; Ferrada, J.J.

    1996-03-19

    The cold war and the development of nuclear energy have resulted in significant inventories of miscellaneous fissile materials (MFMs). MFMs include (1) plutonium scrap and residue, (2) miscellaneous spent nuclear fuel (SNF), (3) certain hot cell wastes, and (4) many one-of-a-kind materials. Major concerns associated with the long-term management of these materials include: safeguards and nonproliferation issues; health, environment, and safety concerns. waste management requirements; and high storage costs. These issues can be addressed by converting the MFMs to glass for secure, long-term storage or repository disposal; however, conventional glass-making processes require oxide-like feed materials. Converting MFMs to oxide-like materials with subsequent vitrification is a complex and expensive process. A new vitrification process has been invented, the Glass Material Oxidation and Dissolution System (GMODS), which directly converts metals, ceramics, and amorphous solids to glass; oxidizes organics with the residue converted to glass; and converts chlorides to borosilicate glass and a secondary sodium chloride (NaCl) stream. Laboratory work has demonstrated the conversion of cerium (a plutonium surrogate), uranium, Zircaloy, stainless steel, multiple oxides, and other materials to glass. However, significant work is required to develop GMODS further for applications at an industrial scale. If implemented, GMODS will provide a new approach to manage these materials.

  11. Glass/BNNT Composite for Sealing Solid Oxide Fuel Cells

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Hurst, Janet B.; Choi, Sung R.

    2007-01-01

    A material consisting of a barium calcium aluminosilicate glass reinforced with 4 weight percent of boron nitride nanotubes (BNNTs) has shown promise for use as a sealant in planar solid oxide fuel cells (SOFCs).

  12. Fe(3+) ions in alkali lead tetraborate glasses--an electron paramagnetic resonance and optical study.

    PubMed

    Chakradhar, R P Sreekanth; Sivaramaiah, G; Rao, J Lakshmana; Gopal, N O

    2005-11-01

    Glass systems of composition 90R(2)B(4)O(7)+9PbO+1Fe(2)O(3) (R=Li, Na and K) and 90Li(2)B(4)O(7)+(10-x)PbO+xFe(2)O(3) (x=0.5, 1, 3, 4, 5, 7 and 9 mol %) have been investigated by means of electron paramagnetic resonance (EPR) and optical absorption techniques. The EPR spectra exhibit three resonance signals at g approximately 6.0, 4.2 and 2.0. The resonances at g approximately 6.0 and 4.2 are attributed to Fe(3+) ions in rhombic and axial symmetry sites, respectively. The g approximately 2.0 resonance signal is due to two or more Fe(3+) ions coupled together with dipolar interaction. The EPR spectra of 1 mol % of Fe(2)O(3) doped in lithium lead tetraborate glass samples have been studied at different temperatures (123-433 K). The intensity of g approximately 4.2 resonance signal decreases and the intensity of g approximately 2.0 resonance signal increases with the increase of temperature. The line widths are found to be independent of temperature. The EPR spectra exhibit a marked concentration dependence on iron content. A decrease in intensity for the resonance signal at g approximately 4.2 with increase in iron content for more than 4 mol % has been observed in lithium lead tetraborate glass samples and this has been attributed to the formation of Fe(3+) ion clusters in the glass samples. The paramagnetic susceptibility (chi) is calculated from the EPR data at various temperatures and the Curie constant (C) has been evaluated from 1/chi versus T graph. The optical absorption spectrum of Fe(3+) ions in lithium lead tetraborate glasses exhibits three bands characteristic of Fe(3+) ions in an octahedral symmetry. The crystal field parameter D(q) and the Racah interelectronic repulsion parameters B and C have also been evaluated. The value of interelectronic repulsion parameter B (825 cm(-1)) obtained in the present work suggests that the bonding is moderately covalent.

  13. A study on optical properties of poly (ethylene oxide) based polymer electrolyte with different alkali metal iodides

    NASA Astrophysics Data System (ADS)

    Rao, B. Narasimha; Suvarna, R. Padma

    2016-05-01

    Polymer electrolytes were prepared by adding poly (ethylene glycol) dimethyl ether (PEGDME), TiO2 (nano filler), different alkali metal iodide salts RI (R+=Li+, Na+, K+, Rb+, Cs+) and I2 into Acetonitrile gelated with Poly (ethylene oxide) (PEO). Optical properties of poly (ethylene oxide) based polymer electrolytes were studied by FTIR, UV-Vis spectroscopic techniques. FTIR spectrum reveals that the alkali metal cations were coordinated to ether oxygen of PEO. The optical absorption studies were made in the wavelength range 200-800 nm. It is observed that the optical absorption increases with increase in the radius of alkali metal cation. The optical band gap for allowed direct transitions was evaluated using Urbach-edges method. The optical properties such as optical band gap, refractive index and extinction coefficient were determined. The studied polymer materials are useful for solar cells, super capacitors, fuel cells, gas sensors etc.

  14. Structural Role of Alkali Cations in Calcium Aluminosilicate Glasses as Examined Using Oxygen-17 Solid-State Nuclear Magnetic Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sukenaga, Sohei; Kanehashi, Koji; Shibata, Hiroyuki; Saito, Noritaka; Nakashima, Kunihiko

    2016-08-01

    The structural roles of alkali and calcium cations are important for understanding the physical and chemical properties of aluminosilicate melts and glasses. Recently, oxygen-17 nuclear magnetic resonance (17O NMR) studies of calcium-sodium aluminosilicate glasses showed that these structural roles are not randomly given, but rather each cation has its own preferential role. However, the relationship between cation type and role preference in calcium aluminosilicate glass is not completely understood. In the present study, the structural roles of lithium, sodium, and potassium cations in selected calcium aluminosilicate glasses are investigated using 17O solid-state NMR experiments. Data from these experiments clearly show that potassium cations have a notably stronger tendency to act as charge compensators within the network structure, compared to sodium and lithium cations. The result of 17O NMR experiment also showed that sodium and lithium cations in part act as network modifier alongside with calcium cations.

  15. Single-Phase Rare-Earth Oxide/Aluminum Oxide Glasses

    NASA Technical Reports Server (NTRS)

    Weber, J. K. Richard; Abadie, John G.; Hixson, April D.; Nordine, Paul C.

    2006-01-01

    Glasses that comprise rare-earth oxides and aluminum oxide plus, optionally, lesser amounts of other oxides, have been invented. The other oxide(s) can include SiO2, B2O3, GeO2, and/or any of a variety of glass-forming oxides that have been used heretofore in making a variety of common and specialty glasses. The glasses of the invention can be manufactured in bulk single-phase forms to ensure near uniformity in optical and mechanical characteristics, as needed for such devices as optical amplifiers, lasers, and optical waveguides (including optical fibers). These glasses can also be formulated to have high indices of refraction, as needed in some of such devices.

  16. Iron Oxidation State in Fulgurite Glass

    NASA Astrophysics Data System (ADS)

    Giuli, G.; Pratesi, G.; Paris, E.; Cibin, G.

    2016-08-01

    XAS data of both fulgurite samples are consistent with Fe being mostly divalent, similar to tektite glasses. whereas the unmolten sand enclosed in the tube fulgurite does not show any sign of reduction, Fe being mostly trivalent in the sand.

  17. Multi-phase glass-ceramics as a waste form for combined fission products: alkalis, alkaline earths, lanthanides, and transition metals

    SciTech Connect

    Crum, Jarrod V.; Turo, Laura A.; Riley, Brian J.; Tang, Ming; Kossoy, Anna

    2012-04-01

    In this study, multi-phase silicate-based glass-ceramics were investigated as an alternate waste form for immobilizing non-fissionable products from used nuclear fuel. Currently, borosilicate glass is the waste form selected for immobilization of this waste stream, however, the low thermal stability and solubility of MoO{sub 3} in borosilicate glass translates into a maximum waste loading in the range of 15-20 mass%. Glass-ceramics provide the opportunity to target durable crystalline phases, e.g., powellite, oxyapatite, celsian, and pollucite, that will incorporate MoO{sub 3} as well as other waste components such as lanthanides, alkalis, and alkaline earths at levels 2X the solubility limits of a single-phase glass. In addition a glass-ceramic could provide higher thermal stability, depending upon the properties of the crystalline and amorphous phases. Glass-ceramics were successfully synthesized at waste loadings of 42, 45, and 50 mass% with the following glass additives: B{sub 2}O{sub 3}, Al{sub 2}O{sub 3}, CaO and SiO{sub 2} by slow cooling form from a glass melt. Glass-ceramics were characterized in terms of phase assemblage, morphology, and thermal stability. The targeted phases: powellite and oxyapatite were observed in all of the compositions along with a lanthanide borosilicate, and cerianite. Results of this initial investigation of glass-ceramics show promise as a potential waste form to replace single-phase borosilicate glass.

  18. Intumescence and pore structure of alkali-activated volcanic glasses upon exposure to high temperatures

    NASA Astrophysics Data System (ADS)

    Erdogan, S. T.

    2015-12-01

    Structures formed with ground perlite, a natural volcanic glass, activated with NaOH solutions, are shown to possess the ability to expand up to ~225 % of their original volumes upon exposure to temperatures in the 200-600 °C range. Porous solid with 3-7 MPa compressive strength and ˜450 kg/m3 or higher density are obtained. The observed expansion is believed to occur due to a loss of silanol condensation water, as vapor and is accompanied by an up to ~20 % loss in mass. A drop in pH to near-neutral values supports this idea. The size and total amount of pores in the final solid are controlled by concentration of the NaOH solution and thermal processing conditions. The pores formed are observed to be ~1-10 μm to mm-sized. The ability of perlite-based solids to intumesce over specific temperature ranges could be beneficial in applications where absorption of thermal energy is necessary, such as passive fire protection.

  19. Borohydride electro-oxidation in a molten alkali hydroxide eutectic mixture and a novel borohydride-periodate battery

    NASA Astrophysics Data System (ADS)

    Wang, Andrew; Gyenge, Előd L.

    2015-05-01

    The electrochemical oxidation of BH4- in a molten NaOH-KOH eutectic mixture (0.515:0.485 mole fractions), is investigated for the first time by cyclic voltammetry and electrochemical impedance spectroscopy. Anodically oxidized Ni is electrocatalytically more active than Pt for BH4- oxidation in the molten alkali electrolyte as shown by the more than three times higher exchange current density (i.e. 15.8 mA cm-2 vs. 4.6 mA cm-2 at 185 °C). Next the proof-of-concept for a novel BH4-/IO4- molten alkali electrolyte battery is presented. Using oxidized Ni mesh anode and Pt mesh cathode a maximum power density of 63 mW cm-2 is achieved at 185 °C.

  20. Generation of alkali-free and high-proton concentration layer in a soda lime glass using non-contact corona discharge

    SciTech Connect

    Ikeda, Hiroshi; Sakai, Daisuke; Nishii, Junji; Funatsu, Shiro; Yamamoto, Kiyoshi; Suzuki, Toshio; Harada, Kenji

    2013-08-14

    Formation mechanisms of alkali-free and high-proton concentration surfaces were investigated for a soda lime glass using a corona discharge treatment under an atmospheric pressure. Protons produced by high DC voltage around an anode needle electrode were incorporated into a sodium ion site in the anode side glass. The sodium ion was swept away to the cathode side as a charge carrier. Then it was discharged. The precipitated sodium was transformed to a Na{sub 2}CO{sub 3} powder when the surface contacted with air. The sodium ion in the glass surface layer of the anode side was replaced completely by protons. The concentration of OH groups in the layer was balanced with the amount of excluded sodium ions. The substitution reaction of sodium ions with protons tends to be saturated according to a square root function of time. The alkali depletion layer formation rate was affected by the large difference in mobility between sodium ions and protons in the glass.

  1. Alkali-silica reactions of mortars produced by using waste glass as fine aggregate and admixtures such as fly ash and Li2CO3.

    PubMed

    Topçu, Ilker Bekir; Boğa, Ahmet Raif; Bilir, Turhan

    2008-01-01

    Use of waste glass or glass cullet (GC) as concrete aggregate is becoming more widespread each day because of the increase in resource efficiency. Recycling of wastes is very important for sustainable development. When glass is used as aggregate in concrete or mortar, expansions and internal stresses occur due to an alkali-silica reaction (ASR). Furthermore, rapid loss in durability is generally observed due to extreme crack formation and an increase in permeability. It is necessary to use some kind of chemical or mineral admixture to reduce crack formation. In this study, mortar bars are produced by using three different colors of glass in four different quantities as fine aggregate by weight, and the effects of these glass aggregates on ASR are investigated, corresponding to ASTM C 1260. Additionally, in order to reduce the expansions of mortars, 10% and 20% fly ash (FA) as mineral admixture and 1% and 2% Li(2)CO(3) as chemical admixture are incorporated by weight in the cement and their effects on expansion are examined. It is observed that among white (WG), green (GG) and brown glass (BG) aggregates, WG aggregate causes the greatest expansion. In addition, expansion increases with an increase in amount of glass. According to the test results, it is seen that over 20% FA and 2% Li(2)CO(3) replacements are required to produce mortars which have expansion values below the 0.2% critical value when exposed to ASR. However, usages of these admixtures reduce expansions occurring because of ASR.

  2. Interactions between the glass fiber coating and oxidized carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Ku-Herrera, J. J.; Avilés, F.; Nistal, A.; Cauich-Rodríguez, J. V.; Rubio, F.; Rubio, J.; Bartolo-Pérez, P.

    2015-03-01

    Chemically oxidized multiwall carbon nanotubes (MWCNTs) were deposited onto commercial E-glass fibers using a dipping procedure assisted by ultrasonic dispersion. In order to investigate the role of the fiber coating (known as "sizing"), MWCNTs were deposited on the surface of as-received E-glass fibers preserving the proprietary coating as well as onto glass fibers which had the coating deliberately removed. Scanning electron microscopy and Raman spectroscopy were used to assess the distribution of MWCNTs onto the fibers. A rather homogeneous coverage with high density of MWCNTs onto the glass fibers is achieved when the fiber coating is maintained. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance (NMR) analyses of the chemical composition of the glass fiber coating suggest that such coating is a complex mixture with multiple oxygen-containing functional groups such as hydroxyl, carbonyl and epoxy. FTIR and XPS of MWCNTs over the glass fibers and of a mixture of MWCNTs and fiber coating provided evidence that the hydroxyl and carboxyl groups of the oxidized MWCNTs react with the oxygen-containing functional groups of the glass fiber coating, forming hydrogen bonding and through epoxy ring opening. Hydrogen bonding and ester formation between the functional groups of the MWCNTs and the silane contained in the coating are also possible.

  3. Improvement of enzymatic hydrolysis and ethanol production from corn stalk by alkali and N-methylmorpholine-N-oxide pretreatments.

    PubMed

    Cai, Ling-Yan; Ma, Yu-Long; Ma, Xiao-Xia; Lv, Jun-Min

    2016-07-01

    A combinative technology of alkali and N-methylmorpholine-N-oxide (NMMO) was used to pretreat corn stalk (CS) for improving the efficiencies of subsequent enzymatic hydrolysis and ethanol fermentation. The results showed that this strategy could not only remove hemicellulose and lignin but also decrease the crystallinity of cellulose. About 98.0% of enzymatic hydrolysis yield was obtained from the pretreated CS as compared with 46.9% from the untreated sample. The yield for corresponding ethanol yield was 64.6% while untreated CS was only 18.8%. Besides, xylose yield obtained from the untreated CS was only 11.1%, while this value was 93.8% for alkali with NMMO pretreated sample. These results suggest that a combination of alkali with 50% (wt/wt) NMMO solution may be a promising alternative for pretreatment of lignocellulose, which can increase the productions of subsequent enzymatic hydrolysis and ethanol fermentation. PMID:27078206

  4. Alkali production associated with malolactic fermentation by oral streptococci and protection against acid, oxidative, or starvation damage.

    PubMed

    Sheng, Jiangyun; Baldeck, Jeremiah D; Nguyen, Phuong T M; Quivey, Robert G; Marquis, Robert E

    2010-07-01

    Alkali production by oral streptococci is considered important for dental plaque ecology and caries moderation. Recently, malolactic fermentation (MLF) was identified as a major system for alkali production by oral streptococci, including Streptococcus mutans. Our major objectives in the work described in this paper were to further define the physiology and genetics of MLF of oral streptococci and its roles in protection against metabolic stress damage. L-Malic acid was rapidly fermented to L-lactic acid and CO(2) by induced cells of wild-type S. mutans, but not by deletion mutants for mleS (malolactic enzyme) or mleP (malate permease). Mutants for mleR (the contiguous regulator gene) had intermediate capacities for MLF. Loss of capacity to catalyze MLF resulted in loss of capacity for protection against lethal acidification. MLF was also found to be protective against oxidative and starvation damage. The capacity of S. mutans to produce alkali from malate was greater than its capacity to produce acid from glycolysis at low pH values of 4 or 5. MLF acted additively with the arginine deiminase system for alkali production by Streptococcus sanguinis, but not with urease of Streptococcus salivarius. Malolactic fermentation is clearly a major process for alkali generation by oral streptococci and for protection against environmental stresses.

  5. Glass/Ceramic Composites for Sealing Solid Oxide Fuel Cells

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Choi, Sung R.

    2007-01-01

    A family of glass/ceramic composite materials has been investigated for use as sealants in planar solid oxide fuel cells. These materials are modified versions of a barium calcium aluminosilicate glass developed previously for the same purpose. The composition of the glass in mole percentages is 35BaO + 15CaO + 5Al2O3 + 10B2O3 + 35SiO2. The glass seal was found to be susceptible to cracking during thermal cycling of the fuel cells. The goal in formulating the glass/ ceramic composite materials was to (1) retain the physical and chemical advantages that led to the prior selection of the barium calcium aluminosilicate glass as the sealant while (2) increasing strength and fracture toughness so as to reduce the tendency toward cracking. Each of the composite formulations consists of the glass plus either of two ceramic reinforcements in a proportion between 0 and 30 mole percent. One of the ceramic reinforcements consists of alumina platelets; the other one consists of particles of yttria-stabilized zirconia wherein the yttria content is 3 mole percent (3YSZ). In preparation for experiments, panels of the glass/ceramic composites were hot-pressed and machined into test bars.

  6. Supported, Alkali-Promoted Cobalt Oxide Catalysts for NOx Removal from Coal Combustion Flue Gases

    SciTech Connect

    Morris D. Argyle

    2005-12-31

    A series of cobalt oxide catalysts supported on alumina ({gamma}-Al{sub 2}O{sub 3}) were synthesized with varying contents of cobalt and of added alkali metals, including lithium, sodium, potassium, rubidium, and cesium. Unsupported cobalt oxide catalysts and several cobalt oxide catalysts supported ceria (CeO{sub 2}) with varying contents of cobalt with added potassium were also prepared. The catalysts were characterized with UV-visible spectroscopy and were examined for NO{sub x} decomposition activity. The CoO{sub x}/Al{sub 2}O{sub 3} catalysts and particularly the CoO{sub x}/CeO{sub 2} catalysts show N{sub 2}O decomposition activity, but none of the catalysts (unsupported Co{sub 3}O{sub 4} or those supported on ceria or alumina) displayed significant, sustained NO decomposition activity. For the Al{sub 2}O{sub 3}-supported catalysts, N{sub 2}O decomposition activity was observed over a range of reaction temperatures beginning about 723 K, but significant (>50%) conversions of N{sub 2}O were observed only for reaction temperatures >900 K, which are too high for practical commercial use. However, the CeO{sub 2}-supported catalysts display N{sub 2}O decomposition rates similar to the Al{sub 2}O{sub 3}-supported catalysts at much lower reaction temperatures, with activity beginning at {approx}573 K. Conversions of >90% were achieved at 773 K for the best catalysts. Catalytic rates per cobalt atom increased with decreasing cobalt content, which corresponds to increasing edge energies obtained from the UV-visible spectra. The decrease in edge energies suggests that the size and dimensionality of the cobalt oxide surface domains increase with increasing cobalt oxide content. The rate data normalized per mass of catalyst that shows the activity of the CeO{sub 2}-supported catalysts increases with increasing cobalt oxide content. The combination of these data suggest that supported cobalt oxide species similar to bulk Co{sub 3}O{sub 4} are inherently more active than

  7. Calcium-borosilicate glass-ceramics wasteforms to immobilize rare-earth oxide wastes from pyro-processing

    NASA Astrophysics Data System (ADS)

    Kim, Miae; Heo, Jong

    2015-12-01

    Glass-ceramics containing calcium neodymium(cerium) oxide silicate [Ca2Nd8-xCex(SiO4)6O2] crystals were fabricated for the immobilization of radioactive wastes that contain large portions of rare-earth ions. Controlled crystallization of alkali borosilicate glasses by heating at T ≥ 750 °C for 3 h formed hexagonal Ca-silicate crystals. Maximum lanthanide oxide waste loading was >26.8 wt.%. Ce and Nd ions were highly partitioned inside Ca-silicate crystals compared to the glass matrix; the rare-earth wastes are efficiently immobilized inside the crystalline phases. The concentrations of Ce and Nd ions released in a material characterization center-type 1 test were below the detection limit (0.1 ppb) of inductively coupled plasma mass spectroscopy. Normalized release values performed by a product consistency test were 2.64·10-6 g m-2 for Ce ion and 2.19·10-6 g m-2 for Nd ion. Results suggest that glass-ceramics containing calcium neodymium(cerium) silicate crystals are good candidate wasteforms for immobilization of lanthanide wastes generated by pyro-processing.

  8. Low melting high lithia glass compositions and methods

    DOEpatents

    Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.

    2003-09-23

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste uranium oxides The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

  9. The formation of crystals in glasses containing rare earth oxides

    NASA Astrophysics Data System (ADS)

    Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod; Siong, Khoo Kok; Ngatiman, Mohammad Fadzlee; Said, Riduan Mt

    2014-02-01

    Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd2O3-22.7CeO2-11.7La2O3-10.9PrO2-1.3Eu2O3-1.3Gd2O3-8.1Sm2O3-4.8Y2O3 with a baseline glass of composition 60.2SiO2-16.0B2O3-12.6Na2O-3.8Al2O3-5.7CaO-1.7ZrO2. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La2O3 and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO5) and oxyapatite (Ca2La8Si6O26) were found in glasses containing La2O3, while oxyapatite (Ca2La8Si6O26 and NaNd9Si6O26) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (TL) of the glasses containing 5%, 10% and 15% La2O3 were 800°C, 959°C and 986°C, respectively; while TL was 825°C, 1059°C and 1267°C for glasses with 5%, 10% and 15% addition of mixed rare earth oxides. The component coefficients TB2O3, TSiO2, TCaO, and TRE2O3 were also evaluated using a recently published study.

  10. Influence of ZnO/MgO substitution on sintering, crystallisation, and bio-activity of alkali-free glass-ceramics.

    PubMed

    Kapoor, Saurabh; Goel, Ashutosh; Correia, Ana Filipa; Pascual, Maria J; Lee, Hye-Young; Kim, Hae-Won; Ferreira, José M F

    2015-08-01

    The present study reports on the influence of partial replacement of MgO by ZnO on the structure, crystallisation behaviour and bioactivity of alkali-free bioactive glass-ceramics (GCs). A series of glass compositions (mol%): 36.07 CaO-(19.24-x) MgO-x ZnO-5.61 P2O5-38.49 SiO2-0.59 CaF2 (x=2-10) have been synthesised by melt-quench technique. The structural changes were investigated by solid-state magic angle spinning nuclear magnetic resonance (MAS-NMR), X-ray diffraction and differential thermal analysis. The sintering and crystallisation behaviours of glass powders were studied by hot-stage microscopy and differential thermal analysis, respectively. All the glass compositions exhibited good densification ability resulting in well sintered and mechanically strong GCs. The crystallisation and mechanical behaviour were studied under non-isothermal heating conditions at 850 °C for 1h. Diopside was the primary crystalline phase in all the GCs followed by fluorapatite and rankinite as secondary phases. Another phase named petedunnite was identified in GCs with ZnO content >4 mol. The proliferation of mesenchymal stem cells (MSCs) and their alkaline phosphatase activity (ALP) on GCs was revealed to be Zn-dose dependent with the highest performance being observed for 4 mol% ZnO.

  11. Preparation of Bi-Sr-Ca-Cu-O superconductors from oxide-glass precursors

    DOEpatents

    Hinks, David G.; Capone, II, Donald W.

    1992-01-01

    A superconductor and precursor therefor from oxide mixtures of Ca, Sr, Bi and Cu. Glass precursors quenched to elevated temperatures result in glass free of crystalline precipitates having enhanced mechanical properties. Superconductors are formed from the glass precursors by heating in the presence of oxygen to a temperature below the melting point of the glass.

  12. Conversion of plutonium-containing materials into borosilicate glass using the glass material oxidation and dissolution system

    SciTech Connect

    Forsberg, C.W.; Beahm, E.C.; Parker, G.W.

    1996-01-27

    The end of the cold war has resulted in excess plutonium-containing materials (PCMs) in multiple chemical forms. Major problems are associated with the long-term management of these materials: safeguards and nonproliferation issues; health, environment, and safety concerns; waste management requirements; and high storage costs. These issues can be addressed by conversion of the PCMs to glass: however, conventional glass processes require oxide-like feed materials. Conversion of PCMs to oxide-like materials followed by vitrification is a complex and expensive process. A new vitrification process has been invented, the Glass Material Oxidation and Dissolution System (GMODS) to allow direct conversion of PCMs to glass. GMODS directly converts metals, ceramics, and amorphous solids to glass; oxidizes organics with the residue converted to glass; and converts chlorides to borosilicate glass and a secondary sodium chloride stream. Laboratory work has demonstrated the conversion of cerium (a plutonium surrogate), uranium (a plutonium surrogate), Zircaloy, stainless steel, multiple oxides, and other materials to glass. Equipment options have been identified for processing rates between 1 and 100,000 t/y. Significant work, including a pilot plant, is required to develop GMODS for applications at an industrial scale.

  13. Optical Properties of K2O-Li2O-WO3-B2O3 Glasses: Evidence of Mixed Alkali Effect

    NASA Astrophysics Data System (ADS)

    Edukondalu, Avula; Sripathi, T.; Kareem Ahmmad, Shaik; Rahman, Syed; Sivakumar, K.

    2016-10-01

    Glass with compositions xK2O-(30 - x)Li2O-10WO3-60B2O3 for 0 ≤ x ≤ 30 mol.% have been prepared using the normal melt quenching technique. The optical reflection and absorption spectra were recorded at room temperature in the wavelength range 300-800 nm. From the absorption edge studies, the values of the optical band gap (E opt) and Urbach energy (ΔE) have been evaluated. The values of E opt and ΔE vary non-linearly with composition parameter, showing the mixed alkali effect. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple Di-Domenico model.

  14. Are Magnetically Doped Transition-metal Oxides Spin-glasses?

    NASA Astrophysics Data System (ADS)

    Lussier, A.; Dvorak, J.; Idzerda, Y. U.; Ogale, S. B.; Shinde, S. R.; Venkatesan, T.; Lofland, S. E.

    2004-03-01

    Many magnetic impurity doped transition-metal oxides exhibit ferromagnetism at room temperature. Some also exhibit strange magnetic aging behavior. One such material is Co-doped SnO2 which displays a saturation magnetization decrease over time, as well as with successive field applications. From the theoretical perspective, there are two prerequisites for spin-glass behavior which are both satisfied for these samples: disorder and frustration. Disorder is readily satisfied because the dilute magnetic impurities are randomly scattered. Additionally, the suggested RKKY interaction between magnetic impurities, coupled with their random spacing, likely results in frustration. Magnetometry, XAS, and XMCD measurements, with temperature, measurement time, and history dependence help elucidate the magnetic order in these materials, and are consistent with spin-glass character. We would like to acknowledge the support of NSF (MSU), the Office of Naval Research (MSU), DARPA SpinS (UMD) and NSF-MRSEC (UMD).

  15. Solid Oxide Fuel Cell Seal Glass - BN Nanotubes Composites

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Choi, Sung R.; Hurst, Janet B.; Garg, Anita

    2005-01-01

    Solid oxide fuel cell seal glass G18 composites reinforced with approx.4 weight percent of BN nanotubes were fabricated via hot pressing. Room temperature strength and fracture toughness of the composite were determined by four-point flexure and single edge V-notch beam methods, respectively. The strength and fracture toughness of the composite were higher by as much as 90% and 35%, respectively, than those of the glass G18. Microscopic examination of the composite fracture surfaces using SEM and TEM showed pullout of the BN nanotubes, similar in feature to fiber-reinforced ceramic matrix composites with weak interfaces. Other mechanical and physical properties of the composite will also be presented.

  16. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... amine salts. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical..., alkali and amine salts. 721.2565 Section 721.2565 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES...

  17. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... amine salts. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical..., alkali and amine salts. 721.2565 Section 721.2565 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES...

  18. Filled glass composites for sealing of solid oxide fuel cells.

    SciTech Connect

    Tandon, Rajan; Widgeon, Scarlett Joyce; Garino, Terry J.; Brochu, Mathieu; Gauntt, Bryan D.; Corral, Erica L.; Loehman, Ronald E.

    2009-04-01

    Glasses filled with ceramic or metallic powders have been developed for use as seals for solid oxide fuel cells (SOFC's) as part of the U.S. Department of Energy's Solid State Energy Conversion Alliance (SECA) Program. The composites of glass (alkaline earth-alumina-borate) and powders ({approx}20 vol% of yttria-stabilized zirconia or silver) were shown to form seals with SOFC materials at or below 900 C. The type and amount of powder were adjusted to optimize thermal expansion to match the SOFC materials and viscosity. Wetting studies indicated good wetting was achieved on the micro-scale and reaction studies indicated that the degree of reaction between the filled glasses and SOFC materials, including spinel-coated 441 stainless steel, at 750 C is acceptable. A test rig was developed for measuring strengths of seals cycled between room temperature and typical SOFC operating temperatures. Our measurements showed that many of the 410 SS to 410 SS seals, made using silver-filled glass composites, were hermetic at 0.2 MPa (2 atm.) of pressure and that seals that leaked could be resealed by briefly heating them to 900 C. Seal strength measurements at elevated temperature (up to 950 C), measured using a second apparatus that we developed, indicated that seals maintained 0.02 MPa (0.2 atm.) overpressures for 30 min at 750 C with no leakage. Finally, the volatility of the borate component of sealing glasses under SOFC operational conditions was studied using weight loss measurements and found by extrapolation to be less than 5% for the projected SOFC lifetime.

  19. Potential for microbial oxidation of ferrous iron in basaltic glass.

    PubMed

    Xiong, Mai Yia; Shelobolina, Evgenya S; Roden, Eric E

    2015-05-01

    Basaltic glass (BG) is an amorphous ferrous iron [Fe(II)]-containing material present in basaltic rocks, which are abundant on rocky planets such as Earth and Mars. Previous research has suggested that Fe(II) in BG can serve as an energy source for chemolithotrophic microbial metabolism, which has important ramifications for potential past and present microbial life on Mars. However, to date there has been no direct demonstration of microbially catalyzed oxidation of Fe(II) in BG. In this study, three different culture systems were used to investigate the potential for microbial oxidation of Fe(II) in BG, including (1) the chemolithoautotrophic Fe(II)-oxidizing, nitrate-reducing "Straub culture"; (2) the mixotrophic Fe(II)-oxidizing, nitrate-reducing organism Desulfitobacterium frappieri strain G2; and (3) indigenous microorganisms from a streambed Fe seep in Wisconsin. The BG employed consisted of clay and silt-sized particles of freshly quenched lava from the TEB flow in Kilauea, Hawaii. Soluble Fe(II) or chemically reduced NAu-2 smectite (RS) were employed as positive controls to verify Fe(II) oxidation activity in the culture systems. All three systems demonstrated oxidation of soluble Fe(II) and/or structural Fe(II) in RS, whereas no oxidation of Fe(II) in BG material was observed. The inability of the Straub culture to oxidize Fe(II) in BG was particularly surprising, as this culture can oxidize other insoluble Fe(II)-bearing minerals such as biotite, magnetite, and siderite. Although the reason for the resistance of the BG toward enzymatic oxidation remains unknown, it seems possible that the absence of distinct crystal faces or edge sites in the amorphous glass renders the material resistant to such attack. These findings have implications with regard to the idea that Fe(II)-Si-rich phases in basalt rocks could provide a basis for chemolithotrophic microbial life on Mars, specifically in neutral-pH environments where acid-promoted mineral dissolution and

  20. Potential for microbial oxidation of ferrous iron in basaltic glass.

    PubMed

    Xiong, Mai Yia; Shelobolina, Evgenya S; Roden, Eric E

    2015-05-01

    Basaltic glass (BG) is an amorphous ferrous iron [Fe(II)]-containing material present in basaltic rocks, which are abundant on rocky planets such as Earth and Mars. Previous research has suggested that Fe(II) in BG can serve as an energy source for chemolithotrophic microbial metabolism, which has important ramifications for potential past and present microbial life on Mars. However, to date there has been no direct demonstration of microbially catalyzed oxidation of Fe(II) in BG. In this study, three different culture systems were used to investigate the potential for microbial oxidation of Fe(II) in BG, including (1) the chemolithoautotrophic Fe(II)-oxidizing, nitrate-reducing "Straub culture"; (2) the mixotrophic Fe(II)-oxidizing, nitrate-reducing organism Desulfitobacterium frappieri strain G2; and (3) indigenous microorganisms from a streambed Fe seep in Wisconsin. The BG employed consisted of clay and silt-sized particles of freshly quenched lava from the TEB flow in Kilauea, Hawaii. Soluble Fe(II) or chemically reduced NAu-2 smectite (RS) were employed as positive controls to verify Fe(II) oxidation activity in the culture systems. All three systems demonstrated oxidation of soluble Fe(II) and/or structural Fe(II) in RS, whereas no oxidation of Fe(II) in BG material was observed. The inability of the Straub culture to oxidize Fe(II) in BG was particularly surprising, as this culture can oxidize other insoluble Fe(II)-bearing minerals such as biotite, magnetite, and siderite. Although the reason for the resistance of the BG toward enzymatic oxidation remains unknown, it seems possible that the absence of distinct crystal faces or edge sites in the amorphous glass renders the material resistant to such attack. These findings have implications with regard to the idea that Fe(II)-Si-rich phases in basalt rocks could provide a basis for chemolithotrophic microbial life on Mars, specifically in neutral-pH environments where acid-promoted mineral dissolution and

  1. The formation of crystals in glasses containing rare earth oxides

    SciTech Connect

    Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod; Siong, Khoo Kok; Ngatiman, Mohammad Fadzlee; Said, Riduan Mt

    2014-02-12

    Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd{sub 2}O{sub 3}–22.7CeO{sub 2}–11.7La{sub 2}O{sub 3}–10.9PrO{sub 2}–1.3Eu{sub 2}O{sub 3}–1.3Gd{sub 2}O{sub 3}–8.1Sm{sub 2}O{sub 3}–4.8Y{sub 2}O{sub 3} with a baseline glass of composition 60.2SiO{sub 2}–16.0B{sub 2}O{sub 3}–12.6Na{sub 2}O–3.8Al{sub 2}O{sub 3}–5.7CaO–1.7ZrO{sub 2}. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La{sub 2}O{sub 3} and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO{sub 5}) and oxyapatite (Ca{sub 2}La{sub 8}Si{sub 6}O{sub 26}) were found in glasses containing La{sub 2}O{sub 3}, while oxyapatite (Ca{sub 2}La{sub 8}Si{sub 6}O{sub 26} and NaNd{sub 9}Si{sub 6}O{sub 26}) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (T{sub L}) of the glasses containing 5%, 10% and 15% La{sub 2}O{sub 3} were 800°C, 959°C and 986°C, respectively; while T{sub L} was 825°C, 1059°C and 1267°C for glasses

  2. Thermal, structural and spectroscopic properties of heavy metal oxide glass and glass-ceramics doped with Er3+ ions

    NASA Astrophysics Data System (ADS)

    Ragin, Tomasz; Zmojda, Jacek; Kochanowicz, Marcin; Miluski, Piotr; Jelen, Piotr; Sitarz, Maciej; Dorosz, Dominik

    2015-09-01

    In this paper, bismuth-germanate oxide glass doped with erbium ions has been synthesized. Composition of the glass has been chosen in terms of the low phonon energy and good transparency in the infrared region. Transparent glass-ceramics sample has been prepared by controlled crystallization process. Fourier transform infrared spectroscopy (FTIR) has been used to determinate structural properties of samples. The absorption coefficient, the luminescence intensity in visible and infrared region and the differential scanning calorimetry have been examined. Difference in the emission intensity and shape of the luminescence bands indicates the presence of crystalline phases in obtained glass-ceramics sample.

  3. Glass coated compressible solid oxide fuel cell seals

    NASA Astrophysics Data System (ADS)

    Rautanen, M.; Thomann, O.; Himanen, O.; Tallgren, J.; Kiviaho, J.

    2014-02-01

    With the growing footprint of solid oxide fuel cell stacks, there is a need to extend the operating range of compressible gaskets towards lower stress levels. This article describes a method to manufacture SOFC seals by coating a compressible sealing material (Thermiculite 866) with glass to obtain good sealing performance even at compression stresses as low as 0.1 MPa. Glass layer can be coated using an organic carrier consisting of terpineol, ethanol and ethyl cellulose. The coated seals can be heat treated by simply ramping the temperature up to operating temperature at 60 Kh-1 and therefore no extra steps, which are typical to glass seals, are required. Coated seals were manufactured using this route and evaluated both ex-situ and in a real stack. Leak rates of 0.1-0.3 ml (m min)-1 were measured at 2-25 mbar overpressure using 50/50 H2/N2. A 30-cell stack was manufactured and tested using coated seals. At nominal operating conditions of 0.25 A cm-2 and 650 °C average cathode temperature, 46% fuel utilization and 20% air utilization the stack had a total hydrogen cross leak of 60 ml min-1 corresponding to 0.7% of the inlet hydrogen flow rate.

  4. Glass Frit Filters for Collecting Metal Oxide Nanoparticles

    NASA Technical Reports Server (NTRS)

    Ackerman, John; Buttry, Dan; Irvine, Geoffrey; Pope, John

    2005-01-01

    Filter disks made of glass frit have been found to be effective as means of high-throughput collection of metal oxide particles, ranging in size from a few to a few hundred nanometers, produced in gas-phase condensation reactors. In a typical application, a filter is placed downstream of the reactor and a valve is used to regulate the flow of reactor exhaust through the filter. The exhaust stream includes a carrier gas, particles, byproducts, and unreacted particle-precursor gas. The filter selectively traps the particles while allowing the carrier gas, the byproducts, and, in some cases, the unreacted precursor, to flow through unaffected. Although the pores in the filters are much larger than the particles, the particles are nevertheless trapped to a high degree: Anecdotal information from an experiment indicates that 6-nm-diameter particles of MnO2 were trapped with greater than 99-percent effectiveness by a filtering device comprising a glass-frit disk having pores 70 to 100 micrometer wide immobilized in an 8-cm-diameter glass tube equipped with a simple twist valve at its downstream end.

  5. Oxidation behavior of Cr(III) during thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides.

    PubMed

    Mao, Linqiang; Gao, Bingying; Deng, Ning; Liu, Lu; Cui, Hao

    2016-02-01

    The oxidation behavior of Cr(III) during the thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides (NaCl, KCl, MgCl2, and CaCl2) was investigated. The amounts of Cr(III) oxidized at various temperatures and heating times were determined, and the Cr-containing species in the residues were characterized. During the transformation of chromium hydroxide to Cr2O3 at 300 °C approximately 5% of the Cr(III) was oxidized to form intermediate compounds containing Cr(VI) (i.e., CrO3), but these intermediates were reduced to Cr2O3 when the temperature was above 400 °C. Alkali and alkaline earth metals significantly promoted the oxidation of Cr(III) during the thermal drying process. Two pathways were involved in the influences the alkali and alkaline earth metals had on the formation of Cr(VI). In pathway I, the alkali and alkaline earth metals were found to act as electron transfer agents and to interfere with the dehydration process, causing more intermediate Cr(VI)-containing compounds (which were identified as being CrO3 and Cr5O12) to be formed. The reduction of intermediate compounds to Cr2O3 was also found to be hindered in pathway I. In pathway II, the alkali and alkaline earth metals were found to contribute to the oxidation of Cr(III) to form chromates. The results showed that the presence of alkali and alkaline earth metals significantly increases the degree to which Cr(III) is oxidized during the thermal drying of chromium-containing sludge.

  6. Ferric oxide quantum dots in stable phosphate glass system and their magneto-optical study

    SciTech Connect

    Garaje, Sunil N.; Apte, Sanjay K.; Kumar, Ganpathy; Panmand, Rajendra P.; Naik, Sonali D.; Mahajan, Satish M.; Chand, Ramesh; Kale, Bharat B.

    2013-02-15

    Graphical abstract: We report synthesis of ferric oxide embedded low melting phosphate glass nanocomposite and also the effect of ferric oxide nanoparticles (NCs) content on the optical and magneto-optical properties of the glasses. Faraday rotation of the glass nanocomposites was measured and showed variation in Verdet constant with concentration of ferric oxide. Interestingly, the host glass itself showed fairly good Verdet constant (11.5°/T cm) and there is a threefold enhancement in the Verdet constant of ferric oxide quantum dot-glass nanocomposite. Highlights: ► We synthesize ferric oxide embedded low melting stable phosphate glass nanocomposite. ► Glasses doped with 0.25 and 2% ferric oxide show particle size in the range of 4–12 nm. ► The host phosphate glass itself shows fairly good Verdet constant (11.5°/T cm). ► Glasses doped with 0.25% ferric oxide show high Verdet constant (30.525°/T cm). ► The as synthesis glasses may have potential application in magneto optical devices. -- Abstract: Herein, we report the synthesis of ferric oxide embedded low melting phosphate glass nanocomposite and also the effect of ferric oxide nanoparticles content on the optical and magneto-optical properties of the glasses. The optical study clearly showed red shift in optical cut off with increasing ferric oxide concentration. The band gap of the host glass was observed to be 3.48 eV and it shifted to 3.14 eV after doping with ferric oxide. The glasses doped with 0.25 and 2% ferric oxide showed particle size of 4–6 nm and 8–12 nm, respectively. Faraday rotation of the glass nanocomposites was measured and showed variation in the Verdet constant as per increasing concentration of ferric oxide. Interestingly, the host glass itself showed fairly good Verdet constant (11.5°/T cm) and threefold enhancement was observed in the Verdet constant of ferric oxide quantum dot-glass nanocomposite.

  7. Reduced graphene oxide-titanate hybrids: Morphologic evolution by alkali-solvothermal treatment and applications in water purification

    NASA Astrophysics Data System (ADS)

    Nguyen-Phan, Thuy-Duong; Pham, Viet Hung; Kim, Eui Jung; Oh, Eun-Suok; Hur, Seung Hyun; Chung, Jin Suk; Lee, Byunghwan; Shin, Eun Woo

    2012-03-01

    The reduced graphene oxide-titanate (RGO-Ti) hybrids were fabricated by incorporating spherical TiO2 nanoparticles with graphene oxide (GO) layers in aqueous NaOH solution following by the solvothermal treatment. The morphologic evolution of RGO-Ti hybrid by varying alkali-solvothermal temperatures has been first investigated. The titanate nanosheets peeled off, folded and scrolled into tubular structure; and eventually, cracked and destroyed to be ribbon-like shape. The chemical interaction and attachment of low-dimensional titanate onto RGO layers and the reverse order were elucidated by X-ray photoelectron spectra. The hybrids in sheet and tubular titanate structures possessed larger surface areas (>350 m2/g) and higher pore volumes (>1 cm3/g) than the other. The presence of RGO sheets as a two-dimensional (2D) platform for the deposition of titanate significantly promoted much better adsorptivity of dye contaminants compared to pure materials.

  8. The Oxidation State of Europium in Halide Glasses

    PubMed Central

    Weber, J.K.R.; Vu, M.; Paßlick, C.; Schweizer, S.; Brown, D.E.; Johnson, C.E.; Johnson, J.A.

    2012-01-01

    The luminescent properties of divalent europium ions can be exploited to produce storage phosphors for x-ray imaging applications. The relatively high cost and limited availability of divalent europium halides makes it desirable to synthesize them from the readily available trivalent salts. In this work, samples of pure EuCl3 and fluoride glass melts doped with EuCl3 were processed at 700-800 °C in an inert atmosphere furnace. The Eu oxidation state in the resulting materials was determined using fluorescence and Mössbauer spectroscopy. Heat treatment of pure EuCl3 for 10 minutes at 710 °C resulted in a material comprising approximately equal amounts of Eu2+ and Eu3+. Glasses made using mixtures of EuCl2 and EuCl3 in the starting material contained both oxidation states. This paper describes the sample preparation and analysis and discusses the results in the context of chemical equilibria in the melts. PMID:22101252

  9. Measurements of alkali concentrations in an oxygen-natural gas-fired soda-lime-silica glass furnace

    SciTech Connect

    S. G. Buckley; P. M. Walsh; D. w. Hahn; R. J. Gallagher; M. K. Misra; J. T. Brown; F. Quan; K. Bhatia; V. I. Henry; R. D. Moore

    1999-10-18

    Sodium species vaporized from melting batch and molten glass in tank furnaces are the principal agents of corrosion of superstructure refractory and main contributors to emissions of particulate matter from glass melting. The use of oxygen in place of air for combustion of natural gas reduces particulate emissions, but is thought to accelerate corrosion in some melting tanks. Methods for measuring sodium are under investigation as means for identifying the volatilization, transport, and deposition mechanisms and developing strategies for control. Three separate methods were used to measure the concentrations of sodium species at various locations in an oxygen-natural gas-fired soda-lime-silica glass melting tank. Measurements were made inside the furnace using the absorption of visible light and in the flue duct using Laser-Induced Breakdown Spectroscopy (LIBS). Measurements in both the furnace and flue were also made by withdrawing and analyzing samples of the furnace gas.

  10. Alkali-Metal-Ion-Functionalized Graphene Oxide as a Superior Anode Material for Sodium-Ion Batteries.

    PubMed

    Wan, Fang; Li, Yu-Han; Liu, Dai-Huo; Guo, Jin-Zhi; Sun, Hai-Zhu; Zhang, Jing-Ping; Wu, Xing-Long

    2016-06-01

    Although graphene oxide (GO) has large interlayer spacing, it is still inappropriate to use it as an anode for sodium-ion batteries (SIBs) because of the existence of H-bonding between the layers and ultralow electrical conductivity which impedes the Na(+) and e(-) transformation. To solve these issues, chemical, thermal, and electrochemical procedures are traditionally employed to reduce GO nanosheets. However, these strategies are still unscalable, consume high amounts of energy, and are expensive for practical application. Here, for the first time, we describe the superior Na storage of unreduced GO by a simple and scalable alkali-metal-ion (Li(+) , Na(+) , K(+) )-functionalized process. The various alkali metals ions, connecting with the oxygen on GO, have played different effects on morphology, porosity, degree of disorder, and electrical conductivity, which are crucial for Na-storage capabilities. Electrochemical tests demonstrated that sodium-ion-functionalized GO (GNa) has shown outstanding Na-storage performance in terms of excellent rate capability and long-term cycle life (110 mAh g(-1) after 600 cycles at 1 A g(-1) ) owing to its high BET area, appropriate mesopore, high degree of disorder, and improved electrical conductivity. Theoretical calculations were performed using the generalized gradient approximation (GGA) to further study the Na-storage capabilities of functionalized GO. These calculations have indicated that the Na-O bond has the lowest binding energy, which is beneficial to insertion/extraction of the sodium ion, hence the GNa has shown the best Na-storage properties among all comparatives functionalized by other alkali metal ions.

  11. Highly sensitive sensors for alkali metal ions based on complementary-metal-oxide-semiconductor-compatible silicon nanowires

    NASA Astrophysics Data System (ADS)

    Zhang, Guo-Jun; Agarwal, Ajay; Buddharaju, Kavitha D.; Singh, Navab; Gao, Zhiqiang

    2007-06-01

    Highly sensitive sensors for alkali metal ions based on complementary-metal-oxide- semiconductor-compatible silicon nanowires (SiNWs) with crown ethers covalently immobilized on their surface are presented. A densely packed organic monolayer terminated with amine groups is introduced to the SiNW surface via hydrosilylation. Amine-modified crown ethers, acting as sensing elements, are then immobilized onto the SiNWs through a cross-linking reaction with the monolayer. The crown ether-functionalized SiNWs recognize Na+ and K+ according to their complexation ability to the crown ethers. The SiNW sensors are highly selective and capable of achieving an ultralow detection limit down to 50nM, over three orders of magnitude lower than that of conventional crown ether-based ion-selective electrodes.

  12. A structural investigation of the alkali metal site distribution within bioactive glass using neutron diffraction and multinuclear solid state NMR.

    PubMed

    Martin, Richard A; Twyman, Helen L; Rees, Gregory J; Smith, Jodie M; Barney, Emma R; Smith, Mark E; Hanna, John V; Newport, Robert J

    2012-09-21

    The atomic-scale structure of Bioglass and the effect of substituting lithium for sodium within these glasses have been investigated using neutron diffraction and solid state magic angle spinning (MAS) NMR. Applying an effective isomorphic substitution difference function to the neutron diffraction data has enabled the Na-O and Li-O nearest-neighbour correlations to be isolated from the overlapping Ca-O, O-(P)-O and O-(Si)-O correlations. These results reveal that Na and Li behave in a similar manner within the glassy matrix and do not disrupt the short range order of the network former. Residual differences are attributed solely to the variation in ionic radius between the two species. Successful simplification of the 2 < r (Å) < 3 region via the difference method has enabled all the nearest neighbour correlations to be deconvolved. The diffraction data provides the first direct experimental evidence of split Na-O nearest-neighbour correlations in these melt quench bioactive glasses, and an analogous splitting of the Li-O correlations. The observed correlations are attributed to the metal ions bonded either to bridging or to non-bridging oxygen atoms. (23)Na triple quantum MAS (3QMAS) NMR data corroborates the split Na-O correlations. The structural sites present will be intimately related to the release properties of the glass system in physiological fluids such as plasma and saliva, and hence to the bioactivity of the material. Detailed structural knowledge is therefore a prerequisite for optimizing material design. PMID:22868255

  13. Tuning indium tin oxide work function with solution-processed alkali carbonate interfacial layers for high-efficiency inverted organic photovoltaic cells.

    PubMed

    Chen, Fei; Chen, Qi; Mao, Lin; Wang, Yixin; Huang, Xun; Lu, Wei; Wang, Bing; Chen, Liwei

    2013-12-01

    Selective electron collection by an interfacial layer modified indium tin oxide cathode is critically important for achieving high-efficiency inverted structure organic photovoltaic (OPV) cells. Here, we demonstrate that solution-processed alkali carbonates, such as Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, are good interfacial layer materials. Both carbonate concentration and annealing conditions can affect cathode work function and surface roughness. By proper optimization, different alkali carbonates can be almost equally effective as the cathode interfacial layer. Furthermore, good device performance can be achieved at a low annealing temperature (<50 ° C), which allows for potential applications in solution-processed inverted OPV cells on plastic substrates. This work indicates that alkali carbonates, not just cesium carbonate, are valid choices as the cathode interlayer in inverted OPV devices.

  14. Impact of Alkali Source on Vitrification of SRS High Level Waste

    SciTech Connect

    LAMBERT, D. P.; MILLER, D. H.; PEELER, D. K.; SMITH, M. E.; STONE, M. E.

    2005-09-08

    The Defense Waste Processing Facility (DWPF) Savannah River Site is currently immobilizing high level nuclear waste sludge by vitrification in borosilicate glass. The processing strategy involves blending a large batch of sludge into a feed tank, washing the sludge to reduce the amount of soluble species, then processing the large ''sludge batch'' through the DWPF. Each sludge batch is tested by the Savannah River National Laboratory (SRNL) using simulants and tests with samples of the radioactive waste to ''qualify'' the batch prior to processing in the DWPF. The DWPF pretreats the sludge by first acidifying the sludge with nitric and formic acid. The ratio of nitric to formic acid is adjusted as required to target a final glass composition that is slightly reducing (the target is for {approx}20% of the iron to have a valence of two in the glass). The formic acid reduces the mercury in the feed to elemental mercury which is steam stripped from the feed. After a concentration step, the glass former (glass frit) is added as a 50 wt% slurry and the batch is concentrated to approximately 50 wt% solids. The feed slurry is then fed to a joule heated melter maintained at 1150 C. The glass must meet both processing (e.g., viscosity and liquidus temperature) and product performance (e.g., durability) constraints The alkali content of the final waste glass is a critical parameter that affects key glass properties (such as durability) as well as the processing characteristics of the waste sludge during the pretreatment and vitrification processes. Increasing the alkali content of the glass has been shown to improve the production rate of the DWPF, but the total alkali in the final glass is limited by constraints on glass durability and viscosity. Two sources of alkali contribute to the final alkali content of the glass: sodium salts in the waste supernate and sodium and lithium oxides in the glass frit added during pretreatment processes. Sodium salts in the waste supernate

  15. Formation of oxide layers on aluminum, niobium, and tantalum in molten alkali metal carbonates

    NASA Astrophysics Data System (ADS)

    Nikitina, E. V.; Kazakovtseva, N. A.

    2013-08-01

    The electrochemical synthesis of niobium, tantalum, and aluminum oxide nanolayers is studied in the melt of lithium, sodium, and potassium carbonates with various additives to a salt phase in an oxidizing atmosphere at a temperature of 773 and 873 K. A scheme is proposed for high-temperature anion local activation of the process.

  16. Lead extraction from cathode ray tube funnel glass melted under different oxidizing conditions.

    PubMed

    Okada, Takashi

    2015-07-15

    Lead was extracted into hydrochloric acid from cathode ray tube funnel glass melted under reducing atmosphere, oxidizing atmosphere, or a sequential combination of both to mechanistically investigate effects of the melting atmosphere on lead extraction. Melting funnel glass in a reductive atmosphere led to the generation of metallic lead particles that were readily soluble in the acid, increasing the quantity of lead extracted into the acid. Meanwhile, the glass product obtained after melting funnel glass in an oxidative atmosphere exhibited higher corrosion resistance in the acid, and the quantity of lead extracted from the treated glass decreased. However, Na2CO3 addition to the glass during melting hindered the enhancement of corrosion resistance and the immobilization of lead in the acid. X-ray photoelectron spectroscopic analysis of the treated glass samples showed that the positions of the peak or the profiles of the spectra attributed to Pb 4f, Si 2p, and O 1s signals were modified by oxidative melting, an indication that oxidative melting results in structural changes in the SiO2 framework of the glass.

  17. Preparation of oxide glasses from metal alkoxides by sol-gel method

    NASA Technical Reports Server (NTRS)

    Kamiya, K.; Yoko, T.; Sakka, S.

    1987-01-01

    An investigation is carried out on the types of siloxane polymers produced in the course of the hydrolysis of silicon tetraethoxide, as well as the preparation of oxide glasses from metal alkoxides by the sol-gel method.

  18. Preparation of Bi-Sr-Ca-Cu-O superconductors from oxide-glass precursors

    NASA Astrophysics Data System (ADS)

    Hinks, D. G.; Soderholm, L.; Capone, D. W., II; Dabrowski, B.; Mitchell, A. W.

    1988-08-01

    Efforts to synthesize the new Ca-Sr-Bi-Cu-O superconductors from amorphous glasses are reported. These glasses are produced by quenching melts of the constituent oxides, followed by firing to produce the supercoducting phase. This synthetic route produces denser, more uniform samples than those obtained from firing intimate mixtures of the constituent binary oxides and carbonates. Ultimately, this technique may yield pure materials with enhanced bulk properties.

  19. Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides

    DOEpatents

    Gordon, John Howard; Alvare, Javier

    2016-10-25

    Alkali metals and sulfur may be recovered from alkali monosulfide and polysulfides in an electrolytic process that utilizes an electrolytic cell having an alkali ion conductive membrane. An anolyte solution includes an alkali monosulfide, an alkali polysulfide, or a mixture thereof and a solvent that dissolves elemental sulfur. A catholyte includes molten alkali metal. Applying an electric current oxidizes sulfide and polysulfide in the anolyte compartment, causes alkali metal ions to pass through the alkali ion conductive membrane to the catholyte compartment, and reduces the alkali metal ions in the catholyte compartment. Liquid sulfur separates from the anolyte solution and may be recovered. The electrolytic cell is operated at a temperature where the formed alkali metal and sulfur are molten.

  20. Fabrication and Characterization of Oxide Heterojunctions Prepared by Electrodepositing Cuprous Oxide on Conductive Glasses

    NASA Astrophysics Data System (ADS)

    Hsu, Fu-Yung; Liu, Shiu-Jen; Lu, Yung-I.; Chen, Liang-Yu; Fang, Hau-Wei

    2009-03-01

    The properties of oxide heterojunctions prepared by electrodepositing Cu2O on commercial F-doped SnO2 (FTO) and Sn-doped In2O3 (ITO) glasses were studied. The X-ray diffraction patterns showed that Cu2O films grown on both FTO and ITO glasses are mainly (111)-oriented. The optical band gap of the electrodeposited Cu2O films grown on FTO glass determined from the absorption spectrum is about 2 eV. A peak with a wavelength of 622 nm that could be correlated to the near band edge emission was observed in the photoluminescence spectrum. Nonlinear and rectifying behaviors were observed in the current-voltage measurements of these fabricated heterojunctions. Furthermore, the high turn-on voltage of 4.7 V indicates the absence of defect states at the interface of the Cu2O/FTO heterojunction. Moreover, thermal annealing on Cu2O/FTO heterojunctions may cause Cu diffusion into the n-type layers.

  1. Concentration dependences of elastooptic coefficients of germanate glasses containing lead and bismuth oxides

    SciTech Connect

    Rabukhin, A.I.

    1995-11-01

    Concentration dependences of elastooptic coefficients of lead - bismuth - germanate glasses with compositions from virtually the entire range of glass formation in the system PbO-Bi{sub 2}O{sub 3}-GeO{sub 2} are investigated. Partial elastooptic coefficients of the oxide ingredients of the investigated glasses are determined. The results are interpreted with consideration of the nature of the elastooptic interaction in glasses subjected to uniaxial stress. The data can be used for designing compositions of optical media for the light and acoustic lines of acoustooptical devices.

  2. Preventing the accelerated low-temperature oxidation of MoSi{sub 2} (pesting) by the application of superficial alkali-salt layers

    SciTech Connect

    Cockeram, B.V.; Wang, G.; Rapp, R.A.

    1996-02-01

    Previous work showed that MoSi{sub 2} diffusion coatings formed by a NaF-activated pack cementation process did not pest. A Na-Al-oxide by-product layer resulting from the NaF activator formed a Na-silicate layer to passivate MoSi{sub 2}. Superficial NaF layers were then used to prevent the pesting of MoSi{sub 2} diffusion coatings that were otherwise susceptible to pest disintegration. In this study, the use of superficial alkali-salt layers to prevent the accelerated oxidation of bulk MoSi{sub 2} at 500{degrees}C is investigated more broadly. The application of Na-halide, KF, LiF, Na{sub 2}B{sub 4}O{sub 7}, or Na-silicate layers prior to oxidation prevented accelerated oxidation and pesting for at least 2000 hr at 500{degrees}C in air. The formation of a fast-growing, Na-silicate layer passivates MoSi{sub 2}. The MoO{sub 3} that forms during oxidation absorbs sodium by intercalation to form stable Na-molybdate precipitates. Na{sub 2}B{sub 4}O{sub 7}, Na-silicate, LiF, and KF prevented accelerated oxidation at 500{degrees}C by a similar mechanism. The application of alkali-halide salts is a simple, effective solution to prevent the accelerated oxidation and pesting of MoSi{sub 2}.

  3. Formation and durability of hydrated layers for several oxide glasses

    SciTech Connect

    Nishii, Junji; Akai, Tomoko; Yamashita, Masaru; Yamanaka, Hiroshi; Wakabayashi, Hajimu

    1995-12-31

    Formations and durabilities of hydrated layers were compared between a soda-aluminosilicate (NAS), a soda-lime-aluminosilicate (NCAS) and a soda-lime-alumino-borosilicate (NCABS) glasses. The first step of the study was to prepare the optically transparent hydrated layers on the surface of specimens by an autoclave (400 C, 20 kgf/cm{sup 2}) treatment. Distributions of OH groups in hydrated layers were analyzed by an etch sectioning and FTIR measurement. The rates of hydration of the glasses were in the order NAS {much_gt} NCAS > NCABS. The hydration of the NCABS glass, which is a modified nuclear waste glass, required the treatment longer than those of the NAS and NCAS glasses. In the second step, the authors investigated the durabilities of hydrated layers by immersing the specimens into a distilled water at 100 C. The dissolutions of hydrated layers were confirmed for each glass. The dissolution rates of hydrated layers were in the order NCAS > NCABS {much_gt} NAS. It has become apparent by an XPS analysis that the highest durability of the hydrated NAS glass was due to the formation of a sodium free Al{sub 2}O{sub 3}-SiO{sub 2} layer on the surface. The hydrated layer of the NCAS glass, while the sodium ions were almost leached out during immersion, dissolved to water most quickly than those of other glasses. In the hydrated layer of the NCABS glass, a half amount of sodium and boron ions remained and inhibited the dissolution of hydrated layer.

  4. Chemical durability of lead-oxide-based, thick-film binder glasses

    SciTech Connect

    Mattox, D.M.; Robinson, J.H.

    1997-05-01

    Lead-oxide-bearing glasses are incompatible with aluminum nitride metallizations, and federal legislation is recommending their replacement in thick-film electronics and labeling. To evaluate alternatives, the benchmark chemical durabilities of the lead borosilicate and lead aluminate thick-film binder glasses have been determined. Aluminum oxide (Al{sub 2}O{sub 3}) benefits water durability moderately, acid durability substantially, and basic durability indistinguishably. The rate of attack in water is approximately two orders of magnitude greater than for soda-lime glass. The thermal contractions of the glasses are compatible. An apparent, spontaneous phase separation in the Al{sub 2}O{sub 3}-free glass is suppressed by Al{sub 2}O{sub 3} that is included as a batch component.

  5. Self-sustained fracture waves in a lead oxide-silica glass

    NASA Astrophysics Data System (ADS)

    Chaudhri, M. Munawar

    2011-07-01

    Using high-speed framing photography operating at 500000 frames per second, it has been shown that in Prince Rupert's drops of a lead oxide-silica glass containing 24% by weight of lead oxide, the fracture waves propagate at a stable and self-sustained manner at a speed of (1300 ± 100) m s-1. This fracture wave speed is close to the terminal crack speed in the glass. These results, along with those from Prince Rupert's drops of soda-lime glass reported by us earlier, confirm that the speed of a self-sustained fracture wave in a glass is controlled by the terminal speed of individual cracks in the glass.

  6. Effect of UV exposure on photochromic glasses doped with transition metal oxides

    NASA Astrophysics Data System (ADS)

    El-Zaiat, S. Y.; Medhat, M.; Omar, Mona F.; Shirif, Marwa A.

    2016-07-01

    Silver halide photochromic glasses doped with one of the transition metal oxides, (Ti O2), (CoO),(Cr2 O3) are prepared using the melt quench technique. Glass samples are exposed to a UV source for 20 min. Spectral reflectance and transmittance at normal incidence of the prepared glasses are recorded before and after UV exposure with a double beam spectrophotometer in the spectral range 200-2500 nm. Dispersion parameters such as: single oscillator energy, dispersion energy and Abbe's number are deduced and compared. Absorption dispersion parameters, like optical energy gap for direct and indirect transitions, Urbach energy and steepness parameter, are deduced for the different glass prepared. Reflection loss, molar refractivity and electronic polarizability are deduced and compared. The effect of UV light exposure of these glasses on transmittance, reflectance, the linear and the predicted nonlinear optical parameters are investigated and discussed for the three transition metals. Nonlinear parameters increase in the three glass samples after UV exposure.

  7. Raman and Photoluminescence Spectroscopy of Er(3+) Doped Heavy Metal Oxide Glasses

    NASA Technical Reports Server (NTRS)

    Dyer, Keith; Pan, Zheng-Da; Morgan, Steve

    1997-01-01

    The potential applications of rare-earth ion doped materials include fiber lasers which can be pumped conveniently by infrared semiconductor laser diodes. The host material systems most widely studied are fluoride crystals and glasses because fluorides have low nonradiative relaxation rates due to their lower phonon energies. However, the mechanical strength, chemical durability and temperature stability of the oxide glasses are generally much better than fluoride glasses. The objective of this research was to investigate the optical and spectroscopic properties of Er(3+)-doped lead-germanate and lead-tellurium-germanate glasses. The maximum vibrational energy of lead-tellurium-germanate glasses are in the range of 740-820/cm, intermediate between those of silicate (1150/cm) and fluoride (530/cm) glasses.

  8. Structural characterization of germanium-arsenic-sulfur chalcogenide glasses and understanding structural relaxation in oxide glasses

    NASA Astrophysics Data System (ADS)

    Soyer-Uzun, Sezen

    The structures of chalcogenide glasses in the GexAsx S100-2x system with 33.3 ≤ 100-2x ≤ 70.0 are investigated using neutron/x-ray diffraction. Ge and As atoms are primarily heteropolar bonded to S atoms in glasses near stoichiometry (x ≤ 18.2). Large scale three-dimensional structural models obtained from reverse Monte Carlo (RMC) simulations are used to investigate the nature of intermediate-range structural order in these ternary glasses. Heteropolar bonded mixed GeS2 and As2S3 network in glasses with compositions near stoichiometry is transformed into a heterogeneous glass with mixed GeS2 network and As-rich clusters with increasing S-deficiency. The latter structure is largely homogenized with further increase in metal content. Combined neutron/x-ray diffraction, Ge and As K-edge EXAFS and Raman spectroscopy are employed to study the compositional dependence of the short- and intermediate- range structures of As-rich GexAsyS 100-x-y glasses with x:y = 1:17.3. The structures of glasses with compositions near stoichiometry consist mainly of heteropolar-bonded As2S 3 network. However, increasing metal content (x+y = 55) results in a novel glass consisting predominantly of As4S3 molecules with near-zero connectivity and dimensionality. Formation of As-As homopolar bonded structural regions that coexist with As4S3 molecules is observed with further increase in metal content (60 ≤ x+y ≤ 65). Structural mechanisms of densification of a molecular chalcogenide glass of composition Ge2.5As51.25S46.25 are studied in situ in a panoramic cell equipped with Moissanite (SiC) anvils at pressures ranging from 1 atm to 11 GPa at ambient temperature as well as ex situ on a sample quenched from 12 GPa in a multi-anvil cell using high-energy x-ray diffraction. 11B MAS NMR spectroscopy is employed to monitor relaxation kinetics of boron coordination environments in a borosilicate glass in response to temperature jumps. The relaxation timescale of the BO4:BO 3 ratio is

  9. Photocatalytic oxidation of nitrogen oxides using TiO2 loading on woven glass fabric.

    PubMed

    Wang, Haiqiang; Wu, Zhongbiao; Zhao, Weirong; Guan, Baohong

    2007-01-01

    TiO2 loading on woven glass fabric is applied to treat nitrogen oxides (NOx) by photocatalytic oxidation (PCO). In this paper, the PCO behavior of NO at high concentrations was studied by PCO of NOx at source levels (20-168 ppm). The PCO efficiency reached 27% in this experiment, while the inlet NOx concentration was 168 ppm (147 ppm NO). The dependency of the reaction rate on several key influencing factors (relative humidity, space time, inlet concentration, oxygen percentage) was also studied. The results illustrate that the resulting hydroxyl radical and active oxide play an important role in the oxidation of NOx. The reactions are limited by the thermodynamic equilibrium after ca. 15s space time. A possible explanation for the catalyst deactivation is the accumulation of nitric acid and nitrous acid on the TiO2 surface during the PCO of NOx. However, the photocatalytic activity can be recovered with a simple heat treatment. The results from the study of the effect of the inlet concentration were described with the Langmuir-Hinshelwood model. PMID:16806397

  10. Mixed polaronic-ionic conduction in lithium borate glasses and glass-ceramics containing copper oxide

    NASA Astrophysics Data System (ADS)

    Khalil, M. M. I.

    2007-03-01

    The effect of electric field strength on conduction in lithium borate glasses doped with CuO with different concentration was studied and the value of the jump distance of charge carrier was calculated. The conductivity measurements indicate that the conduction is due to non-adiabatic hopping of polarons and the activation energies are found to be temperature and concentration dependent. Lithium borate glasses are subjected to carefully-programmed thermal treatments which cause the nucleation and growth of crystalline phases. X-ray diffraction analysis confirmed the amorphous nature for the investigated glass sample and the formation of crystalline phase for annealed samples at 650 °C. The main separated crystalline phase is Li2B8O13. The scanning electron micrographs of some selected glasses showed a significant change in the morphology of the films investigated due to heat treatment of the glass samples. It was found that the dc-conductivity decreases with an increase of the HT temperature. The decrease of dc conductivity, with an increase of the HT temperature, can be related to the decrease in the number of free ions in the glass matrix. There is deviation from linearity at high temperature regions in the logσ-1/T plots for all investigated doped samples at a certain temperature at which the transition from polaronic to ionic conduction occurs. The hopping of small polarons is dominant at low temperatures, whereas the hopping of Li+ ions dominates at high temperatures.

  11. Eu oxidation state in fluorozirconate-based glass ceramics

    PubMed Central

    Henke, B.; Paßlick, C.; Keil, P.; Johnson, J. A.; Schweizer, S.

    2009-01-01

    The influence of InF3 doping and remelting on Eu-doped fluorozirconate-based glass ceramics was investigated using near-edge x-ray absorption and optical spectroscopy. It was found that the addition of InF3 to the melt decreases the Eu2+∕Eu3+ mole ratio, while remelting leads to a significant change in the Eu2+∕Eu3+ ratio in favor of Eu2+. Photoluminescence spectroscopy shows that additional annealing steps lead to the formation of BaCl2 nanoparticles in the glass. In as-made glass ceramics containing InF3, a phase transition of the nanoparticles from hexagonal to orthorhombic structure is observed. This phase transition is not observed in the remelted glasses studied here. PMID:20057931

  12. Eu oxidation state in fluorozirconate-based glass ceramics

    SciTech Connect

    Henke, B.; Passlick, C.; Keil, P.; Johnson, J. A.; Schweizer, S.

    2009-12-01

    The influence of InF{sub 3} doping and remelting on Eu-doped fluorozirconate-based glass ceramics was investigated using near-edge x-ray absorption and optical spectroscopy. It was found that the addition of InF{sub 3} to the melt decreases the Eu{sup 2+}/Eu{sup 3+} mole ratio, while remelting leads to a significant change in the Eu{sup 2+}/Eu{sup 3+} ratio in favor of Eu{sup 2+}. Photoluminescence spectroscopy shows that additional annealing steps lead to the formation of BaCl{sub 2} nanoparticles in the glass. In as-made glass ceramics containing InF{sub 3}, a phase transition of the nanoparticles from hexagonal to orthorhombic structure is observed. This phase transition is not observed in the remelted glasses studied here.

  13. Anomalous mechanical behavior and crack growth of oxide glasses

    NASA Astrophysics Data System (ADS)

    Seaman, Jared Hilliard

    This thesis is concerned with analytically describing anomalous mechanical behaviors of glass. A new slow crack growth model is presented that considers a semi-elliptical crack in a cylindrical glass rod subjected to 4-point bending that is both loaded statically and under a time-dependent load. This model is used to explain a suppression of the loading-rate dependency of ion-exchanged strengthened glass. The stress relaxation behavior of an ion-exchanged strengthened glass is then analyzed in view of a newly observed water-assisted surface stress relaxation mechanism. By making refinements to a time-dependent Maxwell material model for stress buildup and relaxation, the anomalous subsurface compressive stress peak in ion-exchanged strengthened glass is explained. The notion of water-assisted stress relaxation is extended to the crack tip, where high tensile stresses exist. A toughening effect has historically been observed for cracks aged at subcritical stress intensity factors, where crack tip stress relaxation is hypothesized. A simple fracture mechanics model is developed that estimates a shielding stress intensity factor that is then superimposed with the far-field stress intensity factor. The model is used to estimate anomalous "restart" times for aged cracks. The same model predicts a non-linear crack growth rate for cracks loaded near the static fatigue limit. Double cantilever beam slow crack growth experiments were performed and new slow crack growth data for soda-lime silicate glass was collected. Interpretation of this new experimental slow crack growth data suggests that the origin of the static fatigue limit in glass is due to water-assisted stress relaxation. This thesis combines a number of studies that offer a new unified understanding of historical anomalous mechanical behaviors of glass. These anomalies are interpreted as simply the consequence of slow crack growth and water-assisted surface stress relaxation.

  14. Chemical state analysis of trace-level alkali metals sorbed in micaceous oxide by total reflection X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Baba, Y.; Shimoyama, I.; Hirao, N.

    2016-10-01

    In order to determine the chemical states of radioactive cesium (137Cs or 134Cs) sorbed in clay minerals, chemical states of cesium as well as the other alkali metals (sodium and rubidium) sorbed in micaceous oxides have been investigated by X-ray photoelectron spectroscopy (XPS). Since the number of atoms in radioactive cesium is extremely small, we specially focused on chemical states of trace-level alkali metals. For this purpose, we have measured XPS under X-ray total reflection (TR) condition. For cesium, it was shown that ultra-trace amount of cesium down to about 100 pg cm-2 can be detected by TR-XPS. This amount corresponds to about 200 Bq of 137Cs (t1/2 = 30.2 y). It was demonstrated that ultra-trace amount of cesium corresponding to radioactive cesium level can be measured by TR-XPS. As to the chemical states, it was found that core-level binding energy in TR-XPS for trace-level cesium shifted to lower-energy side compared with that for thicker layer. A reverse tendency is observed in sodium. Based on charge transfer within a simple point-charge model, it is concluded that chemical bond between alkali metal and micaceous oxide for ultra-thin layer is more polarized that for thick layer.

  15. Sintering behavior of lanthanide-containing glass-ceramic sealants for solid oxide fuel cells

    SciTech Connect

    Goel, Ashutosh; Reddy, Allu Amarnath; Pascual, Maria J.; Gremillard, Laurent; Malchere, Annie; Ferreira, Jose M.

    2012-05-01

    This article reports on the influence of different lanthanides (La, Nd, Gd and Yb) on sintering behavior of alkaline-earth aluminosilicate glass-ceramics sealants for their application in solid oxide fuel cells (SOFC). All the glasses have been prepared by melt-quench technique. The in situ follow up of sintering behavior of glass powders has been done by high temperature - environmental scanning electron microscope (HT-ESEM) and hot-stage microscope (HSM) while the crystalline phase evolution and assemblage has been analyzed by x-ray diffraction (XRD) and scanning electron microscopy (SEM). All the glass compositions exhibit a glass-in-glass phase separation followed by two stage sintering resulting in well sintered glass powder compacts after heat treatment at 850 C for 1 h. Diopside (CaMgSi{sub 2}O{sub 6}) based phases constituted the major crystalline part in glass-ceramics followed by some minor phases. The increase in lanthanide content in glasses suppressed their tendency towards devitrification, thus, resulting in glass-ceramics with high amount of residual glassy phase (50-96 wt.%) which is expected to facilitate their self-healing behavior during SOFC operation. The electrical conductivity of the investigated glass-ceramics varied between (1.19 and 7.33) x 10{sup -7} S cm{sup -1} (750-800 C), and depended on the ionic field strength of lanthanide cations. Further experimentation with respect to the long term thermal and chemical stability of residual glassy phase under SOFC operation conditions along with high temperature viscosity measurements will be required in order to elucidate the potential of these glass-ceramics as self-healing sealants.

  16. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, S.; Boehm, L.; Volin, K.J.; Delbecq, C.J.

    1982-05-06

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS/sub 2/, B/sub 2/S/sub 2/ and SiS/sub 2/ in mixture with a glass modifier such as Na/sub 2/S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1 - X) Na/sub 2/O:XB/sub 2/S/sub 3/ is disclosed.

  17. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, Sherman; Boehm, Leah; Volin, Kenneth J.; Delbacq, Charles J.

    1985-01-01

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS.sub.2, B.sub.2 S.sub.3 and SiS.sub.2 in mixture with a glass modifier such as Na.sub.2 S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na.sub.2 O:XB.sub.2 S.sub.3 is disclosed.

  18. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, S.; Delbecq, C.J.; Volin, K.J.; Boehm, L.

    1984-02-21

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS[sub 2], B[sub 2]S[sub 3] and SiS[sub 2] in mixture with a glass modifier such as Na[sub 2]S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na[sub 2]O:XB[sub 2]S[sub 3] is disclosed. 4 figs.

  19. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, Sherman; Delbecq, Charles J.; Volin, Kenneth J.; Boehm, Leah

    1984-01-01

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS.sub.2, B.sub.2 S.sub.3 and SiS.sub.2 in mixture with a glass modifier such as Na.sub.2 S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na.sub.2 O:XB.sub.2 S.sub.3 is disclosed.

  20. Optical properties of borotellurite glasses containing metal oxides

    NASA Astrophysics Data System (ADS)

    Kaur, Nirmal; Khanna, Atul; Krishna, P. S. R.; González, Fernando

    2015-06-01

    Glass samples of the system: 5MxOy-20B2O3-75TeO2 : MxOy = WO3, Nb2O5, PbO, Nd2O3, Y2O3, Eu2O3 were prepared by melt quenching and characterized by X-ray diffraction, density, Differential Scanning Calorimetry, UV-visible and FTIR spectroscopy. XRD patterns confirmed the amorphous structure of all samples. Glass transition temperature was maximum in borotellurite glass containing Y2O3. Refractive index, atomic polarizability and basicity increased in the following order of ions: Y3+ < Eu3+ < Pb2+ < Nd3+ < Nb3+ < W6+. FTIR studies showed that PbO is outstanding in enhancing the concentration of tetrahedral borons in the borotellurite network.

  1. Elastic properties of silver borate glasses doped with praseodymium oxide

    SciTech Connect

    Gowda, G. V. Jagadeesha; Eraiah, B.

    2014-04-24

    A series of glasses xPr{sub 6}O{sub 11−}(35−x) Ag{sub 2}O−65B{sub 2}O{sub 3} with x=0, 0.1, 0.2, 0.3, 0.4 and 0.5 mol % were synthesized by melt quenching technique. Longitudinal and shear ultrasonic velocity were measured at 5 MHz frequency and at room temperature. Elastic moduli, Poisson's ratio and Debye temperature have been calculated from the measured density and ultrasonic velocity at room temperature. The experimental results indicate that the elastic constants depend upon the composition of the glasses. The role of the Pr{sub 6}O{sub 11} inside the glass network was discussed.

  2. Universal behavior of changes in elastic moduli of hot compressed oxide glasses

    NASA Astrophysics Data System (ADS)

    Svenson, Mouritz N.; Guerette, Michael; Huang, Liping; Lönnroth, Nadja; Mauro, John C.; Rzoska, Sylwester J.; Bockowski, Michal; Smedskjaer, Morten M.

    2016-05-01

    The elastic moduli of glasses are important for numerous applications, but predicting them based on their chemical composition and forming history remains a great challenge. In this study, we investigate the relationship between densification and changes in elastic moduli as a result of isostatic compression up to 1 GPa of various oxide compositions at elevated temperature (so-called hot compression). An approximately linear relationship is observed between the relative changes in density and elastic moduli across a variety of glass families, although these glasses exhibit a diverse range of structural responses during compression owing to their dramatically different chemistries.

  3. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, R.D.; McPheeters, C.C.

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  4. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, Raymond D.; McPheeters, Charles C.

    1980-01-01

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  5. Mössbauer study of conductive oxide glass

    SciTech Connect

    Matsuda, Koken; Kubuki, Shiro; Nishida, Tetsuaki

    2014-10-27

    Heat treatment of barium iron vanadate glass, BaO‐Fe{sub 2}O{sub 3}‐V{sub 2}O{sub 5}, at temperatures higher than crystallization temperature causes a marked decrease in resistivity (ρ) from several MΩcm to several Ωcm. {sup 57}Fe Mössbauer spectrum of heat-treated vanadate glass shows a marked decrease in quadrupole splitting (Δ) of Fe{sup III}, reflecting a structural relaxation, i.e., an increased symmetry of 'distorted' FeO{sub 4} and VO{sub 4} tetrahedra which are connected to each other by sharing corner oxygen atoms. Structural relaxation of 3D-network of vanadate glass accompanies a decrease in the activation energy for the conduction, reflecting a decreased energy gap between the donor level and conduction band. A marked increase in the conductivity was observed in CuO- or Cu{sub 2}O-containing barium iron vanadate glass after heat treatment at 450 °C for 30 min or more. 'n-type semiconductor model combined with small polaron hopping theory' was proposed in order to explain the high conductivity.

  6. Mössbauer study of conductive oxide glass

    NASA Astrophysics Data System (ADS)

    Matsuda, Koken; Kubuki, Shiro; Nishida, Tetsuaki

    2014-10-01

    Heat treatment of barium iron vanadate glass, BaO - Fe2O3- V2O5, at temperatures higher than crystallization temperature causes a marked decrease in resistivity (ρ) from several MΩcm to several Ωcm. 57Fe Mössbauer spectrum of heat-treated vanadate glass shows a marked decrease in quadrupole splitting (Δ) of FeIII, reflecting a structural relaxation, i.e., an increased symmetry of "distorted" FeO4 and VO4 tetrahedra which are connected to each other by sharing corner oxygen atoms. Structural relaxation of 3D-network of vanadate glass accompanies a decrease in the activation energy for the conduction, reflecting a decreased energy gap between the donor level and conduction band. A marked increase in the conductivity was observed in CuO- or Cu2O -containing barium iron vanadate glass after heat treatment at 450 °C for 30 min or more. "n-type semiconductor model combined with small polaron hopping theory" was proposed in order to explain the high conductivity.

  7. Biological Alteration of Basaltic Glass With Altered Composition and Oxidation States

    NASA Astrophysics Data System (ADS)

    Bailey, B. E.; Staudigel, H.; Templeton, A.; Tebo, B. M.; Ryerson, F.; Plank, T.; Schroder, C.; Klingelhoefer, G.

    2004-12-01

    The ocean crust is an extreme and oligotrophic environment and yet recent studies have shown that reactions between oceanic crust and seawater are capable of supporting microbial life. We are specifically targeting volcanic glass as a source of energy and nutrients necessary to support endolithic microbial communities. A significant amount of chemical energy is available from the process of iron oxidation and our goal is to determine the ability of microorganisms to use Fe(II) as an energy source as well as liberate other essential nutrients from the host rock. In addition, microbes may oxidize Mn or use phosphate from glass. To explore the dependency of microbial life on these nutrients and energy sources, we produce basaltic glasses with varying Fe oxidation states and relative abundance of iron, manganese and phosphate and introduce them to microbial isolates and consortia both in the laboratory and in deep-ocean environments. The natural exposure experiments occur in a variety of settings including hydrothermal vents and cold deep seawater (Loihi Seamount), brines (Mediterranean), and basaltic flows at spreading ridges (EPR), when possible on submarine lava flows of recent and known age. Upon collection of the exposure experiments, we compare basalt colonizing microbial communities on our synthetic glasses with the in situ glass communities through a large culturing effort and molecular (t-RFLP) studies. So far we have produced a number of enrichment cultures and isolated several iron-oxidizing and manganese-oxidizing bacteria that were used to inoculate glasses in the laboratory. Laboratory experiments concentrate on biofilm formation and dissolution of the colonized glasses. Continued collection of exposure experiments on a yearly time-scale provides valuable information regarding spatial and temporal variations in microbial community diversity and structure. We have also analyzed the authigenic reaction products of seafloor, microbially mediated alteration

  8. Alkali-promoted oxidation of Al(111): {Rb}/{O} and {K}/{O} coadsorption and the role of surface structure

    NASA Astrophysics Data System (ADS)

    Driver, S. M.; Lüdecke, J.; Dixon, R. J.; Thompson, P. B. J.; Scragg, G.; Woodruff, D. P.; Cowie, B. C. C.

    1997-11-01

    Synchrotron radiation core-level photoemission from the Al 2p, K 3p and Rb 4p states has been used to characterise the role of preadsorbed Rb and K on the interaction of oxygen with an Al(111) surface. Specific precoverages have been used corresponding to two different (√3 × √3)R30° surface structures, a metastable low temperature phase involving alkali atoms in atop sites, and a stable higher temperature phase with substitutional alkali atoms. In all cases a significant promotion of both dissociation and oxidation is seen relative to the activity of the clean Al(111) surface. In comparison with earlier results for {Na}/{O} coadsorption Rb is found to promote oxidation most strongly and Na least strongly with K being intermediate; the Rb room temperature substitutional phase, in particular, shows oxidation at the lowest oxygen exposures and no indication for the RbO chemisorption precursor comparable with the NaO one identified on the Na-covered surface. By contrast the Rb-atop and K-atop geometry surfaces do show evidence of some discrete chemisorption states in the Al 2p spectra of the type seen on alkali-free Al(111), but only in the presence of other spectral structure assigned to mixed-coordination geometries. At low temperatures the effect of both Rb and K on oxidation, but not on initial oxygen adsorption, is generally suppressed, an effect ascribed to the role of bulk diffusion. Measurements of normal incidence X-ray standing wavefield absorption for the {Rb}/{O} coadsorption structures at very low oxygen exposure also indicate that no simple single sites are occupied, particularly in the case of the more reactive Rb-substitutional phase at room temperature, although there appears to be a relatively well-defined OAl layer spacing attributed to small but laterally incommensurate oxide islands. Measured work function changes at low oxygen exposure in the {Rb}/{O} and {Na}/{O} systems can be reconciled with oxygen penetration of the alkali layer

  9. Chemical stability of glass seal interfaces in intermediate temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Yang, Zhenguo; Xia, Guanguang; Meinhardt, Kerry D.; Weil, K. Scott; Stevenson, Jeff W.

    2004-06-01

    In intermediate temperature planar solid oxide fuel cell (SOFC) stacks, the interconnect, which is typically made from cost-effective, oxidation-resistant, high-temperature alloys, is typically sealed to the ceramic positive electrode-electrolyte-negative electrode (PEN) by a sealing glass. To maintain the structural stability and minimize the degradation of stack performance, the sealing glass has to be chemically compatible with the PEN and alloy interconnects. In the present study, the chemical compatibility of a barium-calcium-aluminosilicate (BCAS) based glass-ceramic (specifically developed as a sealant in SOFC stacks) with a number of selected oxidation resistant high temperature alloys (and the yttria-stabilized zirconia electrolyte) was evaluated. This paper reports the results of that study, with a particular focus on Crofer22 APU, a new ferritic stainless steel that was developed specifically for SOFC interconnect applications.

  10. Copper oxide and selenide nanoparticles embedded into sol-gel-derived silica glasses doped with europium

    NASA Astrophysics Data System (ADS)

    Gurin, Valerij S.; Yumashev, Konstantin V.; Prokoshin, P. V.; Zolotovskaya, S. A.; Alexeenko, A. A.

    2002-11-01

    The silica sol-gel derived glasses co-doped with CuxO and CuxSe nanoparticles and Eu3+ ions have been fabricated. The analysis of luminescence spectra of a series of glasses with different composition allows us to suppose the direct energy transfer between copper oxide nanoparticle and Eu3+ ion. A luminescence signal of europium ions occurs as the result of excitation of the complex active centres (SiO2:Cu2O:Eu3+) in the absorption range of copper oxide.

  11. The oxidative stability of carbon fibre reinforced glass-matrix composites

    NASA Technical Reports Server (NTRS)

    Prewo, K. M.; Batt, J. A.

    1988-01-01

    The environmental stability of carbon fibre reinforced glass-matrix composites is assessed. Loss of composite strength due to oxidative exposure at elevated temperatures under no load, static load and cyclic fatigue as well as due to thermal cycling are all examined. It is determined that strength loss is gradual and predictable based on the oxidation of carbon fibres. The glass matrix was not found to prevent this degradation but simply to limit it to a gradual process progressing from the composite surfaces inward.

  12. Development of tellurium oxide and lead-bismuth oxide glasses for mid-wave infra-red transmission optics

    NASA Astrophysics Data System (ADS)

    Zhou, Beiming; Rapp, Charles F.; Driver, John K.; Myers, Michael J.; Myers, John D.; Goldstein, Jonathan; Utano, Rich; Gupta, Shantanu

    2013-03-01

    Heavy metal oxide glasses exhibiting high transmission in the Mid-Wave Infra-Red (MWIR) spectrum are often difficult to manufacture in large sizes with optimized physical and optical properties. In this work, we researched and developed improved tellurium-zinc-barium and lead-bismuth-gallium heavy metal oxide glasses for use in the manufacture of fiber optics, optical components and laser gain materials. Two glass families were investigated, one based upon tellurium and another based on lead-bismuth. Glass compositions were optimized for stability and high transmission in the MWIR. Targeted glass specifications included low hydroxyl concentration, extended MWIR transmission window, and high resistance against devitrification upon heating. Work included the processing of high purity raw materials, melting under controlled dry Redox balanced atmosphere, finning, casting and annealing. Batch melts as large as 4 kilograms were sprue cast into aluminum and stainless steel molds or temperature controlled bronze tube with mechanical bait. Small (100g) test melts were typically processed in-situ in a 5%Au°/95%Pt° crucible. Our group manufactured and evaluated over 100 different experimental heavy metal glass compositions during a two year period. A wide range of glass melting, fining, casting techniques and experimental protocols were employed. MWIR glass applications include remote sensing, directional infrared counter measures, detection of explosives and chemical warfare agents, laser detection tracking and ranging, range gated imaging and spectroscopy. Enhanced long range mid-infrared sensor performance is optimized when operating in the atmospheric windows from ~ 2.0 to 2.4μm, ~ 3.5 to 4.3μm and ~ 4.5 to 5.0μm.

  13. Optical properties of borotellurite glasses containing metal oxides

    SciTech Connect

    Kaur, Nirmal; Khanna, Atul; Krishna, P. S. R.; González, Fernando

    2015-06-24

    Glass samples of the system: 5M{sub x}O{sub y}-20B{sub 2}O{sub 3}-75TeO{sub 2} : M{sub x}O{sub y} = WO{sub 3}, Nb{sub 2}O{sub 5}, PbO, Nd{sub 2}O{sub 3}, Y{sub 2}O{sub 3}, Eu{sub 2}O{sub 3} were prepared by melt quenching and characterized by X-ray diffraction, density, Differential Scanning Calorimetry, UV-visible and FTIR spectroscopy. XRD patterns confirmed the amorphous structure of all samples. Glass transition temperature was maximum in borotellurite glass containing Y{sub 2}O{sub 3}. Refractive index, atomic polarizability and basicity increased in the following order of ions: Y{sup 3+} < Eu{sup 3+} < Pb{sup 2+} < Nd{sup 3+} < Nb{sup 3+} < W{sup 6+}. FTIR studies showed that PbO is outstanding in enhancing the concentration of tetrahedral borons in the borotellurite network.

  14. Conversion from a Bio-inert Glass to a Glass with Bio-active Layer by Heat-treatment in an Oxidation Atmosphere

    NASA Astrophysics Data System (ADS)

    Kang, Eun-Tae; Kim, Jong-Po

    The surface of iron-bearing bio-inert glasses was modified by heat-treatment in an oxidizing atmosphere near the glass transition temperature. The modified surfaces after 7 days immersion in simulated body fluid (SBF) solution were analyzed by means of micro-Raman spectroscopy, SEM, and EDS. All investigated glasses except for the glass with NC = 2.6 were able to form hyroxycarbonate apatite (HCA) on their surfaces. The thickness of an HCA surface layer increased with decreased oxygen partial pressure. The cross-sectional micrographs were nearly similar to the 45S5 Bioglass®.

  15. Replacement of oxide glass with metallic glass for Ag screen printing metallization on Si emitter

    NASA Astrophysics Data System (ADS)

    Kim, Se Yun; Jee, Sang Soo; Lim, Ka Ram; Kim, Won Tae; Kim, Do Hyang; Lee, Eun-Sung; Kim, Young Hwan; Lee, Sang Mock; Lee, Jun Ho; Eckert, Jürgen

    2011-05-01

    Cu-Zr-based metallic glass (MG) has been applied as a binding agent of Ag paste for front contact formation in Si solar cell by screen printing process. Use of electroconductive MG binder significantly improves the quality of the contact by the formation of highly dense 10-50 nm size Ag crystallites and the noncorrugation of the emitter surface with a very shallow Ag crystallite penetration depth of 10-30 nm. Nanoscale Ag crystallites form on the emitter surface by local Si-Cu-Ag eutectic melting, leading to the formation of pyramidal pits on the Si emitter surface, followed by precipitation of Ag crystallites during cooling.

  16. Physical and electrical properties of copper oxide doped bismuth borate glasses

    NASA Astrophysics Data System (ADS)

    Dhiman, R. L.; Kundu, Virender Singh; Arora, Susheel; Maan, A. S.

    2013-06-01

    The role of CuO on the physical and electrical properties in x CuO.(25-x)Bi2O3.75B2O3;(5≤x≤20) glass system has been investigated. The glasses were prepared by normal melt quench technique. The density and molar volume of the glasses decreases with increase in CuO (mol %). The dc conductivity was measured in the temperature range 413-513 K. The conduction mechanism in these glasses was discussed in terms of small polaron hopping (SPH) theory proposed by Mott. The activation energy is found to decrease with increasing copper oxide content. The dc conductivity increases with increase in CuO content and ranging from 6.02×10-12 (Ωm)-1 to 1.096×10-10 (Ωm)-1 at 450K.

  17. The effects of uranium oxide high-level waste on the structure of iron phosphate glasses.

    SciTech Connect

    Badyal, Y.

    1998-12-23

    Because of their unusually good chemical durability, iron phosphate glasses are a natural candidate for a nuclear waste disposal glass. We have studied the effects of UO{sub 2} high-level waste on the structure of iron phosphate glasses with both neutron and high-energy x-ray diffraction using the GLAD instrument of the Intense Pulsed Neutron Source and the 1-BM bending magnet beamline of the Advanced Photon Source, respectively. The results of neutron scattering, which is mostly sensitive to correlations involving light atoms i.e. O-O, Fe-O and P-O, suggest the main structural features of the base glass are largely unaffected by the addition of UO{sub 2}. The nearest-neighbor P-O, Fe-O and O-O peaks remain at the same position in real space and their intensities scale approximately with concentration. These findings are consistent with the earlier results of Raman scattering and EXAFS on the Fe-K edge wherein both cases the spectra remain similar to the base glass. High-energy x-ray scattering which is sensitive to correlations involving the heavier atoms and thus complements the neutron measurements, is also consistent with uranium occupying interstitial sites in the relatively undisturbed base glass structure. However, important questions remain as to the precise local structure and oxidation state of uranium in these glasses.

  18. Chemical Stability of Glass Seal Interfaces in Intermediate Temperature Solid Oxide Fuel Cells

    SciTech Connect

    Yang, Z Gary; Xia, Gordon; Meinhardt, Kerry D.; Weil, K. Scott; Stevenson, Jeffry W.

    2004-06-01

    In intermediate temperature planar SOFC stacks, the interconnect, which is typically made from cost-effective oxidation resistant high temperature alloys, is typically sealed to the ceramic PEN (Positive electrode-Electrolyte-Negative electrode) by a sealing glass. To maintain ther structural stability and minimize the degradation of stack performance, the sealing glass has to be chemically compatible with the PEN and alloy interconnects. In the present study, the chemical compatibility of a barium-calcium-aluminosilicate (BCAS) based glass-ceramic (specifically developed as a sealant in SOFC stacks) with a number of selected oxidation resistant high temperature alloys (and the YSZ electrolyte) was evaluated. This paper reports the results of that study, with a particular focus on Crofer22 APU, a new ferritic stainless steel that was developed specifically for SOFC interconnect applications.

  19. A Comparative Study of Natural Fiber and Glass Fiber Fabrics Properties with Metal or Oxide Coatings

    NASA Astrophysics Data System (ADS)

    Lusis, Andrej; Pentjuss, Evalds; Bajars, Gunars; Sidorovicha, Uljana; Strazds, Guntis

    2015-03-01

    Rapidly growing global demand for technical textiles industries is stimulated to develop new materials based on hybrid materials (yarns, fabrics) made from natural and glass fibres. The influence of moisture on the electrical properties of metal and metal oxide coated bast (flax, hemp) fibre and glass fibre fabrics are studied by electrical impedance spectroscopy and thermogravimetry. The bast fibre and glass fiber fabrics are characterized with electrical sheet resistance. The method for description of electrical sheet resistance of the metal and metal oxide coated technical textile is discussed. The method can be used by designers to estimate the influence of moisture on technical data of new metal coated hybrid technical textile materials and products.

  20. Femtosecond third-order nonlinear spectra of lead-germanium oxide glasses containing silver nanoparticles.

    PubMed

    De Boni, Leonardo; Barbano, Emerson C; de Assumpção, Thiago A; Misoguti, Lino; Kassab, Luciana R P; Zilio, Sergio C

    2012-03-12

    This work reports on the spectral dependence of both nonlinear refraction and absorption in lead-germanium oxide glasses (PbO-GeO₂) containing silver nanoparticles. We have found that this material is suitable for all-optical switching at telecom wavelengths but at the visible range it behaves either as a saturable absorber or as an optical limiter.

  1. UV-vis spectroscopy of iodine adsorbed on alkali-metal-modified zeolite catalysts for addition of carbon dioxide to ethylene oxide

    SciTech Connect

    Doskocil, E.J.; Bordawekar, S.V.; Kaye, B.G.; Davis, R.J.

    1999-07-29

    The basicity of alkali-metal-exchange (Na, K, Cs) zeolites X and Y was probed by UV-vis diffuse reflectance spectroscopy of adsorbed iodine. The observed blue shift in the visible absorption spectrum of adsorbed iodine, compared to gaseous iodine, correlated well with the negative charge on the framework oxygen atoms calculated from the Sanderson electronegativity equalization principle. The blue shifts associated with iodine adsorbed on classical catalytic supports like silica, alumina, and magnesia suggest that the iodine adsorption technique for probing basicity is applicable to a wide variety of solids. Iodine was also adsorbed on X and Y zeolites containing occluded cesium oxide formed by decomposition of impregnated cesium acetate. However, the iodine appeared to irreversibly react on these strongly basic samples, possibly forming an adsorbed triiodide ions. As a complement to the adsorption studies, the activity of alkali-metal-containing zeolites for the base-catalyzed formation of ethylene carbonate from ethylene oxide and carbon dioxide was investigated. Among the ion-exchanged zeolites, the cesium form of zeolite X exhibited the highest activity for ethylene carbonate formation. The catalytic activity of a zeolite containing occluded cesium was even higher than that of a cesium-exchanged zeolite. The presence of water adsorbed in zeolite pores promoted the rate of ethylene carbonate formation for both cesium-exchanged and cesium-impregnated zeolite X.

  2. Specialty glass raw materials: Status and developments

    SciTech Connect

    Bauer, R.J.; Gray, S.L.

    1996-12-31

    The authors highlight several key raw materials used in the specialty glass industry. The focus here is to update changes and shifts underway in the worldwide availability and processes that will impact both costs and efficient use of these products. The glass types that use these materials generally are those other than container, float, and fiber glass. Those high-volume consumers of glass raw materials are discussed in a companion paper in this volume. In the specialty glass field, the batch materials involve minerals, and the chemicals derived from them, which are less readily available domestically. These are much more critically defined by specifications of assay, contamination, and particle size, resulting in their being more expensive. They are seldom commodity products. The scope of materials for this fragmented industry includes those for leads, borosilicates, aluminosilicates, opals, sealing and frit glasses, optical glass, ophthalmic glass, cathode ray tubes (CRTs) for TV and display, and glass-ceramics as major segments. They use lead oxides, nearly all the alkalies and alkaline earth portions of the periodic table, as well as rare earths, transition element oxides, phosphates, boron minerals and chemicals, zircon, zinc, most of the halogens, and many of the anions. They often require very special particle size specifications. The requirements for these batch materials are often based on chemistry, the absence of contaminants that impact melting, very wide ranges of the electromagnetic spectrum, glass homogeneity, and freedom from solid and gaseous inclusions down to ppm levels in both size and number.

  3. Investigation of potassium containing glass coatings as diesel soot oxidation catalysts

    NASA Astrophysics Data System (ADS)

    Zokoe, James, Jr.

    Diesel engines provide superior fuel economy to gasoline engines, but their emissions contain harmful compounds that endanger human health and the environment. Because of this, government regulations have demanded increasingly cleaner exhaust from diesel engines. Diesel engines are now being fitted with additional "Exhaust aftertreatment units" which utilize catalysts in various components in the exhaust stream to eliminate the unsafe compounds. One harmful diesel exhaust component that has proven difficult to eliminate is solid carbonaceous particulate matter. Diesel particulate filters (DPFs) are currently required of all engines to remove the solid PM, also termed soot, from the exhaust. One means for reducing cost of the aftertreatment unit is to lower the required temperature for soot oxidation (DPF regeneration) by implementing a low cost, low temperature soot oxidation catalysts. Potassium based catalysts provide the low temperature oxidation of soot, but quickly degrade in the harsh conditions of the diesel exhaust. Novel K-glass catalysts have recently been shown to stabilize the K within a silicate matrix and initial degradation studies have shown promise with soot oxidation as low as 380°C in loose catalyst-soot contact conditions. To further the study of these K-glass catalysts, this dissertation will delve into the measurement and characterization of the prolonged degradation mechanisms experienced by the glasses that fall into two categories termed as follows: combustion (K loss) and chemical (hydrothermal) degradation. K-glass catalyst samples were used to measure end of useful lifetime (EUL) testing for an estimated 100,000 mi of engine use. A baseline glass compound (KCS-1) was found to sustain acceptable soot oxidation temperatures after this lifetime (T50 < 500°C). Catalytic degradation was caused by the creation of K-rich carbonate or sulfate precipitates. These precipitates deplete the surrounding glass of active K and also mask active

  4. Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Rao, M. N.; Nyquist, L. E.

    2010-01-01

    Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re

  5. Nonlinear optical properties of sol-gel-type glasses containing oxidized Cu2Se nanoparticles

    NASA Astrophysics Data System (ADS)

    Yumashev, K. V.

    2000-03-01

    Nonlinear absorption of sol-gel-type glasses containing oxidized Cu2Se nanoparticles (25 nm in radius) is investigated with the aid of the picosecond excitation-probing technique. The oxidation of Cu2Se nanoparticles leads to the appearance of a wide absorption band, which has a maximum roughly at 1 µm and which is bleached on exposure to laser pulses. The time of relaxation of the bleached state approaches 300 psec, and the cross section for absorption at 1.06 µm is equal to about 1.3·10-16 cm2, as evaluated from the measured absorption saturation curve. The regime of Q-switching is obtained for a number of solid-state lasers with generation wavelengths 1.06, 1.34, and 1.54 µm, when sol-gel-type glasses containing oxidized Cu2Se nanoparticles were used as passive shutters.

  6. Surface Analysis of Stressed and Control Tin Oxide Thin Films on Soda Lime Glass

    SciTech Connect

    Pankow, J. W.

    2003-05-01

    Surface analysis techniques have been used to investigate tin oxide-coated soda lime glass specimens prior and subsequent to their exposure to DC bias, heat, and humidity. All specimens reported here comprise the following layered structure: tin oxide/silicon oxycarbide/glass. Depth profiling using X-ray photoelectron spectroscopy (XPS) clearly shows the interfacial regions in both control samples and samples exposed to the above-mentioned conditions (stressed). Control samples show distinct and relatively compact interfacial regions as well as an intact silicon oxycarbide diffusion barrier. Stressed films, however, show more diffuse interfacial regions and a physically and chemically altered silicon oxycarbide diffusion barrier. This deterioration of the diffusion barrier is proposed to be a pre-requisite event to enable tin oxide delamination.

  7. Quantitative analysis of boron oxide in borosilicate glasses by infrared spectroscopy

    SciTech Connect

    Haaland, D.M.

    1986-11-01

    Classical multivariate least-squares methods have been applied to the quantitative analysis of boron oxide in bulk borosilicate glasses using transmission infrared spectroscopy. However, molecular interactions in the glass result in deviation from Beer's law and cause the analytical B-O overtone band at --2680 cm/sup -1/ to shift to higher energy with increased boron concentration. Therefore, in order to account for the molecular interactions and achieve higher quantitative accuracy, one must use a nonlinear model relating absorbance and concentration. It has been found that if a quadratic correction term is added to the Beer's-law equation, the observed 15 to 25 cm/sup -1/ shift in frequency of the B-O overtone band can be modeled to within the spectral noise. With the use of a model quadratic in boron oxide concentration, the least-squares analysis of boron in glass was determined with an average relative error of 3.3% for glasses with boron oxide concentrations ranging from 0.88 to 2.58%. This compares favorably with the 3% accuracy claimed for ion chromatography exculsion used for calibration. The methods described in this paper are general, and a variety of nonlinear models can be applied whenever Beer's-law deviations are present.

  8. Identifying glass compositions in fly ash

    NASA Astrophysics Data System (ADS)

    Aughenbaugh, Katherine; Stutzman, Paul; Juenger, Maria

    2016-01-01

    In this study, four Class F fly ashes were studied with a scanning electron microscope; the glassy phases were identified and their compositions quantified using point compositional analysis with k-means clustering and multispectral image analysis. The results showed that while the bulk oxide contents of the fly ashes were different, the four fly ashes had somewhat similar glassy phase compositions. Aluminosilicate glasses (AS), calcium aluminosilicate glasses (CAS), a mixed glass, and, in one case, a high iron glass were identified in the fly ashes. Quartz and iron crystalline phases were identified in each fly ash as well. The compositions of the three main glasses identified, AS, CAS, and mixed glass, were relatively similar in each ash. The amounts of each glass were varied by fly ash, with the highest calcium fly ash containing the most of calcium-containing glass. Some of the glasses were identified as intermixed in individual particles, particularly the calcium-containing glasses. Finally, the smallest particles in the fly ashes, with the most surface area available to react in alkaline solution, such as when mixed with portland cement or in alkali-activated fly ash, were not different in composition than the large particles, with each of the glasses represented. The method used in the study may be applied to a fly ash of interest for use as a cementing material in order to understand its potential for reactivity.

  9. Influence of mixed alkali on the spectral properties of vanadyl ions doped xNa{sub 2}O-(30 - x)K{sub 2}O-60B{sub 2}O{sub 3} glasses-an EPR and optical study

    SciTech Connect

    Sreekanth Chakradhar, R.P. . E-mail: chakra72@physics.iisc.ernet.in; Ramesh, K.P.; Rao, J.L.; Ramakrishna, J.

    2005-06-15

    Electron paramagnetic resonance (EPR) and optical investigations have been performed in the mixed alkali borate xNa{sub 2}O-(30 - x)K{sub 2}O-60B{sub 2}O{sub 3} (5 {<=} x {<=} 25) glasses doped with 10 mol% of vanadyl ions in order to look for the effect of 'mixed alkalis' on the spectral properties of the glasses. The observed EPR spectra have structures for x > 5 mol% which are characteristic of a hyperfine interaction arising from an unpaired electron with the {sup 51}V nucleus and it builds up in intensity as x increases. It is observed that the mixed alkali play a significant role in accommodating the vanadyl ions in these mixed alkali glasses and for x > 5 mol%, shows a well resolved hyperfine structure typical for isolated VO{sup 2+} ions. The spin-Hamiltonian parameters (g and A), the dipolar hyperfine coupling parameter (P) and Fermi contact interaction parameter (k) have been evaluated. It is observed that the spin-Hamiltonian parameters do not vary much with the change in composition. It is observed that with increase of x, an increase occurs in tetragonal distortion for VO{sup 2+}. The number of spins (N) participating in resonance and the paramagnetic susceptibility ({chi}) have been calculated. It is observed that N and {chi} increase with x. The optical bandgap energies evaluated for these glasses slightly increase with x and reach a maximum around x = 20 and thereafter decrease showing the mixed alkali effect. Optical band gap energies obtained in the present work vary from 2.73 to 3.10 eV for both the direct and indirect transitions. The physical parameters of the glasses are also determined with respect to the composition.

  10. The oxidation state of iron in tektite glass

    SciTech Connect

    Fudali, R.F. ); Dyar, M.D. ); Griscom, D.L. ); Schreiber, H.D. )

    1987-10-01

    Fe{sup 3+}/Fe{sup 2+} ratios in tektite glass have the potential for constraining the f{sub O{sub 2}}-T conditions associated with tektite melts prior to quenching. But even discounting older analyses, values of Fe{sup 3+}/Fe{sup 2+} in the literature range from zero to 0.82. The authors have analyzed five tektites from populations that have been reported to have Fe{sup 3+}/Fe{sup 2+} ratios both of zero and also a range of ratios up to 0.67. The authors employed several wet chemical techniques and two instrumental techniques - Moessbauer and Electron Spin Resonance - for all five samples and failed to confirm either extreme. The range they found of 0.02-0.12 is in excellent agreement with the literature values that they consider to be consistently most reliable and they believe that most if not all Fe{sup 3+}/Fe{sup 2+} ratios in tektites fall within this range. The obvious presence of systematic errors in their data set strongly suggests the true range is narrower than their reported range. Additional standardization work is need to address these systematic errors. Nevertheless, the authors present accuracy is sufficient to demonstrate that there is no need to invoke a lunar volcanic origin for tektites or to postulate special formation conditions specific to Muong Nong tektites.

  11. Designing heavy metal oxide glasses with threshold properties from network rigidity

    SciTech Connect

    Chakraborty, Shibalik; Boolchand, P.; Malki, M.; Micoulaut, M.

    2014-01-07

    Here, we show that a new class of glasses composed of heavy metal oxides involving transition metals (V{sub 2}O{sub 5}–TeO{sub 2}) can surprisingly be designed from very basic tools using topology and rigidity of their underlying molecular networks. When investigated as a function of composition, such glasses display abrupt changes in network packing and enthalpy of relaxation at T{sub g}, underscoring presence of flexible to rigid elastic phase transitions. We find that these elastic phases are fully consistent with polaronic nature of electronic conductivity at high V{sub 2}O{sub 5} content. Such observations have new implications for designing electronic glasses which differ from the traditional amorphous electrolytes having only mobile ions as charge carriers.

  12. Optical absorption of gamma-irradiated lithium-borate glasses doped with different transition metal oxides

    NASA Astrophysics Data System (ADS)

    Marzouk, S. Y.; Elalaily, N. A.; Ezz-Eldin, F. M.; Abd-Allah, W. M.

    2006-06-01

    We have investigated the effect of gamma irradiation on the optical properties of Li 2O-B 2O 3 containing two concentrations (0.2 or 0.5 g) of each one of the following transition metals, V, Mn, Fe or Ni oxide glass samples. We studied the impacts of gamma irradiation in terms of the mechanism by which radiation-induced defects are generated. A resolution of the observed absorption spectra showed several bands which were induced by photo-reduction or photo-oxidation assumed to take place by photo-chemical reaction according to the type of transition metal oxide (TMO). Small deviations of these induced bands characteristic of the glass constituents were observed and explained in terms of the physical properties, in relation to different oxidation states of TMO in the glass matrix. The series Mn 2+, Fe 2+ and Ni 2+ ions shows a trend of increased photo-oxidation with increasing electronegativity or decreasing mass of the ions. The prepared samples were studied in terms of their dosimetric characteristics: calibration curves from 1.0524 to 42.096 kGy and fading at (25 and 50 °C). Thermal bleaching of irradiated glass was found to permit the reduction of the larger part of TMO ions in Li 2O-B 2O 3. Also, the results showed that the degeneration of the induced bands was faster at 50 than at 25 °C. The optical energy gap Eg was found to decrease with the increase of the radiation dose, and it is suggested that the mechanism of optical transition is forbidden by indirect transition.

  13. Thermal Cycle Stability of a Novel Glass-Mica Composite Seal for Solid Oxide Fuel Cells: Effect of Glass Volume Fraction and Stresses

    SciTech Connect

    Chou, Y S.; Stevenson, Jeffry W.; Singh, Prabhakar

    2005-12-01

    A novel glass-mica composite seal was developed based on a previously of ''infiltrated'' mica seals for solid oxide fuel cells. Ba-Al-Ca silicate sealing glass-mica composite seals. The seals were leak tested for short-term thermal cyfunction of glass volume fraction. Composite seals with 10 v% and 20 v% glatested under compressive stresses from 3 psi to 100 psi and voltage tests on dense 8YSZ electrolyte with the glas-mica composite seal showed very good thermal cycle stability.

  14. Low melting high lithia glass compositions and methods

    DOEpatents

    Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.

    2004-11-02

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

  15. Low melting high lithia glass compositions and methods

    DOEpatents

    Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.

    2003-10-07

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

  16. Low melting high lithia glass compositions and methods

    DOEpatents

    Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.

    2000-01-01

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

  17. Electrochromic characteristics of niobium-doped titanium oxide film on indium tin oxide/glass by liquid phase deposition

    NASA Astrophysics Data System (ADS)

    Lee, Ming-Kwei; Lee, Chia-Jung

    2015-10-01

    Ammonium hexafluorotitanate and boric acid aqueous solutions were used as precursors for the growth of titanium oxide films on indium tin oxide (ITO)/glass substrate. For as-grown titanium oxide film used in an electrochromic device, Li+ ions from electrolyte will be trapped to hydroxyl groups and degrade the electrochromic durability during the cyclic voltammogram characterization. For niobium doped titanium oxide film, lower growth rate from more HF incorporation from the niobium doped solution and rougher surface morphology from the formation of nanocrystals were obtained. However, niobium doping reduces hydroxyl groups and the electrochromic durability is enhanced from 5 × 103 to 1 × 104 times. The transmittance is enhanced from 37 to 51% at the wavelength of 550 nm.

  18. Ultrapure glass optical waveguide development in microgravity by the sol-gel process

    NASA Technical Reports Server (NTRS)

    Mukherjee, S. P.

    1980-01-01

    The alkali-borosilicate system was selected as the glass system for the preparation of ultrapure low loss glasses suitable for optical communication. The effect of different oxide contents on the absorption loss was critically reviewed. One composition was chosen to develop the gel preparation procedure in the alkali-borosilicate system. In addition, several procedures for the preparation of gels based on two different approaches were developed. The influence of different preparation parameters were investigated qualitatively. Several conclusions are drawn from the results.

  19. Synthesis and Properties of a Barium Aluminosilicate Solid Oxide Fuel Cell Glass-Ceramic Sealant

    SciTech Connect

    Meinhardt, Kerry D.; Kim, Dong-Sang; Chou, Y. S.; Weil, K. Scott

    2008-07-15

    A series of barium aluminosilicate glasses modified with CaO and B2O3, were prepared and evaluated with respect to their suitability in sealing planar solid oxide fuel cells (SOFCs). At a target operating temperature of 750ºC, the long-term CTE of one particular composition (35 mol% BaO, 15 mol% CaO, 10 mol% B2O3, 5 mol% Al2O3, bal. SiO2) was found to be particularly stable, due to devitrification to a mixture of glass and ceramic phases. This sealant composition exhibits minimal chemical interaction with the yttria-stabilized zirconia electrolyte, yet forms a strong bond with this material. Interactions with metal components were found to be more extensive and depended on the composition of the metal oxide scale that formed during sealing. Generally alumina-scale formers exhibited a more compact reaction zone with the glass than chromia-scale forming alloys. Mechanical measurements conducted on the bulk glass-ceramic and on seals formed using these materials indicate that the sealant is anticipated to display adequate long-term strength for most conventional stationary SOFC applications.

  20. Chemical Interactions of Barium-Calcium-Aluminosilicate Based Sealing Glasses with Oxidation Resistant Alloys

    SciTech Connect

    Yang, Z Gary ); Stevenson, Jeffry W. ); Meinhardt, Kerry D. )

    2003-04-04

    In most planar SOFC stack designs, the interconnect, which is typically made from an oxidation resistant alloy, potentially including austenitic chromia-forming, ferritic chromia-forming, and alumina-forming alloys, has to be hermitically sealed to its adjacent components, usually by a sealing glass. To maintain the structural stability and minimize the degradation of stack performance, the sealing glass must be chemically compatible with the alloy used for the interconnect. In this work, Nicrofer6025, AISI446 and a Fecralloy were selected as examples of austenitic chromia-forming, ferritic chromia-forming, and alumina-forming alloys, respectively. Their chemical compatibility with a barium-calcium-aluminosilicate (BCAS) based glass, specifically developed as a sealant in SOFC stacks, was evaluated. It was found that the BCAS sealing glass interacted chemically with both the chromia-forming alloys and the alumina-forming alloys. The extent and nature of the interactions and their final products depended on the matrix alloy compositions, the exposure conditions and/or proximity of the glass/alloy interface to the ambient air. These interactions and their mechanisms will be discussed with the assistance of thermodynamic modeling.

  1. Effect of binder burnout on the sealing performance of glass ceramics for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Ertugrul, Tugrul Y.; Celik, Selahattin; Mat, Mahmut D.

    2013-11-01

    The glass ceramics composite sealants are among few materials suitable for the solid oxide fuel cells (SOFC) due to their high operating temperatures (600 °C-850 °C). The glass ceramics chemically bond to both the metallic interconnector and the ceramic electrolyte and provide a gas tight connection. A careful and several stages manufacturing procedure is required to obtain a gas tight sealing. In this study, effects of binder burnout process on the sealing performance are investigated employing commercially available glass ceramic powders. The glass ceramic laminates are produced by mixing glass ceramic powders with the organic binders and employing a tape casting method. The laminates are sandwiched between the metallic interconnectors of an SOFC cell. The burnout and subsequent sealing quality are analyzed by measuring leakage rate and final macrostructure of sealing region. The effects of heating rate, dead weight load, solid loading, carrier gas and their flow rates are investigated. It is found that sealing quality is affected from all investigated parameters. While a slower heating rate is required for a better burnout, the mass flow rate of sweep gas must be adequate for removal of the burned gas. The leakage rate is reduced to 0.1 ml min-1 with 2 °C min-1 + 1 °C min-1 heating rate, 86.25% solid loading, 200 N dead weight load and 500 ml min-1 sweep gas flow rate.

  2. Structural studies of lithium boro tellurite glasses doped with praseodymium and samarium oxides

    SciTech Connect

    Damas, Pedro; Coelho, João; Hungerford, Graham; Hussain, N. Sooraj

    2012-11-15

    Graphical abstract: [TeO{sub 4}] trigonal bipyramid structural unit, which is formed by two unequivalent pair of oxygen atoms: two equatorial oxygens (O{sub eq}) and two axial oxygens (O{sub ax}). Highlights: ► Pr{sup 3+} and Sm{sup 3+} doped LBT glasses have been prepared and characterized. ► LBT glasses present normal surfaces without metallic clusters. ► Raman spectra revealed the network modifying behaviour of dopant ions. -- Abstract: This paper reports the preparation and structural studies of praseodymium and samarium (0.5, 2 and 4 mol%) oxide doped lithium boro tellurite glasses. These materials were prepared by the quenching technique in a ceramic crucible at 950 °C. Structural characterization was performed by Raman spectroscopy, Scanning Electron Microscopy and Energy Dispersive X-ray spectroscopy techniques. Results from Raman analysis are in good agreement with those reported in the literature, revealing a normal glass structure for the host material. Understanding on how the glasses internal structure changed when the doping concentration increases was also assessed.

  3. Effect of ZnO on phase emergence, microstructure and surface modifications of calcium phosphosilicate glass/glass-ceramics having iron oxide

    NASA Astrophysics Data System (ADS)

    Sharma, K.; Dixit, A.; Bhattacharya, S.; Jagannath; Deo, M. N.; Kothiyal, G. P.

    2010-03-01

    The effect of ZnO on phase emergence and microstructure properties of glass and glass-ceramics with composition 25SiO 2-50CaO-15P 2O 5-(10 - x)Fe 2O 3- xZnO (where x = 0, 2, 5, 7 mol%) has been studied. They have been characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Surface modifications of these glass-ceramics in simulated body fluid have been studied using Fourier transform infrared reflection spectroscopy (FTIR), XPS and SEM. Results have shown a decrease in the fraction of non-bridging oxygen with increase in zinc oxide content. Emergence of crystalline phases in glass-ceramics at different heat treatment temperatures was studied using XRD. When glass is heat treated at 800 °C calcium phosphate, hematite and magnetite are developed as major phases in the glass-ceramics samples with ZnO up to 5 mol%. In addition to these, calcium silicate (Ca 3Si 2O 7) phase is also observed when glass is heat treated at 1000 °C. The microstructure of the glass-ceramics heat treated at 800 °C exhibits the formation of nano-size (40-50 nm) grains. On heat treatment at 1000 °C crystallites grow to above 50 nm size and more than one phase are observed in the microstructure. The formation of thin flake-like structure with coarse particles is observed at high zinc oxide concentration ( x = 7 mol%). In vitro studies have shown the surface modifications and formation of Ca-P-rich layer on the glass-ceramics when immersed in simulated body fluids (SBF) for different durations. The bioactive response was found to depend on ZnO content.

  4. Treatment of pretreated coking wastewater by flocculation, alkali out, air stripping, and three-dimensional electrocatalytic oxidation with parallel plate electrodes.

    PubMed

    Wen-wu, Liu; Xiu-ping, Wang; Xue-yan, Tu; Chang-yong, Wang

    2014-10-01

    The coking wastewater generally comprises highly concentrated, recalcitrant, and toxic organic pollutants, so its treatment has been of great importance to prevent living beings and their environment from these hazardous contaminations. The treatment of pretreated coking wastewater by flocculation-coagulation, alkali out, air stripping, and three-dimensional (3-D) electrocatalytic oxidation was performed (gap between the used β-PbO2/Ti anode and titanium cathode, 12 mm; mass ratio of Cu-Mn/granular activated carbon (GAC) to effluent, 1:4; cell voltage, 7 V). The results showed that the pH adjusting from 3.7 to 6.1 was necessary for coagulants; alkali out played an important role because it brought up precipitation containing higher fatty acids as well as other contaminants to decrease the chemical oxygen demand (COD) in the effluent, and it had also forced the reduction of ammonia nitrogen (NH3-N) by incorporating with air stripping; for 3-D electrocatalytic oxidation with a bleaching liquid assisting, the initial pH 8.5 of effluent was suitable for Cu-Mn/GAC; moreover, it was considered that its Cu component was dedicated to the decrease of COD and NH3-N, while the Mn component specialized in the decay of NH3-N. The residual COD and NH3-N values in the final effluent with pH 6.5 were 95.8 and 8.8 mg/L, respectively, demonstrating that the whole processes applied were feasible and low in cost.

  5. Structural aspects of barium borosilicate glasses containing thorium and uranium oxides

    NASA Astrophysics Data System (ADS)

    Mishra, R. K.; Sudarsan, V.; Kaushik, C. P.; Raj, Kanwar; Kulshreshtha, S. K.; Tyagi, A. K.

    2006-12-01

    Barium borosilicate glasses incorporated with 15.86 wt% ThO 2 and containing different amounts of uranium oxide were prepared by conventional melt quench method. Based on 29Si and 11B magic angle spinning nuclear magnetic resonance (MAS NMR) studies, it has been confirmed that uranium oxide incorporation is associated with distortion of borosilicate network as revealed by the increase in the relative concentration of Q2 structural units of silicon as well as the increase in the quadrupolar coupling constant ( Cq) of BO 3 structural units. The increased number of non-bridging oxygen atoms brought about by the increase in Q2 structural units of silicon facilitates the incorporation of both uranium and thorium ions in the sites created by non-bridging oxygen atoms (network modifying positions) in the glass. Uranium oxide incorporation above 7.5 wt% resulted in the phase separation of ThO 2 as revealed by the X-ray diffraction studies. The present study focuses on the structural changes with the borosilicate network of barium borosilicate glasses brought about by the introduction of thorium and uranium ions.

  6. Super ionic conductive glass

    DOEpatents

    Susman, Sherman; Volin, Kenneth J.

    1984-01-01

    An ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A.sub.1+x D.sub.2-x/3 Si.sub.x P.sub.3-x O.sub.12-2x/3, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

  7. Super ionic conductive glass

    DOEpatents

    Susman, S.; Volin, K.J.

    Described is an ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A/sub 1 + x/D/sub 2-x/3/Si/sub x/P/sub 3 - x/O/sub 12 - 2x/3/, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

  8. Growth and field emission of tungsten oxide nanotip arrays on ITO glass substrate

    NASA Astrophysics Data System (ADS)

    Huang, Kai; Pan, Qingtao; Yang, Feng; Ni, Shibi; He, Deyan

    2007-09-01

    High-density and uniformly aligned tungsten oxide nanotip arrays have been deposited by a conventional thermal evaporation on ITO glass substrates without any catalysts or additives. The temperature of substrate was 450-500 °C. It was shown that the tungsten oxide nanotips are single-crystal grown along [0 1 0] direction. For commercial applications, field emission of the tungsten oxide nanotip arrays was characterized in a poor vacuum at room temperature. The field emission behaviors are in agreement with Fowler-Nordheim theory. The turn-on field is 2.8 V μm -1 as d is 0.3 mm. The excellent field emission performances indicated that the tungsten oxide nanotip arrays grown by the present approach are a good candidate for application in vacuum microelectronic devices.

  9. Fragility of network-forming glasses: A universal dependence on the topological connectivity

    NASA Astrophysics Data System (ADS)

    Sidebottom, D. L.

    2015-12-01

    The fragilities of over 150 different network-forming glass melts are shown to conform to a common dependence on just one parameter: the connectivity of the weakest network structure present in the associated glass solid. This includes both nonoxide network-forming chalcogenide melts as well as a variety of alkali oxide glasses, and spans a broad range of connectivity, ϕ, from polymeric structures (ϕ =2 ) to overconstrained random networks with connectivities well in excess of the rigidity threshold (ϕC=2.4 ) . A theoretical framework for the origin of this universal pattern is offered within the context of entropic models of the glass transition.

  10. Remarkably stable amorphous metal oxide grown on Zr-Cu-Be metallic glass.

    PubMed

    Lim, Ka Ram; Kim, Chang Eun; Yun, Young Su; Kim, Won Tae; Soon, Aloysius; Kim, Do Hyang

    2015-12-14

    In the present study, we investigated the role of an aliovalent dopant upon stabilizing the amorphous oxide film. We added beryllium into the Zr50Cu50 metallic glass system, and found that the amorphous oxide layer of Be-rich phase can be stabilized even at elevated temperature above Tg of the glass matrix. The thermal stability of the amorphous oxide layer is substantially enhanced due to Be addition. As confirmed by high-temperature cross-section HR-TEM, fully disordered Be-added amorphous layer is observed, while the rapid crystallization is observed without Be. To understand the role of Be, we employed ab-initio molecular dynamics to compare the mobility of ions with/without Be dopant, and propose a disordered model where Be dopant occupies Zr vacancy and induces structural disorder to the amorphous phase. We find that the oxygen mobility is slightly suppressed due to Be dopant, and Be mobility is unexpectedly lower than that of oxygen, which we attribute to the aliovalent nature of Be dopant whose diffusion always accompany multiple counter-diffusion of other ions. Here, we explain the origin of superior thermal stability of amorphous oxide film in terms of enhanced structural disorder and suppressed ionic mobility due to the aliovalent dopant.

  11. Remarkably stable amorphous metal oxide grown on Zr-Cu-Be metallic glass

    PubMed Central

    Lim, Ka Ram; Kim, Chang Eun; Yun, Young Su; Kim, Won Tae; Soon, Aloysius; Kim, Do Hyang

    2015-01-01

    In the present study, we investigated the role of an aliovalent dopant upon stabilizing the amorphous oxide film. We added beryllium into the Zr50Cu50 metallic glass system, and found that the amorphous oxide layer of Be-rich phase can be stabilized even at elevated temperature above Tg of the glass matrix. The thermal stability of the amorphous oxide layer is substantially enhanced due to Be addition. As confirmed by high-temperature cross-section HR-TEM, fully disordered Be-added amorphous layer is observed, while the rapid crystallization is observed without Be. To understand the role of Be, we employed ab-initio molecular dynamics to compare the mobility of ions with/without Be dopant, and propose a disordered model where Be dopant occupies Zr vacancy and induces structural disorder to the amorphous phase. We find that the oxygen mobility is slightly suppressed due to Be dopant, and Be mobility is unexpectedly lower than that of oxygen, which we attribute to the aliovalent nature of Be dopant whose diffusion always accompany multiple counter-diffusion of other ions. Here, we explain the origin of superior thermal stability of amorphous oxide film in terms of enhanced structural disorder and suppressed ionic mobility due to the aliovalent dopant. PMID:26658671

  12. Remarkably stable amorphous metal oxide grown on Zr-Cu-Be metallic glass.

    PubMed

    Lim, Ka Ram; Kim, Chang Eun; Yun, Young Su; Kim, Won Tae; Soon, Aloysius; Kim, Do Hyang

    2015-01-01

    In the present study, we investigated the role of an aliovalent dopant upon stabilizing the amorphous oxide film. We added beryllium into the Zr50Cu50 metallic glass system, and found that the amorphous oxide layer of Be-rich phase can be stabilized even at elevated temperature above Tg of the glass matrix. The thermal stability of the amorphous oxide layer is substantially enhanced due to Be addition. As confirmed by high-temperature cross-section HR-TEM, fully disordered Be-added amorphous layer is observed, while the rapid crystallization is observed without Be. To understand the role of Be, we employed ab-initio molecular dynamics to compare the mobility of ions with/without Be dopant, and propose a disordered model where Be dopant occupies Zr vacancy and induces structural disorder to the amorphous phase. We find that the oxygen mobility is slightly suppressed due to Be dopant, and Be mobility is unexpectedly lower than that of oxygen, which we attribute to the aliovalent nature of Be dopant whose diffusion always accompany multiple counter-diffusion of other ions. Here, we explain the origin of superior thermal stability of amorphous oxide film in terms of enhanced structural disorder and suppressed ionic mobility due to the aliovalent dopant. PMID:26658671

  13. Crystallization Kinetics of a Solid Oxide Fuel Cell Seal Glass by Differential Thermal Analysis

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Gamble, Eleanor A.

    2005-01-01

    Crystallization kinetics of a barium calcium aluminosilicate glass (BCAS), a sealant material for planar solid oxide fuel cells, have been investigated by differential thermal analysis (DTA). From variation of DTA peak maximum temperature with heating rate, the activation energy for glass crystallization was calculated to be 259 kJ/mol. Development of crystalline phases on thermal treatments of the glass at various temperatures has been followed by powder x-ray diffraction. Microstructure and chemical composition of the crystalline phases were investigated by scanning electron microscopy and energy dispersive spectroscopic (EDS) analysis. BaSiO3 and hexacelsian (BaAl2Si2O8) were the primary crystalline phases whereas monoclinic celsian (BaAl2Si2O8) and (Ba(x), Ca(y))SiO4 were also detected as minor phases. Needle-shaped BaSiO3 crystals are formed first, followed by the formation of other phases at longer times of heat treatments. The glass does not fully crystallize even after long term heat treatments at 750 to 900 C.

  14. Computer Simulations of Supercooled Liquids and Glasses

    NASA Astrophysics Data System (ADS)

    Kob, Walter

    Glasses are materials that are ubiquitous in our daily life. We find them in such diverse items as window pans, optical fibers, computer chips, ceramics, all of which are oxide glasses, as well as in food, foams, polymers, gels, which are mainly of organic nature. Roughly speaking glasses are solid materials that have no translational or orientational order on the scale beyond O(10) diameters of the constituent particles (atoms, colloids, …) [1]. Note that these materials are not necessarily homogeneous since, e.g., alkali-glasses such as Na2O-SiO2 show (disordered!) structural features on the length scale of 6-10 Å (compare to the interatomic distance of 1-2 Å) and gels can have structural inhomogeneities that extend up to macroscopic length scales.

  15. On-line coating of glass with tin oxide by atmospheric pressure chemical vapor deposition.

    SciTech Connect

    Allendorf, Mark D.; Sopko, J.F. (PPF Industries, Pittsburgh, PA); Houf, William G.; Chae, Yong Kee; McDaniel, Anthony H.; Li, M. (PPF Industries, Pittsburgh, PA); McCamy, J.W.

    2006-11-01

    Atmospheric pressure chemical vapor deposition (APCVD) of tin oxide is a very important manufacturing technique used in the production of low-emissivity glass. It is also the primary method used to provide wear-resistant coatings on glass containers. The complexity of these systems, which involve chemical reactions in both the gas phase and on the deposition surface, as well as complex fluid dynamics, makes process optimization and design of new coating reactors a very difficult task. In 2001 the U.S. Dept. of Energy Industrial Technologies Program Glass Industry of the Future Team funded a project to address the need for more accurate data concerning the tin oxide APCVD process. This report presents a case study of on-line APCVD using organometallic precursors, which are the primary reactants used in industrial coating processes. Research staff at Sandia National Laboratories in Livermore, CA, and the PPG Industries Glass Technology Center in Pittsburgh, PA collaborated to produce this work. In this report, we describe a detailed investigation of the factors controlling the growth of tin oxide films. The report begins with a discussion of the basic elements of the deposition chemistry, including gas-phase thermochemistry of tin species and mechanisms of chemical reactions involved in the decomposition of tin precursors. These results provide the basis for experimental investigations in which tin oxide growth rates were measured as a function of all major process variables. The experiments focused on growth from monobutyltintrichloride (MBTC) since this is one of the two primary precursors used industrially. There are almost no reliable growth-rate data available for this precursor. Robust models describing the growth rate as a function of these variables are derived from modeling of these data. Finally, the results are used to conduct computational fluid dynamic simulations of both pilot- and full-scale coating reactors. As a result, general conclusions are

  16. Atomic-scale models of early-stage alkali depletion and SiO2-rich gel formation in bioactive glasses.

    PubMed

    Tilocca, Antonio

    2015-01-28

    Molecular dynamics simulations of Na(+)/H(+)-exchanged 45S5 Bioglass® models reveal that a large fraction of the hydroxyl groups introduced into the proton-exchanged, hydrated glass structure do not initially form covalent bonds with Si and P network formers but remain free and stabilised by the modifier metal cations, whereas substantial Si-OH and P-OH bonding is observed only at higher Na(+)/H(+) exchange levels. The strong affinity between free OH groups and modifier cations in the highly fragmented 45S5 glass structure appears to represent the main driving force for this effect. This suggests an alternative direct route for the formation of a repolymerised silica-rich gel in the early stages of the bioactive mechanism, not considered before, which does not require sequential repeated breakings of Si-O-Si bonds and silanol condensations.

  17. Controlled oxidative synthesis of Bi nanoparticles and emission centers in bismuth glass nanocomposites for photonic application

    NASA Astrophysics Data System (ADS)

    Singh, Shiv Prakash; Karmakar, Basudeb

    2011-09-01

    Here we demonstrate an oxidative process to control metallic bismuth (Bi 0) nanoparticles (NPs) creation in bismuth glass nanocomposites by using K 2S 2O 8 as oxidant and enhanced transparency of bismuth glasses. Formation of Bi 0 NPs has been monitored by their distinct surface plasmon resonance (SPR) band at 460 nm in the UV-visible absorption spectra. It is further confirmed by the transmission electron microscopy (TEM) images which disclose the formation of spherical Bi 0 NPs whereas the selected area electron diffraction (SAED) pattern reveals their crystalline rhombohedral phase. These glasses are found to exhibit visible and near infrared (NIR) luminescence bands at 630 and 843 nm respectively on excitation at 460 nm of the SPR band. It is realized that the luminescence center of bismuth species is an uncertain issue, however, it is reasonable to consider that the emission band at 630 nm is due to the combination of 2D 5/2 → 4S 3/2 of Bi 0 and 2P 3/2 (1) → 2P 1/2 of Bi 2+ transitions, and that of NIR emission band at 843 nm is attributed to the 2D 3/2 → 4S 3/2 of Bi 0 transition.

  18. Low-Temperature Excess Specific Heat in Oxide Glasses: Comprehensive Study of Thermometrically Observed Boson Peak

    NASA Astrophysics Data System (ADS)

    Nakamura, Kensaku; Takahashi, Yoshihiro; Fujiwara, Takumi

    2014-11-01

    We present the results of low-temperature (˜5 to 20 K) specific-heat measurements performed in numerous oxide glass systems. These results allow us to elucidate the impact of the system or component on the excess specific heat, which when plotted on Cp/T3 vs T appears as a broad band known as the boson peak (BP). By integrating our experimental results with the data of Richet [http://dx.doi.org/10.1016/j.physb.2009.06.146, Physica B 404, 3799 (2009); http://dx.doi.org/10.1063/1.3677194, J. Chem. Phys. 136, 034703 (2012)], we demonstrate a strong negative correlation between the BP amplitude and its maximum temperature. We also describe the BP characteristics of multicomponent systems based on different binary systems in silicate glasses.

  19. Ultrasonic study on some borosilicate glasses doped with different transition metal oxides

    NASA Astrophysics Data System (ADS)

    Marzouk, S. Y.; Gaafar, M. S.

    2007-12-01

    Longitudinal and shear ultrasonic wave velocities were measured in borosilicate glasses doped with different transition metal oxides (TMOs) (where TMO=NiO, V 2O 5, Fe 2O 3, MnO 2, TiO 2, Cr 2O 3, CoO, CuO) using the pulse echo technique. Measurements were carried out at 4 MHz frequency and at room temperature. Elastic moduli and some other physical parameters such as acoustic impedance, softening temperature, Debye temperature, thermal expansion coefficient, and latent heat of melting have been calculated. Results indicated that these parameters depend upon the TMO modifier, i.e., the ionic radius of the transition metal cation. A quantitative analysis has been carried out, in order to obtain more information about the structure of these glasses, based on bond compression model, and the Makishima and Mackenzie model, i.e., the cation-anion bond of each TMO.

  20. Alkali metal nitrate purification

    DOEpatents

    Fiorucci, Louis C.; Morgan, Michael J.

    1986-02-04

    A process is disclosed for removing contaminants from impure alkali metal nitrates containing them. The process comprises heating the impure alkali metal nitrates in solution form or molten form at a temperature and for a time sufficient to effect precipitation of solid impurities and separating the solid impurities from the resulting purified alkali metal nitrates. The resulting purified alkali metal nitrates in solution form may be heated to evaporate water therefrom to produce purified molten alkali metal nitrates suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of purified alkali metal nitrates.

  1. Chromium speciation in oxide-type compounds: application to minerals, gems, aqueous solutions and silicate glasses

    NASA Astrophysics Data System (ADS)

    Farges, François

    2009-09-01

    Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO4 2- moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.

  2. Insights into Silicate and Oxide Melt Structure from Amorphous, Non-Glass-Forming Materials

    NASA Astrophysics Data System (ADS)

    Stebbins, J. F.

    2015-12-01

    Many silicate and oxide liquids of interest in the Earth sciences and in technology cannot readily be quenched to glasses, either because of low silica contents (and hence low viscosity at the melting point and accompanying liquid 'fragility') or because of liquid-liquid unmixing at high temperature. Although in-situ, high temperature structural tools have been in use for decades and are rapidly developing, many methods are still most informative for glass samples quenched to ambient pressure and temperature, e.g. high-resolution solid-state NMR. Amorphous oxides, including alumina and silicate compositions, have widespread technological applications. These are generally deposited by a variety of high-energy sputtering methods, as films of thicknesses of 10's to 100's of nm. Using Al-27, Si-29, and O-17 NMR, we have recently shown that for such films, very similar short-range structure is seen in materials made by very different kinetic pathways, such as sol-gel synthesis vs. ion-beam sputtering. This path-independent structure suggests that these materials pass through transient equilibrium states during their formation, probably that of deeply supercooled liquids just above glass transition temperatures. In the HfO2-SiO2 and ZrO2-SiO2 systems, for example, samples have well-resolved O-17 NMR spectra, allowing quantitation of O sites with only Hf(Zr) neighbors (so-called "free" oxide ions), with mixed Hf(Zr) and Si neighbors, and Si only. The observed oxygen speciation agrees well with a simple thermodynamic model of one of the most fundamental equilibria in silicate systems, namely the reaction of bridging (Si-O-Si) and "free" (e.g. OHf3 and OHf4) oxide ions to produce "non-bridging" oxygens (e.g. Si-OHf2). This new approach to sampling such structural equilibria in compositions far outside the range of normal glass-forming liquids may provide new insights into more geological compositions as well, as well as in more general models of silicate melt chemistry.

  3. Fifty years of Mössbauer spectroscopy: from alloys and oxides to glasses and nanoparticles

    NASA Astrophysics Data System (ADS)

    Johnson, C. E.; Johnson, J. A.

    2012-03-01

    The Mössbauer Effect was discovered in 1957. In 1960 Mössbauer spectroscopy was born when two important papers appeared on (i) the magnetic hyperfine interaction and (ii) the electric monopole (isomer shift) and quadrupole interactions. These transformed an interesting phenomenon into a method for probing solids. Applications to magnetism, metals and alloys, chemical compounds, biological molecules, geology, archaeology and other sciences followed and are still of current interest. Two areas of research where Mössbauer spectroscopy is making unique contributions are in determining oxidation states in (i) glasses and (ii) nanoparticles. Some recent measurements are described.

  4. High temperature alkali corrosion of ceramics in coal gas

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-05-27

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  5. High temperature alkali corrosion of ceramics in coal gas

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1991-11-30

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this program is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  6. High temperature alkali corrosion of ceramics in coal gas

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-08-29

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  7. Hollow microspheres of silica glass and method of manufacture

    DOEpatents

    Downs, Raymond L.; Miller, Wayne J.

    1982-01-01

    A method of manufacturing gel powder suitable for use as a starting material in the manufacture of hollow glass microspheres having a high concentration of silica. The powder is manufactured from a gel containing boron in the amount of about 1% to 20% (oxide equivalent mole percent), alkali metals, specifically potassium and sodium, in an amount exceeding 8% total, and the remainder silicon. Preferably, the ratio of potassium to sodium is greater than 1.5.

  8. The alkali metals: 200 years of surprises.

    PubMed

    Dye, James L

    2015-03-13

    Alkali metal compounds have been known since antiquity. In 1807, Sir Humphry Davy surprised everyone by electrolytically preparing (and naming) potassium and sodium metals. In 1808, he noted their interaction with ammonia, which, 100 years later, was attributed to solvated electrons. After 1960, pulse radiolysis of nearly any solvent produced solvated electrons, which became one of the most studied species in chemistry. In 1968, alkali metal solutions in amines and ethers were shown to contain alkali metal anions in addition to solvated electrons. The advent of crown ethers and cryptands as complexants for alkali cations greatly enhanced alkali metal solubilities. This permitted us to prepare a crystalline salt of Na(-) in 1974, followed by 30 other alkalides with Na(-), K(-), Rb(-) and Cs(-) anions. This firmly established the -1 oxidation state of alkali metals. The synthesis of alkalides led to the crystallization of electrides, with trapped electrons as the anions. Electrides have a variety of electronic and magnetic properties, depending on the geometries and connectivities of the trapping sites. In 2009, the final surprise was the experimental demonstration that alkali metals under high pressure lose their metallic character as the electrons are localized in voids between the alkali cations to become high-pressure electrides!

  9. The alkali metals: 200 years of surprises.

    PubMed

    Dye, James L

    2015-03-13

    Alkali metal compounds have been known since antiquity. In 1807, Sir Humphry Davy surprised everyone by electrolytically preparing (and naming) potassium and sodium metals. In 1808, he noted their interaction with ammonia, which, 100 years later, was attributed to solvated electrons. After 1960, pulse radiolysis of nearly any solvent produced solvated electrons, which became one of the most studied species in chemistry. In 1968, alkali metal solutions in amines and ethers were shown to contain alkali metal anions in addition to solvated electrons. The advent of crown ethers and cryptands as complexants for alkali cations greatly enhanced alkali metal solubilities. This permitted us to prepare a crystalline salt of Na(-) in 1974, followed by 30 other alkalides with Na(-), K(-), Rb(-) and Cs(-) anions. This firmly established the -1 oxidation state of alkali metals. The synthesis of alkalides led to the crystallization of electrides, with trapped electrons as the anions. Electrides have a variety of electronic and magnetic properties, depending on the geometries and connectivities of the trapping sites. In 2009, the final surprise was the experimental demonstration that alkali metals under high pressure lose their metallic character as the electrons are localized in voids between the alkali cations to become high-pressure electrides! PMID:25666067

  10. Mechanical and thermal characterization of a ceramic/glass composite seal for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Dev, Bodhayan; Walter, Mark E.; Arkenberg, Gene B.; Swartz, Scott L.

    2014-01-01

    Solid oxide fuel cells (SOFCs) require seals that can function in harsh, elevated temperature environments. Comprehensive characterization and understanding of seals is needed for commercially viable SOFCs. The present research focuses on a novel ceramic/glass composite seal that is produced by roller compaction or tape casting of glass and ceramic powders and an organic binder. Upon heat treatment, micro-voids and surface anomalies are formed. Increased heating and cooling rates during the heat treatment resulted in more and larger voids. The first goal of the current research is to suggest an appropriate heating and cooling rate to minimize the formation of microstructural defects. After identifying an appropriate cure cycle, seals were thermally cycled and then characterized with laser dilatometry, X-ray diffraction, and sonic resonance. From these experiments the crystalline phases, thermal expansion, and elastic properties were determined. Subsequently compression testing with an acoustic emission (AE) sensor and post-test microstructural analysis were used to identify the formation of damage. By fully understanding the characteristics of this ceramic/glass composite seal, next generation seals can be fabricated for improved performance.

  11. Locally enhanced dissolution rate as a probe for nanocontact-induced densification in oxide glasses.

    PubMed

    Niu, Yi-Fan; Han, Kun; Guin, Jean-Pierre

    2012-07-24

    Atomic force microscopy (AFM) was used to characterize the surface damage (nanoindentations) effect on the chemical durability of glass surfaces (silica and soda-lime silicate glasses, WG). In basic solutions, an enhanced dissolution rate is reported and quantified at indentation sites (+10.5 nm/h and +52 nm/h for silica and WG, respectively) whereas none was observed once the indented surfaces were thermally annealed at 0.9 × T(g) for 2 h, a thermal treatment known for curing high pressure-induced permanent densification in oxides glasses. A direct link between high pressure-induced structural modifications encountered during nanoindentation and the measured dissolution rates is established. It is shown that this property conjointly used with the high resolution of the atomic force microscope may be used for probing, at the nanometer scale, the size and the nature of the structurally modified area underneath residual nanoindentation impressions. As an example, for 10 mN Vickers nanoindentations on WG, the zone affected by the permanently and structurally modified zone under the residual impression is found to be equal to (741 ± 30) nm with a transition zone thickness from the fully densified material to the elastically deformed one ranging between 115 and 165 nm.

  12. Modeling of the Effective Elastic and Thermal Properties of Glass-Ceramic Solid Oxide Fuel Cell Seal Materials

    SciTech Connect

    Milhans, Jacqueline; Ahzi, Said; Garmestani, Hamid; Khaleel, Mohammad A.; Sun, Xin; Koeppel, Brian J.

    2009-05-01

    In this study, the effective elastic properties and coefficients of thermal expansion (CTE) of a glass-ceramic were predicted using homogenization techniques. Using G18, a glass-ceramic solid oxide fuel cell (SOFC) sealant as an initial reference material, the effectiveness of different homogenization models was investigated for a two-phase glass-ceramic. The elastic properties and CTEs of the G18 amorphous phase are currently unknown. Thus, estimated values were used as an input to the models. The predictive model offers accurate macroscopic values on both the elastic modulus and the CTE of glass-ceramic materials, providing the estimated amorphous values are reasonable. This model can be used in designing glass-ceramic SOFC seal materials for its specific operation conditions.

  13. Suppression of alkali-induced oxidative injury in the cornea by mesenchymal stem cells growing on nanofiber scaffolds and transferred onto the damaged corneal surface.

    PubMed

    Cejkova, Jitka; Trosan, Peter; Cejka, Cestmir; Lencova, Anna; Zajicova, Alena; Javorkova, Eliska; Kubinova, Sarka; Sykova, Eva; Holan, Vladimir

    2013-11-01

    The purpose of this study was to investigate whether rabbit bone marrow-derived mesenchymal stem cells (MSCs) effectively decrease alkali-induced oxidative stress in the rabbit cornea. The alkali (0.15 N NaOH) was applied on the corneas of the right eyes and then rinsed with tap water. In the first group of rabbits the injured corneas remained untreated. In the second group MSCs were applied on the injured corneal surface immediately after the injury and eyelids sutured for two days. Then the sutures were removed. In the third group nanofiber scaffolds seeded with MSCs (and in the fourth group nanofibers alone) were transferred onto the corneas immediately after the injury and the eyelids sutured. Two days later the eyelid sutures were removed together with the nanofiber scaffolds. The rabbits were sacrificed on days four, ten or fifteen after the injury, and the corneas were examined immunohistochemically, morphologically, for the central corneal thickness (taken as an index of corneal hydration) using an ultrasonic pachymeter and by real-time PCR. Results show that in untreated injured corneas the expression of malondialdehyde (MDA) and nitrotyrosine (NT) (important markers of lipid peroxidation and oxidative stress) appeared in the epithelium. The antioxidant aldehyde dehydrogenase 3A1 (ALDH3A1) decreased in the corneal epithelium, particularly in superficial parts, where apoptotic cell death (detected by active caspase-3) was high. (In control corneal epithelium MDA and NT are absent and ALDH3A1 highly present in all layers of the epithelium. Cell apoptosis are sporadic). In injured untreated cornea further corneal disturbances developed: The expressions of matrix metalloproteinase 9 (MMP9) and proinflammatory cytokines, were high. At the end of experiment (on day 15) the injured untreated corneas were vascularized and numerous inflammatory cells were present in the corneal stroma. Vascular endothelial growth factor (VEGF) expression and number of macrophages

  14. High-precision determination of iron oxidation state in silicate glasses using XANES

    SciTech Connect

    Cottrell, Elizabeth; Kelley, Katherine A.; Lanzirotti, Antonio; Fischer, Rebecca A.

    2009-11-04

    Fe K-edge X-ray absorption near-edge structure (XANES) and Moessbauer spectra were collected on natural basaltic glasses equilibrated over a range of oxygen fugacity (QFM - 3.5 to QFM + 4.5). The basalt compositions and fO{sub 2} conditions were chosen to bracket the natural range of redox conditions expected for basalts from mid-ocean ridge, ocean island, back-arc basin, and arc settings, in order to develop a high-precision calibration for the determination of Fe{sup 3+}/{Sigma}Fe in natural basalts. The pre-edge centroid energy, corresponding to the 1s {yields} 3d transition, was determined to be the most robust proxy for Fe oxidation state, affording significant advantages compared to the use of other spectral features. A second-order polynomial models the correlation between the centroid and Fe{sup 3+}/{Sigma}Fe, yielding a precision of {+-} 0.0045 in Fe{sup 3+}/{Sigma}Fe for glasses with Fe{sup 3+}/{Sigma}Fe > 8%, which is comparable to the precision of wet chemistry. This high precision relies on a Si (311) monochromator to better define the Fe{sup 2+} and Fe{sup 3+} transitions, accurate and robust modeling of the pre-edge feature, dense fO{sub 2}-coverage and compositional appropriateness of reference glasses, and application of a non-linear drift correction. Through re-analysis of the reference glasses across three synchrotron beam sessions, we show that the quoted precision can be achieved (i.e., analyses are reproducible) across multiple synchrotron beam sessions, even when spectral collection conditions (detector parameters or sample geometry) change. Rhyolitic glasses were also analyzed and yield a higher centroid energy at a given Fe{sup 3+}/{Sigma}Fe than basalts, implying that major variations in melt structure affect the relationship between centroid position and Fe{sup 3+}/{Sigma}Fe, and that separate calibrations are needed for the determination of oxidation state in basalts and rhyolites.

  15. Alkali resistant optical coatings for alkali lasers and methods of production thereof

    SciTech Connect

    Soules, Thomas F; Beach, Raymond J; Mitchell, Scott C

    2014-11-18

    In one embodiment, a multilayer dielectric coating for use in an alkali laser includes two or more alternating layers of high and low refractive index materials, wherein an innermost layer includes a thicker, >500 nm, and dense, >97% of theoretical, layer of at least one of: alumina, zirconia, and hafnia for protecting subsequent layers of the two or more alternating layers of high and low index dielectric materials from alkali attack. In another embodiment, a method for forming an alkali resistant coating includes forming a first oxide material above a substrate and forming a second oxide material above the first oxide material to form a multilayer dielectric coating, wherein the second oxide material is on a side of the multilayer dielectric coating for contacting an alkali.

  16. Method for the safe disposal of alkali metal

    DOEpatents

    Johnson, Terry R.

    1977-01-01

    Alkali metals such as those employed in liquid metal coolant systems can be safely reacted to form hydroxides by first dissolving the alkali metal in relatively inert metals such as lead or bismuth. The alloy thus formed is contacted with a molten salt including the alkali metal hydroxide and possibly the alkali metal carbonate in the presence of oxygen. This oxidizes the alkali metal to an oxide which is soluble within the molten salt. The salt is separated and contacted with steam or steam-CO.sub.2 mixture to convert the alkali metal oxide to the hydroxide. These reactions can be conducted with minimal hydrogen evolution and with the heat of reaction distributed between the several reaction steps.

  17. Investigation of the oxidation states of Cu additive in colored borosilicate glasses by electron energy loss spectroscopy

    SciTech Connect

    Yang, Guang Cheng, Shaodong; Li, Chao; Ma, Chuansheng; Zhong, Jiasong; Xiang, Weidong; Wang, Zhao

    2014-12-14

    Three optically transparent colorful (red, green, and blue) glasses were synthesized by the sol-gel method. Nano-sized precipitates were found in scanning electron microscopy images. The precipitates were analyzed by transmission electron microscopy (TEM) and high resolution TEM. The measured lattice parameters of these precipitates were found to fit the metallic copper in red glass but deviate from single valenced Cu oxides in green and blue glasses. The chemistry of these nano-sized particles was confirmed by electron energy loss spectroscopy (EELS). By fitting the EELS spectra obtained from the precipitates with the linear combination of reference spectra from Cu reference compounds, the oxidation states of Cu in the precipitates have been derived. First principle calculations suggested that the Cu nano-particles, which are in the similar oxidation states as our measurement, would show green color in the visible light range.

  18. Creep Behavior of Glass/Ceramic Sealant and its Effect on Long-term Performance of Solid Oxide Fuel Cells

    SciTech Connect

    Liu, Wenning N.; Sun, Xin; Koeppel, Brian J.; Stephens, Elizabeth V.; Khaleel, Mohammad A.

    2009-10-14

    The creep behavior of glass or glass-ceramic sealant materials used in solid oxide fuel cells (SOFCs) becomes relevant under SOFC operating temperatures. In this paper, the creep of glass-ceramic sealants was experimentally examined, and a standard linear solid model was applied to capture the creep behavior of glass ceramic sealant materials developed for planar SOFCs at high temperatures. The parameters of this model were determined based on the creep test results. Furthermore, the creep model was incorporated into finite-element software programs SOFC-MP and Mentat-FC developed at Pacific Northwest National Laboratory for multi-physics simulation of SOFCs. The effect of creep of glass ceramic sealant materials on the long-term performance of SOFC stacks was investigated by studying the stability of the flow channels and the stress redistribution in the glass seal and on the various interfaces of the glass seal with other layers. Finite element analyses were performed to quantify the stresses in various parts. The stresses in glass seals were released because of creep behavior during operations.

  19. The synthesis of higher oxides of alkali and alkaline earth metals in an electric discharge: Theoretical and experimental studies

    NASA Technical Reports Server (NTRS)

    Bell, A. T.; Sadhukhan, P.

    1974-01-01

    Potassium hydroxide was subjected to the products of an electrical discharge sustained in oxygen and produced both potassium peroxide and superoxide. The conversion to higher oxides was shown to strongly depend upon the particle size of KOH, the position of KOH in the discharge zone, and the operating conditions of the discharge. Similar experiments were performed with hydroxides of lithium and calcium which do not form superoxides, but are converted to peroxides. The yields of peroxides were shown to strongly depend upon the operating conditions of the discharge. The absence of superoxides and the presence of peroxides of lithium and calcium was explained from the consideration of relative thermodynamic stability of the oxides of lithium and calcium. Thermogravimetric analysis was shown to provide a more accurate means for determining the amount of KO2 than previous methods.

  20. Purification, biochemical characterization, and implications of an alkali-tolerant catalase from the spacecraft-associated and oxidation-resistant Acinetobacter gyllenbergii 2P01AA.

    PubMed

    Muster, N; Derecho, I; Dallal, F; Alvarez, R; McCoy, K B; Mogul, R

    2015-04-01

    Herein, we report on the purification, characterization, and sequencing of catalase from Acinetobacter gyllenbergii 2P01AA, an extremely oxidation-resistant bacterium that was isolated from the Mars Phoenix spacecraft assembly facility. The Acinetobacter are dominant members of the microbial communities that inhabit spacecraft assembly facilities and consequently may serve as forward contaminants that could impact the integrity of future life-detection missions. Catalase was purified by using a 3-step chromatographic procedure, where mass spectrometry provided respective subunit and intact masses of 57.8 and 234.6 kDa, which were consistent with a small-subunit tetrameric catalase. Kinetics revealed an extreme pH stability with no loss in activity between pH 5 and 11.5 and provided respective kcat/Km and kcat values of ∼10(7) s(-1) M(-1) and 10(6) s(-1), which are among the highest reported for bacterial catalases. The amino acid sequence was deduced by in-depth peptide mapping, and structural homology suggested that the catalases from differing strains of A. gyllenbergii differ only at residues near the subunit interfaces, which may impact catalytic stability. Together, the kinetic, alkali-tolerant, and halotolerant properties of the catalase from A. gyllenbergii 2P01AA are significant, as they are consistent with molecular adaptations toward the alkaline, low-humidity, and potentially oxidizing conditions of spacecraft assembly facilities. Therefore, these results support the hypothesis that the selective pressures of the assembly facilities impact the microbial communities at the molecular level, which may have broad implications for future life-detection missions.

  1. Purification, biochemical characterization, and implications of an alkali-tolerant catalase from the spacecraft-associated and oxidation-resistant Acinetobacter gyllenbergii 2P01AA.

    PubMed

    Muster, N; Derecho, I; Dallal, F; Alvarez, R; McCoy, K B; Mogul, R

    2015-04-01

    Herein, we report on the purification, characterization, and sequencing of catalase from Acinetobacter gyllenbergii 2P01AA, an extremely oxidation-resistant bacterium that was isolated from the Mars Phoenix spacecraft assembly facility. The Acinetobacter are dominant members of the microbial communities that inhabit spacecraft assembly facilities and consequently may serve as forward contaminants that could impact the integrity of future life-detection missions. Catalase was purified by using a 3-step chromatographic procedure, where mass spectrometry provided respective subunit and intact masses of 57.8 and 234.6 kDa, which were consistent with a small-subunit tetrameric catalase. Kinetics revealed an extreme pH stability with no loss in activity between pH 5 and 11.5 and provided respective kcat/Km and kcat values of ∼10(7) s(-1) M(-1) and 10(6) s(-1), which are among the highest reported for bacterial catalases. The amino acid sequence was deduced by in-depth peptide mapping, and structural homology suggested that the catalases from differing strains of A. gyllenbergii differ only at residues near the subunit interfaces, which may impact catalytic stability. Together, the kinetic, alkali-tolerant, and halotolerant properties of the catalase from A. gyllenbergii 2P01AA are significant, as they are consistent with molecular adaptations toward the alkaline, low-humidity, and potentially oxidizing conditions of spacecraft assembly facilities. Therefore, these results support the hypothesis that the selective pressures of the assembly facilities impact the microbial communities at the molecular level, which may have broad implications for future life-detection missions. PMID:25826195

  2. Graphite oxidation in the Apollo 17 orange glass magma: Implications for the generation of a lunar volcanic gas phase

    NASA Astrophysics Data System (ADS)

    Nicholis, Mike G.; Rutherford, Malcolm J.

    2009-10-01

    An Apollo 17 picritic orange glass composition has been used to experimentally investigate the conditions at which graphite would oxidize to form a CO-rich gas, and ultimately produce lunar fire-fountain eruptions. Isothermal decompression experiments run above the A17 orange glass liquidus temperature (>1350 °C) suggest that the initial CO-rich gas phase produced by graphite oxidation would be generated during magma ascent at a pressure of 40 MPa, ˜8.5 km beneath the lunar surface. Additional experiments with 2000 ppm S and 1000 ppm Cl showed that the presence of these dissolved gas species would not affect the depth of graphite oxidation, verifying that the first volcanic gas phase would be generated by the oxidation of graphite. A simple ideal chemical mixing model for calculating melt FeO activity in a Fe-metal/silicate melt system was tested with a series of 0.1 MPa controlled oxygen fugacity experiments. Agreement between the model and experiments allows the model to be used to calculate oxygen fugacity in picritic lunar glass compositions such as the A17 orange glass. Using this model in a reanalysis of chemical equilibria between the natural A17 orange glass melt and the metal spherules (Fe 85Ni 14Co 1) trapped within the glass beads indicates a log oxygen fugacity of -11.2, 0.7 log units, more oxidized than previous estimates. At the A17 orange glass liquidus temperature (1350 ± 5 °C), this fO2 corresponds to a minimum pressure of 41 MPa on the graphite-C-O surface. The fact that the same critical graphite oxidation pressure was determined in decompression experiments and from the Fe-FeO activity model for the natural A17 orange glass-metal assemblage strongly supports this pressure (8.5 km depth) for volcanic gas formation in lunar basalts. Generation of a gas by oxidation of C in ascending magma is likely to have been important in getting dense lunar magmas to the surface as well as in generating fire-fountain eruptions. The vesicles common in many

  3. Methods of vitrifying waste with low melting high lithia glass compositions

    DOEpatents

    Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.

    2001-01-01

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

  4. Synchrotron Micro-XANES Measurements of Vanadium Oxidation State in Glasses as a Function of Oxygen Fugacity: Experimental Calibration of Data Relevant to Partition Coefficient Determination

    NASA Technical Reports Server (NTRS)

    Delaney, J. S.; Sutton, S. R.; Newville, M.; Jones, J. H.; Hanson, B.; Dyar, M. D.; Schreiber, H.

    2000-01-01

    Oxidation state microanalyses for V in glass have been made by calibrating XANES spectral features with optical spectroscopic measurements. The oxidation state change with fugacity of O2 will strongly influence partitioning results.

  5. Advanced degradation of brominated epoxy resin and simultaneous transformation of glass fiber from waste printed circuit boards by improved supercritical water oxidation processes.

    PubMed

    Liu, Kang; Zhang, Zhiyuan; Zhang, Fu-Shen

    2016-10-01

    This work investigated various supercritical water oxidation (SCWO) systems, i.e. SCWO1 (only water), SCWO2 (water+H2O2) and SCWO3 (water+H2O2/NaOH), for waste printed circuit boards (PCBs) detoxification and recycling. Response surface methodology (RSM) was applied to optimize the operating conditions of the optimal SCWO3 systems. The optimal reaction conditions for debromination were found to be the NaOH of 0.21g, the H2O2 volume of 9.04mL, the time of 39.7min, maximum debromination efficiency of 95.14%. Variance analysis indicated that the factors influencing debromination efficiency was in the sequence of NaOH>H2O2>time. Mechanism studies indicated that the dissociated ions from NaOH in supercritical water promoted the debromination of brominated epoxy resins (BERs) through an elimination reaction and nucleophilic substitution. HO2, produced by H2O2 could induce the oxidation of phenol ring to open (intermediates of BERs), which were thoroughly degraded to form hydrocarbons, CO2, H2O and NaBr. In addition, the alkali-silica reaction between OH(-) and SiO2 induced the phase transformation of glass fibers, which were simultaneously converted into anorthite and albite. Waste PCBs in H2O2/NaOH improved SCWO system were fully degraded into useful products and simultaneously transformed into functional materials. These findings are helpful for efficient recycling of waste PCBs.

  6. Preparation of lead oxide nanoparticles from cathode-ray tube funnel glass by self-propagating method.

    PubMed

    Wang, Yu; Zhu, Jianxin

    2012-05-15

    This paper presents a novel process of extracting lead oxide nanoparticles from cathode-ray tube (CRT) funnel glass using self-propagating high-temperature synthesis (SHS) method. The impacts of added amount of funnel glass on the extraction ratio of lead, the lead extraction velocity and the micromorphology, as well as particle size of extracted nanoparticles were investigated. We found that self-propagating reaction in the presence of Mg and Fe(2)O(3) could separate lead preferentially and superfine lead oxide nanoparticles were obtained from a collecting chamber. The separation ratio was related closely to the amount of funnel glass added in the original mixture. At funnel glass addition of no more than 40wt.%, over 90wt.% of lead was recovered from funnel glass. High extraction yield reveals that the network structure of funnel glass was fractured due to the dramatic energy generated during the SHS melting process. The PbO nanoparticles collected show good dispersion and morphology with a mean grain size of 40-50nm.

  7. Catalytic evaluation of promoted CeO2-ZrO2 by transition, alkali, and alkaline-earth metal oxides for diesel soot oxidation.

    PubMed

    Alinezhadchamazketi, Ali; Khodadadi, Abas Ali; Mortazavi, Yadollah; Nemati, Ahmad

    2013-12-01

    Series of mixed metal oxides were synthesized by gel-combustion method and their catalytic activities for soot oxidation were investigated. The catalysts were M-Ce-Zr (M = Mn, Cu, Fe, K, Ba, Sr), and xK-20Mn-Ce-Zr (x = 0, 5, 10, 20), they were characterized by XRD, SEM, TPR and BET surface area techniques. The results of soot temperature programmed oxidation (TPO) in an O2 oxidizing atmosphere indicate that K-Ce-Zr has the highest catalytic activity for soot oxidation under loose contact condition, due to enhancement of the soot and catalyst contacts. On the other hand, under a tight contact condition, Mn-Ce-Zr and Cu-Ce-Zr nano-composites have high activities for soot oxidation and lower the soot TPO peak temperatures by about 280 and 270 degrees C, respectively, as compared to non-catalytic soot oxidation. Furthermore, the addition of up to 10 wt.% potassium oxides into Mn-Ce-Zr increases its catalytic activity and further reduces the soot TPO peak temperature by about 40 degrees C under loose contact condition.

  8. Improving the chemical compatibility of sealing glass for solid oxide fuel cells: Blocking the reactive species by controlled crystallization

    NASA Astrophysics Data System (ADS)

    Zhang, Teng; Zou, Qi; Zeng, Fanrong; Wang, Shaorong; Tang, Dian; Yang, Hiswen

    2012-10-01

    The chemical compatibility of sealing glass is of great importance for Solid oxide fuel cell (SOFC). In this work, the interfacial reaction between sealing glass and Cr-containing interconnect alloy is characterized by reacting Cr2O3 powders with a representative SrO-containing glass crystallized by different heat-treatment schedules. The crystalline structure and crystalline content of sealing glass are determined by X-ray diffraction. The results show that the fraction of Cr6+ decreases from 39.8 ± 1.9% for quenched glass to 8.2 ± 0.4% for glass crystallized at 900 °C for 2 h. In addition, the interfacial reaction can be further reduced with increasing crystallization temperature and time as well as the addition of nucleation agent (TiO2). The formation of some Sr-containing crystalline phases, Sr2SiO4 and Sr(TiO3), contributes to the improvement of chemical compatibility of sealing glass, in agreement with the results of thermodynamic calculations.

  9. Lipid peroxidation product 4-hydroxynonenal as factor of oxidative homeostasis supporting bone regeneration with bioactive glasses.

    PubMed

    Mrakovcic, Lidija; Wildburger, Renate; Jaganjac, Morana; Cindric, Marina; Cipak, Ana; Borovic-Sunjic, Suzana; Waeg, Georg; Milankovic, Andrea M; Zarkovic, Neven

    2010-01-01

    Bone regeneration is a process of vital importance since fractures of long bones and large joints have a highly deleterious impact on both, individuals and society. Numerous attempts have been undertaken to alleviate this severe medical and social problem by development of novel bioactive materials, among which bioactive glass is the most attractive because of its osteoconductive and osteostimulative properties. Since lipid peroxidation is an important component of systematic stress response in patients with traumatic brain injuries and bone fractures, studies have been undertaken of the molecular mechanisms of the involvement of 4-hydroxynonenal (HNE), an end product of lipid peroxidation, in cellular growth regulation. We found that HNE generated in bone cells grown in vitro on the surfaces of bioactive glasses 45S5 and 13-93. This raises an interesting possibility of combined action of HNE and ionic bioglass dissolution products in enhanced osteogenesis probably through a mitogen-activated protein kinase (MAPK) pathway. While the proposed mechanism still has to be elucidated, the finding of HNE generation on bioglass offers a new interpretation of the osteoinducting mechanisms of bioglass and suggests the possibility of tissue engineering based on manipulations of oxidative homeostasis.

  10. Thermoluminescence properties of lithium magnesium borate glasses system doped with dysprosium oxide.

    PubMed

    Mhareb, M H A; Hashim, S; Ghoshal, S K; Alajerami, Y S M; Saleh, M A; Razak, N A B; Azizan, S A B

    2015-12-01

    We report the impact of dysprosium (Dy(3+)) dopant and magnesium oxide (MgO) modifier on the thermoluminescent properties of lithium borate (LB) glass via two procedures. The thermoluminescence (TL) glow curves reveal a single prominent peak at 190 °C for 0.5 mol% of Dy(3+). An increase in MgO contents by 10 mol% enhances the TL intensity by a factor of 1.5 times without causing any shift in the maximum temperature. This enhancement is attributed to the occurrence of extra electron traps created via magnesium and the energy transfer to trivalent Dy(3+) ions. Good linearity in the range of 0.01-4 Gy with a linear correlation coefficient of 0.998, fading as low as 21% over a period of 3 months, excellent reproducibility without oven annealing and tissue equivalent effective atomic numbers ~8.71 are achieved. The trap parameters, including geometric factor (μg), activation energy (E) and frequency factor (s) associated with LMB:Dy are also determined. These favorable TL characteristics of prepared glasses may contribute towards the development of Li2O-MgO-B2O3 radiation dosimeters.

  11. Thermoluminescence properties of lithium magnesium borate glasses system doped with dysprosium oxide.

    PubMed

    Mhareb, M H A; Hashim, S; Ghoshal, S K; Alajerami, Y S M; Saleh, M A; Razak, N A B; Azizan, S A B

    2015-12-01

    We report the impact of dysprosium (Dy(3+)) dopant and magnesium oxide (MgO) modifier on the thermoluminescent properties of lithium borate (LB) glass via two procedures. The thermoluminescence (TL) glow curves reveal a single prominent peak at 190 °C for 0.5 mol% of Dy(3+). An increase in MgO contents by 10 mol% enhances the TL intensity by a factor of 1.5 times without causing any shift in the maximum temperature. This enhancement is attributed to the occurrence of extra electron traps created via magnesium and the energy transfer to trivalent Dy(3+) ions. Good linearity in the range of 0.01-4 Gy with a linear correlation coefficient of 0.998, fading as low as 21% over a period of 3 months, excellent reproducibility without oven annealing and tissue equivalent effective atomic numbers ~8.71 are achieved. The trap parameters, including geometric factor (μg), activation energy (E) and frequency factor (s) associated with LMB:Dy are also determined. These favorable TL characteristics of prepared glasses may contribute towards the development of Li2O-MgO-B2O3 radiation dosimeters. PMID:25828828

  12. Cytotoxicity, oxidative stress and genotoxicity induced by glass fibers on human alveolar epithelial cell line A549.

    PubMed

    Rapisarda, Venerando; Loreto, Carla; Ledda, Caterina; Musumeci, Giuseppe; Bracci, Massimo; Santarelli, Lory; Renis, Marcella; Ferrante, Margherita; Cardile, Venera

    2015-04-01

    Man-made vitreous fibers have been widely used as insulation material as asbestos substitutes; however their morphology and composition raises concerns. In 1988 the International Agency for Research on Cancer classified fiberglass, rock wool, slag wool, and ceramic fibers as Group 2B, i.e. possibly carcinogenic to humans. In 2002 it reassigned fiberglass, rock and slag wool, and continuous glass filaments to Group 3, not classifiable as carcinogenic to humans. The aim of this study was to verify the cytotoxic and genotoxic effects and oxidative stress production induced by in vitro exposure of human alveolar epithelial cells A549 to glass fibers with a predominant diameter <3 μm (97%) and length >5 μm (93%). A549 cells were incubated with 5, 50, or 100 μg/ml (2.1, 21, and 42 μg/cm(2), respectively) of glass fibers for 72 h. Cytotoxicity and DNA damage were tested by the MTT and the Comet assay, respectively. Oxidative stress was determined by measuring inducible nitric oxide synthase (iNOS) expression by Western blotting, production of nitric oxide (NO) with Griess reagent, and concentration of reactive oxygen species by fluorescent quantitative analysis with 2',7'-dichlorofluorescein-diacetate (DCFH-DA). The results showed that glass fiber exposure significantly reduced cell viability and increased DNA damage and oxidative stress production in a concentration-dependent manner, demonstrating that glass fibers exert cytotoxic and genotoxic effects related to increased oxidative stress on the human alveolar cell line A549.

  13. Fabrication of efficient thermoacoustic device with an interdigitated-like electrode on indium tin oxide glass

    NASA Astrophysics Data System (ADS)

    Tsai, Ming-shan; Yang, Ko-kang; Chen, Sy-hann; Ting, Chen-ching; Jiang, I.-min

    2016-10-01

    A thermoacoustic device was fabricated on indium tin oxide (ITO) glass, exhibiting an interdigitated-like electrode pattern. Our fabrication method enhanced the sound performance by approximately 20 dB compared with that of plain ITO film. Two approaches were adopted in this study to enhance the sound pressure level (SPL). One was to decrease the heat capacity per unit area of the device by reducing the thickness of the conductor film, and the other was to increase the thermal diffusivity of the device by applying a thin Au film on the electrode. We observed that heat generated by electron accumulation on ITO protrusions resulted in a large temperature oscillation of the surroundings and induced an SPL increase. A 4 nm Au film coating on the fabricated thermoacoustic device assisted thermal energy exchange with close-proximity air, improving the efficiency by an SPL of 7 dB.

  14. Glass-ceramic sealant for solid oxide fuel cells application: Characterization and performance in dual atmosphere

    NASA Astrophysics Data System (ADS)

    Sabato, A. G.; Cempura, G.; Montinaro, D.; Chrysanthou, A.; Salvo, M.; Bernardo, E.; Secco, M.; Smeacetto, F.

    2016-10-01

    A glass-ceramic composition was designed and tested for use as a sealant in solid oxide fuel cell (SOFC) planar stack design. The crystallization behaviour was investigated by calculating the Avrami parameter (n) and the activation energy for crystallization (Ec) was obtained. The calculated values for n and Ec were 3 and 413.5 kJ/mol respectively. The results of thermal analyses indicate that this composition shows no overlap between the sintering and crystallization stages and thus an almost pore-free sealant can be deposited and sintered at 850 °C in air for 30 min. A gas tightness test has been carried out at 800 °C for 1100 h in dual atmosphere (Ar-H2 and air) without recording any leakage. Morphological and crystalline phase analyses were conducted prior and following tests in dual atmospheres in order to assess the compatibility of the proposed sealant with the metallic interconnect.

  15. Preparation of Li3BO3-Li2SO4 glass-ceramic electrolytes for all-oxide lithium batteries

    NASA Astrophysics Data System (ADS)

    Tatsumisago, Masahiro; Takano, Ryohei; Tadanaga, Kiyoharu; Hayashi, Akitoshi

    2014-12-01

    Newly designed oxide glass-ceramic electrolyte of Li2.9B0.9S0.1O3.1 with high Li+ ion conductivity and low melting property was prepared by mechanical milling and subsequent heat treatment at 290 °C. This material showed 1.4 × 10-5 S cm-1 at room temperature and excellent deformation properties to obtain powder-compressed pellets with low interfacial resistance like in the case of sulfide solid electrolytes. The glass-ceramic exhibited favorable mechanical properties to form favorable solid-solid contacts in solid-state batteries by pressing without high temperature heat treatments. All-solid-state In/LiCoO2 cells using these oxide glass-ceramic electrolytes operated as secondary batteries at room temperature.

  16. Selective trans-membrane transport of alkali and alkaline earth cations through graphene oxide membranes based on cation-π interactions.

    PubMed

    Sun, Pengzhan; Zheng, Feng; Zhu, Miao; Song, Zhigong; Wang, Kunlin; Zhong, Minlin; Wu, Dehai; Little, Reginald B; Xu, Zhiping; Zhu, Hongwei

    2014-01-28

    Graphene and graphene oxide (G-O) have been demonstrated to be excellent filters for various gases and liquids, showing potential applications in areas such as molecular sieving and water desalination. In this paper, the selective trans-membrane transport properties of alkali and alkaline earth cations through a membrane composed of stacked and overlapped G-O sheets ("G-O membrane") are investigated. The thermodynamics of the ion transport process reveal that the competition between the generated thermal motions and the interactions of cations with the G-O sheets results in the different penetration behaviors to temperature variations for the considered cations (K(+), Mg(2+), Ca(2+), and Ba(2+)). The interactions between the studied metal atoms and graphene are quantified by first-principles calculations based on the plane-wave-basis-set density functional theory (DFT) approach. The mechanism of the selective ion trans-membrane transportation is discussed further and found to be consistent with the concept of cation-π interactions involved in biological systems. The balance between cation-π interactions of the cations considered with the sp(2) clusters of G-O membranes and the desolvation effect of the ions is responsible for the selectivity of G-O membranes toward the penetration of different ions. These results help us better understand the ion transport process through G-O membranes, from which the possibility of modeling the ion transport behavior of cellular membrane using G-O can be discussed further. The selectivity toward different ions also makes G-O membrane a promising candidate in areas of membrane separations.

  17. Oxidation of PAHs in a simplified system using peroxy-acid and glass beads: Identification of oxidizing species.

    PubMed

    Alderman, Norman S; Nyman, Marianne C

    2009-09-01

    Polycyclic aromatic hydrocarbons (PAHs) are organic contaminants of concern due to their ubiquity, persistence in the natural environment and adverse health effects. Numerous studies have looked into the removal and treatment of these contaminants, with mixed results. High molecular weight PAHs have been particularly problematic due to their hydrophobicity and high affinity for organics, resulting in mass transfer limitations for even the fastest advanced oxidation processes (AOPs). The peroxy-acid process has been used to successfully treat PAH contaminated matrices. Experiments were conducted on benzo[a]pyrene contaminated glass beads in order to elucidate the reaction mechanisms responsible for the effectiveness of this process. For the first time peracetic acid (PAA) was identified as the important oxidant in this reaction. Different v/v/v ratios of hydrogen peroxide/acetic acid/DI water were studied which illustrated the importance of reaction ratio on oxidant concentration and rate of formation. Approximately 60% degradation of benzo[a]pyrene was achieved in 24 hours with 1.7% PAA. Observations of the reaction kinetics suggest that the slow desorption/dissolution of benzo[a]pyrene limits the efficiency of the peroxy-acid process. Modifications of the reaction setup supported this observation as treatment efficiencies increased with reactive surface area, and an increase in system agitation. These limitations were also overcome by increasing the concentration of PAA delivered to the contaminated matrix. Greater than 80% degradation of benzo[a]pyrene was achieved in 24 hours with approximately 9.2% PAA. PMID:19847697

  18. Structure of glasses containing transition metal ions. Progress report, February 1, 1979-January 31, 1980

    SciTech Connect

    White, W B; Furukawa, T; Tsong, I S.T.; Fox, K; Herman, J S; Houser, C; Nelson, C

    1980-02-01

    New normal coordinate calculations were used to relate the vibrational frequencies of silicate glasses to Si-O force constants. These appear to account for the observed frequency shifts with degree of silica polymerization. Raman spectroscopy has been used to elucidate the structure of sodium borosilicate glasses and of sodium aluminosilicate glasses. Structures of compositionally complex glasses can be understood if spectra are measured on many glasses spaced at small compositional intervals. Optical absorption spectra were used to investigate the structural setting of iron in alkali silicate glasses. Research on the alkali-hydrogen exchange in alkali silicate glasses was completed and additional work on ternary glasses is under way. A series of appendices present completed work on the structural investigations of alkali borosilicate glasses, on the structural setting of transition metal ions in glasses, and on the diffusion of hydrogen in alkali silicate glasses.

  19. Attaching an alkali metal atom to an alkaline earth metal oxide (BeO, MgO, or CaO) yields a triatomic metal oxide with reduced ionization potential and redirected polarity.

    PubMed

    Nowiak, Grzegorz; Skurski, Piotr; Anusiewicz, Iwona

    2016-04-01

    The existence of a series of neutral triatomic metal oxides MON and their corresponding cations MON (+) (M = Be, Mg, Ca; N = Li, Na, K) was postulated and verified theoretically using ab initio methods at the CCSD(T)/6-311+G(3df)//MP2/6-311+G(3df) level of theory. The calculations revealed that the vertical ionization potentials (IPs) of the MON radicals (calculated using the outer-valence Green's function technique (OVGF) with the 6-311+G(3df) basis set) were ca. 2-3 eV smaller than the IPs of the corresponding MO and NO systems or that of the isolated M atom. Population analysis of the neutral triatomic MON molecules and their corresponding MO counterparts indicated that the attachment of an alkali metal atom to any oxide MO (BeO, MgO, CaO) reverses its polarity, which manifests itself as the redirection of the dipole moment vector. PMID:26994021

  20. IR, Raman, and NMR studies of the short-range structures of 0.5Na2S + 0.5[xGeS2 + (1-x)PS(5/2)] mixed glass-former glasses.

    PubMed

    Bischoff, Christian; Schuller, Katherine; Dunlap, Nathan; Martin, Steve W

    2014-02-20

    A nonlinear and nonadditive composition-dependent change of the ionic conductivity in mixed glass-former (MGF) glasses when one glass former, such as PS(5/2), is replaced by a second glass former, such as GeS2, at constant alkali modifier concentrations, such as Na2S, is known as the mixed glass-former effect (MGFE). Alkali ion conducting glasses are of particular interest for use as solid electrolytes in alkali-based all-solid-state batteries because sulfide amorphous materials have significantly higher alkali ion conductivities than their oxide glass counterparts. In this study of the ternary MGF system Na2S + GeS2 + PS(5/2), we report the careful structural characterization of these glasses using a combination of vibrational, infrared (IR), Raman, and nuclear magnetic resonance (NMR) spectroscopies. Our measurements of the 0.5Na2S + 0.5[xGeS2 + (1-x)PS(5/2)] MGF system show that this glass system exhibits a strongly negative MGFE and non-Arrhenius ionic conductivities. While this negative MGFE in the Na(+) ion conductivity makes these glasses less attractive for use in solid-state Na batteries, the structural origin of this effect is important to better understand the mechanisms of ion conduction in the glassy state. For these reasons, we have examined the structures of ternary 0.5Na2S + 0.5[xGeS2 + (1-x)PS(5/2)] glasses using Raman, IR, and (31)P MAS NMR spectroscopies. In these studies, it is found that the substitution of PS(5/2) by GeS2, that is, increasing x, leads to unequal sharing of the Na(+) in these glasses. Thus, in all MGF compositions, phosphorus groups are associated with a disproportionately larger fraction, f(Na(P)) > 0.5(1 - x), of the Na(+) ions while the germanium groups are found to be Na(+)-deficient relative to the total amount of Na(+) present in the glass, that is, f(Na(Ge)) < 0.5x. From the spectroscopic study of these glasses, a short-range order (SRO) structural model is developed for these glasses and is based on the germanium and

  1. A comparison of ZnO films deposited on indium tin oxide and soda lime glass under identical conditions

    SciTech Connect

    Deka, Angshuman; Nanda, Karuna Kar

    2013-06-15

    ZnO films have been grown via a vapour phase transport (VPT) on soda lime glass (SLG) and indium-tin oxide (ITO) coated glass. ZnO film on ITO had traces of Zn and C which gives them a dark appearance while that appears yellowish-white on SLG. X-ray photoelectron spectroscopy studies confirm the traces of C in the form of C-O. The photoluminescence studies reveal a prominent green luminescence band for ZnO film on ITO.

  2. Characterization of ceramic/glass composite seals for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Dev, Bodhayan

    Solid oxide fuel cells (SOFCs) require seals that can function in harsh, elevated temperature environments. Comprehensive characterization and understanding of seals is needed for commercially viable SOFCs. The present research focuses on a novel ceramic/glass composite seal that is produced by roller compaction or tape casting of glass and ceramic powders and a proprietary organic binder. Upon heat treatment, micro-voids and surface anomalies are formed. Increased heating and cooling rates during the heat treatment resulted in more and larger voids. The first goal of the current research is to suggest an appropriate heating and cooling rate to minimize the formation of microstructural defects. After identifying an appropriate cure cycle, seals were thermally cycled and then characterized with laser dilatometry, X-Ray diffraction, and sonic resonance. From these experiments the crystalline phases, thermal expansion, and elastic properties were determined. Subsequently compression testing with an acoustic emission (AE) sensor and post-test microstructural analysis were used to identify the formation of damage. The research also focuses on the study of Weibull statistics and thermal responses for cured seals. The green seal was initially cured for 1 thermal cycle based on the aforementioned appropriate thermal cycle. The cycled seal was then characterized with a laser dilatometer to identify the glass transition, softening temperature and thermal expansion properties. High temperature ring-on-ring tests were also performed to study the effect of glass transition and softening temperatures on mechanical responses. In addition, Weibull statistics were conducted to determine the cumulative probability of failure/damage in seals. The third part of the research focuses on the construction and use of a controlled leak testing facility for investigating different interfaces involved in sealing electrolyte-supported cells. Simultaneous leak testing with an acoustic emission

  3. Iron and manganese in oxide minerals and in glasses: preliminary consideration of Eh buffering potential at Yucca Mountain, Nevada

    SciTech Connect

    Caporuscio, F.A.; Vaniman, D.T.

    1985-04-01

    The tuffs of Yucca Mountain at the Nevada Test Site are currently under investigation as a possible deep burial site for high-level radioactive waste disposal. One of the main concerns is the effect of oxidizing groundwater on the transport of radionuclides. Rock components that may affect the oxygen content of groundwater include Fe-Ti oxides, Mn oxides, and glasses that contain ferrous iron. Some phenocryst Fe-Ti oxides at Yucca Mountain are in reduced states, whereas groundmass Fe-Ti oxides have been oxidized to hematite, rutile, and pseudobrookite (Fe{sup 3+}-bearing phases) exclusively. Estimates of Fe{sup 2+}-bearing oxides indicate that less than 0.33 vol% phenocrysts is available to act as solid buffering agents of Eh. Of this percentage, significant amounts of Fe-Ti oxides are isolated from effective interaction with groundwater because they occur in densely welded, devitrified tuffs that have low interstitial permeability. Manganese oxides occur primarily along fractures in the ash-flow tuffs. Because the Mn oxides are concentrated along the same pathways (fractures) where transport has occurred in the past, these small volume percentages could act as buffers. However, the oxidation states of actual Mn-oxide phases are high (Mn{sup 4+}), and these minerals have virtually no potential for reducing groundwater Eh. Manganese oxides may even act as oxidizing agents. However, regardless of their poor capabilities as reducing agents, the Mn oxides could be important as sorbents of heavy metals at Yucca Mountain. The lack of accessible, pristine Fe-Ti oxides and the generally high oxidation states of Mn oxides seem to rule out these oxides as Eh buffers of the Yucca Mountain groundwater system. Reduction of ferrous iron within glassy tuffs may have some effect on Eh, but further study is needed. At present it is prudent to assume that minerals and glasses have little or no capacity for reducing oxygen-rich groundwater at Yucca Mountain. 25 refs., 3 figs., 12

  4. Alkali cation specific adsorption onto fcc(111) transition metal electrodes.

    PubMed

    Mills, J N; McCrum, I T; Janik, M J

    2014-07-21

    The presence of alkali cations in electrolyte solutions is known to impact the rate of electrocatalytic reactions, though the mechanism of such impact is not conclusively determined. We use density functional theory (DFT) to examine the specific adsorption of alkali cations to fcc(111) electrode surfaces, as specific adsorption may block catalyst sites or otherwise impact surface catalytic chemistry. Solvation of the cation-metal surface structure was investigated using explicit water models. Computed equilibrium potentials for alkali cation adsorption suggest that alkali and alkaline earth cations will specifically adsorb onto Pt(111) and Pd(111) surfaces in the potential range of hydrogen oxidation and hydrogen evolution catalysis in alkaline solutions.

  5. Novel alkaline earth silicate sealing glass for SOFC, Part I: the effect of nickel oxide on the thermal and mechanical properties

    SciTech Connect

    Chou, Y. S.; Stevenson, Jeffry W.; Gow, Robert N.

    2007-06-01

    This is a two-part study of a novel Sr-Ca-Ni-Y-B silicate sealing glass for solid oxide fuel cells (SOFC). In this paper (Part I), the effect of NiO on glass forming, thermal, and mechanical properties was studied with two different approaches: glass making and composite glass. In the following paper (Part II), sealing and interfacial microstructure of candidate composite glass with 10v percent NiO will be addressed. In Part I, higher NiO content in the glass resulted in precipitation during the glass making process, and the sintered powder compacts of these glasses showed extensive macro- and micro-cracks. Coefficient of thermal expansion (CTE) showed large decrease for glass with higher NiO contents. On the other hand, glass-based composites showed no fracture even with NiO content as high as 15 percent. The CTE of the composite glass, which increased with increasing NiO content (consistent with the rule of mixtures prediction), could be adjusted to match the CTE of SOFC components. Phase characterization by XRD identified phases of YBO3 and NiO in the glass, which were likely responsible for the poor mechanical and thermal properties for the glass making approach.

  6. Alkali metal directed assembly of heterometallic V(v)/M (M = Na, K, Cs) coordination polymers: structures, topological analysis, and oxidation catalytic properties.

    PubMed

    Gupta, Samik; Kirillova, Marina V; Guedes da Silva, M Fátima C; Pombeiro, Armando J L; Kirillov, Alexander M

    2013-08-01

    The reactions of [VO(acac)2] with bis(salicylaldehyde)-oxaloyldihydrazone (H4L) and an alkali metal carbonate M2CO3 (M = K, Na, Cs), in EtOH/H2O medium upon reflux, resulted in the generation of three new heterometallic V(V)/M materials, namely the 1D [(VO2)2(μ4-L){Na2(μ-H2O)2(H2O)2}]n (1), 2D [{V(μ-O)2}2(μ4-L){K2(μ-H2O)2(H2O)2}]n (2), and 3D [{V(μ-O)(μ3-O)}2(μ8-L){Cs2(μ-H2O)2(H2O)2}]n (3) coordination polymers. They were isolated as air-stable solids and fully characterized by IR, UV-vis, (1)H, and (51)V NMR spectroscopy, ESI-MS(±), elemental, thermal, and single-crystal X-ray diffraction analyses, the latter showing that 1-3 are constructed from the resembling [(VO2)2(μ(4/8)-L)](2-) blocks assembled by the differently bound aqua-metal [M2(μ-H2O)2(H2O)2](2+) moieties (M = Na, K, Cs). The main distinctive features of 1-3 arise from the different coordination numbers of Na (5), K (7), and Cs (9) atoms, thus increasing the complexity of the resulting networks from the ladder-like 1D chains in 1 to double 2D layers in 2, and layer-pillared 3D framework in 3. The topological analysis of 2 disclosed a uninodal 4-connected underlying net with a rare kgm [Shubnikov plane net (3.6.3.6)/kagome pattern] topology, while 3 features a trinodal 4,7,8-connected underlying net with an unprecedented topology. Compounds 1-3 also show solubility in water (S(25 °C) ≈ 4-7 mg mL(-1)) and were applied as efficient precatalysts for the homogeneous oxidation of cyclohexane by aqueous H2O2, under mild conditions (50 °C) in MeCN/H2O medium and in the presence of an acid promoter. Total yields (based on substrate) of cyclohexanol and cyclohexanone up to 36% and turnover numbers (TONs) up to 5700 were achieved.

  7. Oxidation of Al-containing austenitic stainless steels as related to the formation of strong glass-ceramic to metal seals

    SciTech Connect

    Moddeman, W.E.; Birkbeck, J.C.; Bowling, W.C.; Burke, A.R.; Cassidy, R.T.

    1996-08-01

    In glass-ceramic to metal seals used in pyrotechnic actuators and ignitors, Ni-based alloys and Al-containing austenitic stainless steels are used. Metal attack by the glass is severe if Ni based alloys are used, less so for the Al-containing alloys. In this paper, lithia-alumina-silica glass-ceramic was sealed to Al-containing alloys that were first oxidized prior to sealing (preoxidation). Results show that this preoxidation substantially reduces the probability of glass/metal reactions during seal formation, thus improving the overall quality of the interface without loss of seal bond strength. Mechanism of surface oxide formation of these Al- containing steels is discussed. Auger data show the composition of the resulting oxides to be a function of oxidation temperature. There are two theories on the oxidation mechanism: (1) oxidation occurring at the air/oxide interface (Abderrazik et al, 1987), and (2) oxidation taking place at the oxide/metal interface (Hindam and Smeltzer, 1980). To test the theories, oxidation of the Al-containing alloys was carried out, first in pure oxygen-16, and then followed by pure oxygen-18. SIMS showed no layered structure, but did show a mixture of oxides. Thus, the oxidation mechanism is not simple and must be allowing oxygen to have access at all stages of the oxidation process.

  8. A Mechanistic-Based Healing Model for Self-Healing Glass Seals Used in Solid Oxide Fuel Cells

    SciTech Connect

    Xu, Wei; Sun, Xin; Stephens, Elizabeth V.; Mastorakos, Ioannis; Khaleel, Mohammad A.; Zbib, Hussein M.

    2012-09-01

    The usage of self-healing glass as hermetic seals is a recent advancement in sealing technology development for the planar solid oxide fuel cells (SOFCs). Because of its capability of restoring the mechanical properties at elevated temperatures, the self-healing glass seal is expected to provide high reliability in maintaining the long-term structural integrity and functionality of SOFCs. In order to accommodate the design and to evaluate the effectiveness of such engineering seals under various thermo-mechanical operating conditions, computational modeling framework needs to be developed to accurately capture and predict the healing behavior of the glass material. In the present work, a mechanistic-based two-stage model was developed to study the stress and temperature-dependent crack healing of the self-healing glass materials. The model was first calibrated by experimental measurements combined with the kinetic Monte Carlo (kMC) simulation results and then implemented into the finite element analysis (FEA). The effects of various factors, i.e. stress, temperature, crack morphology, on the healing behavior of the glass were investigated and discussed.

  9. The electrochemiluminescence of luminol on titania nanotubes functionalised indium tin oxide glass for flow injection analysis.

    PubMed

    Zhao, Qun; Xiao, Changbin; Tu, Yifeng

    2015-10-01

    The titania nanotubes (TiNTs) had been immobilised onto the indium tin oxide (ITO) coated glass to intensify the electrochemiluminescence (ECL) of luminol. The morphology, structure and properties such as specific surface area and transmittance of synthesised TiNTs were characterised. The results indicated that the TiNTs was several hundred nanometres in length with the diameter of 20 nm. In flow injection analysis (FIA) mode, the TiNTs dramatically enhanced the ECL emission of luminol for about 25 multiple, meanwhile decreased the requirement of buffer pH and exciting potential. The ECL emission of luminol on functionalised ITO electrode has sensitive response toward hydrogen peroxide, and extraordinarily responsive toward the antioxidant. Under the optimal conditions, the ECL emission exhibited a linear response within the concentration range from 0.1 mg L(-1) to 30 mg L(-1) and an absolute detection limit of 1.65×10(-10) g of resveratrol. The gross antioxidant activity of blueberry and kiwi were determined with satisfactory recoveries.

  10. Contactless surface conductivity mapping of graphene oxide thin films deposited on glass with scanning electrochemical microscopy.

    PubMed

    Azevedo, Joel; Bourdillon, Céline; Derycke, Vincent; Campidelli, Stéphane; Lefrou, Christine; Cornut, Renaud

    2013-02-01

    The present article introduces a rapid, very sensitive, contactless method to measure the local surface conductivity with Scanning Electrochemical Microscopy (SECM) and obtain conductivity maps of heterogeneous substrates. It is demonstrated through the study of Graphene Oxide (GO) thin films deposited on glass. The adopted substrate preparation method leads to conductivity disparities randomly distributed over approximately 100 μm large zones. Data interpretation is based on an equation system with the dimensionless conductivity as the only unknown parameter. A detailed prospection provides a consistent theoretical framework for the reliable quantification of the conductivity of GO with SECM. Finally, an analytical approximation of the conductivity as a function of the feedback current is proposed, making any further interpretation procedure straightforward, as it does not require iterative numerical simulations any more. The present work thus provides not only valuable information on the kinetics of GO reduction in mild conditions but also a general and simplified interpretation framework that can be extended to the quantitative conductivity mapping of other types of substrates. PMID:23259661

  11. High-contrast visualization of graphene oxide on dye-sensitized glass, quartz, and silicon by fluorescence quenching.

    PubMed

    Treossi, Emanuele; Melucci, Manuela; Liscio, Andrea; Gazzano, Massimo; Samorì, Paolo; Palermo, Vincenzo

    2009-11-01

    We present a novel approach for detecting and visualizing graphene oxide (GO) with high contrast on different substrates, including glass, quartz, and silicon. Visualization of GO sheets is accomplished through quenching the fluorescence of a thiophene dye, giving high optical contrast without the need to use interference methods. A comparison of fluorescence, AFM, and XRD measurements confirmed that even a single GO sheet can completely quench the fluorescence and thus be quickly visualized.

  12. The effect of composition on the viscosity, crystallization and dissolution of simple borate glasses and compositional design of borate based bioactive glasses

    NASA Astrophysics Data System (ADS)

    Goetschius, Kathryn Lynn

    Borate glasses have recently been developed for a variety of medical applications, but much less is known about their structures and properties than more common silicate glasses. Melt properties and crystallization tendency for compositions in the Na2O-CaO-B2O3 system were characterized using differential thermal analysis and viscosity measurements. Characteristic viscosity (isokom) temperatures varied with the ratio between the modifier content (Na2O+CaO) and B2O3, particularly at lower temperatures, consistent with the changes in the relative concentrations of tetrahedral borons in the glass structure. Similar glasses were used to study dissolution processes in water. These alkali-alkaline earth glasses dissolve congruently and follow linear dissolution kinetics. The dissolution rates were dependent on the glass structure, with slower rates associated with greater fractions of four-coordinated boron. For glasses with a fixed alkaline earth identity, the dissolution rates increased in the order Liglasses with a constant alkali identity, the dissolution rates increased in the order Caalkali and alkaline earth oxides on dissolution rates are discussed in terms of competing effects of four-coordinated boron and the field strength of the modifying cation. Finally, a seven component (Na2O, K2O, MgO, CaO, B2O3, SiO2, and P2O5) mixture model design was used to predict composition-property relationships to optimize the properties of new borate-based bioactive compositions for specific applications. Melt viscosity, thermal expansion coefficient, liquidus temperature and crystallization tendency were determined, as were dissolution rates in simulated body fluid (SBF).

  13. Method for Fabricating Textured High-Haze ZnO:Al Transparent Conduction Oxide Films on Chemically Etched Glass Substrates.

    PubMed

    Park, Hyeongsik; Nam, Sang-Hun; Shin, Myunghun; Ju, Minkyu; Lee, Youn-Jung; Yu, Jung-Hoon; Jung, Junhee; Kim, Sunbo; Ahn, Shihyun; Boo, Jin-Hyo; Yi, Junsin

    2016-05-01

    We developed a technique for forming textured aluminum-doped zinc oxide (ZnO:Al) transparent conductive oxide (TCO) films on glass substrates, which were etched using a mixture of hydrofluoric (HF) and hydrochloric (HCl) acids. The etching depth and surface roughness increased with an increase in the HF content and the etching time. The HF-based residues produced insoluble hexafluorosilicate anion- and oxide impurity-based semipermeable films, which reduced the etching rate. Using a small amount of HCl dissolved the Ca compounds, helping to fragment the semipermeable film. This formed random, complex structures on the glass substrates. The angled deposition of three layers of ZnO:Al led to the synthesis of multiscaled ZnO:Al textures on the glass substrates. The proposed approach resulted in textured ZnO:Al TCO films that exhibited high transmittance (-80%) and high haze (> 40%) values over wavelengths of 400-1000 nm, as well as low sheet resistances (< 18 Ω/sq)..Si tandem solar cells based on the ZnO:Al textured TCO films exhibited photocurrents and cell efficiencies that were 40% higher than those of cells with conventional TCO films. PMID:27483840

  14. The effect of chromium oxide on the properties of simulated nuclear waste glasses

    SciTech Connect

    Vojtech, O.; Sussmilch, J.; Urbanec, Z.

    1996-02-01

    A study of the effect of chromium on the properties of selected glasses was performed in the frame of a Contract between Battelle, Pacific Northwest Laboratories and Nuclear Research Institute, ReZ. In the period from July 1994 to June 1995 two borosilicate glasses of special composition were prepared according to the PNL procedure and their physical and structural characteristics of glasses were studied. This Final Report contains a vast documentation on the properties of all glasses studied. For the preparation of the respective technology more detailed study of physico-chemical properties and crystallinity of investigated systems would be desirable.

  15. GLASSES CONTAINING IRON (II III) OXIDES FOR IMMOBILIZATION OF RADIOACTIVE TECHNETIUM

    SciTech Connect

    KRUGER AA; HEO J; XU K; CHOI JK; HRMA PR; UM W

    2011-11-07

    Technetium-99 (Tc-99) has posed serious environmental threats as US Department of Energy's high-level waste. This work reports the vitrification of Re, as surrogate for Tc-99, by iron-borosilicate and iron-phosphate glasses, respectively. Iron-phosphate glasses can dissolve Re as high as {approx} 1.2 wt. %, which can become candidate waste forms for Tc-99 disposal, while borosilicate glasses can retain less than 0.1 wt. % of Re due to high melting temperature and long melting duration. Vitrification of Re as Tc-99's mimic was investigated using iron-borosilicate and iron-phosphate glasses. The retention of Re in borosilicate glasses was less than 0.1 wt. % and more than 99 wt. % of Re were volatilized due to high melting temperature and long melting duration. Because the retention of Re in iron-phosphate glasses is as high as 1.2 wt. % and the volatilization is reduced down to {approx}50 wt. %, iron-phosphate glasses can be one of the glass waste form candidates for Tc (or Re) disposal. The investigations of chemical durability and leaching test of iron-phosphate glasses containing Re are now underway to test the performance of the waste form.

  16. Alkali metal ionization detector

    DOEpatents

    Bauerle, James E.; Reed, William H.; Berkey, Edgar

    1978-01-01

    Variations in the conventional filament and collector electrodes of an alkali metal ionization detector, including the substitution of helical electrode configurations for either the conventional wire filament or flat plate collector; or, the substitution of a plurality of discrete filament electrodes providing an in situ capability for transferring from an operationally defective filament electrode to a previously unused filament electrode without removing the alkali metal ionization detector from the monitored environment. In particular, the helical collector arrangement which is coaxially disposed about the filament electrode, i.e. the thermal ionizer, provides an improved collection of positive ions developed by the filament electrode. The helical filament design, on the other hand, provides the advantage of an increased surface area for ionization of alkali metal-bearing species in a monitored gas environment as well as providing a relatively strong electric field for collecting the ions at the collector electrode about which the helical filament electrode is coaxially positioned. Alternatively, both the filament and collector electrodes can be helical. Furthermore, the operation of the conventional alkali metal ionization detector as a leak detector can be simplified as to cost and complexity, by operating the detector at a reduced collector potential while maintaining the sensitivity of the alkali metal ionization detector adequate for the relatively low concentration of alkali vapor and aerosol typically encountered in leak detection applications.

  17. Sulfate Fining Chemistry in Oxidized and Reduced Soda-Lime-Silica Glasses

    SciTech Connect

    Matyas, Josef; Hrma, Pavel R.

    2005-05-13

    Various reducing agents were used and their additions were varied to (1) increase glass quality through eliminating defects from silica scum, (2) decrease SOx emissions through changing the kind and quantity of reducing agents, and (3) improve production efficiency through increased flexibility of glass redox control during continuous processing. The work included measuring silica sand dissolution and sulfate decomposition in melts from glass batches. Glass batches were heated at a temperature-increase rate deemed similar to that experienced in the melting furnace. The sulfate decomposition kinetics was investigated with thermogravimetric analysis-differential thermal analysis and evolved gas analysis. Sulfur concentrations in glasses quenched at different temperatures were determined using X-ray fluorescence spectroscopy. The distribution of residual sand (that which was not dissolved during the initial batch reactions) in the glass was obtained as a function of temperature with optical microscopy in thin-sections of melts. The fraction of undissolved sand was measured with X-ray diffraction. The results of the present study helped Visteon Inc. reduce the energy consumption and establish the batch containing 0.118 mass% of graphite as the best candidate for Visteon glass production. The improved glass batch has a lower potential for silica scum formation and for brown fault occurrence in the final glass product. It was established that bubbles trapped in the melt even at 1450 C have a high probability to be refined when reaching the hot zone in the glass furnace. Furthermore, silica sand does not accumulate at the glass surface and dissolves faster in the batch with graphite than in the batch with carbocite.

  18. The comparison of calculated transition probabilities with luminescence characteristics of erbium(III) in fluoride glasses and in the mixed yttrium-zirconium oxide crystal

    NASA Astrophysics Data System (ADS)

    Reisfeld, R.; Katz, G.; Jacoboni, C.; De Pape, R.; Drexhage, M. G.; Brown, R. N.; Jørgensen, C. K.

    1983-07-01

    Fluorozirconate glasses containing 2 mole% ErF 3 were prepared by melting the binary fluorides with ammonium bifluoride under an atmosphere of carbon tetrachloride and argon at 850°C. Absorption spectra of these glasses were obtained and the Judd-Ofelt parameters were calculated. Emission spectra and lifetimes of erbium in fluorozirconate glass, in lead-gallium-zinc fluoride glass, and in yttrium-zirconium oxide crystal were measured and compared with the theoretical calculations. Laser emission lines in these materials are deduced from these measurements. It is suggested that materials doped with erbium may serve as light sources for fiber optic waveguides made from the undoped materials.

  19. The oxidation state of Fe in MORB glasses and the oxygen fugacity of the upper mantle

    NASA Astrophysics Data System (ADS)

    Cottrell, Elizabeth; Kelley, Katherine A.

    2011-05-01

    Micro-analytical determination of Fe3+/∑Fe ratios in mid-ocean ridge basalt (MORB) glasses using micro X-ray absorption near edge structure (μ-XANES) spectroscopy reveals a substantially more oxidized upper mantle than determined by previous studies. Here, we show that global MORBs yield average Fe3+/∑Fe ratios of 0.16 ± 0.01 (n = 103), which trace back to primary MORB melts equilibrated at the conditions of the quartz-fayalite-magnetite (QFM) buffer. Our results necessitate an upward revision of the Fe3+/∑Fe ratios of MORBs, mantle oxygen fugacity, and the ferric iron content of the mantle relative to previous wet chemical determinations. We show that only 0.01 (absolute, or < 10%) of the difference between Fe3+/∑Fe ratios determined by micro-colorimety and XANES can be attributed to the Mössbauer-based XANES calibration. The difference must instead derive from a bias between micro-colorimetry performed on experimental vs. natural basalts. Co-variations of Fe3+/∑Fe ratios in global MORB with indices of low-pressure fractional crystallization are consistent with Fe3+ behaving incompatibly in shallow MORB magma chambers. MORB Fe3+/∑Fe ratios do not, however, vary with indices of the extent of mantle melting (e.g., Na2O(8)) or water concentration. We offer two hypotheses to explain these observations: The bulk partition coefficient of Fe3+ may be higher during peridotite melting than previously thought, and may vary with temperature, or redox exchange between sulfide and sulfate species could buffer mantle melting at ~ QFM. Both explanations, in combination with the measured MORB Fe3+/∑Fe ratios, point to a fertile MORB source with greater than 0.3 wt.% Fe2O3.

  20. Theoretical simulations of protective thin film Fabry-Pérot filters for integrated optical elements of diode pumped alkali lasers (DPAL)

    SciTech Connect

    Quarrie, L. E-mail: lindsay.o.quarrie@gmail.com

    2014-09-15

    The lifetime of Diode-Pumped Alkali Lasers (DPALs) is limited by damage initiated by reaction of the glass envelope of its gain medium with rubidium vapor. Rubidium is absorbed into the glass and the rubidium cations diffuse through the glass structure, breaking bridging Si-O bonds. A damage-resistant thin film was developed enhancing high-optical transmission at natural rubidium resonance input and output laser beam wavelengths of 780 nm and 795 nm, while protecting the optical windows of the gain cell in a DPAL. The methodology developed here can be readily modified for simulation of expected transmission performance at input pump and output laser wavelengths using different combination of thin film materials in a DPAL. High coupling efficiency of the light through the gas cell was accomplished by matching the air-glass and glass-gas interfaces at the appropriate wavelengths using a dielectric stack of high and low index of refraction materials selected to work at the laser energies and protected from the alkali metal vapor in the gain cell. Thin films as oxides of aluminum, zirconium, tantalum, and silicon were selected allowing the creation of Fabry-Perot optical filters on the optical windows achieving close to 100% laser transmission in a solid optic combination of window and highly reflective mirror. This approach allows for the development of a new whole solid optic laser.

  1. Theoretical simulations of protective thin film Fabry-Pérot filters for integrated optical elements of diode pumped alkali lasers (DPAL)

    NASA Astrophysics Data System (ADS)

    Quarrie, L.

    2014-09-01

    The lifetime of Diode-Pumped Alkali Lasers (DPALs) is limited by damage initiated by reaction of the glass envelope of its gain medium with rubidium vapor. Rubidium is absorbed into the glass and the rubidium cations diffuse through the glass structure, breaking bridging Si-O bonds. A damage-resistant thin film was developed enhancing high-optical transmission at natural rubidium resonance input and output laser beam wavelengths of 780 nm and 795 nm, while protecting the optical windows of the gain cell in a DPAL. The methodology developed here can be readily modified for simulation of expected transmission performance at input pump and output laser wavelengths using different combination of thin film materials in a DPAL. High coupling efficiency of the light through the gas cell was accomplished by matching the air-glass and glass-gas interfaces at the appropriate wavelengths using a dielectric stack of high and low index of refraction materials selected to work at the laser energies and protected from the alkali metal vapor in the gain cell. Thin films as oxides of aluminum, zirconium, tantalum, and silicon were selected allowing the creation of Fabry-Perot optical filters on the optical windows achieving close to 100% laser transmission in a solid optic combination of window and highly reflective mirror. This approach allows for the development of a new whole solid optic laser.

  2. Engineering rare-earth-doped heavy metal oxide glasses for 2-5 μm lasers

    NASA Astrophysics Data System (ADS)

    Richards, Billy D. O.; Jha, Animesh; Dorofeev, Vitaly; Manzur, Tariq

    2010-04-01

    The electronic states in trivalent rare-earth ions offer an excellent opportunity for designing efficient fibre and bulk lasers for atmospheric remote sensing and LIDAR technology. The first part of this review article focuses on engineering passive fibres for 2-5 μm transmission. The fabrication of single-mode tungsten tellurite optical fibres from high purity bulk glass rods is described. Fibres with a numerical aperture of 0.1 and core diameter of 10+/-2 μm have been drawn using suction and rod-in-tube techniques of fibre preform fabrication. Losses of 2.3 dBm-1 at 974 nm have been measured. These fibres are of interest for use as passive transmission fibre or active fibres for lasing in the 2-5 μm spectral region. The use of heavy metal oxides in the fabrication of glass leads to extended infrared transmission. In the 2nd part of the review we compare the slope efficiencies of Tm3+ and Tm3+/Ho3+ doped glasses and fibres for 1950-2080 nm lasers using a range of pumping schemes in tellurite and germanium oxide hosts. We also explain the importance of choosing 1950-2080 nm tunable lasers as a pump source for stimulated emission at longer wavelengths.

  3. Redox equilibria of multivalent ions in silicate glasses

    NASA Technical Reports Server (NTRS)

    Lauer, H. V., Jr.; Morris, R. V.

    1977-01-01

    Experimental studies were made on the compositional dependence of the redox equilibrium of Eu in synthetic silicate liquids, together with an empirical model describing the observed compositional dependence. Electron paramagnetic resonance (EPR) was used to measure the concentration ratio of Eu(2+) to Eu(3+) in various glasses formed by rapidly quenching silicate liquids. The compositional field studied comprised mixtures of SiO2, TiO2, Al2O3, CaO, MgO, and Na2O. The proposed model describes the Eu(2+)/Eu(3+) ratio over the entire compositional field in terms of parameters easily related to each glass composition. The general applicability and utility of the model is further demonstrated by its application to the Fe(2+)-Fe(3+), Ce(3+)-Ce(4+), and Cr(3+)-Cr(6+) redox reactions in binary alkali oxide silicate glasses of Li, Na, and K.

  4. Spectroscopic investigations of neptunium`s and plutonium`s oxidation states in sol-gel glasses as a function of initial valance and thermal history

    SciTech Connect

    Stump, N.A.; Haire, R.G.; Dai, S.

    1996-12-01

    Several oxidation states of neptunium and plutonium, Pu(III),Pu (IV), PU(VI), Np(IV), Np(V) and Np (VI), were studied in glasses prepared by a sol-gel technology. The oxidation state of these actinides was determined primarily by absorption spectrometry and followed as a function of the solidification process, subsequent aging and thermal treatments. It was determined that the initial oxidation state of the actinides in the starting solutions was essentially maintained through the solidification process to form the glasses. However, during densification and removal of residual solvents at elevated temperatures, both actinides in the different sol-gel products converted completely to their tetravalent states. These results are discussed in terms of our findings in comparable studies that only the tetravalent states of plutonium and neptunium are formed in glasses prepared by dissolving their dioxides in different molten- glass formulations.

  5. Preparation and second-harmonic generation in Pb-doped oxide glasses

    NASA Astrophysics Data System (ADS)

    Liu, Qiming; Wang, Mingliang; Zhao, Xiujian

    2008-12-01

    PbO-B2O3 glasses were prepared by traditional melting method. XRD and optical spectra measurements were done to check properties. Second-harmonic generation was observed in the glasses induced by thermal treatment and thermally poling process, respectively. But second-harmonic generation intensity was normally larger for the later, and it increased with increasing PbO content, poling voltage, temperature and time. The mechanism of second-harmonic generation in the PbO-B2O3 glasses was also discussed. A promising material for all-optical switching devices is expected.

  6. The IR emitting centers in Bi-doped Mg-Al-Si oxide glasses

    NASA Astrophysics Data System (ADS)

    Denker, B.; Galagan, B.; Osiko, V.; Shulman, I.; Sverchkov, S.; Dianov, E.

    2009-05-01

    The properties of IR emission centers are investigated in Bi-doped Mg-Al-silicate glasses having moderate melting temperatures to be fabricated by routine melting in alumina crucibles. The quadratic concentration dependence of absorption in the visible range indicates that the considered optical centers can be Bi2 dimers forming in a balanced chemical reaction in the glass melt. Their formation enthalpy is evaluated from their concentration variations with the synthesis temperature. The high (up to 85% at low concentrations) luminescence quantum yield and wide emission spectrum makes this glass a promising material for tunable lasers.

  7. Effects of alkali treatments on Ag nanowire transparent conductive films

    NASA Astrophysics Data System (ADS)

    Kim, Sunho; Kang, Jun-gu; Eom, Tae-yil; Moon, Bongjin; Lee, Hoo-Jeong

    2016-06-01

    In this study, we employ various alkali materials (alkali metals with different base strengths, and ammonia gas and solution) to improve the conductivity of silver nanowire (Ag NW)-networked films. The alkali treatment appears to remove the surface oxide and improve the conductivity. When applied with TiO2 nanoparticles, the treatment appears more effective as the alkalis gather around wire junctions and help them weld to each other via heat emitted from the reduction reaction. The ammonia solution treatment is found to be quick and aggressive, damaging the wires severely in the case of excessive treatment. On the other hand, the ammonia gas treatment seems much less aggressive and does not damage the wires even after a long exposure. The results of this study highlight the effectiveness of the alkali treatment in improving of the conductivity of Ag NW-networked transparent conductive films.

  8. Analysis of early medieval glass beads - Glass in the transition period

    NASA Astrophysics Data System (ADS)

    Šmit, Žiga; Knific, Timotej; Jezeršek, David; Istenič, Janka

    2012-05-01

    Glass beads from graves excavated in Slovenia and dated archaeologically to the 7th-10th century AD were analysed by the combined PIXE-PIGE method. The results indicate two groups of glass; natron glass made in the Roman tradition and glass made with alkalis from the ash of halophytic plants, which gradually replaced natron glass after c. 800 AD. The alkalis used in the second group of glass seem to be in close relation to a variant of the Venetian white glass that appeared several centuries later. The origin of this glass may be traced to glass production in Mesopotamia and around the Aral Sea. All the mosaic beads with eye decoration, as well as most of the drawn-segmented and drawn-cut beads analysed, are of plant-ash glass, which confirms their supposed oriental origin.

  9. Compositional dependence of absorption and fluorescence of Yb{sup 3+} in oxide glasses

    SciTech Connect

    Takebe, Hiromichi; Murata, Takahiro; Morinaga, Kenji

    1996-03-01

    The integrated absorption cross section, the spontaneous emission probability, and the stimulated emission cross section of Yb{sup 3+} were determined in silicate, phosphate, borate, germanate, aluminate, gallate, and ZBLAN host glasses. The compositional dependence of the stimulated emission cross section of the {sup 2}F{sub 5/2} {yields} {sup 2}F{sub 7/2} transition is determined mainly by the integrated absorption cross section in the glasses. A peak stimulated emission cross section above 1 pm{sup 2}, which is the highest value in glasses, was obtained in a gallate glass with a composition of 40K{sub 2}O{center_dot}20Ta{sub 2}O{sub 5}{center_dot}40Ga{sub 2}O{sub 3}. The factors affecting the integrated absorption cross section are discussed using the Judd-Ofelt parameters of Er{sup 3+} calculated in previous studies.

  10. Effect of copper oxide on structure and physical properties of lithium lead borate glasses

    NASA Astrophysics Data System (ADS)

    Kashif, I.; Ratep, A.

    2015-09-01

    Copper-doped Lead lithium borate glass samples with the composition of (35- x) Pb3O4- xCuO-65Li2B4O7, where x = 5, 10, 15 or 20 mol%, have been prepared by melt quenching technique. Glass-forming ability, density, electrical conductivity, magnetic susceptibility and structural properties of lead lithium borate glasses have been investigated. IR spectroscopic data show that the copper ions play the role of glass modifier. Addition of CuO influences BO3 ↔ BO4 conversion. Density is expressed in terms of the structural modifications that take place in glass matrix. The increase in Tg reflects an increase in bond strength, and samples obtain more rigid glass structure. Electrical conductivity and magnetic susceptibility χ data show a variable behavior with the increase in the copper content in two valance states Cu+ and Cu+2. In addition, optical properties depend on the change of the role of copper ions in the samples' structure. Optical energy band gap E opt and Urbach energy E tail are determined. The increase in E opt and UV cutoff with an increase in CuO content is due to the decrease in non-bridging oxygen concentration. The decrease in E tail at higher concentrations is attributed to the copper ion accumulation in the interstitial positions and to the formation of orthoborate groups. These samples are suitable for the green light longpass filters.

  11. Low-temperature formation of high-quality gate oxide by ultraviolet irradiation on spin-on-glass

    SciTech Connect

    Usuda, R.; Uchida, K.; Nozaki, S.

    2015-11-02

    Although a UV cure was found to effectively convert a perhydropolysilazane (PHPS) spin-on-glass film into a dense SiO{sub x} film at low temperature, the electrical characteristics were never reported in order to recommend the use of PHPS as a gate-oxide material that can be formed at low temperature. We have formed a high-quality gate oxide by UV irradiation on the PHPS film, and obtained an interface midgap trap density of 3.4 × 10{sup 11 }cm{sup −2} eV{sup −1} by the UV wet oxidation and UV post-metallization annealing (PMA), at a temperature as low as 160 °C. In contrast to the UV irradiation using short-wavelength UV light, which is well known to enhance oxidation by the production of the excited states of oxygen, the UV irradiation was carried out using longer-wavelength UV light from a metal halide lamp. The UV irradiation during the wet oxidation of the PHPS film generates electron-hole pairs. The electrons ionize the H{sub 2}O molecules and facilitate dissociation of the molecules into H and OH{sup −}. The OH{sup −} ions are highly reactive with Si and improve the stoichiometry of the oxide. The UV irradiation during the PMA excites the electrons from the accumulation layer, and the built-in electric field makes the electron injection into the oxide much easier. The electrons injected into the oxide recombine with the trapped holes, which have caused a large negative flat band voltage shift after the UV wet oxidation, and also ionize the H{sub 2}O molecules. The ionization results in the electron stimulated dissociation of H{sub 2}O molecules and the decreased interface trap density.

  12. Low-temperature formation of high-quality gate oxide by ultraviolet irradiation on spin-on-glass

    NASA Astrophysics Data System (ADS)

    Usuda, R.; Uchida, K.; Nozaki, S.

    2015-11-01

    Although a UV cure was found to effectively convert a perhydropolysilazane (PHPS) spin-on-glass film into a dense SiOx film at low temperature, the electrical characteristics were never reported in order to recommend the use of PHPS as a gate-oxide material that can be formed at low temperature. We have formed a high-quality gate oxide by UV irradiation on the PHPS film, and obtained an interface midgap trap density of 3.4 × 1011 cm-2 eV-1 by the UV wet oxidation and UV post-metallization annealing (PMA), at a temperature as low as 160 °C. In contrast to the UV irradiation using short-wavelength UV light, which is well known to enhance oxidation by the production of the excited states of oxygen, the UV irradiation was carried out using longer-wavelength UV light from a metal halide lamp. The UV irradiation during the wet oxidation of the PHPS film generates electron-hole pairs. The electrons ionize the H2O molecules and facilitate dissociation of the molecules into H and OH-. The OH- ions are highly reactive with Si and improve the stoichiometry of the oxide. The UV irradiation during the PMA excites the electrons from the accumulation layer, and the built-in electric field makes the electron injection into the oxide much easier. The electrons injected into the oxide recombine with the trapped holes, which have caused a large negative flat band voltage shift after the UV wet oxidation, and also ionize the H2O molecules. The ionization results in the electron stimulated dissociation of H2O molecules and the decreased interface trap density.

  13. The Oxidation State of Fe in MORB Glasses and the Oxygen Fugacity of the Upper Mantle

    SciTech Connect

    E Cottrell; K Kelley

    2011-12-31

    Micro-analytical determination of Fe{sup 3+}/{Sigma}Fe ratios in mid-ocean ridge basalt (MORB) glasses using micro X-ray absorption near edge structure ({mu}-XANES) spectroscopy reveals a substantially more oxidized upper mantle than determined by previous studies. Here, we show that global MORBs yield average Fe{sup 3+}/{Sigma}Fe ratios of 0.16 {+-} 0.01 (n = 103), which trace back to primary MORB melts equilibrated at the conditions of the quartz-fayalite-magnetite (QFM) buffer. Our results necessitate an upward revision of the Fe{sup 3+}/{Sigma}Fe ratios of MORBs, mantle oxygen fugacity, and the ferric iron content of the mantle relative to previous wet chemical determinations. We show that only 0.01 (absolute, or < 10%) of the difference between Fe{sup 3+}/{Sigma}Fe ratios determined by micro-colorimety and XANES can be attributed to the Moessbauer-based XANES calibration. The difference must instead derive from a bias between micro-colorimetry performed on experimental vs. natural basalts. Co-variations of Fe{sup 3+}/{Sigma}Fe ratios in global MORB with indices of low-pressure fractional crystallization are consistent with Fe{sup 3+} behaving incompatibly in shallow MORB magma chambers. MORB Fe{sup 3+}/{Sigma}Fe ratios do not, however, vary with indices of the extent of mantle melting (e.g., Na{sub 2}O(8)) or water concentration. We offer two hypotheses to explain these observations: The bulk partition coefficient of Fe{sup 3+} may be higher during peridotite melting than previously thought, and may vary with temperature, or redox exchange between sulfide and sulfate species could buffer mantle melting at {approx} QFM. Both explanations, in combination with the measured MORB Fe{sup 3+}/{Sigma}Fe ratios, point to a fertile MORB source with greater than 0.3 wt.% Fe{sub 2}O{sub 3}.

  14. Alkali metal ion battery with bimetallic electrode

    SciTech Connect

    Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

    2015-04-07

    Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

  15. Methods of recovering alkali metals

    DOEpatents

    Krumhansl, James L; Rigali, Mark J

    2014-03-04

    Approaches for alkali metal extraction, sequestration and recovery are described. For example, a method of recovering alkali metals includes providing a CST or CST-like (e.g., small pore zeolite) material. The alkali metal species is scavenged from the liquid mixture by the CST or CST-like material. The alkali metal species is extracted from the CST or CST-like material.

  16. Fast Response and High Sensitivity ZnO/glass Surface Acoustic Wave Humidity Sensors Using Graphene Oxide Sensing Layer

    PubMed Central

    Xuan, Weipeng; He, Mei; Meng, Nan; He, Xingli; Wang, Wenbo; Chen, Jinkai; Shi, Tianjin; Hasan, Tawfique; Xu, Zhen; Xu, Yang; Luo, J. K.

    2014-01-01

    We report ZnO/glass surface acoustic wave (SAW) humidity sensors with high sensitivity and fast response using graphene oxide sensing layer. The frequency shift of the sensors is exponentially correlated to the humidity change, induced mainly by mass loading effect rather than the complex impedance change of the sensing layer. The SAW sensors show high sensitivity at a broad humidity range from 0.5%RH to 85%RH with < 1 sec rise time. The simple design and excellent stability of our GO-based SAW humidity sensors, complemented with full humidity range measurement, highlights their potential in a wide range of applications. PMID:25425458

  17. Chlor-Alkali Technology.

    ERIC Educational Resources Information Center

    Venkatesh, S.; Tilak, B. V.

    1983-01-01

    Chlor-alkali technology is one of the largest electrochemical industries in the world, the main products being chlorine and caustic soda (sodium hydroxide) generated simultaneously by the electrolysis of sodium chloride. This technology is reviewed in terms of electrochemical principles and manufacturing processes involved. (Author/JN)

  18. In Vitro Biocompatibility and Mechanical Performance of Titanium Doped High Calcium Oxide Metaphosphate-Based Glasses

    PubMed Central

    Abou Neel, Ensanya A.; Chrzanowski, Wojciech; Georgiou, George; Dalby, Matthew J.; Knowles, Jonathan C.

    2010-01-01

    This study challenged to produce phosphate-based glasses (PBG) for the treatment of osseous defects. The glasses contained, among other components, 40 mol% CaO and 1–5 mol% TiO2. The mechanical performance and in vitro biocompatibility using both human osteosarcoma and primary osteoblasts were carried out. Incorporation of TiO2 into PBG had no significant effect on strength and modulus. These glasses encouraged attachment and maintained high viability of osteosarcoma cells similar to the positive control surface. Cells grown directly (on glasses) or indirectly (in the presence of glass extracts) showed similar proliferation pattern to the positive control cells with no significant effect of TiO2 detected. Increasing TiO2 content, however, has a profound effect on cytoskeleton organization and spreading and maturation of primary osteoblasts. It is believed that TiO2 might have acted as a chemical cue-modulating cells response, and hence the substrates supported maturation/mineralization of the primary osteoblasts. PMID:21350644

  19. (abstract) Fundamental Mechanisms of Electrode Kinetics and Alkali Metal Atom Transport at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kisor, A.; Kikkert, S. K.

    1993-01-01

    The mechanisms of electrode kinetics and mass transport of alkali metal oxidation and alkali metal cation reduction at the solid electrolyte/porous electrode boundary as well as alkali metal transport through porous metal electrodes has important applications in optimizing device performance in alkali metal thermal to electric converter (AMTEC) cells which are high temperature, high current density electrochemical cells. Basic studies of these processes also affords the opportunity to investigate a very basic electrochemical reaction over a wide range of conditions; and a variety of mass transport modes at high temperatures via electrochemical techniques. The temperature range of these investigations covers 700K to 1240K; the alkali metal vapor pressures range from about 10(sup -2) to 10(sup 2) Pa; and electrodes studied have included Mo, W, Mo/Na(sub 2)MoO(sub 4), W/Na(sub 2)WO(sub 4), WPt(sub x), and WRh(sub x) (1.0 < x < 6.0 ) with Na at Na-beta'-alumina, and Mo with K at K-beta'-alumina. Both liquid metal/solid electrolyte/alkali metal vapor and alkali metal vapor/solid electrolyte/vapor cells have been used to characterize the reaction and transport processes. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes.

  20. High temperature alkali corrosion of ceramics in coal gas

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-02-24

    The high temperature alkali corrosion kinetics of SiC have been systematically investigated from 950 to 1100[degrees]C at 0.63 vol % alkali vapor concentration. The corrosion rate in the presence of alkaliis approximately 10[sup 4] to 10[sup 5] times faster than the oxidation rate of SiC in air. The activation energy associated with the alkali corrosion is 406 kJ/mol, indicating a highly temperature-dependent reaction rate. The rate-controlling step of the overall reaction is likely to be the dissolution of silica in the sodium silicate liquid, based on the oxygen diffusivity data.

  1. Prize for a Faculty Member for Research in an Undergraduate Institution Lecture: Studies of the Structure and Properties of Oxide Glasses with Applications

    NASA Astrophysics Data System (ADS)

    Affatigato, Mario

    2013-03-01

    This presentation will summarize the research work carried out by Prof. Affatigato and his undergraduate students over the past eighteen years. It will focus on some highlighted projects, namely: the determination of glass structure using laser ionization time of flight mass spectrometry; studies of glass modification by laser irradiation; bactericidal glass; and, most recently, glass manufacturing by aerolevitation and glasses for particle detection. The work on mass spectrometry will cover a broad range of oxide glass systems, including the borates, borosilicates, germanate, and gallate families. It has provided novel insights into the structure of glasses at intermediate length scales, measurements that are hard to obtain by any other techniques. The studies of glass structure modification will primarily center on vanadate glasses, which also form the basis for more recent electronic conductivity work at the heart of new particle calorimeter detectors. This project shows the power of serendipity and the strong capabilities of undergraduate students involved in advanced work and state of the art instrumentation. Bactericidal glass illustrates a nice collaborative project that involved simple borate glasses and helped pioneer their use in the human body--work that has led to significant medical developments by other colleagues and researchers. Finally, the aerolevitation project gives new insight into the crystallization and property behavior of glasses and melts at very high temperatures (from 2000 °C to 3000 °C). The work by Prof. Affatigato and his students has been supported by grants from the Research Corporation, the Petroleum Research Fund, and, primarily, by the U.S. National Science Foundation.

  2. Creep rupture of the joint of a solid oxide fuel cell glass-ceramic sealant with metallic interconnect

    NASA Astrophysics Data System (ADS)

    Lin, Chih-Kuang; Lin, Kun-Liang; Yeh, Jing-Hong; Wu, Si-Han; Lee, Ruey-Yi

    2014-01-01

    Creep properties of sandwich joint specimens made of a newly developed BaO-B2O3-Al2O3-SiO2 glass-ceramic sealant (GC-9) and a ferritic-stainless-steel interconnect (Crofer 22 H) for planar solid oxide fuel cells (pSOFCs) are investigated at 800 °C under constant shear and tensile loadings. The creep rupture time of Crofer 22 H/GC-9/Crofer 22 H joint specimens is increased with a decrease in applied load for both shear and tensile loading modes. The given metal/sealant/metal joint has a greater degradation of joint strength at 800 °C under prolonged, constant tensile loading as compared to shear loading. The tensile creep strength at a rupture time of 1000 h is about 9% of the average tensile joint strength, while the shear creep strength at 1000 h is about 23% of the average shear joint strength. Failure patterns of both shear and tensile joint specimens are similar regardless of the creep rupture time. In general, creep cracks initiate at the interface between the (Cr,Mn)3O4 spinel layer and the BaCrO4 chromate layer, penetrate through the BaCrO4 layer, and propagate along the interface between the chromate layer and glass-ceramic substrate until final fracture. Final, fast fracture occasionally takes place within the glass-ceramic layer.

  3. Nd:YVO4 laser direct ablation of indium tin oxide films deposited on glass and polyethylene terephthalate substrates.

    PubMed

    Wang, Jian-Xun; Kwon, Sang Jik; Han, Jae-Hee; Cho, Eou Sik

    2013-09-01

    A Q-switched diode-pumped neodymium-doped yttrium vanadate (Nd:YVO4, lambda = 1064 nm) laser was applied to obtain the indium tin oxide (ITO) patterns on flexible polyethylene terephthalate (PET) substrate by a direct etching method. After the ITO films were deposited on a soda-lime glass and PET substrate, laser ablations were carried out on the ITO films for various conditions and the laser ablated results on the ITO films were investigated and analyzed considering the effects of substrates on the laser etching. The laser ablated widths on ITO deposited on glass were found to be much narrower than those on ITO deposited on PET substrate, especially, at a higher scanning speed of laser beam such as 1000 mm/s and 2000 mm/s. As the thermal conductivity of glass substrate is about 7.5 times higher than that of PET, more thermal energy would be spread and transferred to lateral direction in the ITO film in case of PET substrate. PMID:24205645

  4. Thermal insulation of muscovite/glass ceramic foam for solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Liaw, Da-Wei; Tsai, Chu-Yu; Wei, Wen-Cheng J.

    2011-10-01

    A direct foaming method of dispersed suspensions containing muscovite particulates and a glass powder (47BaO-21B2O3-27SiO2-5Al2O3, in mol%) is used to prepare porous ceramic structures. The sintered foams exhibit extremely low thermal conductivity and slight expansion during the thermal treatment at 1000 °C. Both the foam stability and its thermal conductivity are investigated by considering foaming agents, muscovite/glass ratios, solid contents, microwave drying, wetting behaviors, and foam consolidation. One of the muscovite/glass ceramic foam, thermally treated at 950 °C for 1 h, showed the lowest thermal conductivity of 0.18 W m-1 K-1 at 800 °C among all of the prepared samples. Its gas permeability and compressive strength are 0.1 × 10-7 cm2 and 440 kPa, respectively.

  5. EPR measurement of the effect of glass composition on the oxidation states of europium

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Haskin, L. A.

    1974-01-01

    An investigation was conducted concerning the dependence of the concentration ratio of Eu(2+) to Eu(3+) on composition for silicate liquids whose compositional end members are CaAl2Si2O8 and MgSiO3, MG2SiO4, CaMgSi2O6, CaMgSiO4, CaSiO3, or Ca2SiO4. The liquids were quenched to produce glasses. An electron paramagnetic resonance spectrometer was used to determine the concentration ratios of Eu(2+) to Eu(3+) in the glasses.

  6. Hydrothermal alkali metal recovery process

    DOEpatents

    Wolfs, Denise Y.; Clavenna, Le Roy R.; Eakman, James M.; Kalina, Theodore

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by treating them with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of an added base to establish a pH during the treatment step that is higher than would otherwise be possible without the addition of the base. During the treating process the relatively high pH facilitates the conversion of water-insoluble alkali metal compounds in the alkali metal residues into water-soluble alkali metal constituents. The resultant aqueous solution containing water-soluble alkali metal constituents is then separated from the residue solids, which consist of the treated particles and any insoluble materials formed during the treatment step, and recycled to the gasification process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preferably, the base that is added during the treatment step is an alkali metal hydroxide obtained by water washing the residue solids produced during the treatment step.

  7. The Oxidation State of Fe in Glasses from the Galapagos Archipelago: Variable Oxygen Fugacity as a Function of Mantle Source

    NASA Astrophysics Data System (ADS)

    Peterson, M. E.; Kelley, K. A.; Cottrell, E.; Saal, A. E.; Kurz, M. D.

    2015-12-01

    The oxidation state of the mantle plays an intrinsic role in the magmatic evolution of the Earth. Here we present new μ-XANES measurements of Fe3+/ΣFe ratios (a proxy for ƒO2) in a suite of submarine glasses from the Galapagos Archipelago. Using previously presented major, trace, and volatile elements and isotopic data for 4 groups of glass that come from distinct mantle sources (depleted upper mantle, 2 recycled, and a primitive mantle source) we show that Fe3+/ΣFe ratios vary both with the influence of shallow level processes and with variations in mantle source. Fe3+/ΣFe ratios increase with differentiation (i.e. decreasing MgO), but show a large variation at a given MgO. Progressive degassing of sulfur accompanies decreasing Fe3+/ΣFe ratios, while assimilation of hydrothermally altered crust (as indicated by increasing Sr/Sr*) is shown to increase Fe3+/ΣFe ratios. After taking these processes into account, there is still variability in the Fe3+/ΣFe ratios of the isotopically distinct sample suites studied, yielding a magmatic ƒO2 that ranges from ΔQFM = +0.16 to +0.74 (error < 0.5 log units) and showing that oxidation state varies as a function of mantle source composition in the Galapagos hotspot system. After correcting back to a common MgO content = 8.0 wt%, the trace element depleted group similar to MORB (ITD), and the group similar to Pinta (WD = high Th/La, Δ7/4, Δ8/4 ratios) show Fe3+/ΣFe ratios within the range of MORB (average ITD = 0.162 ± 0.003 and WD = 0.164 ± 0.006). Another trace element enriched group similar to Sierra Negra and Cerro Azul (ITE = enriched Sr and Pb isotopes) shows evidence of mixing between oxidized and reduced sources (ITE oxidized end-member = 0.177). This suggests that mantle sources in the Galapagos that are thought to contain recycled components (i.e., WD and ITE groups) have distinct oxidation states. The high 3He/4He Fernandina samples (HHe group) are shown to be the most oxidized (ave. 0.175 ± 0

  8. Bidimensional codes recorded on an oxide glass surface using a continuous wave CO2 laser

    NASA Astrophysics Data System (ADS)

    Andreeta, M. R. B.; Cunha, L. S.; Vales, L. F.; Caraschi, L. C.; Jasinevicius, R. G.

    2011-02-01

    Surface heat treatment in glasses and ceramics, using CO2 lasers, has attracted the attention of several researchers around the world due to its impact in technological applications, such as lab-on-a-chip devices, diffraction gratings and microlenses. Microlens fabrication on a glass surface has been studied mainly due to its importance in optical devices (fiber coupling, CCD signal enhancement, etc). The goal of this work is to present a systematic study of the conditions for microlens fabrications, along with the viability of using microlens arrays, recorded on the glass surface, as bidimensional codes for product identification. This would allow the production of codes without any residues (like the fine powder generated by laser ablation) and resistance to an aggressive environment, such as sterilization processes. The microlens arrays were fabricated using a continuous wave CO2 laser, focused on the surface of flat commercial soda-lime silicate glass substrates. The fabrication conditions were studied based on laser power, heating time and microlens profiles. A He-Ne laser was used as a light source in a qualitative experiment to test the viability of using the microlenses as bidimensional codes.

  9. Glass Formulation Development for INEEL Sodium-Bearing Waste

    SciTech Connect

    Vienna, John D.; Buchmiller, William C.; Crum, Jarrod V.; Graham, Dennis D.; Kim, Dong-Sang; Macisaac, Brett D.; Schweiger, Michael J.; Peeler, David K.; Edwards, Tommy B.; Reamer, Irene A.; Workman, R. J.

    2002-08-01

    Studies were performed to develop and test a glass formulation for immobilization of sodium-bearing waste (SBW). SBW is a high soda, acid high activity waste stored at the INEEL in 10 underground tanks. It was determined in previous studies that SBW?s sulfur content dictates the its loading in borosilicate glasses to be melted by currently assumed processes. If the sulfur content (which is ~4.5 mass% SO3 on a non-volatile oxide basis in SBW) of the melter feed is too high then a molten alkali sulfate containing salt phase accumulates on the melt surface. The avoidance of salt accumulation during the melter process and the maximization of sulfur incorporation into the glass melt were the main focus of this development work. A glass was developed for 20 mass% SBW (on a non-volatile oxide basis), which contained 0.91 mass% SO3, that met all the processing and product quality constraint determined for SBW vitrification at a planned INEEL treatment plant?SBW-22-20. This report summarizes the formulation efforts and presents the data developed on a series of glasses with simulated SBW. Summary

  10. Oriented conductive oxide electrodes on SiO2/Si and glass

    DOEpatents

    Jia, Quanxi; Arendt, Paul N.

    2001-01-01

    A thin film structure is provided including a silicon substrate with a layer of silicon dioxide on a surface thereof, and a layer of cubic oxide material deposited upon the layer of silicon dioxide by ion-beam-assisted-deposition, said layer of cubic oxide material characterized as biaxially oriented. Preferably, the cubic oxide material is yttria-stabilized zirconia. Additional thin layers of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide are deposited upon the layer of yttria-stabilized zirconia. An intermediate layer of cerium oxide is employed between the yttria-stabilized zirconia layer and the lanthanum strontium cobalt oxide layer. Also, a layer of barium strontium titanium oxide can be upon the layer of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide. Also, a method of forming such thin film structures, including a low temperature deposition of a layer of a biaxially oriented cubic oxide material upon the silicon dioxide surface of a silicon dioxide/silicon substrate is provided.

  11. Influence of modifier oxide on emission features of Dy3+ ion in Pb3O4 ‒ZnO‒P2O5 glasses

    NASA Astrophysics Data System (ADS)

    Ravi kumar, Valluri; Giridhar, G.; Veeraiah, N.

    2016-10-01

    Glasses of the composition Pb2O3‒ZnO‒P2O5: Dy3+ mixed with three different modifier oxides viz., MgO, CaO and SrO are prepared. The influence of modifier oxide on the luminescence characteristics of Dy3+ ions has been investigated. Using the intensities of various absorption bands of Dy3+ ions, the Judd-Ofelt parameters Ω2, Ω4 and Ω6 have been evaluated. Together with the J‒O parameters and the luminescence spectra, various radiative properties like transition probability A, branching ratio βr, the radiative life time τr, and the emission cross-section σE for various emission levels of Dy3+ ions have been evaluated and reported. The values of these parameters were found to be influenced by modifier oxides. Among the three modifier oxides mixed glasses, the glasses mixed with CaO mixed glasses exhibited the highest luminescence efficiency. The results have been analyzed in the light of structural modifications taking place in the glass network with the help of IR spectral studies.

  12. Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

    NASA Technical Reports Server (NTRS)

    Day, Delbert E.; Ray, Chandra S.

    2001-01-01

    This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on Earth (1 g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on Earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials.

  13. Glass microspheres

    SciTech Connect

    Day, D.E.; Ehrhardt, G.J.

    1988-12-06

    This patent describes a glass microsphere having a diameter of about 54 micrometers or less and adapted for radiation therapy of a mammal. The glass consists of essentially an yttrium oxide-aluminosilicate glass composition lying substantially within a quadrilateral region of the ternary composition diagram of the yttria-alumina-silica system, the quadrilateral region being defined by its four corners having the following combination of weight proportions of the components: 20% silica, 10% alumina, 70% yttria; 70% silica, 10% alumina, 20% yttria; 70% silica, 20% alumina, 10% yttria; and 20% silica, 45% alumina, 35% yttria, the glass having a chemical durability such that subsequent to irradiation and administration of the microsphere to the mammal, the mircosphere will not release a significant amount of yttrium-90 into the mammal's system.

  14. Alkali-vapor lasers

    NASA Astrophysics Data System (ADS)

    Zweiback, J.; Komashko, A.; Krupke, W. F.

    2010-02-01

    We report on the results from several of our alkali laser systems. We show highly efficient performance from an alexandrite-pumped rubidium laser. Using a laser diode stack as a pump source, we demonstrate up to 145 W of average power from a CW system. We present a design for a transversely pumped demonstration system that will show all of the required laser physics for a high power system.

  15. Effect of boron doping on optical properties of sol-gel based nanostructured zinc oxide films on glass

    SciTech Connect

    Jana, Sunirmal; Vuk, Angela Surca; Mallick, Aparajita; Orel, Boris; Biswas, Prasanta Kumar

    2011-12-15

    Graphical abstract: Room temperature fine structured UV-vis PL emissions (a) as phonon replicas in 1 at.% boron doped film originated from LO phonon evidenced from Near Grazing Incidence Angle (NGIA) IR spectral study (b). Highlights: Black-Right-Pointing-Pointer Sol-gel based boron doped nanostructured ZnO thin films deposited on pure silica glass using crystalline boric acid as boron source. Black-Right-Pointing-Pointer Observed first time, room temperature fine structured PL emissions in 1 at.% doped film as phonon replicas originated from LO phonon (both IR and Raman active). Black-Right-Pointing-Pointer Boron doping controls the LO phonon energy in addition to visible reflection, band gap and grain size. Black-Right-Pointing-Pointer The films possessed mixed crystal phases with hexagonal as major phase. -- Abstract: Boron doped zinc oxide thin films ({approx}80 nm) were deposited onto pure silica glass by sol-gel dip coating technique from the precursor sol/solution of 4.0 wt.% equivalent oxide content. The boron concentration was varied from 0 to 2 at.% w.r.t. Zn using crystalline boric acid. The nanostructured feature of the films was visualized by FESEM images and the largest cluster size of ZnO was found in 1 at.% boron doped film (B1ZO). The presence of mixed crystal phases with hexagonal as major phase was identified from XRD reflections of the films. Particle size, optical band gap, visible specular reflection, room temperature photoluminescence (PL) emissions (3.24-2.28 eV), infra-red (IR) and Raman active longitudinal optical (LO) phonon vibration were found to be dependent on dopant concentration. For the first time, we report the room temperature fine structured PL emissions as phonon replicas originated from the LO phonon (both IR and Raman active) in 1 at.% boron doped zinc oxide film.

  16. Production and characterization of H3BO3-Li2CO3-K2CO3-MgO glass for dosimetry

    NASA Astrophysics Data System (ADS)

    Marini, Andrea; Valença, João V. B.; Oliveira, Raquel A. P.; Souza, Susana O.; Ciolini, Riccardo; d'Errico, Francesco

    2015-11-01

    Borate glasses are suitable for thermoluminescent dosimetry. In particular, borate glasses doped with different elements show good characteristics in terms of linearity, sensitivity and effective atomic number. However, these glasses are also hygroscopic, which can reduce their viability as dosimeters. In this work, the characteristics of borate glasses made with lithium and potassium oxides (LKB) were studied. To improve the glass features new formulations adding different amounts of magnesium oxide were developed. Mg improves the stability of the glasses since it reduces the mobility of the alkali ions and thus may reduce the hygroscopicity of the LKB glass. Three glass formulations containing 0, 5 and 11 mol% of magnesium oxide were produced by wet quenching method in order to determine the effect of Mg specifically on hygroscopicity and high-temperature resistance. The possibility to use this material for optically stimulated luminescence dosimetry was demonstrated. The LKB glass containing 11 mol% of Mg was found to withstand higher temperatures and to present the lower hygroscopicity compared to the other formulations.

  17. The nature of the glass transition in a silica-rich oxide melt.

    PubMed

    Farnan, I; Stebbins, J F

    1994-08-26

    The atomic-scale dynamics of the glass-to-liquid transition are, in general, poorly understood in inorganic materials. Here, two-dimensional magic angle spinning nuclear magnetic resonance spectra collected just above the glass transition of K(2)Si(4)O(9) at temperatures as high as 583 degrees C are presented. Rates of exchange for silicon among silicate species, which involves Si-O bond breaking, have been measured and are shown to be closely related in time scale to those defined by viscosity. Thus, even at viscosities as high as 10(10) pascal seconds, local bond breaking (in contrast to the cooperative motion of large clusters) is of major importance in the control of macroscopic flow and diffusion. PMID:17787585

  18. The Nature of the Glass Transition in a Silica-Rich Oxide Melt

    NASA Astrophysics Data System (ADS)

    Farnan, Ian; Stebbins, Jonathan F.

    1994-08-01

    The atomic-scale dynamics of the glass-to-liquid transition are, in general, poorly understood in inorganic materials. Here, two-dimensional magic angle spinning nuclear magnetic resonance spectra collected just above the glass transition of K_2Si_4O_9 at temperatures as high as 583^circC are presented. Rates of exchange for silicon among silicate species, which involves Si-O bond breaking, have been measured and are shown to be closely related in time scale to those defined by viscosity. Thus, even at viscosities as high as 1010 pascal seconds, local bond breaking (in contrast to the cooperative motion of large clusters) is of major importance in the control of macroscopic flow and diffusion.

  19. Glass corrosion in natural environment

    NASA Technical Reports Server (NTRS)

    Thorpe, Arthur N.

    1989-01-01

    A series of studies of the effects of solutes which appear in natural aqueous environments, specifically Mg and Al, under controlled conditions, permit characterization of the retardation of silicate glass leaching in water containing such solutes. In the case of Mg the interaction with the glass appears to consist of exchange with alkali ions present in the glass to a depth of several microns. The effect of Al can be observed at much lower levels, indicating that the mechanism in the case of Al involves irreversible formation of aluminosilicate species at the glass surface.

  20. Secondary electron emission from sodium chloride, glass and aluminum oxide at various temperature

    NASA Technical Reports Server (NTRS)

    Shulman, A. R.; Makedonskiy, V. L.; Yaroshetskiy, I. D.

    1980-01-01

    The method of single impulses was used to measure the coefficients of the secondary electronic emission for 2 types of Al2O2, monocrystalline NaCl and glass at different temperatures and for different values of the energy of the primary electrons. The value of the secondary electron emission does not depend upon temperature. The effect of a gas film on the value of the secondary electron emission was detected.

  1. Crystallization of rhenium salts in a simulated low-activity waste borosilicate glass

    SciTech Connect

    Riley, Brian J.; McCloy, John S.; Goel, Ashutosh; Liezers, Martin; Schweiger, Michael J.; Liu, Juan; Rodriguez, Carmen P.; Kim, Dong-Sang

    2013-04-01

    This study presents a new method for looking at the solubility of volatile species in simulated low-activity waste glass. The present study looking at rhenium salts is also applicable to real applications involving radioactive technetium salts. In this synthesis method, oxide glass powder is mixed with the volatiles species, vacuum-sealed in a fused quartz ampoule, and then heat-treated under vacuum in a furnace. This technique restricts the volatile species to the headspace above the melt but still within the sealed ampoule, thus maximizing the volatile concentration in contact with the glass. Various techniques were used to measure the solubility of rhenium in glass and include energy dispersive spectroscopy, wavelength dispersive spectroscopy, laser ablation inductively-coupled plasma mass spectroscopy, and inductively-coupled plasma optical emission spectroscopy. The Re-solubility in this glass was determined to be ~3004 parts per million Re atoms. Above this concentration, the salts separated out of the melt as inclusions and as a low viscosity molten salt phase on top of the melt observed during and after cooling. This salt phase was analyzed with X-ray diffraction, scanning electron microscopy as well as some of the other aforementioned techniques and identified to be composed of alkali perrhenate and alkali sulfate.

  2. Bioactive glasses with improved processing. Part 1. Thermal properties, ion release and apatite formation.

    PubMed

    Groh, Daniel; Döhler, Franziska; Brauer, Delia S

    2014-10-01

    Bioactive glasses, particularly Bioglass® 45S5, have been used to clinically regenerate human bone since the mid-1980s; however, they show a strong tendency to undergo crystallization upon heat treatment, which limits their range of applications. Attempts at improving their processing (by reducing their tendency to crystallize) have included increasing their silica content (and thus their network connectivity), incorporating intermediate oxides or reducing their phosphate content, all of which reduce glass bioactivity. Therefore, bioactive glasses known for their good processing (e.g. 13-93) are considerably less bioactive. Here, we investigated if the processing of 45S5 bioactive glass can be improved while maintaining its network connectivity and phosphate content. The results show that, by increasing the calcium:alkali cation ratio, partially substituting potassium for sodium (thereby making use of the mixed alkali effect) and adding small amounts of fluoride, bioactive glasses can be obtained which have a larger processing window (suggesting that they can be processed more easily, allowing for sintering of scaffolds or drawing into fibres) while degrading readily and forming apatite in aqueous solution within a few hours. PMID:24880003

  3. Sol-gel synthesis of magnesium oxide-silicon dioxide glass compositions

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.

    1988-01-01

    MgO-SiO2 glasses containing up to 15 mol pct MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol pct MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol pct MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol pct) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

  4. Bioactive glass coupling with natural polyphenols: Surface modification, bioactivity and anti-oxidant ability

    NASA Astrophysics Data System (ADS)

    Cazzola, Martina; Corazzari, Ingrid; Prenesti, Enrico; Bertone, Elisa; Vernè, Enrica; Ferraris, Sara

    2016-03-01

    Polyphenols are actually achieving an increasing interest due to their potential health benefits, such as antioxidant, anticancer, antibacterial and bone stimulation abilities. However their poor bioavailability and stability hamper an effective clinical application as therapeutic principles. The opportunity to couple these biomolecules with synthetic biomaterials, in order to obtain local delivery at the site of interest, improve their bioavailability and stability and combine their properties with the ones of the substrate, is a challenging opportunity for the biomedical research. A silica based bioactive glass, CEL2, has been successfully coupled with gallic acid and natural polyphenols extracted from red grape skins and green tea leaves. The effectiveness of grafting has been verified by means of XPS analyses and the Folin&Ciocalteu tests. In vitro bioactivity has been investigated by soaking in simulated body fluid (SBF). Surface modification after functionalization and early stage reactivity in SBF have been studied by means of zeta potential electrokinetic measurements in KCl and SBF. Finally the antioxidant properties of bare and modified bioactive glasses has been investigated by means of the evaluation of free radical scavenging activity by Electron Paramagnetic Resonance (EPR)/spin trapping technique after UV photolysis of H2O2 highlighting scavenging activity of the bioactive glass.

  5. Unusual magnetic transitions and nature of magnetic resonance spectra in oxide glasses containing gadolinium

    NASA Astrophysics Data System (ADS)

    Kliava, Janis; Malakhovskii, Alexander; Edelman, Irina; Potseluyko, Anatoly; Petrakovskaja, Eleonora; Melnikova, Svetlana; Zarubina, Tat'Jana; Petrovskii, Gurii; Bruckental, Yishay; Yeshurun, Yosef

    2005-03-01

    Magnetic susceptibility, electron paramagnetic resonance (EPR), and optical properties have been studied in a glass system {20La2O3-22Al2O3-23B2O3-35(SiO2+GeO2)} with a part of La2O3 substituted by Gd2O3 in different concentrations. Positive Weiss constants have been found in the more heavily doped glasses and ascribed to clustering of Gd3+ ions. Two magnetic phase transitions at 55 and 12 K were detected and ascribed, respectively, to ferromagnetic and antiferromagnetic clusters containing Gd ions. The overall shape of the EPR spectra shows the presence of clustering at the higher Gd contents. At low temperatures the cluster-related resonance signal is altered in shape, indicating an onset of magnetic anisotropy field. This signal is convincingly fitted to superparamagnetic resonance arising from ferromagnetic nanoparticles. The clustering, depending on the Gd concentration, correlates with a significant shift to lower energies of the strong optical absorption band edge, ascribed to a charge transfer transition between Gd ions. A nonmonotonous change of refractive index with the increase of the Gd content indicates changes in the glass matrix and in Gd cluster structure.

  6. Optical and crystallization studies of titanium dioxide doped sodium and potassium silicate glasses

    NASA Astrophysics Data System (ADS)

    ElBatal, F. H.; Marzouk, M. A.; ElBatal, H. A.

    2016-10-01

    Combined optical and FTIR spectral analysis were used to investigate prepared invert two alkali silicate glasses (Na2O·SiO2sbnd K2O·SiO2) containing high titanium oxide content. Glass ceramic derivatives were prepared through thermal two step regime of the parent glasses and they were characterized by FTIR and X-ray diffraction measurements. Experimental optical spectra indicate the appearance of an additional UV band due to absorption of tetravalent titanium ions beside the UV bands due to trace ferric ions impurities. FT infrared absorption spectra reveal composite vibrational bands due to vibrational modes of both silicate groups and TiO4 or Sisbnd Osbnd Ti units. Such tetravalent groupings of titanium ions confirm the stability of such invert glasses containing as such two main glass forming oxides. FTIR spectra of the glass - ceramic derivatives show nearly the same IR vibrational modes as their parent glasses. X-ray diffraction analysis show the separation of crystalline sodium or potassium titanate phases beside a minor form of silica and the results confirm that TiO2 acts mainly as network forming units leading to the formation of crystalline titanate phases.

  7. Effect of hydrothermal condition on the formation of multi-component oxides of Ni-based metallic glass under high temperature water near the critical point

    DOE PAGES

    Kim, J. S.; Kim, S. Y.; Kim, D. H.; Ott, R. T.; Kim, H. G.; Lee, M. H.

    2015-07-01

    The specific feature of multi-component oxides synthesized by hydrothermal process under high temperature (633 K) and highly pressurized water (18.9 MPa) near critical point. Effects of hydrothermal processing duration times 24 hours and 72 hours, respectively, on the oxide formation of the Ni59Zr20Ti16Si2Sn3 metallic glass synthesized by powder metallurgy process were characterized by X-ray diffractometer, differential scanning calorimeter along with the particle size, morphology and crystalline phase of the oxides. The crystallization of the needle-shape NiTiO3, ZrTiO4 and ZrSnO4 ternary oxide phases observed on the surface of metallic glass at below glass transition temperature and the morphology of oxide phasesmore » changed to plate-shape around 2 μm in diameter by the increase processing time. This hydrothermal processing in subcritical water provides accelerated dense metal oxide crystals due to the reaction medium being at higher pressure than conventional oxidation processing.« less

  8. Effect of hydrothermal condition on the formation of multi-component oxides of Ni-based metallic glass under high temperature water near the critical point

    SciTech Connect

    Kim, J. S.; Kim, S. Y.; Kim, D. H.; Ott, R. T.; Kim, H. G.; Lee, M. H.

    2015-07-01

    The specific feature of multi-component oxides synthesized by hydrothermal process under high temperature (633 K) and highly pressurized water (18.9 MPa) near critical point. Effects of hydrothermal processing duration times 24 hours and 72 hours, respectively, on the oxide formation of the Ni59Zr20Ti16Si2Sn3 metallic glass synthesized by powder metallurgy process were characterized by X-ray diffractometer, differential scanning calorimeter along with the particle size, morphology and crystalline phase of the oxides. The crystallization of the needle-shape NiTiO3, ZrTiO4 and ZrSnO4 ternary oxide phases observed on the surface of metallic glass at below glass transition temperature and the morphology of oxide phases changed to plate-shape around 2 μm in diameter by the increase processing time. This hydrothermal processing in subcritical water provides accelerated dense metal oxide crystals due to the reaction medium being at higher pressure than conventional oxidation processing.

  9. Effect of hydrothermal condition on the formation of multi-component oxides of Ni-based metallic glass under high temperature water near the critical point

    SciTech Connect

    Kim, J. S.; Lee, M. H.; Kim, S. Y.; Kim, D. H.; Ott, R. T.; Kim, H. G.

    2015-07-15

    The specific feature of multi-component oxides synthesized by hydrothermal process under high temperature (633 K) and highly pressurized water (18.9 MPa) near critical point. Effects of hydrothermal processing duration times 24 hours and 72 hours, respectively, on the oxide formation of the Ni{sub 59}Zr{sub 20}Ti{sub 16}Si{sub 2}Sn{sub 3} metallic glass synthesized by powder metallurgy process were characterized by X-ray diffractometer, differential scanning calorimeter along with the particle size, morphology and crystalline phase of the oxides. The crystallization of the needle-shape NiTiO{sub 3}, ZrTiO{sub 4} and ZrSnO{sub 4} ternary oxide phases observed on the surface of metallic glass at below glass transition temperature and the morphology of oxide phases changed to plate-shape around 2 μm in diameter by the increase processing time. This hydrothermal processing in subcritical water provides accelerated dense metal oxide crystals due to the reaction medium being at higher pressure than conventional oxidation processing.

  10. Oxynitride glass fibers

    NASA Technical Reports Server (NTRS)

    Patel, Parimal J.; Messier, Donald R.; Rich, R. E.

    1991-01-01

    Research at the Army Materials Technology Laboratory (AMTL) and elsewhere has shown that many glass properties including elastic modulus, hardness, and corrosion resistance are improved markedly by the substitution of nitrogen for oxygen in the glass structure. Oxynitride glasses, therefore, offer exciting opportunities for making high modulus, high strength fibers. Processes for making oxynitride glasses and fibers of glass compositions similar to commercial oxide glasses, but with considerable enhanced properties, are discussed. We have made glasses with elastic moduli as high as 140 GPa and fibers with moduli of 120 GPa and tensile strengths up to 2900 MPa. AMTL holds a U.S. patent on oxynitride glass fibers, and this presentation discusses a unique process for drawing small diameter oxynitride glass fibers at high drawing rates. Fibers are drawn through a nozzle from molten glass in a molybdenum crucible at 1550 C. The crucible is situated in a furnace chamber in flowing nitrogen, and the fiber is wound in air outside of the chamber, making the process straightforward and commercially feasible. Strengths were considerably improved by improving glass quality to minimize internal defects. Though the fiber strengths were comparable with oxide fibers, work is currently in progress to further improve the elastic modulus and strength of fibers. The high elastic modulus of oxynitride glasses indicate their potential for making fibers with tensile strengths surpassing any oxide glass fibers, and we hope to realize that potential in the near future.

  11. Role of Yb3+ ions on enhanced ~2.9 μm emission from Ho3+ ions in low phonon oxide glass system

    NASA Astrophysics Data System (ADS)

    Balaji, Sathravada; Gupta, Gaurav; Biswas, Kaushik; Ghosh, Debarati; Annapurna, Kalyandurg

    2016-07-01

    The foremost limitation of an oxide based crystal or glass host to demonstrate mid- infrared emissions is its high phonon energy. It is very difficult to obtain radiative mid-infrared emissions from these hosts which normally relax non-radiatively between closely spaced energy levels of dopant rare earth ions. In this study, an intense mid-infrared emission around 2.9 μm has been perceived from Ho3+ ions in Yb3+/Ho3+ co-doped oxide based tellurite glass system. This emission intensity has increased many folds upon Yb3+: 985 nm excitation compared to direct Ho3+ excitations due to efficient excited state resonant energy transfer through Yb3+: 2F5/2 → Ho3+: 5I5 levels. The effective bandwidth (FWHM) and cross-section (σem) of measured emission at 2.9 μm are assessed to be 180 nm and 9.1 × 10‑21 cm2 respectively which are comparable to other crystal/glass hosts and even better than ZBLAN fluoride glass host. Hence, this Ho3+/Yb3+ co-doped oxide glass system has immense potential for the development of solid state mid-infrared laser sources operating at 2.9 μm region.

  12. Role of Yb3+ ions on enhanced ~2.9 μm emission from Ho3+ ions in low phonon oxide glass system

    PubMed Central

    Balaji, Sathravada; Gupta, Gaurav; Biswas, Kaushik; Ghosh, Debarati; Annapurna, Kalyandurg

    2016-01-01

    The foremost limitation of an oxide based crystal or glass host to demonstrate mid- infrared emissions is its high phonon energy. It is very difficult to obtain radiative mid-infrared emissions from these hosts which normally relax non-radiatively between closely spaced energy levels of dopant rare earth ions. In this study, an intense mid-infrared emission around 2.9 μm has been perceived from Ho3+ ions in Yb3+/Ho3+ co-doped oxide based tellurite glass system. This emission intensity has increased many folds upon Yb3+: 985 nm excitation compared to direct Ho3+ excitations due to efficient excited state resonant energy transfer through Yb3+: 2F5/2 → Ho3+: 5I5 levels. The effective bandwidth (FWHM) and cross-section (σem) of measured emission at 2.9 μm are assessed to be 180 nm and 9.1 × 10−21 cm2 respectively which are comparable to other crystal/glass hosts and even better than ZBLAN fluoride glass host. Hence, this Ho3+/Yb3+ co-doped oxide glass system has immense potential for the development of solid state mid-infrared laser sources operating at 2.9 μm region. PMID:27374129

  13. Evaluation of Silica-based/Nickel and Borate-based/ Silver Glass Composites Seals for Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Aguilar-Diaz, Yaneth

    The increasing demand for energy and the necessity to overcome the depletion of fossil fuel supplies requires that alternative energy sources be developed. Solid Oxide Fuel Cells (SOFCs) are one of the alternative technologies to minimise our dependence on fossil fuel due to their numerous advantages including high efficiency, long-term stability, fuel flexibility and low emissions. However, the development of reliable sealing techniques remains a crucial challenge to overcome to allow usable efficiency and facilitate commercialization. Sealing technology has been object of research for several years. Nevertheless, the optimal solution is yet to be found. The use of a glass composite approach is attractive as it allows the possibility of engineering the properties of the seal, by independently adjusting the particle size distribution and volume fraction of the additives. In the present work, the interaction between various SiO2 based glasses with nickel and B2O3 based glasses with silver were studied. Results as a function of additive particle size distribution (7-100 microns) and volume fraction (0-18%) will be presented. Micrographs, X-ray patterns and CTE measurements showed that the proposed systems have adequate characteristics for usage as seal for fuel cells due to the inertness of the additive particles with the respective glass matrix and predictable long-term chemical and thermal stability. The use of DTMA as a technique to calculate the onset of residual stresses, explores the influence of the additive and its interfacial interactions on the dissipation of energy during deformation. The multi-frequency test lead to an activation energy for stress relaxation between 400 and 600 kJ/mol depending on the different additive content. Furthermore, the temperature difference between de Tg and the onset of residual stresses was calculated showing that increments on the additive content results on a larger temperature range that allows stress relaxation. The

  14. L-edge XANES measurements of the oxidation state of tungsten in iron bearing and iron free silicate glasses

    SciTech Connect

    Danielson, L.R.; Righter, K.; Sutton, S.; Newville, M.; Le, L.

    2008-04-28

    W{sup 4+} is relevant to core formation but W{sup 6+} may also occur. Silicate glasses show W{sup 6+} above IW and mixed valence below IW. The transition to W{sup 4+} only, appears to happen at or below IW-2 for iron free systems, but below IW-3 for iron bearing systems. Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted {approx} 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies (Fig. 1) are inconsistent on whether W occurs as W{sup 4+} or W{sup 6+}. It is assumed that W{sup 4+} is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO{sub 2} is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO{sub 2} most relevant to core formation, around IW-2.

  15. Silicon nitride anti-reflection coating on the glass and transparent conductive oxide interface for thin film solar cells and modules

    NASA Astrophysics Data System (ADS)

    Iwahashi, T.; Morishima, M.; Fujibayashi, T.; Yang, R.; Lin, J.; Matsunaga, D.

    2015-10-01

    Anti-reflection coating (ARC) is well known as an important technique to enhance solar cell performance. Typical ARC has been applied on the glass surface to reduce light reflection loss at the air/glass interface. However, reflection loss occurs not only at glass surface but also at other interfaces such as glass/transparent conductive oxide (TCO) interface. The refractive index of SiNx is tunable from 1.6 to 2.7, and the range from 1.7 to 2.0 is suitable for ARC at glass/TCO interface. In this study, we examined the AR effect of silicon nitride (SiNx) deposited by plasma enhanced chemical vapor deposition at the glass/TCO interface with thin film silicon solar cell and module. Reflectivity reduction of 1.6% for glass/ZnO substrate has been obtained with optimal SiNx layer, which contribute 2.0% gain in cell efficiency. Besides, we also confirmed the relative efficiency gain of around 2% for large-sized solar module, leading to a world-record large area stabilized module conversion efficiency of 12.34%.

  16. Long-term evaluation of solid oxide fuel cell candidate materials in a 3-cell generic short stack fixture, Part II: Sealing glass stability, microstructure and interfacial reactions

    NASA Astrophysics Data System (ADS)

    Chou, Yeong-Shyung; Stevenson, Jeffry W.; Choi, Jung-Pyung

    2014-03-01

    A generic solid oxide fuel cell stack test fixture was developed to evaluate candidate materials and processing methods under realistic conditions. Part II of the work examined the sealing glass stability, microstructure development, interfacial reaction, and volatility issues of a 3-cell stack with LSM-based cells. After 6000 h of testing, the refractory sealing glass YSO7 showed desirable chemical compatibility with YSZ electrolyte in that no discernable interfacial reaction was identified. In addition, no glass penetration into the thin electrolyte was observed. At the aluminized AISI441 interface, the protective alumina coating appeared to be corroded by the sealing glass. Air side interactions appeared to be more severe than fuel side interactions. Metal species such as Cr, Mn, and Fe were detected in the glass, but were limited to the vicinity of the interface. No alkaline earth chromates were found at the air side. Volatility was also studied in a similar glass and weight loss in a wet reducing environment was determined. Using the steady-state volatility data, the life time weight loss of refractory sealing glass YSO77 was estimated to be less than 0.1 wt%.

  17. Bioactivity of SiO 2-CaO-P 2O 5-Na 2O glasses containing zinc-iron oxide

    NASA Astrophysics Data System (ADS)

    Singh, Rajendra Kumar; Srinivasan, A.

    2010-01-01

    Glasses with composition x(ZnO,Fe 2O 3)(65 - x)SiO 220(CaO,P 2O 5)15Na 2O (6 ≤ x ≤ 21 mol%) were prepared by melt-quenching technique. Bioactivity of the glasses was investigated in vitro by examining apatite formation on the surface of glasses treated in acellular simulated body fluid (SBF) with ion concentrations nearly equal to those in human blood plasma. Formation of bioactive apatite layer on the samples treated in SBF was confirmed by using Fourier transform infrared reflection (FTIR) spectroscopy, grazing incidence X-ray diffraction (GI-XRD) and scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer. Development of an apatite structure on the surface of the SBF treated glass samples as functions of composition and time could be established using the GI-XRD data. FTIR spectra of the glasses treated in SBF show features at characteristic vibration frequencies of apatite after 1-day of immersion in SBF. SEM observations revealed that the spherical particles formed on the glass surface were made of calcium and phosphorus with the Ca/P molar ratio being close to 1.67, corresponding to the value in crystalline apatite. Increase in bioactivity with increasing zinc-iron oxide content was observed. The results have been used to understand the evolution of the apatite surface layer as a function of glass composition and immersion time in SBF.

  18. Up-conversion luminescence analysis in ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses.

    PubMed

    Sun, Hongtao; Yu, Chunlei; Zhou, Gang; Duan, Zhongchao; Liao, Meisong; Zhang, Junjie; Hu, Lili; Jiang, Zhonghong

    2005-12-01

    Ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses have been synthesized by conventional melting method. Intense green and red emissions centered at 525, 546 and 657 nm, corresponding to the transitions 2H11/2-->4I15/2, 4S3/2-->4I15/2 and 4F9/2-->4I15/2, respectively, were simultaneously observed at room temperature in these glasses. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. Tellurite glass showed a weaker up-conversion emission than germanate-niobic-lead glass, which is inconsistent with the prediction from the difference of maximum phonon energy between tellurite and germanate-niobic-lead glasses. In this paper, Raman spectroscopy was employed to investigate the origin of the difference in up-conversion luminescence in the two glasses. Compared with phonon side-band spectroscopy, Raman spectroscopy extracts more information including both phonon energy and phonon density. Our results reveal that the phonon density and the maximum phonon energy of host glasses are both important factors in determining the up-conversion efficiency.

  19. Part 2: Ultra-short pulse laser patterning of very thin indium tin oxide on glass substrates

    NASA Astrophysics Data System (ADS)

    McDonnell, C.; Milne, D.; Chan, H.; Rostohar, D.; O'Connor, G. M.

    2016-06-01

    We investigate selective patterning of ultra-thin 20 nm Indium Tin Oxide (ITO) thin films on glass substrates, using 343, 515, and 1030 nm femtosecond (fs), and 1030 nm picoseconds (ps) laser pulses. An ablative removal mechanism is observed for all wavelengths at both femtosecond and picoseconds time-scales. The absorbed threshold fluence values were determined to be 12.5 mJ cm-2 at 343 nm, 9.68 mJ cm-2 at 515 nm, and 7.50 mJ cm-2 at 1030 nm for femtosecond and 9.14 mJ cm-2 at 1030 nm for picosecond laser exposure. Surface analysis of ablated craters using atomic force microscopy confirms that the selective removal of the film from the glass substrate is dependent on the applied fluence. Film removal is shown to be primarily through ultrafast lattice deformation generated by an electron blast force. The laser absorption and heating process was simulated using a two temperature model (TTM). The predicted surface temperatures confirm that film removal below 1 J cm-2 to be predominately by a non-thermal mechanism.

  20. Photocatalytic oxidation of H2S in the gas phase over TiO2-coated glass fiber filter.

    PubMed

    Brancher, Marlon; Franco, Davide; de Melo Lisboa, Henrique

    2016-11-01

    To promote the photocatalytic oxidation (PCO) of hydrogen sulfide (H2S) in the gas phase, TiO2-coated glass fiber filters were packed in an annular photoreactor. Glass fibers coated with TiO2 thin films were characterized structurally and morphologically by field emission gun scanning electron microscopy (FEG-SEM), scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS) and X-ray diffractometry (XRD). Flow rate and H2S inlet concentration were evaluated to determine the performance of the reactor. Removal efficiencies up to 99% were achieved for flow rate of 25 L h(-1) (residence time of 121 s) and H2S inlet concentration from 12 to 14 ppmv. The long-term experiment presented H2S removal of 89% for 16 h. After 28 h of continuous use, H2S degradation was observed at 64%, which suggests that the photocatalyst was losing activity due to deactivation. Moreover, the kinetics of the PCO of H2S according to the Langmuir-Hinshelwood (L-H) approach along with the mass balance of a plug-flow reactor was modeled. The reaction constant (k) was calculated at approximately 10.5 μmol m(-3) s(-1) and the adsorption constant (K) of approximately 5263 m(-3) mol with linearity (R2) of 0.98.

  1. Materials discovery by crystal growth: Lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt) from molten alkali metal hydroxides

    SciTech Connect

    Mugavero, Samuel J.; Gemmill, William R.; Roof, Irina P.; Loye, Hans-Conrad zur

    2009-07-15

    This review addresses the process of materials discovery via crystal growth, specifically of lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt). It provides a detailed overview of the use of hydroxide fluxes for crystal growth. The melt chemistry of hydroxide fluxes, specifically, the extensive acid base chemistry, the metal cation solubility, and the ability of hydroxide melts to oxidize metals are described. Furthermore, a general methodology for the successful crystal growth of oxides is provided, including a discussion of experimental considerations, suitable reaction vessels, reaction profiles and temperature ranges. Finally, a compilation of complex platinum group metal oxides recently synthesized using hydroxide melts, focusing on their crystal growth and crystal structures, is included. - Graphical abstract: A review that addresses the process of materials discovery via crystal growth using hydroxide fluxes. It provides a detailed overview of the use of hydroxide fluxes for crystal growth and describes the melt chemistry of hydroxide fluxes, specifically, the extensive acid base chemistry, the metal cation solubility, and the ability of hydroxide melts to oxidize metals. In addition, a compilation of complex platinum group metal oxides recently synthesized using hydroxide melts is included.

  2. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    SciTech Connect

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    2014-12-08

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

  3. Structural investigation of Zn doped sodium bismuth borate glasses

    NASA Astrophysics Data System (ADS)

    Bhatia, V.; Kumar, D.; Singh, D.; Singh, S. P.

    2016-05-01

    A series of Bismuth Borate Oxide Glass samples with composition x(ZnO):(15-x)Na2O:15Bi2O3:70B2O3 (variation in x is from 6 to 12 mole %) have been prepared by conventional melt quenching technique. All the chemicals used were of Analytical Grade. In order to verify the amorphous nature of the prepared samples the X-Ray Diffraction (XRD) was done. The physical and structural properties have been explored by using the techniques such as density, molar volume and FTIR in order to understand the effect of alkali and transition metal ions on the structure of these glasses. The results obtained by these techniques are in good agreement to one another and with literature as well. With the increase in the content of ZnO, the increase in density and some variations in structural coordination (ratio of BO3 & BO4 structural units) have been observed.

  4. Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

    NASA Technical Reports Server (NTRS)

    Day, Delbert E.; Ray, Chandra S.

    2003-01-01

    This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one1 of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on earth (1g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials. The classical theories for nucleation and crystal growth for a glass or melt do not contain any parameter that is directly dependent upon the g-value, so it is not readily apparent why glasses prepared in microgravity should be

  5. Optical properties of Lead bismuth borate glasses doped with neodymium oxide.

    PubMed

    Farouk, M; Abd El-Maboud, A; Ibrahim, M; Ratep, A; Kashif, I

    2015-10-01

    Neodymium doped Lead bismuth borate glasses with the composition of 25PbO-25Bi2O3-50B2O3:xNd2O3, where x=0.5, 1, 1.5 and 2 mol%, have been prepared by melt quenching technique. The behavior of the density and molar volume allows concluding that, addition of Nd2O3 leads to the formation of non-bridging oxygen. Rare earth ion parameters have been calculated and studied. The optical band gap (Eg), and band tails (Ee) were determined. Judd-Ofelt theory for the intensity analysis of induced electric dipole transitions has been applied to the measured oscillator strengths of the absorption bands to determine the three phenomenological intensity parameters Ω2, Ω4 and Ω6 for glass. It was observed that the deviation parameters, rms, was found to be 0.56:0.58(×10(-6)). The estimated Judd-Ofelt parameters were found to be Nd2O3concentration dependent. The hypersensitive transition, (4)I9/2→(4)G5/2+(2)G7/2, is closely related to Ω2 parameter.

  6. Transport properties of lead phosphate glass doped by cobalt, vanadium and chromium oxides

    NASA Astrophysics Data System (ADS)

    Roumaih, Kh.; Kaiser, M.; Elbatal, Fatma H.; Ali, I. S.

    2011-10-01

    The electrical transport properties were investigated of a glass system of basic composition 50 mol. % Pb3O4-50 mol. % P2O5 containing CoO, Cr2O3 or V2O5 dopanys. The ac conductivity and the thermoelectric power were measured as a function of temperature. Properties such as dielectric constant, loss factor tangent and electrical conductivity are reported in the frequency range 200 Hz-100 kHz and temperature range 300-450 K. The variation in electrical conductivity with temperature was found to depend on the types of transition metal ions involved. The temperature dependence of the frequency exponent, s, was analyzed using different theoretical models. The variation of the thermoelectric power with temperature indicated the presence of more than one conduction mechanism for the investigated samples. This result was confirmed with the results of the dielectric properties at different frequencies. The introduction of cobalt ions in glass formers improves the electrical properties of non-crystalline ionic conductors.

  7. Surface Conductive Glass.

    ERIC Educational Resources Information Center

    Tanaka, John; Suib, Steven L.

    1984-01-01

    Discusses the properties of surface-conducting glass and the chemical nature of surface-conducting stannic (tin) oxide. Also provides the procedures necessary for the preparation of surface-conducting stannic oxide films on glass substrates. The experiment is suitable for the advanced inorganic chemistry laboratory. (JN)

  8. Research on oxidation by air and tempering of Raney nickel electrocatalysts for the H2 anodes of alkali combustion materials cells. Thesis - Braunschweig Technische Univ., 1982

    NASA Technical Reports Server (NTRS)

    Selbach, H. J.

    1984-01-01

    The controlled oxidation in air of Raney nickel electrocatalysts was studied, with special attention paid to the quantitative analysis of nickel hydroxide. The content of the latter was determined through X-ray studies, thermogravimetric measurements, and spectral photometric examinations. The dependence of the content on the drying of activated catalyst is determined. The influence of nickel hydroxide on the electrochemical parameters of the catalyst, such as diffusion polarization, is studied, including a measurement of the exchange current density using the potential drop method. Conservation by oxidation in air with ancillary stabilization of the oxide in an H2 flow at 300 C is explored, including reduction by H2, the influence of tempering time, and structural studies on conserved and stabilized catalyst, long term research on the catalyst, including the influence of aging on the reduced catalyst, and the results of impedance measurements are presented.

  9. Carbon dioxide in silica-undersaturated melt. Part I: The effect of mixed alkalis (K and Na) on CO2 solubility and speciation

    NASA Astrophysics Data System (ADS)

    Morizet, Yann; Paris, Michael; Gaillard, Fabrice; Scaillet, Bruno

    2014-09-01

    Silica undersaturated melts such as nephelinites are very peculiar magmatic materials. Their occurrence on Earth is often associated with carbonatite melts. These low-silica melts can dissolve a large quantity of CO2 and are rich in alkalis. However, the way CO2 dissolves into these melts and the effect of different alkali elements are poorly constrained. We present experimental results on the CO2 solubility and speciation in synthetic nephelinite in the NKCMAS system, equilibrated at high-pressure (50-300 MPa), high-temperature (1250 °C) with an excess C-O-H fluid phase. The nephelinitic glasses with 20 mol.% total alkali oxides were synthesized with varying K2O/(K2O + Na2O) ratio (denoted as #K) in order to investigate the differential effect of those two alkali cations on CO2 solubility and speciation. All experiments were conducted under oxidizing conditions (>NNO+3) resulting in binary fluid phase compositions with CO2 and H2O species. The CO2 content and speciation were investigated using micro-Raman and Solid State NMR spectroscopies for 13C nucleus. We observe an increase in CO2 content as a function of pressure, consistent with previous studies but CO2 solubility is much higher than in alkali-poorer melts. The CO2 content is above 1 wt.% at 50 MPa and increases up to 4.5 wt.% at 300 MPa. The progressive replacement of Na by K (#K between 0 and 1) induces an increase in CO2 content. At 50 MPa, the CO2 solubility is ∼1.75 wt.% in the K-free glass (#K = 0) and increases up to ∼3.0 wt.% CO2 in Na-free glass (#K = 1). The change in CO2 solubility as a function of #K is discussed in terms of carbonatite genesis. The 13C NMR spectra show that carbonate (CO32-) environments can be attributed to carbonate species associated to non-bridging oxygen in agreement with the depolymerized nature of the investigated compositions. Two singular additional carbonated species were also identified with 13C NMR signatures at 161 and 165 ppm. Those species are assigned to

  10. PROCESS OF RECOVERING ALKALI METALS

    DOEpatents

    Wolkoff, J.

    1961-08-15

    A process is described of recovering alkali metal vapor by sorption on activated alumina, activated carbon, dehydrated zeolite, activated magnesia, or Fuller's earth preheated above the vaporization temperature of the alkali metal and subsequent desorption by heating the solvent under vacuum. (AEC)

  11. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 12, June 1--August 31, 1994

    SciTech Connect

    Pickrell, G.R.; Brown, J.J.

    1994-09-01

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions.

  12. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 3, March 1, 1992--May 31, 1992

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-05-27

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  13. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 1, September 1, 1991--November 31, 1991

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1991-11-30

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this program is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  14. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 4, June 1, 1992--August 31, 1992

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-08-29

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  15. Purification of alkali metal nitrates

    DOEpatents

    Fiorucci, Louis C.; Gregory, Kevin M.

    1985-05-14

    A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

  16. Phospho-silicate glass gated 4H-SiC metal-oxide-semiconductor devices: Phosphorus concentration dependence

    NASA Astrophysics Data System (ADS)

    Jiao, C.; Ahyi, A. C.; Xu, C.; Morisette, D.; Feldman, L. C.; Dhar, S.

    2016-04-01

    The correlation between phosphorus concentration in phospho-silicate glass (PSG) gate dielectrics and electrical properties of 4H-SiC MOS devices has been investigated. Varying P uptake in PSG is achieved by changing the POCl3 post-oxidation annealing temperature. The density of interface traps (Dit) at the PSG/4H-SiC interface decreases as the amount of interfacial P increases. Most significantly, the MOSFET channel mobility does not correlate with Dit for all samples, which is highly unusual for SiC MOSFETs. Further analysis reveals two types of field-effect mobility (μfe) behavior, depending on the annealing temperature. Annealing at 1000 °C improves the channel mobility most effectively, with a peak value ˜105 cm2 V-1 s-1, and results in a surface phonon scattering limited mobility at high oxide field. On the other hand, PSG annealed at other temperatures results in a surface roughness scattering limited mobility at similar field.

  17. High-performance calcium-doped zinc oxide thin-film transistors fabricated on glass at low temperature

    NASA Astrophysics Data System (ADS)

    Yu, Wen; Han, Dedong; Cui, Guodong; Cong, Yingying; Dong, Junchen; Zhang, Xiaomi; Zhang, Xing; Wang, Yi; Zhang, Shengdong

    2016-04-01

    High-performance calcium-doped zinc oxide thin-film transistors (Ca-ZnO TFTs) have been successfully fabricated on transparent glass at low temperature by RF magnetron sputtering. To study the effects of calcium doping on zinc oxide thin-film transistors, the characteristics of Ca-ZnO TFTs and ZnO TFTs are compared and analyzed in detail from different perspectives, including electrical performance, surface morphology, and crystal structure of the material. The results suggest that the incorporation of calcium element can decrease the root-mean-square roughness of the material, suppress growth of a columnar structure, and improve device performance. The TFTs with Ca-ZnO active layer exhibit excellent electrical properties with the saturation mobility (μsat) of 147.1 cm2 V-1 s-1, threshold voltage (V t) of 2.91 V, subthreshold slope (SS) of 0.271 V/dec, and I on/I off ratio of 2.34 × 108. In addition, we also study the uniformity of the devices. The experimental results show that the Ca-ZnO TFTs possess good uniformity, which is important for large-area application.

  18. Electrical behavior of aluminosilicate glass-ceramic sealants and their interaction with metallic solid oxide fuel cell interconnects

    NASA Astrophysics Data System (ADS)

    Goel, Ashutosh; Tulyaganov, Dilshat U.; Kharton, Vladislav V.; Yaremchenko, Aleksey A.; Ferreira, José M. F.

    A series of alkaline-earth aluminosilicate glass-ceramics (GCs) were appraised with respect to their suitability as sealants for solid oxide fuel cells (SOFCs). The parent composition with general formula Ca 0.9MgAl 0.1La 0.1Si 1.9O 6 was modified with Cr 2O 3 and BaO. The addition of BaO led to a substantial decrease in the total electrical conductivity of the GCs, thus improving their insulating properties. BaO-containing GCs exhibited higher coefficient of thermal expansion (CTE) in comparison to BaO-free GCs. An extensive segregation of oxides of Ti and Mn, components of the Crofer22 APU interconnect alloy, along with negligible formation of BaCrO 4 was observed at the interface between GC/interconnects diffusion couples. Thermal shock resistance and gas-tightness of GC sealants in contact with yttria-stabilized zirconia electrolyte (8YSZ) was evaluated in air and water. Good matching of CTE and strong, but not reactive, adhesion to the solid electrolyte and interconnect, in conjunction with a high level of electrical resistivity, are all advantageous for potential SOFC applications.

  19. Joint strength of a solid oxide fuel cell glass-ceramic sealant with metallic interconnect in a reducing environment

    NASA Astrophysics Data System (ADS)

    Lin, Chih-Kuang; Liu, Yu-An; Wu, Si-Han; Liu, Chien-Kuo; Lee, Ruey-Yi

    2015-04-01

    Effects of reducing environment and thermal aging on the joint strength of a BaO-B2O3-Al2O3-SiO2 glass-ceramic sealant (GC-9) with a ferritic-stainless-steel interconnect (Crofer 22 H) for planar solid oxide fuel cells are investigated. A technique is developed for conducting mechanical tests at room temperature and 800 °C in H2-7 vol% H2O under shear and tensile loadings. Given an aged condition and loading mode, the joint strength at 800 °C is lower than that at room temperature in the given humidified hydrogen atmosphere. A thermal aging at 800 °C in H2-7 vol% H2O for 100 h or 1000 h enhances both shear and tensile joint strengths at room temperature but degrades them at 800 °C in the same reducing environment. Non-aged specimens show a comparable joint strength and fracture mode when tested in humidified hydrogen and in air under a given loading mode and testing temperature. The shear strength at 800 °C for joint specimens after a 1000-h thermal aging at 800 °C in air or humidified hydrogen is reduced by a similar extent of 19%, compared to the counterpart of non-aged joint specimens tested in the same oxidizing or reducing environment.

  20. Effects of sputtering power on properties of copper oxides thin films deposited on glass substrates

    SciTech Connect

    Ooi, P. K.; Ng, S. S.; Abdullah, M. J.

    2015-04-24

    Copper oxides are deposited by radio frequency sputtering using copper target in the mixture of argon and oxygen gasses. The structural and optical properties of the copper oxides deposited at different sputtering powers have been investigated. All the films are single phase polycrystalline. At low RF power (100 W), the film is monoclinic structure of cupric oxide (CuO). Meanwhile, the films are cubic structure of cuprous oxide (Cu2O) at higher RF power. Field emission scanning electron microscopy images show the films have different morphologies with small grain size and consist of a lot of voids. The analysis of energy dispersive X-ray spectroscopy shows that the ratio of Cu to O is increased as the RF power increased. From the ultraviolet–visible spectroscopy, the films have a broad absorption edge in the range of 300–500 nm. The band gap of the films grown at RF power of 100 W, and 120 W and above, were 1.18 eV and 2.16 eV, respectively.

  1. Predicting Young’s Modulus of Glass/Ceramic Sealant for Solid Oxide Fuel Cell Considering the Combined Effects of Aging, Micro-Voids and Self-Healing

    SciTech Connect

    Liu, Wenning N.; Sun, Xin; Khaleel, Mohammad A.

    2008-12-01

    We study the temperature dependent Young’s modulus for the glass/ceramic seal material used in Solid Oxide Fuel Cells (SOFCs). With longer heat treatment or aging time during operation, further devitrification may reduce the residual glass content in the seal material while boosting the ceramic crystalline content. In the meantime, micro-voids induced by the cooling process from the high operating temperature to room temperature can potentially degrade the mechanical properties of the glass/ceramic sealant. Upon reheating to the SOFC operating temperature, possible self-healing phenomenon may occur in the glass/ceramic sealant which can potentially restore some of its mechanical properties. A phenomenological model is developed to model the temperature dependent Young’s modulus of glass/ceramic seal considering the combined effects of aging, micro-voids, and possible self-healing. An aging-time-dependent crystalline content model is first developed to describe the increase of the crystalline content due to the continuing devitrification under high operating temperature. A continuum damage mechanics (CDM) model is then adapted to model the effects of both cooling induced micro-voids and reheating induced self-healing. This model is applied to model the glass-ceramic G18, a candidate SOFC seal material previously developed at PNNL. Experimentally determined temperature dependent Young’s modulus is used to validate the model predictions

  2. Structural and compositional modification of a barium boroaluminosilicate glass surface by thermal poling

    NASA Astrophysics Data System (ADS)

    Smith, Nicholas J.; Pantano, Carlo G.

    2014-08-01

    In addition to inducing second-order nonlinear properties, significant structural and compositional alteration can be imparted to glass surfaces during the process of thermal poling. In this work, we focus on how thermal poling affects a structurally complex, nominally alkali-free boroaluminosilicate display glass composition. We provide evidence for electrolysis of the glass network, characterized by the migration of both cations (Ba2+, Na+) and anions (O-, F-) towards opposing electrode interfaces. This process results in oxidation of the positively biased electrode and forms a network-former rich, modifier-depleted glass surface layer adjacent to the anodic interface. The modified glass layer thickness is qualitatively correlated to the oxidation resistance of the electrode material, while extrinsic ions such as H+/H3O+ at not found in the depletion layer to compensate for the migration of modifier cations out of the region. Rather, FTIR spectroscopy suggests a local restructuring of the B2O3-Al2O3-SiO2 network species to accommodate the charge imbalance created by the exodus of network-modifying cations, specifically the conversion of tetrahedral B(4) to trigonal B(3) as Ba or Na ions are removed from B-related sites in the parent network. The resultant poling-induced depletion layer exhibits enhanced hydrolytic resistance under acidic conditions, and the IR spectra are substantially unlike those produced by acid leaching the same glass.

  3. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  4. The influence of biofilms on the mobility of bare and capped zinc oxide nanoparticles in saturated sand and glass beads.

    PubMed

    Kurlanda-Witek, H; Ngwenya, B T; Butler, I B

    2015-08-01

    Biofilms are a common constituent of the subsurface and are known to influence contaminant transport; however only a few studies to date have addressed microbial controls on nanoparticle mobility in porous media. The impact of a 3-day Pantoea agglomerans biofilm on the mobility of zinc oxide (ZnO) nanoparticles was studied in column experiments containing sand and glass beads at near-neutral pH and constant ionic strength. Bare ZnO nanoparticles (bZnO-NPs) and ZnO nanoparticles capped with tri-aminopropyltriethoxysilane (cZnO-NPs) were used in the experiments. Breakthrough curves demonstrate that the biofilm particularly slowed nanoparticle migration of bZnO-NPs in glass bead columns and cZnO-NPs in sand columns. With the exception of bZnO-NPs in sand columns, biofilm-coated porous media retained more nanoparticles than those of controls without biofilm. The biofilm may bear an impact on the surface charge of the porous medium, nullifying porous medium-specific effects. Although viable cell counts (VCCs) decreased after the introduction of electrolyte and before nanoparticle transport experiments, SEM and CLSM imaging of porous medium samples taken from columns after nanoparticle transport experiments, as well as total organic carbon (TOC) measurements reveal that biofilm was present in the columns throughout the experiments. Hence, it can be concluded that even a thin amount of biofilm can hinder nanoparticle migration in small-scale porous medium experiments. Moreover, nanoparticle mobility is dependent on the binding capacity of biofilms, rather than the type of porous media.

  5. Alkali hydrolysis of trinitrotoluene.

    PubMed

    Karasch, Christian; Popovic, Milan; Qasim, Mohamed; Bajpai, Rakesh K

    2002-01-01

    Data for alkali hydrolysis of 2,4,6-trinitrotoluene (TNT) in aqueous solution at pH 12.0 under static (pH-controlled) as well as dynamic (pH-uncontrolled) conditions are reported. The experiments were conducted at two different molar ratios of TNT to hydroxyl ions at room temperature. The TNT disappeared rapidly from the solution as a first-order reaction. The complete disappearance of aromatic structure from the aqueous solution within 24 h was confirmed by the ultraviolet-visible (UV-VIS) spectra of the samples. Cuvet experiments in a UV-VIS spectrophotometer demonstrated the formation of Meisenheimer complex, which slowly disappeared via formation of aromatic compounds with fewer nitro groups. The known metabolites of TNT were found to accumulate only in very small quantities in the liquid phase.

  6. Oxidative DNA damage estimated by urinary 8-hydroxy-2'-deoxyguanosine and arsenic in glass production workers.

    PubMed

    Lin, Tser-Sheng; Wu, Chin-Ching; Wu, Jyun-De; Wei, Chun-Han

    2012-07-01

    A total of 130 male glass workers, including 33 administrative workers, 18 batch house workers, 42 craftsmen, and 37 melting process workers, were recruited to investigate the potential DNA damage resulting from toxic element exposure. The occupational exposure to trace elements, including arsenic (As), cadmium (Cd), manganese (Mn), nickel (Ni), lead (Pb), and selenium (Se), was estimated by their urinary levels as internal doses. In addition, all participants filled a self-filled questionnaire indicating their individual information. The average levels of urinary As, Cd, Mn, Ni, Pb, Se, and 8-hydroxy-2'-deoxyguanosine (8-OHdG) were 282.3 ± 464.6, 3.07 ± 5.39, 3.81 ± 11.43, 81.48 ± 138.9, 18.23 ± 49.61, 165.2 ± 224.9, and 17.21 ± 26.34 μg/g creatinine, respectively. The urinary levels of 8-OHdG and toxic elements were strongly associated with the work nature of the worker, with an exception of Mn and Pb. In contrast, the levels of toxic element were not influenced by age, smoking behavior, and alcohol consumption. The urinary 8-OHdG was found significantly higher in higher internal exposure groups of As, Cd, Ni, and Se. However, the stepwise multiple regression models showed that urinary 8-OHdG was only associated with urinary As and heat stress but inversely with age.

  7. Oxidative DNA damage estimated by urinary 8-hydroxy-2'-deoxyguanosine and arsenic in glass production workers.

    PubMed

    Lin, Tser-Sheng; Wu, Chin-Ching; Wu, Jyun-De; Wei, Chun-Han

    2012-07-01

    A total of 130 male glass workers, including 33 administrative workers, 18 batch house workers, 42 craftsmen, and 37 melting process workers, were recruited to investigate the potential DNA damage resulting from toxic element exposure. The occupational exposure to trace elements, including arsenic (As), cadmium (Cd), manganese (Mn), nickel (Ni), lead (Pb), and selenium (Se), was estimated by their urinary levels as internal doses. In addition, all participants filled a self-filled questionnaire indicating their individual information. The average levels of urinary As, Cd, Mn, Ni, Pb, Se, and 8-hydroxy-2'-deoxyguanosine (8-OHdG) were 282.3 ± 464.6, 3.07 ± 5.39, 3.81 ± 11.43, 81.48 ± 138.9, 18.23 ± 49.61, 165.2 ± 224.9, and 17.21 ± 26.34 μg/g creatinine, respectively. The urinary levels of 8-OHdG and toxic elements were strongly associated with the work nature of the worker, with an exception of Mn and Pb. In contrast, the levels of toxic element were not influenced by age, smoking behavior, and alcohol consumption. The urinary 8-OHdG was found significantly higher in higher internal exposure groups of As, Cd, Ni, and Se. However, the stepwise multiple regression models showed that urinary 8-OHdG was only associated with urinary As and heat stress but inversely with age. PMID:22033425

  8. Composition Dependence of the Na(+) Ion Conductivity in 0.5Na2S + 0.5[xGeS2 + (1 - x)PS5/2] Mixed Glass Former Glasses: A Structural Interpretation of a Negative Mixed Glass Former Effect.

    PubMed

    Martin, Steve W; Bischoff, Christian; Schuller, Katherine

    2015-12-24

    A negative mixed glass former effect (MGFE) in the Na(+) ion conductivity of glass has been found in 0.5Na2S + 0.5[xGeS2 + (1 - x)PS5/2] glasses where the Na(+) ion conductivity is significantly smaller for all of the ternary glasses than either of the binary end-member glasses. The minimum conductivity of ∼0.4 × 10(-6) (Ω cm)(-1) at 25 °C occurs for the x = 0.7 glass. Prior to this observation, the alkali ion conductivity of sulfide glasses at constant alkali concentration, but variable ratio of one glass former for another (x) ternary mixed glass former (MGF) glasses, has always produced a positive MGFE in the alkali ion conductivity; that is, the ternary glasses have always had higher ion conductivities that either of the end-member binary glasses. While the Na(+) ion conductivity exhibits a single global minimum value, the conductivity activation energy exhibits a bimodal double maximum at x ≈ 0.4 and x ≈ 0.7. The modified Christensen-Martin-Anderson-Stuart (CMAS) model of the activation energies reveals the origin of the negative MGFE to be due to an increase in the dielectric stiffness (a decrease in relative dielectric permittivity) of these glasses. When coupled with an increase in the average Na(+) ion jump distance and a slight increase in the mechanical stiffness of the glass, this causes the activation energy to go through maximum values and thereby produce the negative MGFE. The double maximum in the conductivity activation energy is coincident with double maximums in CMAS calculated strain, ΔES, and Coulombic, ΔEC, activation energies. In these ternary glasses, the increase in the dielectric stiffness of the glass arises from a negative deviation of the limiting high frequency dielectric permittivity as compared to the binary end-member glasses. While the CMAS calculated total activation energies ΔEact = ΔES + ΔEC are found to reproduce the overall shape of the composition dependence of the measured ΔEact values, they are consistently

  9. Indium tin oxide-coated glass modified with reduced graphene oxide sheets and gold nanoparticles as disposable working electrodes for dopamine sensing in meat samples

    NASA Astrophysics Data System (ADS)

    Yang, Jiang; Strickler, J. Rudi; Gunasekaran, Sundaram

    2012-07-01

    Sensitive, rapid, and accurate detection of dopamine (DA) at low cost is needed for clinical diagnostic and therapeutic purposes as well as to prevent illegal use of DA in animal feed. We employed a simple approach to synthesize reduced graphene oxide sheets (rGOS) and gold nanoparticles (AuNPs) at room temperature on indium tin oxide-coated glass (ITO) slides as disposable working electrodes for sensing DA. Graphene oxide (GO) was directly reduced on ITO to remove oxygenated species via a rapid and green process without using chemical reducing reagents. AuNPs were electrochemically deposited in situ on rGOS-ITO with fairly uniform density and size. The sensitivity of the AuNPs-rGOS-ITO sensor for DA detection is 62.7 μA mM-1 cm-2 with good selectivity against common electrochemically interfering species such as ascorbic acid (AA) and uric acid (UA), and the detection limit measured by differential pulse voltammetry (DPV), at a signal-noise ratio of 3, was 6.0 × 10-8 M. The electrochemical catalysis of DA was proven to be a surface process with an electron transfer coefficient (α) of 0.478 and a rate constant (ks) of 1.456 s-1. It correlates well with the conventional UV-vis spectrophotometric approach (R = 0.9973) but with more than thrice the dynamic range (up to 4.5 mM). The sensor also exhibited good stability and capability to detect DA in beef samples, and thus is a promising candidate for simple and inexpensive sub-nanomolar detection of DA, especially in the presence of UV-absorbing compounds.

  10. Efficient destruction of CF4 through in situ generation of alkali metals from heated alkali halide reducing mixtures.

    PubMed

    Lee, Myung Churl; Choi, Wonyong

    2002-03-15

    Perfluorocarbons (PFCs) are the most potent green house gases that are very recalcitrant at destruction. An effective way of converting PFCs using hot solid reagents into safe products has been recently introduced. By investigating the thermal reductive destruction of tetrafluoromethane (CF4) we provided new insight and more physicochemical consideration on this novel process. The complete destruction of CF4was successfully achieved by flowing the gas through a heated reagent bed (400-950 degrees C) that contained powder mixtures of alkali halides, CaO, and Si. The silicon acted as a reducing agent of alkali halides for the in-situ production of alkali metals, and the calcium oxide played the role of a halide ion acceptor. The absence of any single component in this ternary mixture drastically reduced the destruction efficiency of CF4. The CF4 destruction efficiencies with the solid reagent containing the alkali halide, MX, increased in the order of Li approximately Na < K < Cs for alkali cations and I < Br < Cl < F for halide anions. This trend agreed with the endothermicity of the alkali metal generation reaction: the higher the endothermicity, the lower the destruction efficiency. Alkali metal generation was indirectly detected by monitoring H2 production from its reaction with water. The production of alkali metals increased with NaF, KF, and CsF in this order. The CsF/CaO/Si system exhibited the complete destruction of CF4 at as low as 600 degrees C. The solid product analysis by X-ray diffraction (XRD) showed the formation of CaF2 and the depletion of Si with black carbon particles formed in the solid reagent residue. No CO/CO2 and toxic HF and SiF4 formation were detected in the exhaust gas.

  11. Role of Mobile Interstitial Oxygen Atoms in Defect Processes in Oxides: Interconversion between Oxygen-Associated Defects in SiO2 Glass

    NASA Astrophysics Data System (ADS)

    Kajihara, Koichi; Skuja, Linards; Hirano, Masahiro; Hosono, Hideo

    2004-01-01

    The role of mobile interstitial oxygen atoms (O0) in defect processes in oxides is demonstrated by interconversion between the oxygen dangling bond and the peroxy radical (POR) in SiO2 glass. Superstoichiometric O0 was created by F2 laser photolysis of the interstitial O2. On annealing above 300 °C, O0 migrated and converted the oxygen dangling bond to POR. Exposure to 5.0eV light converted POR back to a pair of the oxygen dangling bond and O0 (quantum yield: ˜0.1). These findings suggest that various defect processes typically occurring in SiO2 glass at ˜300 500 °C are related to migration of O0, which exists in the glass network in the peroxy linkage form.

  12. Reaction cured glass and glass coatings

    NASA Technical Reports Server (NTRS)

    Goldstein, H. E.; Leiser, D. B.; Katvala, V. W. (Inventor)

    1978-01-01

    The invention relates to reaction cured glass and glass coatings prepared by reacting a compound selected from the group consisting of silicon tetraboride, silicon hexaboride, other boron silicides, boron and mixtures with a reactive glass frit composed of a porous high silica borosilicate glass and boron oxide. The glassy composites of the present invention are useful as coatings on low density fibrous porous silica insulations used as heat shields and for articles such as reaction vessels that are subjected to high temperatures with rapid heating and cooling and that require resistance to temperature and repeated thermal shock at temperatures up to about 1482C (2700PF).

  13. Radiation coloration resistant glass

    DOEpatents

    Tomozawa, M.; Watson, E.B.; Acocella, J.

    1986-11-04

    A radiation coloration resistant glass is disclosed which is used in a radiation environment sufficient to cause coloration in most forms of glass. The coloration resistant glass includes higher proportions by weight of water and has been found to be extremely resistant to color change when exposed to such radiation levels. The coloration resistant glass is free of cerium oxide and has more than about 0.5% by weight water content. Even when exposed to gamma radiation of more than 10[sup 7] rad, the coloration resistant glass does not lose transparency. 3 figs.

  14. Oxynitride glass production procedure

    DOEpatents

    Weidner, Jerry R.; Schuetz, Stanley T.; O'Brien, Michael H.

    1991-01-01

    The invention is a process for the preparation of high quality oxynitride glasses without resorting to high pressures. Nitrogen-containing compounds such as Si.sub.3 N.sub.4 are first encapsulated in a low melting temperature glass. Particles of the encapsulated nitrogen-containing compound are mixed with other oxide glass-formers and melted in an atmosphere of flowing nitrogen and in the presence of buffering gas to form the oxynitride glass. Glasses containing up to 15 at % nitrogen have been prepared by this method.

  15. Radiation coloration resistant glass

    DOEpatents

    Tomozawa, Minoru; Watson, E. Bruce; Acocella, John

    1986-01-01

    A radiation coloration resistant glass is disclosed which is used in a radiation environment sufficient to cause coloration in most forms of glass. The coloration resistant glass includes higher proportions by weight of water and has been found to be extremely resistant to color change when exposed to such radiation levels. The coloration resistant glass is free of cerium oxide and has more than about 0.5% by weight water content. Even when exposed to gamma radiation of more than 10.sup.7 rad, the coloration resistant glass does not lose transparency.

  16. Study of Geometric Stability and Structural Integrity of Self-Healing Glass Seal System Used in Solid Oxide Fuel Cells

    SciTech Connect

    Liu, Wenning N.; Sun, Xin; Khaleel, Mohammad A.

    2011-02-15

    A self-healing glass seal has the potential of restoring its mechanical properties upon being reheated to SOFC stack operating temperature, even when it has experienced some cooling induced damage/cracking at room temperature. Such a self-healing feature is desirable for achieving high seal reliability during thermal cycling. On the other hand, self-healing glass is also characterized by its low mechanical stiffness and high creep rate at the typical operating temperature of SOFCs. Therefore, geometry stability and structural integrity of the glass seal system becomes critical to its successful application in SOFCs. In this paper, the geometry stability of the self-healing glass and the influence of various interfacial conditions of ceramic stoppers with the PEN, IC, and glass seal on the structural integrity of the glass seal during the operating and cooling down processes are studied using finite element analyses. For this purpose, the test cell used in the leakage tests for compliant glass seals conducted at PNNL is taken as the initial modeling geometry. The effect of the ceramic stopper on the geometry stability of the self-healing glass sealants is studied first. Two interfacial conditions of the ceramic stopper and glass seals, i.e., bonded (strong) or un-bonded (weak), are considered. Then the influences of interfacial strengths at various interfaces, i.e., stopper/glass, stopper/PEN, as well as stopper/IC plate, on the geometry stability and reliability of glass during the operating and cooling processes are examined.

  17. High capacity nickel battery material doped with alkali metal cations

    DOEpatents

    Jackovitz, John F.; Pantier, Earl A.

    1982-05-18

    A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

  18. FABRICATION AND CHARACTERIZATION OF BOROSILICATE GLASSES CONTAINING ALPHA-RADIONUCLIDES AND SILVER FROM CONVERSION AND MIXED-OXIDE FACILITIES PROPOSED FOR RUSSIA

    SciTech Connect

    Aloy, A; Trofimenko, V; Uspensky, A; Jardine, L

    2005-10-25

    Liquid and solid radioactive wastes are formed during conversion of plutonium metal to oxide and during fabrication of weapons-grade plutonium into mixed-oxide (MOX) fuel. In Russia, these wastes are to be processed for disposition by immobilization in either borosilicate glass or cement matrices depending upon the waste stream-specific radionuclide contents. Vitrification is planned for the liquid high-level waste raffinate stream containing the bulk of the Am-241 produced from Pu-241 decay. Previous work on the Russian MOX Fuel Fabrication Facility (R-MFFF) by the Public Joint Stock Corporation (TVEL) [1] showed that this waste stream may contain significant amounts of silver derived from the electrochemical dissolution of PuO2 using a Ag(II) catalyst. The work reported here further investigated silver solubility limits, which, if exceeded in a production glass melter, allow discrete silver grains to form in the glass and also deposit over time on the bottom of a joule-heated ceramic melter. In melters with immersed electrodes, such as the Russian EP-100 for phosphate glasses or the US Duratek DP-100 type melters for borosilicate glasses that are being considered for use at the Siberian Chemical Combine (SCC) Tomsk site, the undissolved silver could cause a short circuit and an unacceptable production melter failure. The silver solubility limit of 3.85 wt% Ag{sub 2}O in liquid, alpha-bearing wastes determined in this work will guide the production scale use of borosilicate glass compositions, and effectively increase the capacity of the ceramic melters and reduce the total volume of solidified vitrified wastes at SCC Tomsk that require storage prior to geologic disposal.

  19. Effect of aluminizing of Cr-containing ferritic alloys on the seal strength of a novel high-temperature solid oxide fuel cell sealing glass

    SciTech Connect

    Chou, Y. S.; Stevenson, Jeffry W.; Singh, Prabhakar

    2008-12-01

    A novel high-temperature alkaline-earth silicate sealing glass was developed for solid oxide fuel cell (SOFC) applications. The glass was used to join two metallic coupons of Cr-containing ferritic stainless steel for seal strength evaluation. In previous work, SrCrO4 was found to form along the glass/steel interface, which led to severe strength degradation. In the present study, aluminization of the steel surface was investigated as a remedy to minimize or prevent the strontium chromate formation. Three different processes for aluminization were evaluated with Crofer22APU stainless steel: pack cementation, vapor phase deposition, and aerosol spraying. It was found that pack cementation resulted in a rough surface with occasional cracks in the Al-diffused region. Vapor phase deposition yielded a smoother surface, but the resulting high Al content increased the coefficient of thermal expansion (CTE), resulting in failure of joined coupons. Aerosol spraying of an Al-containing salt resulted in formation of a thin aluminum oxide layer without any surface damage. The room temperature seal strength was evaluated in the as-fired state and in environmentally aged conditions. In contrast to earlier results with uncoated Crofer22APU, the aluminized samples showed no strength degradation even for samples aged in air. Interfacial and chemical compatibility was also investigated. The results showed aluminization to be a viable candidate approach to minimize undesirable chromate formation between alkaline earth silicate sealing glass and Cr-containing interconnect alloys for SOFC applications.

  20. The influence of internal oxidation during decarburization of a grain oriented silicon steel on the morphology of the glass film formed at high temperature annealing

    NASA Astrophysics Data System (ADS)

    Silveira, Carolina Cesconetto; da Cunha, Marco Antônio; Buono, Vicente Tadeu Lopes

    2014-05-01

    Fourier transform infrared spectroscopy (FTIR) was applied to evaluate the amount of fayalite formed during decarburization of a grain-oriented silicon steel, in order to assess its influence on the morphology of the glass film developed at the final high temperature annealing. The decarburization conditions varied within the temperature range of 740-950 °C and pH2O/pH2 from 0.28 to 0.58. The decarburized specimens were then coated with magnesia slurry and submitted to the high temperature annealing at 1200 °C for 15 h. Characterization of the oxide layer and glass film samples was performed by scanning and transmission electron microscopy. The FTIR analysis showed that the amount of fayalite increased as the temperature and the dew point increased during decarburization. The morphology of the glass film obtained after high temperature annealing was related to the amount of fayalite and silica previously formed. A higher amount of subsurface particles in the glass film, which can deteriorate magnetic properties by restraining domain wall movements, was obtained from oxide layers rich in fayalite and thus with a low amount of silica.

  1. Long-term evaluation of solid oxide fuel cell candidate materials in a 3-cell generic short stack fixture, Part II: sealing glass stability, microstructure and interfacial reactions.

    SciTech Connect

    Chou, Y. S.; Stevenson, Jeffry W.; Choi, Jung-Pyung

    2014-03-15

    A generic solid oxide fuel cell stack test fixture was developed to evaluate candidate materials and processing methods under realistic conditions. Part I of the work addressed the stack fixture, seal system and cell performance of a 3-cell short stack tested at 800oC for 6000h. Commercial NiO-YSZ anode-supported thin YSZ electrolyte cells with LSM cathodes were used for assessment and were tested in constant current mode with dilute (~50% H2) fuel versus air. Part II of the work examined the sealing glass stability, microstructure development, interfacial reactions, and volatility issues. Part III of the work investigated the stability of Ce-(Mn,Co) spinel coating, AISI441 metallic interconnect, alumina coating, and cell degradation. After 6000h of testing, the refractory sealing glass YSO77 (Ba-Sr-Y-B-Si) showed desirable chemical compatibility with YSZ electrolyte in that no discernable interfacial reaction was identified, consistent with thermodynamic calculations. In addition, no glass penetration into the thin electrolyte was observed. At the aluminized AISI441 interface, the protective alumina coating appeared to be corroded by the sealing glass. Air side interactions appeared to be more severe than fuel side interactions. Metal species such as Cr, Mn, and Fe were detected in the glass, but were limited to the vicinity of the interface. No alkaline earth chromates were found at the air side. Volatility was also studied in a similar glass and weight loss in a wet reducing environment was determined. Using the steady-state volatility data, the life time (40,000h) weight loss of refractory sealing glass YSO77 was estimated to be less than 0.1 wt%.

  2. Plasmonic Three-Dimensional Transparent Conductor Based on Al-Doped Zinc Oxide-Coated Nanostructured Glass Using Atomic Layer Deposition

    SciTech Connect

    Malek, Gary A.; Aytug, Tolga; Liu, Qingfeng; Wu, Judy

    2015-04-02

    Transparent nanostructured glass coatings, fabricated on glass substrates, with a unique three-dimensional (3D) architecture were utilized as the foundation for the design of plasmonic 3D transparent conductors. Transformation of the non-conducting 3D structure to a conducting 3D network was accomplished through atomic layer deposition of aluminum-doped zinc oxide (AZO). After AZO growth, gold nanoparticles (AuNPs) were deposited by electronbeam evaporation to enhance light trapping and decrease the overall sheet resistance. Field emission scanning electron microscopy and atomic force microcopy images revealed the highly porous, nanostructured morphology of the AZO coated glass surface along with the in-plane dimensions of the deposited AuNPs. Sheet resistance measurements conducted on the coated samples verified that the electrical properties of the 3D network are comparable to that of the untextured two-dimensional AZO coated glass substrates. In addition, transmittance measurements of the glass samples coated with various AZO thicknesses showed preservation of the highly transparent nature of each sample, while the AuNPs demonstrated enhanced light scattering as well as light-trapping capability.

  3. Plasmonic Three-Dimensional Transparent Conductor Based on Al-Doped Zinc Oxide-Coated Nanostructured Glass Using Atomic Layer Deposition

    DOE PAGES

    Malek, Gary A.; Aytug, Tolga; Liu, Qingfeng; Wu, Judy

    2015-04-02

    Transparent nanostructured glass coatings, fabricated on glass substrates, with a unique three-dimensional (3D) architecture were utilized as the foundation for the design of plasmonic 3D transparent conductors. Transformation of the non-conducting 3D structure to a conducting 3D network was accomplished through atomic layer deposition of aluminum-doped zinc oxide (AZO). After AZO growth, gold nanoparticles (AuNPs) were deposited by electronbeam evaporation to enhance light trapping and decrease the overall sheet resistance. Field emission scanning electron microscopy and atomic force microcopy images revealed the highly porous, nanostructured morphology of the AZO coated glass surface along with the in-plane dimensions of the depositedmore » AuNPs. Sheet resistance measurements conducted on the coated samples verified that the electrical properties of the 3D network are comparable to that of the untextured two-dimensional AZO coated glass substrates. In addition, transmittance measurements of the glass samples coated with various AZO thicknesses showed preservation of the highly transparent nature of each sample, while the AuNPs demonstrated enhanced light scattering as well as light-trapping capability.« less

  4. Plasmonic three-dimensional transparent conductor based on Al-doped zinc oxide-coated nanostructured glass using atomic layer deposition.

    PubMed

    Malek, Gary A; Aytug, Tolga; Liu, Qingfeng; Wu, Judy

    2015-04-29

    Transparent nanostructured glass coatings, fabricated on glass substrates, with a unique three-dimensional (3D) architecture were utilized as the foundation for designing plasmonic 3D transparent conductors. Transformation of the nonconducting 3D structure to a conducting porous surface network was accomplished through atomic layer deposition of aluminum-doped zinc oxide (AZO). After AZO growth, gold nanoparticles (AuNPs) were deposited by electron-beam evaporation to enhance light trapping and decrease the overall sheet resistance. Field emission scanning electron microscopy and atomic force microcopy images revealed the highly porous, nanostructured morphology of the AZO-coated glass surface along with the in-plane dimensions of the deposited AuNPs. Sheet resistance measurements conducted on the coated samples verified that the electrical properties of the 3D network are comparable to those of untextured two-dimensional AZO-coated glass substrates. In addition, transmittance measurements of the glass samples coated at various AZO thicknesses showed preservation of the transparent nature of each sample, and the AuNPs demonstrated enhanced light scattering as well as light-trapping capabilities.

  5. Plasmonic three-dimensional transparent conductor based on Al-doped zinc oxide-coated nanostructured glass using atomic layer deposition.

    PubMed

    Malek, Gary A; Aytug, Tolga; Liu, Qingfeng; Wu, Judy

    2015-04-29

    Transparent nanostructured glass coatings, fabricated on glass substrates, with a unique three-dimensional (3D) architecture were utilized as the foundation for designing plasmonic 3D transparent conductors. Transformation of the nonconducting 3D structure to a conducting porous surface network was accomplished through atomic layer deposition of aluminum-doped zinc oxide (AZO). After AZO growth, gold nanoparticles (AuNPs) were deposited by electron-beam evaporation to enhance light trapping and decrease the overall sheet resistance. Field emission scanning electron microscopy and atomic force microcopy images revealed the highly porous, nanostructured morphology of the AZO-coated glass surface along with the in-plane dimensions of the deposited AuNPs. Sheet resistance measurements conducted on the coated samples verified that the electrical properties of the 3D network are comparable to those of untextured two-dimensional AZO-coated glass substrates. In addition, transmittance measurements of the glass samples coated at various AZO thicknesses showed preservation of the transparent nature of each sample, and the AuNPs demonstrated enhanced light scattering as well as light-trapping capabilities. PMID:25835062

  6. Strong, Tough Glass Composites Developed for Solid Oxide Fuel Cell Seals

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Choi, Sung R.

    2005-01-01

    A fuel cell is an electrochemical device that continuously converts the chemical energy of a fuel directly into electrical energy. It consists of an electrolyte, an anode, and a cathode. Various types of fuel cells are available, such as direct methanol fuel cells, alkaline fuel cells, proton-exchange-membrane fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, and solid oxide fuel cells (SOFCs). The salient features of an SOFC are all solid construction and high-temperature electrochemical-reaction-based operation, resulting in clean, efficient power generation from a variety of fuels. SOFCs are being developed for a broad range of applications, such as portable electronic devices, automobiles, power generation, and aeronautics.

  7. Catalytic oxidation of carbon monoxide over radiolytically prepared Pt nanoparticles supported on glass

    SciTech Connect

    Kapoor, S. . E-mail: sudhirk@apsara.barc.ernet.in; Belapurkar, A.D.; Mittal, J.P.; Mukherjee, T. . E-mail: mukherji@magnum.barc.ernet.in

    2005-10-06

    Platinum nanoparticles have been prepared by radiolytic and chemical methods in the presence of stabilizer gelatin and SiO{sub 2} nanoparticles. The formation of Pt nanoparticles was confirmed using UV-vis absorption spectroscopy and transmission electron microscopy (TEM). The prepared particles were coated on the inner walls of the tubular pyrex reactor and tested for their catalytic activity for oxidation of CO. It was observed that Pt nanoparticles prepared in the presence of a stabilizer (gelatin) showed a higher tendency to adhere to the inner walls of the pyrex reactor as compared to that prepared in the presence of silica nanoparticles. The catalyst was found to be active at {>=}150 deg. C giving CO{sub 2}. Chemically reduced Pt nanoparticles stabilized on silica nanoparticles gave {approx}7% CO conversion per hour. However, radiolytically prepared Pt nanoparticles stabilized by gelatin gave {approx}10% conversion per hour. Catalytic activity of radiolytically prepared platinum catalyst, coated on the inner walls of the reactor, was evaluated as a function of CO concentration and reaction temperature. The rate of reaction increased with increase in reaction temperature and the activation energy for the reaction was found to be {approx}108.8 kJ mol{sup -1}. The rate of CO{sub 2} formation was almost constant ({approx}1.5 x 10{sup -4} mol dm{sup -3} h{sup -1}) at constant O{sub 2} concentration (6.5 x 10{sup -3} mol dm{sup -3}) with increase in CO concentration from 2 x 10{sup -4} mol dm{sup -3} to 3.25 x 10{sup -3} mol dm{sup -3}. The data indicate that catalytic oxidation of CO takes place by Eley-Rideal mechanism.

  8. Growth mechanism and optical properties of Ti thin films deposited onto fluorine-doped tin oxide glass substrate

    SciTech Connect

    Einollahzadeh-Samadi, Motahareh; Dariani, Reza S.

    2015-03-15

    In this work, a detailed study of the influence of the thickness on the morphological and optical properties of titanium (Ti) thin films deposited onto rough fluorine-doped tin oxide glass by d.c. magnetron sputtering is carried out. The films were characterized by several methods for composition, crystallinity, morphology, and optical properties. Regardless of the deposition time, all the studied Ti films of 400, 1500, 2000, and 2500 nm in thickness were single crystalline in the α-Ti phase and also very similar to each other with respect to composition. Using the atomic force microscopy (AFM) technique, the authors analyzed the roughness evolution of the Ti films characteristics as a function of the film thickness. By applying the dynamic scaling theory to the AFM images, a steady growth roughness exponent α = 0.72 ± 0.02 and a dynamic growth roughness exponent β = 0.22 ± 0.02 were determined. The value of α and β are consistent with nonlinear growth model incorporating random deposition with surface diffusion. Finally, measuring the reflection spectra of the samples by a spectrophotometer in the spectral range of 300–1100 nm allowed us to investigate the optical properties. The authors observed the increments of the reflection of Ti films with thickness, which by employing the effective medium approximation theory showed an increase in thickness followed by an increase in the volume fraction of metal.

  9. Photoluminescence properties of Ho{sup 3+} ion in lithium-fluoroborate glass containing different modifier oxides

    SciTech Connect

    Balakrishna, A. Rajesh, D. Ratnakaram, Y. C.

    2014-04-24

    Trivalent holmium (0.5 mol%) doped lithium fluoro-borate glasses with the chemical compositions 49.5Li{sub 2}B{sub 4}O{sub 7−}20BaF{sub 2−}10NaF−20MO (where M=Mg, Ca, Cd and Pb), 49.5Li{sub 2}B{sub 4}O{sub 7−}20BaF{sub 2−}10NaF−10MgO−10CaO and 49.5Li{sub 2}B{sub 4}O{sub 7−}20BaF{sub 2−}10NaF−10CdO−10PbO were synthesized and investigated their photoluminescence properties. The variation in chemical composition by varying modifier oxides causes changes in the structural spectroscopic behavior of Ho{sup 3+} ions. These changes are examined by UV-VIS- NIR and luminescence spectroscopic techniques. The visible luminescence spectra were obtained by exciting samples at 409 nm radiation.

  10. Upgrading platform using alkali metals

    SciTech Connect

    Gordon, John Howard

    2014-09-09

    A process for removing sulfur, nitrogen or metals from an oil feedstock (such as heavy oil, bitumen, shale oil, etc.) The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  11. Room temperature oxidative intercalation with chalcogen hydrides: Two-step method for the formation of alkali-metal chalcogenide arrays within layered perovskites

    SciTech Connect

    Ranmohotti, K.G. Sanjaya; Montasserasadi, M. Dariush; Choi, Jonglak; Yao, Yuan; Mohanty, Debasish; Josepha, Elisha A.; Adireddy, Shiva; Caruntu, Gabriel; Wiley, John B.

    2012-06-15

    Highlights: ► Topochemical reactions involving intercalation allow construction of metal chalcogenide arrays within perovskite hosts. ► Gaseous chalcogen hydrides serve as effect reactants for intercalation of sulfur and selenium. ► New compounds prepared by a two-step intercalation strategy are presented. -- Abstract: A two-step topochemical reaction strategy utilizing oxidative intercalation with gaseous chalcogen hydrides is presented. Initially, the Dion-Jacobson-type layered perovskite, RbLaNb{sub 2}O{sub 7}, is intercalated reductively with rubidium metal to make the Ruddlesden-Popper-type layered perovskite, Rb{sub 2}LaNb{sub 2}O{sub 7}. This compound is then reacted at room-temperature with in situ generated H{sub 2}S gas to create Rb-S layers within the perovskite host. Rietveld refinement of X-ray powder diffraction data (tetragonal, a = 3.8998(2) Å, c = 15.256(1) Å; space group P4/mmm) shows the compound to be isostructural with (Rb{sub 2}Cl)LaNb{sub 2}O{sub 7} where the sulfide resides on a cubic interlayer site surrounded by rubidium ions. The mass increase seen on sulfur intercalation and the refined S site occupation factor (∼0.8) of the product indicate a higher sulfur content than expected for S{sup 2−} alone. This combined with the Raman studies, which show evidence for an H-S stretch, indicate that a significant fraction of the intercalated sulfide exists as hydrogen sulfide ion. Intercalation reactions with H{sub 2}Se{sub (g)} were also carried out and appear to produce an isostructural selenide compound. The utilization of such gaseous hydride reagents could significantly expand multistep topochemistry to a larger number of intercalants.

  12. Elemental and Isotopic Analysis of Uranium Oxide an NIST Glass Standards by FEMTOSECOND-LA-ICP-MIC-MS

    SciTech Connect

    Ebert, Chris; Zamzow, Daniel S.; McBay, Eddie H.; Bostick, Debra A.; Bajic, Stanley J.; Baldwin, David P.; Houk, R.S.

    2009-06-01

    The objective of this work was to test and demonstrate the analytical figures of merit of a femtosecond-laser ablation (fs-LA) system coupled with an inductively coupled plasma-multi-ion collector-mass spectrometer (ICP-MIC-MS). The mobile fs-LA sampling system was designed and assembled at Ames Laboratory and shipped to Oak Ridge National Laboratory (ORNL), where it was integrated with an ICP-MIC-MS. The test period of the integrated systems was February 2-6, 2009. Spatially-resolved analysis of particulate samples is accomplished by 100-shot laser ablation using a fs-pulsewidth laser and monitoring selected isotopes in the resulting ICP-MS transient signal. The capability of performing high sensitivity, spatially resolved, isotopic analyses with high accuracy and precision and with virtually no sample preparation makes fs-LA-ICP-MIC-MS valuable for the measurement of actinide isotopes at low concentrations in very small samples for nonproliferation purposes. Femtosecond-LA has been shown to generate particles from the sample that are more representative of the bulk composition, thereby minimizing weaknesses encountered in previous work using nanosecond-LA (ns-LA). The improvement of fs- over ns-LA sampling arises from the different mechanisms for transfer of energy into the sample in these two laser pulse-length regimes. The shorter duration fs-LA pulses induce less heating and cause less damage to the sample than the longer ns pulses. This results in better stoichiometric sampling (i.e., a closer correlation between the composition of the ablated particles and that of the original solid sample), which improves accuracy for both intra- and inter-elemental analysis. The primary samples analyzed in this work are (a) solid uranium oxide powdered samples having different {sup 235}U to {sup 238}U concentration ratios, and (b) glass reference materials (NIST 610, 612, 614, and 616). Solid uranium oxide samples containing {sup 235}U in depleted, natural, and enriched

  13. Synthesis of zinc oxide nanostructures on graphene/glass substrate by electrochemical deposition: effects of current density and temperature

    PubMed Central

    2014-01-01

    The electrochemical growth of zinc oxide (ZnO) nanostructures on graphene on glass using zinc nitrate hexahydrate was studied. The effects of current densities and temperatures on the morphological, structural, and optical properties of the ZnO structures were studied. Vertically aligned nanorods were obtained at a low temperature of 75°C, and the diameters increased with current density. Growth temperature seems to have a strong effect in generating well-defined hexagonal-shape nanorods with a smooth top edge surface. A film-like structure was observed for high current densities above -1.0 mA/cm2 and temperatures above 80°C due to the coalescence between the neighboring nanorods with large diameter. The nanorods grown at a temperature of 75°C with a low current density of -0.1 mA/cm2 exhibited the highest density of 1.45 × 109 cm-2. X-ray diffraction measurements revealed that the grown ZnO crystallites were highly oriented along the c-axis. The intensity ratio of the ultraviolet (UV) region emission to the visible region emission, IUV/IVIS, showed a decrement with the current densities for all grown samples. The samples grown at the current density below -0.5 mA/cm2 showed high IUV/IVIS values closer to or higher than 1.0, suggesting their fewer structural defects. For all the ZnO/graphene structures, the high transmittance up to 65% was obtained at the light wavelength of 550 nm. Structural and optical properties of the grown ZnO structures seem to be effectively controlled by the current density rather than the growth temperature. ZnO nanorod/graphene hybrid structure on glass is expected to be a promising structure for solar cell which is a conceivable candidate to address the global need for an inexpensive alternative energy source. PMID:25411567

  14. Theoretical study of the alkali and alkaline-earth monosulfides

    NASA Technical Reports Server (NTRS)

    Partridge, Harry; Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.

    1988-01-01

    Ab initio calculations have been used to obtain accurate spectroscopic constants for the X2Pi and A2Sigma(+) states of the alkali sulfides and the X1Sigma(+), a3Pi, and A1Pi states of the alkaline-earth sulfides. In contrast to the alkali oxides, the alkali sulfides are found to have X2Pi ground states, due to the larger electrostatic interaction. Dissociation energies of 3.27 eV for BeS, 2.32 eV for MgS, 3.29 eV for CaS, and 3.41 eV for SrS have been obtained for the X1Sigma(+) states of the alkaline-earth sulfides, in good agreement with experimental results. Core correlation is shown to increase the Te values for the a3Pi and A1Pi states of MgS, CaS, and SrS.

  15. Compositional dependence of bioactivity of glasses in the system Na2O-K2O-MgO-CaO-B2O3-P2O5-SiO2.

    PubMed

    Brink, M; Turunen, T; Happonen, R P; Yli-Urpo, A

    1997-10-01

    The bioactivity, i.e., bone-bonding ability, of 26 glasses in the system Na2O-K2O-MgO-CaO-B2O3-P2O5-SiO2 was studied in vivo. This investigation of bioactivity was performed to establish the compositional dependence of bioactivity, and enabled a model to be developed that describes the relation between reactions in vivo and glass composition. Reactions in vivo were investigated by inserting glass implants into rabbit tibia for 8 weeks. The glasses and the surrounding tissue were examined using scanning electron microscopy (SEM), light microscopy, and energy-dispersive X-ray analysis (EDXA). For most of the glasses containing < 59 mol % SiO2, SEM and EDXA showed two distinct layers at the glass surface after implantation, one silica-rich and another containing calcium phosphate. The build-up of these layers in vivo was taken as a sign of bioactivity. The in vivo experiments showed that glasses in the investigated system are bioactive when they contain 14-30 mol % alkali oxides, 14-30 mol % alkaline earth oxides, and < 59 mol % SiO2. Glasses containing potassium and magnesium bonded to bone in a similar way as bioactive glasses developed so far.

  16. IMPACTS OF ANTIFOAM ADDITIONS AND ARGON BUBBLING ON DEFENSE WASTE PROCESSING FACILITY REDUCTION/OXIDATION

    SciTech Connect

    Jantzen, C.; Johnson, F.

    2012-06-05

    During melting of HLW glass, the REDOX of the melt pool cannot be measured. Therefore, the Fe{sup +2}/{Sigma}Fe ratio in the glass poured from the melter must be related to melter feed organic and oxidant concentrations to ensure production of a high quality glass without impacting production rate (e.g., foaming) or melter life (e.g., metal formation and accumulation). A production facility such as the Defense Waste Processing Facility (DWPF) cannot wait until the melt or waste glass has been made to assess its acceptability, since by then no further changes to the glass composition and acceptability are possible. therefore, the acceptability decision is made on the upstream process, rather than on the downstream melt or glass product. That is, it is based on 'feed foward' statistical process control (SPC) rather than statistical quality control (SQC). In SPC, the feed composition to the melter is controlled prior to vitrification. Use of the DWPF REDOX model has controlled the balanjce of feed reductants and oxidants in the Sludge Receipt and Adjustment Tank (SRAT). Once the alkali/alkaline earth salts (both reduced and oxidized) are formed during reflux in the SRAT, the REDOX can only change if (1) additional reductants or oxidants are added to the SRAT, the Slurry Mix Evaporator (SME), or the Melter Feed Tank (MFT) or (2) if the melt pool is bubble dwith an oxidizing gas or sparging gas that imposes a different REDOX target than the chemical balance set during reflux in the SRAT.

  17. Correlation of the oxidation state of cerium in sol?gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies

    NASA Astrophysics Data System (ADS)

    Assefa, Zerihun; Haire, R. G.; Caulder, D. L.; Shuh, D. K.

    2004-07-01

    Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce 3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 °C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 °C and up to ˜1000 °C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 °C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

  18. Cathodoluminescence Characterization of Maskelynite and Alkali Feldspar in Shergottite (Dhofar 019)

    SciTech Connect

    Kayama, M.; Nakazato, T.; Nishido, H.; Ninagawa, K.; Gucsik, A.

    2009-08-17

    Dhofar 019 is classified as an olivine-bearing basaltic shergottite and consists of subhedral grains of pyroxene, olivine, feldspar mostly converted to maskelynite and minor alkali feldspar. The CL spectrum of its maskelynite exhibits an emission band at around 380 nm. Similar UV-blue emission has been observed in the plagioclase experimentally shocked at 30 and 40 GPa, but not in terrestrial plagioclase. This UV-blue emission is a notable characteristic of maskelynite. CL spectrum of alkali feldspar in Dhofar 019 has an emission bands at around 420 nm with no red emission. Terrestrial alkali feldspar actually consists of blue and red emission at 420 and 710 nm assigned to Al-O{sup -}-Al and Fe{sup 3+} centers, respectively. Maskelynite shows weak and broad Raman spectral peaks at around 500 and 580 cm{sup -1}. The Raman spectrum of alkali feldspar has a weak peak at 520 cm{sup -1}, whereas terrestrial counterpart shows the emission bands at 280, 400, 470, 520 and 1120 cm{sup -1}. Shock pressure on this meteorite transformed plagioclase and alkali feldspar into maskelynite and almost glass phase, respectively. It eliminates their luminescence centers, responsible for disappearance of yellow and/or red emission in CL of maskelynite and alkali feldspar. The absence of the red emission band in alkali feldspar can also be due to the lack of Fe{sup 3+} in the feldspar as it was reported for some lunar feldspars.

  19. Hydrothermal alkali metal catalyst recovery process

    DOEpatents

    Eakman, James M.; Clavenna, LeRoy R.

    1979-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles primarily in the form of water soluble alkali metal formates by treating the particles with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of added carbon monoxide. During the treating process the water insoluble alkali metal compounds comprising the insoluble alkali metal residues are converted into water soluble alkali metal formates. The resultant aqueous solution containing water soluble alkali metal formates is then separated from the treated particles and any insoluble materials formed during the treatment process, and recycled to the gasification process where the alkali metal formates serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. This process permits increased recovery of alkali metal constituents, thereby decreasing the overall cost of the gasification process by reducing the amount of makeup alkali metal compounds necessary.

  20. Structural, optical, and electrical properties of Cu2O nanocubes grown on indium-tin-oxide-coated glass substrates by using seed-layer-free electrochemical deposition method

    NASA Astrophysics Data System (ADS)

    No, Young Soo; Oh, Do Hyon; Kim, Su Yeon; Yoo, Keon-Ho; Kim, Tae Whan

    2012-07-01

    Electrochemical deposition was employed to fabricate Cu2O nanocubes on indium-tin-oxide (ITO)-coated glass substrates at 75 °C without using any template, catalyst, or seed layer. Scanning electron microscopy images showed that the Cu2O nanocubes with a nanoscale size were uniformly formed on ITO-coated glass substrates. X-ray patterns of the Cu2O nanocubes exhibited the dominant peaks corresponding to the Cu2O cubic structures. The current-voltage curves of an Au/n-type Al-doped ZnO/p-type Cu2O nanocube/ITO device clearly showed current rectifying behavior with a turn-on voltage of 3.6 V.

  1. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report {number_sign}9: September 1--December 1, 1993

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1993-12-01

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions.

  2. Origin of hydrous alkali feldspar-silica intergrowth in spherulites from intra-plate A2-type rhyolites at the Jabal Shama, Saudi Arabia

    NASA Astrophysics Data System (ADS)

    Surour, Adel A.; El-Nisr, Said A.; Bakhsh, Rami A.

    2016-03-01

    Miocene rhyolites (19.2 ± 0.9 Ma) at the Jabal Shama in western Saudi Arabia represent an example of rift-related silicic volcanism that took place during the formation of the Red Sea. They mostly consist of tuffaceous varieties with distinct flow banding, and pea-sized spherulites, obsidian and perlitized rhyolite tuffs. Although they have the geochemical signature of A2-type rhyolites, these silicic rocks are not typically alkaline but alkali-calcic to calc-alkaline. They developed in a within-plate regime and possibly derived from a recycled mafic subducted slab in depleted sub-continental mantle beneath the western Arabian plate. The Jabal Shama rhyolites are younger in age than their Miocene counterparts in Yemen and Ethiopia. The Jabal Shama spherulites consist of hydrous alkali feldspar-silica radial intergrowths with an occasional brown glass nucleus. Carbonate- and glass-free spherulites give up to 4.45 wt% L.O.I. The hydrous nature of these silicates and the absence of magnetite in the spherulites is a strong indication of oxidizing conditions. The spherulites contain hydrous feldspars with up to ∼6 wt% H2O, and they develop by diffusion and devitrification of glass in the rhyolite tuff at ∼800 °C. Owing to higher undercooling due to supersaturation, the radial hydrous phases within spherulites might grow faster and led to coagulation. The polygonal contacts between spherulites and the ∼120° dihedral angle suggest solid-state modification and recrystallization as the process of devitrification proceeds as low as ∼300 °C. The sum of FeO + MgO is positively correlated with total alkalies along with magnetite oxidation in the matrix to Fe-oxyhydroxides, and to the incorporation of OH- into silicates within the spehrulites themselves. Structural H2O in glass of the Jabal Shama perlite (obsidian) is considerable (∼9-12 wt%) with 3.72-5.6 wt% L.O.I. of the whole-rock. The presence of deleterious silica impurities would lower the ore grade due to

  3. Iron Oxidizing and Reducing Bacteria as Contributors to Basaltic Glass Colonization and Subsequent Weathering in Active Hydrothermal Vent Systems on Loihi and Vailulu'u Seamounts

    NASA Astrophysics Data System (ADS)

    Bailey, B.; Templeton, A.; Haucke, L.; Staudigel, H.; Tebo, B. M.

    2005-12-01

    The extreme oligotrophic nature of the oceanic crust was once believed to be an inhospitable environment to support microbial life. However, numerous studies in the past two decades have revealed diverse chemolithotrophic microbial communities inhabiting the deep biosphere within the oceanic crust. Vailulu'u Seamount in American Samoa and Loihi Seamount in Hawai'i provide access to the deep biosphere environments through the study of the interaction of hydrothermal vent water, basaltic substrates and microbial communities. Both seamounts have been found to exhibit similar iron-encrusted microbial mats surrounding both high and low temperature hydrothermal vent orifices. We are targeting iron as the main electron donor/acceptor in these environments due to the relative abundance and availability in basalts. Through the use of the HURL Pisces submersibles, we exposed amended basaltic glasses of several different compositions to a host of different environments on both seamounts in order to study the colonization and biofilm characteristics of the microbial communities. A large culturing effort reveals multiple iron oxidizing and reducing bacteria as members of the microbial community responsible for the colonization and subsequent dissolution and alteration of basaltic glass. We employ an annular reactor to expose the same suite of chemically altered basaltic glasses to a sample of iron microbial mats taken from Vailulu'u to provide a laboratory complement the environmental exposure experiments. Here cell counts reveal a 90% enhanced colonization and growth on the basalt glass versus the surrounding epoxy and borosilicate glass. The ability of microbes to leach nutrients (such as iron) out of the host substrate has far reaching astrobiological implications for nutrient sources available to sustain life in a Mars or Europa biosphere.

  4. Irradiation study of PNNL synthesized glass-ceramics

    SciTech Connect

    Kossoy-simakov, Anna-eden; Tang, Ming; Valdez, James A; Usov, Igor O; Sickafus, Kurt E

    2011-01-18

    Two types of glass-ceramic were investigated: (1) for immobilization of Ln, alkali, and alkaline earths (GC4); and (2) same as above + high (7%) molybdenum content (Mo7) multiphase specimens. The purpose was to study the radiation stability of PNNL synthesized glass-ceramics and changes in microstructure/phase composition.

  5. Healing of lithographically introduced flaws in glass and glass containing ceramics

    SciTech Connect

    Ackler, H.D.

    1992-12-01

    The morphological evolution of cylindrical pores or ``channels`` and crack-like cavities in glass and glass-containing ceramics at elevated temperatures was studied. The systems studied were: Coming 7056 alkali borosilicate glass, soda-lime glass (microscope slides), a commercially available 96% Al{sub 2}O{sub 3}with {approx}5--10% intergranular glass, 96% Al{sub 2}O{sub 3} bonded to sapphire, and a model sapphire/glass/sapphire system fabricated by diffusion bonding etched and unetched pieces of sapphire onto which 30--50 nm of SiO{sub 2} had been sputter deposited. These systems span a broad range of glass contents, and permit observation of healing behavior with varying glass content. The results were compared with analytical models and results of similar studies in completely crystalline systems.

  6. Healing of lithographically introduced flaws in glass and glass containing ceramics

    SciTech Connect

    Ackler, H.D.

    1992-12-01

    The morphological evolution of cylindrical pores or channels'' and crack-like cavities in glass and glass-containing ceramics at elevated temperatures was studied. The systems studied were: Coming 7056 alkali borosilicate glass, soda-lime glass (microscope slides), a commercially available 96% Al[sub 2]O[sub 3]with [approx]5--10% intergranular glass, 96% Al[sub 2]O[sub 3] bonded to sapphire, and a model sapphire/glass/sapphire system fabricated by diffusion bonding etched and unetched pieces of sapphire onto which 30--50 nm of SiO[sub 2] had been sputter deposited. These systems span a broad range of glass contents, and permit observation of healing behavior with varying glass content. The results were compared with analytical models and results of similar studies in completely crystalline systems.

  7. Direct vitrification of plutonium-containing materials (PCM`s) with the glass material oxidation and dissolution system (GMODS)

    SciTech Connect

    Forsberg, C.W. Beahm, E.C.; Parker, G.W.; Rudolph, J.C.; Haas, P.A.; Malling, G.F.; Elam, K.; Ott, L.

    1995-10-30

    The end of the cold war has resulted in excess PCMs from nuclear weapons and associated production facilities. Consequently, the US government has undertaken studies to determine how best to manage and dispose of this excess material. The issues include (a) ensurance of domestic health, environment, and safety in handling, storage, and disposition, (b) international arms control agreements with Russia and other countries, and (c) economics. One major set of options is to convert the PCMs into glass for storage or disposal. The chemically inert characteristics of glasses make them a desirable chemical form for storage or disposal of radioactive materials. A glass may contain only plutonium, or it may contain plutonium along with other radioactive materials and nonradioactive materials. GMODS is a new process for the direct conversion of PCMs (i.e., plutonium metal, scrap, and residues) to glass. The plutonium content of these materials varies from a fraction of a percent to pure plutonium. GMODS has the capability to also convert other metals, ceramics, and amorphous solids to glass, destroy organics, and convert chloride-containing materials into a low-chloride glass and a secondary clean chloride salt strewn. This report is the initial study of GMODS for vitrification of PCMs as input to ongoing studies of plutonium management options. Several tasks were completed: initial analysis of process thermodynamics, initial flowsheet analysis, identification of equipment options, proof-of-principle experiments, and identification of uncertainties.

  8. A Radically New Method for Hydrogen Storage in Hollow Glass Microspheres

    SciTech Connect

    James E. Shelby; Matthew M. Hall; Fabienne C. Raszewski

    2007-08-31

    Photo-induced hydrogen diffusion has been applied to the problem of storage of high pressure hydrogen in hollow glass microspheres. Results of this study indicate that this phenomenon can be used to provide a high mass efficiency, safe, cheap, non-toxic method for storage of high pressure hydrogen. The photo-induced response is immediate upon exposure to infrared light for hollow glass microspheres doped with iron, nickel, or cobalt oxide, which is consistent with previous results for transition metal oxide-doped bulk glass samples. This effect is not observed for HGMS which do not contain these transition metal oxide, where the slight release of hydrogen observed occurs only by heating from absorption of the light. The initial rate of hydrogen release increases with increasing concentration of the metal oxide and with increasing hydrogen fill pressure within the microspheres. To date, hydrogen storage efficiencies of 2.2 wt% have been obtained, but results suggest that storage values can be increased to at least 6 wt%. Hydrogen losses over a 5 week period are minimal at room temperature in all compositions, with somewhat greater, but acceptable, losses at 50 C. Hollow glass microspheres have been produced from an alkali alkaline earth borosilicate glass containing either 1 or 5 wt% of the oxides of iron, nickel, and cobalt. Photo-driven gas diffusion has been demonstrated for these HGMS. Demonstration of photo-induced diffusion in these samples provides the first proof-of-concept for eventual applications of HGMS for large scale hydrogen storage.

  9. Process for direct conversion of reactive metals to glass

    DOEpatents

    Rajan, John B.; Kumar, Romesh; Vissers, Donald R.

    1990-01-01

    Radioactive alkali metal is introduced into a cyclone reactor in droplet form by an aspirating gas. In the cyclone metal reactor the aspirated alkali metal is contacted with silica powder introduced in an air stream to form in one step a glass. The sides of the cyclone reactor are preheated to ensure that the initial glass formed coats the side of the reactor forming a protective coating against the reactants which are maintained in excess of 1000.degree. C. to ensure the formation of glass in a single step.

  10. Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

    SciTech Connect

    Joshi, Ashok V.; Balagopal, Shekar; Pendelton, Justin

    2011-12-13

    Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

  11. Alkali and transition metal phospholides

    NASA Astrophysics Data System (ADS)

    Bezkishko, I. A.; Zagidullin, A. A.; Milyukov, V. A.; Sinyashin, O. G.

    2014-06-01

    Major tendencies in modern chemistry of alkali and transition metal phospholides (phosphacyclopentadienides) are systematized, analyzed and generalized. Basic methods of synthesis of these compounds are presented. Their chemical properties are considered with a special focus on their complexing ability. Potential applications of phospholides and their derivatives are discussed. The bibliography includes 184 references.

  12. Cooling rate and size effects on the medium-range structure of multicomponent oxide glasses simulated by molecular dynamics

    NASA Astrophysics Data System (ADS)

    Tilocca, Antonio

    2013-09-01

    A set of molecular dynamics simulations were performed to investigate the effect of cooling rate and system size on the medium-range structure of melt-derived multicomponent silicate glasses, represented by the quaternary 45S5 Bioglass composition. Given the significant impact of the glass degradation on applications of these materials in biomedicine and nuclear waste disposal, bulk structural features which directly affect the glass dissolution process are of particular interest. Connectivity of the silicate matrix, ion clustering and nanosegregation, distribution of ring and chain structural patterns represent critical features in this context, which can be directly extracted from the models. A key issue is represented by the effect of the computational approach on the corresponding glass models, especially in light of recent indications questioning the suitability of conventional MD approaches (that is, involving melt-and-quench of systems containing ˜103 atoms at cooling rates of 5-10 K/ps) when applied to model these glasses. The analysis presented here compares MD models obtained with conventional and nonconventional cooling rates and system sizes, highlighting the trend and range of convergence of specific structural features in the medium range. The present results show that time-consuming computational approaches involving much lower cooling rates and/or significantly larger system sizes are in most cases not necessary in order to obtain a reliable description of the medium-range structure of multicomponent glasses. We identify the convergence range for specific properties and use them to discuss models of several glass compositions for which a possible influence of cooling-rate or size effects had been previously hypothesized. The trends highlighted here represent an important reference to obtain reliable models of multicomponent glasses and extract converged medium-range structural features which affect the glass degradation and thus their application

  13. Cooling rate and size effects on the medium-range structure of multicomponent oxide glasses simulated by molecular dynamics

    SciTech Connect

    Tilocca, Antonio

    2013-09-21

    A set of molecular dynamics simulations were performed to investigate the effect of cooling rate and system size on the medium-range structure of melt-derived multicomponent silicate glasses, represented by the quaternary 45S5 Bioglass composition. Given the significant impact of the glass degradation on applications of these materials in biomedicine and nuclear waste disposal, bulk structural features which directly affect the glass dissolution process are of particular interest. Connectivity of the silicate matrix, ion clustering and nanosegregation, distribution of ring and chain structural patterns represent critical features in this context, which can be directly extracted from the models. A key issue is represented by the effect of the computational approach on the corresponding glass models, especially in light of recent indications questioning the suitability of conventional MD approaches (that is, involving melt-and-quench of systems containing ∼10{sup 3} atoms at cooling rates of 5-10 K/ps) when applied to model these glasses. The analysis presented here compares MD models obtained with conventional and nonconventional cooling rates and system sizes, highlighting the trend and range of convergence of specific structural features in the medium range. The present results show that time-consuming computational approaches involving much lower cooling rates and/or significantly larger system sizes are in most cases not necessary in order to obtain a reliable description of the medium-range structure of multicomponent glasses. We identify the convergence range for specific properties and use them to discuss models of several glass compositions for which a possible influence of cooling-rate or size effects had been previously hypothesized. The trends highlighted here represent an important reference to obtain reliable models of multicomponent glasses and extract converged medium-range structural features which affect the glass degradation and thus their

  14. Cooling rate and size effects on the medium-range structure of multicomponent oxide glasses simulated by molecular dynamics.

    PubMed

    Tilocca, Antonio

    2013-09-21

    A set of molecular dynamics simulations were performed to investigate the effect of cooling rate and system size on the medium-range structure of melt-derived multicomponent silicate glasses, represented by the quaternary 45S5 Bioglass composition. Given the significant impact of the glass degradation on applications of these materials in biomedicine and nuclear waste disposal, bulk structural features which directly affect the glass dissolution process are of particular interest. Connectivity of the silicate matrix, ion clustering and nanosegregation, distribution of ring and chain structural patterns represent critical features in this context, which can be directly extracted from the models. A key issue is represented by the effect of the computational approach on the corresponding glass models, especially in light of recent indications questioning the suitability of conventional MD approaches (that is, involving melt-and-quench of systems containing ~10(3) atoms at cooling rates of 5-10 K/ps) when applied to model these glasses. The analysis presented here compares MD models obtained with conventional and nonconventional cooling rates and system sizes, highlighting the trend and range of convergence of specific structural features in the medium range. The present results show that time-consuming computational approaches involving much lower cooling rates and/or significantly larger system sizes are in most cases not necessary in order to obtain a reliable description of the medium-range structure of multicomponent glasses. We identify the convergence range for specific properties and use them to discuss models of several glass compositions for which a possible influence of cooling-rate or size effects had been previously hypothesized. The trends highlighted here represent an important reference to obtain reliable models of multicomponent glasses and extract converged medium-range structural features which affect the glass degradation and thus their application

  15. Fabrication and characterization of sub-100/10 nm planar nanofluidic channels by triple thermal oxidation and silicon-glass anodic bonding

    PubMed Central

    Ouyang, Wei; Wang, Wei

    2014-01-01

    We reported the fabrication and characterization of nanofluidic channels by Triple Thermal Oxidation and Silicon-Glass Anodic Bonding. Planar nanochannels with depths from sub-100 nm down to sub-10 nm were realized by this method. A theoretical model was developed to precisely predict the depth of nanochannels. The depth and uniformity of nanochannels showed good stability during anodic bonding. This method is promising for various nanofluidic studies, such as nanofluidic electrokinetics, biomolecule manipulation, and energy conversion. PMID:25538802

  16. Phosphate glass useful in high energy lasers

    DOEpatents

    Hayden, Yuiko T.; Guesto-Barnak, Donna

    1992-01-01

    A low-or no-silica, low- or no-alkali phosphate glass useful as a laser amplifier in a multiple pass, high energy laser system having a high thermal conductivity, K.sub.90.degree. C. >0.85 W/mK, a low coefficient of thermal expansion, .alpha..sub.20.degree.-300.degree. C. <80.times.10.sup.-7 /.degree.C., low emission cross section, .sigma.<2.5.times.10.sup.-20 cm.sup.2, and a high fluorescence lifetime, .tau.>325 .mu.secs at 3 wt. % Nd doping, consisting essentially of (on an oxide composition basis): wherein Ln.sub.2 O.sub.3 is the sum of lanthanide oxides; .SIGMA.R.sub.2 O is <5, R being Li, Na, K, Cs, and Rb; the sum of Al.sub.2 O.sub.3 and MgO is <24 unless .SIGMA.R.sub.2 O is 0, then the sum of Al.sub.2 O.sub.3 and MgO is <42; and the ratio of MgO to B.sub.2 O.sub.3 is 0.48-4.20.

  17. Agricultural wastes as a resource of raw materials for developing low-dielectric glass-ceramics

    NASA Astrophysics Data System (ADS)

    Danewalia, Satwinder Singh; Sharma, Gaurav; Thakur, Samita; Singh, K.

    2016-04-01

    Agricultural waste ashes are used as resource materials to synthesize new glass and glass-ceramics. The as-prepared materials are characterized using various techniques for their structural and dielectric properties to check their suitability in microelectronic applications. Sugarcane leaves ash exhibits higher content of alkali metal oxides than rice husk ash, which reduces the melting point of the components due to eutectic reactions. The addition of sugarcane leaves ash in rice husk ash promotes the glass formation. Additionally, it prevents the cristobalite phase formation. These materials are inherently porous, which is responsible for low dielectric permittivity i.e. 9 to 40. The presence of less ordered augite phase enhances the dielectric permittivity as compared to cristobalite and tridymite phases. The present glass-ceramics exhibit lower losses than similar materials synthesized using conventional minerals. The dielectric permittivity is independent to a wide range of temperature and frequency. The glass-ceramics developed with adequately devitrified phases can be used in microelectronic devices and other dielectric applications.

  18. Agricultural wastes as a resource of raw materials for developing low-dielectric glass-ceramics

    PubMed Central

    Danewalia, Satwinder Singh; Sharma, Gaurav; Thakur, Samita; Singh, K.

    2016-01-01

    Agricultural waste ashes are used as resource materials to synthesize new glass and glass-ceramics. The as-prepared materials are characterized using various techniques for their structural and dielectric properties to check their suitability in microelectronic applications. Sugarcane leaves ash exhibits higher content of alkali metal oxides than rice husk ash, which reduces the melting point of the components due to eutectic reactions. The addition of sugarcane leaves ash in rice husk ash promotes the glass formation. Additionally, it prevents the cristobalite phase formation. These materials are inherently porous, which is responsible for low dielectric permittivity i.e. 9 to 40. The presence of less ordered augite phase enhances the dielectric permittivity as compared to cristobalite and tridymite phases. The present glass-ceramics exhibit lower losses than similar materials synthesized using conventional minerals. The dielectric permittivity is independent to a wide range of temperature and frequency. The glass-ceramics developed with adequately devitrified phases can be used in microelectronic devices and other dielectric applications. PMID:27087123

  19. Thermotriggered Catalyst-Free Modification of a Glass Surface with an Orthogonal Agent Possessing Nitrile N-Oxide and Masked Ketene Functions.

    PubMed

    Cheawchan, Sumitra; Uchida, Satoshi; Sogawa, Hiromitsu; Koyama, Yasuhito; Takata, Toshikazu

    2016-01-12

    The thermotriggered modification of surfaces was performed under catalyst-free conditions using an orthogonal agent possessing both nitrile N-oxide and Meldrum's acid moieties. The nitrile N-oxide moiety of the orthogonal agent successfully underwent catalyst-free 1,3-dipolar cycloaddition to unsaturated bonds of glass surfaces to produce Meldrum's acid-functionalized surfaces. The subsequent thermal decomposition of Meldrum's acid moiety in the presence of nucleophiles afforded versatile nucleophile-modified surfaces (e.g., wet, waterproof, and photoactive surfaces). Surface characteristics were investigated with the water contact angle, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and X-ray photoelectron spectroscopy (XPS). In addition, the surface modification of silica nanoparticles using the orthogonal agent was also achieved to evaluate the density of the functional group concentration on the surface.

  20. Thermotriggered Catalyst-Free Modification of a Glass Surface with an Orthogonal Agent Possessing Nitrile N-Oxide and Masked Ketene Functions.

    PubMed

    Cheawchan, Sumitra; Uchida, Satoshi; Sogawa, Hiromitsu; Koyama, Yasuhito; Takata, Toshikazu

    2016-01-12

    The thermotriggered modification of surfaces was performed under catalyst-free conditions using an orthogonal agent possessing both nitrile N-oxide and Meldrum's acid moieties. The nitrile N-oxide moiety of the orthogonal agent successfully underwent catalyst-free 1,3-dipolar cycloaddition to unsaturated bonds of glass surfaces to produce Meldrum's acid-functionalized surfaces. The subsequent thermal decomposition of Meldrum's acid moiety in the presence of nucleophiles afforded versatile nucleophile-modified surfaces (e.g., wet, waterproof, and photoactive surfaces). Surface characteristics were investigated with the water contact angle, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and X-ray photoelectron spectroscopy (XPS). In addition, the surface modification of silica nanoparticles using the orthogonal agent was also achieved to evaluate the density of the functional group concentration on the surface. PMID:26652940

  1. Nano crystalline Bi2(VO5) phases in lithium bismuth borate glasses containing mixed vanadium-nickel oxides

    NASA Astrophysics Data System (ADS)

    Yadav, Arti; Khasa, S.; Dahiya, M. S.; Agarwal, A.

    2016-05-01

    Glass composition 7V2O5.23Li2O.20Bi2O3.50B2O3 and x(2NiO.V2O5).(30-x)Li2O.20Bi2O3.50B2O3, x=0, 2, 5, 7 and 10, were produced by conventional melt quenching technique. The quenched amorphous glass samples were annealed at temperatures 400°C and 500°C for 6 hours. The Bi2(VO5) crystallite were grown in all prepared glass matrix. Tn vanadium lithium bismuth borate glass (annealed), the some phrase of V2O5-crystal were observed along with the nano crystalline Bi2(VO5) phase. The sharp peaks in FTTR spectra of all annealed compositions were also compatible with the XRD diffraction peaks of the system under investigation. Average crystalline size (D) of the Bi2(VO5) nano-crystallite was ~30nm for samples annealed at 400°C and ~42nm for samples annealed at 500°C. Lattice parameter and the lattice strain for all the samples was also calculated corresponding to the (113) plane of Bi2(VO5) crystallite.

  2. Alkali metal/sulfur battery

    DOEpatents

    Anand, Joginder N.

    1978-01-01

    Alkali metal/sulfur batteries in which the electrolyte-separator is a relatively fragile membrane are improved by providing means for separating the molten sulfur/sulfide catholyte from contact with the membrane prior to cooling the cell to temperatures at which the catholyte will solidify. If the catholyte is permitted to solidify while in contact with the membrane, the latter may be damaged. The improvement permits such batteries to be prefilled with catholyte and shipped, at ordinary temperatures.

  3. In vivo evaluation of plasma-sprayed titanium coating after alkali modification.

    PubMed

    Xue, Weichang; Liu, Xuanyong; Zheng, XueBin; Ding, Chuanxian

    2005-06-01

    In this paper, plasma-sprayed titanium coatings were modified by alkali treatment. The changes in chemical composition and structure of coatings were examined by SEM and AES. The results obtained indicated that a net-like microscopic texture feature, which was full of the interconnected fine porosity, appeared on the surface of alkali-modified titanium coatings. The surface chemical composition was also altered by alkali modification. A sodium titanate compound was formed on the surface of the titanium coating and replaced the native passivating oxide layer. Its thickness was measured as about 150 nm which was about 10 times of that of the as-sprayed coating. The bone bonding ability of titanium coatings were investigated using a canine model. The histological examination and SEM observation demonstrated that more new bone was formed on the surface of alkali-modified implants and grew more rapidly into the porosity. The alkali-modified implants were found to appose directly to the surrounding bone. In contrast, a gap was observed at the interface between the as-sprayed implants and bone. The push-out test showed that alkali-modified implants had a higher shear strength than as-sprayed implants after 1 month of implantation. An interfacial layer, containing Ti, Ca and P, was found to form at the interface between bone and the alkali-modified implant by EDS analysis.

  4. Kinetics of Coloration in Photochromic Tungsten(VI) Oxide/Silicon Oxycarbide/Silica Hybrid Xerogel: Insight into Cation Self-diffusion Mechanisms.

    PubMed

    Adachi, Kenta; Tokushige, Masataka; Omata, Kaoru; Yamazaki, Suzuko; Iwadate, Yoshiaki

    2016-06-01

    Silicon oxycarbide/silica composites with well-dispersed tungsten(VI) oxide (WO3) nanoparticles were obtained as transparent hybrid xerogels via an acid-catalyzed sol-gel process (hydrolysis/condensation polymerization) of 3-(triethoxysilyl)propyl methacrylate (TESPMA) and tetraethoxysilane (TEOS). The self-diffusion mechanism of alkali-metal cations and the kinetics of the photochromic coloration process in the WO3/TESPMA/TEOS hybrid xerogel systems have been systematically investigated. Under continuous UV illumination, a gradual color change (colorless → blue) corresponding to the reduction of W(6+) into W(5+) states in WO3 nanoparticles can be confirmed from the WO3/TESPMA/TEOS hybrid xerogels containing alkali-metal sulfates, although no coloration of the hybrid xerogel without alkali-metal sulfate was observed. The coloration behavior depended exclusively on a variety of alkali-metal cations present in the hybrid xerogel system. Furthermore, a detailed analysis of the self-diffusion mechanism confirmed that the alkali-metal cations electrostatically interact with a layer of unreacted silanol groups on the TESPMA/TEOS matrix surface, and subsequently pass through the interconnected pore network of the hybrid xerogel. More interestingly, in the context of an Arrhenius analysis, we found a good coincidence between the activation energies for alkali-metal cation self-diffusion and UV-induced coloration in the WO3/TESPMA/TEOS hybrid xerogel system containing the corresponding alkali-metal sulfate. It is experimentally obvious that the photochromic properties are dominated by the diffusion process of alkali-metal cations in the WO3/TESPMA/TEOS hybrid xerogel system. Such hybrid materials with cation-controlled photochromic properties will show promising prospects in applications demanding energy-efficient "smart windows" and "smart glasses". PMID:27159661

  5. High modulus high temperature glass fibers

    NASA Technical Reports Server (NTRS)

    Bacon, J. F.

    1973-01-01

    The search for a new high-modulus, high-temperature glass fiber involved the preparation of 500 glass compositions lying in 12 glass fields. These systems consisted primarily of low atomic number oxides and rare-earth oxides. Direct optical measurements of the kinetics of crystallization of the cordierite-rare earth system, for example, showed that the addition of rare-earth oxides decreased the rate of formation of cordierite crystals. Glass samples prepared from these systems proved that the rare-earth oxides made large specific contributions to the Young's modulus of the glasses. The best glasses have moduli greater than 21 million psi, the best glass fibers have moduli greater than 18 million psi, and the best glass fiber-epoxy resin composites have tensile strengths of 298,000 psi, compressive strengths of at least 220,000 psi, flexural strengths of 290,000 psi, and short-beam shear strengths of almost 17,000 psi.

  6. Glass sealing

    SciTech Connect

    Brow, R.K.; Kovacic, L.; Chambers, R.S.

    1996-04-01

    Hernetic glass sealing technologies developed for weapons component applications can be utilized for the design and manufacture of fuel cells. Design and processing of of a seal are optimized through an integrated approach based on glass composition research, finite element analysis, and sealing process definition. Glass sealing procedures are selected to accommodate the limits imposed by glass composition and predicted calculations.

  7. Glass transition temperature and conductivity in Li2O and Na2O doped borophosphate glasses

    NASA Astrophysics Data System (ADS)

    Ashwajeet, J. S.; Sankarappa, T.; Ramanna, R.; Sujatha, T.; Awasthi, A. M.

    2015-08-01

    Two alkali doped Borophosphate glasses in the composition, (B2O3)0.2. (P2O5)0.3. (Na2O)(0.5-x). (Li2O)x, where x = 0.05 to 0.50 were prepared by standard melt quenching method at 1200K. Non-crystalline nature was confirmed by XRD studies. Room temperature density was measured by Archimedes principle. DC conductivity in the temperature range from 300K to 575K has been measured. Samples were DSC studied in the temperature range from 423K to 673K and glass transition temperature was determined. Glass transition temperature passed through minima for Li2O con.2centration between 0.25 and 0.30 mole fractions. Activation energy of conduction has been determined by analyzing temperature variation of conductivity determining Arrhenius law. Conductivity passed through minimum and activation passed through maximum for Li2O content from 0.25 to 0.30 mole fractions. Glass transition temperature passed through minimum for the same range of Li2O content. These results revealed mixed alkali effect taking place in these glasses. It is for the first time borophosphate glasses doped with Li2O and Na2O have been studied for density and dc conductivity and, the mixed alkali effect (MAE) has been observed.

  8. Durabiliy of two simulated nuclear waste glasses, a frit glass, and tektite in aqueous solutions: Final report, Volume I

    SciTech Connect

    Hagen, D.A.; Altstetter, C.J.; Brown, S.D.

    1988-05-01

    High level nuclear waste is commonly incorporated into glass for disposal. Therefore the long term aqueous durability of the waste glass is important. The leaching behavior of three simulated nuclear waste glasses (AH10, AH165, and Frit 165) and a natural glass (tektite) were examined using nuclear reaction analysis, leachate solution analysis, and microscopy. The three simulated waste glasses developed hydrated layers which increased in thickness by t/sup /1/2//. The hydrated layer in Frit 165 reached a constant thickness of about one micron. Alkali were preferentially removed from the Frit 165 and AH10. The tektite corroded by slow uniform dissolution. 94 refs., 68 figs., 13 tabs.

  9. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 7, March 1, 1993--June 1, 1993

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1993-05-25

    Corrosion kinetics of SiC were investigated from 950 to 1100C at 0.63 vol% alkali vapor concentration. Corrosion rate in alkali is 10{sup 4} to 10{sup 5} times faster than oxidation rate of SiC in air. Activation energy of the alkali corrosion is 406 kj/mol, indicating a high sensitivity to temperature changes. Overall reaction appears to be controlled by the oxidation of SiC. The alkali corrosion kinetics of Si{sub 3}N{sub 4} from 950 to 1050{degrees}C were also examined in the same atmosphere (0.63 vol% alkali vapors). Reaction thickness of Si{sub 3}N{sub 4} appears to vary linearly with reaction time from 950 to 1050C, suggesting that the alkali corrosion process is controlled by the oxidation of Si{sub 3}N{sub 4}. At 1050{degrees}C, the alkali-enhanced oxidation of Si{sub 3}N{sub 4} is approximately 10{sup 7} times faster than the oxidation of Si{sub 3}N{sub 4} in dry oxygen. Compared to SiC corroded in the same alkali atmosphere, Si{sub 3}N{sub 4} seems to be less alkali-resistant than SiC. Phase relations of the Na{sub 2}O-Al{sub 2}TiO{sub 5} vertical section from 5--40 wt% Na{sub 2}O and 840-1100C were studied. Phase analysis indicates that this section is not a true binary system. A tentative phase diagram for the Na{sub 2}O-Al{sub 2}O{sub 3}-TiO{sub 2} system was constructed.

  10. Thermoluminescence dosimetry properties and kinetic parameters of lithium potassium borate glass co-doped with titanium and magnesium oxides.

    PubMed

    Hashim, S; Alajerami, Y S M; Ramli, A T; Ghoshal, S K; Saleh, M A; Abdul Kadir, A B; Saripan, M I; Alzimami, K; Bradley, D A; Mhareb, M H A

    2014-09-01

    Lithium potassium borate (LKB) glasses co-doped with TiO2 and MgO were prepared using the melt quenching technique. The glasses were cut into transparent chips and exposed to gamma rays of (60)Co to study their thermoluminescence (TL) properties. The TL glow curve of the Ti-doped material featured a single prominent peak at 230 °C. Additional incorporation of MgO as a co-activator enhanced the TL intensity threefold. LKB:Ti,Mg is a low-Z material (Z(eff)=8.89) with slow signal fading. Its radiation sensitivity is 12 times lower that the sensitivity of TLD-100. The dose response is linear at doses up to 10(3) Gy. The trap parameters, such as the kinetics order, activation energy, and frequency factor, which are related to the glow peak, were determined using TolAnal software.

  11. Bose-glass melting in the cubic (K,Ba)BiO3 high-Tc oxide with columnar defects

    NASA Astrophysics Data System (ADS)

    Klein, T.; Conde-Gallardo, A.; Joumard, I.; Marcus, J.; van der Beek, C. J.; Konczykowski, M.

    2000-02-01

    The Bose-glass transition in the fully isotropic (K,Ba)BiO3 superconductor with columnar defects produced by irradiation with 7.2 GeV Ta ions was studied by transport and nonlinear susceptibility measurements. For fields smaller than the dose equivalent field Bφ, the Bose-glass transition line HBG(T) shifts progressively upwards with increasing dose, dHBG/dT~1+αB1/2φ. The critical exponents have been deduced from the scaling properties of the transport measurements; we obtain z=5.3+/-0.3 and ν=1.1+/-0.2. For tilted magnetic fields, the transition temperature scales as TBG(0)-TBG(θ)~\\|sin(θ)\\|1/ν, as recently suggested by Lidmar and Wallin.

  12. The BRAG and GM2003 Models for Glass Dissolution

    SciTech Connect

    Aertsens, Marc

    2007-07-01

    The GM2003 model extends the r(t) glass dissolution model with water diffusion through the diffusion layer. Boron and alkali diffusion through the diffusion layer is described by introducing a retention factor K{sub d,i} between boron/alkali and water in the diffusion layer. Introducing a boron/alkali diffusion coefficient, the BRAG model describes boron/alkali diffusion in the diffusion layer as well. It is shown that both models are consistent with each other and an expression is derived for the boron/alkali diffusion coefficient (BRAG) as a function of both parameters of GM2003: the retention factor K{sub d,i} and the water diffusion coefficient D{sub H{sub 2}}{sub O} in the diffusion layer. From dissolution data only, it is possible to fit the value for the boron/alkali diffusion coefficient in the diffusion layer but due to correlations the individual values of both parameters K{sub d,i} and DH{sub 2}O of GM2003 cannot be determined. From theoretical considerations follows that the K{sub d,i} value for boron/alkali should be slightly larger than 0.1 kg/liter. A user friendly code for the BRAG model allows automatic fits of glass dissolution data in water. (authors)

  13. Chemiluminescence from excited c 2- -alkali cation complexes formed in alkali atom-halocarbon flames

    NASA Astrophysics Data System (ADS)

    Lin, K. K.; Balling, L. C.; Wright, J. J.

    1987-01-01

    Vapor phase reactions between alkali atoms and several halocarbon molecules containing C-C bonds have been observed to produce chemiluminescence which appears to originate from C 2-- (alkali) + complexes.

  14. Glass Membrane For Controlled Diffusion Of Gases

    DOEpatents

    Shelby, James E.; Kenyon, Brian E.

    2001-05-15

    A glass structure for controlled permeability of gases includes a glass vessel. The glass vessel has walls and a hollow center for receiving a gas. The glass vessel contains a metal oxide dopant formed with at least one metal selected from the group consisting of transition metals and rare earth metals for controlling diffusion of the gas through the walls of the glass vessel. The vessel releases the gas through its walls upon exposure to a radiation source.

  15. Modeling of cluster organization in metal-doped oxide glasses irradiated by a train of femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Smetanina, Evgeniya; Chimier, Benoit; Petit, Yannick; Varkentina, Nadezda; Fargin, Evelyne; Hirsch, Lionel; Cardinal, Thierry; Canioni, Lionel; Duchateau, Guillaume

    2016-01-01

    The formation of silver cluster structures at submicrometer spatial scales under the irradiation by high-power femtosecond laser pulses with high repetition rate was observed in various glasses containing silver ions. In order to account for the formation of these structures in metal-doped glasses, we present a theoretical model for the organization of noble metallic clusters induced by a train of femtosecond laser pulses. The model includes photoionization and laser heating of the sample, diffusion, kinetic reactions, and dissociation of metallic species. This model was applied to reproduce the formation of cluster structures in silver-doped phosphate glass. The parameters of the silver structures were obtained numerically under various incident pulse intensities and number of pulses. Numerical modeling shows that the involved microscopic physical and chemical processes naturally lead to the emergence of a silver cluster organization, together with charge migration and subsequent trapping giving rise to a strong static electric field buried in the irradiated area as experimentally observed. Based on this modeling, a theoretical basis is provided for the design of new metallic cluster structures with nanoscale size.

  16. Attack of high-strength, oxidation-resistant alloys during in-can melting of simulated waste glasses

    SciTech Connect

    Rankin, W.N.

    1980-01-01

    The restistance of candidate canister alloys to penetration under the most severe conditions expected during in-can melting was directly proportional to the chromium content of the alloy, and inversely proportional to the Na/sub 2/O content of the glass melt. Specimens were exposed for 24 hours, which is the time required for in-can melting full-size waste-glass forms based on tests carried out at Pacific Northwest Laboratories (PNL) and at SRL. The penetration resistance to Frit 211 at 1150/sup 0/C for 24 hours of most alloys tested was satisfactory. The amount of penetration would not affect the integrity of the waste form. Inconel 625, Hastelloy X, and Inconel 601 were penetrated < 20 mils. This was considered excellent. Incoloy 801, Type 310 stainless steel, Type 304L stainless steel, Inconel 600, and Type 347 stainless steel were penetrated < 40 mils. This was considered good. Hastelloy C-4 was penetrated > 100 mils by a glass composed of 65 wt % Frit 21 and 35 wt % composite sludge (with uranium) at 1150/sup 0/C for only 7 hours. This amount of penetration of an in-can melting canister would not be satisfactory. 12 figures.

  17. Space processing of chalcogenide glasses

    NASA Technical Reports Server (NTRS)

    Larsen, D. C.; Ali, M. A.

    1975-01-01

    Chalcogenide glasses are discussed as good infrared transmitters, possessing the strength, corrosion resistance, and scale-up potential necessary for large 10.6-micron windows. The disadvantage of earth-produced chalcogenide glasses is shown to be an infrared absorption coefficient which is unacceptably high relative to alkali halides. This coefficient is traced to optical nonhomogeneities resulting from environmental and container contamination. Space processing is considered as a means of improving the infrared transmission quality of chalcogenides and of eliminating the following problems: optical inhomogeneities caused by thermal currents and density fluctuation in the l-g earth environment; contamination from the earth-melting crucible by oxygen and other elements deleterious to infrared transmission; and, heterogeneous nucleation at the earth-melting crucible-glass interface.

  18. Glass Ceramic Formulation Data Package

    SciTech Connect

    Crum, Jarrod V.; Rodriguez, Carmen P.; McCloy, John S.; Vienna, John D.; Chung, Chul-Woo

    2012-06-17

    A glass ceramic waste form is being developed for treatment of secondary waste streams generated by aqueous reprocessing of commercial used nuclear fuel (Crum et al. 2012b). The waste stream contains a mixture of transition metals, alkali, alkaline earths, and lanthanides, several of which exceed the solubility limits of a single phase borosilicate glass (Crum et al. 2009; Caurant et al. 2007). A multi-phase glass ceramic waste form allows incorporation of insoluble components of the waste by designed crystallization into durable heat tolerant phases. The glass ceramic formulation and processing targets the formation of the following three stable crystalline phases: (1) powellite (XMoO4) where X can be (Ca, Sr, Ba, and/or Ln), (2) oxyapatite Yx,Z(10-x)Si6O26 where Y is alkaline earth, Z is Ln, and (3) lanthanide borosilicate (Ln5BSi2O13). These three phases incorporate the waste components that are above the solubility limit of a single-phase borosilicate glass. The glass ceramic is designed to be a single phase melt, just like a borosilicate glass, and then crystallize upon slow cooling to form the targeted phases. The slow cooling schedule is based on the centerline cooling profile of a 2 foot diameter canister such as the Hanford High-Level Waste canister. Up to this point, crucible testing has been used for glass ceramic development, with cold crucible induction melter (CCIM) targeted as the ultimate processing technology for the waste form. Idaho National Laboratory (INL) will conduct a scaled CCIM test in FY2012 with a glass ceramic to demonstrate the processing behavior. This Data Package documents the laboratory studies of the glass ceramic composition to support the CCIM test. Pacific Northwest National Laboratory (PNNL) measured melt viscosity, electrical conductivity, and crystallization behavior upon cooling to identify a processing window (temperature range) for melter operation and cooling profiles necessary to crystallize the targeted phases in the

  19. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, Sheldon H. D.

    1992-01-01

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases.

  20. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, S.H.D.

    1992-12-22

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases. 6 figs.

  1. Volcanic glasses, their origins and alteration processes

    USGS Publications Warehouse

    Friedman, I.; Long, W.

    1984-01-01

    Natural glass can be formed by volcanic processes, lightning (fulgarites) burning coal, and by meteorite impact. By far the most common process is volcanic - basically the glass is rapidly chilled molten rock. All natural glasses are thermodynamically unstable and tend to alter chemically or to crystallize. The rate of these processes is determined by the chemical composition of the magma. The hot and fluid basaltic melts have a structure that allows for rapid crystal growth, and seldom forms glass selvages greater than a few centimeters thick, even when the melt is rapidly cooled by extrusion in the deep sea. In contrast the cooler and very viscous rhyolitic magmas can yield bodies of glass that are tens of meters thick. These highly polymerized magmas have a high silica content - often 71-77% SiO2. Their high viscosity inhibits diffusive crystal growth. Basalt glass in sea water forms an alteration zone called palagonite whose thickness increases linearly with time. The rate of diffusion of water into rhyolitic glass, which follows the relationship - thickness = k (time) 1 2, has been determined as a function of the glass composition and temperature. Increased SiO2 increases the rate, whereas increased CaO, MgO and H2O decrease the rate. The activation energy of water diffusion varies from about 19 to 22 kcal/mol. for the glasses studied. The diffusion of alkali out of rhyolite glass occurs simultaneously with water diffusion into the glass. The rate of devitrification of rhyolitic glass is a function of the glass viscosity, which in turn is a function of water content and temperature. Although all of the aforementioned processes tend to destroy natural glasses, the slow rates of these processes, particularly for rhyolitic glass, has allowed samples of glass to persist for 60 million years. ?? 1984.

  2. Borosilicate glass alteration driven by magnesium carbonates

    NASA Astrophysics Data System (ADS)

    Debure, M.; Frugier, P.; De Windt, L.; Gin, S.

    2012-01-01

    The alteration of simplified synthetic glass, representative of the French reference nuclear glass R7T7, in presence of hydromagnesite has been experimentally investigated and modeled. Magnesium in solution is known to potentially enhance glass alteration; nuclear glass clayed host rocks contain magnesium and can dissolve to maintain the concentration of magnesium in solution. For modeling purposes, it was suitable to study a simple system. Hydromagnesite was therefore chosen as a simple model mineral in order to check the influence of an Mg-rich mineral on glass alteration. Since the models use thermodynamic and kinetic parameters measured in pure water and pH-buffered solutions, changing the solution composition or adding minerals is a key step towards the validation of the modeling assumptions before using the model for predictive purposes. Experiments revealed that glass alteration is enhanced in presence of hydromagnesite. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC reactive transport code. Modeling proved useful both for explaining the mechanisms involved and quantifying the impact on glass alteration: Mg coming from hydromagnesite dissolution reacts with Si provided by the glass in order to form magnesium silicates. This reaction decreases the pH down to neutral conditions where magnesium silicates are more soluble than at the natural alkali pH imposed by glass or hydromagnesite dissolution. The driving force of the magnesium silicate precipitation is eventually the interdiffusion of alkali within the altered amorphous glass layer as this mechanism consumes protons. The model's ability to describe the concentrations of elements in solution and formed solids whatever the glass/hydromagnesite ratio strongly supports the basic modeling hypothesis.

  3. Alkali-Metal Spin Maser.

    PubMed

    Chalupczak, W; Josephs-Franks, P

    2015-07-17

    Quantum measurement is a combination of a read-out and a perturbation of the quantum system. We explore the nonlinear spin dynamics generated by a linearly polarized probe beam in a continuous measurement of the collective spin state in a thermal alkali-metal atomic sample. We demonstrate that the probe-beam-driven perturbation leads, in the presence of indirect pumping, to complete polarization of the sample and macroscopic coherent spin oscillations. As a consequence of the former we report observation of spectral profiles free from collisional broadening. Nonlinear dynamics is studied through exploring its effect on radio frequency as well as spin noise spectra. PMID:26230788

  4. Alkali-Metal Spin Maser

    NASA Astrophysics Data System (ADS)

    Chalupczak, W.; Josephs-Franks, P.

    2015-07-01

    Quantum measurement is a combination of a read-out and a perturbation of the quantum system. We explore the nonlinear spin dynamics generated by a linearly polarized probe beam in a continuous measurement of the collective spin state in a thermal alkali-metal atomic sample. We demonstrate that the probe-beam-driven perturbation leads, in the presence of indirect pumping, to complete polarization of the sample and macroscopic coherent spin oscillations. As a consequence of the former we report observation of spectral profiles free from collisional broadening. Nonlinear dynamics is studied through exploring its effect on radio frequency as well as spin noise spectra.

  5. Alternating copolymerization of propylene oxide with biorenewable terpene-based cyclic anhydrides: a sustainable route to aliphatic polyesters with high glass transition temperatures.

    PubMed

    Van Zee, Nathan J; Coates, Geoffrey W

    2015-02-23

    The alternating copolymerization of propylene oxide with terpene-based cyclic anhydrides catalyzed by chromium, cobalt, and aluminum salen complexes is reported. The use of the Diels-Alder adduct of α-terpinene and maleic anhydride as the cyclic anhydride comonomer results in amorphous polyesters that exhibit glass transition temperatures (Tg ) of up to 109 °C. The polymerization conditions and choice of catalyst have a dramatic impact on the molecular weight distribution, the relative stereochemistry of the diester units along the polymer chain, and ultimately the Tg of the resulting polymer. The aluminum salen complex exhibits exceptional selectivity for copolymerization without transesterification or epimerization side reactions. The resulting polyesters are highly alternating and have high molecular weights and narrow polydispersities.

  6. An Evaluation of Fracture Strength of Zirconium Oxide Posts Fabricated Using CAD-CAM Technology Compared with Prefabricated Glass Fibre Posts.

    PubMed

    Dayalan, Malathi; Jairaj, Abhishek; Nagaraj, K R; Savadi, Ravindra C

    2010-12-01

    Post and core therapy is regarded as the treatment of choice for restoring severely damaged endodontically treated teeth. Critical control of endodontic materials in the coronal third of the canal and pulp chamber is essential in order to maintain its colour and translucency. In addition to this, the duplication of the optical characteristics of an intact tooth, including shade translucency and fluorescence is often made difficult by the use of metal infrastructures. As a result of this tooth colored posts have gained popularity especially in aesthetic areas. Besides aesthetics, the post is also responsible for transmitting the occlusal forces to the remaining tooth structure making the mechanical properties of the post critical. However, there is no clear consensus regarding an ideal system as far as strength of the post is concerned. Hence this study aims to analyses and compares the fracture strength of traditional prefabricated glass fibre posts with zirconium oxide posts constructed using CAD CAM technology. PMID:22131666

  7. Spin-glass behavior and pyroelectric anomalies in a new lithium-based oxide, Li3FeRuO5.

    PubMed

    Upadhyay, Sanjay Kumar; Paulose, P L; Iyer, Kartik K; Sampathkumaran, E V

    2016-08-17

    The results of dc and ac magnetization, heat capacity, (57)Fe Mössbauer spectroscopy, dielectric, pyroelectric current and isothermal magneto-capacitance measurements of a recently reported lithium-rich layered oxide, Li3FeRuO5, related to LiCoO2-type (rhombohedral, space group R3[combining macron]m), are presented. The results reveal that the compound undergoes spin-glass freezing at 15 K. There is a peak around 34 K in pyroelectric data, which cannot be attributed to ferroelectricity, but to the phenomenon of thermally stimulated depolarization current. As revealed by magnetocapacitance data above and below the magnetic ordering temperature, magnetic and electric dipoles appear to be coupled, thereby offering evidence for magnetodielectric coupling. PMID:27498689

  8. Study on effect of poly (ethylene oxide) addition and in-situ porosity generation on poly (vinylidene fluoride)-glass ceramic composite membranes for lithium polymer batteries

    NASA Astrophysics Data System (ADS)

    Shubha, Nageswaran; Prasanth, Raghavan; Hng, Huey Hoon; Srinivasan, Madhavi

    2014-12-01

    The effect of blending polyethylene oxide with poly (vinylidene fluoride)-lithium aluminum germanium phosphate (LAGP) composite and in-situ porosity generation on the electrochemical performance of polymer electrolytes based on non-woven fibrous mats is studied. Electrospinning process parameters are controlled to get a fibrous membrane consisting of bead-free, multilayered, three dimensional network structure of ultrafine fibers. The electrospun membranes are subjected to a preferential polymer dissolution process to prepare a highly porous structure. The membranes show high surface roughness with uniformly sized and distributed pores on the fibers. The membranes with good mechanical strength, thermal stability and high porosity exhibit high swelling when activated with liquid electrolyte. The prepared composite polymer electrolytes show high ionic conductivity. The addition of the glass ceramic improves the mechanical and thermal stability, while blending and in-situ porosity generation improves the ionic conductivity, charge-discharge performance, cycling stability, interface properties and compatibility with lithium electrode.

  9. Combined use of lightweight magnetic Fe3O4-coated hollow glass spheres and electrically conductive reduced graphene oxide in an epoxy matrix for microwave absorption

    NASA Astrophysics Data System (ADS)

    Wang, Junpeng; Wang, Jun; Zhang, Bin; Sun, Yu; Chen, Wei; Wang, Tao

    2016-03-01

    Epoxy resin based lightweight composites comprising Fe3O4-coated hollow glass spheres (HGS@Fe3O4) and reduced graphene oxide (RGO) were prepared. Impedance matching condition and electromagnetic wave attenuation characteristic are used for analysis of the reflection loss (RL) performance of the composites. Compared with pure HGS@Fe3O4 and RGO composite, the -10 dB absorption bandwidth and the minimum RL of the hybrid composites are enhanced. RL values less than -10 dB are obtained in a wide frequency range and the corresponding bandwidth can reach up to 3.6 GHz when an appropriate absorber thickness is chosen. The density of the hybrid composite is in the range of 0.57-0.72 g/cm3, which is attractive candidate for a new type of lightweight microwave absorber.

  10. Chemical bath deposition growth and characterization of zinc oxide nanostructures on plain and platinum-coated glass substrates for hydrogen peroxide gas sensor application

    NASA Astrophysics Data System (ADS)

    Jamasali, Y. D. J.; Alguno, A. C.

    2015-06-01

    Growth of zinc oxide on plain and Pt-coated glass substrate via chemical bath deposition technique (CBD) were studied. Aqueous solutions of ammonium hydroxide (NH4OH) and zinc sulfate (ZnSO4) were used as the precursor substances in the synthesis. Ultraviolet-visible spectroscopy (UV-Vis) was performed to determine the energy band gap and X-ray diffraction (XRD) to examine crystallinity. Sensitivity measurements were carried out in order to examine its potential to be fabricated as hydrogen peroxide (H2O2) gas sensor. Experimental results in the sensitivity experiment show that in the presence of H2O2 gas, the resistance of ZnOincrease which can be used as the basis for H2O-2 detection. UV-Vis showed variation of energy band gap values but were all near the generally accepted value. XRD spectra further verify that ZnOwere indeed synthesized.

  11. Effect of TiO2 on the optical, structural and crystallization behavior of barium borate glasses

    NASA Astrophysics Data System (ADS)

    Marzouk, M. A.; ElBatal, F. H.; ElBatal, H. A.

    2016-07-01

    Collective characterizations of prepared binary barium borate glass (50 mol % BaO - 50 mol % B2O3) together with samples containing increasing added TiO2 contents (5% → 30%) were carried out by optical and FT infrared absorption measurements. FT infrared and X-ray diffraction analysis were done for heat treated glass - ceramic derivatives prepared through two step regime process. Optical spectra of the glasses reveal the presence of titanium ions mainly in the tetravalent state imparting additional UV band beside strong UV absorption due to trace iron impurity. IR spectral studies indicate the presence of triangular and tetrahedral borate groups through the modification of BaO to some BO3 to BO4 groups beside the presence of titanium ions as interfering or overlapping TiO4 or Bsbnd Osbnd Ti groupings in the glassy network. Crystalline X-ray diffraction results indicate the separation of crystalline barium borate of the composition (2BaO.5 B2O3) as a main constituent together with some crystalline alkali titanates confirming the role of TiO2 of both as nucleating agent beside acting as structural forming through reaction with alkali oxides to form crystalline titanates. The optical band gap values reveal progressive decrease and increase of Urbach energy with TiO2 content and the same for the refractive index values and all these parameters are correlated with the proposed changes in the glass constitution with the introduction of TiO2. The additional thermal expansion measurements indicate the peculiar characteristic negative expansion up to 300 °C and after which an increase in the coefficient of thermal expansion is identified with the increase in temperature. The thermal parameters are also correlated with the modification of the glass structure by the introduction of titanium ions.

  12. Characteristic thermoluminescence of gamma-irradiated alumina ceramics doped with some alkali metals

    NASA Astrophysics Data System (ADS)

    Henaish, B. A.; El-Agrami, A. M.; Abdel-Fattah, W. I.; Osiris, W. G.

    1994-07-01

    Thermoluminescence properties of pure Al2O3-ceramic discs doped with some oxides of alkali metals and B were investigated. Two groups of samples were studied: one with a low concentration of B and alkali oxides and the other with higher concentration. The first group shows a relatively higher stability and better reproducibility for γ-radiation and neutron-induced TL, which could be utilized in mixed radiation field dosimetry. The main disadvantage of these TL-materials is the relatively high rate of signal fading. A simple course of post irradiation heat annealing is proposed to overcome this drawback.

  13. Chemical durability of simulated nuclear glasses containing water

    SciTech Connect

    Li, H.; Tomozawa, M.

    1995-04-01

    The chemical durability of simulated nuclear waste glasses having different water contents was studied. Results from the product consistency test (PCT) showed that glass dissolution increased with water content in the glass. This trend was not observed during MCC-1 testing. This difference was attributed to the differences in reactions between glass and water. In the PCT, the glass network dissolution controlled the elemental releases, and water in the glass accelerated the reaction rate. On the other hand, alkali ion exchange with hydronium played an important role in the MCC-1. For the latter, the amount of water introduced into a leached layer from ion-exchange was found to be much greater than that of initially incorporated water in the glass. Hence, the initial water content has no effect on glass dissolution as measured by the MCC-1 test.

  14. Structural study and DC conductivity of vanadyl doped zinc lithium borate glasses

    SciTech Connect

    Seema; Khasa, S. Dahiya, M. S.; Yadav, Arti; Agarwal, A.; Dahiya, S.

    2015-06-24

    Glasses with composition xZnO⋅(30 − x)⋅Li{sub 2}O⋅70B{sub 2}O{sub 3} containing 2 mol% of V{sub 2}O{sub 5} (x = 0, 2, 5, 7 and 10) were prepared by standard melt-quench technique. The amorphous nature of the glass samples was confirmed by using x-ray diffraction. The structural changes in these glasses have been investigated by employing IR spectroscopy in the mid-IR range. The infrared spectroscopic analysis confirms the presence of both triangular and tetraheldral coordinated boron units and absence of boroxol ring. It also shows that metal-oxide vibrations are present which are due to the bonding of lithium and zinc ions with oxygen. The dc conductivity was measured in the temperature range 353-523 K. The dc conductivity results show that conductivity decreases and activation energy increases when Li{sub 2}O is replaced by ZnO, keeping the concentration of B{sub 2}O{sub 3} constant. Decrease in conductivity and increase in activation energy shows that addition of ZnO to the glass matrix shows a “blocking effect” on the overall mobility of alkali ions, but at higher concentration the hopping effect was also observed.

  15. Structure of glasses containing transition metal ions. Progress report, February 1, 1980-January 31, 1981

    SciTech Connect

    White, W.B.; Fox, K.; Herman, J.S.; Houser, C.; Nelson, C.

    1981-01-01

    This research is concerned with the structure and properties of insulator glasses, particularly as these are modified by transition metal ions in solution. This progress report spans a one-year period and describes the status of the work two-thirds into the sixth contract year. Work on the host glasses has been concentrated on the alkali borosilicate, alkali aluminosilicate and alkali-gallia-silicate glasses. The main interest here is the structure setting for aluminum. The optical absorption spectra of nickel and iron in a variety of glasses have been examined. Utilization of luminescence in addition to optical absorption spectra has permitted the identification of several iron arrangements in glass. The investigation of diffusion processes, particularly hydrogen diffusion, by sputter-induced photon spectrometry (SIPS) has moved from qualitative demonstration to quantitative calculation.

  16. Water Content of Lunar Alkali Fedlspar

    NASA Technical Reports Server (NTRS)

    Mills, R. D.; Simon, J. I.; Wang, J.; Alexander, C. M. O'D.; Hauri, E. H.

    2016-01-01

    Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of < 1 ppm in urKREEP. Using these data, predict that the bulk water content of the magma ocean would have <10 ppm. In contrast, estimate water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was

  17. Accelerated bone ingrowth by local delivery of Zinc from bioactive glass: oxidative stress status, mechanical property, and microarchitectural characterization in an ovariectomized rat model

    PubMed Central

    Samira, Jbahi; Saoudi, Monji; Abdelmajid, Kabir; Hassane, Oudadesse; Treq, Rebai; Hafed, Efeki; Abdelfatteh, Elfeki; Hassib, Keskes

    2015-01-01

    Background Synthetic bone graft substitutes such as bioactive glass (BG) material are developed in order to achieve successful bone regeneration. Zn plays an important role in the proper bone growth, development, and maintenance of healthy bones. Aims This study aims to evaluate in vivo the performance therapy of zinc-doped bioactive glass (BG-Zn) and its applications in biomedicine. Methods Female Wistar rats were ovariectomized. BG and BG-Zn were implanted in the femoral condyles of Wistar rats and compared to that of control group. Grafted bone tissues were carefully removed to evaluate the oxidative stress status, histomorphometric profile, mechanical property, and mineral bone distribution by using inductively coupled plasma optical emission spectrometry. Results A significant decrease of thiobarbituric acid–reactive substances was observed after BG-Zn implantation. Superoxide dismutase, catalase (CAT), and glutathione peroxidase (GPx) activities significantly increased in ovariectomized group implanted with Zinc-doped bioactive glass (OVX-BG-Zn) as compared to ovariectomized group implanted with bioactive glass (OVX-BG). An improved mechanical property was noticed in contact of OVX-BG-Zn (39±6 HV) when compared with that of OVX-BG group (26±9 HV). After 90 days of implantation, the histomorphometric analysis showed that trabecular thickness (Tb.Th) and trabecular number (Tb.N) were significantly increased with 28 and 24%, respectively, in treated rats of OVX-BG-Zn group as compared to those of OVX-BG groups. Trabecular separation (Tb.Sp) and trabecular bone pattern factor (TBPf) were significantly decreased in OVX-BG-Zn group with 29.5 and 54% when compared with those of OVX-BG rat groups. On the other hand, a rise in Ca and P ion concentrations in the implanted microenvironment was shown and lead to the formation/deposition of Ca-P phases. The ratio of pyridinoline [Pyr] to dihydroxylysinonorleucine [DHLNL] cross-links was normalized to the control level

  18. Process for the disposal of alkali metals

    DOEpatents

    Lewis, Leroy C.

    1977-01-01

    Large quantities of alkali metals may be safely reacted for ultimate disposal by contact with a hot concentrated caustic solution. The alkali metals react with water in the caustic solution in a controlled reaction while steam dilutes the hydrogen formed by the reaction to a safe level.

  19. Purification of sulfide-alkali effluent with the aid of ionizing radiation. [Gamma radiation

    SciTech Connect

    Petryaev, E.P.; Gerasimovich, O.A.; Kovalevskaya, A.M.; Plyuto, I.Ch.; Shlyk, V.G.

    1984-03-01

    The treatment of sulfide-alkali effluent under the effect of ionizing radiation was investigated. The source was an LMB-..gamma..-1M ..gamma..-apparatus with /sup 137/Cs source. The dose rate was 52 rad/s. Irradiation was done in glass ampules and in vessels allowing bubbling with air and irradiation to be carried out at the same time. 7 references, 1 figure, 1 table.

  20. High temperature corrosion by deposits of alkali salts

    SciTech Connect

    Kloewer, J.

    1996-12-01

    In order to understand and predict how corrosion behavior of metallic high temperature materials is affected by deposits of alkali salts, eight commercial high temperature alloys (AISI 314, alloy 800H, alloy 31, AC66, alloy 45-TM, alloy 625, alloy 59 and alloy C-4) coated with alkali sulfates and chlorides (Na{sub 2}SO{sub 4}/KCl) were investigated in both air and in HCl/SO{sub 2}-containing waste incineration environments. The corrosion rates were found to depend sensitively on the alloy composition, especially on the concentration of molybdenum and silicon. Both stainless steels and nickel base alloys without molybdenum were resistant to dissolution by sulfates in air. Molybdenum-containing steels and nickel base alloys, on the other hand, were extremely susceptible to acidic dissolution in sodium sulfate. These high corrosion rates can be attributed to an increase in salt acidity caused by dissolution of MoO{sub 3}. The effect of HCI in the gas atmosphere was contradictory. All alloys without molybdenum suffered severe internal oxidation, when chlorine was present in the gas atmosphere. The corrosion rates of the nickel-molybdenum alloys, however, were decreased when chlorine was added to the gas phase. The highest corrosion resistance to synthetic waste incineration gas in combination with deposits of alkali sulfates and chlorides was found in the nickel base alloys 45 TM and alloy 625.

  1. Design strategies for development of SCR catalyst: improvement of alkali poisoning resistance and novel regeneration method.

    PubMed

    Peng, Yue; Li, Junhua; Shi, Wenbo; Xu, Jiayu; Hao, Jiming

    2012-11-20

    Based on the ideas of the additives modification and regeneration method update, two different strategies were designed to deal with the traditional SCR catalyst poisoned by alkali metals. First, ceria doping on the V(2)O(5)-WO(3)/TiO(2) catalyst could promote the SCR performance even reducing the V loading, which resulted in the enhancement of the catalyst's alkali poisoning resistance. Then, a novel method, electrophoresis treatment, was employed to regenerate the alkali poisoned V(2)O(5)-WO(3)/TiO(2) catalyst. This novel technique could dramatically enhance the SCR activities of the alkali poisoned catalysts by removing approximately 95% K or Na ions from the catalyst and showed less hazardous to the environment. Finally, the deactivation mechanisms by the alkali metals were extensively studied by employing both the experimental and DFT theoretical approaches. Alkali atom mainly influences the active site V species rather than W oxides. The decrease of catalyst surface acidity might directly reduce the catalytic activity, while the reducibility of catalysts could be another important factor.

  2. Enhanced luminescence of Tb{sup 3+}/Eu{sup 3+} doped tellurium oxide glass containing silver nanostructures

    SciTech Connect

    Kassab, Luciana R. P.; Araujo, Cid B. de

    2009-05-15

    We report on energy transfer studies in terbium (Tb{sup 3+})--europium (Eu{sup 3+}) doped TeO{sub 2}-ZnO-Na{sub 2}O-PbO glass containing silver nanostructures. The samples excitation was made using ultraviolet radiation at 355 nm. Luminescence spectra were recorded from approx =480 to approx =700 nm. Enhanced Eu{sup 3+} luminescence at approx =590 nm (transition {sup 5}D{sub 0}-{sup 7}F{sub 1}) and approx =614 nm (transition {sup 5}D{sub 0}-{sup 7}F{sub 2}) are observed. The large luminescence enhancement was obtained due to the simultaneous contribution of the Tb{sup 3+}-Eu{sup 3+} energy transfer and the contribution of the intensified local field on the Eu{sup 3+} ions located near silver nanostructures.

  3. Nitric oxide permits hypoxia-induced lymphatic perfusion by controlling arterial-lymphatic conduits in zebrafish and glass catfish

    PubMed Central

    Dahl Ejby Jensen, Lasse; Cao, Renhai; Hedlund, Eva-Maria; Söll, Iris; Lundberg, Jon O.; Hauptmann, Giselbert; Steffensen, John Fleng; Cao, Yihai

    2009-01-01

    The blood and lymphatic vasculatures are structurally and functionally coupled in controlling tissue perfusion, extracellular interstitial fluids, and immune surveillance. Little is known, however, about the molecular mechanisms that underlie the regulation of bloodlymphatic vessel connections and lymphatic perfusion. Here we show in the adult zebrafish and glass catfish (Kryptopterus bicirrhis) that blood-lymphatic conduits directly connect arterial vessels to the lymphatic system. Under hypoxic conditions, arterial-lymphatic conduits (ALCs) became highly dilated and linearized by NO-induced vascular relaxation, which led to blood perfusion into the lymphatic system. NO blockage almost completely abrogated hypoxia-induced ALC relaxation and lymphatic perfusion. These findings uncover mechanisms underlying hypoxia-induced oxygen compensation by perfusion of existing lymphatics in fish. Our results might also imply that the hypoxia-induced NO pathway contributes to development of progression of pathologies, including promotion of lymphatic metastasis by modulating arterial-lymphatic conduits, in the mammalian system. PMID:19822749

  4. Glasses in coarse-grained micrometeorites

    NASA Astrophysics Data System (ADS)

    Varela, M. E.; Kurat, G.

    2009-06-01

    Micrometeorites (MMs, interplanetary dust particles with 25 - 500 μm diameters) carry the main mass of extraterrestrial matter that is captured by Earth. The coarse-grained MMs mainly consist of olivine aggregates, which - as their counterparts in CC chondrites - also contain pyroxenes and glass. We studied clear glasses in four coarse-grained crystalline MMs (10M12, M92-6b, AM9, and Mc7-10), which were collected from the ice at Cap Prudhomme, Antarctica. Previous studies of glasses (e.g., glass inclusions trapped in olivine and clear mesostasis glass) in carbonaceous and ordinary chondrites showed that these phases could keep memory of the physical-chemical conditions to which extraterrestrial matter was exposed. Here we compare the chemical compositions of MM glasses and glasses from CM chondrites with that in experimentally heated objects from the Allende CV chondrite and with glasses from cometary particles. Our results show that MMs were heated to variable degrees (during entry through the terrestrial atmosphere), which caused a range from very little chemical modification of the glass to total melting of the precursor object. Such modifications include dissolution of minerals in the melted glass precursor and some loss of volatile alkali elements. The chemical composition of all precursor glasses in the MMs investigated is not primitive such as glasses in CM and CR chondrite objects. It shows signs of pre-terrestrial chemical modification, e.g., metasomatic enrichments in Na and Fe 2+ presumably in the solar nebula. Glasses of MMs heated to very low degree have a chemical composition indistinguishable from that of glasses in comet Wild 2 particles; giving additional evidence that interplanetary dust (e.g., Antarctic MMs) possibly represents samples from comets.

  5. High performance dye-sensitized solar cells using graphene modified fluorine-doped tin oxide glass by Langmuir–Blodgett technique

    SciTech Connect

    Roh, Ki-Min; Jo, Eun-Hee; Chang, Hankwon; Han, Tae Hee; Jang, Hee Dong

    2015-04-15

    Since the introduction of dye-sensitized solar cells (DSSCs) with low fabrication cost and high power conversion efficiency, extensive studies have been carried out to improve the charge transfer rate and performance of DSSCs. In this paper, we present DSSCs that use surface modified fluorine-doped tin oxide (FTO) substrates with reduced graphene oxide (r-GO) sheets prepared using the Langmuir–Blodgett (LB) technique to decrease the charge recombination at the TiO{sub 2}/FTO interface. R-GO sheets were excellently attached on FTO surface without physical deformations such as wrinkles; effects of the surface coverage of r-GO on the DSSC performance were also investigated. By using graphene modified FTO substrates, the resistance at the interface of TiO{sub 2}/FTO was reduced and the power conversion efficiency was increased to 8.44%. - Graphical abstract: DSSCs with graphene modified FTO glass were fabricated with the Langmuir Blodgett technique. GO sheets were transferred to FTO at various surface pressures in order to change the surface density of graphene and the highest power conversion efficiency of the DSSC was 8.44%. - Highlights: • By LB technique, r-GO sheets were coated on FTO without physical deformation. • DSSCs were fabricated with, r-GO modified FTO substrates. • With surface modification by r-GO, the interface resistance of DSSC decreased. • Maximum PCE of the DSSC was increased up to 8.44%.

  6. Highly sensitive nonenzymatic glucose and H2O2 sensor based on Ni(OH)2/electroreduced graphene oxide--multiwalled carbon nanotube film modified glass carbon electrode.

    PubMed

    Gao, Wei; Tjiu, Weng Weei; Wei, Junchao; Liu, Tianxi

    2014-03-01

    In this article, a nonenzymatic sensor based on Ni(OH)2/electroreduced graphene oxide (ERGO)-multiwalled carbon nanotube (MWNT) nanocomposites is fabricated via convenient electrodeposition of Ni(OH)2 nanoparticles on ERGO-MWNT film modified glass carbon electrode (GCE). Graphene oxide (GO) sheets can serve as surfactants to stabilize the dispersion of pristine MWNTs in aqueous solution, rendering a fine coverage of ERGO-MWNT film on GCE during the fabrication process. MWNTs perform as conducting bridges between ERGO sheets to enhance the electron transfer rate in the substrate. By combining the advantages of ERGO and MWNTs, together with electrocatalytic effect of Ni(OH)2 nanoparticles, the well-designed nanocomposites exhibit excellent sensing behavior towards glucose and hydrogen peroxide (H2O2). The linear detection ranges for glucose and H2O2 are 10-1500 µM and 10 µM-9050 µM while the detection limits are 2.7 µM and 4.0 µM, respectively. Furthermore, a very high sensitivity is achieved with 2042 µAm M(-1) cm(-2) estimated for glucose and 711 µAm M(-1) cm(-2) for H2O2. These results suggest that Ni(OH)2/ERGO-MWNT nanocomposites thus easily prepared through a green electrochemical method are promising electrode materials for biosensing. Additionally, good recoveries of analytes in real samples like urine and milk confirm the reliability of the prepared sensor in practical applications.

  7. Feed Preparation for Source of Alkali Melt Rate Tests

    SciTech Connect

    Stone, M. E.; Lambert, D. P.

    2005-02-26

    The purpose of the Source of Alkali testing was to prepare feed for melt rate testing in order to determine the maximum melt-rate for a series of batches where the alkali was increased from 0% Na{sub 2}O in the frit (low washed sludge) to 16% Na{sub 2}O in the frit (highly washed sludge). This document summarizes the feed preparation for the Source of Alkali melt rate testing. The Source of Alkali melt rate results will be issued in a separate report. Five batches of Sludge Receipt and Adjustment Tank (SRAT) product and four batches of Slurry Mix Evaporator (SME) product were produced to support Source of Alkali (SOA) melt rate testing. Sludge Batch 3 (SB3) simulant and frit 418 were used as targets for the 8% Na{sub 2}O baseline run. For the other four cases (0% Na{sub 2}O, 4% Na{sub 2}O, 12% Na{sub 2}O, and 16% Na{sub 2}O in frit), special sludge and frit preparations were necessary. The sludge preparations mimicked washing of the SB3 baseline composition, while frit adjustments consisted of increasing or decreasing Na and then re-normalizing the remaining frit components. For all batches, the target glass compositions were identical. The five SRAT products were prepared for testing in the dry fed melt-rate furnace and the four SME products were prepared for the Slurry-fed Melt-Rate Furnace (SMRF). At the same time, the impacts of washing on a baseline composition from a Chemical Process Cell (CPC) perspective could also be investigated. Five process simulations (0% Na{sub 2}O in frit, 4% Na{sub 2}O in frit, 8% Na{sub 2}O in frit or baseline, 12% Na{sub 2}O in frit, and 16% Na{sub 2}O in frit) were completed in three identical 4-L apparatus to produce the five SRAT products. The SRAT products were later dried and combined with the complementary frits to produce identical glass compositions. All five batches were produced with identical processing steps, including off-gas measurement using online gas chromatographs. Two slurry-fed melter feed batches, a 4% Na

  8. Glass Artworks

    NASA Technical Reports Server (NTRS)

    1988-01-01

    Several NASA technologies have played part in growth and cost containment of studio glass art, among them a foam type insulation developed to meet a need for lightweight material that would reduce flame spread in aircraft fire. Foam comes in several forms and is widely used by glass artists, chiefly as an insulator for the various types of ovens used in glass working. Another Spinoff is alumina crucibles to contain molten glass. Before alumina crucibles were used, glass tanks were made of firebrick which tended to erode under high temperatures and cause impurities; this not only improved quality but made the process more cost effective. One more NASA technology that found its way into glass art working is a material known as graphite board, a special form of graphite originally developed for rocket motor applications. This graphite is used to exact compound angles and creates molds for poured glass artworks of dramatic design.

  9. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 6, December 1, 1992--February 28, 1993

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-02-24

    The high temperature alkali corrosion kinetics of SiC have been systematically investigated from 950 to 1100{degrees}C at 0.63 vol % alkali vapor concentration. The corrosion rate in the presence of alkaliis approximately 10{sup 4} to 10{sup 5} times faster than the oxidation rate of SiC in air. The activation energy associated with the alkali corrosion is 406 kJ/mol, indicating a highly temperature-dependent reaction rate. The rate-controlling step of the overall reaction is likely to be the dissolution of silica in the sodium silicate liquid, based on the oxygen diffusivity data.

  10. Alkali-metal silicate binders and methods of manufacture

    NASA Technical Reports Server (NTRS)

    Schutt, J. B. (Inventor)

    1979-01-01

    A paint binder is described which uses a potassium or sodium silicate dispersion having a silicon dioxide to alkali-metal oxide mol ratio of from 4.8:1 to 6.0:1. The binder exhibits stability during both manufacture and storage. The process of making the binder is predictable and repeatable and the binder may be made with inexpensive components. The high mol ratio is achieved with the inclusion of a silicon dioxide hydrogel. The binder, which also employs a silicone, is in the final form of a hydrogel sol.

  11. Measurement of alkali in PFBC exhaust

    SciTech Connect

    Lee, S.H.D.; Swift, W.M.

    1992-11-01

    This project supports the DOE/METC Fossil Energy Program for the development of PFBC technology. Based on the analytical activated-bauxite sorber-bed technique, we are developing the RABSAM as an altemative to the on-line alkali analyzer for field application. As shown in Fig. 1, the RABSAM is a sampling probe containing a regenerable activated-bauxite adsorbent (RABA). It can be inserted directly into the PFBC exhaust duct and requires no HTHP sampling line. Alkali vapors are captured by the adsorbent purely through physical adsorption. The adsorbent is regenerated by a simple water-leaching process, which also recovers the adsorbed alkalis. The alkali analysis of the leachate by atomic absorption (AA) provides a basis for calculating the time-averaged alkali-vapor concentration in the PFBC exhaust. If the RABA is to use commercial grade activated bauxite, the clay impurities in activated bauxite can react with alkali vapors and, therefore, need to be either removed or deactivated. In earlier work, a 6M-LiCl-solution impregnation technique was shown to deactivate these impurities in fresh activated bauxite [8]. During this year, RABA prepared by this technique was tested in a pressurized alkali-vapor sorption test unit to determine its NaCl-vapor capture efficiency and the regenerability of the sorbent by water extraction. Results of this study are presented and discussed.

  12. Measurement of alkali in PFBC exhaust

    SciTech Connect

    Lee, S.H.D.; Swift, W.M.

    1992-01-01

    This project supports the DOE/METC Fossil Energy Program for the development of PFBC technology. Based on the analytical activated-bauxite sorber-bed technique, we are developing the RABSAM as an altemative to the on-line alkali analyzer for field application. As shown in Fig. 1, the RABSAM is a sampling probe containing a regenerable activated-bauxite adsorbent (RABA). It can be inserted directly into the PFBC exhaust duct and requires no HTHP sampling line. Alkali vapors are captured by the adsorbent purely through physical adsorption. The adsorbent is regenerated by a simple water-leaching process, which also recovers the adsorbed alkalis. The alkali analysis of the leachate by atomic absorption (AA) provides a basis for calculating the time-averaged alkali-vapor concentration in the PFBC exhaust. If the RABA is to use commercial grade activated bauxite, the clay impurities in activated bauxite can react with alkali vapors and, therefore, need to be either removed or deactivated. In earlier work, a 6M-LiCl-solution impregnation technique was shown to deactivate these impurities in fresh activated bauxite [8]. During this year, RABA prepared by this technique was tested in a pressurized alkali-vapor sorption test unit to determine its NaCl-vapor capture efficiency and the regenerability of the sorbent by water extraction. Results of this study are presented and discussed.

  13. The oxidation state of sulfur in synthetic and natural glasses determined by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Métrich, Nicole; Berry, Andrew J.; O'Neill, Hugh St. C.; Susini, Jean

    2009-04-01

    Sulfur K-edge X-ray absorption near edge structure (XANES) spectra were recorded for experimental glasses of various compositions prepared at different oxygen fugacities ( fO 2) in one-atmosphere gas-mixing experiments at 1400 °C. This sample preparation method only results in measurable S concentrations under either relatively reduced (log fO 2 < -9) or oxidised (log fO 2 > -2) conditions. The XANES spectra of the reduced samples are characterised by an absorption edge crest at 2476.4 eV, typical of S 2-. In addition, spectra of Fe-bearing compositions exhibit a pronounced absorption edge shoulder. Spectra for all the Fe-free samples are essentially identical, as are the spectra for the Fe-bearing compositions, despite significant compositional variability within each group. The presence of a sulfide phase, such as might exsolve on cooling, can be inferred from a pre-edge feature at 2470.5 eV. The XANES spectra of the oxidised samples are characterised by an intense transition at 2482.1 eV, typical of the sulfate anion SO 42-. Sulfite (SO 32-) has negligible solubility in silicate melts at low pressures. The previous identification of sulfite species in natural glass samples is attributed to an artefact of the analysis (photoreduction of S 6+). S 4+ does, however, occur unambiguously with S 6+ in Fe-free and Fe-poor compositions prepared in equilibrium with CaSO 4 at 4-16 kbar, and when buffered with Re/ReO 2 at 10 kbar. Solubility of S 4+ thus requires partial pressures of SO 2 considerably in excess of 1 bar. A number of experiments were undertaken in an attempt to access intermediate fO 2s more applicable to terrestrial volcanism. Although these were largely unsuccessful, S 2- and S 6+ were found to coexist in some samples that were not in equilibrium with the imposed fO 2. The XANES spectra of natural olivine-hosted melt inclusions and submarine glasses representative of basalts at, or close to, sulfide saturation show mainly dissolved S 2-, but with minor

  14. Development and characterization of glass-ceramic sealants in the (CaO-Al2O3-SiO2-B2O3) system for Solid Oxide Electrolyzer Cells

    NASA Astrophysics Data System (ADS)

    Khedim, Hichem; Nonnet, Hélène; Méar, François O.

    2012-10-01

    The efficiency of glass-ceramic sealants plays a crucial role in Solid Oxide Electrolyzer Cell performance and durability. In order to develop suitable sealants, operating around 800 °C, two parent glass compositions, CAS1B and CAS2B, from the CaO-Al2O3-SiO2-B2O3 system were prepared and explored. The thermal and physicochemical properties of the glass ceramics and their crystallization behavior were investigated by HSM, DTA and XRD analyses. The microstructure and chemical compositions of the crystalline phases were investigated by microprobe analysis. Bonding characteristic as well as chemical interactions of the parent glass with yttria-stabilized zirconia (YSZ) electrolyte and ferritic steel-based interconnect (Crofer®) were also investigated. The preliminary results revealed the superiority of CAS2B glass for sealing application in SOECs. The effect of minor additions of V2O5, K2O and TiO2 on the thermal properties was also studied and again demonstrated the advantages of the CAS2B glass composition. Examining the influence of heat treatment on the seal behavior showed that the choice of the heating rate is a compromise between delaying the crystallization process and delaying the viscosity drop. The thermal Expansion Coefficients (TEC) obtained for the selected glass ceramic are within the desired range after the heat treatment of crystallization. The crystallization kinetic parameters of the selected glass composition were also determined under non-isothermal conditions by means of differential thermal analysis (DTA) and using the formal theory of transformations for heterogeneous nucleation.

  15. Dissolution Process of Palladium in Hydrochloric Acid: A Route via Alkali Metal Palladates

    NASA Astrophysics Data System (ADS)

    Kasuya, Ryo; Miki, Takeshi; Morikawa, Hisashi; Tai, Yutaka

    2015-12-01

    To improve the safety of the Pd recovery processes that use toxic oxidizers, dissolution of Pd in hydrochloric acid with alkali metal palladates was investigated. Alkali metal palladates were prepared by calcining a mixture of Pd black and alkali metal (Li, Na, and K) carbonates in air. Almost the entire amount of Pd was converted into Li2PdO2 after calcination at 1073 K (800 °C) using Li2CO3. In contrast, PdO was obtained by calcination at 1073 K (800 °C) using Na and K carbonates. Our results indicated that Li2CO3 is the most active reagent among the examined alkali metal carbonates for the formation of palladates. In addition, dissolution of the resulting Li2PdO2 in HCl solutions was evaluated under various conditions. In particular, Li2PdO2 rapidly dissolved in diluted (0.1 M) HCl at ambient temperature. Solubility of Pd of Li2PdO2 was found to be 99 pct or larger after dissolution treatment at 353 K (80 °C) for 5 minutes; in contrast, PdO hardly dissolved in 0.1 M HCl. The dissolution mechanism of Li2PdO2 in HCl was also elucidated by analysis of crystal structures and particulate properties. Since our process is completely free from toxic oxidizers, the dissolution process via alkali metal palladates is much safer than currently employed methods.

  16. Molecular glasses for nuclear waste encapsulation

    SciTech Connect

    Ropp, R.C.

    1982-09-28

    A molecular glass based upon a phosphate of aluminum, or other trivalent metal, provides significant improvement over prior art glasses for encapsulation of high level radioactive nuclear waste. When containing a controlled amount of those elemental oxides found in a typical nuclear waste, the waste-glass would not devitrify under conditions which produced devitrification in the non-nuclear-waste-containing glass, exhibited hydrolysis losses lower by an order of magnitude, had high solvency power for those elemental oxides, exhibited little tendency for internal crystallite formation, and possessed other desirable physical characteristics, all in direct antithesis to the properties of the best prior-known glasses used for this application.

  17. Glass Research

    NASA Technical Reports Server (NTRS)

    Weinberg, M. C.

    1985-01-01

    Research efforts span three general areas of glass science: glass refining, gel-derived glasses, and nucleation and crystallization of glasses. Gas bubbles which are present in a glass product are defects which may render the glass totally useless for the end application. For example, optical glasses, laser host glasses, and a variety of other specialty glasses must be prepared virtually defect free to be employable. Since a major mechanism of bubble removal, buoyant rise, is virtually inoperative in microgravity, glass fining will be especially difficult in space. On the other hand, the suppression of buoyant rise and the ability to perform containerless melting experiments in space allows the opportunity to carry out several unique bubble experiments in space. Gas bubble dissolution studies may be performed at elevated temperatures for large bubbles with negligible bubble motion. Also, bubble nucleation studies may be performed without the disturbing feature of heterogeneous bubble nucleation at the platinum walls. Ground based research efforts are being performed in support of these potential flight experiments.

  18. Diode pumped alkali vapor fiber laser

    DOEpatents

    Payne, Stephen A.; Beach, Raymond J.; Dawson, Jay W.; Krupke, William F.

    2007-10-23

    A method and apparatus is provided for producing near-diffraction-limited laser light, or amplifying near-diffraction-limited light, in diode pumped alkali vapor photonic-band-gap fiber lasers or amplifiers. Laser light is both substantially generated and propagated in an alkali gas instead of a solid, allowing the nonlinear and damage limitations of conventional solid core fibers to be circumvented. Alkali vapor is introduced into the center hole of a photonic-band-gap fiber, which can then be pumped with light from a pump laser and operated as an oscillator with a seed beam, or can be configured as an amplifier.

  19. Diode pumped alkali vapor fiber laser

    DOEpatents

    Payne, Stephen A.; Beach, Raymond J.; Dawson, Jay W.; Krupke, William F.

    2006-07-26

    A method and apparatus is provided for producing near-diffraction-limited laser light, or amplifying near-diffraction-limited light, in diode pumped alkali vapor photonic-band-gap fiber lasers or amplifiers. Laser light is both substantially generated and propagated in an alkali gas instead of a solid, allowing the nonlinear and damage limitations of conventional solid core fibers to be circumvented. Alkali vapor is introduced into the center hole of a photonic-band-gap fiber, which can then be pumped with light from a pump laser and operated as an oscillator with a seed beam, or can be configured as an amplifier.

  20. Alkali Silicate Vehicle Forms Durable, Fireproof Paint

    NASA Technical Reports Server (NTRS)

    Schutt, John B.; Seindenberg, Benjamin

    1964-01-01

    The problem: To develop a paint for use on satellites or space vehicles that exhibits high resistance to cracking, peeling, or flaking when subjected to a wide range of temperatures. Organic coatings will partially meet the required specifications but have the inherent disadvantage of combustibility. Alkali-silicate binders, used in some industrial coatings and adhesives, show evidence of forming a fireproof paint, but the problem of high surface-tension, a characteristic of alkali silicates, has not been resolved. The solution: Use of a suitable non-ionic wetting agent combined with a paint incorporating alkali silicate as the binder.

  1. Advancements in flowing diode pumped alkali lasers

    NASA Astrophysics Data System (ADS)

    Pitz, Greg A.; Stalnaker, Donald M.; Guild, Eric M.; Oliker, Benjamin Q.; Moran, Paul J.; Townsend, Steven W.; Hostutler, David A.

    2016-03-01

    Multiple variants of the Diode Pumped Alkali Laser (DPAL) have recently been demonstrated at the Air Force Research Laboratory (AFRL). Highlights of this ongoing research effort include: a) a 571W rubidium (Rb) based Master Oscillator Power Amplifier (MOPA) with a gain (2α) of 0.48 cm-1, b) a rubidium-cesium (Cs) Multi-Alkali Multi-Line (MAML) laser that simultaneously lases at both 795 nm and 895 nm, and c) a 1.5 kW resonantly pumped potassium (K) DPAL with a slope efficiency of 50%. The common factor among these experiments is the use of a flowing alkali test bed.

  2. L-Edge Xanes Measurements of the Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Righter, K.; Sutton, S.; Newville, M.

    2008-01-01

    Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies are inconsistent on whether W occurs as W(4+) or W(6+). It is assumed that W(4+) is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO2 is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO2 most relevant to core formation, around IW-2.

  3. Crystallization of copper metaphosphate glass

    NASA Technical Reports Server (NTRS)

    Bae, Byeong-Soo; Weinberg, Michael C.

    1993-01-01

    The effect of the valence state of copper in copper metaphosphate glass on the crystallization behavior and glass transition temperature has been investigated. The crystallization of copper metaphosphate is initiated from the surface and its main crystalline phase is copper metaphosphate (Cu(PO)3),independent of the (Cu sup 2+)/(Cu(total)). However, the crystal morphology, the relative crystallization rates, and their temperature dependences are affected by the (Cu sup 2+)/(Cu (total)) ratio in the glass. On the other hand, the totally oxidized glass crystallizes from all over the surface. The relative crystallization rate of the reduced glass to the totally oxidized glass is large at low temperature, but small at high temperature. The glass transition temperature of the glass increases as the (Cu sup 2+)/(Cu(total)) ratio is raised. It is also found that the atmosphere used during heat treatment does not influence the crystallization of the reduced glass, except for the formation of a very thin CuO surface layer when heated in air.

  4. Preliminary report on a glass burial experiment in granite

    SciTech Connect

    Clark, D.E.; Zhu, B.F.; Robinson, R.S.; Wicks, G.G.

    1983-01-01

    Preliminary results of a two-year burial experiment in granite are discussed. Three compositions of simulated alkali borosilicate waste glasses were placed in boreholes approximately 350 meters deep. The glass sample configurations include mini-cans (stainless steel rings into which glass has been cast) and pineapple slices (thin sections from cylindrical blocks). Assemblies of these glass samples were prepared by stacking them together with granite, compacted bentonite and metal rings to provide several types of interfaces that are expected to occur in the repository. The assemblies were maintained at either ambient mine temperature (8 to 10/sup 0/C) or 90/sup 0/C. The glasses were analyzed before burial and after one month storage at 90/sup 0/C. The most extensive surface degradation occurred on the glasses interfaced with bentonite. In general, very little attack was observed on glass surfaces in contact with the other materials. The limited field and laboratory data are compared.

  5. Substrate biasing effect on the physical properties of reactive RF-magnetron-sputtered aluminum oxide dielectric films on ITO glasses.

    PubMed

    Liang, Ling Yan; Cao, Hong Tao; Liu, Quan; Jiang, Ke Min; Liu, Zhi Min; Zhuge, Fei; Deng, Fu Ling

    2014-02-26

    High dielectric constant (high-k) Al2O3 thin films were prepared on ITO glasses by reactive RF-magnetron sputtering at room temperature. The effect of substrate bias on the subband structural, morphological, electrode/Al2O3 interfacial and electrical properties of the Al2O3 films is systematically investigated. An optical method based on spectroscopic ellipsometry measurement and modeling is adopted to probe the subband electronic structure, which facilitates us to vividly understand the band-tail and deep-level (4.8-5.0 eV above the valence band maximum) trap states. Well-selected substrate biases can suppress both the trap states due to promoted migration of sputtered particles, which optimizes the leakage current density, breakdown strength, and quadratic voltage coefficient of capacitance. Moreover, high porosity in the unbiased Al2O3 film is considered to induce the absorption of atmospheric moisture and the consequent occurrence of electrolysis reactions at electrode/Al2O3 interface, as a result ruining the electrical properties. PMID:24490685

  6. Direct conversion of halogen-containing wastes to borosilicate glass

    SciTech Connect

    Forsberg, C.W.; Beahm, E.C.; Rudolph, J.C.

    1996-12-09

    Glass has become a preferred waste form worldwide for radioactive wastes: however, there are limitations. Halogen-containing wastes can not be converted to glass because halogens form poor-quality waste glasses. Furthermore, halides in glass melters often form second phases that create operating problems. A new waste vitrification process, the Glass Material Oxidation and dissolution System (GMODS), removes these limitations by converting halogen-containing wastes into borosilicate glass and a secondary, clean, sodium-halide stream.

  7. Alkali slurry ozonation to produce a high capacity nickel battery material

    DOEpatents

    Jackovitz, John F.; Pantier, Earl A.

    1984-11-06

    A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

  8. The Impact of the Source of Alkali on Sludge Batch 3 Melt Rate (U)

    SciTech Connect

    Smith, M

    2005-04-01

    Previous Savannah River National Laboratory (SRNL) melt rate tests in support of the Defense Waste Processing Facility (DWPF) have indicated that improvements in melt rate can be achieved through an increase in the total alkali of the melter feed. Higher alkali can be attained by the use of an ''underwashed'' sludge, a high alkali frit, or a combination of the two. Although the general trend between melt rate and total alkali (in particular Na{sub 2}O content) has been demonstrated, the question of ''does the source of alkali (SOA) matter?'' still exists. Therefore the purpose of this set of tests was to determine if the source of alkali (frit versus sludge) can impact melt rate. The general test concept was to transition from a Na{sub 2}O-rich frit to a Na{sub 2}O-deficient frit while compensating the Na{sub 2}O content in the sludge to maintain the same overall Na{sub 2}O content in the melter feed. Specifically, the strategy was to vary the amount of alkali in frits and in the sludge batch 3 (SB3) sludge simulant (midpoint or baseline feed was SB3/Frit 418 at 35% waste loading) so that the resultant feeds had the same final glass composition when vitrified. A set of SOA feeds using frits ranging from 0 to 16 weight % Na{sub 2}O (in 4% increments) was first tested in the Melt Rate Furnace (MRF) to determine if indeed there was an impact. The dry-fed MRF tests indicated that if the alkali is too depleted from either the sludge (16% Na{sub 2}O feed) or the frit (the 0% Na{sub 2}O feed), then melt rate was negatively impacted when compared to the baseline SB3/Frit 418 feed currently being processed at DWPF. The MRF melt rates for the 4 and 12% SOA feeds were similar to the baseline SB3/Frit 418 (8% SOA) feed. Due to this finding, a smaller subset of SOA feeds that could be processed in the DWPF (4 and 12% SOA feeds) was then tested in the Slurry-fed Melt Rate Furnace (SMRF). The results from a previous SMRF test with SB3/Frit 418 (Smith et al. 2004) were used as the

  9. Electron- and Photon-stimulated Desorption of Alkali Atoms from Lunar Sample and a Model Mineral Surface

    NASA Technical Reports Server (NTRS)

    Yakshinskiy, B. V.; Madey, T. E.

    2003-01-01

    We report recent results on an investigation of source mechanisms for the origin of alkali atoms in the tenuous planetary atmospheres, with focus on non-thermal processes (photon stimulated desorption (PSD), electron stimulated desorption (ESD), and ion sputtering). Whereas alkaline earth oxides (MgO, CaO) are far more abundant in lunar samples than alkali oxides (Na2O, K2O), the atmosphere of the Moon contains easily measurable concentrations of Na and K, while Ca and Mg are undetected there; traces of Ca have recently been seen in the Moon's atmosphere (10-3 of Na). The experiments have included ESD, PSD and ion sputtering of alkali atoms from model mineral surface (amorphous SiO2) and from a lunar basalt sample obtained from NASA. The comparison is made between ESD and PSD efficiency of monovalent alkalis (Na, K) and divalent alkaline earths (Ba, Ca).The ultrahigh vacuum measurement scheme for ESD and PSD of Na atoms includes a highly sensitive alkali metal detector based on surface ionization, and a time-of-flight technique. For PSD measurements, a mercury arc light source (filtered and chopped) is used. We find that bombardment of the alkali covered surfaces by ultraviolet photons or by low energy electrons (E>4 eV) causes desorption of hot alkali atoms. This results are consistent with the model developed to explain our previous measurements of sodium desorption from a silica surface and from water ice: electron- or photon-induced charge transfer from the substrate to the ionic adsorbate causes formation of a neutral alkali atom in a repulsive configuration, from which desorption occurs. The two-electron charge transfer to cause desorption of divalent alkaline eath ions is a less likely process.The data support the suggestion that PSD by UV solar photons is a dominant source process for alkalis in the tenuous lunar atmosphere.

  10. HIGH-LEVEL WASTE GLASS FORMULATION MODEL SENSITIVITY STUDY 2009 GLASS FORMULATION MODEL VERSUS 1996 GLASS FORMULATION MODEL

    SciTech Connect

    BELSHER JD; MEINERT FL

    2009-12-07

    This document presents the differences between two HLW glass formulation models (GFM): The 1996 GFM and 2009 GFM. A glass formulation model is a collection of glass property correlations and associated limits, as well as model validity and solubility constraints; it uses the pretreated HLW feed composition to predict the amount and composition of glass forming additives necessary to produce acceptable HLW glass. The 2009 GFM presented in this report was constructed as a nonlinear optimization calculation based on updated glass property data and solubility limits described in PNNL-18501 (2009). Key mission drivers such as the total mass of HLW glass and waste oxide loading are compared between the two glass formulation models. In addition, a sensitivity study was performed within the 2009 GFM to determine the effect of relaxing various constraints on the predicted mass of the HLW glass.

  11. Alkali metal for ultraviolet band-pass filter

    NASA Technical Reports Server (NTRS)

    Mardesich, Nick (Inventor); Fraschetti, George A. (Inventor); Mccann, Timothy A. (Inventor); Mayall, Sherwood D. (Inventor); Dunn, Donald E. (Inventor); Trauger, John T. (Inventor)

    1993-01-01

    An alkali metal filter having a layer of metallic bismuth deposited onto the alkali metal is provided. The metallic bismuth acts to stabilize the surface of the alkali metal to prevent substantial surface migration from occurring on the alkali metal, which may degrade optical characteristics of the filter. To this end, a layer of metallic bismuth is deposited by vapor deposition over the alkali metal to a depth of approximately 5 to 10 A. A complete alkali metal filter is described along with a method for fabricating the alkali metal filter.

  12. Scintillating glass fiber-optic neutron sensors

    NASA Astrophysics Data System (ADS)

    Abel, K. H.; Arthur, R. J.; Bliss, M.

    1994-04-01

    Pacific Northwest Laboratory (PNL) has fabricated cerium-activated lithium silicate scintillating fibers via a hot-downdraw process. These fibers, which, as produced, typically have a transmission length (e(sup -1) length) of greater than 2 meters, are found to undergo aging when subjected to room air. The aging, which is complete in a few weeks, reduces the transmission length to the order of 0.5 meter. Because of the high alkali content of the glass (on the order of 20-30 mole percent lithia), we have attributed this aging to aqueous corrosion at the polymer cladding/glass interface. Changes in transmission with chemical treatment of the surface support the corrosion model. Fiber transmission performance has been preserved by modifying the hot-downdraw to a double crucible to produce glass-on-glass waveguides.

  13. Cytocompatibility, mechanical and dissolution properties of high strength boron and iron oxide phosphate glass fibre reinforced bioresorbable composites.

    PubMed

    Sharmin, Nusrat; Hasan, Muhammad S; Parsons, Andrew J; Rudd, Chris D; Ahmed, Ifty

    2016-06-01

    In this study, Polylactic acid (PLA)/phosphate glass fibres (PGF) composites were prepared by compression moulding. Fibres produced from phosphate based glasses P2O5-CaO-MgO-Na2O (P45B0), P2O5-CaO-MgO-Na2O-B2O3 (P45B5), P2O5-CaO-MgO-Na2O-Fe2O3 (P45Fe3) and P2O5-CaO-MgO-Na2O-B2O3-Fe2O3 (P45B5Fe3) were used to reinforce the bioresorbable polymer PLA. Fibre mechanical properties and degradation rate were investigated, along with the mechanical properties, degradation and cytocompatibility of the composites. Retention of the mechanical properties of the composites was evaluated during degradation in PBS at 37°C for four weeks. The fibre volume fraction in the composite varied from 19 to 23%. The flexural strength values (ranging from 131 to 184MPa) and modulus values (ranging from 9.95 to 12.29GPa) obtained for the composites matched those of cortical bone. The highest flexural strength (184MPa) and modulus (12.29GPa) were observed for the P45B5Fe3 composite. After 28 days of immersion in PBS at 37°C, ~35% of the strength profile was maintained for P45B0 and P45B5 composites, while for P45Fe3 and P45B5Fe3 composites ~40% of the initial strength was maintained. However, the overall wet mass change of P45Fe3 and P45B5Fe3 remained significantly lower than that of the P45B0 and P45B5 composites. The pH profile also revealed that the P45B0 and P45B5 composites degraded quicker, correlating well with the degradation profile. From SEM analysis, it could be seen that after 28 days of degradation, the fibres in the fractured surface of P45B5Fe3 composites remain fairly intact as compared to the other formulations. The in vitro cell culture studies using MG63 cell lines revealed both P45Fe3 and P45B5Fe3 composites maintained and showed higher cell viability as compared to the P45B0 and P45B5 composites. This was attributed to the slower degradation rate of the fibres in P45Fe3 and P45B5Fe3 composites as compared with the fibres in P45B0 and P45B5 composites.

  14. Irreversibility temperatures in superconducting oxides: The flux-line-lattice melting, the glass-liquid transition, or the depinning temperatures

    SciTech Connect

    Xu, Y.; Suenaga, M. )

    1991-03-01

    The magnetic-field dependence of the irreversibility temperatures follows an {ital H}={ital a}(1{minus}{ital T}{sub {ital r}}({ital H})/{ital T}{sub {ital c}}(0)){sup {ital n}} relationship with {ital n}{congruent}1.5, for pure and alloyed YBa{sub 2}(Cu{sub 1{minus}{ital x}}M{sub {ital x}}){sub 3}O{sub 7+{delta}} with {ital x}=0 and 0.02, where {ital M}=Al, Fe, Ni, and Zn, measured for an applied field parallel to the {ital c} axis. However, for {ital M}=Ni and {ital x}=0.04 and 0.06, {ital n}{congruent}2.0. This relationship is not applicable for either Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} or (Bi,Pb){sub 2}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10} powders. It is also shown that the irreversibility temperature is a strong function of the magnetic hysteresis width {Delta}{ital M} for pure and alloyed YBa{sub 2}Cu{sub 3}O{sub 7}. These results and the measurements of the flux creep {Delta}{ital M}({ital t}) for these specimens suggest that {ital T}{sub {ital r}}({ital H}) is a depinning line rather than a lattice melting or glass-to-liquid phase-transition temperature. However, the conventional flux-creep model cannot account for all of the observed temporal dependences of {Delta}{ital M}({ital t}).

  15. Alkali Metal Salts with Designable Aryltrifluoroborate Anions.

    PubMed

    Iwasaki, Kazuki; Yoshii, Kazuki; Tsuzuki, Seiji; Matsumoto, Hajime; Tsuda, Tetsuya; Kuwabata, Susumu

    2016-09-01

    Aryltrifluoroborate ([ArBF3](-)) has a designable basic anion structure. Various [ArBF3](-)-based anions were synthesized to create novel alkali metal salts using a simple and safe process. Nearly 40 novel alkali metal salts were successfully obtained, and their physicochemical characteristics, particularly their thermal properties, were elucidated. These salts have lower melting points than those of simple inorganic alkali halide salts, such as KCl and LiCl, because of the weaker interactions between the alkali metal cations and the [ArBF3](-) anions and the anions' larger entropy. Moreover, interestingly, potassium cations were electrochemically reduced in the potassium (meta-ethoxyphenyl)trifluoroborate (K[m-OEtC6H4BF3]) molten salt at 433 K. These findings contribute substantially to furthering molten salt chemistry, ionic liquid chemistry, and electrochemistry. PMID:27510799

  16. Alkali Metal Handling Practices at NASA MSFC

    NASA Technical Reports Server (NTRS)

    Salvail, Patrick G.; Carter, Robert R.

    2002-01-01

    NASA Marshall Space Flight Center (MSFC) is NASA s principle propulsion development center. Research and development is coordinated and carried out on not only the existing transportation systems, but also those that may be flown in the near future. Heat pipe cooled fast fission cores are among several concepts being considered for the Nuclear Systems Initiative. Marshall Space Flight Center has developed a capability to handle high-purity alkali metals for use in heat pipes or liquid metal heat transfer loops. This capability is a low budget prototype of an alkali metal handling system that would allow the production of flight qualified heat pipe modules or alkali metal loops. The processing approach used to introduce pure alkali metal into heat pipe modules and other test articles are described in this paper.

  17. Rb-Sr Isotopic Systematics of Alkali-Rich Fragments in the Yamato-74442 LL-Chondritic Breccia

    NASA Technical Reports Server (NTRS)

    Yokoyama, T.; Misawa, K.; Okano, O.; Shih, C.-Y.; Nyquist, L. E.; Simo, J. I.; Tappa, M. J.; Yoneda, S.

    2012-01-01

    Alkali-rich igneous fragments were identified in the brecciated LL-chondrites, Kr henberg (LL5)], Bhola (LL3-6) and Yamato (Y)-74442 (LL4), and show characteristic fractionation patterns of alkaline elements. The K-Rb-Cs-rich fragments in Kr henberg, Bhola, and Y-74442 are very similar in mineralogy and petrography (olivine + pyroxene + glass), suggesting that they could have come from related precursor materials. We have undertaken Rb-Sr isotopic studies on alkali-rich fragments in Y-74442 to precisely determine their crystallization ages and the isotopic signatures of their precursor material(s).

  18. Effect of Al2O3 nano-filler on properties of glass-based seals for solid oxide fuel cells.

    PubMed

    Lee, Dong Bok; Choi, Myong-Jae; Park, Sung; Lee, Jae Chun

    2013-01-01

    This study compares the viscosity and strength of three glass-based seals prepared with or without nano or micron-sized alumina powder used as filler material. Measurements of the viscosity and bending strength of the glass-based seals showed that addition of the nano-sized alumina powder to the glass increased both the high-temperature viscosity and the strength of the sintered glass matrix. Strength tests and observations of the microstructure of the fracture surface of the seal samples confirmed the strengthening of the glass network structure. Conversion of non-bridging oxygen to bridging oxygen is presumed to occur upon the addition of alumina to the glass sample. The strengthening of the alumina-glass composite seal was attributed to the alumina nano-filler and prolonged heat treatment at elevated temperatures.

  19. Effect of Al2O3 nano-filler on properties of glass-based seals for solid oxide fuel cells.

    PubMed

    Lee, Dong Bok; Choi, Myong-Jae; Park, Sung; Lee, Jae Chun

    2013-01-01

    This study compares the viscosity and strength of three glass-based seals prepared with or without nano or micron-sized alumina powder used as filler material. Measurements of the viscosity and bending strength of the glass-based seals showed that addition of the nano-sized alumina powder to the glass increased both the high-temperature viscosity and the strength of the sintered glass matrix. Strength tests and observations of the microstructure of the fracture surface of the seal samples confirmed the strengthening of the glass network structure. Conversion of non-bridging oxygen to bridging oxygen is presumed to occur upon the addition of alumina to the glass sample. The strengthening of the alumina-glass composite seal was attributed to the alumina nano-filler and prolonged heat treatment at elevated temperatures. PMID:23646787

  20. Alkali basalts and enclosed ultramafic xenoliths near Ushuaia, Tierra Del Fuego, Argentina.

    PubMed

    Acevedo, Rogelio Daniel

    2016-01-01

    At the southernmost part of Tierra del Fuego a few outcrops and erratic boulders of alkali basaltic rocks with ultramafic enclaves have been studied. Alkali basalt plugs or pipes hitherto identified are scarce, and host rocks are constituted by slates that belong to Mesozoic deposition. The petrography, texture and composition of the basalt and xenoliths were investigated by petrographic microscope and electron microprobe analysis. Xenocrysts of amphibole and alkali feldspar, phenocrysts of nepheline, olivine, spinel, phlogopite and Fe-Ti minerals (10 %) and a diversity of xenoliths, mainly lherzolitic, pyroxenite and wehrlitic nodules (15 %), but also from metamorphic rocks provenance, are contained in the basalt groundmass (75 %). This finer-grained material is made up of laths or needles of plagioclase, pyroxene, opaque minerals, apatite and glass, with intersertal, hyalopilitic and pilotaxitic. Locally, rock has an even granoblastic texture. Former amygdules are filled by analcite, zeolites, sodalite and calcite. The normative classification, based on nepheline content, conclude that this rock is an alkali basalt. The chemical classification, considering immobile elements as Zr/TiO2 versus Nb/Y indicate an alkali basalt too and plots over the TAS diagram fall in the foidite (Na-rich or nephelinite) and basanite fields. The REE patterns are fractionated (La/Yb primitive mantle normalized is approximately 30). The K-Ar isotopic technique on individual macrocrysts gave ages of 146 ± 5 Ma (amphibole) and 127 ± 4 Ma (alkali feldspar); and K-Ar whole rock datum reported 8.3 ± 0.3 Ma. Nevertheless, fertile samples show geochemical features typical of deep derived material thus, based on the position in the actual tectonic setting, indicate that the basalt is older than its isotopic age. PMID:27610313