Selective adsorption of cationic dyes by UiO-66-NH{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Chen, Qi; He, Qinqin; Lv, Mengmeng; Xu, Yanli; Yang, Hanbiao; Liu, Xueting, E-mail: wmlxt@163.com; Wei, Fengyu, E-mail: weifyliuj@163.com

2015-02-01

Graphical abstract: - Highlights: • Two Zr(IV)-based MOFs can remove cationic dyes more effectively than anionic dyes. • UiO-66 has higher selectivity for cationic dyes after modification with NH{sub 2}. • The mechanism for adsorption selectivity is rationally proposed. - Abstract: Herein, two zirconium(IV)-based MOFs UiO-66 and UiO-66-NH{sub 2} had been successfully prepared by a facile solvothermal method and were characterized by X-ray diffraction (XRD), field emission transmission electron microscopy (FETEM), N{sub 2} adsorption–desorption (BET), X-ray photoelectron spectroscopy (XPS), and zeta potential. They exhibit small size, large surface area, and can remove cationic dyes from aqueous solution more effectively than anionic dyes. This adsorption selectivity is due to the favorable electrostatic interactions between the adsorbents and cationic dyes. Furthermore, owing to the individual micropore structure of UiO-66-NH{sub 2} and its more negative zeta potential resulted from the charge balance for the protonation of –NH{sub 2}, UiO-66-NH{sub 2} displays much higher adsorption capacity for cationic dyes and lower adsorption capacity for anionic dyes than UiO-66.

Vibronic spectra of Gd3+ in metaphosphate glasses: Comparison with Raman and infrared spectra

International Nuclear Information System (INIS)

Hall, D.W.; Brawer, S.A.; Weber, M.J.

1982-01-01

Vibronic sidebands associated with the 6 P/sub 7/2/→ 8 S/sub 7/2/ transition of Gd 3+ -doped metaphosphate glasses are observed using line-narrowed fluorescence techniques. Glasses having metal cations of different mass and charge (La,Al,Mg,Ba) are examined. Vibronic spectra, which probe vibrations about the rare-earth element site, are compared with polarized Raman scattering data and the infrared dielectric constant obtained from near-normal reflectance measurements. Results indicate that in metaphosphate glasses vibronic selection rules are similar to HV (vertical height) Raman selection rules. The wavelengths and relative intensities of peaks in the high-frequency portion of the vibronic spectra change with respect to corresponding peaks in the Raman spectra when the mass and/or charge of Gd 3+ differs significantly from that of the metal cation

Review on cation exchange selectivity coefficients for MX-80 bentonite

International Nuclear Information System (INIS)

Domenech, C.; Arcos, D.; Duro, L.; Sellin, P.

2005-01-01

Full text of publication follows: Bentonite is considered as engineered barrier in the near field of a nuclear waste repository due to its low permeability, what impedes groundwater flow to the nuclear waste, and its high retention capacity (sorption) of radionuclides in the eventuality of groundwater intrusion. One of the main retention processes occurring at the bentonite surface is ion exchange. This process may exert a strong control on the mobility of major pore water cations. Changes in major cation concentration, especially calcium, can affect the dissolution-precipitation of calcite, which in turn controls one of the key parameters in the system: pH. The cation exchange process is usually described according to the Gaines-Thomas convention: Ca 2+ + 2 NaX = CaX 2 + 2 Na + , K Ca = (N Ca x a 2 Na + )/(N 2 Na x a Ca 2+ ) where K Ca is the selectivity coefficient for the Ca by Na exchange, ai is the activity of cation 'i' in solution and NJ the equivalent fractional occupancy of cation 'J' in bentonite. Parameters such as solid to liquid (S:L) ratio and dry density of the solid have an important influence on the value of selectivity coefficients (K ex ). Although in most geochemical modelling works, K ex values are directly taken from experiments conducted at low S:L ratios and low dry densities, the expected conditions in a deep geological nuclear waste repository are higher S:L and higher bentonite density (1.6 g.cm -3 in the SKB design to obtain a fully water saturated density of around 2.0 g.cm -3 ). Experiments focused at obtaining selectivity coefficients under the conditions of interest face the difficulty of achieving a proper extraction and analyses of pore water without disturbing the system by the sampling method itself. In this work we have conducted a complete analyses of published data on MX-80 bentonite cationic exchange in order to assess the effect of the S:L ratio and dry density on the value of the selectivity coefficients determined so far

X-ray luminescent glasses

International Nuclear Information System (INIS)

Takahashi, T.; Yamada, O.

1981-01-01

X-ray luminescent glasses comprising a divalent cation such as an alkaline earth metal or other divalent cations such as pb, cd, or zn, and certain rare earth metaphosphates are suitable as vitreous, x-ray phosphors or x-ray luminescent glass fibers in an x-ray intensifying screen. The glasses have the composition n(Mo X p2o5)((1-y)tb2o3 X yce2o3 X 3p2o5) wherein N is greater than zero but less than or equal to 16, M is an alkaline earth metal or other divalent cation such as pb, cd, or zn, and Y is greater than or equal to zero but less than one

A hydrophobic filter confers the cation selectivity of Zygosaccharomyces rouxii plasma-membrane Na+/H+ antiporter.

Science.gov (United States)

Kinclova-Zimmermannova, Olga; Falson, Pierre; Cmunt, Denis; Sychrova, Hana

2015-04-24

Na(+)/H(+) antiporters may recognize all alkali-metal cations as substrates but may transport them selectively. Plasma-membrane Zygosaccharomyces rouxii Sod2-22 antiporter exports Na(+) and Li(+), but not K(+). The molecular basis of this selectivity is unknown. We combined protein structure modeling, site-directed mutagenesis, phenotype analysis and cation efflux measurements to localize and characterize the cation selectivity region. A three-dimensional model of the ZrSod2-22 transmembrane domain was generated based on the X-ray structure of the Escherichia coli NhaA antiporter and primary sequence alignments with homologous yeast antiporters. The model suggested a close proximity of Thr141, Ala179 and Val375 from transmembrane segments 4, 5 and 11, respectively, forming a hydrophobic hole in the putative cation pathway's core. A series of mutagenesis experiments verified the model and showed that structural modifications of the hole resulted in altered cation selectivity and transport activity. The triple ZrSod2-22 mutant T141S-A179T-V375I gained K(+) transport capacity. The point mutation A179T restricted the antiporter substrate specificity to Li(+) and reduced its transport activity, while serine at this position preserved the native cation selectivity. The negative effect of the A179T mutation can be eliminated by introducing a second mutation, T141S or T141A, in the preceding transmembrane domain. Our experimental results confirm that the three residues found through modeling play a central role in the determination of cation selectivity and transport activity in Z. rouxii Na(+)/H(+) antiporter and that the cation selectivity can be modulated by repositioning a single local methyl group. Copyright © 2015 Elsevier Ltd. All rights reserved.

The role of different network modifying cations on the speciation of the Co2 + complex in silicates and implication in the investigation of historical glasses

Science.gov (United States)

Fornacelli, Cristina; Ceglia, Andrea; Bracci, Susanna; Vilarigues, Marcia

2018-01-01

In the last decades the speciation of the cobalt complex in a glass matrix has been extensively studied. Bivalent cobalt ions in glasses of different composition commonly adopt a tetrahedral coordination, though hexa- or penta-coordinated species are also possible. Changes in the absorbance spectrum of Co-doped glasses were attested in previous studies according to the introduction of different modifying cations. A shifting of the first sub-band characterizing the typical triplets of tetrahedral Co2 + ions in both the visible and near infrared regions was observed, but discrepancies in literature suggested a relevant role of glass composition on the definition of the optical signature of cobalt. Co-doped glasses with different composition (soda-lime, potash-lime, mixed alkali and ZnO-Na2O-CaO-SiO2) were studied via Fiber Optic Reflectance Spectroscopy (FORS). Pseudo-Voigt functions were used for the deconvolution of the absorbance spectra and the features of the bands characteristic of each cobalt complex were investigated. The structural role played by each modifying cation and the fundamental implications of glass basicity on the speciation of different Co-complexes were stressed. Changes in glass structure resulted in different equilibria between the three absorbing species whose specific optical signatures in the 480-530 nm region interact to determine the resulting absorbance spectrum.

Cations form sequence selective motifs within DNA grooves via a combination of cation-pi and ion-dipole/hydrogen bond interactions.

Science.gov (United States)

Stewart, Mikaela; Dunlap, Tori; Dourlain, Elizabeth; Grant, Bryce; McFail-Isom, Lori

2013-01-01

The fine conformational subtleties of DNA structure modulate many fundamental cellular processes including gene activation/repression, cellular division, and DNA repair. Most of these cellular processes rely on the conformational heterogeneity of specific DNA sequences. Factors including those structural characteristics inherent in the particular base sequence as well as those induced through interaction with solvent components combine to produce fine DNA structural variation including helical flexibility and conformation. Cation-pi interactions between solvent cations or their first hydration shell waters and the faces of DNA bases form sequence selectively and contribute to DNA structural heterogeneity. In this paper, we detect and characterize the binding patterns found in cation-pi interactions between solvent cations and DNA bases in a set of high resolution x-ray crystal structures. Specifically, we found that monovalent cations (Tl⁺) and the polarized first hydration shell waters of divalent cations (Mg²⁺, Ca²⁺) form cation-pi interactions with DNA bases stabilizing unstacked conformations. When these cation-pi interactions are combined with electrostatic interactions a pattern of specific binding motifs is formed within the grooves.

Glass–water interaction: Effect of high-valence cations on glass structure and chemical durability

Energy Technology Data Exchange (ETDEWEB)

Hopf, J.; Kerisit, Sebastien N.; Angeli, F.; Charpentier, Thibault M.; Icenhower, Jonathan P.; McGrail, Bernard P.; Windisch, Charles F.; Burton, Sarah D.; Pierce, Eric M.

2016-05-15

Borosilicate glass is a durable solid, but it dissolves when in contact with aqueous fluids. The dissolution mechanism, which involves a variety of sequential reactions that occur at the solid-fluid interface, has important implications for the corrosion resistance of industrial and nuclear waste glasses. In this study, spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high–valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na2O–Al2O3–B2O3–HfO2–SiO2 system (e.g., Na/[Al+B] = 1.0 and HfO2/SiO2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N4 (tetrahedral boron/total boron) and increases the amount of Si—O—Hf moieties in the glass. Results from flow–through experiments conducted under dilute and near–saturated conditions show a decrease of approximately 100× or more in the dissolution rate over the series from 0 to 20 mol% HfO2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveals a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the stronger binding of Si sites that deposit on the surface from the influent when Hf is present in the glass. As a result, the residence time at the glass surface of these newly-formed Si sites is longer in the presence of Hf, which increases the density of anchor sites from which altered layers

Inversion of membrane surface charge by trivalent cations probed with a cation-selective channel.

Science.gov (United States)

Gurnev, Philip A; Bezrukov, Sergey M

2012-11-13

We demonstrate that the cation-selective channel formed by gramicidin A can be used as a reliable sensor for studying the multivalent ion accumulation at the surfaces of charged lipid membranes and the "charge inversion" phenomenon. In asymmetrically charged membranes with the individual leaflets formed from pure negative and positive lipids bathed by 0.1 M CsCl solutions the channel exhibits current rectification, which is comparable to that of a typical n/p semiconductor diode. We show that even at these highly asymmetrical conditions the channel conductance can be satisfactorily described by the electrodiffusion equation in the constant field approximation but, due to predictable limitations, only when the applied voltages do not exceed 50 mV. Analysis of the changes in the voltage-dependent channel conductance upon addition of trivalent cations allows us to gauge their interactions with the membrane surface. The inversion of the sign of the effective surface charge takes place at the concentrations, which correlate with the cation size. Specifically, these concentrations are close to 0.05 mM for lanthanum, 0.25 mM for hexaamminecobalt, and 4 mM for spermidine.

Investigations of glass structure using fluorescence line narrowing and moleuclar dynamics simulations

International Nuclear Information System (INIS)

Weber, M.J.; Brawer, S.A.

1982-01-01

The local structure at individual ion sites in simple and multicomponent glasses is simulated using methods of molecular dynamics. Computer simulations of fluoroberyllate glasses predict a range of ion separations and coordination numbers that increases with increasing complexity of the glass composition. This occurs at both glass forming and glass modifying cation sites. Laser-induced fluorescence line-narrowing techniques provide a unique probe of the local environments of selected subsets of ions and are used to measure site to site variations in the electronic energy levels and transition probabilities of rare earth ions. These and additional results from EXAFS, neutron and x-ray diffraction, and NMR experiments are compared with simulated glass structures

Selective Facet Reactivity During Cation Exchange in Cadmium Sulfide Nanorods

Energy Technology Data Exchange (ETDEWEB)

Sadtler, Bryce; Demchenko, Denis; Zheng, Haimei; Hughes, Steven; Merkle, Maxwell; Dahmen, Ulrich; Wang, Lin-Wang; Alivisatos, A. Paul

2008-12-18

The partial transformation of ionic nanocrystals through cation exchange has been used to synthesize nanocrystal heterostructures. We demonstrate that the selectivity for cation exchange to take place at different facets of the nanocrystal plays an important role in determining the resulting morphology of the binary heterostructure. In the case of copper I (Cu+) cation exchange in cadmium sulfide (CdS) nanorods, the reaction starts preferentially at the ends of the nanorods such that copper sulfide (Cu2S) grows inwards from either end. The resulting morphology is very different from the striped pattern obtained in our previous studies of silver I (Ag+) exchange in CdS nanorods where non-selective nucleation of silver sulfide (Ag2S) occurs. From interface formation energies calculated for several models of epitaxialconnections between CdS and Cu2S or Ag2S, we infer the relative stability of each interface during the nucleation and growth of Cu2S or Ag2S within the CdS nanorods. The epitaxial connections of Cu2S to the end facets of CdS nanorods minimize the formation energy, making these interfaces stable throughout the exchange reaction. However, as the two end facets of wurtzite CdS nanorods are crystallographically nonequivalent, asymmetric heterostructures can be produced.

Selective functionalization of patterned glass surfaces

NARCIS (Netherlands)

Ploetz, E.; Visser, B.; Slingenbergh, W.; Evers, K.; Martinez-Martinez, D.; Pei, Y. T.; Feringa, B. L.; De Hosson, J. Th. M.; Cordes, T.; van Dorp, W. F.

2014-01-01

Tailored writing and specific positioning of molecules on nanostructures is a key step for creating functional materials and nano-optical devices, or interfaces for synthetic machines in various applications. We present a novel approach for the selective functionalization of patterned glass surfaces

Fixation by ion exchange of toxic materials in a glass matrix

International Nuclear Information System (INIS)

Litovitz, T.A.; Simmons, C.J.; Simmons, J.H.; Macedo, P.B.

1981-01-01

A process for disposing of toxic materials such as radioactive waste comprises reacting a porous silicate glass or silica gel, having interconnected pores and alkali metal cations. Group 1b metal cations and/or ammonium cation bonded to silicon through divalent oxygen linkages on the internal surfaces of said pores, with a toxic material containing toxic cations as well as non-cationic portions. The toxic cations are capable of displacing the alkali metal cations, Group 1b metal cations and/or ammonium cations to provide a distribution of internal silicon-bonded toxic cation oxide groups within the pores of the glass or silica gel. (author)

Effect of the nature of alkali and alkaline-earth oxides on the structure and crystallization of an alumino-borosilicate glass developed to immobilize highly concentrated nuclear waste solutions

International Nuclear Information System (INIS)

Quintas, A.; Caurant, D.; Majerus, O.; Charpentier, T.; Dussossoy, J.L.

2008-01-01

A complex rare-earth rich alumino-borosilicate glass has been proved to be a good candidate for the immobilization of new high level radioactive wastes. A simplified seven-oxides composition of this glass was selected for this study. In this system, sodium and calcium cations were supposed in other works to simulate respectively all the other alkali (R + = Li + , Rb + , Cs + ) and alkaline-earth (R 2+ = Sr 2+ , Ba 2+ ) cations present in the complex glass composition. Moreover, neodymium or lanthanum are used here to simulate all the rare-earths and actinides occurring in waste solutions. In order to study the impact of the nature of R + and R 2+ cations on both glass structure and melt crystallization tendency during cooling, two glass series were prepared by replacing either Na + or Ca 2+ cations in the simplified glass by respectively (Li + , K + , Rb + , Cs + ) or (Mg 2+ , Sr 2+ , Ba 2+ ) cations. From these substitutions, it was established that alkali ions are preferentially involved in the charge compensation of (AlO 4 ) - entities in the glass network comparatively to alkaline-earth ions. The glass compositions containing calcium give way to the crystallization of an apatite silicate phase bearing calcium and rare-earth ions. The melt crystallization tendency during cooling strongly varies with the nature of the alkaline-earth. (authors)

Cation selectivity of the plasma membrane of tobacco protoplasts in the electroporated state.

Science.gov (United States)

Wegner, Lars H

2013-08-01

Cation selectivity of the cellular membrane of tobacco culture cells (cell line 'bright yellow-2') exposed to pulsed electric fields in the millisecond range was investigated. The whole cell configuration of the patch clamp technique was established on protoplasts prepared from these cells. Ion selectivity of the electroporated membrane was investigated by measuring the reversal potential of currents passing through field-induced pores. To this end the membrane was hyper- or depolarized for 10ms (prepulse); subsequently the voltage was driven to opposite polarity at a constant rate (+40 or -40mV/ms, respectively). The experiment was started by polarizing the membrane to moderately negative or positive voltages (prepulse potential ±150mV) that would not induce pore formation. Subsequently, an extended voltage range was scanned in the porated state of the membrane (prepulse potential ±600mV). IV curves in the porated and the non-porated state (obtained at the same prepulse polarity) were superimposed to determine the voltage at which both curves intersected ('Intersection potential'). Using a modified version of the Goldmann-Hodgkin-Katz equation relative permeabilities to Ca(2+) and various monovalent alkali and organic cations were calculated. Pores were found to be fairly cation selective, with a selectivity sequence determined to be Ca(2+)>Li(+)>Rb(+)≈K(+)≈Na(+)>TEA(+)≈TBA(+)>Cl(-). Relative permeability to monovalent cations was inversely related to the ionic diameter. By fitting a formalism suggested by Dwyer at al. (J. Gen. Physiol. 75 (1980), 469-492) the effective average diameter of field induced pores was estimated to be about 1.8nm. Implications of these results for biotechnology and electroporation theory are discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

Fixation by ion exchange of toxic materials in a glass matrix

International Nuclear Information System (INIS)

Simmons, C.J.; Simmons, J.H.; Macedo, P.B.; Litovitz, T.A.

1982-01-01

A process is reported for reacting a porous silicate or borosilicate glass or silica gel with alkali metal cations, Group lb cations and/or ammonium cations bonded to the silicon through divalent oxygen linkages on the internal surfaces of the pores. Ion exchange of the cations with toxic or radioactive cations was possible resulting in a distribution of internal silicon-bonded toxic cation oxide groups within the pores of the glass or silica gel. The ion exchange reaction may be done successfully with acidic, neutral or alkaline pH solutions. The aim of the immobilization is for permanent storage of hazardous materials such as Hg 2+ , Hg + , Cd 2+ , Tl + , Pb 2+ and radioactive cations

Selective crystallization of cations with crown ethers; Selektive Kristallisation von Kationen mit Kronenethern

Energy Technology Data Exchange (ETDEWEB)

Heffels, Dennis Egidius

2014-07-04

The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

Selection of Optical Glasses Using Buchdahl's Chromatic Coordinate

Science.gov (United States)

Griffin, DeVon W.

1999-01-01

This investigation attempted to extend the method of reducing the size of glass catalogs to a global glass selection technique with the hope of guiding glass catalog offerings. Buchdahl's development of optical aberration coefficients included a transformation of the variable in the dispersion equation from wavelength to a chromatic coordinate omega defined as omega = (lambda - lambda(sub 0))/ 1 + 2.5(lambda - lambda(sub 0)) where lambda is the wavelength at which the wavelength is calculated and lambda(sub 0) is a base wavelength about which the expansion is performed. The advantage of this approach is that the dispersion equation may be written in terms of a simple power series and permits direct calculation of dispersion coefficients. While several promising examples were given, a systematic application of the technique to an entire glass catalog and analysis of the subsequent predictions was not performed. The goal of this work was to apply the technique in a systematic fashion to glasses in the Schoft catalog and assess the quality of the predictions.

Facile synthesis of surface-functionalized magnetic nanocomposites for effectively selective adsorption of cationic dyes

Science.gov (United States)

Hua, Yani; Xiao, Juan; Zhang, Qinqin; Cui, Chang; Wang, Chuan

2018-04-01

A new magnetic nano-adsorbent, polycatechol modified Fe3O4 magnetic nanoparticles (Fe3O4/PCC MNPs) were prepared by a facile chemical coprecipitation method using iron salts and catechol solution as precursors. Fe3O4/PCC MNPs owned negatively charged surface with oxygen-containing groups and showed a strong adsorption capacity and fast adsorption rates for the removal of cationic dyes in water. The adsorption capacity of methylene blue (MB), cationic turquoise blue GB (GB), malachite green (MG), crystal violet (CV) and cationic pink FG (FG) were 60.06 mg g- 1, 70.97 mg g- 1, 66.84 mg g- 1, 66.01 mg g- 1 and 50.27 mg g- 1, respectively. The adsorption mechanism was proposed by the analyses of the adsorption isotherms and adsorption kinetics of cationic dyes on Fe3O4/PCC MNPs. Moreover, the cationic dyes adsorbed on the MNPs as a function of contact time, pH value, temperature, coexisting cationic ions and ion strength were also investigated. These results suggested that the Fe3O4/PCC MNPs is promising to be used as a magnetic adsorbent for selective adsorption of cationic dyes in wastewater treatment.

Investigation into structure of berylliumaluminium silicate glasses and crystals by X-ray spectroscopy

International Nuclear Information System (INIS)

Tykachinskij, I.D.; Gorbachev, V.V.; Petrakov, V.N.; Varshal, B.G.; Bystrakov, A.S.; Dmitriev, I.D.; Zatsepin, A.F.; Blaginina, L.A.

1983-01-01

For the purpose of elucidating the structural state of Be 2+ and Al 3+ ions as well as the nature of Be-O bond the investigation of glasses obtained from BeO, Al 2 O 3 and SiO 2 with different component composition is undertaken by X-ray spectroscopy. In three-component beryllium alumosilicate glasses at the ratio γ=Al 2 O 3 /BeO=0.34-1.92 the main part of Al 3+ cations forms AlO 4 groups. Be 2+ cations probably occupy several non-equivalent states. At the ''crystal-glass'' transition the reorganization of near structure of beryllium alumosilicate frame with appearance in a glass in contrast to crystal analog of beryllium cations playing the role of a glass former (being a part of glass net) as well as a modifier role occurs. For compositions with γ=1 the degree of ionic character of the Be-O bond is the greatest. The increase of Be 2+ cations fraction being a part of the glass net is characteristic feature of the glasses with parameter values γ not equal to 1

Selective alkylation by photogenerated aryl and vinyl cation

NARCIS (Netherlands)

Slegt, Micha

2006-01-01

Seven para-substituted phenyl cations and the parent phenyl cation were prepared from iodonium salt precursors. Product studies revealed remarkable chemoselectivity and regioselectivity that could be related to the spin multiplicity of the cations. Also an universal method to fingerprint singlet and

Analysis of Broad-band Frequency Selective Shielding Glass by FDTD method

OpenAIRE

笠嶋, 善憲; Kasashima, Yoshinori

2010-01-01

A frequency Selective shielding (FSS) glass is a print of many same size antennas on a sheet of glass, and it has high shielding properties for one specific frequency. In the past, the author analyzed theoretically the characteristics of the FSS, as a large scale array antenna. The FSS has narrow-band shielding characteristics. This time, the author analyzed accurately the characteristics of a FSS glass being a print of many same size dipole antennas on a sheet of glass by FDTD method. As the...

Molecular dynamics study of a nuclear waste glass matrix with plutonium

International Nuclear Information System (INIS)

Meis, C.; Delaye, J.M.; Ghaleb, D.

1999-01-01

Molecular dynamics simulation techniques were applied to model the incorporation of plutonium in the French nuclear waste glass matrix. Born-Mayer-Huggins analytical potentials were established to characterize short-range interactions between Pu-O and Pu-Pu pairs; the potentials were fitted to the structural properties of plutonium dioxide in the light of a recent experimental study showing that plutonium is found as Pu(IV) in the glass. The transferability of the established potentials to the glass structure is discussed, and the potential parameters are further refined by molecular dynamics simulations in an aluminoborosilicate glass to obtain mean Pu-O interatomic distances and first-neighbor coordination numbers matching the experimental values as closely as possible. Previously published Born-Mayer-Huggins potentials supplemented by Stillinger-Weber three-body terms were used for oxygen-cation and cation-cation interactions. The difficulties encountered in establishing a Pu-O potential that provides satisfactory results in both oxides and glasses are also discussed

Selectivity of externally facing ion-binding sites in the Na/K pump to alkali metals and organic cations.

Science.gov (United States)

Ratheal, Ian M; Virgin, Gail K; Yu, Haibo; Roux, Benoît; Gatto, Craig; Artigas, Pablo

2010-10-26

The Na/K pump is a P-type ATPase that exchanges three intracellular Na(+) ions for two extracellular K(+) ions through the plasmalemma of nearly all animal cells. The mechanisms involved in cation selection by the pump's ion-binding sites (site I and site II bind either Na(+) or K(+); site III binds only Na(+)) are poorly understood. We studied cation selectivity by outward-facing sites (high K(+) affinity) of Na/K pumps expressed in Xenopus oocytes, under voltage clamp. Guanidinium(+), methylguanidinium(+), and aminoguanidinium(+) produced two phenomena possibly reflecting actions at site III: (i) voltage-dependent inhibition (VDI) of outwardly directed pump current at saturating K(+), and (ii) induction of pump-mediated, guanidinium-derivative-carried inward current at negative potentials without Na(+) and K(+). In contrast, formamidinium(+) and acetamidinium(+) induced K(+)-like outward currents. Measurement of ouabain-sensitive ATPase activity and radiolabeled cation uptake confirmed that these cations are external K(+) congeners. Molecular dynamics simulations indicate that bound organic cations induce minor distortion of the binding sites. Among tested metals, only Li(+) induced Na(+)-like VDI, whereas all metals tested except Na(+) induced K(+)-like outward currents. Pump-mediated K(+)-like organic cation transport challenges the concept of rigid structural models in which ion specificity at site I and site II arises from a precise and unique arrangement of coordinating ligands. Furthermore, actions by guanidinium(+) derivatives suggest that Na(+) binds to site III in a hydrated form and that the inward current observed without external Na(+) and K(+) represents cation transport when normal occlusion at sites I and II is impaired. These results provide insights on external ion selectivity at the three binding sites.

Influence of processing conditions on the glass-crystal transition into borosilicate glasses

Energy Technology Data Exchange (ETDEWEB)

Deschanels, X.; Cachia, J.N.; Lopez, C.; Peuget, S. [CEA Marcoule, BP 17171, 30207 Bagnols sur Ceze (France)

2008-07-01

The precipitation of a crystalline phase in glass is observed when one element exceeds its loading limit (i.e.: solubility limit). In this work we have studied the solubility of different actinides and surrogates (lanthanides and hafnium) in borosilicate glass used for the immobilization of the high-level nuclear waste (HLW glasses). The results obtained show an increase of the solubility limits of these elements with the processing temperature and the redox potential of the melt. The elements at the oxidation state (III) exhibit a higher solubility than the element at oxidation state (IV). In this framework, cerium is an interesting element because its oxidation state tunes from (IV) to (III) as a function of the processing conditions. It is shown that the solubility of cerium can be multiplied by a factor of 20 at 1100 C. degrees. In order to have a better understanding of the mechanisms that underline the evolution of the solubility, XAFS and NMR investigation has been undertaken. Trivalent elements present the characteristics of network-modified cations while tetravalent elements look like network-former cations.

Properties of M1-M2-Si-Al-O-N glasses (M1 = La or Nd, M2 = Y or Er)

Energy Technology Data Exchange (ETDEWEB)

Pomeroy, M.J.; Nestor, E.; Hampshire, S. [Limerick Univ. (Ireland). Materials and Surface Science Inst.; Ramesh, R. [Littelfuse Ireland, Dundalk, Co. Louth (Ireland)

2002-07-01

Mixed lanthanide cation oxynitride glasses have been prepared in the M1 - M2 - Si-Al-O-N systems where M1 = La or Nd and M2 = Y or Er. The densities ({rho}), Young's moduli (E), microhardnesses (H{sub v}), glass transition temperatures (T{sub g}), dilatometric softening temperatures (T{sub dil}) and coefficients of thermal expansion (CTE) of 13 glasses were determined. The molar volume values (MV) calculated from density data, E, H{sub v}, T{sub g}, T{sub dil} and CTE values were all found to vary linearly with the effective cation field strength arising from the M1 and M2 modifier cations. Least squares intercept and slope values are presented which correlate each property to effective cation field strength together with error values which arise from glass and specimen preparation and measurement inconsistencies. These linear correlations clearly indicate that the overall glass structure remains the same for each of the thirteen glasses with only the modifier cation(s) having any influence. This influence appears to be a cross-linking effect, the strength of which increases as the effective cation field strength of the M1, M2 modifiers increases. (orig.)

Liquid-solid extraction of metallic cations by cationic amphiphiles

International Nuclear Information System (INIS)

Mueller, Wolfram; Sievers, Torsten K.; Zemb, Thomas; Diat, Olivier; Sievers, Torsten K.; Dejugnat, Christophe

2012-01-01

In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

Use of cation selective membrane and acid addition for PH control in two-dimensional electrokinetic remediation of copper

Energy Technology Data Exchange (ETDEWEB)

Chan, M.S.M.; Lynch, R.J. [Cambridge Univ., Engineering Dept. (United Kingdom); Ilett, D.J. [AEA Technology, Harwell, Oxfordshire (United Kingdom)

2001-07-01

The feasibility of using a combination of a cation selective membrane and acid addition for pH control in electrokinetic remediation to toxic and heavy metals from low-permeability soil has been investigated. The high pH generated during the remediation process, as a result of surplus OH{sup -} ions, may cause metal ions to precipitate as hydroxides at or near the cathodes. This region of high pH is known to be associated with high electrical resistance, which limits the remediation efficiency by inhibiting current flow through the soil. One way to control pH is by adding acid to neutralize the OH{sup -} ions. However, preliminary work showed that addition of acid to the cathodic region was not effective in preventing the spread of the alkaline zone from cathodes toward anodes. Precipitates were formed before metal ions reached the cathodic region. Therefore, another method of pH control was investigated, using a cation selective membrane to enhance the electrokinetic process. The membrane was placed in front of the cathodes to contain the OH{sup -} ions generated, and confine the precipitates of metal hydroxide to a small cathodic region. The clean-up of a contaminated site was modelled in a rectangular tank, using silt as the low permeability soul and copper to simulate the contamination. The objective was to redistribute the contaminant so as to concentrate it into a small area. Three experiments were performed with the following methods of pH control: (1) acid addition, (2) use of a cation selective membrane and (3) a combination of acid addition and a cation selective membrane. Using the combined approach, it was found that 75% of the target clean-up section (bounded by the cation selective membrane and the anodes) had more than 40% of the initial copper removed. The general efficiency of remediation increased in the following order. (orig.)

Hydrothermal reaction of albite and a sodium aluminosilicate glass: A solid-state NMR study

Science.gov (United States)

Yang, Wang-hong Alex; Kirkpatrick, R. James

1989-04-01

We present here a solid-state NMR study of the structure and chemical composition of the products and mechanisms of the reaction of crystalline low albite and a glass of nearly albite composition with aqueous solutions of pH from 1 to 11 at 250°C. For the crystalline albite, there are no detectable bulk or surface structural changes due to aqueous attack, consistent with the idea that both cation exchange and disruption of the aluminosilicate framework occur only near the mineral/solution interface and that the hydrated surface layer, if it exists, is not more than about 30 Å thick. This reaction occurs by solution/reprecipitation, and its rate decreases with increasing solution pH, supporting the idea that the dissolution of feldspar is initiated by cation-exchange. For the glass, the reaction proceeds by cation exchange of protons for Na +, incorporation of molecular water into the bulk glass, and a small amount of depolymerization of the aluminosilicate framework in the interior of the glass. Cation exchange becomes less important with increasing solution pH. The incorporation of molecular water and cation-exchange cause structural changes in the glass via solidstate adjustment without dissolution/reprecipitation. The large cations in the hydrated glass (Na and K) probably have a shell of water molecules around them, with a maximum average coordination number of six. The secondary phases formed from both albite and the glass are often amorphous and can be well characterized by NMR. The compositional and structural variations of the amorphous phases are important factors in these reactions and cannot be ignored in theoretical models of aluminosilicate dissolution. As expected, the aluminum coordination in the secondary phases changes from six-fold to four-fold as the solution pH increases.

Development of phosphate glass microspheres containing holmium for selective internal radiotherapy

International Nuclear Information System (INIS)

Barros Filho, Eraldo Cordeiro

2016-01-01

The selective internal radiotherapy is an alternative for some kinds of cancer as the hepatocellular carcinoma (HCC) or primary liver cancer treatment. In this treatment, glass or polymer microspheres containing radionuclides inside their structure are introduced in the liver through hepatic artery and trapped at the arterioles that feed the tumor. In this work, the development of phosphate glasses containing holmium for production of microspheres and their application in Brazil are proposed. The developed glasses presented suitable chemical durability, density of 2,7(3) g/cm 3 , high thermal stability and the impurities contained therein do not preclude the treatment. The microspheres were produced by the flame method and the gravitational fall method, and were characterized by means of several techniques to evaluate shape, average particle size, activity and biocompatibility suitable for selective internal radiotherapy. Based in the main results, the submission to in vivo tests is proposed. (author)

Diphtheria toxin-induced channels in Vero cells selective for monovalent cations

International Nuclear Information System (INIS)

Sandvig, K.; Olsnes, S.

1988-01-01

Ion fluxes associated with translocation of diphtheria toxin across the surface membrane of Vero cells were studied. When cells with surface-bound toxin were exposed to low pH to induce toxin entry, the cells became permeable to Na+, K+, H+, choline+, and glucosamine+. There was no increased permeability to Cl-, SO4(-2), glucose, or sucrose, whereas the uptake of 45 Ca2+ was slightly increased. The influx of Ca2+, which appears to be different from that of monovalent cations, was reduced by several inhibitors of anion transport and by verapamil, Mn2+, Co2+, and Ca2+, but not by Mg2+. The toxin-induced fluxes of N+, K+, and protons were inhibited by Cd2+. Cd2+ also protected the cells against intoxication by diphtheria toxin, suggesting that the open cation-selective channel is required for toxin translocation. The involvement of the toxin receptor is discussed

Analysis of Various Frequency Selective Shielding Glass by FDTD method

OpenAIRE

笠嶋, 善憲; Kasashima, Yoshinori

2012-01-01

A frequency Selective shielding (FSS) glass is a print of many same size antennas on a sheet of glass, and it has high shielding properties for one specific frequency. This time, the author analyzed characteristics of various FSSs whose antenna types are different by FDTD method. The antenna types are cross dipole, circular loop, square loop, circular patch, and square patch. As the result, the FSSs can be composed of the various types of the antennas, and the FSSs have broad-band shielding c...

Glass and Glass-Ceramic Materials from Simulated Composition of Lunar and Martian Soils: Selected Properties and Potential Applications

Science.gov (United States)

Ray, C. S.; Sen, S.; Reis, S. T.; Kim, C. W.

2005-01-01

In-situ resource processing and utilization on planetary bodies is an important and integral part of NASA's space exploration program. Within this scope and context, our general effort is primarily aimed at developing glass and glass-ceramic type materials using lunar and martian soils, and exploring various applications of these materials for planetary surface operations. Our preliminary work to date have demonstrated that glasses can be successfully prepared from melts of the simulated composition of both lunar and martian soils, and the melts have a viscosity-temperature window appropriate for drawing continuous glass fibers. The glasses are shown to have the potential for immobilizing certain types of nuclear wastes without deteriorating their chemical durability and thermal stability. This has a direct impact on successfully and economically disposing nuclear waste generated from a nuclear power plant on a planetary surface. In addition, these materials display characteristics that can be manipulated using appropriate processing protocols to develop glassy or glass-ceramic magnets. Also discussed in this presentation are other potential applications along with a few selected thermal, chemical, and structural properties as evaluated up to this time for these materials.

Theoretical studies on selectivity of dibenzo-18-crown-6-ether for alkaline earth divalent cations

Energy Technology Data Exchange (ETDEWEB)

Heo, Jiyoung [Sangmyung Univ., Seoul (Korea, Republic of)

2012-04-15

Crown ether is one of well-known host molecules and able to selectively sequester metal cation. We employed M06-2X density functional theory with IEFPCM and SMD continuum solvation models to study selectivity of dibenzo-18-crown-6-ether (DB18C6) for alkaline earth dications, Ba{sup 2+}, Sr{sup 2+}, Ca{sup 2+}, and Mg{sup 2+} in the gas phase and in aqueous solution. Mg{sup 2+} showed predominantly strong binding affinity in the gas phase because of strong polarization of CO bonds by cation. In aqueous solution, binding free energy differences became smaller among these dications. However, Mg{sup 2+} had the best binding, being incompatible with experimental observations in aqueous solution. The enthalpies of the dication exchange reaction between DB18C6 and water cluster molecules were computed as another estimation of selectivity in aqueous solution. These results also demonstrated that Mg{sup 2+} bound to DB18C6 better than Ba{sup 2+}. We speculated that the species determining selectivity in water could be 2:1 complexes of two DB18C6s and one dication.

Q-Speciation and Network Structure Evolution in Invert Calcium Silicate Glasses.

Science.gov (United States)

Kaseman, Derrick C; Retsinas, A; Kalampounias, A G; Papatheodorou, G N; Sen, S

2015-07-02

Binary silicate glasses in the system CaO-SiO2 are synthesized over an extended composition range (42 mol % ≤ CaO ≤ 61 mol %), using container-less aerodynamic levitation techniques and CO2-laser heating. The compositional evolution of Q speciation in these glasses is quantified using (29)Si and (17)O magic angle spinning nuclear magnetic resonance spectroscopy. The results indicate progressive depolymerization of the silicate network upon addition of CaO and significant deviation of the Q speciation from the binary model. The equilibrium constants for the various Q species disproportionation reactions for these glasses are found to be similar to (much smaller than) those characteristic of Li (Mg)-silicate glasses, consistent with the corresponding trends in the field strengths of these modifier cations. Increasing CaO concentration results in an increase in the packing density and structural rigidity of these glasses and consequently in their glass transition temperature Tg. This apparent role reversal of conventional network-modifying cations in invert alkaline-earth silicate glasses are compared and contrasted with that in their alkali silicate counterparts.

Actinide cation-cation complexes

International Nuclear Information System (INIS)

Stoyer, N.J.; Seaborg, G.T.

1994-12-01

The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO 2 + ) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO 2 + ; therefore, cation-cation complexes indicate something unique about AnO 2 + cations compared to actinide cations in general. The first cation-cation complex, NpO 2 + ·UO 2 2+ , was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO 2 + species, the cation-cation complexes of NpO 2 + have been studied most extensively while the other actinides have not. The only PuO 2 + cation-cation complexes that have been studied are with Fe 3+ and Cr 3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO 2 + ·UO 2 2+ , NpO 2 + ·Th 4+ , PuO 2 + ·UO 2 2+ , and PuO 2 + ·Th 4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M -1

Liquid-solid extraction of cationic metals by cationic amphiphiles

International Nuclear Information System (INIS)

Muller, W.

2010-01-01

In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author) [fr

Structural and crystallisation study of a rare earth alumino borosilicate glass designed for nuclear waste confinement

International Nuclear Information System (INIS)

Quintas, A.

2007-09-01

This work is devoted to the study of a rare earth alumino borosilicate glass, which molar composition is 61,81 SiO 2 - 3,05 Al 2 O 3 - 8,94 B 2 O 3 - 14,41 Na 2 O - 6,33 CaO - 1,90 ZrO 2 - 3,56 Nd 2 O 3 , and envisaged for the immobilization of nuclear wastes originating from the reprocessing of high discharge burn up spent fuel. From a structural viewpoint, we investigated the role of the modifier cations on the arrangement of the glass network through different modifications of the glass composition: variation of the Na/Ca ratio and modification of the nature of the alkali and alkaline earth cations. The NMR and Raman spectroscopic techniques were useful to determine the distribution of modifier cations among the glass network and also to cast light on the competition phenomena occurring between alkali and alkaline earth cations for charge compensation of [AlO 4 ] - and [BO 4 ] - species. The neodymium local environment could be probed by optical absorption and EXAFS spectroscopies which enabled to better understand the insertion mode of Nd 3+ ions among the silicate domains of the glass network. Concerning the crystallization behavior we were interested in how the glass composition may influence the crystallization processes and especially the formation of the apatite phase of composition Ca 2 Nd 8 (SiO 4 ) 6 O 2 . In particular, this work underlined the important role of both alkaline earth and rare earth cations on the crystallization of the apatite phase. (author)

Liquid-Liquid Phase Separation in Model Nuclear Waste Glasses: A Solid-State Double-Resonance NMR Study

Energy Technology Data Exchange (ETDEWEB)

Martineau, Ch.; Michaelis, V.K.; Kroeker, S. [Univ Manitoba, Dept Chem, Winnipeg, MB R3T 2N2 (Canada); Schuller, S. [CEA Valrho Marcoule, LDMC, SECM, DTCD, DEN, F-30207 Bagnols Sur Ceze (France)

2010-07-01

Double-resonance nuclear magnetic resonance (NMR) techniques are used in addition to single-resonance NMR experiments to probe the degree of mixing between network-forming cations Si and B, along with the modifier cations Cs{sup +} and Na{sup +} in two molybdenum-bearing model nuclear waste glasses. The double-resonance experiments involving {sup 29}Si in natural abundance are made possible by the implementation of a CPMG pulse-train during the acquisition period of the usual REDOR experiments. For the glass with lower Mo content, the NMR results show a high degree of Si-B mixing, as well as an homogeneous distribution of the cations within the borosilicate network, characteristic of a non-phase-separated glass. For the higher-Mo glass, a decrease of B-Si(Q{sup 4}) mixing is observed, indicating phase separation. {sup 23}Na and {sup 133}Cs NMR results show that although the Cs{sup +} cations, which do not seem to be influenced by the molybdenum content, are spread within the borate network, there is a clustering of the Na{sup +} cations, very likely around the molybdate units. The segregation of a Mo-rich region with Na{sup +} cations appears to shift the bulk borosilicate glass composition toward the metastable liquid liquid immiscibility region and induce additional phase separation. Although no crystallization is observed in the present case, this liquid liquid phase separation is likely to be the first stage of crystallization that can occur at higher Mo loadings or be driven by heat treatment. From this study emerges a consistent picture of the nature and extent of such phase separation phenomena in Mo-bearing glasses, and demonstrates the potential of double-resonance NMR methods for the investigation of phase separation in amorphous materials. (authors)

Glass Durability Modeling, Activated Complex Theory (ACT)

International Nuclear Information System (INIS)

CAROL, JANTZEN

2005-01-01

atomic ratios is shown to represent the structural effects of the glass on the dissolution and the formation of activated complexes in the glass leached layer. This provides two different methods by which a linear glass durability model can be formulated. One based on the quasi- crystalline mineral species in a glass and one based on cation ratios in the glass: both are related to the activated complexes on the surface by the law of mass action. The former would allow a new Thermodynamic Hydration Energy Model to be developed based on the hydration of the quasi-crystalline mineral species if all the pertinent thermodynamic data were available. Since the pertinent thermodynamic data is not available, the quasi-crystalline mineral species and the activated complexes can be related to cation ratios in the glass by the law of mass action. The cation ratio model can, thus, be used by waste form producers to formulate durable glasses based on fundamental structural and activated complex theories. Moreover, glass durability model based on atomic ratios simplifies HLW glass process control in that the measured ratios of only a few waste components and glass formers can be used to predict complex HLW glass performance with a high degree of accuracy, e.g. an R 2 approximately 0.97

Modifying glass surfaces via internal diffusion

DEFF Research Database (Denmark)

Smedskjaer, M.M.; Yue, Y.Z.; Deubener, J.

2010-01-01

leads to outward diffusion (OD) of divalent cations (primarily Mg2+), i.e., diffusion from the interior of the glass to the surface, and thereby, to formation of an oxide surface nano-layer. in contrast, when the glasses are heat-treated in H-2/N-2 gas containing 10 vol.% H-2, reduction of Fe3+ to Fe2...... on some properties such as hardness, chemical durability, and surface wettability....

Cationization increases brain distribution of an amyloid-beta protofibril selective F(ab')2 fragment

OpenAIRE

Syvänen, Stina; Edén, Desireé; Sehlin, Dag

2017-01-01

Antibodies and fragments thereof are, because of high selectivity for their targets, considered as potential therapeutics and biomarkers for several neurological disorders. However, due to their large molecular size, antibodies/fragments do not easily penetrate into the brain. The aim of the present study was to improve the brain distribution via adsorptive-mediated transcytosis of an amyloid-beta (A beta) protofibril selective F(ab')2 fragment (F(ab')2-h158). F(ab')2-h158 was cationized to d...

Solvent-Free Selective Oxidation of Toluene with O2 Catalyzed by Metal Cation Modified LDHs and Mixed Oxides

Directory of Open Access Journals (Sweden)

Xiaoli Wang

2016-01-01

Full Text Available A series of metal cation modified layered-double hydroxides (LDHs and mixed oxides were prepared and used to be the selective oxidation of toluene with O2. The results revealed that the modified LDHs exhibited much higher catalytic performance than their parent LDH and the modified mixed oxides. Moreover, the metal cations were also found to play important roles in the catalytic performance and stabilities of modified catalysts. Under the optimal reaction conditions, the highest toluene conversion reached 8.7% with 97.5% of the selectivity to benzyldehyde; moreover, the catalytic performance remained after nine catalytic runs. In addition, the reaction probably involved a free-radical mechanism.

Influence of anionic and cationic polyelectrolytes on the conductivity and morphology of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) films

Energy Technology Data Exchange (ETDEWEB)

Valtakari, Dimitar, E-mail: dimitar.valtakari@abo.fi [Abo Akademi University, Laboratory of Paper Coating and Converting, Center for Functional Materials at Biological Interfaces (FUNMAT), Porthansgatan 3, FI-20500 Åbo/Turku (Finland); Bollström, Roger [Omya International AG, CH 4665 Oftringen (Switzerland); Toivakka, Martti; Saarinen, Jarkko J. [Abo Akademi University, Laboratory of Paper Coating and Converting, Center for Functional Materials at Biological Interfaces (FUNMAT), Porthansgatan 3, FI-20500 Åbo/Turku (Finland)

2015-09-01

Conductivity of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) strongly depends on the film morphology, which can be altered by the presence of polyelectrolytes. Aqueous dispersion of PEDOT:PSS was studied with anionic sodium polyacrylate (PA) and cationic poly(dimethyldiallylammonium chloride) (pDADMAC) polyelectrolytes that are typically used in papermaking as retention aids and dispersing agents in the paper pigment coating formulations. Spin-coated PEDOT:PSS films on a PA coated glass formed non-uniform layers with lowered conductivity compared to the reference PEDOT:PSS films on a clean glass substrate. On contrary, spin-coated PEDOT:PSS on a pDADMAC coated glass formed uniform layers with good conductivity. These results point out the importance of surface chemistry when using renewable and recyclable paper-based substrates with the PEDOT:PSS films. - Highlights: • PEDOT:PSS polymer was studied in the presence of polyelectrolytes. • Uniform layers of PEDOT:PSS and polyelectrolytes were spin-coated on glass. • Cationic polyelectrolyte was found to be more susceptible to humidity. • Cationic polyelectrolyte improves the conductivity of PEDOT:PSS. • PEDOT:PSS forms non-uniform layers on anionic polyelectrolyte coated glass.

Influence of anionic and cationic polyelectrolytes on the conductivity and morphology of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) films

International Nuclear Information System (INIS)

Valtakari, Dimitar; Bollström, Roger; Toivakka, Martti; Saarinen, Jarkko J.

2015-01-01

Conductivity of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) strongly depends on the film morphology, which can be altered by the presence of polyelectrolytes. Aqueous dispersion of PEDOT:PSS was studied with anionic sodium polyacrylate (PA) and cationic poly(dimethyldiallylammonium chloride) (pDADMAC) polyelectrolytes that are typically used in papermaking as retention aids and dispersing agents in the paper pigment coating formulations. Spin-coated PEDOT:PSS films on a PA coated glass formed non-uniform layers with lowered conductivity compared to the reference PEDOT:PSS films on a clean glass substrate. On contrary, spin-coated PEDOT:PSS on a pDADMAC coated glass formed uniform layers with good conductivity. These results point out the importance of surface chemistry when using renewable and recyclable paper-based substrates with the PEDOT:PSS films. - Highlights: • PEDOT:PSS polymer was studied in the presence of polyelectrolytes. • Uniform layers of PEDOT:PSS and polyelectrolytes were spin-coated on glass. • Cationic polyelectrolyte was found to be more susceptible to humidity. • Cationic polyelectrolyte improves the conductivity of PEDOT:PSS. • PEDOT:PSS forms non-uniform layers on anionic polyelectrolyte coated glass

Magnesium-phosphate-glass cements with ceramic-type properties

Science.gov (United States)

Sugama, T.; Kukacka, L.E.

1982-09-23

Rapid setting magnesium phosphate (Mg glass) cementitious materials consisting of magnesium phosphate cement paste, polyborax and water-saturated aggregate, exhibits rapid setting and high early strength characteristics. The magnesium glass cement is prepared from a cation-leachable powder and a bivalent metallic ion-accepting liquid such as an aqueous solution of diammonium phosphate and ammonium polyphosphate. The cation-leachable powder includes a mixture of two different magnesium oxide powders processed and sized differently which when mixed with the bivalent metallic ion-accepting liquid provides the magnesium glass cement consisting primarily of magnesium ortho phosphate tetrahydrate, with magnesium hydroxide and magnesium ammonium phosphate hexahydrate also present. The polyborax serves as a set-retarder. The resulting magnesium mono- and polyphosphate cements are particularly suitable for use as a cementing matrix in rapid repair systems for deteriorated concrete structures as well as construction materials and surface coatings for fireproof structures.

Magnesium phosphate glass cements with ceramic-type properties

Science.gov (United States)

Sugama, Toshifumi; Kukacka, Lawrence E.

1984-03-13

Rapid setting magnesium phosphate (Mg glass) cementitious materials consisting of magnesium phosphate cement paste, polyborax and water-saturated aggregate exhibiting rapid setting and high early strength characteristics. The magnesium glass cement is prepared from a cation-leachable powder and a bivalent metallic ion-accepting liquid such as an aqueous solution of diammonium phosphate and ammonium polyphosphate. The cation-leachable powder includes a mixture of two different magnesium oxide powders processed and sized differently which when mixed with the bivalent metallic ion-accepting liquid provides the magnesium glass cement consisting primarily of magnesium ortho phosphate tetrahydrate, with magnesium hydroxide and magnesium ammonium phosphate hexahydrate also present. The polyborax serves as a set-retarder. The resulting magnesium mono- and polyphosphate cements are particularly suitable for use as a cementing matrix in rapid repair systems for deteriorated concrete structures as well as construction materials and surface coatings for fireproof structures.

Porous glasses as a host of luminescent materials, their applications and site selective determination

Energy Technology Data Exchange (ETDEWEB)

Reisfeld, Renata, E-mail: renata.reisfeld@mail.huji.ac.il [Institute of Chemistry, Hebrew University of Jerusalem, Givat-Ram, Jerusalem 91904 (Israel); Jasinska, Bozena [Institute of Physics, Maria Curie-Sklodowska University, Pl. M. Curie-Skłodowsskiej 1, 20-031 Lublin (Poland); Levchenko, Viktoria [Institute of Chemistry, Hebrew University of Jerusalem, Givat-Ram, Jerusalem 91904 (Israel); Gorgol, Marek [Institute of Physics, Maria Curie-Sklodowska University, Pl. M. Curie-Skłodowsskiej 1, 20-031 Lublin (Poland); Saraidarov, Tsiala; Popov, Inna [Institute of Chemistry, Hebrew University of Jerusalem, Givat-Ram, Jerusalem 91904 (Israel); Antropova, Tatiana [I. V. Grebenshchikov Institute of the Chemistry of Silicates, Russian Academy of Sciences, Nab. Makarova, 2, Liter B, Saint-Petersburg 199034 (Russian Federation); Rysiakiewicz-Pasek, Ewa [Institute of Physics, Wroclaw University of Technology, W. Wyspianskiego 27, 50-370 Wroclaw (Poland)

2016-01-15

The site selective distribution of pore sizes in pure porous glasses and glasses doped by a luminescent colorant is determined by luminescent spectroscopy, SEM, SAXS and PALS. The potential applications of the studied materials as environmental and biological sensors are outlined. We suggest how luminescent porous glasses doped by complexes of Gd can act as solid scintillators in tracing elementary particles like neutrino. - Highlights: • Porous glasses are a medium for large number of luminescent materials. • Size distribution of empty and filled pores is studied. • The validity of data obtained by different methods is analyzed.

Structure peculiarities of mixed alkali silicate glasses

International Nuclear Information System (INIS)

Bershtein, V.A.; Gorbachev, V.V.; Egorov, V.

1980-01-01

The thermal porperties and structure of alkali and mixed alkali (Li, Na, K) silicate glasses by means of differential scanning calorimetry (DSC), the positron annihilation method, X-ray fluorescence and infrared (300-30 cm -1 ) spectroscopy were studied. Introduction of different alkali cations in glass results in nonadditive change in their electron structure (bond covalence degree growth) and the thermal behaviour. The different manifestations of mixed alkali effect can be explained by the lessening of long distance Coulomb interactions and strengthening the short-range forces in the mixed alkali glasses. (orig.)

Study of nuclear glasses alteration gel and synthesis of some model gels

International Nuclear Information System (INIS)

Ricol, S.

1995-01-01

This work deals with the general problem of alteration of the reference nuclear glass R7T7. Attention is paid particularly to the altered layer formed at the glass surface during alteration process. In opposition to previous works, related essentially to glass dissolution kinetics based on chemical analyses of lixiviated elements, this thesis deals with alteration problems through structural studies of the reference glass and derived gel. This approach allows the determination of mechanisms for the gel formation and a better understanding of the behaviour of glasses towards lixiviation. Both approaches appeared complementary. Based on several spectroscopic techniques, this work showed the particular role of cations such as calcium, zirconium and iron. Studies of silica-based synthetic gels showed the synergic effect of formers cation and of one highly coordinated cation. The variation of the wavenumber related to Si-O-Si asymmetric stretching vibration can be correlated to O/Si ratio for ternary systems Si/Na/Zr. On the contrary, the Si losses of the materials depend on the number of non-bridging oxygen atoms. In the perspective of long-term behaviour, the alteration gel presents better characteristics than initial glass. It is therefore a highly stable material in static conditions. In the same way, synthetic gels are materials with very low solubilities (much lower than the alteration gel) and could be used as confining matrices. (authors). refs., 71 figs., 37 tabs

Ionic conductivity of ZrF4-BaF2-MFsub(n) fluoride glasses (M : The group I--V metal elements)

International Nuclear Information System (INIS)

Kawamoto, Yoji; Nohara, Ichiro

1985-01-01

To glass transition temperature in argon atmosphere using the complex capacitance and complex impedance methods. The ionic conductivity of glasses, represented by log σ = log σ 0 - ΔE/2.303 kT, was nearly dependent only upon the activation energy. The polarizability of cation was found to be a dominant factor which governs activation energy. Thus, glasses with high meanpolarizability of glass-constituting cations exhibited high ionic conductivity, and the ZrF 4 -BaF 2 -CsF system was suggested to be a promising system that may provide a glass with higher fluoride-ion conduction. (author)

First-principles calculation study of mechanism of cation adsorption selectivity of zeolites. A guideline for effective removal of radioactive cesium

International Nuclear Information System (INIS)

Nakamura, Hiroki; Okumura, Masahiko; Machida, Masahiko

2013-01-01

Zeolites have attracted attention in the reprocessing of radioactive nuclear waste because of their high selective affinity for radioisotopes of Cs. Very recently, their useful properties have been widely utilized in decontamination after the accident at the Fukushima Daiichi Nuclear Power Plants. In this study, we study the high selectivity in the Cs adsorption of zeolites using first-principles calculations and clarify the mechanism of the cation selectivity of zeolites. We obtain energy surfaces on all capture locations for Cs/Na ions inside the micropores of a zeolite, 'mordenite', and find three crucial conditions for the highly ion-selective exchange of Na for Cs: 1) micropores with a radius of ∼3 Å, 2) a moderate Al/Si ratio, and 3) a uniform distribution of Al atoms around each micropore. These insights suggest a guideline for developing zeolites with high Cs selectivity and for enhancing the cation selectivity in more general situations. (author)

Cation-π interactions in structural biology

OpenAIRE

Gallivan, Justin P.; Dougherty, Dennis A.

1999-01-01

Cation-pi interactions in protein structures are identified and evaluated by using an energy-based criterion for selecting significant sidechain pairs. Cation-pi interactions are found to be common among structures in the Protein Data Bank, and it is clearly demonstrated that, when a cationic sidechain (Lys or Arg) is near an aromatic sidechain (Phe, Tyr, or Trp), the geometry is biased toward one that would experience a favorable cation-pi interaction. The sidechain of Arg is more likely tha...

Mixed mobile ion effect in fluorozincate glasses

International Nuclear Information System (INIS)

Ghosh, S; Ghosh, A

2005-01-01

The mixed mobile ion effect has been investigated for the first time in zinc fluoride glasses where in addition to alkali cations fluorine anions also participate in the diffusion process, unlike mixed alkali oxide glasses. The minimum in the conductivity, conductivity relaxation frequency, crossover frequency and decoupling index indicates the existence of the mixed mobile ion effect in these fluoride glasses. It has been observed that the non-exponential parameter and the frequency exponent are independent of temperature. It has been established that alkali ions and fluorine anions exhibit lower dimensionality of the conduction pathways in mixed alkali zinc fluoride glasses than that in the single alkali lithium based zinc fluoride glasses while they are migrating. From the scaling of the conductivity spectra, it has been established that the relaxation dynamics in mixed alkali zinc fluoride glasses is independent of temperature and composition

Selective cation-exchange separation of cesium(I) on chromium ferricyanide gel

International Nuclear Information System (INIS)

Jain, A.K.; Agrawal, S.; Singh, R.P.

1980-01-01

The removal of 137 Cs from liquid streams of nuclear power plants and from processed radioactive waste of nuclear fission has received increasing attention from ion-exchange chemists. A desirable exchanger (adsorbent) for 137 Cs removal is one which can adsorb it significantly and selectively in the presence of appreciable amounts (approx. 2molL -1 ) of Na + , NH 4 + , and H + . This paper deals with the exchange properties of the inorganic exchanger, chromium ferricyanide gel (CFiC). The stability of the gel in both acid and salt solutions and its high specificity for cesium are responsible for its good scavanger properties in removing long lived 137 Cs from radioactive waste. The chromium ferricyanide exchanger is highly selective for monovalent cations, the order being Ag + >Tl + >Cs + >Rb + >K + >Na + . It does not adsorb any bivalent, trivalent, and tetravalent ions even when present in trace amounts. (2 figures, 3 tables)

Molybdenum modified phosphate glasses studied by 31P MAS NMR and Raman spectroscopy.

Science.gov (United States)

Szumera, Magdalena

2015-02-25

Glasses have been synthesized in the system P2O5-SiO2-K2O-MgO-CaO modified by addition of MoO3. Glasses were prepared by conventional fusion method from 40 g batches. The influence of Mo-cations on the analysed glass structure was investigated by means of Raman and (31)P MAS-NMR techniques. It has been found that molybdate units can form Mo[MoO4/MoO6]-O-P and/or Mo[MoO4/MoO6]-O-Si bonds with non-bridging oxygens atoms of Q2 methaphosphate units, resulting in the transformation of chain methaphosphate structure into pyrophosphate and finally into orthophosphate structure. It has been also found that increasing amount of MoO3 in the structure of investigated glasses causes their gradual depolymerization and molybdenum ions in the analysed glass matrix act as modifying cations. Copyright © 2014 Elsevier B.V. All rights reserved.

Survey of glass plutonium contents and poison selection

Energy Technology Data Exchange (ETDEWEB)

Plodinec, M.J.; Ramsey, W.G. [Westinghouse Savannah River Company, Aiken, SC (United States); Ellison, A.J.G.; Shaw, H. [Lawrence Livermore National Laboratory, CA (United States)

1996-05-01

If plutonium and other actinides are to be immobilized in glass, then achieving high concentrations in the glass is desirable. This will lead to reduced costs and more rapid immobilization. However, glasses with high actinide concentrations also bring with them undersirable characteristics, especially a greater concern about nuclear criticality, particularly in a geologic repository. The key to achieving a high concentration of actinide elements in a glass is to formulate the glass so that the solubility of actinides is high. At the same time, the glass must be formulated so that the glass also contains neutron poisons, which will prevent criticality during processing and in a geologic repository. In this paper, the solubility of actinides, particularly plutonium, in three types of glasses are discussed. Plutonium solubilities are in the 2-4 wt% range for borosilicate high-level waste (HLW) glasses of the type which will be produced in the US. This type of glass is generally melted at relatively low temperatures, ca. 1150{degrees}C. For this melting temperature, the glass can be reformulated to achieve plutonium solubilities of at least 7 wt%. This low melting temperature is desirable if one must retain volatile cesium-137 in the glass. If one is not concerned about cesium volatility, then glasses can be formulated which can contain much larger amounts of plutonium and other actinides. Plutonium concentrations of at least 15 wt% have been achieved. Thus, there is confidence that high ({ge}5 wt%) concentrations of actinides can be achieved under a variety of conditions.

The glass cliff: when and why women are selected as leaders in crisis contexts.

Science.gov (United States)

Bruckmüller, Susanne; Branscombe, Nyla R

2010-09-01

The glass cliff refers to women being more likely to rise to positions of organizational leadership in times of crisis than in times of success, and men being more likely to achieve those positions in prosperous times. We examine the role that (a) a gendered history of leadership and (b) stereotypes about gender and leadership play in creating the glass cliff. In Expt 1, participants who read about a company with a male history of leadership selected a male future leader for a successful organization, but chose a female future leader in times of crisis. This interaction--between company performance and gender of the preferred future leader--was eliminated for a counter-stereotypic history of female leadership. In Expt 2, stereotypically male attributes were most predictive of leader selection in a successful organization, while stereotypically female attributes were most predictive in times of crisis. Differences in the endorsement of these stereotypes, in particular with regard to the ascription of lower stereotypically female attributes to the male candidate mediated the glass cliff effect. Overall, results suggest that stereotypes about male leadership may be more important for the glass cliff effect than stereotypes about women and leadership.

Effect of compositional variations on charge compensation of AlO4 and BO4 entities and on crystallization tendency of a rare-earth-rich aluminoborosilicate glass

International Nuclear Information System (INIS)

Quintas, A.; Caurant, D.; Majerus, O.; Charpentier, T.; Dussossoy, J.-L.

2009-01-01

This paper presents the structural and crystallization study of a rare-earth-rich aluminoborosilicate glass that is a simplified version of a new nuclear glass proven to be a potential candidate for the immobilization of highly concentrated radioactive wastes that will be produced in the future. In this work, we studied the impact of changing the nature of alkali (Li + , Na + , K + , Rb + , Cs + ) or alkaline-earth (Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ) cations present in glass composition on glass structure (by 27 Al and 11 B nuclear magnetic resonance spectroscopy) and on its crystallization tendency during melt cooling at 1 K/min (average cooling rate during industrial process). From these composition changes, it was established that alkali cations were preferentially involved in charge compensation of (AlO 4 ) - and (BO 4 ) - entities in the glassy network comparatively to alkaline-earth cations. Whatever the nature of alkali cations, glass compositions containing calcium gave way to the crystallization of an apatite silicate phase bearing calcium and rare-earth (RE) cations (Ca 2 RE 8 (SiO 4 ) 6 O 2 , RE = Nd or La) but melt crystallization tendency during cooling strongly varied with the nature of alkaline-earth cations.

Free volume of mixed cation borosilicate glass sealants elucidated by positron annihilation lifetime spectroscopy and its correlation with glass properties

Science.gov (United States)

Ojha, Prasanta K.; Rath, Sangram K.; Sharma, Sandeep K.; Sudarshan, Kathi; Pujari, Pradeep K.; Chongdar, Tapas K.; Gokhale, Nitin M.

2015-01-01

The role of La+3/Sr+2 ratios, which is varied from 0.08 to 5.09, on density, molar volume, packing fraction, free volume, thermal and electrical properties in strontium lanthanum aluminoborosilicate based glass sealants intended for solid oxide fuel cell (SOFC) applications is evaluated. The studies reveal expansion of the glass network evident from increasing molar volume and decreasing packing fraction of glasses with progressive La+3 substitutions. The molecular origin of these macroscopic structural features can be accounted for by the free volume parameters measured from positron annihilation lifetime spectroscopy (PALS). The La+3 induced expanded glass networks show increased number of subnanoscopic voids with larger sizes, as revealed from the ortho-positronium (o-Ps) lifetime and its intensity. A remarkably direct correspondence between the molar volume and fractional free volume trend is established with progressive La2O3 substitution in the glasses. The effect of these structural changes on the glass transition temperature, softening temperature, coefficient of thermal expansion, thermal stability as well as electrical conductivity has been studied.

Inward Cationic Diffusion and Formation of Silica-Rich Surface Nanolayer of Glass

DEFF Research Database (Denmark)

Smedskjær, Morten Mattrup; Deubener, Joachim; Yue, Yuanzheng

2009-01-01

form and are incorporated into the glass structure. Both the V4+ and the hydroxyl contents increase with increasing ta and hydrogen partial pressure. The inward diffusion enhances the hardness of the glass surface. The mechanism of the inward diffusion is suggested on the basis of a model describing...

Effect of glass composition on waste form durability: A critical review

International Nuclear Information System (INIS)

Ellison, A.J.G.; Mazer, J.J.; Ebert, W.L.

1994-11-01

This report reviews literature concerning the relationship between the composition and durability of silicate glasses, particularly glasses proposed for immobilization of radioactive waste. Standard procedures used to perform durability tests are reviewed. It is shown that tests in which a low-surface area sample is brought into contact with a very large volume of solution provide the most accurate measure of the intrinsic durability of a glass composition, whereas high-surface area/low-solution volume tests are a better measure of the response of a glass to changes in solution chemistry induced by a buildup of glass corrosion products. The structural chemistry of silicate and borosilicate glasses is reviewed to identify those components with the strongest cation-anion bonds. A number of examples are discussed in which two or more cations engage in mutual bonding interactions that result in minima or maxima in the rheologic and thermodynamic properties of the glasses at or near particular optimal compositions. It is shown that in simple glass-forming systems such interactions generally enhance the durability of glasses. Moreover, it is shown that experimental results obtained for simple systems can be used to account for durability rankings of much more complex waste glass compositions. Models that purport to predict the rate of corrosion of glasses in short-term durability tests are evaluated using a database of short-term durability test results for a large set of glass compositions. The predictions of these models correlate with the measured durabilities of the glasses when considered in large groupings, but no model evaluated in this review provides accurate estimates of durability for individual glass compositions. Use of these models in long-term durability models is discussed. 230 refs

ADSORPTION METHOD FOR SEPARATING METAL CATIONS

Science.gov (United States)

Khym, J.X.

1959-03-10

The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

Local structure near actinides and nucleating elements in borosilicate glass for nuclear industry: Results of X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Petit-Maire, D.

1988-01-01

Possibilities and limits of X-ray absorption spectroscopy for cation site description in silicate glasses and possible applications for complex glasses, like glass for fission product containment, are examined. In borosilicate glasses two types of sites are evidenced for actinides at the valence 4: Coordinance 6 sites with a narrow radial distribution for the distance An-0; higher coordination (7, 8 or more) with a wider and asymmetrical radial distribution. Proportion of low coordinance sites increases when cation size decreases (Th > Np). U and Np VI and V are characterized as actinyles with a chain 0-An-0 practically linear, coordinance in a plane perpendicular to this complex is probably 5. X-ray absorption spectroscopy allows an accurate description of actinide sites in fission product glasses [fr

Omni-directional selective shielding material based on amorphous glass coated microwires.

Science.gov (United States)

Ababei, G; Chiriac, H; David, V; Dafinescu, V; Nica, I

2012-01-01

The shielding effectiveness of the omni-directional selective shielding material based on CoFe-glass coated amorphous wires in 0.8 GHz-3 GHz microwave frequency range is investigated. The measurements were done in a controlled medium using a TEM cell and in the free space using horn antennas, respectively. Experimental results indicate that the composite shielding material can be developed with desired shielding effectiveness and selective absorption of the microwave frequency range by controlling the number of the layers and the length of microwires.

Joule-heated glass-furnace system for the incineration of low-level radioactive wastes

International Nuclear Information System (INIS)

Armstrong, K.M.; Klingler, L.M.; Doty, J.W.; Kramer, D.P.

1982-01-01

For the past 1-1/2 years, Mound has been preparing and evaluating a commercially available joule-heated glass furnace unit, coupled with a wet scrubbing system. The purpose of the glass furnace evaluation is to advance and document incinerator technology for such combustibles as solids, resins, and sludges, and to develop a stable waste form for subsequent disposal. Four (4) waste nonradioactive types were selected to determine the combustion efficiency of the furnace unit: (1) dry solid waste composed of paper, plastics, rubber, and cloth, (2) ion exchange resin of both the anionic and cationic type, (3) filter sludge composed of diatomaceous earth, organic cellulosic filter aid, and powdered ion exchange resin, and (4) cartridge filters having glass and plastic filter surfaces and nonmetallic cores. When completed, the combustion efficiency experiments for the proposed nonradioactive waste-types revealed the ability of the furnace to easily incinerate waste at feedrates of up to 150 lb/hr. During the course of the experiments, combustibles in the offgas remained consistently low, suggesting excellent combustion efficiency. Furthermore, ash produced by the combustion process was effectively incorporated into the melt by convective currents in the glass. Future work on the glass furnace incinerator will include spiking the waste to determine radioisotope behavior in the furnace

Radiation impact on the characteristics of optical glasses test results on a selected set of materials

Science.gov (United States)

Fruit, Michel; Gussarov, Andrei; Berghmans, Francis; Doyle, Dominic; Ulbrich, Gerd

2017-11-01

It is well known within the Space optics community that radiation may significantly affect transmittance of glasses. To overcome this drawback, glass manufacturers have developed Cerium doped counterparts of classical glasses. This doped glasses display much less transmittance sensitivity to radiation. Still, the impact of radiation on refractive index is less known and may affect indifferently classical or Cerium doped glasses. ESTEC has initialised an R&D program with the aim of establishing a comprehensive data base gathering radiation sensitivity data, called Dose coefficients, for all the glass optical parameters (transmittance / refractive index / compaction……). The first part of this study, to define the methodology for such a data base, is run by ASTRIUM SAS in co-operation with SCK CEN. This covers theoretical studies associated to testing of a selected set of classical and "radiation hardened" glasses. It is proposed here to present first the theoretical backgrounds of this study and then to give results which have been obtained so far.

Glass sealing

Energy Technology Data Exchange (ETDEWEB)

Brow, R.K.; Kovacic, L.; Chambers, R.S. [Sandia National Labs., Albuquerque, NM (United States)

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.

STRESS RELAXATION CHARACTERISTICS OF SELECTED COMMERCIALLY PRODUCED GLASSES

Directory of Open Access Journals (Sweden)

Chocholoušek J.

2013-06-01

Full Text Available This paper describes a quantitative method of stress relaxation measurement in prismatic glass samples during two different time-temperature regimes using the Sénarmont compensator. Four types of glass (Barium crystal glass, Eutal, Simax, and Container glass were subjected to observation in an assembled measuring device. Results will be used for parameterization of the Tool-Narayanaswamy-Mazurin model and consequently implemented in a finite element method code.

Zirconolite glass-ceramics for plutonium immobilization: The effects of processing redox conditions on charge compensation and durability

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yingjie, E-mail: yzx@ansto.gov.au; Gregg, Daniel J.; Kong, Linggen; Jovanovich, Miodrag; Triani, Gerry

2017-07-15

Zirconolite glass-ceramic samples doped with plutonium have been prepared via hot isostatic pressing. The effects of processing redox and plutonium loadings on plutonium valences, the presence of cation vacancies, zirconolite phase compositions, microstructures and durability have been investigated. Either tetravalent or trivalent plutonium ions may be incorporated on the Ca-site of CaZrTi{sub 2}O{sub 7} zirconolite with the Ca-site cation vacancies and the incorporation of Al{sup 3+} ions on the Ti-site for charge compensation. Plutonium and gadolinium (as a neutron absorber) are predominantly partitioned in zirconolite phases leading to the formation of chemically durable glass-ceramics suitable for the immobilization of impure plutonium wastes arising from the nuclear fuel cycle. - Highlights: •Plutonium validations of zirconolite glass-ceramics. •Effects of processing redox and plutonium loading. •Zirconolite phase compositions and plutonium valences. •Cation vacancies and chemical durability.

Structure of cesium loaded iron phosphate glasses: An infrared and Raman spectroscopy study

International Nuclear Information System (INIS)

Joseph, Kitheri; Premila, M.; Amarendra, G.; Govindan Kutty, K.V.; Sundar, C.S.; Vasudeva Rao, P.R.

2012-01-01

The structure of cesium loaded iron phosphate glasses (IPG) was investigated using infrared and Raman spectroscopy. The spectra of the cesium doped samples revealed a structural modification of the parent glass owing to the incorporation of cesium. The structural changes could be correlated with the variation observed in the glass transition temperature of these glasses. Increased Cs-mediated cationic cross linking appears to be the reason for the initial rise in glass transition temperature up to 21 mol% Cs 2 O in IPG; while, breakdown of the phosphate network with increasing cesium content, brings down the glass transition temperature.

Immobilisation of radwastes in glass containers and products formed thereby

International Nuclear Information System (INIS)

Macedo, P.B.; Simmons, C.J.; Lagakos, N.; Simmons, J.H.; Tran, D.C.

1980-01-01

A method of preventing the dissemination of toxic material to the environment comprises forming an admixture of toxic material and glass packing in a hollow doped glass container of high silica content, or forming the admixture in a first container and then depositing at least a portion of the admixture in a hollow doped glass container of high silica content. The glass container is then heated to collapse its walls and to seal the container so that the toxic material is entrapped and sealed within the collapsed doped glass container. The thermal expansion coefficient of the container may be decreased prior to use by exchanging hydrogen ion in pores thereof with other cations followed by collapsing the pores. (author)

Selective adsorption and release of cationic organic dye molecules on mesoporous borosilicates

International Nuclear Information System (INIS)

Paul, Manidipa; Pal, Nabanita; Bhaumik, Asim

2012-01-01

Mesoporous materials can play a pivotal role as a host material for delivery application to a specific part of a system. In this work we explore the selective adsorption and release of cationic organic dye molecules such as safranine T (ST) and malachite green (MG) on mesoporous borosilicate materials. The mesoporous silica SBA-15 and borosilicate materials (MBS) were prepared using non-ionic surfactant Pluronic P123 as template via evaporation induced self-assembly (EISA) method. After template removal the materials show high surface areas and in some cases ordered mesopores of dimensions ca. 6–7 nm. High surface area, mesoporosity and the presence of heteroatom (boron) help this mesoporous borosilicate material to adsorb high amount of cationic dye molecules at its surface from the respective aqueous solutions. Furthermore, the mesoporous borosilicate samples containing higher percentage adsorbed dyes show excellent release of ST or MG dye in simulated body fluid (SBF) solution at physiological pH = 7.4 and temperature 310 K. The adsorption and release efficiency of mesoporous borosilicate samples are compared with reference boron-free mesoporous pure silica material to understand the nature of adsorbate–adsorbent interaction at the surfaces. - Graphical abstract: Highly ordered 2D-hexagonal mesoporous borosilicate materials have been synthesized by using Pluronic P123 as template. The materials show very good adsorption and release of organic cationic dye molecules under physiological conditions. Highlights: ► Highly ordered 2D-hexagonal mesoporous borosilicate. ► Nonionic Pluoronic P123 templated mesoporous material. ► Adsorption of organic dyes at the mesopore surface. ► Controlled release of dyes under physiological pH and temperature. ► Release of safranine T (ST) and malachite green (MG) dyes in simulated body fluids.

Comparative investigation on cation-cation (Al-Sn) and cation-anion (Al-F) co-doping in RF sputtered ZnO thin films: Mechanistic insight

Energy Technology Data Exchange (ETDEWEB)

Mallick, Arindam; Basak, Durga, E-mail: sspdb@iacs.res.in

2017-07-15

Highlights: • Comparative study on Al, Al-Sn and Al-F doped ZnO films has been carried out. • High transparent Al-F co-doped film shows three times enhanced carrier density. • Al-F co-doped film shows larger carrier relaxation time. • Al-Sn co-doped films shows carrier transport dominated by impurity scattering. • Al-F co-doped ZnO film can be applied as transparent electrode. - Abstract: Herein, we report a comparative mechanistic study on cation-cation (Al-Sn) and cation-anion (Al-F) co-doped nanocrystalline ZnO thin films grown on glass substrate by RF sputtering technique. Through detailed analyses of crystal structure, surface morphology, microstructure, UV-VIS-NIR transmission-reflection and electrical transport property, the inherent characteristics of the co-doped films were revealed and compared. All the nanocrystalline films retain the hexagonal wurtzite structure of ZnO and show transparency above 90% in the visible and NIR region. As opposed to expectation, Al-Sn (ATZO) co-doped film show no enhanced carrier concentration consistent with the probable formation of SnO{sub 2} clusters supported by the X-ray photoelectron spectroscopy study. Most interestingly, it has been found that Al-F (AFZO) co-doped film shows three times enhanced carrier concentration as compared to Al doped and Al-Sn co-doped films attaining a value of ∼9 × 10{sup 20} cm{sup −3} due to the respective cation and anion substitution. The carrier relaxation time increases in AFZO while it decreases significantly for ATZO film consistent with the concurrence of the impurity scattering in the latter.

Selective adsorption of cationic dyes from aqueous solution by polyoxometalate-based metal–organic framework composite

Energy Technology Data Exchange (ETDEWEB)

Liu, Xiaoxia; Gong, Wenpeng; Luo, Jing; Zou, Chentao; Yang, Yun; Yang, Shuijin, E-mail: yangshuijin@163.com

2016-01-30

Graphical abstract: Selective adsorption ability of H{sub 6}P{sub 2}W{sub 18}O{sub 62}/MOF-5 toward MO (a), Rhb (b) and the removal rate of Rhb, MO and MB (c). - Highlights: • Using metal–organic framework (MOF) composite as an adsorbent was investigated. • Selective adsorption ability of the composite towards cationic dyes was proposed. • The removal rate of MOF was raised greatly by the modification of polyoxometalate. • The adsorption kinetic and isotherm were used to describe the adsorption process. • The thermodynamic parameters of the composite were investigated in detail. - Abstract: A novel environmental friendly adsorbent H{sub 6}P{sub 2}W{sub 18}O{sub 62}/MOF-5 was synthesized by a simple one-step reaction under solvothermal conditions and characterized by XRD, FTIR, thermogravimetric analyses (TGA) and N{sub 2} adsorption–desorption isotherms. The removal rate of H{sub 6}P{sub 2}W{sub 18}O{sub 62}/MOF-5 was quite greater (85%) than that of MOF-5 (almost zero), showing that the adsorption performance of porous MOF-5 can be improved through the modification of H{sub 6}P{sub 2}W{sub 18}O{sub 62}. Further study revealed that H{sub 6}P{sub 2}W{sub 18}O{sub 62}/MOF-5 exhibited a fast adsorption rate and selective adsorption ability towards the cationic dyes in aqueous solution. The removal rate was up to 97% for cationic dyes methylene blue (MB) and 68% for rhodamine B(Rhb) within 10 min. However, anionicdye methyl orange(MO) can only reach to 10%. The influences including initial concentration, contact time, initial solution pH and temperature of MB adsorption onto H{sub 6}P{sub 2}W{sub 18}O{sub 62}/MOF-5 were investigated in detail. The kinetic study indicated that the adsorption of MB onto H{sub 6}P{sub 2}W{sub 18}O{sub 62}/MOF-5 followed the pseudo second-order model well. The isotherm obtained from experimental data fitted the Langmuir model, yielding maximum adsorption capacity of 51.81 mg/g. The thermodynamic parameters analysis

In situ one-year burial experiments with simulated nuclear waste glasses

International Nuclear Information System (INIS)

Hench, L.L.; Spilman, D.; Buonaquisti, T.; Werme, L.

1985-01-01

Two simulated nuclear waste glasses were corroded in an in-situ experiment in the Stripa mine up to one year at 90 degree C and ambient temperature. Changes in compositional in-depth profiles were measured using Fourier transform infrared reflection spectroscopy, SIMS and Rutherford back-scattering. For glass/glass interfaces, both glasses showed depletion of Na, Cs and B, but for the more corrosion resistant glass, the lower depletion is ascribed to the formation of a thin (0.2 nm) coherent and dense outer layer enriched in Mg, Ca, Sr, Ba, Zn-Al and Si, which impedes both ion exchange and network attack of the bulk underneath. For the bentonite interfaces, cation exchange of Ca, Mg, Al and Fe from the bentonite for primarily Na and B is found to produce a glass surface that has three silicate-rich layers. The larger concentrations of M/super2+/ and M/super3+/ cation and the high silica content of the reaction layers result in a considerably retarded rate of ion exchange after the formation of these layers during the first three months of burial. The granite interfaces showed the lowest rate of attack. This appears to be due to a large increase of Fe and Al within the glass surfaces exposed to granite. The results obtained using Rutheford back-scattering confirm the results obtained using the other techniques for surface analysis. Analysis of burial samples cast in steel mini-canisters show no significant effects associated with the steel canister-glass interface. (author)

Chalcogenide glasses as optical and ion-conducting materials. Kogaku oyobi ion dendo zairyo toshite no chalcogenide glass

Energy Technology Data Exchange (ETDEWEB)

Toge, N.; Minami, T. (Univ. of Osaka Prefecture, Osaka (Japan))

1991-12-01

Nonoxide glasses whose main constituent are chalcogen elements like S, Se, or Te etc. show a lot of various properties, for instance, high infrared transmittancy and semi-conductivity which are already well known. Additionally, the optical properties change a lot along with the phase transition's happening between crystal and noncrystal under comparative low temperature. Further, it is also observed that the glasses containing proper cation appear high ion-conductivity. This paper supplies a brief reviews of chalcogenide glasses used as materials for infrared fiber, phase transition optical memory and superionic conductor, wherein the former two have already on the stage of utilization, particularly the realization of a rewritable optical memory is possible by using chalcogenide glasses film, and ion-conductor is in the phase to have shown the possibility of high conductivity while the development thereof is being expected. 22 refs., 8 figs.

Development of a novel bioactive glass for air-abrasion to selectively remove orthodontic adhesives.

Science.gov (United States)

Taha, Ayam A; Hill, Robert G; Fleming, Padhraig S; Patel, Mangala P

2018-05-01

To develop a novel, bioactive glass for removing residual orthodontic adhesive via air-abrasion, following bracket debonding, and to evaluate its effectiveness against a proprietary bioactive glass 45S5(Sylc™)-air-abrasion, and a slow-speed tungsten carbide (TC) bur. Three glasses were prepared and their bioactivity was proved. One novel glass (QMAT3) was selected due to its appropriate hardness, lower than that of enamel/45S5(Sylc™). Sixty extracted human premolars were randomly assigned to adhesive removal using: (a) QMAT3-air-abrasion, (b) 45S5(Sylc™)-air-abrasion, and (c) TC bur, which were further subdivided (n = 10) based on the adhesive used (Transbond XT™ or Fuji Ortho LC™). Enamel roughness was assessed using scanning electron microscopy (SEM) and non-contact profilometry before bracket bonding, after removing residual adhesive following bracket debonding and after polishing. QMAT3 formed apatite faster (6 h) than 45S5(Sylc™) (24 h) in Tris solution. QMAT3-air-abrasion gave the lowest enamel roughness (Ra) after removing the adhesives. SEM images showed a pitted, roughened enamel surface in the TC bur group and to a lesser extent with 45S5(Sylc™), while a virtually smooth surface without any damage was observed in the QMAT3-air-abrasion group. The time taken for adhesive removal with QMAT3 was comparable to 45S5(Sylc™) but was twice as long with the TC bur. QMAT3-air-abrasion is a promising technique for selective removal of adhesives without inducing tangible enamel damage. A novel bioactive glass has been developed as an alternative to the use of TC burs for orthodontic adhesive removal.

Modifier constraints in alkali ultraphosphate glasses

DEFF Research Database (Denmark)

Rodrigues, B.P.; Mauro, J.C.; Yue, Yuanzheng

2014-01-01

In applying the recently introduced concept of cationic constraint strength [J. Chem. Phys. 140, 214501 (2014)] to bond constraint theory (BCT) of binary phosphate glasses in the ultraphosphate region of xR2O-(1-x)P2O5 (with x ≤ 0.5 and R = {Li, Na, Cs}), we demonstrate that a fundamental limitat...

High-capacity cation-exchange column for enhanced resolution of adjacent peaks of cations in ion chromatography.

Science.gov (United States)

Rey, M A

2001-06-22

One of the advantages of ion chromatography [Anal Chem. 47 (1975) 1801] as compared to other analytical techniques is that several ions may be analyzed simultaneously. One of the most important contributions of cation-exchange chromatography is its sensitivity to ammonium ion, which is difficult to analyze by other techniques [J. Weiss, in: E.L. Johnson (Ed.), Handbook of Ion Chromatography, Dionex, Sunnyvale, CA, USA]. The determination of low concentrations of ammonium ion in the presence of high concentrations of sodium poses a challenge in cation-exchange chromatography [J. Weiss, Ion Chromatography, VCH, 2nd Edition, Weinheim, 1995], as both cations have similar selectivities for the common stationary phases containing either sulfonate or carboxylate functional groups. The task was to develop a new cation-exchange stationary phase (for diverse concentration ratios of adjacent peaks) to overcome limitations experienced in previous trails. Various cation-exchange capacities and column body formats were investigated to optimize this application and others. The advantages and disadvantages of two carboxylic acid columns of different cation-exchange capacities and different column formats will be discussed.

Network topology for the formation of solvated electrons in binary CaO–Al2O3 composition glasses

Science.gov (United States)

Akola, Jaakko; Kohara, Shinji; Ohara, Koji; Fujiwara, Akihiko; Watanabe, Yasuhiro; Masuno, Atsunobu; Usuki, Takeshi; Kubo, Takashi; Nakahira, Atsushi; Nitta, Kiyofumi; Uruga, Tomoya; Weber, J. K. Richard; Benmore, Chris J.

2013-01-01

Glass formation in the CaO–Al2O3 system represents an important phenomenon because it does not contain typical network-forming cations. We have produced structural models of CaO–Al2O3 glasses using combined density functional theory–reverse Monte Carlo simulations and obtained structures that reproduce experiments (X-ray and neutron diffraction, extended X-ray absorption fine structure) and result in cohesive energies close to the crystalline ground states. The O–Ca and O–Al coordination numbers are similar in the eutectic 64 mol % CaO (64CaO) glass [comparable to 12CaO·7Al2O3 (C12A7)], and the glass structure comprises a topologically disordered cage network with large-sized rings. This topologically disordered network is the signature of the high glass-forming ability of 64CaO glass and high viscosity in the melt. Analysis of the electronic structure reveals that the atomic charges for Al are comparable to those for Ca, and the bond strength of Al–O is stronger than that of Ca–O, indicating that oxygen is more weakly bound by cations in CaO-rich glass. The analysis shows that the lowest unoccupied molecular orbitals occurs in cavity sites, suggesting that the C12A7 electride glass [Kim SW, Shimoyama T, Hosono H (2011) Science 333(6038):71–74] synthesized from a strongly reduced high-temperature melt can host solvated electrons and bipolarons. Calculations of 64CaO glass structures with few subtracted oxygen atoms (additional electrons) confirm this observation. The comparable atomic charges and coordination of the cations promote more efficient elemental mixing, and this is the origin of the extended cage structure and hosted solvated (trapped) electrons in the C12A7 glass. PMID:23723350

Resonance Raman investigation of the radical cation of 1,3,5-hexatriene

DEFF Research Database (Denmark)

Keszhelyi, T.; Wilbrandt, R.; Cave, R.J.

1994-01-01

The resonance Raman spectrum of the 1,3,5-hexatriene radical cation generated by gamma-irradiation in a Freon glass is reported. The spectrum is excited at 395 nm in resonance with the second absorption band. Identical spectra are obtained from ionized (E)- and (Z)-1,3,5-hexatriene. The presence...

ENHANCED DOE HIGH LEVEL WASTE MELTER THROUGHPUT STUDIES: SRNL GLASS SELECTION STRATEGY

Energy Technology Data Exchange (ETDEWEB)

Raszewski, F; Tommy Edwards, T; David Peeler, D

2008-01-23

The Department of Energy has authorized a team of glass formulation and processing experts at the Savannah River National Laboratory (SRNL), the Pacific Northwest National Laboratory (PNNL), and the Vitreous State Laboratory (VSL) at Catholic University of America to develop a systematic approach to increase high level waste melter throughput (by increasing waste loading with minimal or positive impacts on melt rate). This task is aimed at proof-of-principle testing and the development of tools to improve waste loading and melt rate, which will lead to higher waste throughput. Four specific tasks have been proposed to meet these objectives (for details, see WSRC-STI-2007-00483): (1) Integration and Oversight, (2) Crystal Accumulation Modeling (led by PNNL)/Higher Waste Loading Glasses (led by SRNL), (3) Melt Rate Evaluation and Modeling, and (4) Melter Scale Demonstrations. Task 2, Crystal Accumulation Modeling/Higher Waste Loading Glasses is the focus of this report. The objective of this study is to provide supplemental data to support the possible use of alternative melter technologies and/or implementation of alternative process control models or strategies to target higher waste loadings (WLs) for the Defense Waste Processing Facility (DWPF)--ultimately leading to higher waste throughputs and a reduced mission life. The glass selection strategy discussed in this report was developed to gain insight into specific technical issues that could limit or compromise the ability of glass formulation efforts to target higher WLs for future sludge batches at the Savannah River Site (SRS). These technical issues include Al-dissolution, higher TiO{sub 2} limits and homogeneity issues for coupled-operations, Al{sub 2}O{sub 3} solubility, and nepheline formation. To address these technical issues, a test matrix of 28 glass compositions has been developed based on 5 different sludge projections for future processing. The glasses will be fabricated and characterized based on

A new viscosity model for waste glass formulations

International Nuclear Information System (INIS)

Sadler, A.L.K.

1996-01-01

Waste glass formulation requires prediction, with reasonable accuracy, of properties over much wider ranges of composition than are typically encountered in any single industrial application. Melt viscosity is one such property whose behavior must be predicted in formulating new waste glasses. A model was developed for silicate glasses which relates the Arrhenius activation energy for flow to an open-quotes effectiveclose quotes measure of non-bridging oxygen content in the melt, NBO eff . The NBO eff parameter incorporates the differing effects of modifying cations on the depolymerization of the silicate network. The activation energy-composition relationship implied by the model is in accordance with experimental behavior. The model was validated against two different databases, with satisfactory results

Waste glass corrosion modeling: Comparison with experimental results

International Nuclear Information System (INIS)

Bourcier, W.L.

1994-01-01

Models for borosilicate glass dissolution must account for the processes of (1) kinetically-controlled network dissolution, (2) precipitation of secondary phases, (3) ion exchange, (4) rate-limiting diffusive transport of silica through a hydrous surface reaction layer, and (5) specific glass surface interactions with dissolved cations and anions. Current long-term corrosion models for borosilicate glass employ a rate equation consistent with transition state theory embodied in a geochemical reaction-path modeling program that calculates aqueous phase speciation and mineral precipitation/dissolution. These models are currently under development. Future experimental and modeling work to better quantify the rate-controlling processes and validate these models are necessary before the models can be used in repository performance assessment calculations

Surface modification of glass beads with glutaraldehyde: Characterization and their adsorption property for metal ions

Energy Technology Data Exchange (ETDEWEB)

Ozmen, Mustafa; Can, Keziban; Akin, Ilker; Arslan, Gulsin [Department of Chemistry, Selcuk University, 42031, Konya (Turkey); Tor, Ali, E-mail: ali.alitor@gmail.com [Department of Environmental Engineering, Selcuk University, Engineering Faculty, Campus, 42031, Konya (Turkey); Cengeloglu, Yunus; Ersoz, Mustafa [Department of Chemistry, Selcuk University, 42031, Konya (Turkey)

2009-11-15

In this study, a new material that adsorbs the metal ions was prepared by modification of the glass beads surfaces with glutaraldehyde. First, the glass beads were etched with 4 M NaOH solution. Then, they were reacted with 3-aminopropyl-triethoxysilane (APTES). Finally, silanized glass beads were treated with 25% of glutaraldehyde solution. The characterization studies by using Fourier Transform Infrared Spectroscopy (FT-IR), Thermal Gravimetric Analysis (TGA), elemental analysis and Scanning Electron Microscopy (SEM) indicated that modification of the glass bead surfaces was successfully performed. The adsorption studies exhibited that the modified glass beads could be efficiently used for the removal of the metal cations and anion (chromate ion) from aqueous solutions via chelation and ion-exchange mechanisms. For both Pb(II) and Cr(VI), selected as model ions, the adsorption equilibrium was achieved in 60 min and adsorption of both ions followed the second-order kinetic model. It was found that the sorption data was better represented by the Freundlich isotherm in comparison to the Langmuir and Redlich-Peterson isotherm models. The maximum adsorption capacities for Pb(II) and Cr(VI) were 9.947 and 11.571 mg/g, respectively. The regeneration studies also showed that modified glass beads could be re-used for the adsorption of Pb(II) and Cr(VI) from aqueous solutions over three cycles.

Rapid prototyping of 2D glass microfluidic devices based on femtosecond laser assisted selective etching process

Science.gov (United States)

Kim, Sung-Il; Kim, Jeongtae; Koo, Chiwan; Joung, Yeun-Ho; Choi, Jiyeon

2018-02-01

Microfluidics technology which deals with small liquid samples and reagents within micro-scale channels has been widely applied in various aspects of biological, chemical, and life-scientific research. For fabricating microfluidic devices, a silicon-based polymer, PDMS (Polydimethylsiloxane), is widely used in soft lithography, but it has several drawbacks for microfluidic applications. Glass has many advantages over PDMS due to its excellent optical, chemical, and mechanical properties. However, difficulties in fabrication of glass microfluidic devices that requires multiple skilled steps such as MEMS technology taking several hours to days, impedes broad application of glass based devices. Here, we demonstrate a rapid and optical prototyping of a glass microfluidic device by using femtosecond laser assisted selective etching (LASE) and femtosecond laser welding. A microfluidic droplet generator was fabricated as a demonstration of a microfluidic device using our proposed prototyping. The fabrication time of a single glass chip containing few centimeter long and complex-shaped microfluidic channels was drastically reduced in an hour with the proposed laser based rapid and simple glass micromachining and hermetic packaging technique.

Influence of Radiation and Multivalent Cation Additions on Phase Separation and Crystallization of Glass

Energy Technology Data Exchange (ETDEWEB)

Michael C. Weinberg; Donald R. Uhlmann; Gary L. Smith

2002-08-09

This report presents results of: (1) measurement of valence state ratios of iron in glass, and (2) a study of the effect of iron redox ratio on phase separation behavior in a glass. The redox ratio of iron in two sodium silicate (NS) glasses has been determined using a colorimetric method, Moessbauer analysis, and optical absorption. The experimental procedures were described in a previous report. We found that these three methods gave excellent agreement for the values of the Fe++/Fe+++ (redox ratio) in the glasses. Also, using the results of the colorimetric analysis we were able to find the extinction coefficients for the18.56% NS and the 13% NS glasses. We have utilized the optical absorption data that was taken for purposes of determining redox ratios to provide glass structural information. In particular, it has been suggested that the band centered near 14,500 cm-1 is indicative of Fe2+ - O2- - Fe3+ formation. In addition, the relative band intensities at 10,000 cm-1 and 4,800 cm-1 could give us information as to the environment around the Fe2+ responsible for the 4,800 cm-1 band. The Moessbauer data will provide supporting structural information. For example, the relative number of clustered and free ferric ions can be computed from the ratio of areas under the doublet and sextet in the liquid He spectra. Also, the change in shift parameter with redox ratio will provide an indication of whether there is an increase or decrease in tetrahedral site symmetry about both ferrous and ferric ions. Finally, the quadrupole splitting parameter provides information regarding the site symmetries about the Fe++ and Fe+++. Currently, we are analyzing the spectral data for these purposes. The Moessbauer work was done in conjunction with colleagues at PNNL, and a manuscript is currently in preparation. The effect of oxidation state of iron on the phase separation of xNa2O {center_dot}(100-x)SiO2 glasses, x = 18.56 and 13, containing 0.5 mole % iron oxide was studied. The

Aluminium and hydrogen ions inhibit a mechanosensory calcium-selective cation channel

Science.gov (United States)

Ding, J. P.; Pickard, B. G.

1993-01-01

The tension-dependent activity of mechanosensory calcium-selective cation channels in excised plasmalemmal patches from onion bulb scale epidermis is modulated by pH in the physiologically meaningful range between 4.5 and 7.2. It is rapidly lowered by lowering pH and rapidly raised by raising pH. Channel activity is effectively inhibited by low levels of aluminium ions and activity can be partially restored by washing for a few minutes. We suggest that under normal conditions the sensitivity of the mechanosensory channels to pH of the wall free space plays important roles in regulation of plant activities such as growth. We further suggest that, when levels of acid and aluminium ions in the soil solution are high, they might inhibit similar sensory channels in cells of the root tip, thus contributing critically to the acid soil syndrome.

Affinity functions for modeling glass dissolution rates

Energy Technology Data Exchange (ETDEWEB)

Bourcier, W.L. [Lawrence Livermore National Lab., CA (United States)

1997-07-01

Glass dissolution rates decrease dramatically as glass approach ''saturation'' with respect to the leachate solution. Most repository sites are chosen where water fluxes are minimal, and therefore the waste glass is most likely to dissolve under conditions close to ''saturation''. The key term in the rate expression used to predict glass dissolution rates close to ''saturation'' is the affinity term, which accounts for saturation effects on dissolution rates. Interpretations of recent experimental data on the dissolution behaviour of silicate glasses and silicate minerals indicate the following: 1) simple affinity control does not explain the observed dissolution rate for silicate minerals or glasses; 2) dissolution rates can be significantly modified by dissolved cations even under conditions far from saturation where the affinity term is near unity; 3) the effects of dissolved species such as Al and Si on the dissolution rate vary with pH, temperature, and saturation state; and 4) as temperature is increased, the effect of both pH and temperature on glass and mineral dissolution rates decrease, which strongly suggests a switch in rate control from surface reaction-based to diffusion control. Borosilicate glass dissolution models need to be upgraded to account for these recent experimental observations. (A.C.)

Rapid and selective adsorption of cationic dyes by a unique metal-organic framework with decorated pore surface

Science.gov (United States)

Zhang, Jie; Li, Fan; Sun, Qian

2018-05-01

Organic dye pollutants become a big headache due to their toxic nature to the environment, and it should be one of the best solutions if we can remove and separate them. Here, a metal-organic framework (MOF) (denoted as Zn-MOF) with carbonyl group based on fluorenone-2,7-dicarboxylate ligand, was directly synthesized without post-synthesis method and applied to selectively absorb cationic dyes such as MB, CV, RhB from aqueous solution, while anionic or neutral dyes were excluded. Characterization of the Zn-MOF was achieved by X-ray diffraction, scanning electron microscope, Fourier transform infrared spectrometry and elemental analysis. The Zn-MOF mainly possesses open pore channels, high surface area, big pore volume, and most important, the pore surface is furnished with carbonyl groups arising from the ligand and pointing toward the centers of the large chambers of the framework, which are benefit for the adsorption of the cationic dyes. The MB maximum adsorption capacities can attain 326 mg g-1, which is probably due to the suitable pore size, higher solvent-accessible void, and the prominent adsorption capacity of the mesoporous material. The dye adsorption process for the material is proven to be charge-selective and size-selective, and the adsorption isotherms, as well as kinetics characteristic of dye adsorption onto the Zn-MOF were also investigated.

UV curing silicon-containing epoxy resin and its glass cloth reinforced composites

International Nuclear Information System (INIS)

Yang Guang; Tang Zhuo; Huang Pengcheng

2007-01-01

A UV-curable cationic silicon-containing epoxy resin formulation was developed. The gel conversion of the cured resin after 10-min UV irradiation reached 80% in the presence of 5% diaryliodonium salt photoinitiator and 5.5% polyol chain transfer agent by cationic ring-opening polymerization. The glass cloth-reinforced composites were fabricated with the silicon-containing epoxy resin using the wet lay-up technique and UV irradiation. The mechanical properties of the composites were evaluated. Compared with glass cloth reinforced bisphenol A epoxy resin matrix composites, the silicon-containing epoxy resin matrix composites possessed higher tensile strength and interlayer shear strength which was 158.5MPa and 9.9MPa respectively while other mechanical properties such as flexural property and tensile modulus were similar. (authors)

Predicting liquid immiscibility in multicomponent nuclear waste glasses

International Nuclear Information System (INIS)

Peeler, D.K.; Hrma, P.R.

1994-04-01

Taylor's model for predicting amorphous phase separation in complex, multicomponent systems has been applied to high-level (simulated) radioactive waste glasses at the US Department of Energy's Hanford site. Taylor's model is primarily based on additions of modifying cations to a Na 2 O-B 2 O 3 -SiO 2 (NBS) submixture of the multicomponent glass. The position of the submixture relative to the miscibility dome defines the development probability of amorphous phase separation. Although prediction of amorphous phase separation in Hanford glasses (via experimental SEM/TEM analysis) is the primary thrust of this work; reported durability data is also provides limited insight into the composition/durability relationship. Using a modified model similar to Taylor's, the results indicate that immiscibility may be predicted for multicomponent waste glasses by the addition of Li 2 O to the ''alkali'' corner of the NBS submixture

Yttrium-90 Selective Internal Radiation Therapy with Glass Microspheres for Hepatocellular Carcinoma: Current and Updated Literature Review

Energy Technology Data Exchange (ETDEWEB)

Lee, Edward Wolfgang; Alanis, Lourdes [Division of Interventional Radiology, Department of Radiology, UCLA Medical Center, David Geffen School of Medicine at UCLA, Los Angeles, CA 90095 (United States); Cho, Sung-Ki [Division of Interventional Radiology, Department of Radiology, Samsung Medical Center, Sungkyunkwan University School of Medicine, Seoul 06351 (Korea, Republic of); Saab, Sammy [Division of Hepatology, Department of Medicine, Pfleger Liver Institute, University of California at Los Angeles, Los Angeles, CA 90024 (United States)

2016-11-01

Hepatocellular carcinoma is the most common primary liver cancer and it represents the majority of cancer-related deaths in the world. More than 70% of patients present at an advanced stage, beyond potentially curative options. Ytrrium-90 selective internal radiation therapy (Y90-SIRT) with glass microspheres is rapidly gaining acceptance as a potential therapy for intermediate and advanced stage primary hepatocellular carcinoma and liver metastases. The technique involves delivery of Y90 infused glass microspheres via the hepatic arterial blood flow to the appropriate tumor. The liver tumor receives a highly concentrated radiation dose while sparing the healthy liver parenchyma due to its preferential blood supply from portal venous blood. There are two commercially available devices: TheraSphere® and SIR-Spheres®. Although, Y90-SIRT with glass microspheres improves median survival in patients with intermediate and advanced hepatocellular carcinoma and has the potential to downstage hepatocellular carcinoma so that the selected candidates meet the transplantable criteria, it has not gained widespread acceptance due to the lack of large randomized controlled trials. Currently, there are various clinical trials investigating the use of Y90-SIRT with glass microspheres for treatment of hepatocellular carcinoma and the outcomes of these trials may result in the incorporation of Y90-SIRT with glass microspheres into the treatment guidelines as a standard therapy option for patients with intermediate and advanced stage hepatocellular carcinoma.

Yttrium-90 selective internal radiation therapy with glass microspheres for hepatocellular carcinoma: Current and updated literature review

International Nuclear Information System (INIS)

Lee, Edward Wolfgang; Alanic, Lourdes; Cho, Sung Ki; Saab, Sammy

2016-01-01

Hepatocellular carcinoma is the most common primary liver cancer and it represents the majority of cancer-related deaths in the world. More than 70% of patients present at an advanced stage, beyond potentially curative options. Ytrrium-90 selective internal radiation therapy (Y90-SIRT) with glass microspheres is rapidly gaining acceptance as a potential therapy for intermediate and advanced stage primary hepatocellular carcinoma and liver metastases. The technique involves delivery of Y90 infused glass microspheres via the hepatic arterial blood flow to the appropriate tumor. The liver tumor receives a highly concentrated radiation dose while sparing the healthy liver parenchyma due to its preferential blood supply from portal venous blood. There are two commercially available devices: TheraSphere® and SIR-Spheres®. Although, Y90-SIRT with glass microspheres improves median survival in patients with intermediate and advanced hepatocellular carcinoma and has the potential to downstage hepatocellular carcinoma so that the selected candidates meet the transplantable criteria, it has not gained widespread acceptance due to the lack of large randomized controlled trials. Currently, there are various clinical trials investigating the use of Y90-SIRT with glass microspheres for treatment of hepatocellular carcinoma and the outcomes of these trials may result in the incorporation of Y90-SIRT with glass microspheres into the treatment guidelines as a standard therapy option for patients with intermediate and advanced stage hepatocellular carcinoma

Yttrium-90 Selective Internal Radiation Therapy with Glass Microspheres for Hepatocellular Carcinoma: Current and Updated Literature Review

International Nuclear Information System (INIS)

Lee, Edward Wolfgang; Alanis, Lourdes; Cho, Sung-Ki; Saab, Sammy

2016-01-01

Hepatocellular carcinoma is the most common primary liver cancer and it represents the majority of cancer-related deaths in the world. More than 70% of patients present at an advanced stage, beyond potentially curative options. Ytrrium-90 selective internal radiation therapy (Y90-SIRT) with glass microspheres is rapidly gaining acceptance as a potential therapy for intermediate and advanced stage primary hepatocellular carcinoma and liver metastases. The technique involves delivery of Y90 infused glass microspheres via the hepatic arterial blood flow to the appropriate tumor. The liver tumor receives a highly concentrated radiation dose while sparing the healthy liver parenchyma due to its preferential blood supply from portal venous blood. There are two commercially available devices: TheraSphere® and SIR-Spheres®. Although, Y90-SIRT with glass microspheres improves median survival in patients with intermediate and advanced hepatocellular carcinoma and has the potential to downstage hepatocellular carcinoma so that the selected candidates meet the transplantable criteria, it has not gained widespread acceptance due to the lack of large randomized controlled trials. Currently, there are various clinical trials investigating the use of Y90-SIRT with glass microspheres for treatment of hepatocellular carcinoma and the outcomes of these trials may result in the incorporation of Y90-SIRT with glass microspheres into the treatment guidelines as a standard therapy option for patients with intermediate and advanced stage hepatocellular carcinoma

Yttrium-90 selective internal radiation therapy with glass microspheres for hepatocellular carcinoma: Current and updated literature review

Energy Technology Data Exchange (ETDEWEB)

Lee, Edward Wolfgang; Alanic, Lourdes [Div. of Interventional Radiology, Dept. of Radiology, UCLA Medical Center, David Geffen School of Medicine at UCLA, Los Angeles (United States); Cho, Sung Ki [Div. of Interventional Radiology, Dept. of Radiology, Samsung Medical Center, Sungkyunkwan University School of Medicine, Seoul (Korea, Republic of); Saab, Sammy [Div. of Hepatology, Dept. of Medicine, Pfleger Liver Institute, University of California at Los Angeles, Los Angeles (United States)

2016-07-15

Hepatocellular carcinoma is the most common primary liver cancer and it represents the majority of cancer-related deaths in the world. More than 70% of patients present at an advanced stage, beyond potentially curative options. Ytrrium-90 selective internal radiation therapy (Y90-SIRT) with glass microspheres is rapidly gaining acceptance as a potential therapy for intermediate and advanced stage primary hepatocellular carcinoma and liver metastases. The technique involves delivery of Y90 infused glass microspheres via the hepatic arterial blood flow to the appropriate tumor. The liver tumor receives a highly concentrated radiation dose while sparing the healthy liver parenchyma due to its preferential blood supply from portal venous blood. There are two commercially available devices: TheraSphere® and SIR-Spheres®. Although, Y90-SIRT with glass microspheres improves median survival in patients with intermediate and advanced hepatocellular carcinoma and has the potential to downstage hepatocellular carcinoma so that the selected candidates meet the transplantable criteria, it has not gained widespread acceptance due to the lack of large randomized controlled trials. Currently, there are various clinical trials investigating the use of Y90-SIRT with glass microspheres for treatment of hepatocellular carcinoma and the outcomes of these trials may result in the incorporation of Y90-SIRT with glass microspheres into the treatment guidelines as a standard therapy option for patients with intermediate and advanced stage hepatocellular carcinoma.

Yttrium-90 Selective Internal Radiation Therapy with Glass Microspheres for Hepatocellular Carcinoma: Current and Updated Literature Review.

Science.gov (United States)

Lee, Edward Wolfgang; Alanis, Lourdes; Cho, Sung-Ki; Saab, Sammy

2016-01-01

Hepatocellular carcinoma is the most common primary liver cancer and it represents the majority of cancer-related deaths in the world. More than 70% of patients present at an advanced stage, beyond potentially curative options. Ytrrium-90 selective internal radiation therapy (Y90-SIRT) with glass microspheres is rapidly gaining acceptance as a potential therapy for intermediate and advanced stage primary hepatocellular carcinoma and liver metastases. The technique involves delivery of Y90 infused glass microspheres via the hepatic arterial blood flow to the appropriate tumor. The liver tumor receives a highly concentrated radiation dose while sparing the healthy liver parenchyma due to its preferential blood supply from portal venous blood. There are two commercially available devices: TheraSphere® and SIR-Spheres®. Although, Y90-SIRT with glass microspheres improves median survival in patients with intermediate and advanced hepatocellular carcinoma and has the potential to downstage hepatocellular carcinoma so that the selected candidates meet the transplantable criteria, it has not gained widespread acceptance due to the lack of large randomized controlled trials. Currently, there are various clinical trials investigating the use of Y90-SIRT with glass microspheres for treatment of hepatocellular carcinoma and the outcomes of these trials may result in the incorporation of Y90-SIRT with glass microspheres into the treatment guidelines as a standard therapy option for patients with intermediate and advanced stage hepatocellular carcinoma.

Cation exchange properties of zeolites in hyper alkaline aqueous media.

Science.gov (United States)

Van Tendeloo, Leen; de Blochouse, Benny; Dom, Dirk; Vancluysen, Jacqueline; Snellings, Ruben; Martens, Johan A; Kirschhock, Christine E A; Maes, André; Breynaert, Eric

2015-02-03

Construction of multibarrier concrete based waste disposal sites and management of alkaline mine drainage water requires cation exchangers combining excellent sorption properties with a high stability and predictable performance in hyper alkaline media. Though highly selective organic cation exchange resins have been developed for most pollutants, they can serve as a growth medium for bacterial proliferation, impairing their long-term stability and introducing unpredictable parameters into the evolution of the system. Zeolites represent a family of inorganic cation exchangers, which naturally occur in hyper alkaline conditions and cannot serve as an electron donor or carbon source for microbial proliferation. Despite their successful application as industrial cation exchangers under near neutral conditions, their performance in hyper alkaline, saline water remains highly undocumented. Using Cs(+) as a benchmark element, this study aims to assess the long-term cation exchange performance of zeolites in concrete derived aqueous solutions. Comparison of their exchange properties in alkaline media with data obtained in near neutral solutions demonstrated that the cation exchange selectivity remains unaffected by the increased hydroxyl concentration; the cation exchange capacity did however show an unexpected increase in hyper alkaline media.

Elastic properties and short-range structural order in mixed network former glasses.

Science.gov (United States)

Wang, Weimin; Christensen, Randilynn; Curtis, Brittany; Hynek, David; Keizer, Sydney; Wang, James; Feller, Steve; Martin, Steve W; Kieffer, John

2017-06-21

Elastic properties of alkali containing glasses are of great interest not only because they provide information about overall structural integrity but also they are related to other properties such as thermal conductivity and ion mobility. In this study, we investigate two mixed-network former glass systems, sodium borosilicate 0.2Na 2 O + 0.8[xBO 1.5 + (1 - x)SiO 2 ] and sodium borogermanate 0.2Na 2 O + 0.8[xBO 1.5 + (1 - x)GeO 2 ] glasses. By mixing network formers, the network topology can be changed while keeping the network modifier concentration constant, which allows for the effect of network structure on elastic properties to be analyzed over a wide parametric range. In addition to non-linear, non-additive mixed-glass former effects, maxima are observed in longitudinal, shear and Young's moduli with increasing atomic number density. By combining results from NMR spectroscopy and Brillouin light scattering with a newly developed statistical thermodynamic reaction equilibrium model, it is possible to determine the relative proportions of all network structural units. This new analysis reveals that the structural characteristic predominantly responsible for effective mechanical load transmission in these glasses is a high density of network cations coordinated by four or more bridging oxygens, as it provides for establishing a network of covalent bonds among these cations with connectivity in three dimensions.

Commercial Ion Exchange Resin Vitrification in Borosilicate Glass

International Nuclear Information System (INIS)

Cicero-Herman, C.A.; Workman, P.; Poole, K.; Erich, D.; Harden, J.

1998-05-01

Bench-scale studies were performed to determine the feasibility of vitrification treatment of six resins representative of those used in the commercial nuclear industry. Each resin was successfully immobilized using the same proprietary borosilicate glass formulation. Waste loadings varied from 38 to 70 g of resin/100 g of glass produced depending on the particular resin, with volume reductions of 28 percent to 68 percent. The bench-scale results were used to perform a melter demonstration with one of the resins at the Clemson Environmental Technologies Laboratory (CETL). The resin used was a weakly acidic meth acrylic cation exchange resin. The vitrification process utilized represented a approximately 64 percent volume reduction. Glass characterization, radionuclide retention, offgas analyses, and system compatibility results will be discussed in this paper

Selected anionic and cationic surface active agents: case study on the Kłodnica sediments

Directory of Open Access Journals (Sweden)

Olkowska Ewa

2017-03-01

Full Text Available Surface active agents (surfactants are a group of chemical compounds, which are used as ingredients of detergents, cleaning products, cosmetics and functional products. After use, wastes containing surfactants or their degradation products are discharged to wastewater treatment plants or directly into surface waters. Due to their specific properties of SAAs, compounds are able to migrate between different environmental compartments such as soil, sediment, water or even living organisms and accumulate there. Surfactants can have a harmful effect on living organisms. They can connect with bioactive molecules and modify their function. Additionally, they have the ability to migrate into cells and cause their damage or death. For these reasons investigation of individual surfactants should be conducted. The presented research has been undertaken to obtain information about SAA contamination of sediment from the River Kłodnica catchment caused by selected anionic (linear alkylbenzene sulfonates (LAS C10-C13 and cationic (alkylbenzyldimethylammonium (BDMA-C12-16, alkyl trimethyl ammonium (DTMA, hexadecyl piridinium chloride (HP chlorides surfactants. This river flows through an area of the Upper Silesia Industrial Region where various companies and other institutions (e.g. coal mining, power plants, metallurgy, hospitals are located. To determine their concentration the following analytical tools have been applied: accelerated solvent extraction– solid phase extraction – high performance liquid chromatography – UV-Vis (anionic SAAs and conductivity (cationic SAAs detectors. In all sediments anionic SAAs have been detected. The concentrations of HTMA and BDMA-C16 in tested samples were higher than other cationic analytes. Generally, levels of surfactants with longer alkyl chains were higher and this observation can confirm their higher susceptibility to sorption on solid surfaces.

Waste glass corrosion modeling: Comparison with experimental results

International Nuclear Information System (INIS)

Bourcier, W.L.

1993-11-01

A chemical model of glass corrosion will be used to predict the rates of release of radionuclides from borosilicate glass waste forms in high-level waste repositories. The model will be used both to calculate the rate of degradation of the glass, and also to predict the effects of chemical interactions between the glass and repository materials such as spent fuel, canister and container materials, backfill, cements, grouts, and others. Coupling between the degradation processes affecting all these materials is expected. Models for borosilicate glass dissolution must account for the processes of (1) kinetically-controlled network dissolution, (2) precipitation of secondary phases, (3) ion exchange, (4) rate-limiting diffusive transport of silica through a hydrous surface reaction layer, and (5) specific glass surface interactions with dissolved cations and anions. Current long-term corrosion models for borosilicate glass employ a rate equation consistent with transition state theory embodied in a geochemical reaction-path modeling program that calculates aqueous phase speciation and mineral precipitation/dissolution. These models are currently under development. Future experimental and modeling work to better quantify the rate-controlling processes and validate these models are necessary before the models can be used in repository performance assessment calculations

A Decision Support Concept for a construction design project – selecting the type of glass façade

Directory of Open Access Journals (Sweden)

Franjo Šimić

2017-01-01

Full Text Available The paper describes research into the possibility of developing a concept for supporting decisions in planning construction projects (one of the most important stages of construction project management. The focus is on supporting decisions in selecting the type of and solution for the glass façade in the main design. Materials and types of soluteons for a glass façade were analyzed and alternative solutions were obtained. The concept was developed in that it included relevant stakeholders in the decision-making process during the construction design. These stakeholders were the investor, architect, and construction contractor. The analysis was carried out and a hierarchical structure of objectives was formed as a goal tree. The criteria at the last hierarchical level were used to evaluate alternative solutions for the glass façade, and their weights were determined by all stakeholders using the AHP method (Analytic Hierarchy Process. Using PROMETHEE (Preference Ranking Method for Enrichment Evaluation, a comparison of alternative solutions for the glass façade was conducted and the alternatives were ranked according to the priorities for inclusion into the main design. The concept was tested by selecting a type of glass façade on a residential-commercial building in the city of Rijeka, Croatia.

Singlet and doublet states UV-vis spectrum and electronic properties of 3-methylchrysene and 4-methylchrysene in glass matrix.

Science.gov (United States)

Husain, Mudassir M; Tandon, H C; Varadwaj, Pradeep R

2008-03-01

The ultraviolet-visual spectrum of 3-methylchrysene, 4-methylchrysene and their radical cations formed by ultraviolet radiations, were measured in glass matrix at the room temperature. In the measured singlet state spectrum we were able to identify the alpha, p, beta, beta' (Clar's) or (1)L(b), (1)L(a)(1)B(b), (1)B(a) (Platt's notation) bands. The presence of alpha, beta or (1)L(b), (1)B(b) was confirmed by calculating their wavelength ratio lambda(alpha)/lambda(beta). Since matrix induces perturbation in the measured spectrum; it becomes necessary to take into account the perturbation while computing the spectrum. An effort has been made in this work to simulate the electronic spectrum in the same environment as is measured. This study presents the first calculated spectrum of these systems and their cations in glass matrix by semi empirical methods. To observe the magnitude of perturbation and hence to see the spectral shift in glass matrix, the spectrum was calculated in the free state as well. Spectral properties such as frontier orbitals gap, dipole moment, mean polarizabilities and its tensors were also computed both in glass matrix and free state using semiemperical method. The measured bands of 3-methylchrysene cation at wavelength 416.50 and 473.85 nm closely match with the available diffuse intersteallar bands (DIBs) at 417.55 and 472.64 nm, respectively. Also the observed 474.85 nm band of 4-methylchrysene cation matches the DIB at 476.00 nm.

Selectivity and stoichiometry boosting of beta-cyclodextrin in cationic/anionic surfactant systems: when host-guest equilibrium meets biased aggregation equilibrium.

Science.gov (United States)

Jiang, Lingxiang; Yu, Caifang; Deng, Manli; Jin, Changwen; Wang, Yilin; Yan, Yun; Huang, Jianbin

2010-02-18

Cationic surfactant/anionic surfactant/beta-CD ternary aqueous systems provide a platform for the coexistence of the host-guest (beta-CD/surfactant) equilibrium and the biased aggregation (monomeric/aggregated surfactants) equilibrium. We report here that the interplay between the two equilibria dominates the systems as follows. (1) The biased aggregation equilibrium imposes an apparent selectivity on the host-guest equilibrium, namely, beta-CD has to always selectively bind the major surfactant (molar fraction > 0.5) even if binding constants of beta-CD to the pair of surfactants are quite similar. (2) In return, the host-guest equilibrium amplifies the bias of the aggregation equilibrium, that is, the selective binding partly removes the major surfactant from the aggregates and leaves the aggregate composition approaching the electroneutral mixing stoichiometry. (3) This composition variation enhances electrostatic attractions between oppositely charged surfactant head groups, thus resulting in less-curved aggregates. In particular, the present apparent host-guest selectivity is of remarkably high values, and the selectivity stems from the bias of the aggregation equilibrium rather than the difference in binding constants. Moreover, beta-CD is defined as a "stoichiometry booster" for the whole class of cationic/anionic surfactant systems, which provides an additional degree of freedom to directly adjust aggregate compositions of the systems. The stoichiometry boosting of the compositions can in turn affect or even determine microstructures and macroproperties of the systems.

Predicting liquid immiscibility in multicomponent nuclear waste glasses

International Nuclear Information System (INIS)

Peeler, D.K.; Hrma, P.R.

1994-01-01

Taylor's model for predicting amorphous phase separation in complex, multicomponent systems has been applied to high-level (simulated) radioactive waste glasses at the U.S. Department of Energy's Hanford site. Taylor's model is primarily based on additions of modifying cations to a Na 2 O-B 2 O 3 -SiO 2 (NBS) submixture of the multicomponent glass. The position of the submixture relative to the immiscibility dome defines the development probability of amorphous phase separation. Although prediction of amorphous phase separation in Hanford glasses (via experimental SEM/TEM analysis) is the primary thrust of this work; reported durability data is also provides limited insight into the composition/durability relationship. Using a modified model similar to Taylor's, the results indicate that immiscibility may be predicted for multicomponent waste glasses by the addition of Li 2 O to the open-quotes alkaliclose quotes corner of the NBS submixture

Study of the spheroidization process of glass particles for selective internal radiotherapy

International Nuclear Information System (INIS)

Barros Filho, Eraldo Cordeiro

2012-01-01

The selective internal radiotherapy is an alternative method to treat hepatocellular carcinoma. Glass microspheres containing radionuclides are introduced in the liver through the hepatic artery, and they are housed preferentially in the region where the cancer cells are located. The microspheres are trapped in the arterioles which feed the tumors, and the β - particles annihilate the cancer cells. When these particles simultaneously emit γ rays, they can also be used to provide images of the tumor. The glass particles must be spherical to avoid unnecessary bleeding, and the particle size must be restricted to a range which is appropriated to trap them and avoid the migration to other parts of the body. Furthermore, they must have a good chemical durability and be nontoxic. The particle size distribution of microspheres is not easily predicted based on the original irregular particles since the variation of the aspect ratio and the presence of agglomerates can influence the final result. In the present work, the spheroidization process to obtain microspheres for radiotherapy treatment was studied. The glass microspheres were characterized by X-rays diffraction, Energy Dispersive X-rays Fluorescence Spectroscopy, Differential Scanning Calorimetry, Specific Superficial Area and cytotoxicity test. The dissolution rate in distilled water at 90 degree C (DR∼10 -8 g.cm - 2.min -1 ), density (2.79g.cm -3 ), viscosity, and size particle distribution were determined. The surface morphological aspect was evaluated by Scanning Electron Microscopy before and after the chemical durability tests in SBF and after the neutron irradiation. It is proposed that the produced material should be sieved to select the most suitable microspheres

Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

Science.gov (United States)

Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A

2017-06-06

With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (K d ). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (K d ) decreasing as follows: K d Na + > K d NH 4 + ≥ K d K + > K d Ca 2+ ≥ K d Mg 2+ > K d Al 3+ . This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium K d values, allowed for

A structural bond strength model for glass durability

International Nuclear Information System (INIS)

Feng, Xiangdong; Metzger, T.B.

1996-01-01

A glass durability model, structural bond strength (SBS) model was developed to correlate glass durability with its composition. This model assumes that the strengths of the bonds between cations and oxygens and the structural roles of the individual elements in the glass arc the predominant factors controlling the composition dependence of the chemical durability of glasses. The structural roles of oxides in glass are classified as network formers, network breakers, and intermediates. The structural roles of the oxides depend upon glass composition and the redox state of oxides. Al 2 O 3 , ZrO 2 , Fe 2 O 3 , and B 2 O 3 are assigned as network formers only when there are sufficient alkalis to bind with these oxides. CaO can also improve durability by sharing non-bridging oxygen with alkalis, relieving SiO 2 from alkalis. The percolation phenomenon in glass is also taken into account. The SBS model is applied to correlate the 7-day product consistency test durability of 42 low-level waste glasses with their composition with an R 2 of 0.87, which is better than 0.81 obtained with an eight-coefficient empirical first-order mixture model on the same data set

Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

Energy Technology Data Exchange (ETDEWEB)

Saykally, Richard J; Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

2008-01-08

We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings.

Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

International Nuclear Information System (INIS)

Saykally, Richard J; Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

2008-01-01

We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings

A Molecular Dynamics Study on Selective Cation Depletion from an Ionic Liquid Droplet under an Electric Field

Science.gov (United States)

Yang, Yudong; Ahn, Myungmo; Im, Dojin; Oh, Jungmin; Kang, Inseok

2017-11-01

General electrohydrodynamic behavior of ionic liquid droplets under an electric field is investigated using MD simulations. Especially, a unique behavior of ion depletion of an ionic liquid droplet under a uniform electric field is studied. Shape deformation due to electric stress and ion distributions inside the droplet are calculated to understand the ionic motion of imidazolium-based ionic liquid droplets with 200 ion pairs of 2 kinds of ionic liquids: EMIM-NTf2 and EMIM-ES. The intermolecular force between cations and anions can be significantly different due to the nature of the structure and charge distribution of the ions. Together with an analytical interpretation of the conducting droplet in an electric field, the MD simulation successfully explains the mechanism of selective ion depletion of an ionic liquid droplet in an electric field. The selective ion depletion phenomenon has been adopted to explain the experimentally observed retreating motion of a droplet in a uniform electric field. The effect of anions on the cation depletion phenomenon can be accounted for from a direct approach to the intermolecular interaction. This research was supproted by the National Research Foundation of Korea (NRF) Grant funded by the Korea government (MSIP) (No. 2017R1D1A1B05035211).

Hafnium in peralkaline and peraluminous boro-aluminosilicate glass, and glass subcomponents: a solubility study

International Nuclear Information System (INIS)

Davis, Linda L.; Darab, John G.; Qian, Maoxu; Zhao, Donggao; Palenik, Christopher S.; Li, Hong; Strachan, Denis M.; Li, Liyu

2003-01-01

A relationship between the solubility of hafnia (HfO2) and the host glass composition was explored by determining the solubility limits of HfO2 in peralkaline and peraluminous borosilicate glasses in the system SiO2-Al2O3-B2O3-Na2O, and in glasses in the system SiO2-Na2O-Al2O3 in air at 1450 C. The only Hf-bearing phase to crystallize in the peralkaline borosilicate melts is hafnia, while in the boron-free melts sodium-hafnium silicates crystallize. All peraluminous borosilicate melts crystallize hafnia, but the slightly peraluminous glasses also have sector-zoned hafnia crystals that contain Al and Si. The more peraluminous borosilicate glasses also crystallize a B-containing mullite. The general morphology of the hafnia crystals changes as peralkalinity (Na2O/(Na2O+Al2O3)) decreases, as expected in melts with increasing viscosity. In all of the glasses with Na2O > Al2O3, the solubility of hafnia is linearly and positively correlated with Na2O/(Na2O + Al2O3) or Na2O - Al2O3 (excess sodium), despite the presence of 5 to 16 mol% B2O3. The solubility of hafnia is higher in the sodium-aluminum borosilicate glasses than in the sodium-aluminosilicate glasses, suggesting that the boron is enhancing the effect that excess sodium has on the incorporation of Hf into the glass structure. The results of this solubility study are compared to other studies of high-valence cation solubility in B-free silicate melts. From this, for peralkaline B-bearing glasses, it is shown that, although the solubility limits are higher, the solution behavior of hafnia is the same as in B-free silicate melts previously studied. By comparison, also, it is shown that in peraluminous melts, there must be a different solution mechanism for hafnia: different than for peralkaline sodium-aluminum borosilicate glasses and different than for B-free silicate melts studied by others

CATION EXCHANGE METHOD FOR THE RECOVERY OF PROTACTINIUM

Science.gov (United States)

Studier, M.H.; Sullivan, J.C.

1959-07-14

A cation exchange prccess is described for separating protactinium values from thorium values whereby they are initially adsorbed together from an aqueous 0.1 to 2 N hydrochloric acid on a cation exchange resin in a column. Then selectively eluting the thorium by an ammonium sulfate solution and subsequently eluting the protactinium by an oxalate solution.

Mie scattering in heavy-metal fluoride glasses

International Nuclear Information System (INIS)

Edgar, A.

1996-01-01

Heavy-metal fluoride glasses comprise mixtures of heavy-cation fluorides such as those of zirconium, barium, and lanthanum together with some stabilising fluorides such as AlF 3 . For particular relative proportions, the mixtures form a glass rather than a polycrystalline material when quenched from the melt. The particularly useful features of these glasses are the wide spectral region (∼200nm-8000nm) over which they are transparent, the low minimum attenuation at the centre of the spectral window, and the ease with which optically-active rare-earth ions can be incorporated, leading to potential applications in passive and active fibre optics. The minimal attenuation, which is potentially lower than for silica fibre, is generally limited by wavelength-independent scattering by particle and gas bubble inclusions. We have observed a new wavelength-dependent scattering effect in fluoride glass of the well-known composition ZLABN20. In this paper, we report on work in progress on the optical extinction and scattering spectrum of the fluoride glasses, and discuss the spectra in terms of Mie's scattering theory. The chemical nature of the scattering centres in these nominally 'pure' glasses is at present a puzzle, and relative merits of various possible models will be compared

Selective adsorption and ion exchange of metal cations and anions with silico-titanates and layered titanates

International Nuclear Information System (INIS)

Anthony, R.G.; Philip, C.V.

1993-01-01

Metal ions may be removed from aqueous wastes from metal processing plants and from refineries. They may also be used in concentrating radioactive elements found in dilute, aqueous, nuclear wastes. A new series of silico-titanates and alkali titanates are shown to have specific selectivity for cations of lead, mercury, and cadmium and the dichromate anion in solutions with low and high pH. Furthermore, one particular silico-titanate, TAM-5, was found to be highly selective for Cs + and Sr 2+ in solutions of 5.7 M Na + and 0.6 M Oh - . A high potential exists for these materials for removing Cs + and Sr 2+ from radioactive aqueous wastes containing high concentrations of Na + at high and low pH

Drug loading to lipid-based cationic nanoparticles

International Nuclear Information System (INIS)

Cavalcanti, Leide P.; Konovalov, Oleg; Torriani, Iris L.; Haas, Heinrich

2005-01-01

Lipid-based cationic nanoparticles are a new promising option for tumor therapy, because they display enhanced binding and uptake at the neo-angiogenic endothelial cells, which a tumor needs for its nutrition and growth. By loading suitable cytotoxic compounds to the cationic carrier, the tumor endothelial and consequently also the tumor itself can be destroyed. For the development of such novel anti-tumor agents, the control of drug loading and drug release from the carrier matrix is essential. We have studied the incorporation of the hydrophobic anti-cancer agent Paclitaxel (PXL) into a variety of lipid matrices by X-Ray reflectivity measurements. Liposome suspensions from cationic and zwitterionic lipids, comprising different molar fractions of Paclitaxel, were deposited on planar glass substrates. After drying at controlled humidity, well ordered, oriented multilayer stacks were obtained, as proven by the presence of bilayer Bragg peaks to several orders in the reflectivity curves. The presence of the drug induced a decrease of the lipid bilayer spacing, and with an excess of drug, also Bragg peaks of drug crystals could be observed. From the results, insight into the solubility of Paclitaxel in the model membranes was obtained and a structural model of the organization of the drug in the membrane was derived. Results from subsequent pressure/area-isotherm and grazing incidence diffraction (GID) measurements performed with drug/lipid Langmuir monolayers were in accordance with these conjectures

Aqueous corrosion of french R7T7 nuclear waste glass: selective then congruent dissolution by pH increase

International Nuclear Information System (INIS)

Advocat, T.; Vernaz, E.; Crovisier, J.L.

1991-01-01

A study of the corrosion of a borosilicate nuclear glass shows the strong effect of the pH on the dissolution mechanism. Acidic media lead to selective extraction of the glass modifier elements (Li, Na, Ca) as well as B, while dissolution is congruent under alkaline conditions. The silica dissolution rate significantly increases with increasing pH [fr

Glass formation, properties, and structure of soda-yttria-silicate glasses

Science.gov (United States)

Angel, Paul W.; Hann, Raiford E.

1991-01-01

The glass formation region of the soda yttria silicate system was determined. The glasses within this region were measured to have a density of 2.4 to 3.1 g/cu cm, a refractive index of 1.50 to 1.60, a coefficient of thermal expansion of 7 x 10(exp -6)/C, softening temperatures between 500 and 780 C, and Vickers hardness values of 3.7 to 5.8 GPa. Aqueous chemical durability measurements were made on select glass compositions while infrared transmission spectra were used to study the glass structure and its effect on glass properties. A compositional region was identified which exhibited high thermal expansion, high softening temperatures, and good chemical durability.

Glass formation, properties and structure of soda-yttria-silica glasses

Science.gov (United States)

Angel, Paul W.; Hann, Raiford E.

1992-01-01

The glass formation region of the soda yttria silicate system was determined. The glasses within this region were measured to have a density of 2.4 to 3.1 g/cu cm, a refractive index of 1.50 to 1.60, a coefficient of thermal expansion of 7 x 10(exp -6)/C, softening temperatures between 500 and 780 C, and Vickers hardness values of 3.7 to 5.8 GPa. Aqueous chemical durability measurements were made on select glass compositions while infrared transmission spectra were used to study the glass structure and its effect on glass properties. A compositional region was identified which exhibited high thermal expansion, high softening temperatures, and good chemical durability.

Selective dissolution of halide perovskites as a step towards recycling solar cells

Science.gov (United States)

Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; Park, So Yeon; Li, Zhen; Zhu, Kai; Jung, Hyun Suk

2016-05-01

Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Herein, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easily decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb2+ cations. After 10 cycles of recycling, a mesoporous TiO2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells.

Selective dissolution of halide perovskites as a step towards recycling solar cells.

Science.gov (United States)

Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; Park, So Yeon; Li, Zhen; Zhu, Kai; Jung, Hyun Suk

2016-05-23

Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Herein, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easily decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb(2+) cations. After 10 cycles of recycling, a mesoporous TiO2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells.

Cationic mobility in polystyrene sulfone exchangers - Application to the elution of a cation on an exchange column

International Nuclear Information System (INIS)

Menin, Jean-Pierre

1969-01-01

The aim of this work is to improve elutions and separations carried out on inorganic exchangers by selective electromigration of the ionic species to be displaced. To do this, it has been found indispensable to make a fundamental study of the mobility of cations in exchangers. As the field for this research we have chosen those organic exchangers whose structure and behaviour with respect to ion-exchange are much better known that in the case of their inorganic equivalents. We have related the idea of the equivalent conductivity to that of the cation mobility in the exchanger, and this has entailed determining the specific conductivity of the exchanger and the cation concentration in the resin. The results obtained have allowed us to draw up a hypothesis concerning the cation migration mechanism in the exchanger. The third part of our work has been the application of the preceding results to an operation on an ion-exchange column, viz. the elution by an acid solution of a single fixed ion, magnesium or strontium. This work has enabled us to show that the electromigration of a cation during its elution can markedly accelerate or retard this elution. (author) [fr

Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

Science.gov (United States)

Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

2016-12-22

Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

Spatio-selective surface modification of glass assisted by laser-induced deposition of gold nanoparticles

International Nuclear Information System (INIS)

Takahashi, Hironobu; Niidome, Yasuro; Hisanabe, Hideyuki; Kuroiwa, Keita; Kimizuka, Nobuo; Yamada, Sunao

2006-01-01

Using pulsed laser irradiation (532 nm), dodecanethiol-capped gold nanoparticles (DT-Au) were deposited on the laser-irradiated region of a hydrophobic glass substrate modified with dimethyloctadecylchlorosilane (DMOS). After removal of deposited DT-Au, the laser-deposited region on the substrate was hydrophilic, as verified by static water contact angles. X-ray photoelectron spectroscopy suggested that the naked glass surface was not exposed at the hydrophilic region. Immersion of the substrate into gold nanorod (NR) solution selectively immobilized NRs on the hydrophilic surface via electrostatic interactions, indicating that the hydrophilic region was an anionic surface. From these results, it is expected that some immobilized DMOS groups on the laser-irradiated region of the substrate were oxidized during DT-Au deposition and fragmentation of the deposited DT-Au

Identifi cation of Sectarianism

Directory of Open Access Journals (Sweden)

Martinovich Vladimir

2016-03-01

Full Text Available «New religious movements and society» is traditionally one of the most sophisticated topics in the area of new religions studies. Its problem field is so huge that up to now by far not all important research themes where even touched by scientists from all over the world. The problem of the process of the identification of sectarianism by diff erent societal institutions is one of such untouched themes that is taken as the main subject of this article. This process by itself is an inseparable part of the every societal deliberate reaction to the very existence of unconventional religiosity, its unstructured and mainly structured types. The focal point of the article is step-by-step analysis of the general structure elements of the process of the identification of sectarianism without any reference to the specific time and place of its flow. Special attention is paid to the analysis of the subjects of the identification of sectarianism, to the criteria for religious groups to be qualified as new religious movements, and to the specific features of the process of documents filtration. The causes of selective perception of sectarianism are disclosed. Some main consequences and unpredictable outcomes of the process of the identification of sectarianism are described.

Cation radicals of xanthophylls.

Science.gov (United States)

Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

2007-10-01

Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

Qualitative and quantitative analysis of cations and anions using ion selective detectors in capillary electrophoresis

International Nuclear Information System (INIS)

Nann, A.

1994-01-01

The present work reports on the application of ion-selective microelectrodes as potentiometric detectors for the qualitative and quantitative analysis of cations and anions separated by capillary electrophoresis. Due to the high internal resistance of microelectrodes, their potentials are strongly affected by external electrical fields. Therefore, the influence of the electrophoretic field on the electrode response had to be kept at a minimum. With the electrode tip inserted in the capillary aperture (on-column detection), heavy drifts and noise of the signals were observed, mainly because the electrophoretic potential is superimposed on the Nernstian electrode response. As the potential inside the capillary is site-dependent, already minor movements and vibrations not perceptible under the light microscopy cause unacceptable disturbances of the electrode signal. One possibility to solve the problem consists in post- or off-column detection, i.e., with the detector located outside the influence of the electrophoretic field. If quantitative analyses with maximum resolution are to be achieved, only on-column detection is suitable because outside the capillary, the separation efficiency drops drastically. By etching the detector-side capillary end to a conical aperture, the field strength in the last 10 μm fell approximately 1/25 as compared with that in a cylindrical one. Thus, potential drifts and noise were reduced correspondingly so that on-column detection can also be used for potentiometric detection. To obtain quantitative results, the signals of the ion-selective detector were first delogarithmized and then integrated over time. Thus, it was possible to quantify cations and anions with a coefficient of variations ≤5%. (author) figs., tabs., 179 refs

The relationship between structural and optical properties of Se-Ge-As glasses

Science.gov (United States)

Ghayebloo, M.; Rezvani, M.; Tavoosi, M.

2018-05-01

In this study, the structural and optical characterization of bulk Se-Ge-As glasses has been investigated. In this regards, six different Se60Ge40-xAsx (0 ≤ x ≤ 25) glasses were prepared by conventional melt quenching technique in quartz ampoule. The produced samples were characterized using X-ray diffraction (XRD), Raman spectroscopy, differential thermal analysis (DTA), ultraviolet-visible (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. The fundamental absorption edge for all the glasses was analyzed in terms of the theory proposed by Davis and Mott. According to achieved results, fully amorphous phase can easily form in different Se-Ge-As systems. The thermal and optical characteristic of Se60Ge40-xAsx glasses shows anomalous behavior at 5 mol% of As for the glass transition temperature, transmittance, absorption edge, optical energy gap and Urbach energy. The highest glass transition temperature, transmittance, optical energy gap and Urbach energy properties were achieved in Se60Ge35As5 glass as a result of the highest connectivity of cations and anions in glass network.

Rare earth impact on glass structure and alteration kinetics

International Nuclear Information System (INIS)

Molieres, E.

2012-01-01

This work is related to the question of the geological deep repository of high-level waste glass. These wastes include fission products and minor actinides, elements which can be simulated by rare earths. As new glass compositions could enable increased rare earth concentrations, it is crucial to know and understand rare earth impact on glass structure on the one hand, and on glass alteration kinetics or their incorporation into an altered layer. This work studied simplified borosilicate glasses in order to limit synergetic effects between rare earths and other elements. Various complementary techniques were used to characterize pristine and altered glasses (solid-high resolution NMR, Raman spectroscopy, fluorescence, SIMS, SAXS). Firstly, the structural role of a rare earth is discussed and is compared to a calcium cation. The local environment of rare earths is also probed. Secondly, rare earth (nature and concentration) impact on several alteration regimes was studied (initial rate, rate drop). Then, after alteration, rare earth elements being retained within the altered layer, the structural impact of rare earth elements (and their local environment) in this alteration layer was also investigated. (author) [fr

Temperature-induced structural changes in fluorozirconate glasses and liquids

International Nuclear Information System (INIS)

Sen, S.; Youngman, R.E.

2002-01-01

The atomic structure and its temperature dependence in fluorozirconate glasses and supercooled liquids have been studied with high-resolution and high-temperature 19 F and 23 Na nuclear-magnetic-resonance (NMR) spectroscopy. The 19 F NMR spectra in these glasses show the presence of multiple F environments. Temperature dependence of the 19 F magic-angle-spinning NMR spectra indicates a progressive change in the average F coordination environment in the glass structure, besides motional narrowing due to substantial mobility of F - ions. The observed change in the average 19 F NMR chemical shift is consistent with progressive breaking of the Zr-F-Zr linkages in the glass structure with increasing temperature. The onset of such a change in F speciation is observed at temperatures well below T g . This result is evidence of changes in the average equilibrium structure in an inorganic glass-forming liquid at T g , albeit on a local scale. The 23 Na NMR spectra indicate that the cations in these glasses become significantly mobile only at temperatures T≥T g , which allows for the onset of global structural relaxation and viscous flow

Synthesis and SMM behaviour of trinuclear versus dinuclear 3d-5f uranyl(v)-cobalt(ii) cation-cation complexes.

Science.gov (United States)

Chatelain, Lucile; Tuna, Floriana; Pécaut, Jacques; Mazzanti, Marinella

2017-05-02

Trinuclear versus dinuclear heterodimetallic U V O 2 + Co 2+ complexes were selectively assembled via a cation-cation interaction by tuning the ligand. The trimeric complex 2, with a linear [Co-O[double bond, length as m-dash]U[double bond, length as m-dash]O-Co] core, exhibits magnetic exchange and slow relaxation with a reversal barrier of 30.5 ± 0.9 K providing the first example of a U-Co exchange-coupled SMM.

Heavy metal cations permeate the TRPV6 epithelial cation channel.

Science.gov (United States)

Kovacs, Gergely; Danko, Tamas; Bergeron, Marc J; Balazs, Bernadett; Suzuki, Yoshiro; Zsembery, Akos; Hediger, Matthias A

2011-01-01

TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications. Copyright © 2010 Elsevier Ltd. All rights reserved.

Baseline LAW Glass Formulation Testing

International Nuclear Information System (INIS)

Kruger, Albert A.; Mooers, Cavin; Bazemore, Gina; Pegg, Ian L.; Hight, Kenneth; Lai, Shan Tao; Buechele, Andrew; Rielley, Elizabeth; Gan, Hao; Muller, Isabelle S.; Cecil, Richard

2013-01-01

The major objective of the baseline glass formulation work was to develop and select glass formulations that are compliant with contractual and processing requirements for each of the LAW waste streams. Other objectives of the work included preparation and characterization of glasses with respect to the properties of interest, optimization of sulfate loading in the glasses, evaluation of ability to achieve waste loading limits, testing to demonstrate compatibility of glass melts with melter materials of construction, development of glass formulations to support ILAW qualification activities, and identification of glass formulation issues with respect to contract specifications and processing requirements

Magnetic Glass Ceramics by Sintering of Borosilicate Glass and Inorganic Waste

Directory of Open Access Journals (Sweden)

Inès M. M. M. Ponsot

2014-07-01

Full Text Available Ceramics and glass ceramics based on industrial waste have been widely recognized as competitive products for building applications; however, there is a great potential for such materials with novel functionalities. In this paper, we discuss the development of magnetic sintered glass ceramics based on two iron-rich slags, coming from non-ferrous metallurgy and recycled borosilicate glass. The substantial viscous flow of the glass led to dense products for rapid treatments at relatively low temperatures (900–1000 °C, whereas glass/slag interactions resulted in the formation of magnetite crystals, providing ferrimagnetism. Such behavior could be exploited for applying the obtained glass ceramics as induction heating plates, according to preliminary tests (showing the rapid heating of selected samples, even above 200 °C. The chemical durability and safety of the obtained glass ceramics were assessed by both leaching tests and cytotoxicity tests.

Properties Of Soda/Yttria/Silica Glasses

Science.gov (United States)

Angel, Paul W.; Hann, Raiford E.

1994-01-01

Experimental study of glass-formation compositional region of soda/ yttria/silicate system and of selected physical properties of glasses within compositional region part of continuing effort to identify glasses with high coefficients of thermal expansion and high softening temperatures, for use as coatings on superalloys and as glass-to-metal seals.

Effect of alkali ion on relaxation properties of binary alkali-borate glasses

International Nuclear Information System (INIS)

Lomovskoj, V.A.; Bartenev, G.M.

1992-01-01

Method of relaxation spectrometry were used to analyze the data on internal friction spectra of lithium, sodium, potassium and rubidium alkali-borate glasses in wide range of temperatures and frequencies. The nature of two relaxation processes was clarified: β m -process, related with mobility of alkaline metal cations, and α-process (vitrification), conditioned by system transformation from viscous-flow to vitreous state. It is shown that atomic-molecular mechanism of vitrification process changes when passing from vitreous B 2 O 3 to alkali-borate glasses

Titanium (III) cation selective electrode based on synthesized tris(2pyridyl) methylamine ionophore and its application in water samples

Science.gov (United States)

Rezayi, Majid; Karazhian, Reza; Abdollahi, Yadollah; Narimani, Leila; Sany, Seyedeh Belin Tavakoly; Ahmadzadeh, Saeid; Alias, Yatimah

2014-04-01

The introduction of low detection limit ion selective electrodes (ISEs) may well pave the way for the determination of trace targets of cationic compounds. This research focuses on the detection of titanium (III) cation using a new PVC-membrane sensor based on synthesized tris(2pyridyl) methylamine (tpm) ionophore. The application and validation of the proposed sensor was done using potentiometric titration, inductively coupled plasma atomic emission spectrometry (ICP-AES), and atomic absorption spectrometry (AAS). The membrane sensor exhibited a Nernstian response to the titanium (III) cation over a concentration range of 1.0 × 10-6-1.0 × 10-2 M and pH range from 1-2.5. The Nernstian slope, the lower of detection (LOD), and the response time (t95%) of the proposed sensor were 29.17 +/- 0.24 mV/dec, 7.9 × 10-7 M, and 20 s, respectively. The direct determination of 4-39 μg/ml of titanium (III) standard solution showed an average recovery of 94.60 and a mean relative standard deviation of 1.8 at 100.0 μg/ml. Finally, the utilization of the electrodes as end-point indicators for potentiometric titration with EDTA solutions for titanium (III) sensor was successfully carried out.

Structural and energetic study of cation-π-cation interactions in proteins.

Science.gov (United States)

Pinheiro, Silvana; Soteras, Ignacio; Gelpí, Josep Lluis; Dehez, François; Chipot, Christophe; Luque, F Javier; Curutchet, Carles

2017-04-12

Cation-π interactions of aromatic rings and positively charged groups are among the most important interactions in structural biology. The role and energetic characteristics of these interactions are well established. However, the occurrence of cation-π-cation interactions is an unexpected motif, which raises intriguing questions about its functional role in proteins. We present a statistical analysis of the occurrence, composition and geometrical preferences of cation-π-cation interactions identified in a set of non-redundant protein structures taken from the Protein Data Bank. Our results demonstrate that this structural motif is observed at a small, albeit non-negligible frequency in proteins, and suggest a preference to establish cation-π-cation motifs with Trp, followed by Tyr and Phe. Furthermore, we have found that cation-π-cation interactions tend to be highly conserved, which supports their structural or functional role. Finally, we have performed an energetic analysis of a representative subset of cation-π-cation complexes combining quantum-chemical and continuum solvation calculations. Our results point out that the protein environment can strongly screen the cation-cation repulsion, leading to an attractive interaction in 64% of the complexes analyzed. Together with the high degree of conservation observed, these results suggest a potential stabilizing role in the protein fold, as demonstrated recently for a miniature protein (Craven et al., J. Am. Chem. Soc. 2016, 138, 1543). From a computational point of view, the significant contribution of non-additive three-body terms challenges the suitability of standard additive force fields for describing cation-π-cation motifs in molecular simulations.

Sulphate solubility and sulphate diffusion in oxide glasses: implications for the containment of sulphate-bearing nuclear wastes

International Nuclear Information System (INIS)

Lenoir, M.

2009-09-01

The thesis deals with sulphate solubility and sulphate diffusion in oxide glasses, in order to control sulphate incorporation and sulphate volatilization in nuclear waste glasses. It was conducted on simplified compositions, in the SiO 2 -B 2 O 3 -R 2 O (R = Li, Na, K, Cs), SiO 2 -B 2 O 3 -BaO and V 2 O 5 -B 2 O 3 -BaO systems. These compositions allowed us to study the influence of the nature of network-modifying ions (Li + , Na + , K + , Cs + or Ba 2+ ) and also of former elements (Si, B, V), on structure and properties of glasses. Sulphate volatility is studied in sodium borosilicate melts using an innovative technique of sulphate quantitation with Raman spectroscopy. This technique is useful to obtain kinetic curves of sulphate volatilization. The establishment of a model to fit these curves leads to the determination of diffusion coefficients of sulphate. These diffusion coefficients can thus be compared to diffusion coefficients of other species, determined by other techniques and presented in the literature. They are also linked to diffusion coefficients in relation with the viscosity of the melts. Concerning sulphate solubility in glasses, it depends on glass composition and on the nature of sulphate incorporated. Sulphate incorporation in alkali borosilicate glasses leads to the formation of a sulphate layer floating on top of the melt. Sulphate incorporation in barium borosilicate and boro-vanadate glasses leads to the crystallization of sulphate species inside the vitreous matrix. Moreover, sulphate solubility is higher in these glasses than in alkali borosilicates. Finally, exchanges between cations present in glasses and cations present in the sulphate phase are also studied. (author)

Accuracy of a selection criterion for glass forming ability in the Ni–Nb–Zr system

International Nuclear Information System (INIS)

Déo, L.P.; Oliveira, M.F. de

2014-01-01

Highlights: • We applied a selection in the Ni–Nb–Zr system to find alloys with high GFA. • We used the thermal parameter γ m to evaluate the GFA of alloys. • The correlation between the γ m parameter and R c in the studied system is poor. • The effect of oxygen impurity reduced dramatically the GFA of alloys. • Unknown intermetallic compounds reduced the accuracy of the criterion. - Abstract: Several theories have been developed and applied in metallic systems in order to find the best stoichiometries with high glass forming ability; however there is no universal theory to predict the glass forming ability in metallic systems. Recently a selection criterion was applied in the Zr–Ni–Cu system and it was found some correlation between experimental and theoretical data. This criterion correlates critical cooling rate for glass formation with topological instability of stable crystalline structures; average work function difference and average electron density difference among the constituent elements of the alloy. In the present work, this criterion was applied in the Ni–Nb–Zr system. It was investigated the influence of factors not considered in the calculation and on the accuracy of the criterion, such as unknown intermetallic compounds and oxygen contamination. Bulk amorphous specimens were produced by injection casting. The amorphous nature was analyzed by X-ray diffraction and differential scanning calorimetry; oxygen contamination was quantified by the inert gas fusion method

Method for in situ determination cation exchange capacities of subsurface formations

International Nuclear Information System (INIS)

Fertl, W.H.; Welker, D.W.

1980-01-01

A method is disclosed for the in situ examination of each subsurface formation penetrated by a borehole to ascertain the cation exchange capacity of such formations within a geological region. Natural γ ray logging is used to develop signals functionally related to the total γ radiation and to the potassium-40, uranium and thorium energy-band radiations. A first borehole is traversed by a potential γ ray spectrometer to provide selected measurements of natural γ radiation. Core samples are taken from the logged formation and laboratory tests performed to determine the cation exchange capacity thereof. The cation exchange capacities thus are developed then correlated with selected parameters provided by the γ ray spectrometer to establish functional relationships. Cation exchange capacities of formations in subsequent boreholes within the region are then determined in situ by use of the natural γ ray spectrometer and these established relationships. (author)

Study of nuclear glasses alteration gel and synthesis of some model gels; Etude du gel d`alteration des verres nucleaires et synthese de gels modeles

Energy Technology Data Exchange (ETDEWEB)

Ricol, S

1995-10-05

This work deals with the general problem of alteration of the reference nuclear glass R7T7. Attention is paid particularly to the altered layer formed at the glass surface during alteration process. In opposition to previous works, related essentially to glass dissolution kinetics based on chemical analyses of lixiviated elements, this thesis deals with alteration problems through structural studies of the reference glass and derived gel. This approach allows the determination of mechanisms for the gel formation and a better understanding of the behaviour of glasses towards lixiviation. Both approaches appeared complementary. Based on several spectroscopic techniques, this work showed the particular role of cations such as calcium, zirconium and iron. Studies of silica-based synthetic gels showed the synergic effect of formers cation and of one highly coordinated cation. The variation of the wavenumber related to Si-O-Si asymmetric stretching vibration can be correlated to O/Si ratio for ternary systems Si/Na/Zr. On the contrary, the Si losses of the materials depend on the number of non-bridging oxygen atoms. In the perspective of long-term behaviour, the alteration gel presents better characteristics than initial glass. It is therefore a highly stable material in static conditions. In the same way, synthetic gels are materials with very low solubilities (much lower than the alteration gel) and could be used as confining matrices. (authors). refs., 71 figs., 37 tabs.

The glass block site radionuclide migration study

International Nuclear Information System (INIS)

Killey, R.W.D.; Champ, D.R.

1990-01-01

In 1960 25 nepheline syenite glass blocks containing 14 TBq of mixed fission products in 50 kg of glass were placed below the water table in a shallow sand aquifer at Chalk River Laboratories. Experimental studies undertaken at the site since 1960 have included detailed mapping of the plume of 90 Sr in 1963, 1966 and 1971. Mathematical modeling studies have employed the radiostrontium plume data in determining the split between ion exchange and chemisorption of 90 Sr, and in obtaining reaction rate data for chemisorption. The distribution of 137 Cs on downgradient soils was mapped in 1963 and 1979. An extended plume of low-level 137 Cs contamination observed in the 1979 study prompted an investigation of the role of particulate materials in radionuclide transport. IN 1983, large volume groundwater sampling and separation of cationic, anionic, and neutral dissolved species, as well as particulates, detected anionic and cationic dissolved europium isotopes (154 and 155), and again encountered particulate 137 Cs. A variety of investigations of cesium and strontium sorption have provided a data base on sediment mineralogy, particle surface features, and information on sorption sites and processes. The year 1990 saw the inauguration of a three-year program to update investigations of radionuclide release, transport, and sorption at the glass block site. The first stage of the program has been a detailed definition and simulation of the hydrogeologic setting. Plume mapping and aqueous speciation studies are in progress. This paper summarizes past investigations, reviews the status of the current program, and discusses components of future studies, including investigations of sediment sorption mechanisms. (Author) (17 refs., 8 figs.)

Evaluation of long-term leaching of borosilicate glass in pure water

International Nuclear Information System (INIS)

Lanza, F.; Parnisari, E.

1979-01-01

In order to confirm the validity of the model of the dissolving sphere, a series of tests of leaching of borosilicate glasses has been performed. The leaching rate is followed by measurements of weight loss and analysis of the surface composition. An accumulation at the surface of the less soluble cations is observed

A cell shrinkage-induced non-selective cation conductance with a novel pharmacology in Ehrlich-Lettre-ascites tumour cells

DEFF Research Database (Denmark)

Lawonn, Peter; Hoffmann, Else K; Hougaard, Charlotte

2003-01-01

In whole-cell recordings on Ehrlich-Lettre-ascites tumour (ELA) cells, the shrinkage-induced activation of a cation conductance with a selectivity ratio P(Na):P(Li):P(K):P(choline):P(NMDG) of 1.00:0.97:0.88:0.03:0.01 was observed. In order of potency, this conductance was blocked by Gd(3+)=benzam......-sensitive and -insensitive channels. In addition, because of its pharmacological profile, it may possibly be related to epithelial Na+ channels (ENaCs)....

Energy Saving Glass Lamination via Selective Radio Frequency Heating

Energy Technology Data Exchange (ETDEWEB)

Allan, Shawn M; Baranova, Inessa; Poley, Joseph; Reis, Henrique

2012-02-27

This project focused on advancing radio-frequency (RF) lamination technology closer to commercial implementation, in order to reduce the energy intensity of glass lamination by up to 90%. Lamination comprises a wide range of products including autoglass, architectural safety and innovative design glass, transparent armor (e.g. bullet proof glass), smart glass, mirrors, and encapsulation of photovoltaics. Lamination is also the fastest growing segment of glass manufacturing, with photovoltaics, architectural needs, and an anticipated transition to laminated side windows in vehicles. The state-of-the-art for glass lamination is to use autoclaves, which apply heat and uniform gas pressure to bond the laminates over the course of 1 to 18 hours. Laminates consist of layers of glass or other materials bonded with vinyl or urethane interlayers. In autoclaving, significant heat energy is lost heating the chamber, pressurized air, glass racks, and the glass. In RF lamination, the heat is generated directly in the vinyl interlayer, causing it to heat and melt quickly, in just 1 to 10 minutes, without significantly heating the glass or the equipment. The main purpose of this project was to provide evidence that low energy, rapid RF lamination quality met the same standards as conventionally autoclaved windows. The development of concepts for laminating curved glass with RF lamination was a major goal. Other primary goals included developing a stronger understanding of the lamination product markets described above, and to refine the potential benefits of commercial implementation. The scope of the project was to complete implementation concept studies in preparation for continuation into advanced development, pilot studies, and commercial implementation. The project consisted of 6 main tasks. The first dealt with lamination with poly-vinyl butyral (PVB) interlayers, which prior work had shown difficulties in achieving good quality laminates, working with Pilkington North

Energy Saving Glass Lamination via Selective Radio Frequency Heating

Energy Technology Data Exchange (ETDEWEB)

Allan, Shawn M.

2012-02-27

This project focused on advancing radio-frequency (RF) lamination technology closer to commercial implementation, in order to reduce the energy intensity of glass lamination by up to 90%. Lamination comprises a wide range of products including autoglass, architectural safety and innovative design glass, transparent armor (e.g. bullet proof glass), smart glass, mirrors, and encapsulation of photovoltaics. Lamination is also the fastest growing segment of glass manufacturing, with photovoltaics, architectural needs, and an anticipated transition to laminated side windows in vehicles. The state-of-the-art for glass lamination is to use autoclaves, which apply heat and uniform gas pressure to bond the laminates over the course of 1 to 18 hours. Laminates consist of layers of glass or other materials bonded with vinyl or urethane interlayers. In autoclaving, significant heat energy is lost heating the chamber, pressurized air, glass racks, and the glass. In RF lamination, the heat is generated directly in the vinyl interlayer, causing it to heat and melt quickly, in just 1 to 10 minutes, without significantly heating the glass or the equipment. The main purpose of this project was to provide evidence that low energy, rapid RF lamination quality met the same standards as conventionally autoclaved windows. The development of concepts for laminating curved glass with RF lamination was a major goal. Other primary goals included developing a stronger understanding of the lamination product markets described above, and to refine the potential benefits of commercial implementation. The scope of the project was to complete implementation concept studies in preparation for continuation into advanced development, pilot studies, and commercial implementation. The project consisted of 6 main tasks. The first dealt with lamination with poly-vinyl butyral (PVB) interlayers, which prior work had shown difficulties in achieving good quality laminates, working with Pilkington North

Effect of the Callovian-Oxfordian clayey fraction on borosilicate glass alteration

International Nuclear Information System (INIS)

Debure, M.; Frugier, P.; GIN, S.; De Windt, L.; Michau, N.

2012-01-01

easily exchangeable Mg and to check whether remaining Mg, especially structural Mg could still feed the solution. The cation exchange capacity (CEC) and the exchangeable cation population after treatment were measured by the cobaltihexamine test, indicating an enrichment of Na (from 14% to 79% in equivalents) of the exchangeable population at the expense of Ca (from 50% to 4%), Mg (from 15% to 6%) and K (from 18% to 7%) compared to the pristine clay-stone. Synthetic borosilicate Mg-free glasses were used as simplified references of the French nuclear glass R7T7. Batch experiments were performed in closed system at 90 deg. C during 150 days. The clay/glass (C/G) weight ratio ranged from 0.01 to 100 for a liquid/solid (L/S) weight ratio of 20. The specific surface was estimated to be around 0.06 m 2 /g and 100 m 2 /g for the glass powder and the clayey fraction, respectively. Chemical analysis of the batch solutions were carried out with time, as well as XRD, SEM and TOF-SIMS analysis of the solids after completion of the batch experiments. Modeling was performed with the GRAAL kinetic model of glass dissolution that considers elements and water diffusion in the alteration layer (Frugier et al., 2008), implemented within the reactive transport code HYTEC (van der Lee et al., 2003). The experiments showed that the higher the clay/glass ratio, the lower the pH 90deg.C and the higher the glass alteration. As shown in Fig. 1, the pH 90deg.C varied from 8.9 for the lowest clay/glass proportion (C/G 1) to 5.4 for the highest one (C/G = 100). The corresponding mean glass dissolution rates are 15 nm/d and 300 nm/d, respectively. A batch test performed with the sole clayey fraction in pure water yielded a pH 90deg.C of 5.2, whereas the test made with the glass alone led to a pH 90deg.C around 9. The main effect of the clayey fraction in the batch tests seems to drop the pH down to more acidic values that concentrations of B (a tracer of the glass alteration) on the one hand, and of

Degradation of glass in the soil

Energy Technology Data Exchange (ETDEWEB)

Romich, H.; Gerlach, S.; Mottner, P. [Fraunhofer-Institut fur Silicatforschung (ISC), Wertheim-Bronnbach (Germany)

2004-07-01

Full text of publication follows: Glass has been produced and used in Europe for over 2000 years. Glass objects from the Roman period onwards have been excavated during the last centuries. In general, Roman glass is chemically quite stable, and often the only sign of chemical alteration is an iridescent surface, caused by the leaching of cations, which leads to the formation of a hydrated silica-rich layer. Medieval potash glasses are much less durable, and their surfaces are often found deeply leached, sometimes to a point that no unaltered glass remains. These surfaces may be coherent, though fragile, or they are laminar, with no cohesion between the layers at all. In this study an analytical examination of a series of fragments of archaeological glass retrieved from different sites near Cologne and Stuttgart (Germany) has been carried out. Samples of corroded glasses were analysed by optical microscopy and SEM/EDX (surface and cross sections) in order to obtain information about the chemical composition of the bulk glass and the weathered layers. Since the environmental parameters have constantly varied for archaeological objects, mechanistic studies have to rely on laboratory experiments under controlled conditions. For an extensive exposure programme standardised soil or natural garden earth was used, for which the pH was modified. Several corrosion sensitive potash-lime silicate glasses have been designed to study the effect of glass composition. A model glass consisting of SiO{sub 2} (54.2), CaO (28.8) and K{sub 2}O (17.0 weight-%) mostly lead to the formation of a crust on the leached layer, with a total thickness of 100 micrometer (for soil with pH 7 to 8, 12 months exposure). Model glasses also containing Al, Mg and P have built up preferably laminated structures (total thickness up to 200 micrometer). This presentation will give an overview about the variety of degradation phenomena observed on originals and compare the results with controlled laboratory

BNFL Report Glass Formers Characterization

Energy Technology Data Exchange (ETDEWEB)

Schumacher, R.F.

2000-07-27

The objective of this task was to obtain powder property data on candidate glass former materials, sufficient to guide conceptual design and estimate the cost of glass former handling facilities as requested under Part B1 of BNFL Technical and Development Support. Twenty-nine glass forming materials were selected and obtained from vendors for the characterization of their physical properties, durability in caustic solution, and powder flow characteristics. A glass former was selected based on the characterization for each of the ten oxide classes required for Envelope A, B, and C mixtures. Three blends (A, B, and C) were prepared based on formulations provided by Vitreous State Laboratory and evaluated with the same methods employed for the glass formers. The properties obtained are presented in a series of attached Tables. It was determined that five of the ten glass formers, (kyanite, iron oxide, titania, zircon, and zinc oxide) have the potential to cause some level of solids f low problems. The problems might include arching or ratholing in the silo/hopper. In addition, all of the blends may require consideration for their handling.

BNFL Report Glass Formers Characterization

International Nuclear Information System (INIS)

Schumacher, R.F.

2000-01-01

The objective of this task was to obtain powder property data on candidate glass former materials, sufficient to guide conceptual design and estimate the cost of glass former handling facilities as requested under Part B1 of BNFL Technical and Development Support. Twenty-nine glass forming materials were selected and obtained from vendors for the characterization of their physical properties, durability in caustic solution, and powder flow characteristics. A glass former was selected based on the characterization for each of the ten oxide classes required for Envelope A, B, and C mixtures. Three blends (A, B, and C) were prepared based on formulations provided by Vitreous State Laboratory and evaluated with the same methods employed for the glass formers. The properties obtained are presented in a series of attached Tables. It was determined that five of the ten glass formers, (kyanite, iron oxide, titania, zircon, and zinc oxide) have the potential to cause some level of solids f low problems. The problems might include arching or ratholing in the silo/hopper. In addition, all of the blends may require consideration for their handling

π-Cation Interactions in Molecular Recognition: Perspectives on Pharmaceuticals and Pesticides.

Science.gov (United States)

Liang, Zhibin; Li, Qing X

2018-04-04

The π-cation interaction that differs from the cation-π interaction is a valuable concept in molecular design of pharmaceuticals and pesticides. In this Perspective we present an up-to-date review (from 1995 to 2017) on bioactive molecules involving π-cation interactions with the recognition site, and categorize into systems of inhibitor-enzyme, ligand-receptor, ligand-transporter, and hapten-antibody. The concept of π-cation interactions offers use of π systems in a small molecule to enhance the binding affinity, specificity, selectivity, lipophilicity, bioavailability, and metabolic stability, which are physiochemical features desired for drugs and pesticides.

Divalent cation shrinks DNA but inhibits its compaction with trivalent cation.

Science.gov (United States)

Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

2016-05-28

Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

Selective transport of metal ions through cation exchange membrane in the presence of a complexing agent

Energy Technology Data Exchange (ETDEWEB)

Tingchia Huang; Jaukai Wang (National Cheng Kung Univ., Tainan (Taiwan, Province of China))

1993-01-01

Selective transport of metal ions through a cation exchange membrane was studied in stirred batch dialyzer for the systems Ni[sup 2+]-Cu[sup 2+] and Cu[sup 2+]-Fe[sup 3+]. Oxalic acid, malonic acid, citric acid, glycine, and ethylenediaminetetraacetic acid were employed as the complexing agents added in the feed solution in order to increase the permselectivity of metal ions. The experimental results show that the selective transport behavior of metal ions depends on the valence and the concentration of metal ions, the stoichiometric ratio of complexing agent to metal ions, and the pH value of the feed solution, but is independent of the concentration of counterion in the stripping phase. A theoretical approach was formulated on the basis of the Nernst-Planck equation and interface quasi-equilibrium. Theoretical solutions obtained from numerical calculation were in agreement with the experimental data.

Structural and crystallisation study of a rare earth alumino borosilicate glass designed for nuclear waste confinement; Etude de la structure et du comportement en cristallisation d'un verre nucleaire d'aluminoborosilicate de terre rare

Energy Technology Data Exchange (ETDEWEB)

Quintas, A

2007-09-15

This work is devoted to the study of a rare earth alumino borosilicate glass, which molar composition is 61,81 SiO{sub 2} - 3,05 Al{sub 2}O{sub 3} - 8,94 B{sub 2}O{sub 3} - 14,41 Na{sub 2}O - 6,33 CaO - 1,90 ZrO{sub 2} - 3,56 Nd{sub 2}O{sub 3}, and envisaged for the immobilization of nuclear wastes originating from the reprocessing of high discharge burn up spent fuel. From a structural viewpoint, we investigated the role of the modifier cations on the arrangement of the glass network through different modifications of the glass composition: variation of the Na/Ca ratio and modification of the nature of the alkali and alkaline earth cations. The NMR and Raman spectroscopic techniques were useful to determine the distribution of modifier cations among the glass network and also to cast light on the competition phenomena occurring between alkali and alkaline earth cations for charge compensation of [AlO{sub 4}]{sup -} and [BO{sub 4}]{sup -} species. The neodymium local environment could be probed by optical absorption and EXAFS spectroscopies which enabled to better understand the insertion mode of Nd{sup 3+} ions among the silicate domains of the glass network. Concerning the crystallization behavior we were interested in how the glass composition may influence the crystallization processes and especially the formation of the apatite phase of composition Ca{sub 2}Nd{sub 8}(SiO{sub 4}){sub 6}O{sub 2}. In particular, this work underlined the important role of both alkaline earth and rare earth cations on the crystallization of the apatite phase. (author)

Development and evaluation of holmium doped phosphate glass microspheres for selective internal radiotherapy

International Nuclear Information System (INIS)

Barros Filho, Eraldo C.; Martinelli, Jose Roberto; Squair, Peterson L; Osso Junior, Joao A.; Sene, Frank Ferrer

2013-01-01

Selective Internal Radiotherapy is used to treat hepatocellular carcinoma. In this treatment 90 Y -doped aluminosilicate glass microspheres are introduced in the hepatic artery and they migrate to the liver near to the tumor where they are trapped in the arterioles. The radiation β- emitted by the decay of 90 Y annihilates the cancer cells. A macroaggregate of albumin containing technetium is previously used to monitor the lung shunt and to prevent the spreading of 90 Y during the treatment. In the present work, 165 Ho- doped phosphate glass microspheres were developed aiming that application. 165 Ho has high cross section for neutron capture (64 bars) and 166 Ho decays emitting β- radiation with appropriate energy for killing cancer cells, and gamma rays with low energy which can be used to obtain images of the microspheres location and to check possible occurrence of lung shunt. Holmium also is highly paramagnetic and can be used to obtain images whereby NMR. The glass matrix consists of (P 2 O 5 ) tetrahedrons and can be produced by a relatively lower melting temperature of chemical compounds. The 31 P decays by emitting β- radiation and contributes to the absorbed dose, helping to annihilate the cancer cells. The microspheres were produced by using two methods: the flame and the gravitation falling methods to obtain microspheres with appropriate properties. (author)

The use of Interferometric Microscopy to assess 3D modifications of deteriorated medieval glass.

Science.gov (United States)

Gentaz, L.; Lombardo, T.; Chabas, A.

2012-04-01

Due to low durability, Northern European medieval glass undergoes the action of the atmospheric environment leading in some cases to a state of dramatic deterioration. Modification features varies from a simple loss of transparency to a severe material loss. In order to understand the underlying mechanisms and preserve this heritage, fundamental research is necessary too. In this optic, field exposure of analogues and original stained glass was carried out to study the early stages of the glass weathering. Model glass and original stained glass (after removal of deterioration products) were exposed in real conditions in an urban site (Paris) for 48 months. A regular withdrawal of samples allowed a follow-up of short-term glass evolution. Morphological modifications of the exposed samples were investigated through conventional and non destructive microscopy, using respectively a Scanning Electron Microscope (SEM) and an Interferometric Microscope (IM). This latter allows a 3D quantification of the object with no sample preparation. For all glasses, both surface recession and build-up of deposit were observed as a consequence of a leaching process (interdiffusion of protons and glass cations). The build-up of a deposit comes from the reaction between the extracted glass cations and atmospheric gases. Instead, surface recession is due mainly to the formation of brittle layer of altered glass at the sub-surface, where a fracture network can appear, leading to the scaling of parts of this modified glass. Finally, dissolution of the glass takes place, inducing the formation of pits and craters. The arithmetic roughness (Ra) was used as an indicator of weathering increase, in order to evaluate the deterioration state. For instance, the Ra grew from few tens of nm for pristine glass to thousands of nm for scaled areas. This technique also allowed a precise quantification of dimensions (height, depth and width) of deposits and pits, and the estimation of their overall

Structural investigations of borosilicate glasses containing MoO{sub 3} by MAS NMR and Raman spectroscopies

Energy Technology Data Exchange (ETDEWEB)

Caurant, D., E-mail: daniel-caurant@enscp.f [Laboratoire de Chimie de la Matiere Condensee de Paris, UMR-CNRS 7574, Ecole Nationale Superieure de Chimie de Paris (ENSCP, ParisTech), 11 rue Pierre et Marie Curie, 75231 Paris (France); Majerus, O.; Fadel, E.; Quintas, A. [Laboratoire de Chimie de la Matiere Condensee de Paris, UMR-CNRS 7574, Ecole Nationale Superieure de Chimie de Paris (ENSCP, ParisTech), 11 rue Pierre et Marie Curie, 75231 Paris (France); Gervais, C. [Laboratoire de Chimie de la Matiere Condensee de Paris, UMR-CNRS 7574, Universite Pierre et Marie Curie, 75252 Paris (France); Charpentier, T. [CEA, IRAMIS, Service Interdisciplinaire sur les Systemes Moleculaires et Materiaux, CEA Saclay, 91191 Gif-sur-Yvette (France); Neuville, D. [Physique des Mineraux et des Magmas, UMR-CNRS 7047, Institut de Physique du Globe, place Jussieu, 75252 Paris (France)

2010-01-01

High molybdenum concentration in glass compositions may lead to alkali and alkaline-earth molybdates crystallization during melt cooling that must be controlled particularly during the preparation of highly radioactive nuclear glassy waste forms. To understand the effect of molybdenum addition on the structure of a simplified nuclear glass and to know how composition changes can affect molybdates crystallization tendency, the structure of two glass series belonging to the SiO{sub 2}-B{sub 2}O{sub 3}-Na{sub 2}O-CaO-MoO{sub 3} system was studied by {sup 29}Si, {sup 11}B, {sup 23}Na MAS NMR and Raman spectroscopies by increasing MoO{sub 3} or B{sub 2}O{sub 3} concentrations. Increasing MoO{sub 3} amount induced an increase of the silicate network reticulation but no significant effect was observed on the proportion of BO{sub 4}{sup -} units and on the distribution of Na{sup +} cations in glass structure. By increasing B{sub 2}O{sub 3} concentration, a strong evolution of the distribution of Na{sup +} cations was observed that could explain the evolution of the nature of molybdate crystals (CaMoO{sub 4} or Na{sub 2}MoO{sub 4}) formed during melt cooling.

High electric field conduction in low-alkali boroaluminosilicate glass

Science.gov (United States)

Dash, Priyanka; Yuan, Mengxue; Gao, Jun; Furman, Eugene; Lanagan, Michael T.

2018-02-01

Electrical conduction in silica-based glasses under a low electric field is dominated by high mobility ions such as sodium, and there is a transition from ionic transport to electronic transport as the electric field exceeds 108 V/m at low temperatures. Electrical conduction under a high electric field was investigated in thin low-alkali boroaluminosilicate glass samples, showing nonlinear conduction with the current density scaling approximately with E1/2, where E is the electric field. In addition, thermally stimulated depolarization current (TSDC) characterization was carried out on room-temperature electrically poled glass samples, and an anomalous discharging current flowing in the same direction as the charging current was observed. High electric field conduction and TSDC results led to the conclusion that Poole-Frenkel based electronic transport occurs in the mobile-cation-depleted region adjacent to the anode, and accounts for the observed anomalous current.

Modelling the local atomic structure of molybdenum in nuclear waste glasses with ab initio molecular dynamics simulations.

Science.gov (United States)

Konstantinou, Konstantinos; Sushko, Peter V; Duffy, Dorothy M

2016-09-21

The nature of chemical bonding of molybdenum in high level nuclear waste glasses has been elucidated by ab initio molecular dynamics simulations. Two compositions, (SiO 2 ) 57.5 -(B 2 O 3 ) 10 -(Na 2 O) 15 -(CaO) 15 -(MoO 3 ) 2.5 and (SiO 2 ) 57.3 -(B 2 O 3 ) 20 -(Na 2 O) 6.8 -(Li 2 O) 13.4 -(MoO 3 ) 2.5 , were considered in order to investigate the effect of ionic and covalent components on the glass structure and the formation of the crystallisation precursors (Na 2 MoO 4 and CaMoO 4 ). The coordination environments of Mo cations and the corresponding bond lengths calculated from our model are in excellent agreement with experimental observations. The analysis of the first coordination shell reveals two different types of molybdenum host matrix bonds in the lithium sodium borosilicate glass. Based on the structural data and the bond valence model, we demonstrate that the Mo cation can be found in a redox state and the molybdate tetrahedron can be connected with the borosilicate network in a way that inhibits the formation of crystalline molybdates. These results significantly extend our understanding of bonding in Mo-containing nuclear waste glasses and demonstrate that tailoring the glass composition to specific heavy metal constituents can facilitate incorporation of heavy metals at high concentrations.

Physical Property Investigation of Contemporary Glass lonomer and Resin Modified Glass lonomer Restorative Materials

Science.gov (United States)

2016-05-24

selected physical properties of nine contemporary and recently-marketed glass-ionomer cement (GIC) and four resin-modified glass-ionomer cement {RMGIC...stainless steel molds. Testing was completed on a universal testing machine unt il failure. Knoop Hardness was obtained using fai led fracture toughness...address caries, function, biocompatibility, and minimal environmental impact. 2·3 Glass-ionomer cements were invented and developed by Wilson and Kent

High ion-exchange properties of hybrid materials from X-type zeolite and ground glass powder

Science.gov (United States)

Taira, Nobuyuki; Yoshida, Kohei

2017-10-01

Zeolites are crystalline aluminosilicates with a homogeneous distribution of micropores with a superior cation-exchange capacity. Because they have especially excellent selective exchange properties, a considerable number of studies have been conducted on treating water containing radioisotopes using the zeolites. When using artificial zeolites, they have inferior sinterability; in addition, it is quite hard for them to remove from polluted liquid since these artificial zeolites are principally synthesized as a form of powder, which is a disadvantage. In this study, hybrid materials were prepared from X-type zeolite and waste glass powder. Their ion-removal effect and mechanical strength were investigated. The zeolite and waste glass were ground in an agate mortar in several ratios. 0.5 g of the mixture was pressure-molded into pellets having a diameter of 7 mm. These pellets were slowly heated at the speed of 240°C/h to 700°C and maintained at 700°C for 2 h. The removal rate of Sr2+ ions increased as the amount of X-type zeolite in the hybrid materials increased; the former increased up to 100% when the content of latter exceeded 50%. The mechanical strength increased by increasing the amount of glass in the hybrid materials. This is attributed to the fact that the glass powder acts as a binder that improves the densification and consequently the mechanical strength of the hybrid materials.

Study of fluorine ion structural role in Al(PO3)3-MF glass by the 19F nuclear magnetic resonance method

International Nuclear Information System (INIS)

Gurova, N.N.; Vopilov, V.A.; Buznik, V.M.; Urusovskaya, L.N.

1989-01-01

Results of investigation into Al(PO 3 ) 3 -xMF glasses (M=Li, Na, K) by the 19 F NMR method are presented. Investigation supported the structural identity of glasses, containing NaF and KF. One structural position, related to fluorine atoms, coordinating lithium and aluminium ions, is observed in glasses, containing lithium fluoride. The highest mobility of fluorine atoms was revealed in glasses with lithium fluoride. Mobility of fluorine atoms is lower in glasses, containing potassium and sodium fluoride modifications. Dynamic heterogeneity in these glasses is conditioned both by distribution of frequencies of atom motion in the glass and by structural nonequivalence of positions. Fluorine atoms, coordinating cations of alkaline metals, appear to be more mobile

Physical properties and chemical durability of selected zirconia containing silicate glasses

Directory of Open Access Journals (Sweden)

ELEONÓRA GAŠPÁREKOVÁ

2011-12-01

Full Text Available Density, thermal expansion, glass transition temperature, refractive index, molar refractivity and chemical durability of five- and six-component glasses with as weighted composition xNa2O·(15-xK2O·yCaO∙(10-yZnO∙zZrO2∙(75-zSiO2 (x = 0, 7.5, 15; y = 0, 5, 10; z = 5, 7 were measured. The obtained experimental data were merged together with the previous results obtained for analogous glasses with lower zirconia content. The full set of glasses enabled the quantitative statistical estimation of possible mixed-oxide effects. The results of the multilinear regression analysis pointed out the ideal behavior of molar volume and molar refractivity. The strongest influence of mutual oxide interactions was found for chemical durability and glass transition temperature. The regression analysis of compositional dependence of metastable melt thermal expansion coefficient practically failed. The need of property-composition study based on the thermodynamic model was pointed out. Qualitatively the obtained results confirmed those previously obtained for the analogous glasses with zirconia content reaching up to 3 mol. %.

Study of the spheronization process of glass particles by the gravitational falling process for internal selective radiotherapy

International Nuclear Information System (INIS)

Barros Filho, E.C.; Martinelli, J.R.; Sene, F.F.

2011-01-01

The internal selective radiotherapy is an alternative to treat hepatocellular carcinoma. Glass microspheres containing β - emitter radionuclide are introduced in the liver, and they are housed preferentially in the region where the cancer cells are located. The microspheres are trapped in the arterioles which feed the tumors, and the β - particles annihilate the cancer cells. The glass particles must be spherical to avoid unnecessary bleeding, and the particle size must be restricted to a range which optimizes the blocking effect and avoid the migration to other parts of the human body. The particle size distribution of microspheres is not easily predicted since the variation of the aspect ratio and the presence of agglomerates can influence the resulting particle size distribution. In the present work, the spheronization process to obtain microspheres from irregular shape glass particles with suitable diameter and shape for radiotherapy treatment is studied. (author)

Local Structures around Si, Al and Na in Hydrated Silicate Glasses

International Nuclear Information System (INIS)

Farges, Francois; Wispelaere, Sidoine de; Rossano, Stephanie; Munos, Manuel; Wilke, Max; Flank, Anne-Marie; Lagarde, Pierre

2007-01-01

XANES spectra were collected at the Si-, Al-, and Na K-edge in hydrous silicate glasses to understand the effect of water on the local structure around these cations. Around network forming Si and Al, no drastic changes are observed. Around Na, the dissolution of water creates more ordered environments in Al-bearing glasses and less ordered environment in Al-free glasses. Ab-initio XANES calculations were undertaken to understand the structural origins for these features. Based on these results, a bond valence model was refined that considers not only the present XANES experiments and models but also NMR information. The double percolation model refined explains, among others, the explosive properties of water-bearing hydrous melts, at the origin of a number of cataclysmic eruptions in subduction zones

Women's participation in parliament: 'Glass ceiling' syndrome and party selection

Directory of Open Access Journals (Sweden)

Čičkarić Lilijana

2014-01-01

Full Text Available The impact of 'glass ceiling' syndrome and party selection on participation of women in parliament and other political institutions are examined in this article. 'Glass ceiling' syndrome, which means invisible, but almost impenetrable border that women face in professional life, keeping them away from positions of influence and progress in career, is the main reason for the small number of women involved in politics. According to the focus of the research, there are three groups of barriers to women's political participation. Most researchers examine the influence of the political system, institutional and legal mechanisms, the question of their transparency and functional improvement. Significantly less frequent approach came from authors who are concentrated on the social and economic barriers, financial conditions and the broader social context. The third group consists of those who are considering the ideological and psychological barriers, patriarchal cultural patterns, traditional gender roles, self-confidence, ambition and women's desire to be involved in politics. Political parties are key actors in the process of discrimination against women, because they do not allow them to be selected in a number of political functions. There are many factors that determine that the issue of gender equality is variously interpreted in political parties. The most present are contextual and ideological factors, referring to a different definition of the status of women on the political agenda, the social climate in terms of gender equality and respect for human rights, the level of social development and political freedom. Then come organizational factors pertaining to the structure of parties, the manner in which the leadership is elected, whether there are internal women's pressure groups and lobbying, and are women leaders are visible on high positions in decision-making process. Finally, there are institutional-legal factors, which include the type

Ion conductivities of ZrF4-BaF2-CsF glasses

International Nuclear Information System (INIS)

Kawamoto, Yoji; Nohara, Ichiro

1987-01-01

The glass-forming region in the ZrF 4 -BaF 2 -CsF glass system has been determined and the ac conductivity and the transport number of fluoride ions have been measured. The conductivities of compounds β-Cs 2 ZrF 6 , α-SrZrF 6 , α-BaZrF 6 , β-BaZrF 6 and α-PbZrF 6 have also been measured. These results and a previous study of ZrF 4 -BaF 2 -MF n (M: the groups I-IV metals) glasses revealed the following: (1) the ZrF 4 -BaF 2 -CsF glasses are exclusively fluoride-ion conductors; (2) the ionic conductivities of ZrF 4 -based glasses are predominantly determined by the activation energies for conduction; (3) the activation energy for conduction decreases with an increase in the average polarizability of glass-constituting cations; (4) a decrease in average Zr-F bond length and a lowering of the average F coordination number of Zr are presumed to increase the activation energy for conduction. Principles of developing ZrF 4 -based glasses with higher conductivities have also been proposed. (Auth.)

Cluster formation of network-modifier cations in cesium silicate glasses

Science.gov (United States)

Jardón-Álvarez, Daniel; Sanders, Kevin J.; Phyo, Pyae; Baltisberger, Jay H.; Grandinetti, Philip J.

2018-03-01

Natural abundance 29Si two-dimensional magic-angle flipping (2D MAF) NMR spectra were measured in a series of ten cesium silicate glass compositions xCs2O.(1 - x)SiO2, where x is 0.067, 0.113, 0.175, 0.179, 0.218, 0.234, 0.263, 0.298, 0.31, and 0.36. The Q3 shielding anisotropy decreases with increasing Cs content—interpreted as an increase in the non-bridging oxygen (NBO) bond length from increasing Cs coordination (clustering) around the NBO. The 29Si 2D MAF spectra for four glass compositions x = 0.218, 0.234, 0.263, 0.298 exhibit a second co-existing and distinctly smaller shielding anisotropy corresponding to a significantly longer Si-NBO length arising from a higher degree of Cs clustering around the NBO. This second Q3 site appears at a Cs2O mole fraction close to the critical mole fraction of x = 0.24 associated with the percolation threshold of non-bridging oxygen in random close packing of oxygen, thus suggesting that the longer Si-NBO length is associated with an infinite size spanning cluster while the sites with larger anisotropies are associated with shorter Si-NBO lengths and belong to finite size clusters. The equilibrium constant of the Q3 disproportionation reaction was determined as k3 = 0.005, indicating a Qn anionic species distribution close to a binary model as expected for a low field strength modifier such as cesium. It is also found that evolution of the isotropic Q4 and line shapes with increasing Cs content are consistent with a random connectivity model between Qn of differing number of bridging oxygen, n.

In vivo cation exchange in quantum dots for tumor-specific imaging.

Science.gov (United States)

Liu, Xiangyou; Braun, Gary B; Qin, Mingde; Ruoslahti, Erkki; Sugahara, Kazuki N

2017-08-24

In vivo tumor imaging with nanoprobes suffers from poor tumor specificity. Here, we introduce a nanosystem, which allows selective background quenching to gain exceptionally tumor-specific signals. The system uses near-infrared quantum dots and a membrane-impermeable etchant, which serves as a cation donor. The etchant rapidly quenches the quantum dots through cation exchange (ionic etching), and facilitates renal clearance of metal ions released from the quantum dots. The quantum dots are intravenously delivered into orthotopic breast and pancreas tumors in mice by using the tumor-penetrating iRGD peptide. Subsequent etching quenches excess quantum dots, leaving a highly tumor-specific signal provided by the intact quantum dots remaining in the extravascular tumor cells and fibroblasts. No toxicity is noted. The system also facilitates the detection of peritoneal tumors with high specificity upon intraperitoneal tumor targeting and selective etching of excess untargeted quantum dots. In vivo cation exchange may be a promising strategy to enhance specificity of tumor imaging.The imaging of tumors in vivo using nanoprobes has been challenging due to the lack of sufficient tumor specificity. Here, the authors develop a tumor-specific quantum dot system that permits in vivo cation exchange to achieve selective background quenching and high tumor-specific imaging.

Crystallization of Yttrium and Samarium Aluminosilicate Glasses

OpenAIRE

Lago, Diana Carolina; Prado, Miguel Oscar

2016-01-01

Aluminosilicate glasses containing samarium and yttrium (SmAS and YAS glasses) exhibit high glass transition temperatures, corrosion resistance, and glass stability on heating which make them useful for technological applications. Yttrium aluminosilicate glass microspheres are currently being used for internal selective radiotherapy of liver cancer. During the preparation process, crystallization needs to be totally or partially avoided depending on the final application. Thus knowing the cry...

Selection of a glass-ceramic formulation to immobilize fluorinel- sodium calcine

International Nuclear Information System (INIS)

Staples, B.A.; Wood, H.C.

1994-12-01

One option for immobilizing calcined high level wastes produced by nuclear fuel reprocessing activities at the Idaho Chemical Processing Plant (ICPP) is conversion to a glass-ceramic form through hot isostatic pressing. Calcines exist in several different chemical compositions, and thus candidate formulations have been developed for converting each to glass-ceramic forms which are potentially resistant to aqueous corrosion and stable enough to qualify for repository storage. Fluorinel/Na, a chemically complex calcine type, is one of the types being stored at ICPP, and development efforts have identified three formulations with potential for immobilizing it. These are a glass forming additive that uses aluminum metal to enhance reactivity, a second glass forming additive that uses titanium metal to enhance reactivity and a third that uses not only a combination of silicon and titanium metals but enough phosphorous pentoxide to form a calcium phosphate host phase in the glass-ceramic product. Glass-ceramics of each formulation performed well in restricted characterization tests. However, none of the three was subjected to rigorous testing that would provide information on whether each was processable, that is able to retain favorable characteristics over a practical range of processing conditions

Flux Decoupling and Chemical Diffusion in Redox Dynamics in Aluminosilicate Melts and Glasses (Invited)

Science.gov (United States)

Cooper, R. F.

2010-12-01

Measurements of redox dynamics in silicate melts and glasses suggest that, for many compositions and for many external environments, the reaction proceeds and is rate-limited by the diffusive flux of divalent-cation network modifiers. Application of ion-backscattering spectrometry either (i) on oxidized or reduced melts (subsequently quenched before analysis) or (ii) on similarly reacted glasses, both of basalt-composition polymerization, demonstrates that the network modifiers move relative to the (first-order-rigid) aluminosilicate network. Thus, the textures associated with such reactions are often surprising, and frequently include metastable or unstable phases and/or spatial compositional differences. This response is only possible if the motion of cations can be decoupled from that of anions. In many cases, decoupling is accomplished by the presence in the melt/glass of transition-metal cations, whose heterovalency creates distortions in the electronic band structure resulting in electronic defects: electron “holes” in the valence band or electrons in the conduction band. (The prevalence of holes or electrons being a function of bulk chemistry and oxygen activity.) These electronic species make the melt/glass a “defect semiconductor.” Because (a) the critical issue in reaction dynamics is the transport coefficient (the product of species mobility and species concentration) and (b) the electronic species are many orders of magnitude more mobile than are the ions, very low concentrations of transition-metal ions are required for flux decoupling. For example, 0.04 at% Fe keeps a magnesium aluminosilicate melt/glass a defect semiconductor down to 800°C [Cook & Cooper, 2000]. Depending on composition, high-temperature melts can see ion species having a high-enough transport coefficient to allow decoupling, e.g., alkali cations in a basaltic melt [e.g., Pommier et al., 2010]. In this presentation, these ideas will be illustrated by examining redox dynamics

Temperature Effects on Aluminoborosilicate Glass and Melt Structure

Science.gov (United States)

Wu, J.; Stebbins, J. F.

2008-12-01

Quantitative determination of the atomic-scale structure of multi-component oxide melts, and the effects of temperature on them, is a complex problem. Ca- and Na- aluminoborosilicates are especially interesting, not only because of their major role in widespread technical applications (flat-panel computer displays, fiber composites, etc.), but because the coordination environments of two of their main network cations (Al3+ and B3+) change markedly with composition and temperature is ways that may in part be analogous to processes in silicate melts at high pressures in the Earth. Here we examine a series of such glasses with different cooling rates, chosen to evaluate the role modifier cation field strength (Ca2+ vs. Na+) and of non-bridging oxygen (NBO) content. To explore the effects of fictive temperature, fast quenched and annealed samples were compared. We have used B-11 and Al-27 MAS NMR to measure the different B and Al coordinations and calculated the contents of non-bridging oxygens (NBO). Lower cooling rates increase the fraction of [4]B species in all compositions. The conversion of [3]B to [4]B is also expected to convert NBO to bridging oxygens, which should affect thermodynamic properties such as configurational entropy and configurational heat capacity. For four compositions with widely varying compositions and initial NBO contents, analysis of the speciation changes with the same, simple reaction [3]B = [4]B + NBO yields similar enthalpy values of 25±7 kJ/mol. B-11 triple quantum MAS NMR allows as well the proportions of [3]B boroxol ring and non-ring sites to be determined, and reveals more [3]B boroxol ring structures present in annealed (lower temperature) glasses. In situ, high-temperature MAS NMR spectra have been collected on one of the Na-aluminoborosilicate and on a sodium borate glass at 14.1 T. The exchange of boron between the 3- and 4-coordinated sites is clearly observed well above the glass transition temperatures, confirming the

Photodissociation of spatially aligned acetaldehyde cations.

Science.gov (United States)

Lee, Suk Kyoung; Silva, Ruchira; Kim, Myung Hwa; Shen, Lei; Suits, Arthur G

2007-07-26

Photofragment translational energy and angular distributions are reported for the photodissociation of acetaldehyde cations in the wavelength range 354-363 nm obtained using the DC slice ion imaging technique. Vibrationally selected parent ions were produced by 2+1 resonance-enhanced multiphoton ionization (REMPI) via the 3sCH3CO+, and CH4+. The angular distributions reveal that all product channels have a predominantly parallel recoil anisotropy although the lower beta2 parameter of CH3CO+ indicates the concomitant presence of a perpendicular component. Furthermore, the distinct angular distribution of the CH3CO+ fragments shows a large value of the higher order Legendre polynomial term, providing evidence that acetaldehyde cations are spatially aligned during the ionization process.

Radioresistance of inorganic glasses

International Nuclear Information System (INIS)

Vorob'ev, A.A.; Zavadovskaya, E.K.; Fedorov, B.V.; Starodubtsev, V.A.

1977-01-01

Regularities are considered in the variation of properties of glass due to irradiations. On the basis of previous theoretical statements and experimental investigations, it is inferred that the irradiation resistance of glasses of the same type, synthesis conditions, content of impurities and amount of imperfections, is a function of the ''element-oxygen'' bond energy. The irradiation resistance depends on the number and the nature of glass structure imperfections. The averaged level of bonding forces is indicative of the glass formation temperature; the imperfections in glasses are formed in structure elements whose amount predominates as compared to the others. Electric charges which accumulate on the crack surface tend to increase its size, thus lessening even further the electric strength of the dielectric. The greater the irradiation time, the greater the number of irradiation imperfections causing a drop in the electric strength of glass. When choosing a glass for service in a radiation field, it is necessary to select those of a highest temperature of glass formation and with a least amount of imperfections

Cation-selective extraction column study for the conception of nuclear medical radionuclide generators

International Nuclear Information System (INIS)

Streng, Roman

2012-01-01

The topic of the present work is the conception of a Yttrium-90 radionuclide generator for nuclear medicine applications. Due to its physical properties Yttrium-90 is considered as one of the most useful nuclides for radiotherapeutic cancer treatment. The parent nuclide Strontium-90 is gained during reprocessing of fission products. Thus, the sustained availability of large quantities of Yttrium-90 is limited to a number of research facilities. A radionuclide generator provides an independent Yttrium-90 source and enhances the capacities for radiopharmaceutical research and biomedical applications. The present work focussed on the identification of appropriate column materials for the separation of Strontium and Yttrium. The results for two materials are reported: AnaLig registered Sr-01 and crystalline antimonic acid. Based on the mode of operation of the Technetium-99m generator the aim was to enable the construction of a compact, enclosed apparatus. The projected device comprises a reservoir for the eluant, the ion-exchange column, pipings and radiation shielding. Elution of Yttrium-90 could then be easily performed by connecting evacuated vials to the outlet tube. The prospected concept involves physical and chemical confinements that exclude most of the known processes for Strontium-Yttrium separation. For example no ligands, no oxidizing reactants (e.g. nitric acid) and no organic solvents are to be used, but small volumes of isotonic or buffer solutions and dilute acids respectively. AnaLig registered Sr-01 is a commercially available resin used in extraction chromatography. Its high selectivity for Strontium cations results from the strictly defined cavity of the imbedded cryptand. Determination of weight distribution coefficients, elution studies and pre-generator experiments were carried out. Quantitative separation of Yttrium from Strontium and Zirconium is possible using small volumes of 0,05 M hydrochloric acid as eluant. Furthermore, high flow rates

Silicate glasses corrosion. Texture analysis of the corrosion layer

International Nuclear Information System (INIS)

Portal, Sabine

2001-01-01

We have studied the kinetic and the texture evolution of the corroded layer that forms on glass surfaces exposed to acidic solutions. The corroded layer is depleted in alkali cations and is produced by an ion exchange mechanism. It is porous and shows a lower refractive index than the one of the bulk glass. Spectroscopic ellipsometry allows determining the thickness of the layer and its refractive index. Several other techniques have been developed for characterizing the corrosion behaviour of glass surfaces: porosity is thus investigated by adsorption-desorption of nitrogen; the thickness and the composition of the layer are studied by secondary ion mass spectroscopy (S.I.M.S.); sodium concentration in the solution has been analyzed by atomic absorption. This study shows the importance of leaching conditions and glass preparation. The type of drying employed is susceptible to modify the texture and the structure of the layer. The layers produced in the early stages of the leaching process are not easily detectable. The different results lead however to the same conclusion: after a strong increase of porosity, a densification of the layer is observed with increasing time. The evolution of the layer texture could therefore modify the kinetic of the glass corrosion. (author) [fr

A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

Science.gov (United States)

Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

2016-09-27

Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO 2 utilizing pinacolborane at r.t. and 1 atm CO 2 , with the combination of [Ru(CNC Bn )(CO) 2 (H)][PF 6 ] and KOCO 2 t Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

A model for phosphate glass topology considering the modifying ion sub-network

DEFF Research Database (Denmark)

Hermansen, Christian; Mauro, J.C.; Yue, Yuanzheng

2014-01-01

In the present paper we establish a temperature dependent constraint model of alkali phosphate glasses considering the structural and topological role of the modifying ion sub-network constituted by alkali ions and their non-bonding oxygen coordination spheres. The model is consistent with availa......In the present paper we establish a temperature dependent constraint model of alkali phosphate glasses considering the structural and topological role of the modifying ion sub-network constituted by alkali ions and their non-bonding oxygen coordination spheres. The model is consistent...... with available structural data by NMR and molecular dynamics simulation and dynamic data such glass transition temperature (Tg) and liquid fragility (m). Alkali phosphate glasses are exemplary systems for developing constraint model since the modifying cation network plays an important role besides the primary...... phosphate network. The proposed topological model predicts the changing trend of the Tg and m with increasing alkali oxide content for alkali phosphate glasses, including an anomalous minimum at around 20 mol% alkali oxide content. We find that the minimum in Tg and m is caused by increased connectivity...

Exploring backbone-cation alkyl spacers for multi-cation side chain anion exchange membranes

Science.gov (United States)

Zhu, Liang; Yu, Xuedi; Hickner, Michael A.

2018-01-01

In order to systematically study how the arrangement of cations on the side chain and length of alkyl spacers between cations impact the performance of multi-cation AEMs for alkaline fuel cells, a series of polyphenylene oxide (PPO)-based AEMs with different cationic side chains were synthesized. This work resulted in samples with two or three cations in a side chain pendant to the PPO backbone. More importantly, the length of the spacer between cations varied from 3 methylene (-CH2-) (C3) groups to 8 methylene (C8) groups. The highest conductivity, up to 99 mS/cm in liquid water at room temperature, was observed for the triple-cation side chain AEM with pentyl (C5) or hexyl (C6) spacers. The multi-cation AEMs were found to have decreased water uptake and ionic conductivity when the spacer chains between cations were lengthened from pentyl (C5) or hexyl (C6) to octyl (C8) linking groups. The triple-cation membranes with pentyl (C5) or hexyl (C6) groups between cations showed greatest stability after immersion in 1 M NaOH at 80 °C for 500 h.

Toward a consistent model for glass dissolution

International Nuclear Information System (INIS)

Strachan, D.M.; McGrail, B.P.; Bourcier, W.L.

1994-01-01

Understanding the process of glass dissolution in aqueous media has advanced significantly over the last 10 years through the efforts of many scientists around the world. Mathematical models describing the glass dissolution process have also advanced from simple empirical functions to structured models based on fundamental principles of physics, chemistry, and thermodynamics. Although borosilicate glass has been selected as the waste form for disposal of high-level wastes in at least 5 countries, there is no international consensus on the fundamental methodology for modeling glass dissolution that could be used in assessing the long term performance of waste glasses in a geologic repository setting. Each repository program is developing their own model and supporting experimental data. In this paper, we critically evaluate a selected set of these structured models and show that a consistent methodology for modeling glass dissolution processes is available. We also propose a strategy for a future coordinated effort to obtain the model input parameters that are needed for long-term performance assessments of glass in a geologic repository. (author) 4 figs., tabs., 75 refs

Electric behavior of functional glasses based on TeO2

International Nuclear Information System (INIS)

Terny, S.; Rubia, M. a. de la; Barolin, S.; Alonso, R. E.; Frutos, J. de; Frechero, M. A.

2014-01-01

In this paper we study the structural and electrical behavior of glass-ceramic material of general formula: xMgO (1-x) (0.5V 2 O 5 .0.5MoO 3 )2TeO 2 (0≤ x≤0.9) through measurements of density, molar volume, oxygen packing density (OPD), differential scanning calorimetry (DSC) and Raman spectroscopy: electric behavior was studied by impedance spectroscopy. We found that magnesium cation induces the growth of slightly crystallized areas inside the material. Those nanocrystallizations were detected to a greater extent by atomic force microscopy (AFM) and in lesser extent by X-ray diffraction (XRD). Regarding the electrical measurements, it can be established that magnesium cation does not act as good ionic conductor in this material. (Author)

Information-theoretical feature selection using data obtained by Scanning Electron Microscopy coupled with and Energy Dispersive X-ray spectrometer for the classification of glass traces

International Nuclear Information System (INIS)

Ramos, Daniel; Zadora, Grzegorz

2011-01-01

Highlights: → A selection of the best features for multivariate forensic glass classification using SEM-EDX was performed. → The feature selection process was carried out by means of an exhaustive search, with an Empirical Cross-Entropy objective function. → Results show remarkable accuracy of the best variables selected following the proposed procedure for the task of classifying glass fragments into windows or containers. - Abstract: In this work, a selection of the best features for multivariate forensic glass classification using Scanning Electron Microscopy coupled with an Energy Dispersive X-ray spectrometer (SEM-EDX) has been performed. This has been motivated by the fact that the databases available for forensic glass classification are sparse nowadays, and the acquisition of SEM-EDX data is both costly and time-consuming for forensic laboratories. The database used for this work consists of 278 glass objects for which 7 variables, based on their elemental compositions obtained with SEM-EDX, are available. Two categories are considered for the classification task, namely containers and car/building windows, both of them typical in forensic casework. A multivariate model is proposed for the computation of the likelihood ratios. The feature selection process is carried out by means of an exhaustive search, with an Empirical Cross-Entropy (ECE) objective function. The ECE metric takes into account not only the discriminating power of the model in use, but also its calibration, which indicates whether or not the likelihood ratios are interpretable in a probabilistic way. Thus, the proposed model is applied to all the 63 possible univariate, bivariate and trivariate combinations taken from the 7 variables in the database, and its performance is ranked by its ECE. Results show remarkable accuracy of the best variables selected following the proposed procedure for the task of classifying glass fragments into windows (from cars or buildings) or containers

Glass Membrane For Controlled Diffusion Of Gases

Science.gov (United States)

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.

Comparison of different cationized proteins as biomaterials for nanoparticle-based ocular gene delivery.

Science.gov (United States)

Zorzi, Giovanni K; Párraga, Jenny E; Seijo, Begoña; Sanchez, Alejandro

2015-11-01

Cationized polymers have been proposed as transfection agents for gene therapy. The present work aims to improve the understanding of the potential use of different cationized proteins (atelocollagen, albumin and gelatin) as nanoparticle components and to investigate the possibility of modulating the physicochemical properties of the resulting nanoparticle carriers by selecting specific protein characteristics in an attempt to improve current ocular gene-delivery approaches. The toxicity profiles, as well as internalization and transfection efficiency, of the developed nanoparticles can be modulated by modifying the molecular weight of the selected protein and the amine used for cationization. The most promising systems are nanoparticles based on intermediate molecular weight gelatin cationized with the endogenous amine spermine, which exhibit an adequate toxicological profile, as well as effective association and protection of pDNA or siRNA molecules, thereby resulting in higher transfection efficiency and gene silencing than the other studied formulations. Copyright © 2015 Elsevier B.V. All rights reserved.

Formulation and Characterization of Waste Glasses with Varying Processing Temperature

Energy Technology Data Exchange (ETDEWEB)

Kim, Dong-Sang; Schweiger, M. J.; Rodriguez, Carmen P.; Lepry, William C.; Lang, Jesse B.; Crum, Jarrod V.; Vienna, John D.; Johnson, Fabienne; Marra, James C.; Peeler, David K.

2011-10-17

This report documents the preliminary results of glass formulation and characterization accomplished within the finished scope of the EM-31 technology development tasks for WP-4 and WP-5, including WP-4.1.2: Glass Formulation for Next Generation Melter, WP-5.1.2.3: Systematic Glass Studies, and WP-5.1.2.4: Glass Formulation for Specific Wastes. This report also presents the suggested studies for eventual restart of these tasks. The initial glass formulation efforts for the cold crucible induction melter (CCIM), operating at {approx}1200 C, with selected HLW (AZ-101) and LAW (AN-105) successfully developed glasses with significant increase of waste loading compared to that is likely to be achieved based on expected reference WTP formulations. Three glasses formulated for AZ-101HLW and one glass for AN-105 LAW were selected for the initial CCIM demonstration melter tests. Melter tests were not performed within the finished scope of the WP-4.1.2 task. Glass formulations for CCIM were expanded to cover additional HLWs that have high potential to successfully demonstrate the unique advantages of the CCIM technologies based on projected composition of Hanford wastes. However, only the preliminary scoping tests were completed with selected wastes within the finished scope. Advanced glass formulations for the reference WTP melter, operating at {approx}1200 C, were initiated with selected specific wastes to determine the estimated maximum waste loading. The incomplete results from these initial formulation efforts are summarized. For systematic glass studies, a test matrix of 32 high-aluminum glasses was completed based on a new method developed in this study.

Formulation and Characterization of Waste Glasses with Varying Processing Temperature

International Nuclear Information System (INIS)

Kim, Dong-Sang; Schweiger, M.J.; Rodriguez, Carmen P.; Lepry, William C.; Lang, Jesse B.; Crum, Jarrod V.; Vienna, John D.; Johnson, Fabienne; Marra, James C.; Peeler, David K.

2011-01-01

This report documents the preliminary results of glass formulation and characterization accomplished within the finished scope of the EM-31 technology development tasks for WP-4 and WP-5, including WP-4.1.2: Glass Formulation for Next Generation Melter, WP-5.1.2.3: Systematic Glass Studies, and WP-5.1.2.4: Glass Formulation for Specific Wastes. This report also presents the suggested studies for eventual restart of these tasks. The initial glass formulation efforts for the cold crucible induction melter (CCIM), operating at ∼1200 C, with selected HLW (AZ-101) and LAW (AN-105) successfully developed glasses with significant increase of waste loading compared to that is likely to be achieved based on expected reference WTP formulations. Three glasses formulated for AZ-101HLW and one glass for AN-105 LAW were selected for the initial CCIM demonstration melter tests. Melter tests were not performed within the finished scope of the WP-4.1.2 task. Glass formulations for CCIM were expanded to cover additional HLWs that have high potential to successfully demonstrate the unique advantages of the CCIM technologies based on projected composition of Hanford wastes. However, only the preliminary scoping tests were completed with selected wastes within the finished scope. Advanced glass formulations for the reference WTP melter, operating at ∼1200 C, were initiated with selected specific wastes to determine the estimated maximum waste loading. The incomplete results from these initial formulation efforts are summarized. For systematic glass studies, a test matrix of 32 high-aluminum glasses was completed based on a new method developed in this study.

Parametric effects on glass reaction in the unsaturated test method

International Nuclear Information System (INIS)

Woodland, A.B.; Bates, J.K.; Gerding, T.J.

1991-12-01

The Unsaturated Test Method has been applied to study glass reaction under conditions that may be present at the potential Yucca Mountain site, currently under evaluation for storage of reprocessed high-level nuclear waste. The results from five separate sets of parametric experiments are presented wherein test parameters ranging from water contact volume to sensitization of metal in contact with the glass were examined. The most significant effect was observed when the volume of water, as controlled by the water inject volume and interval period, was such to allow exfoliation of reacted glass to occur. The extent of reaction was also influenced to a lesser extent by the degree of sensitization of the 304L stainless steel. For each experiment, the release of cations from the glass and alteration of the glass were examined. The major alteration product is a smectite clay that forms both from precipitation from solution and from in-situ alteration of the glass itself. It is this clay that undergoes exfoliation as water drips from the glass. A comparison is made between the results of the parametric experiments with those of static leach tests. In the static tests the rates of release become progressively reduced through 39 weeks while, in contrast, they remain relatively constant in the parametric experiments for at least 300 weeks. This differing behavior may be attributable to the dripping water environment where fresh water is periodically added and where evaporation can occur

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

Science.gov (United States)

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.

Energy Saving Glass Lamination via Selective Radio-Frequency Heating

Energy Technology Data Exchange (ETDEWEB)

Shulman, Holly S.; Allan, Shawn M.

2009-11-11

This Inventions and Innovations program supported the technical and commercial research and development needed to elevate Ceralink's energy saving process for flat glass lamination from bench scale to a self-supporting technology with significant potential for growth. Radio-frequency heating was any un-explored option for laminating glass prior to this program. With significant commercial success through time and energy savings in the wood, paper, and plastics industries, RF heating was found to have significant promise for the energy intensive glass lamination industry. A major technical goal of the program was to demonstrate RF lamination across a wide range of laminate sizes and materials. This was successfully accomplished, dispelling many skeptics' concerns about the abilities of the technology. Ceralink laminated panels up to 2 ft x 3 ft, with four sets processed simultaneously, in a 3 minute cycle. All major categories of interlayer materials were found to work with RF lamination. In addition to laminating glass, other materials including photovoltaic silicon solar cells, light emitting diodes, metallized glass, plastics (acrylic and polycarbonate), and ceramics (alumina) were found compatible with the RF process. This opens up a wide range of commercial opportunities beyond the initially targeted automotive industry. The dramatic energy savings reported for RF lamination at the bench scale were found to be maintained through the scale up of the process. Even at 2 ft x 3 ft panel sizes, energy savings are estimated to be at least 90% compared to autoclaving or vacuum lamination. With targeted promotion through conference presentations, press releases and internet presence, RF lamination has gained significant attention, drawing large audiences at American Ceramic Society meetings. The commercialization success of the project includes the establishment of a revenue-generating business model for providing process development and demonstrations for

Aqueous solutions/nuclear glasses interactions

International Nuclear Information System (INIS)

Delage, F.; Advocat, T.; Vernaz, E.; Crovisier, J.L.

1991-01-01

Interactions results of the borosilicate glass used in radioactive wastes confinement and aqueous solutions at various temperature and PH show that for the glass components: - the release rate evolution follows an Arrhenius law, - in acid PH, there is a selective dissolution, - in basic PH, there is a stoechiometric dissolution [fr

THERMODYNAMIC MODEL AND VISCOSITY OF SELECTED ZIRCONIA CONTAINING SILICATE GLASSES

Directory of Open Access Journals (Sweden)

MÁRIA CHROMČÍKOVÁ

2013-03-01

Full Text Available The compositional dependence of viscosity, and viscous flow activation energy of glasses with composition xNa2O∙(15-x K2O∙yCaO∙(10-yZnO∙zZrO2∙(75-zSiO2 (x = 0, 7.5, 15; y = 0, 5, 10; z = 0, 1, 3, 5, 7 was analyzed. The studied glasses were described by the thermodynamic model of Shakhmatkin and Vedishcheva considering the glass as an equilibrium ideal solution of species with stoichiometry given by the composition of stable crystalline phases of respective glass forming system. Viscosity-composition relationships were described by the regression approach considering the viscous flow activation energy and the particular isokome temperature as multilinear function of equilibrium molar amounts of system components. The classical approach where the mole fractions of individual oxides are considered as independent variables was compared with the thermodynamic model. On the basis of statistical analysis there was proved that the thermodynamic model is able to describe the composition property relationships with higher reliability. Moreover, due its better physical justification, thermodynamic model can be even used for predictive purposes.

Organic cation rhodamines for screening organic cation transporters in early stages of drug development.

Science.gov (United States)

Ugwu, Malachy C; Oli, Angus; Esimone, Charles O; Agu, Remigius U

The aim of this study was to investigate the suitability of rhodamine-123, rhodamine-6G and rhodamine B as non-radioactive probes for characterizing organic cation transporters in respiratory cells. Fluorescent characteristics of the compounds were validated under standard in vitro drug transport conditions (buffers, pH, and light). Uptake/transport kinetics and intracellular accumulation of the compounds were investigated. Uptake/transport mechanisms were investigated by comparing the effect of pH, temperature, concentration, polarity, OCTs/OCTNs inhibitors/substrates, and metabolic inhibitors on the cationic dyes uptake in Calu-3 cells. Fluorescence stability and intensity of the compounds were altered by buffer composition, light, and pH. Uptake of the dyes was concentration-, temperature- and pH-dependent. OCTs/OCTNs inhibitors significantly reduced intracellular accumulation of the compounds. Whereas rhodamine-B uptake was sodium-dependent, pH had no effect on rhodamine-123 and rhodamine-6G uptake. Transport of the dyes across the cells was polarized: (AP→BL>BL→AP transport) and saturable: {V max =14.08±2.074, K m =1821±380.4 (rhodamine-B); V max =6.555±0.4106, K m =1353±130.4 (rhodamine-123) and V max =0.3056±0.01402, K m =702.9±60.97 (rhodamine-6G)}. The dyes were co-localized with MitoTracker®, the mitochondrial marker. Cationic rhodamines, especially rhodamine-B and rhodamine- 6G can be used as organic cation transporter substrates in respiratory cells. During such studies, buffer selection, pH and light exposure should be taken into consideration. Copyright © 2016 Elsevier Inc. All rights reserved.

BNFL Report Glass Formers Characterization

Energy Technology Data Exchange (ETDEWEB)

Schumacher, R.F.

2000-07-27

The objective of this task was to obtain powder property data on candidate glass former materials, sufficient to guide conceptual design and estimate the cost of glass former handling facilities as requested under Part B1 of BNFL Technical and Development Support. Twenty-nine glass forming materials were selected and obtained from vendors for the characterization of their physical properties, durability in caustic solution, and powder flow characteristics. A glass former was selected based on the characterization for each of the ten oxide classes required for Envelope A, B, and C mixtures. Three blends (A, B, and C) were prepared based on formulations provided by Vitreous State Laboratory and evaluated with the same methods employed for the glass formers. The properties obtained are presented in a series of attached Tables. It was determined that five of the ten glass formers, (kyanite, iron oxide, titania, zircon, and zinc oxide) have the potential to cause some level of solids f low problems. In addition, all of the blends may require consideration for their handling. A number of engineering considerations and recommendations were prepared based on the experimental findings, experience, and other process considerations. Recommendations for future testing are included. In conjunction with future work, it is recommended that a professional consultant be engaged to guide and assist with testing and design input.

BNFL Report Glass Formers Characterization

International Nuclear Information System (INIS)

Schumacher, R.F.

2000-01-01

The objective of this task was to obtain powder property data on candidate glass former materials, sufficient to guide conceptual design and estimate the cost of glass former handling facilities as requested under Part B1 of BNFL Technical and Development Support. Twenty-nine glass forming materials were selected and obtained from vendors for the characterization of their physical properties, durability in caustic solution, and powder flow characteristics. A glass former was selected based on the characterization for each of the ten oxide classes required for Envelope A, B, and C mixtures. Three blends (A, B, and C) were prepared based on formulations provided by Vitreous State Laboratory and evaluated with the same methods employed for the glass formers. The properties obtained are presented in a series of attached Tables. It was determined that five of the ten glass formers, (kyanite, iron oxide, titania, zircon, and zinc oxide) have the potential to cause some level of solids f low problems. In addition, all of the blends may require consideration for their handling. A number of engineering considerations and recommendations were prepared based on the experimental findings, experience, and other process considerations. Recommendations for future testing are included. In conjunction with future work, it is recommended that a professional consultant be engaged to guide and assist with testing and design input

β-cyclodextrin functionalized on glass micro-particles: A green catalyst for selective oxidation of toluene to benzaldehyde

Energy Technology Data Exchange (ETDEWEB)

Tahir, M. Nazir, E-mail: tahir.muhammad_nazir@courrier.uqam.ca [Department of Chemistry and Bioscience, Aalborg University, Frederik Bajers Vej 7H, DK-9220, Aalborg East (Denmark); Department of Chemistry, University of Quebec at Montreal, QC, H3C 3P8 (Canada); Nielsen, Thorbjørn T.; Larsen, Kim L. [Department of Chemistry and Bioscience, Aalborg University, Frederik Bajers Vej 7H, DK-9220, Aalborg East (Denmark)

2016-12-15

Highlights: • Functionalization of βCD onto glass micro-particles (GMP-βCD). • Application of GMP-βCD as a green catalyst for the oxidation of toluene. • 82% yield at room temperature. • Repeated use of the catalyst for several cycles. - Abstract: Oxidation of toluene is considered an important process which often requires high temperatures and specific conditions along with heavy-metals based catalysts. In this study, we have developed a green catalyst by functionalizing beta-cyclodextrin onto glass micro-particle surfaces. All surfaces were characterized by X-ray photoelectron spectroscopy and applied to catalyze the selective oxidation of toluene into benzaldehyde (82% yield) at room temperature. The catalyst was stable and could be used repeatedly for several cycles without losing efficiency.

The cation-π interaction.

Science.gov (United States)

Dougherty, Dennis A

2013-04-16

The chemistry community now recognizes the cation-π interaction as a major force for molecular recognition, joining the hydrophobic effect, the hydrogen bond, and the ion pair in determining macromolecular structure and drug-receptor interactions. This Account provides the author's perspective on the intellectual origins and fundamental nature of the cation-π interaction. Early studies on cyclophanes established that water-soluble, cationic molecules would forego aqueous solvation to enter a hydrophobic cavity if that cavity was lined with π systems. Important gas phase studies established the fundamental nature of the cation-π interaction. The strength of the cation-π interaction (Li(+) binds to benzene with 38 kcal/mol of binding energy; NH4(+) with 19 kcal/mol) distinguishes it from the weaker polar-π interactions observed in the benzene dimer or water-benzene complexes. In addition to the substantial intrinsic strength of the cation-π interaction in gas phase studies, the cation-π interaction remains energetically significant in aqueous media and under biological conditions. Many studies have shown that cation-π interactions can enhance binding energies by 2-5 kcal/mol, making them competitive with hydrogen bonds and ion pairs in drug-receptor and protein-protein interactions. As with other noncovalent interactions involving aromatic systems, the cation-π interaction includes a substantial electrostatic component. The six (four) C(δ-)-H(δ+) bond dipoles of a molecule like benzene (ethylene) combine to produce a region of negative electrostatic potential on the face of the π system. Simple electrostatics facilitate a natural attraction of cations to the surface. The trend for (gas phase) binding energies is Li(+) > Na(+) > K(+) > Rb(+): as the ion gets larger the charge is dispersed over a larger sphere and binding interactions weaken, a classical electrostatic effect. On other hand, polarizability does not define these interactions. Cyclohexane is

Rare earth ion controlled crystallization of mica glass-ceramics

International Nuclear Information System (INIS)

Garai, Mrinmoy; Karmakar, Basudeb

2016-01-01

In understanding the effects of rare earth ions to control the crystallization and microstructure of alkaline boroaluminosilicate system, the CeO_2, Nd_2O_3, Sm_2O_3 and Gd_2O_3 doped K_2O−MgO−B_2O_3−Al_2O_3−SiO_2−F glasses were synthesized by melt-quenching at 1550 °C. Higher density (2.82–3.06 g cm"−"3) and thermal stability (glass phase) is experiential on addition of rare earth content, which also affects in increasing the glass transition temperature (T_g) and crystallization temperature (T_c). Decrease of thermal expansion in glasses with rare earth ion content is maintained by the stabilization of glass matrix owing to their large cationic field strength. A significant change in the non-isothermal DSC thermogram observed at 750–1050 °C is attributed to fluorophlogopite crystallization. Opaque glass-ceramics were prepared from such glasses by single step heat-treatment at 1050 °C; and the predominant crystalline phases are identified as fluorophlogopite mica, KMg_3(AlSi_3O_1_0)F_2 by XRD and EDX analysis. The compact glass-ceramic microstructure by the agglomeration of fluorophlogopite mica crystallites (crystal size ∼ 100–500 nm, FESEM) is achieved in attendance of rare earth ion; and such microstructure controlled the variation of density, thermal expansion and microhardness value. Higher thermal expansion (11.11–14.08 × 10"−"6/K at 50–800 °C and 50–900 °C) of such glass-ceramics approve that these rare earth containing glasses can be useful for high temperature vacuum sealing application with metal or solid electrolyte. The increase of Vickers microhardness (5.27–5.61 GPa) in attendance of rare earth ions is attributed to the compact crystallinity of fluorophlogopite mica glass-ceramic microstructure. - Highlights: • Synthesis of rare earth oxide doped alkaline boroaluminosilicate glasses. • Development of opaque fluorophlogopite mica glass-ceramics by single-step heat treatment. • Nanocrystalline glass

On the relations between ISE and structure in some RE(Mg)SiAlO(N) glasses

DEFF Research Database (Denmark)

Keding, Ralf; Dauce, Rachel; Sangleboeuf, J. C.

2008-01-01

silicate units and SiO3N and SiO2N2 units are created when nitrogen is introduced into the glass network. The average number of rigid bonds per network former was calculated from the glasses’ composition. A discrepancy between and the Raman spectra of the glasses suggests that parts of the magnesium...... Six oxide and oxynitride glasses were synthesized in the Y–Mg–Si–Al–O–N, Nd–Mg–Si–Al–O–N and La–Mg–Si–Al–O–N systems. As already known, nitrogen introduction increases the T g, packing factor and mechanical properties of the glasses. Cationic substitution also has an influence on the glasses......’ behavior, particularly in terms of sensitivity to indentation load/size effect (ISE). The structure of the yttrium-containing glasses was investigated by mean of 27Al and 29Si MAS-NMR. Al is found to occur for 2/3 as a network former and for 1/3 as a modifier. The oxide glass mainly contains Q2 and Q3...

Development and modification of glass membranes for aggressive gas separations

Energy Technology Data Exchange (ETDEWEB)

Lindbraaten, Arne

2004-07-01

Chlorine as a chemical is widespread in industry and found in a great variety of processes ranging from water purification to plastic production. In this thesis, a magnesium production factory was chosen as an example because it involved both chlorine - air separation and hydrogen -hydrogen chloride separation. Previously, various types of membrane materials have been tested out for their applicability in the chosen process. The materials previously tested either lacked sufficient membrane performance or sufficient membrane stability. As an attempt to improve both the membrane performance and stability, glass membranes are used in this thesis. Glass membranes are prepared from a borosilicate glass, via a phase separation followed by an acid leaching route. By choosing the appropriate phase separation temperature and acid to glass ratio, the membrane can be produced with an average pore diameter of 2 nm (or 4 nm). However, the 2 nm average pore size is still too large to separate gases with separation selectivities beyond the selectivities predicted from Knudsen diffusion theory. If the pores are narrowed, the selectivity may be raised while the flux hopefully is maintained. The narrowing of the pores was done by a silane coupling to the surface OH-groups on the glass. The silane coupling agent is of the dimethyl-acyl-chlorosilane type, where the length of the acyl chain varies from 1 carbon up to 18 carbons. Glass fibres are also tested in this work, which are produced without phase separation and their average pore size is smaller than the surface-modified glasses. To be able to compare the performance of the various membranes, performance measurements are performed and these measurements are evaluated by the separation power (product of the selectivity and the permeability of the fastest permeating compound). Because of the harsh chlorine or hydrogen chloride environment, to which the membranes are exposed in this work, the membrane stability is at least as

Tricarbonyldichlororuthenium (II) dimer (CORM2) activates non-selective cation current in human endothelial cells independently of carbon monoxide releasing.

Science.gov (United States)

Dong, De-Li; Chen, Chang; Huang, Wei; Chen, Yan; Zhang, Xiao-Lan; Li, Zhe; Li, Yue; Yang, Bao-Feng

2008-08-20

Tricarbonyldichlororuthenium (II) dimer (CORM2) has been developed as carbon monoxide (CO) donor. We found that CORM2 activated a type of specific current which was distinct from the big-conductance Ca(2+)-activated K(+) current activated by CO in human umbilical vein endothelial cells (HUVECs). So the aim of the present study was to characterize the CORM2-induced current and to access the relation with CO releasing. CORM2 (100 microM) activated a kind of bi-directional current in HUVECs when the ramp protocol (holding potential 0 mV, from -120 mV to +120 mV) was applied. The current was not blocked by apamin, TRAM-34 and iberiotoxin, the small, intermediate and big-conductance Ca(2+) -activated K(+) channel blockers, and it was not sensitive to the pipette solution chelated with EGTA. CORM2 still activated the current when the chloride in the pipette solution was substituted by equal mol gluconic acid. Substitution of the sodium in the bath with choline significantly reduced the current activated by CORM2. The current was regarded as the non-selective cation current. The current showed slightly inward rectifier property and was not sensitive to Gd(3+) (100 microM), La(3+) (10 microM) or 2-aminoethoxydiphenyl borate (100 microM). CO (10 microM), CORM3 (100, 200 microM) and RuCl(3) (100 microM) were used as controls and showed no effect of the current activation. In conclusion, CORM2 activated the non-selective cation current in HUVECs independently of its CO releasing.

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

Energy Technology Data Exchange (ETDEWEB)

Mohd Fadzil, Syazwani, E-mail: mfsyazwani86@postech.ac.kr [Division of Advanced Nuclear Engineering, Pohang University of Science and Technology, 790784 Pohang, Gyeongbuk (Korea, Republic of); School of Applied Physics, Faculty of Science and Technology, The National University of Malaysia, 43650 Bandar Baru Bangi, Selangor (Malaysia); Hrma, Pavel [Division of Advanced Nuclear Engineering, Pohang University of Science and Technology, 790784 Pohang, Gyeongbuk (Korea, Republic of); Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA (United States); Schweiger, Michael J.; Riley, Brian J. [Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA (United States)

2015-10-15

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 (T{sub L}): 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% RE{sub 2}O{sub 3}) while possessing an acceptable chemical durability. - Highlights: • We investigated crystallization in borosilicate glasses containing rare earth oxides. • New crystallinity and durability data are shown for glasses proposed in the literature. • Both liquidus temperature and chemical durability increased as the waste loading increased.

Platinoids and molybdenum in nuclear waste containment glasses: a structural study

International Nuclear Information System (INIS)

Le Grand, M.

2000-01-01

This work deals with the structure of borosilicate nuclear glasses and with some relationships between structure and macroscopic properties. Two types of elements which may disturb the industrial process - platinoids (Ru and Pd) and molybdenum - are central to this work. Platinoids induce weak modifications on the structure of the glass, causing a depolymerization of the glassy network, an increase of the [3] B/ [4] B ratio and a modification of the medium range order around Si between 3.3 and 4.5 angstrom. The modifications of viscosity and density induced by platinoids in the glass are not due to the structural effect of the platinoids. The increase of viscosity is attributed to needle shaped RuO 2 . It can be moderated by imposing reducing conditions during the elaboration of the glass. The slight difference between experimental and calculated densities is due to the increase of the volume percentage of bubbles in the glass with increasing platinoid content. Mo is either present in the glass as molybdic groupings, or mobilized in chemically complex molybdic crystalline phases. The chemical composition and mineralogy of these phases has been obtained using electronic microprobe data and XRD with Rietveld analysis. The distribution of the different elements between the crystalline phases and the glass is strongly influenced by the structural role of the various cations in the glass. The Mo present in the glass appears as MoO 4 tetrahedra, independent of the borosilicate network. The formation of the crystalline phases can be explained by the existence of a precursor in which the MoO 4 tetrahedra are concentrated in rich alkali and earth-alkali bearing areas of the glass. (author)

Non-toxic invert analog glass compositions of high modulus

Science.gov (United States)

Bacon, J. F. (Inventor)

1974-01-01

Glass compositions having a Young's modulus of at least 15 million psi are described. They and a specific modulus of at least 110 million inches consist essentially of, in mols, 15 to 40% SiO2, 6 to 15% Li2O, 24 to 45% of at least two bivalent oxides selected from the group consisting of Ca, NzO, MgO and CuO; 13 to 39% of at least two trivalent oxides selected from the group consisting of Al2O3, Fe2O3, B2O3, La2O3, and Y2O3 and up to 15% of one or more tetravelent oxides selected from the group consisting of ZrO2, TiO2 and CeO2. The high modulus, low density glass compositions contain no toxic elements. The composition, glass density, Young's modulus, and specific modulus for 28 representative glasses are presented. The fiber modulus of five glasses are given.

Energy Saving Glass Lamination via Selective Radio Frequency Heating

Energy Technology Data Exchange (ETDEWEB)

Shawn M. Allan; Patricia M. Strickland; Holly S. Shulman

2009-11-11

Ceralink Inc. developed FastFuse™, a rapid, new, energy saving process for lamination of glass and composites using radio frequency (RF) heating technology. The Inventions and Innovations program supported the technical and commercial research and development needed to elevate the innovation from bench scale to a self-supporting technology with significant potential for growth. The attached report provides an overview of the technical and commerical progress achieved for FastFuse™ during the course of the project. FastFuse™ has the potential to revolutionize the laminate manufacturing industries by replacing energy intensive, multi-step processes with an energy efficient, single-step process that allows higher throughput. FastFuse™ transmits RF energy directly into the interlayer to generate heat, eliminating the need to directly heat glass layers and the surrounding enclosures, such as autoclaves or vacuum systems. FastFuse™ offers lower start-up and energy costs (up to 90% or more reduction in energy costs), and faster cycles times (less than 5 minutes). FastFuse™ is compatible with EVA, TPU, and PVB interlayers, and has been demonstrated for glass, plastics, and multi-material structures such as photovoltaics and transparent armor.

CO 2 adsorption in mono-, di- and trivalent cation-exchanged metal-organic frameworks: A molecular simulation study

KAUST Repository

Chen, Yifei

2012-02-28

A molecular simulation study is reported for CO 2 adsorption in rho zeolite-like metal-organic framework (rho-ZMOF) exchanged with a series of cations (Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, and Al 3+). The isosteric heat and Henry\\'s constant at infinite dilution increase monotonically with increasing charge-to-diameter ratio of cation (Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ < Al 3+). At low pressures, cations act as preferential adsorption sites for CO 2 and the capacity follows the charge-to-diameter ratio. However, the free volume of framework becomes predominant with increasing pressure and Mg-rho-ZMOF appears to possess the highest saturation capacity. The equilibrium locations of cations are observed to shift slightly upon CO 2 adsorption. Furthermore, the adsorption selectivity of CO 2/H 2 mixture increases as Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ ≈ Al 3+. At ambient conditions, the selectivity is in the range of 800-3000 and significantly higher than in other nanoporous materials. In the presence of 0.1% H 2O, the selectivity decreases drastically because of the competitive adsorption between H 2O and CO 2, and shows a similar value in all of the cation-exchanged rho-ZMOFs. This simulation study provides microscopic insight into the important role of cations in governing gas adsorption and separation, and suggests that the performance of ionic rho-ZMOF can be tailored by cations. © 2012 American Chemical Society.

Electronic polarizability, optical basicity and interaction parameter for Nd2O3 doped lithium-zinc-phosphate glasses

Science.gov (United States)

Algradee, M. A.; Sultan, M.; Samir, O. M.; Alwany, A. Elwhab B.

2017-08-01

The Nd3+-doped lithium-zinc-phosphate glasses were prepared by means of conventional melt quenching method. X-ray diffraction results confirmed the glassy nature of the studied glasses. The physical parameters such as the density, molar volume, ion concentration, polaron radius, inter-ionic distance, field strength and oxygen packing density were calculated using different formulae. The transmittance and reflectance spectra of glasses were recorded in the wavelength range 190-1200 nm. The values of optical band gap and Urbach energy were determined based on Mott-Davis model. The refractive indices for the studied glasses were evaluated from optical band gap values using different methods. The average electronic polarizability of the oxide ions, optical basicity and an interaction parameter were investigated from the calculated values of the refractive index and the optical band gap for the studied glasses. The variations in the different physical and optical properties of glasses with Nd2O3 content were discussed in terms of different parameters such as non-bridging oxygen and different concentrations of Nd cation in glass system.

Effect of Gamma Irradiation on Some Properties of Bismuth Silicate Glasses and Their Glass Derivatives

International Nuclear Information System (INIS)

Abo Hussein, E.M.K.

2014-01-01

Glasses containing bismuth oxide have attracted considerable attention, although it is non-conventional glass forming oxide, but it has wide applications. In this work, it is aimed to prove that bismuth silicate glass can act as a good shielding material for γ- rays. For this purpose glass containing 20% bismuth oxide and 80% SiO_2 was prepared using melting-annealing technique. Also effects of adding some alkali heavy metal oxides to this glass such as PbO, BaO or SrO were also studied. The formed glasses were also heat treated at 450 degree C for 4 hours to give the corresponding heat treated glasses. Electron Paramagnetic Resonance (EPR) measurements show that the prepared glasses and heat treated glasses have very good stability when exposed to γ- irradiation, which encourage the assumption of using these glasses as gamma ray shielding materials. Many properties have been investigated, such as density to understand the structural properties, also mechanical properties were verified by measuring microhardness, while the chemical resistance was identified by testing their durability in both acidic and basic solutions. The EPR results were supported by measuring electrical conductivity of the glass and heat treated glass samples at different temperatures ranging from 298 to 553 K, which proved that these glasses have very low conductivity even at high temperature. The formed phases of heat treated glass or glass ceramic samples were demonstrated by means of X-ray diffraction (XRD). Also studying the structure of glasses and heat treated glasses before and after irradiation was investigated by the Infrared transmitting spectra. Calculations of optical band gap energies were demonstrated for some selected glasses and heat treated glasses from the data of UV optical absorption spectra to support the probability of using these bismuth silicate glasses for gamma radiation shielding processing.

Analysis of leachants from strontium chlorapatite glass ceramics

International Nuclear Information System (INIS)

Vijayalakshmi, S.; Ushalakshmi, K.; Annapoorani, S.; Sriram, S.; Uma Maheshwari, R.; Deivanayaki, R.; Sekar, J.K.; Sankaran, K.

2013-01-01

Strontium chlorapatite glass ceramics is being tried out as one of the candidate matrices for immobilizing pyrochemical salt waste produced in the nuclear industry. To find-out the suitability of such material for immobilising the waste, leaching of various constituents of the ceramics in water is required. Therefore, in Chemistry Group of IGCAR experiments are being carried out with simulated salt waste (chlorides of Li, Na, K, Cs, Ba, Nd and Ce) of pyrochemical reprocessing method for studying the utilisation of strontium chlorapatite glass ceramics towards the immobilization of radioactive waste. Leaching behaviour study requires the determination of alkali, alkaline earth and rare earth elements in the leachant solutions of the glass ceramic material. Apart from cations, leaching study of anions especially chloride is required as the chloride salts are used in pyrochemical experiments. Considering the good sensitivity of alkali elements in Flame-AES method, all the alkali elements were determined by flame-AES. Ba, Sr and rare earth elements in the leachant solutions were determined using ICP-OES. Chloride was determined using ISE and IC. Standardisation of instrumental techniques and the application of various techniques for the sample analysis will be discussed in the paper. (author)

Glass-Ceramic Waste Forms for Uranium and Plutonium Residues Wastes - 13164

International Nuclear Information System (INIS)

Stewart, Martin W.A.; Moricca, Sam A.; Zhang, Yingjie; Day, R. Arthur; Begg, Bruce D.; Scales, Charlie R.; Maddrell, Ewan R.; Hobbs, Jeff

2013-01-01

A program of work has been undertaken to treat plutonium-residues wastes at Sellafield. These have arisen from past fuel development work and are highly variable in both physical and chemical composition. The principal radiological elements present are U and Pu, with small amounts of Th. The waste packages contain Pu in amounts that are too low to be economically recycled as fuel and too high to be disposed of as lower level Pu contaminated material. NNL and ANSTO have developed full-ceramic and glass-ceramic waste forms in which hot-isostatic pressing is used as the consolidation step to safely immobilize the waste into a form suitable for long-term disposition. We discuss development work on the glass-ceramic developed for impure waste streams, in particular the effect of variations in the waste feed chemistry glass-ceramic. The waste chemistry was categorized into actinides, impurity cations, glass formers and anions. Variations of the relative amounts of these on the properties and chemistry of the waste form were investigated and the waste form was found to be largely unaffected by these changes. This work mainly discusses the initial trials with Th and U. Later trials with larger variations and work with Pu-doped samples further confirmed the flexibility of the glass-ceramic. (authors)

Alkali metal cation selectivity of [17]ketonand in methanol: free energy perturbation and molecular dynamics simulation studies

International Nuclear Information System (INIS)

Hwang, Sun Gu; Chung, Doo Soo; Jang, Yun Hee; Ryu, Gean Ha

1999-01-01

Free energy perturbation and molecular dynamics simulations were carried out to investigate the relative binding affinities of [1 7 ]ketonand (1) toward alkali metal cations in methanol. The binding affinities of 1 toward the alkali metal cations were calculated to be in the order Li + >Na + >K + >Rb + >Cs + , whereas our recent theoretically predicted and experimentally observed binding affinities for [1 8 ]starand (2) were in the order K + >Rb + >Cs + >Na + >Li + . The extremely different affinities of 1 and 2 toward smaller cations, Li + and Na + , were explained in terms of the differences in their ability to change the conformation to accommodate cations of different sizes. The carbonyl groups constituting the central cavity of 1 can reorganize to form a cavity with the optimal M + -O distance, even for the smallest Li + , without imposing serious strain on 1. The highest affinity of 1 for Li + was predominantly due to the highest Coulombic attraction between the smallest Li + and the carbonyl oxygens of 1

UV-assisted selective chemical etching of relief gratings in Er/Yb-codoped IOG1 phosphate glass

Energy Technology Data Exchange (ETDEWEB)

Pappas, C; Pissadakis, S [Foundation for Research and Technology-Hellas, Institute of Electronic Structure and Laser, Vasilika Vouton, PO Box 1527, Heraklion 71 110, GREECE (Greece)

2007-04-15

The patterning of sub-micron periodicity Bragg reflectors in Er/Yb-codoped IOG1, phosphate glass is demonstrated. A high yield patterning technique is presented, wherein high volume damage is induced into the glass matrix by exposure to intense UV radiation, and subsequently a chemical development in a strong acid selectively etches the exposed areas. The grating reflectors were fabricated by employing an elliptical Talbot interferometer and the output of a 213nm, 150ps frequency quintupled Nd:YAG laser. The grating depth of the etched relief pattern in time was measured at fixed time intervals and the dependence is presented in upon the etching time and exposure conditions. The gratings fabricated are examined by atomic and scanning electron microscopy for revealing the topology of the relief structure. Gratings with period of the order of 500nm were fabricated, having a maximum depth of 60nm.

Medium range order and structural relaxation in As–Se network glasses through FSDP analysis

International Nuclear Information System (INIS)

Golovchak, R.; Lucas, P.; Oelgoetz, J.; Kovalskiy, A.; York-Winegar, J.; Saiyasombat, Ch; Shpotyuk, O.; Feygenson, M.; Neuefeind, J.; Jain, H.

2015-01-01

Synchrotron X-ray diffraction and neutron scattering studies are performed on As–Se glasses in two states: as-prepared (rejuvenated) and aged for ∼27 years. The first sharp diffraction peak (FSDP) obtained from the structure factor data as a function of composition and temperature indicates that the cooperative processes that are responsible for structural relaxation do not affect FSDP. The results are correlated with the composition dependence of the complex heat capacity of the glasses and concentration of different structural fragments in the glass network. The comparison of structural information shows that density fluctuations, which were thought previously to have a significant contribution to FSDP, have much smaller effect than the cation–cation correlations, presence of ordered structural fragments or cage molecules. - Highlights: • Aged and non-aged As–Se glasses are studied with XRD and neutron scattering. • Compositional and temperature dependences of FSDP are analyzed. • FSDP parameters are correlated with (non)isothermal structural relaxation data

Medium range order and structural relaxation in As–Se network glasses through FSDP analysis

Energy Technology Data Exchange (ETDEWEB)

Golovchak, R., E-mail: holovchakr@apsu.edu [Department of Physics and Astronomy, Austin Peay State University, Clarksville, TN 37044 (United States); Lucas, P. [Department of Materials Science and Engineering, University of Arizona, Tucson, AZ 85712 (United States); Oelgoetz, J.; Kovalskiy, A.; York-Winegar, J. [Department of Physics and Astronomy, Austin Peay State University, Clarksville, TN 37044 (United States); Saiyasombat, Ch [Department of Materials Science and Engineering, Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015-3195 (United States); Shpotyuk, O. [Institute of Physics, Jan Dlugosz University of Czestochowa, al. Armii Krajowej 13/15, Czestochowa 42200 (Poland); Feygenson, M.; Neuefeind, J. [Chemical and Engineering Materials Division, Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Jain, H. [Department of Materials Science and Engineering, Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015-3195 (United States)

2015-03-01

Synchrotron X-ray diffraction and neutron scattering studies are performed on As–Se glasses in two states: as-prepared (rejuvenated) and aged for ∼27 years. The first sharp diffraction peak (FSDP) obtained from the structure factor data as a function of composition and temperature indicates that the cooperative processes that are responsible for structural relaxation do not affect FSDP. The results are correlated with the composition dependence of the complex heat capacity of the glasses and concentration of different structural fragments in the glass network. The comparison of structural information shows that density fluctuations, which were thought previously to have a significant contribution to FSDP, have much smaller effect than the cation–cation correlations, presence of ordered structural fragments or cage molecules. - Highlights: • Aged and non-aged As–Se glasses are studied with XRD and neutron scattering. • Compositional and temperature dependences of FSDP are analyzed. • FSDP parameters are correlated with (non)isothermal structural relaxation data.

Potentiometric titration of polyhexamethylene biguanide hydrochloride with potassium poly(vinyl sulfate) solution using a cationic surfactant-selective electrode.

Science.gov (United States)

Masadome, Takashi; Yamagishi, Yuichi; Takano, Masaki; Hattori, Toshiaki

2008-03-01

A potentiometric titration method using a cationic surfactant as an indicator cation and a plasticized poly(vinyl chloride) membrane electrode sensitive to the cationic surfactant is proposed for the determination of polyhexamethylene biguanide hydrochloride (PHMB-HCl), which is a cationic polyelectrolyte. A sample solution of PHMB-HCl containing an indicator cation (hexadecyltrimethylammonium ion, HTA) was titrated with a standard solution of an anionic polyelectrolyte, potassium poly(vinyl sulfate) (PVSK). The end-point was detected as a sharp potential change due to an abrupt decrease in the concentration of the indicator cation, HTA, which is caused by its association with PVSK. The effects of the concentrations of HTA ion and coexisting electrolytes in the sample solution on the degree of the potential change at the end-point were examined. A linear relationship between the concentration of PHMB-HCl and the end-point volume of the titrant exists in the concentration range from 2.0 x 10(-5) to 4.0 x 10(-4) M in the case that the concentration of HTA is 1.0 x 10(-5) M, and that from 1.0 x 10(-6) to 1.2 x 10(-5) M in the case that the concentration of HTA is 5.0 x 10(-6) M, respectively. The proposed method was applied to the determination of PHMB-HCl in some contact-lens detergents.

Structure of AgxNa1-xPO3 glasses by neutron diffraction and reverse Monte Carlo modelling

International Nuclear Information System (INIS)

Hall, Andreas; Swenson, Jan; Karlsson, Christian; Adams, Stefan; Bowron, Daniel T

2007-01-01

We have performed structural studies of mixed mobile ion phosphate glasses Ag x Na 1-x PO 3 using diffraction experiments and reverse Monte Carlo simulations. This glass system is particularly interesting as a model system for investigations of the mixed mobile ion effect, due to its anomalously low magnitude in the system. As for previously studied mixed alkali phosphate glasses, with a much more pronounced mixed mobile ion effect, we find no substantial structural alterations of the phosphorous-oxygen network and the local coordination of the mobile cations. Furthermore, the mobile Ag + and Na + ions are randomly mixed with no detectable preference for either similar or dissimilar pairs of cations. However, in contrast to mixed mobile ion systems with a very pronounced mixed mobile ion effect, the two types of mobile ions have, in this case, very similar local environments. For all the studied glass compositions the average Ag-O and Na-O distances in the first coordination shell are determined to be 2.5 ± 0.1 and 2.5 ± 0.1 A, and the corresponding average coordination numbers are approximately 3.2 and 3.7, respectively. The similar local coordinations of the two types of mobile ions suggests that the energy mismatch for a Na + ion to occupy a site that previously has been occupied by a Ag + ion (and vice versa) is low, and that this low energy mismatch is responsible for the anomalously weak mixed mobile ion effect

Chemical surface modification of glass beads for the treatment of paper machine process waters

International Nuclear Information System (INIS)

Jradi, Khalil; Daneault, Claude; Chabot, Bruno

2011-01-01

Adsorption of detrimental contaminants on a solid sorbent is proposed to remove these contaminants from process waters to increase water recycling and reduce effluent loads in the papermaking industry. A self-assembly process of attaching (covalent grafting) cationic aminosilane molecules to glass beads was investigated. The existence and the hydrolytic stability of self-assembled monolayers and multilayers were confirmed by X-Ray Photoelectron Spectroscopy and contact angle measurements. Effects of reaction time and curing on aminosilane layer structures are also discussed. The curing step after silanization seems to be crucial in the hydrophobization of the quaternary ammonium silane coated onto glass beads, and curing could affect the final chemical structure of the ammonium groups of grafted organosilane. Results indicated that modified glass beads have a strong hydrophobicity, which is attributed to the hydrophobic property of the longest carbon chain grafted onto the glass surface. Adsorption of a model contaminant (stearic acid) onto chemically modified glass beads was determined using colloidal titration. Hydrophobic interactions could be the main driving force involved between the long carbon chains of stearic acid and the carbon chains of the aminosilane layers on glass bead surfaces. Finally, self-assembly processes applied onto glass beads may have two promising applications for papermaking and self-cleaning systems.

Untitled

Indian Academy of Sciences (India)

Sol-Gel Laboratory, Central Glass & Ceramic Research Institute, Calcutta 700 032, India. Abstract. Gelation times of tetraethyl orthosilicate-derived sols containing selected di- to tetravalent cations as ... polymers in sols, thereby accelerating gelation and (ii) hydrolyzed cations retarded the process by offering molecular ...

Super ionic conductive glass

Science.gov (United States)

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.

Fluconazole affects the alkali-metal-cation homeostasis and susceptibility to cationic toxic compounds of Candida glabrata.

Science.gov (United States)

Elicharova, Hana; Sychrova, Hana

2014-08-01

Candida glabrata is a salt-tolerant and fluconazole (FLC)-resistant yeast species. Here, we analyse the contribution of plasma-membrane alkali-metal-cation exporters, a cation/proton antiporter and a cation ATPase to cation homeostasis and the maintenance of membrane potential (ΔΨ). Using a series of single and double mutants lacking CNH1 and/or ENA1 genes we show that the inability to export potassium and toxic alkali-metal cations leads to a slight hyperpolarization of the plasma membrane of C. glabrata cells; this hyperpolarization drives more cations into the cells and affects cation homeostasis. Surprisingly, a much higher hyperpolarization of C. glabrata plasma membrane was produced by incubating cells with subinhibitory concentrations of FLC. FLC treatment resulted in a substantially increased sensitivity of cells to various cationic drugs and toxic cations that are driven into the cell by negative-inside plasma-membrane potential. The effect of the combination of FLC plus cationic drug treatment was enhanced by the malfunction of alkali-metal-cation transporters that contribute to the regulation of membrane potential and cation homeostasis. In summary, we show that the combination of subinhibitory concentrations of FLC and cationic drugs strongly affects the growth of C. glabrata cells. © 2014 The Authors.

A Cadmium Ion-selective Membrane Electrode Based on Strong Acidic Organic-inorganic Composite Cation-exchanger: Polyaniline Ce(IV Molybdate

Directory of Open Access Journals (Sweden)

Syed Ashfaq NABI

2008-05-01

Full Text Available A cadmium ion-selective composite cation-exchanger polyaniline Ce(IV molybdate was used as electroactive component for the construction of a ion-selective membrane electrode. The membrane electrode showed a Nerstian response for Cd(II ions over a wide concentration range 5 × 10-6 – 1 × 10-1 with a sub-Nerstian slope of 27 mV per decade change in concentration of cadmium ions. The limit of detection was also ascertained to be 5 × 10-6 M. It has a fast response time 15 s and can be very well utilized for more than three months with out any appreciable divergence in potentials. The optimum pH for the smooth functioning of this electrode was found to be in the Ph range of 2.5 – 7.5. The electrode also showed better selectivity for Cd(II ions over many other interfering ions. The practical utility of membrane electrode was demonstrated by using as indicator electrode for the potentiometric titration of Cd(II with EDTA and determination of cadmium content in drain water.

Rare earth ion controlled crystallization of mica glass-ceramics

Energy Technology Data Exchange (ETDEWEB)

Garai, Mrinmoy; Karmakar, Basudeb, E-mail: basudebk@cgcri.res.in

2016-09-05

In understanding the effects of rare earth ions to control the crystallization and microstructure of alkaline boroaluminosilicate system, the CeO{sub 2}, Nd{sub 2}O{sub 3}, Sm{sub 2}O{sub 3} and Gd{sub 2}O{sub 3} doped K{sub 2}O−MgO−B{sub 2}O{sub 3}−Al{sub 2}O{sub 3}−SiO{sub 2}−F glasses were synthesized by melt-quenching at 1550 °C. Higher density (2.82–3.06 g cm{sup −3}) and thermal stability (glass phase) is experiential on addition of rare earth content, which also affects in increasing the glass transition temperature (T{sub g}) and crystallization temperature (T{sub c}). Decrease of thermal expansion in glasses with rare earth ion content is maintained by the stabilization of glass matrix owing to their large cationic field strength. A significant change in the non-isothermal DSC thermogram observed at 750–1050 °C is attributed to fluorophlogopite crystallization. Opaque glass-ceramics were prepared from such glasses by single step heat-treatment at 1050 °C; and the predominant crystalline phases are identified as fluorophlogopite mica, KMg{sub 3}(AlSi{sub 3}O{sub 10})F{sub 2} by XRD and EDX analysis. The compact glass-ceramic microstructure by the agglomeration of fluorophlogopite mica crystallites (crystal size ∼ 100–500 nm, FESEM) is achieved in attendance of rare earth ion; and such microstructure controlled the variation of density, thermal expansion and microhardness value. Higher thermal expansion (11.11–14.08 × 10{sup −6}/K at 50–800 °C and 50–900 °C) of such glass-ceramics approve that these rare earth containing glasses can be useful for high temperature vacuum sealing application with metal or solid electrolyte. The increase of Vickers microhardness (5.27–5.61 GPa) in attendance of rare earth ions is attributed to the compact crystallinity of fluorophlogopite mica glass-ceramic microstructure. - Highlights: • Synthesis of rare earth oxide doped alkaline boroaluminosilicate glasses. • Development of opaque

An on-line monitor for cation exchange elution chromatography using lithium silicate glass beads as solid scintillator

International Nuclear Information System (INIS)

Zhu Rongbao; Yang Liucheng; Wei Liansheng; Ji Liqiang; Zhang Zengrui

1988-03-01

A new type of on-line monitoring system used to monitor radioactive nuclides with α or soft β radiation in the effluent from a high pressure ion exchange column is described. The beads made of cerium-impregnated lithium silicate glass are used as scientillation material. They are filled into a quartz glass tube to form a flow cell. By reducing the diameter of glass beads to more closly approximate the average range of α or soft β radiation in solution, the absolute counting efficiency for 241 Am, 242 Cm α radiation have reached and 85.8% and 92.8% respectively, for 14 C, 90 Sr- 90 Y β radiation, 62.1% and 88.6% respectively. These values can be comparable to those achieved with on-line liquid scientillation technique. When the total amount of 241 Am added into column is decreased to 7.4 Bq it is still possible to obtain a clear chromatography peak (half peak width = 0.22 mL)

Structure and aqueous reactivity of silicate glasses high-resolution nuclear magnetic resonance contribution; Structure et reactivite aqueuse des verres silicates apport de la resonance magnetique nucleaire haute-resolution

Energy Technology Data Exchange (ETDEWEB)

Angeli, F

2000-10-25

This research aims at getting a better understanding of the relations which may exist between the chemical composition of the oxide silicate glasses, the structure and the aqueous reactivity. We study the cations present in most glasses, more particularly the radioactive waste glasses, and those which are more liable to bring information both about structure and reactivity. Among the experimental methods used, the nuclear magnetic resonance of multi-quantum magic-angle spinning (NMR MQ-MAS) has been carried out for the structural characterization of the pristine and altered glasses. In the first part, we discuss the possibility of deducting a type of information from a quantitative approach of the {sup 23}Na, {sup 27}Al and {sup 17}O NMR MQ-MAS. In the second part, we apply this method to glasses containing between two and six oxides. The vitreous compositions studied permit to focus our attention on the influence of sodium, aluminum and calcium on their local structural environment. We point out an evolution of the distributions of bond distances and angles in relation to the glass chemical composition. We show the strong potentiality of the {sup 17}O used to probe the pristine and altered glasses. The influence of the different cations studied on the rate of glass dissolution is debated from the alterations made on short periods. On the basis of all these data, we discuss the importance of the structural effect which may influence the kinetic phenomena of alteration. (author)

Coordination Environments of Highly Charged Cations (Ti, Cr, and Light REE's) in Borosilicate Glass/Melts to 1120C

Energy Technology Data Exchange (ETDEWEB)

Farges, Francois; /Museum Natl. Hist. Natur. /Stanford U., Geo. Environ. Sci.; Brown, Gordon E., Jr.; /Stanford U., Geo. Environ Sci. /SLAC, SSRL

2007-01-02

The local environments around Ti, Cr, and several light rare-earth elements (La, Ce, and Nd) were investigated by in-situ XANES spectroscopy in a number of complex borosilicate glasses and melts (to 1120 C) that are used for nuclear waste storage. Examination of the high-resolution XANES spectra at the Ti K-edge shows that the average coordination of Ti changes from {approx}5 to {approx}4.5. Cr is dominantly trivalent in the melts studied. However, its average coordination is probably lower in the melt (tetrahedral ?) as revealed by the more intense Cr-K pre-edge feature. Ce also changes its average valence from dominantly +4 to +3.5 upon glass melting. These changes are reversible at T{sub g}, the glass transition temperature ({approx}500-550 C for these glasses). In contrast, the local environments of Nd, Pr, and La are unaffected by melting. Therefore, structural reorganization of these borosilicate glass/melts above T{sub g} is variable, not only in terms of valence (as for Ce) but also speciation (Ti and Cr). Both the ability of B to adopt various coordination geometries (triangular and tetrahedral) and the chemical complexity of the glass/melts explain these changes.

Development of phosphate glass microspheres containing holmium for selective internal radiotherapy; Desenvolvimento de microesferas de vidro fosfato contendo holmio para uso em radioterapia interna seletiva

Energy Technology Data Exchange (ETDEWEB)

Barros Filho, Eraldo Cordeiro

2016-11-01

The selective internal radiotherapy is an alternative for some kinds of cancer as the hepatocellular carcinoma (HCC) or primary liver cancer treatment. In this treatment, glass or polymer microspheres containing radionuclides inside their structure are introduced in the liver through hepatic artery and trapped at the arterioles that feed the tumor. In this work, the development of phosphate glasses containing holmium for production of microspheres and their application in Brazil are proposed. The developed glasses presented suitable chemical durability, density of 2,7(3) g/cm{sup 3}, high thermal stability and the impurities contained therein do not preclude the treatment. The microspheres were produced by the flame method and the gravitational fall method, and were characterized by means of several techniques to evaluate shape, average particle size, activity and biocompatibility suitable for selective internal radiotherapy. Based in the main results, the submission to in vivo tests is proposed. (author)

Electrochemistry of cations in diopsidic melt - Determining diffusion rates and redox potentials from voltammetric curves

Science.gov (United States)

Colson, Russell O.; Haskin, Larry A.; Crane, Daniel

1990-01-01

Results are presented on determinations of reduction potentials and their temperature dependence of selected ions in diopsidic melt, by using linear sweep voltammetry. Diffusion coefficients were measured for cations of Eu, Mn, Cr, and In. Enthalpies and entropies of reduction were determined for the cations V(V), Cr(3+), Mn(2+), Mn(3+), Fe(2+), Cu(2+), Mo(VI), Sn(IV), and Eu(3+). Reduction potentials were used to study the structural state of cations in the melt.

The behaviour of selected yttrium containing bioactive glass microspheres in simulated body environments.

Science.gov (United States)

Cacaina, D; Ylänen, H; Simon, S; Hupa, M

2008-03-01

The study aims at the manufacture and investigation of biodegradable glass microspheres incorporated with yttrium potentially useful for radionuclide therapy of cancer. The glass microspheres in the SiO2-Na2O-P2O5-CaO-K2O-MgO system containing yttrium were prepared by conventional melting and flame spheroidization. The behaviour of the yttrium silicate glass microspheres was investigated under in vitro conditions using simulated body fluid (SBF) and Tris buffer solution (TBS), for different periods of time, according to half-life time of the Y-90. The local structure of the glasses and the effect of yttrium on the biodegradability process were evaluated by Fourier Transform Infrared (FT-IR) spectroscopy and Back Scattered Electron Imaging of Scanning Electron Microscopy (BEI-SEM) equipped with Energy Dispersive X-ray (EDX) analysis. UV-VIS spectrometry and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used for analyzing the release behaviour of silica and yttrium in the two used solutions. The results indicate that the addition of yttrium to a bioactive glass increases its structural stability which therefore, induced a different behaviour of the glasses in simulated body environments.

Structure-solubility relationships in fluoride-containing phosphate based bioactive glasses

Science.gov (United States)

Shaharyar, Yaqoot

The dissolution of fluoride-containing bioactive glasses critically affects their biomedical applications. Most commercial fluoride-releasing bioactive glasses have been designed in the soda-lime-silica system. However, their relatively slow chemical dissolution and the adverse effect of fluoride on their bioactivity are stimulating the study of novel biodegradable materials with higher bioactivity, such as biodegradable phosphate-based bioactive glasses, which can be a viable alternative for applications where a fast release of active ions is sought. In order to design new biomaterials with controlled degradability and high bioactivity, it is essential to understand the connection between chemical composition, molecular structure, and solubility in physiological fluids.Accordingly, in this work we have combined the strengths of various experimental techniques with Molecular Dynamics (MD) simulations, to elucidate the impact of fluoride ions on the structure and chemical dissolution of bioactive phosphate glasses in the system: 10Na2O - (45-x) CaO - 45P2O5 - xCaF2, where x varies between 0 -- 10 mol.%. NMR and MD data reveal that the medium-range atomic-scale structure of thse glasses is dominated by Q2 phosphate units followed by Q1 units, and the MD simulations further show that fluoride tends to associate with network modifier cations to form alkali/alkaline-earth rich ionic aggregates. On a macroscopic scale, we find that incorporating fluoride in phosphate glasses does not affect the rate of apatite formation on the glass surface in simulated body fluid (SBF). However, fluoride has a marked favorable impact on the glass dissolution in deionized water. Similarly, fluoride incorporation in the glasses results in significant weight gain due to adsorption of water (in the form of OH ions). These macroscopic trends are discussed on the basis of the F effect on the atomistic structure of the glasses, such as the F-induced phosphate network re-polymerization, in a

Tunnel restorations using glass ionomer or glass cermet: in vitro marginal ridge fracture and microleakage.

Science.gov (United States)

Shetty, R; Munshi, A K

1996-01-01

The purpose of this in vitro study was to compare the marginal ridge fracture resistance and microleakage following restorations of partial tunnel preparations using glass ionomer and glass cermet cements. Sixty eight sound premolars were selected for this study and were divided randomly into six groups. A standardized partial tunnel preparation was done on all the teeth except specimens belonging to Group I. The partial tunnel preparations of Groups III & V were restored with glass ionomer and that of Groups IV & VI were restored with glass cermet. The teeth belonging to Groups I, II, III & IV were subjected to marginal ridge fracture resistance testing. The teeth of Groups V & VI were tested for microleakage after immersing them in 5% methylene blue solution for 4 hours. The results indicated that the teeth restored with glass cermet were marginally better than that with glass ionomer in terms of marginal ridge fracture resistance. Both the materials failed to reinforce the marginal ridge to the level of an intact tooth. The microleakage which occurred around both the materials were statistically insignificant, but on comparison glass ionomer showed better results. Hence, glass ionomer is preferred as a restorative material for partial tunnel preparations because of additional inherent advantages like superior esthetics and fluoride leachability.

Selective adsorption of ions in charged slit-systems

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M.Valiskó

2013-01-01

Full Text Available We study the selective adsorption of various cations into a layered slit system using grand canonical Monte Carlo simulations. The slit system is formed by a series of negatively charged membranes. The electrolyte contains two kinds of cations with different sizes and valences modeled by charged hard spheres immersed in a continuum dielectric solvent. We present results for various cases depending on the combinations of the properties of the competing cations. We concentrate to the case when the divalent cations are larger than the monovalent cations. In this case, size and charge have counterbalancing effects, which results in interesting selectivity phenomena.

Electronic polarizability, optical basicity and interaction parameter for Nd{sub 2}O{sub 3} doped lithium-zinc-phosphate glasses

Energy Technology Data Exchange (ETDEWEB)

Algradee, M.A.; Sultan, M.; Samir, O.M.; Alwany, A.E.B. [Ibb University, Department of Physics, Faculty of Science, Ibb (Yemen)

2017-08-15

The Nd{sup 3+}-doped lithium-zinc-phosphate glasses were prepared by means of conventional melt quenching method. X-ray diffraction results confirmed the glassy nature of the studied glasses. The physical parameters such as the density, molar volume, ion concentration, polaron radius, inter-ionic distance, field strength and oxygen packing density were calculated using different formulae. The transmittance and reflectance spectra of glasses were recorded in the wavelength range 190-1200 nm. The values of optical band gap and Urbach energy were determined based on Mott-Davis model. The refractive indices for the studied glasses were evaluated from optical band gap values using different methods. The average electronic polarizability of the oxide ions, optical basicity and an interaction parameter were investigated from the calculated values of the refractive index and the optical band gap for the studied glasses. The variations in the different physical and optical properties of glasses with Nd{sub 2}O{sub 3} content were discussed in terms of different parameters such as non-bridging oxygen and different concentrations of Nd cation in glass system. (orig.)

Complexing and analysis of cation selectivity of neutral phosphoryl-containing tripodaud of tris((0-diphenyl-phosphinoylmethyl)phenoxyethyl)amine to lithium sodium and potassium, in acetonitrile. Lithium selectivity and polymeclear compleses

International Nuclear Information System (INIS)

Baulin, V.E.; Solov'ev, V.P.; Strakhova, N.N.; Kazachenko, V.P.

1996-01-01

A new phosphoryl-containing tripodand-tris-[(0-diphenyl-phosphinoylmethyl)phenoxyethyl] amine-was synthesized. Constants of stability, enthalpy and entropy of reactions of tripodond complexing with lithium, sodium, potassium thiocyanates in acetonitrile at 298 k were determined. Investigation of complexing by the methods of calorimetry, 7 Li and 23 Na NMR, mass-spectrometry enabled to conclude that ligand formed polynuclear complexes with lithium thiocyanate of 2/1 and 3/1 composition along with 1/1 complex. High selectivity of podand to lithium cation in acetonitrile was conditioned by formation of polynuclear complexes. Refs. 29, figs. 3

Separation of Th and U using borosilicate glasses

International Nuclear Information System (INIS)

Chandramouleeswaran, S.; Ramkumar, Jayshree; Singhal, R.K.; Reddy, A.V.R.; Sudarsan, V.

2010-01-01

Boroaluminosilicate glasses having B 2 O 3 to Na 2 O ratio 0.23 and 9.8 were prepared by conventional melt-quench method and used as room temperature ion exchanger for the sorption of thorium from aqueous solutions. Various experimental conditions were optimized to achieve selective and maximum uptake of thorium. The studies were extended to synthetic mixtures of thorium and uranium, wherein thorium could be selectively removed in presence of 10 fold excess of uranium. Structural elucidation studies were carried out to understand the ion exchange property of glasses. It is seen that presence of linkages like Si-O - and B-O - in the glasses was responsible for the uptake of metal ions. It is seen that the uptake depends on pH of the solution, composition of glass and the initial concentration of thorium ion in solution. (author)

Strontium chloroapatite based glass-ceramics composites for nuclear waste immobilisation

International Nuclear Information System (INIS)

Jena, Hrudananda; Maji, Binoy Kumar; Asuvathraman, R.; Govindan Kutty, K.V.

2013-01-01

Apatites are naturally occurring minerals with a general formula of M 10 (PO 4 ) 6 X 2 , (M= Ca, Sr, Ba, X= OH, Cl, F) with a hexagonal crystal structure (S.G :P6 3 /m) and can accommodate alkaline earth and various other aliovalent cations and anions into its crystal structure. Apatites are also known to have high resistance to leaching of the constituent elements under geological conditions. It may not often be possible to immobilize the whole spectrum of the radioactive waste in a single phase M 10 (PO 4 ) 6 Cl 2 , then a combination of M-chloroapatite encapsulated in borosilicate glass (BSG) can immobilize most of the radwaste elements in the composite glass-ceramic matrix (glass bonded chloroapatite), thus utilizing the immobilizing efficiency of both the ceramic phase and glass. In the present study, the synthesis, characterization and thermo-physical property measurements of the Sr-chloroapatite (SrApCI) and some glass-bonded composites based on it have been investigated. The Sr-chloroapatite glass-ceramics were prepared by solid state reactions among stoichiometric concentrations of apatite forming reagents, 20 wt. % borosilicate glass (BSG), and known concentrations (10, 13 and 16 wt. %) of a simulated waste in chloride form. The products were characterized by XRD to confirm the formation of Sr 10 (PO 4 ) 6 Cl 2 and glass bonded-chloroapatite composites. The surface morphology and qualitative chemical composition of the powders were examined by SEM and EDX. Thermal expansion and glass transition temperature of the matrices were measured by dilatometry. Glass transition temperature of the glass-bonded composites was also examined by differential scanning calorimetry and differential thermal analysis. The 10-16 wt.% waste loaded matrices showed similar thermal expansion as that of SrApCI, indicating the thermal stability of the matrix to chloride waste immobilization. The glass transition temperature of the waste loaded matrices decreases on increasing the

Physical and chemical characterization of borosilicate glasses containing Hanford high-level wastes

International Nuclear Information System (INIS)

Kupfer, M.J.; Palmer, R.A.

1980-10-01

Scouting studies are being performed to develop and evaluate silicate glass forms for immobilization of Hanford high-level wastes. Detailed knowledge of the physical and chemical properties of these glasses is required to assess their suitability for long-term storage or disposal. Some key properties to be considered in selecting a glass waste form include leach resistance, resistance to radiation, microstructure (includes devitrification behavior or crystallinity), homogeneity, viscosity, electrical resistivity, mechanical ruggedness, thermal expansion, thermal conductivity, density, softening point, annealing point, strain point, glass transformation temperature, and refractive index. Other properties that are important during processing of the glass include volatilization of glass and waste components, and corrosivity of the glass on melter components. Experimental procedures used to characterize silicate waste glass forms and typical properties of selected glass compositions containing simulated Hanford sludge and residual liquid wastes are presented. A discussion of the significance and use of each measured property is also presented

Chemical Surface, Thermal and Electrical Characterization of Nafion Membranes Doped with IL-Cations

Directory of Open Access Journals (Sweden)

María del Valle Martínez de Yuso

2014-04-01

Full Text Available Surface and bulk changes in a Nafion membrane as a result of IL-cation doping (1-butyl-3-methylimidazolium tetrafluoroborate or BMIM+BF4 and phenyltrimethylammonium chloride or TMPA+Cl− were studied by X-ray photoelectron spectroscopy (XPS, contact angle, differential scanning calorimetry (DSC and impedance spectroscopy (IS measurements performed with dry samples after 24 h in contact with the IL-cations BMIM+ and TMPA+. IL-cations were selected due to their similar molecular weight and molar volume but different shape, which could facilitate/obstruct the cation incorporation in the Nafion membrane structure by proton/cation exchange mechanism. The surface coverage of the Nafion membrane by the IL-cations was confirmed by XPS analysis and contact angle, while the results obtained by the other two techniques (DSC and IS seem to indicate differences in thermal and electrical behaviour depending on the doping-cation, being less resistive the Nafion/BMIM+ membrane. For that reason, determination of the ion transport number was obtained for this membrane by measuring the membrane or concentration potential with the samples in contact with HCl solutions at different concentrations. The comparison of these results with those obtained for the original Nafion membrane provides information on the effect of IL-cation BMIM+ on the transport of H+ across wet Nafion/BMIM+ doped membranes.

Radiation induced graft copolymerization for preparation of cation exchange membranes: a review

International Nuclear Information System (INIS)

Mohamed Mahmoud Nasef; Hamdani Saidi; Hussin Mohd Nor

1999-01-01

Cation exchange membranes are regarded as the ideal solid polymer electrolyte materials for the development of various electrochemical energy conversion applications where significant improvements in the current density are required. Such membranes require special polymers and preparation techniques to maintain high chemical , mechanical and thermal stability in addition to high ionic conductivity and low resistance. A lot of different techniques have been proposed in the past to prepare such membranes. Radiation-induced graft copolymerization provides an attractive ft method for modification of chemical and physical properties of polymeric materials and is of particular interest in achieving specially desired cation exchange membranes as well as excellent membrane properties. This is due to the ability to control the membrane compositions as well as properties by proper selection of grafting conditions. Therefore numerous parameters have to be investigated to properly select the right polymeric materials, radiation grafting technique and the grafting conditions to be employed. In this paper a state-of-the-art of radiation-induced graft copolymerization for preparation of cation exchange membranes and their applications are briefly reviewed. (Author)

Dualism of Sensitivity and Selectivity of Porphyrin Dimers in Electroanalysis.

Science.gov (United States)

Lisak, Grzegorz; Tamaki, Takashi; Ogawa, Takuji

2017-04-04

This work uncovers the application of porphyrin dimers for the use in electroanalysis, such as potentiometric determination of ions. It also puts in question a current perception of an occurrence of the super-Nernstian response, as a result of the possible dimerization of single porphyrins within an ion-selective membrane. To study that, four various porphyrin dimers were used as ionophores, namely, freebase-freebase, Zn-Zn, Zn-freebase, and freebase-Zn. Since the Zn-freebase and freebase-Zn porphyrin dimers carried both anion- and cation-sensitive porphyrin units, their application in ISEs was utilized in both anion- and cation-sensitive sensors. With respect to the lipophilic salt added, both porphyrins dimers were found anion- and cation-sensitive. This allowed using a single molecule as novel type of versatile ionophore (anion- and cation-selective), simply by varying the membrane composition. All anion-sensitive sensors were perchlorate-sensitive, while the cation-selective sensors were silver-sensitive. The selectivity of the sensors depended primarily on the porphyrin dimers in the ion-selective membrane. Furthermore, the selectivity of cation-sensitive dimer based sensors was found significantly superior to the ones measured for the single porphyrin unit based sensors (precursors of the porphyrin dimers). Thus, the dimerization of single porphyrins may actually be a factor to increase or modulate porphyrin selectivity. Moreover, in the case of cation-sensitive sensors, the selectivity vastly depended on the order of porphyrin units in the dimer. This opens a new approach of regulating and adjusting sensitivity and selectivity of the sensor through the application of complex porphyrin systems with more than one porphyrin units with mix sensitive porphyrins.

Reducible cationic lipids for gene transfer.

Science.gov (United States)

Wetzer, B; Byk, G; Frederic, M; Airiau, M; Blanche, F; Pitard, B; Scherman, D

2001-01-01

One of the main challenges of gene therapy remains the increase of gene delivery into eukaryotic cells. We tested whether intracellular DNA release, an essential step for gene transfer, could be facilitated by using reducible cationic DNA-delivery vectors. For this purpose, plasmid DNA was complexed with cationic lipids bearing a disulphide bond. This reduction-sensitive linker is expected to be reduced and cleaved in the reducing milieu of the cytoplasm, thus potentially improving DNA release and consequently transfection. The DNA--disulphide-lipid complexation was monitored by ethidium bromide exclusion, and the size of complexes was determined by dynamic light scattering. It was found that the reduction kinetics of disulphide groups in DNA--lipid complexes depended on the position of the disulphide linker within the lipid molecule. Furthermore, the internal structure of DNA--lipid particles was examined by small-angle X-ray scattering before and after lipid reduction. DNA release from lipid complexes was observed after the reduction of disulphide bonds of several lipids. Cell-transfection experiments suggested that complexes formed with selected reducible lipids resulted in up to 1000-fold higher reporter-gene activity, when compared with their analogues without disulphide bonds. In conclusion, reduction-sensitive groups introduced into cationic lipid backbones potentially allow enhanced DNA release from DNA--lipid complexes after intracellular reduction and represent a tool for improved vectorization. PMID:11389682

Recycle Glass in Foam Glass Production

DEFF Research Database (Denmark)

Petersen, Rasmus Rosenlund; König, Jakob; Yue, Yuanzheng

The foam glass industry turn recycle glass into heat insulating building materials. The foaming process is relative insensitive to impurities in the recycle glass. It is therefore considered to play an important role in future glass recycling. We show and discuss trends of use of recycled glasses...... in foam glass industry and the supply sources and capacity of recycle glass....

Phase selection and microstructure in directional solidification of glass forming Pd-Si-Cu alloys

Science.gov (United States)

Huo, Yang

Phase selection and microstructure formation during the rapid solidification of alloy melts has been a topic of substantial interest over the last several decades, attributed mainly to the access to novel structures involving metastable crystalline and non-crystalline phases. In this work, Bridgeman type directional solidification was conducted in Pd-Si-Cu glass forming system to study such cooling rate dependent phase transition and microstructure formation. The equilibrium state for Pd-Si-Cu ternary system was investigated through three different works. First of all, phase stabilities for Pd-Si binary system was accessed with respects of first-principles and experiments, showing Pd5Si, Pd9Si2, Pd3Si and Pd 2Si phase are stable all way to zero Kevin while PdSi phase is a high temperature stable phase, and Pd2Si phase with Fe2P is a non-stoichiometry phase. A thermodynamic database was developed for Pd-Si system. Second, crystal structures for compounds with ternary compositions were studied by XRD, SEM and TEM, showing ordered and disordered B2/bcc phases are stable in Pd-rich part. At last, based on many phase equilibria and phase transitions data, a comprehensive thermodynamic discrption for Pd-Si-Cu ternary system was first time to be developed, from which different phase diagrams and driving force for kinetics can be calculated. Phase selection and microstructure formation in directional solidification of the best glass forming composition, Pd 77.5Si16.5Cu6, in this system with growth velocities from 0.005 to 7.5mm/s was systematically studied and the solidification pathways at different conditions were interpreted from thermodynamic simulation. The results show that for growth velocities are smaller than 0.1mm/s Pd 3Si phase is primary phase and Pd9Si2 phase is secondary phase, the difficulty for Pd9Si2 phase nucleation gives rise to the formation of two different eutectic structure. For growth velocities between 0.4 and 1mm/s, instead of Pd3Si phase, Pd9Si2

Cation-Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

Energy Technology Data Exchange (ETDEWEB)

Mougel, Victor; Horeglad, Pawel; Nocton, Gregory; Pecaut, Jacques; Mazzanti, Marinella [CEA, INAC, SCIB, Laboratoire de Reconnaissance Ionique et Chimie de Coordination, CEA-Grenoble, 38054 GRENOBLE, Cedex 09 (France)

2010-07-01

Three new cation cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO{sub 2}py{sub 5})-(KI{sub 2}py{sub 2})]{sub n} (1) with the Schiff base ligands salen{sup 2-}, acacen{sup 2-}, and salophen{sup 2-} (H{sub 2}salen N, N'-ethylene-bis(salicylidene-imine), H{sub 2}acacen=-N, N'-ethylenebis(acetylacetone-imine), H{sub 2}salophen=N, N'-phenylene-bis(salicylidene-imine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen{sup 2-} in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetra-nuclear complexes ([UO{sub 2}-(acacen)]{sub 4}[{mu}{sub 8}-]{sub 2}[K([18]C-6)(py)]{sub 2}) (3) and ([UO{sub 2}(acacen)](4)[{mu}{sub 8}-]).2[K([222])(py)] (4) ([UO{sub 2}(salophen)](4)[{mu}{sub 8}-K]{sub 2}[mu(5)-KI]{sub 2}[(K([18]C-6)]).2 [K([18]C-6)-(thf){sub 2}].2I (5), and ([UO{sub 2}(salen)(4)][{mu}{sub 8}-Rb]{sub 2}[Rb([18]C-6)]{sub 2}) (9) ([222] = [222]cryptand, py =pyridine), presenting a T-shaped cation cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetra-nuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U{sup V}O{sub 2}(salen)(py)][Cp*{sub 2}Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation cation complexes. The nature of the cation plays a key role in the preparation of stable cation cation complexes. Stable tetra-nuclear complexes form in the presence of K

Sorption by cation exchange

International Nuclear Information System (INIS)

Bradbury, M.H.; Baeyens, B.

1994-04-01

A procedure for introducing exchange into geochemical/surface complexation codes is described. Beginning with selectivity coefficients, K c , defined in terms of equivalent fractional ion occupancies, a general expression for the molar based exchange code input parameters, K ex , is derived. In natural systems the uptake of nuclides onto complex sorbents often occurs by more than one mechanism. The incorporation of cation exchange and surface complexation into a geochemical code therefore enables sorption by both mechanisms to be calculated simultaneously. The code and model concepts are tested against sets of experimental data from widely different sorption studies. A proposal is made to set up a data base of selectivity coefficients. Such a data base would form part of a more general one consisting of sorption mechanism specific parameters to be used in conjunction with geochemical/sorption codes to model and predict sorption. (author) 6 figs., 6 tabs., 26 refs

Structure relationship of cationic lipids on gene transfection mediated by cationic liposomes.

Science.gov (United States)

Paecharoenchai, Orapan; Niyomtham, Nattisa; Apirakaramwong, Auayporn; Ngawhirunpat, Tanasait; Rojanarata, Theerasak; Yingyongnarongkul, Boon-ek; Opanasopit, Praneet

2012-12-01

The aim of this study was to investigate the transfection efficiency of cationic liposomes formulated with phosphatidylcholine (PC) and novel synthesized diethanolamine-based cationic lipids at a molar ratio of 5:1 in comparison with Lipofectamine™ 2000. Factors affecting transfection efficiency and cell viability, including the chemical structure of the cationic lipids, such as different amine head group (diamine and polyamine; and non-spermine and spermine) and acyl chain lengths (C14, C16, and C18) and the weight ratio of liposomes to DNA were evaluated on a human cervical carcinoma cell line (HeLa cells) using the pDNA encoding green fluorescent protein (pEGFP-C2). Characterizations of these lipoplexes in terms of size and charge measurement and agarose gel electrophoresis were performed. The results from this study revealed that almost no transfection was observed in the liposome formulations composed of cationic lipids with a non-spermine head group. In addition, the transfection efficiency of these cationic liposomes was in the following order: spermine-C14 > spermine-C16 > spermine-C18. The highest transfection efficiency was observed in the formulation of spermine-C14 liposomes at a weight ratio of 25; furthermore, this formulation was safe for use in vitro. In conclusion, cationic liposomes containing spermine head groups demonstrated promising potential as gene carriers.

pH triggered superior selective adsorption and separation of both cationic and anionic dyes and photocatalytic activity on a fully exfoliated titanate layer-natural polymer based nanocomposite.

Science.gov (United States)

Sarkar, Amit Kumar; Saha, Arka; Panda, Asit Baran; Pal, Sagar

2015-11-18

A fully exfoliated titanate layer-natural polymer amylopectin based nanocomposite, with pH responsive superior selective adsorption, separation of both cationic (MB: 599 mg g(-1) at pH 9) and anionic (MO: 558 mg g(-1) at pH 3) dyes and photodegradation properties, has been realized through simultaneous in situ layered titanate formation, exfoliation and polymerization.

New TiO2/DSAT Immobilization System for Photodegradation of Anionic and Cationic Dyes

Directory of Open Access Journals (Sweden)

Wan Izhan Nawawi Wan Ismail

2015-01-01

Full Text Available A new immobilized TiO2 technique was prepared by coating TiO2 solution onto double-sided adhesive tape (DSAT as a thin layer binder without adding any organic additives. Glass plate was used as support material to immobilized TiO2/DSAT. Two different charges of dyes were applied, namely, anionic reactive red 4 (RR4 and cationic methylene blue (MB dyes. Photocatalytic degradation of RR4 and MB dyes was observed under immobilized TiO2/DSAT with the degradation rate slightly lower and higher, respectively, compared with TiO2 in suspension mode. It was observed that DSAT is able to provide a very strong intact between glass and TiO2 layers thus making the reusability of immobilized TiO2/DSAT be up to 30 cycles. In fact, a better photodegradation activity was observed by number of cycles due to increasing formation of pores on TiO2 surface observed by SEM analysis.

Plutonium immobilization in glass and ceramics

Energy Technology Data Exchange (ETDEWEB)

Knecht, D.A. [Lockheed Martin Idaho Technologies, Idaho Falls (United States); Murphy, W.M. [Southwest Research Institute, San Antonio, TX (United States)

1996-05-01

The Materials Research Society Nineteenth Annual Symposium on the Scientific Basis for Nuclear Waste Management was held in Boston on November 27 to December 1, 1995. Over 150 papers were presented at the Symposium dealing with all aspects of nuclear waste management and disposal. Fourteen oral sessions and on poster session included a Plenary session on surplus plutonium dispositioning and waste forms. The proceedings, to be published in April, 1996, will provide a highly respected, referred compilation of the state of scientific development in the field of nuclear waste management. This paper provides a brief overview of the selected Symposium papers that are applicable to plutonium immobilization and plutonium waste form performance. Waste forms that were described at the Symposium cover most of the candidate Pu immobilization options under consideration, including borosilicate glass with a melting temperature of 1150 {degrees}C, a higher temperature (1450 {degrees}C) lanthanide glass, single phase ceramics, multi-phase ceramics, and multi-phase crystal-glass composites (glass-ceramics or slags). These Symposium papers selected for this overview provide the current status of the technology in these areas and give references to the relevant literature.

Plutonium immobilization in glass and ceramics

International Nuclear Information System (INIS)

Knecht, D.A.; Murphy, W.M.

1996-01-01

The Materials Research Society Nineteenth Annual Symposium on the Scientific Basis for Nuclear Waste Management was held in Boston on November 27 to December 1, 1995. Over 150 papers were presented at the Symposium dealing with all aspects of nuclear waste management and disposal. Fourteen oral sessions and on poster session included a Plenary session on surplus plutonium dispositioning and waste forms. The proceedings, to be published in April, 1996, will provide a highly respected, referred compilation of the state of scientific development in the field of nuclear waste management. This paper provides a brief overview of the selected Symposium papers that are applicable to plutonium immobilization and plutonium waste form performance. Waste forms that were described at the Symposium cover most of the candidate Pu immobilization options under consideration, including borosilicate glass with a melting temperature of 1150 degrees C, a higher temperature (1450 degrees C) lanthanide glass, single phase ceramics, multi-phase ceramics, and multi-phase crystal-glass composites (glass-ceramics or slags). These Symposium papers selected for this overview provide the current status of the technology in these areas and give references to the relevant literature

Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

Science.gov (United States)

Kunhi Mouvenchery, Yamuna; Jaeger, Alexander; Aquino, Adelia J A; Tunega, Daniel; Diehl, Dörte; Bertmer, Marko; Schaumann, Gabriele Ellen

2013-01-01

It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+), Ca(2+) or Na(+), respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>2 h) than deprotonation of functional groups (cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for CaB and aging-induced structural reorganisation can enhance cross-link formation.

The Free Tricoordinated Silyl Cation Problem

Directory of Open Access Journals (Sweden)

Čičak, H.

2010-03-01

Full Text Available As the importance and abundance of silicon in our environment is large, it has been thought that silicon might take the place of carbon in forming a host of similar compounds and silicon-based life. However, until today there is no experimental evidence for such a hypothesis and carbon is still unique among the elements in the vast number and variety of compounds it can form. Also, the corresponding derivatives of the two elements show considerable differences in their chemical properties.The essential debate concerning organosilicon chemistry relates to the existence of the free planar tricoordinated silyl cations in condensed phase (R3Si+, in analogy to carbocations (R3C+ which have been known and characterized as free species. Although silyl cations are thermodynamically more stable than their carbon analogs, they are very reactive due to their high inherent electrophilicity and the ability of hypervalent coordination. On the other hand, stabilization by inductive and hyperconjugative effects and larger steric effects of carbocations make them less sensitive to solvation or other environmental effects than silyl cations. Hence, observation of free silyl cations in the condensed phase proved extremely difficult and the actual problem is the question of the degree of the (remaining silyl cation character.The first free silyl cation, trimesitylsilyl cation, and in analogy with it tridurylsilyl cation, were synthesized by Lambert et al. Free silyl cations based on analogy to aromatic ions (homocyclopropenylium and tropylium have also been prepared. However, in these silyl cations the cationic character is reduced by internal π -conjugation. Čičak et al. prepared some silyl-cationic intermediates (Me3Si--CH≡CR+in solid state. With the help of quantum-mechanical calculations it was concluded that these adducts have much more silyl cation than carbocation character.

Simultaneous Analysis of Monovalent Anions and Cations with a Sub-Microliter Dead-Volume Flow-Through Potentiometric Detector for Ion Chromatography

Science.gov (United States)

Dumanli, Rukiye; Attar, Azade; Erci, Vildan; Isildak, Ibrahim

2016-01-01

A microliter dead-volume flow-through cell as a potentiometric detector is described in this article for sensitive, selective and simultaneous detection of common monovalent anions and cations in single column ion chromatography for the first time. The detection cell consisted of less selective anion- and cation-selective composite membrane electrodes together with a solid-state composite matrix reference electrode. The simultaneous separation and sensitive detection of sodium (Na+), potassium (K+), ammonium (NH4+), chloride (Cl−) and nitrate (NO3−) in a single run was achieved by using 98% 1.5 mM MgSO4 and 2% acetonitrile eluent with a mixed-bed ion-exchange separation column without suppressor column system. The separation and simultaneous detection of the anions and cations were completed in 6 min at the eluent flow-rate of 0.8 mL/min. Detection limits, at S/N = 3, were ranged from 0.2 to 1.0 µM for the anions and 0.3 to 3.0 µM for the cations, respectively. The developed method was successfully applied to the simultaneous determination of monovalent anions and cations in several environmental and biological samples. PMID:26786906

On the chemical variability of Middelburg glass beads and rods

International Nuclear Information System (INIS)

Karklins, K.; Kottman, J.; Hancock, R.G.V.; Sempowski, M.L.; Nohe, A.W.; Moreau, J.-F.; Aufreiter, S.; Kenyon, I.

2001-01-01

Forty-three glass samples from a late 16th-early 17th century, glass beadmaking house in Middelburg, the Netherlands, were selected for maximum colouring variability, including plain and multi-coloured varieties. The glass chemistries were quite diverse, within each colour grouping. For each single colour of glass, anticipated colouring elements (copper for turquoise blue, cobalt for dark blue, manganese for rose, and tin for white) were used, with the exception of two beads that were opacified wih antimony rather than with tin. Multi-coloured glass glasses (chevron beads) produced chemistries that match the mixing of the different coloured glasses. In some cases, low relative amounts of some inter-mixed glasses were not detectable against the composition of the major glass component. (author). 16 refs., 3 tabs

Evaluation of the Seismic Characterision of Select Engineered Nanoparticles in Saturated Glass Beads

Science.gov (United States)

A laboratory testing apparatus was developed for the study of seismic body wave propagation through nanoparticles dispersed in pore fluid that is essentially saturating glass beads. First, the responses of water-saturated glass bead specimens were studied to establish baseline si...

Infrared Spectroscopic and Theoretical Study of the HC_nO^+(N=5-12) Cations

Science.gov (United States)

Li, Wei; Jin, Jiaye; Wang, Guanjun; Zhou, Mingfei

2017-06-01

Carbon chains and derivatives are highly active species, which are widely existed as reactive intermediates in many chemical processes including atmospheric chemistry, hydrocarbon combustion, as well as interstellar chemistry. The carbon chain cations, HC_nO^+ (n = 5-12) are produced via pulsed laser vaporization of a graphite target in supersonic expansions containing carbon monoxide and hydrogen. The infrared spectra are measured via mass-selected infrared photodissociation spectroscopy of the CO "tagged" [HC_nO.CO] cation complexes in the 1600-3500 \\wn region. The geometries and electronic ground states of these cation complexes are determined by their infrared spectra in conjunction with theoretical calculations. All the HC_nO^+ (n = 5-12) core cations are characterized to be linear carbon chain derivatives terminated by hydrogen and oxygen. The HC_nO^+ cations with odd n have closed-shell singlet ground states with polyyne-like structures, while those with even n have triplet ground states with allene-like structures.

Crystal growth in zinc borosilicate glasses

Science.gov (United States)

Kullberg, Ana T. G.; Lopes, Andreia A. S.; Veiga, João P. B.; Monteiro, Regina C. C.

2017-01-01

Glass samples with a molar composition (64+x)ZnO-(16-x)B2O3-20SiO2, where x=0 or 1, were successfully synthesized using a melt-quenching technique. Based on differential thermal analysis data, the produced glass samples were submitted to controlled heat-treatments at selected temperatures (610, 615 and 620 °C) during various times ranging from 8 to 30 h. The crystallization of willemite (Zn2SiO4) within the glass matrix was confirmed by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Under specific heat-treatment conditions, transparent nanocomposite glass-ceramics were obtained, as confirmed by UV-vis spectroscopy. The influence of temperature, holding time and glass composition on crystal growth was investigated. The mean crystallite size was determined by image analysis on SEM micrographs. The results indicated an increase on the crystallite size and density with time and temperature. The change of crystallite size with time for the heat-treatments at 615 and 620 °C depended on the glass composition. Under fixed heat-treatment conditions, the crystallite density was comparatively higher for the glass composition with higher ZnO content.

Synthesis and Structural Studies of Er3+ Containing Lead Cadmium Fluoroborate Glasses and Glass-Ceramics

Directory of Open Access Journals (Sweden)

Silva Maurício A.P.

2002-01-01

Full Text Available The vitreous domain was established in the PbF2-CdF2-B2O 3 system from melting and quenching experiments. Er3+ containing glasses were prepared and glass ceramics were obtained by selected heat-treatments. Lead fluoride was identified (beta-PbF2 as the crystalline phase. Structural studies were performed in some glassy and partially crystallized samples by means of X-ray Diffraction (XRD and Extended X-ray Absorption Fine Structure (EXAFS measurements. The role of Cd2+ and Pb2+ atoms on the glass network formation and also on the crystallization behavior was put forward by these techniques. After crystallization Er3+ atoms segregated in the crystal phase.

A Hydrogen Ion-Selective Sensor Based on Non-Plasticised Methacrylic-acrylic Membranes

Directory of Open Access Journals (Sweden)

Musa Ahmad

2002-08-01

Full Text Available A methacrylic-acrylic polymer was synthesised for use as a non-plasticised membrane for hydrogen ion-selective sensor incorporating tridodecylamine as an ionophore. The copolymer consisted of methyl methacrylate and n-butyl acrylate monomers in a ratio of 2:8. Characterisation of the copolymer using FTNMR demonstrated that the amount of each monomer incorporated during solution polymerisation was found to be similar to the amount used in the feed before polymerisation. The glass transition temperature of the copolymer determined by differential scanning calorimetry was -30.9 ºC. Potentiometric measurements conducted showed a linear pH response range of 4.3 – 9.6 with the response slope of 56.7 mV/decade. The selectivity of the sensors towards hydrogen ions was similar to other plasticiser based membrane electrodes and the logarithmic selectivity coefficients for discrimination against interference cations is close to –9.7. However, the incorporation of a lipophilic anion as membrane additive is essential in ensuring optimum performance of the hydrogen ion sensor.

Mixed hemimicelles solid-phase extraction based on sodium dodecyl sulfate-coated nano-magnets for selective adsorption and enrichment of illegal cationic dyes in food matrices prior to high-performance liquid chromatography-diode array detection detection.

Science.gov (United States)

Qi, Ping; Liang, Zhi-An; Wang, Yu; Xiao, Jian; Liu, Jia; Zhou, Qing-Qiong; Zheng, Chun-Hao; Luo, Li-Ni; Lin, Zi-Hao; Zhu, Fang; Zhang, Xue-Wu

2016-03-11

In this study, mixed hemimicelles solid-phase extraction (MHSPE) based on sodium dodecyl sulfate (SDS) coated nano-magnets Fe3O4 was investigated as a novel method for the extraction and separation of four banned cationic dyes, Auramine O, Rhodamine B, Basic orange 21 and Basic orange 22, in condiments prior to HPLC detection. The main factors affecting the extraction of analysts, such as pH, surfactant and adsorbent concentrations and zeta potential were studied and optimized. Under optimized conditions, the proposed method was successful applied for the analysis of banned cationic dyes in food samples such as chili sauce, soybean paste and tomato sauce. Validation data showed the good recoveries in the range of 70.1-104.5%, with relative standard deviations less than 15%. The method limits of determination/quantification were in the range of 0.2-0.9 and 0.7-3μgkg(-1), respectively. The selective adsorption and enrichment of cationic dyes were achieved by the synergistic effects of hydrophobic interactions and electrostatic attraction between mixed hemimicelles and the cationic dyes, which also resulted in the removal of natural pigments interferences from sample extracts. When applied to real samples, RB was detected in several positive samples (chili powders) within the range from 0.042 to 0.177mgkg(-1). These results indicate that magnetic MHSPE is an efficient and selective sample preparation technique for the extraction of banned cationic dyes in a complex matrix. Copyright © 2016 Elsevier B.V. All rights reserved.

Cation depletion by the sodium pump in red cells with pathologic cation leaks. Sickle cells and xerocytes.

Science.gov (United States)

Joiner, C H; Platt, O S; Lux, S E

1986-12-01

The mechanism by which sickle cells and xerocytic red cells become depleted of cations in vivo has not been identified previously. Both types of cells exhibit elevated permeabilities to sodium and potassium, in the case of sickle cells, when deoxygenated. The ouabain-insensitive fluxes of sodium and potassium were equivalent, however, in both cell types under these conditions. When incubated 18 hours in vitro, sickle cells lost cations but only when deoxygenated. This cation depletion was blocked by ouabain, removal of external potassium, or pretreatment with 4,4'-diisothiocyanostilbene-2,2'-disulfonate, which blocks the increase in cation permeability induced by deoxygenation. The loss of cation exhibited by oxygenated xerocytes similarly incubated was also blocked by ouabain. These data support the hypothesis that the elevated "passive" cation fluxes of xerocytes and deoxygenated sickle cells are not directly responsible for cation depletion of these cells; rather, these pathologic leaks interact with the sodium pump to produce a net loss of cellular cation.

Spectroscopic study of biologically active glasses

Science.gov (United States)

Szumera, M.; Wacławska, I.; Mozgawa, W.; Sitarz, M.

2005-06-01

It is known that the chemical activity phenomenon is characteristic for some inorganic glasses and they are able to participate in biological processes of living organisms (plants, animals and human bodies). An example here is the selective removal of silicate-phosphate glass components under the influence of biological solutions, which has been applied in designing glasses acting as ecological fertilizers of controlled release rate of the nutrients for plants. The structure of model silicate-phosphate glasses containing the different amounts of the glass network formers, i.e. Ca 2+ and Mg 2+, as a binding components were studied. These elements besides other are indispensable of the normal growth of plants. In order to establish the function and position occupied by the particular components in the glass structure, the glasses were examined by FTIR spectroscopy (with spectra decomposition) and XRD methods. It has been found that the increasing amount of MgO in the structure of silicate-phosphate glasses causes the formation of domains the structure of which changes systematically from a structure of the cristobalite type to a structure corresponding to forsterite type. Whilst the increasing content of CaO in the structure of silicate-phosphate glasses causes the formation of domains the structure of which changes from a structure typical for cristobalite through one similar to the structure of calcium orthophosphate, to a structure corresponding to calcium silicates. The changing character of domains structure is the reason of different chemical activity of glasses.

Structure of high alumina content Al2O3-SiO2 composition glasses.

Science.gov (United States)

Weber, Richard; Sen, Sabyasachi; Youngman, Randall E; Hart, Robert T; Benmore, Chris J

2008-12-25

The structure of binary aluminosilicate glasses containing 60-67 mol % Al2O3 were investigated using high-resolution 27Al NMR and X-ray and neutron diffraction. The glasses were made by aerodynamic levitation of molten oxides. The 67% alumina composition required a cooling rate of approximately 1600 degrees C s(1-) to form glass from submillimeter sized samples. NMR results show that the glasses contain aluminum in 4-, 5-, and 6-fold coordination in the approximate ratio 4:5:1. The average Al coordination increases from 4.57 to 4.73 as the fraction of octahedral Al increases with alumina content. The diffraction results on the 67% composition are consistent with a disordered Al framework with Al ions in a range of coordination environments that are substantially different from those found in the equilibrium crystalline phases. Analysis of the neutron and X-ray structure factors yields an average bond angle of 125 +/- 4 degrees between an Al ion and the adjoining cation via a bridging oxygen. We propose that the structure of the glass is a "transition state" between the alumina-rich liquid and the equilibrium mullite phase that are dominated by 4- and 6-coordinated aluminum ions, respectively.

Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

Directory of Open Access Journals (Sweden)

Yamuna Kunhi Mouvenchery

Full Text Available It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM molecules via cation bridges (CaB. The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+, Ca(2+ or Na(+, respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>>2 h than deprotonation of functional groups (<2 h and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB and molecular mobility of water (NMR analysis suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is

Characterization of Fe 3 + -doped silver phosphate glasses

Indian Academy of Sciences (India)

The relationship among the composition, structure and selected properties for five series of silver phosphate glasses containing 0, 5, 10, 15 and 20wt% Fe 2 O 3 has been investigated. The synthesized glasses have been characterized using different experimental techniques. X-ray diffraction studies revealed that the ...

Glass consistency and glass performance

International Nuclear Information System (INIS)

Plodinec, M.J.; Ramsey, W.G.

1994-01-01

Glass produced by the Defense Waste Processing Facility (DWPF) will have to consistently be more durable than a benchmark glass (evaluated using a short-term leach test), with high confidence. The DWPF has developed a Glass Product Control Program to comply with this specification. However, it is not clear what relevance product consistency has on long-term glass performance. In this report, the authors show that DWPF glass, produced in compliance with this specification, can be expected to effectively limit the release of soluble radionuclides to natural environments. However, the release of insoluble radionuclides to the environment will be limited by their solubility, and not glass durability

Composition-structure-property relation of oxide glasses

DEFF Research Database (Denmark)

Hermansen, Christian

also increases such properties. Yet, these rules are not strictly followed even for the simplest binary oxide glasses, such as alkali silicates, borates and phosphates. In this thesis it is argued that the missing link between composition and properties is the glass structure. Structural models...... are proposed based on topological selection rules and experimentally verified. The relation between structure and properties is evaluated using topological constraint theory, which in its essence is a theory that quantifies the two intuitions of the glass scientist. The end result is a quantitative model...

Modeling hysteresis observed in the human erythrocyte voltage-dependent cation channel

DEFF Research Database (Denmark)

Flyvbjerg, Henrik; Gudowska-Nowak, Ewa; Christophersen, Palle

2012-01-01

The non-selective voltage-activated cation channel from human red cells, which is activated at depolarizing potentials, has been shown to exhibit counter-clockwise gating hysteresis. Here, we analyze this phenomenon with the simplest possible phenomenological models. Specifically, the hysteresis ...

A comparison of the performance of nuclear waste glasses by modeling

International Nuclear Information System (INIS)

Grambow, B.; Strachan, D.M.

1988-01-01

A model selected for the licensing process must be based on a physical and chemical understanding of the glass corrosion mechanism. The purpose of this paper is to show that a dissolution/precipitation model can be used to better understand the effects of various system variables on glass dissolution. The application and validation of this model are also discussed. A dissolution/precipitation model developed appears applicable to experiments with a wide range of solution compositions as well as to more complex systems, such as the bentonite/glass/water system the steel corrosion product/glass/water system, or the dissolution of natural basalt glass in a geologic environment. This model is based on solution chemistry and transition state theory. The theoretical background of this model is discussed elsewhere and is used to describe the dissolution behavior of three nuclear waste glasses. These glasses were selected because they represent a wide range of behavior and, therefore, could be used to illustrate the capabilities of the dissolution/precipitation model. The effects of parameters, such as temperature and starting solution composition, on the dissolution behavior of glass are also discussed. 27 refs., 10 figs., 1 tab

Characterization of ion distributions near the surface of sodium-containing and sodium-depleted calcium aluminosilicate glass melts

International Nuclear Information System (INIS)

Corrales, Louis R.; Du, Jincheng

2006-01-01

The distribution of cation and anion components of sodium containing calcium aluminosilicate glass was studied by classical molecular dynamics simulations in a high temperature melt in the bulk and at the vacuum-melt interface. A significant redistribution of the sodium and non-bridging oxygen ions was observed. Subsequently, a sodium depleted calcium aluminosilicate glass melt was simulated to determine the sensitivity of the redistribution of ions near the vacuum-melt interface to the presence of sodium ions. It is found that the thermodynamic equilibrium condition near a surface favors the enrichment of non-bridging oxygen ions that is closely associated with enrichment of the sodium ions

Heavy metal oxide glasses as gamma rays shielding material

International Nuclear Information System (INIS)

Kaur, Preet; Singh, Devinder; Singh, Tejbir

2016-01-01

The gamma rays shielding parameters for heavy metal oxide glasses and concrete samples are comparable. However, the transparent nature of glasses provides additional feature to visualize inside the shielding material. Hence, different researchers had contributed in computing/measuring different shielding parameters for different configurations of heavy metal oxide glass systems. In the present work, a detailed study on different heavy metal (_5_6Ba, _6_4Gd, _8_2Pb, _8_3Bi) oxide glasses has been presented on the basis of different gamma rays shielding parameters as reported by different researchers in the recent years. It has been observed that among the selected heavy metal oxide glass systems, Bismuth based glasses provide better gamma rays shielding. Hence, Bismuth based glasses can be better substitute to concrete walls at nuclear reactor sites and nuclear labs.

Heavy metal oxide glasses as gamma rays shielding material

Energy Technology Data Exchange (ETDEWEB)

Kaur, Preet; Singh, Devinder; Singh, Tejbir, E-mail: dr.tejbir@gmail.com

2016-10-15

The gamma rays shielding parameters for heavy metal oxide glasses and concrete samples are comparable. However, the transparent nature of glasses provides additional feature to visualize inside the shielding material. Hence, different researchers had contributed in computing/measuring different shielding parameters for different configurations of heavy metal oxide glass systems. In the present work, a detailed study on different heavy metal ({sub 56}Ba, {sub 64}Gd, {sub 82}Pb, {sub 83}Bi) oxide glasses has been presented on the basis of different gamma rays shielding parameters as reported by different researchers in the recent years. It has been observed that among the selected heavy metal oxide glass systems, Bismuth based glasses provide better gamma rays shielding. Hence, Bismuth based glasses can be better substitute to concrete walls at nuclear reactor sites and nuclear labs.

Fluorescence line-narrowing studies of Nd:glass laser materials

International Nuclear Information System (INIS)

Riseberg, L.A.; Brecher, C.

The increasing importance of Nd glass lasers in laser fusion technology has emphasized the inadequacy in the understanding of the optical properties of rare earth ions in glasses. Indeed, it has been difficult to generate models for the performance of these devices, and the selection of host glasses could be done by little more than a trial-and-error approach. The technique of laser-induced fluorescence line-narrowing developed within the last few years provides a new and powerful tool for the study of these systems. In this technique, a laser excites within the inhomogeneously broadened absorption bands a selected subgroup of the ions in the system, namely those whose absorption energy is resonant with the laser. If the excitation does not migrate among the entire collection of ions prior to fluorescence, the fluorescence that is observed is only from the group that was excited and is narrowed. This permits the selective study of classes of ion sites within the ensemble. The concept is indicated schematically. By the use of a tunable laser, such as a dye laser, it is possible to vary the class of sites, defined by energy, that is excited and thereby study the important spectroscopic properties and their variations, unclouded by the averaging that occurs under excitation of the entire system. Furthermore, it is then possible to use the spectroscopic information to infer a description of the variation of the microscopic environment, and a rationalization of the effects of compositional changes. Use of a pulsed dye laser and time-resolved detection permits the study of the dynamics, including, for example, the energy transfer among ions of different energies within the inhomogeneously-broadened spectrum. The goal of this project has been to apply such studies to glasses of interest to glass laser technology, providing information for device modeling, and establishing design criteria for glass selection

Green sample preparation for liquid chromatography and capillary electrophoresis of anionic and cationic analytes.

Science.gov (United States)

Wuethrich, Alain; Haddad, Paul R; Quirino, Joselito P

2015-04-21

A sample preparation device for the simultaneous enrichment and separation of cationic and anionic analytes was designed and implemented in an eight-channel configuration. The device is based on the use of an electric field to transfer the analytes from a large volume of sample into small volumes of electrolyte that was suspended into two glass micropipettes using a conductive hydrogel. This simple, economical, fast, and green (no organic solvent required) sample preparation scheme was evaluated using cationic and anionic herbicides as test analytes in water. The analytical figures of merit and ecological aspects were evaluated against the state-of-the-art sample preparation, solid-phase extraction. A drastic reduction in both sample preparation time (94% faster) and resources (99% less consumables used) was observed. Finally, the technique in combination with high-performance liquid chromatography and capillary electrophoresis was applied to analysis of quaternary ammonium and phenoxypropionic acid herbicides in fortified river water as well as drinking water (at levels relevant to Australian guidelines). The presented sustainable sample preparation approach could easily be applied to other charged analytes or adopted by other laboratories.

The role of cationic precursors in structural, morphological and optical properties of PbS thin films

International Nuclear Information System (INIS)

Preetha, K C; Murali, K V; Ragina, A J; Deepa, K; Dhanya, A C; Remadevi, T L

2013-01-01

Thin films of Lead sulphide (PbS) were grown on soda lime glass substrate by Successive Ionic Layer Adsorption and Reaction (SILAR) method using lead acetate, lead chloride, lead nitrate, and lead sulphate as cationic precursors and thioacetamide as sulphur source. The experiments were carried out at room temperature under normal pressure utilizing aqueous conditions. The structural and morphological aspects of the as prepared samples were investigated by means of XRD and SEM results. The prepared samples were polycrystalline with nanometer-sized grains and identified as galena type cubic structure (FCC). The values of average crystallite size were found to be in the range 22 to 30 nm. The SEM micrographs show variations in morphology. Optical studies revealed that the absorption edges of the films indicated strong blue shifts with respect to bulk sample. In this work, we establish that the cationic precursor sources and in turn the size of the crystallites affects the structural, morphological and optical properties of PbS thin films.

Electrical properties and structure of glasses in the Ba(PO3)2-MF2 systems, where M = Mg, Ca, Sr, Ba

International Nuclear Information System (INIS)

Sokolov, I.A.; Tarlakov, Yu.P.; Murin, I.V.; Pronkin, A.A.

2000-01-01

Using the methods of conductometry and IR spectroscopy the concentrational dependences of electric conductivity are studied, the nature of current carriers is determined, the concentrational dependence of transfer numbers is ascertained and structural changes in glasses of the system Ba(PO 3 ) 2 -MF 2 (M = Mg, Ca, Sr, Ba), depending on MF 2 content, are considered. It is shown that F - ions take part in electric current transfer. Influence of crystallochemical nature of alkaline-earth cations on physicochemical properties and structure of the glasses studied is analyzed [ru

Cation disorder in Ga1212.

Science.gov (United States)

Greenwood, K B; Ko, D; Vander Griend, D A; Sarjeant, G M; Milgram, J W; Garrity, E S; DeLoach, D I; Poeppelmeier, K R; Salvador, P A; Mason, T O

2000-07-24

Substitution of calcium for strontium in LnSr2-xCaxCu2GaO7 (Ln = La, Pr, Nd, Gd, Ho, Er, Tm, and Yb) materials at ambient pressure and 975 degrees C results in complete substitution of calcium for strontium in the lanthanum and praseodymium systems and partial substitution in the other lanthanide systems. The calcium saturation level depends on the size of the Ln cation, and in all cases, a decrease in the lattice parameters with calcium concentration was observed until a common, lower bound, average A-cation size is reached. Site occupancies from X-ray and neutron diffraction experiments for LnSr2-xCaxCu2GaO7 (x = 0 and x = 2) confirm that the A-cations distribute between the two blocking-layer sites and the active-layer site based on size. A quantitative link between cation distribution and relative site-specific cation enthalpy for calcium, strontium, and lanthanum within the gallate structure is derived. The cation distribution in other similar materials can potentially be modeled.

Electron beam induced cationic polymerization of epoxy resins. Dependence of Tg on conversion

International Nuclear Information System (INIS)

Degrand, H.; Cazaux, F.; Coqueret, X.

2002-01-01

Complete text of publication follows. The high-energy radiation curing of monomer blends polymerizing by a free radical or by a cationic mechanism receives increasing attention in the perspective of high performance composite materials. In the present work, we have focused our attention on epoxy formulations as models of the matrices polymerizing by a cationic mechanism that could be used in fiber-reinforced composites for aerospace applications. We have examined the progress of the electron beam (EB) induced polymerization of diglycidylether of bisphenol A (DGEBA) in the presence of a diaryliodonium salt (DAIS) by FTIR spectroscopy and by dynamic mechanical thermal analysis (DMA). The obtained results allow to draw the gradual increase of the temperature for the network thermomechanical transition (T a , associated with the glass transition temperature T g ) over a broad range of conversion (p) and reveal a peculiar behavior at high conversion. In this domain (p > 0.90), the material's T g is shown to decrease when conversion approaches unity. Moreover, the post-irradiation thermal treatment of the materials, that generally yields effective 'dark curing', appears to induce a decrease of T g , with an amplitude correlated with the amount of DAIS in the formulation. Owing to the particular nature of the propagating centers in cationic polymerisation, the thermal relaxation of ionic clusters trapped in the glassy matrix can be reasonably invoked as a possible cause for this behavior

Cationic niosomes an effective gene carrier composed of novel spermine-derivative cationic lipids: effect of central core structures.

Science.gov (United States)

Opanasopit, Praneet; Leksantikul, Lalita; Niyomtham, Nattisa; Rojanarata, Theerasak; Ngawhirunpat, Tanasait; Yingyongnarongkul, Boon-Ek

2017-05-01

Cationic niosomes formulated from Span 20, cholesterol (Chol) and novel spermine-based cationic lipids of multiple central core structures (di(oxyethyl)amino, di(oxyethyl)amino carboxy, 3-amino-1,2-dioxypropyl and 2-amino-1,3-dioxypropyl) were successfully prepared for improving transfection efficiency in vitro. The niosomes composed of spermine cationic lipid with central core structure of di(oxyethyl)amino revealed the highest gene transfection efficiency. To investigate the factors affecting gene transfection and cell viability including differences in the central core structures of cationic lipids, the composition of vesicles, molar ratio of cationic lipids in formulations and the weight ratio of niosomes to DNA. Cationic niosomes composed of nonionic surfactants (Span20), cholesterol and spermine-based cationic lipids of multiple central core structures were formulated. Gene transfection and cell viability were evaluated on a human cervical carcinoma cell line (HeLa cells) using pDNA encoding green fluorescent protein (pEGFP-C2). The morphology, size and charge were also characterized. High transfection efficiency was obtained from cationic niosomes composed of Span20:Chol:cationic lipid at the molar ratio of 2.5:2.5:0.5 mM. Cationic lipids with di(oxyethyl)amino as a central core structure exhibited highest transfection efficiency. In addition, there was also no serum effect on transfection efficiency. These novel cationic niosomes may constitute a good alternative carrier for gene transfection.

Moessbauer effect and infrared study of some borate glass containing Mn and Fe oxides

International Nuclear Information System (INIS)

Gabr, M.

2005-01-01

Lithium borate glasses containing transition metals appeared now of very high technological and scientific interest. Therefore some lithium borate glasses containing mixed transition metal ions (manganese and iron) were investigated. The glass batches were melted at 1250 degree C for three hours and annealed at 350 degree C -over night- to obtain strain free glasses. Moessbauer Effect spectroscopy and Infrared analysis were employed to investigate the structural changes due to the change of their batches composition. Differential thermal analysis, magnetic susceptibility, density and molar volume measurements were also performed to study the effect of changing both manganese and iron oxides at the expense of boron oxide on these properties. Infrared analysis indicated the presence of different structural groups such as BO 3 , BO 4 , FeO 4 and MnO 6 as well as different vibrations indicated the presence of various bonds in the glass network. The values of the characteristic temperatures (T g , T c and T m ) showed gradual increase except those of the last sample where they showed a decrease. The mid sample showed the lowest stability value. It was found that the molar volume showed its highest value at R=0.33 [where R is the ratio of glass network modifier to the glass network former]. After that it showed gradual linear decrease. The magnetic susceptibility measurements showed approximately stable value between R=0.29 and 0.33, then it increased up to R=0.38, and after that, it decreased up to R= 0.43. The obtained magnetic susceptibility values indicated that all these glasses are paramagnetic. The obtained Moessbauer spectra and the calculated parameters confirmed that iron ions participated in the glass network as network former cations. It confirmed also that all glasses reflect paramagnetic character. The observed structural change were explained and correlated with the change of the measured physical properties

PLUTONIUM SOLUBILITY IN HIGH-LEVEL WASTE ALKALI BOROSILICATE GLASS

Energy Technology Data Exchange (ETDEWEB)

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

Plutonium Solubility In High-Level Waste Alkali Borosilicate Glass

International Nuclear Information System (INIS)

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

2011-01-01

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 ∼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 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 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 incorporation of 1 wt

The current status of glass leaching studies in France

International Nuclear Information System (INIS)

Laude, F.

1983-11-01

Glass has been selected in France as the material used to confine the activity of fission product solutions, and a continuous vitrification process has been developed at the Marcoule Vitrification Facility (AVM), the first industrial plant. Borosilicate glass was chosen in various compositions for its properties: it is a homogeneous, non-porous material that incorporates appreciable quantities of most of the fission product oxides, and is only alterable at the surface interface layer. Glass thus constitutes the primary radioactivity containment barrier, and it is essential to determine its long-term behavior. Water constitutes the principal hazard during temporary or definitive storage of the glass blocks. Two types of inherent material properties are studied from the standpoint of glass stability under leaching conditions: - chemical durability; - radioactive containability with regard to the various radionuclides, fission products and especially the actinides. Durability tests are carried out in SOXHLET devices and the alteration rates are measured by the weight loss. The containability is measured by the leach rate, i.e. by the rate of activity loss into the water. Leaching tests are conducted for several major objectives: - selection of glass compositions (leach rates); - leaching mechanism studies (hydrolyzed layer characteristics, effects of temperature, pressure, pH, etc.); - long-term behavior studies (glass specimens doped with alpha-emitters); - simulation of geological repository environments [fr

Glass Transitions and Low-Frequency Dynamics of Room-Temperature Ionic Liquids

International Nuclear Information System (INIS)

Yamamuro, O.; Inamura, Y.; Hayashi, S.; Hamaguchi, H.

2006-01-01

We have measured the heat capacity and neutrion quasi- and inelastic scattering spectra of some salts of 1-butyl-3-methylimidazolium ion bmim+, which is a typical cation of room-temperature ionic liquids, and its derivatives. The heat capacity measurements revealed that the room-temperature ionic liquids have glass transitions as molecular liquids. The temperature dependence of configurational entropy demonstrated that the room-temperature ionic liquids are 'fragile liquids'. Both heat capacity and inelastic neutron scattering data revealed that the glassy phases exhibit large low-energy excitations usually called 'boson peak'. The quasielastic neutron scattering data showed that so-called 'fast process' appears around Tg as in molecular and polymer glasses. The temperature dependence of the self-diffusion coefficient derived from the neutron scattering data indicated that the orientation of bmim+ ions and/or butyl-groups of bmim+ ions is highly disordered and very flexible in an ionic liquid phase

Cationic polymeric gene delivery of beta-glucuronidase for doxorubicin prodrug therapy

NARCIS (Netherlands)

Fonseca, MJ; Storm, G; Hennink, WE; Gerritsen, WR; Haisma, HJ

1999-01-01

Background An approach to improve current chemotherapy is the selective transduction of tumor cells with suicide genes to sensitize these cells to prodrugs of cytostatic agents; Methods In this study, gene transfer was accomplished with the cationic polymer poly(2-(dimethylamino)ethyl methacrylate)

Protein structure and ionic selectivity in calcium channels: Selectivity filter size, not shape, matters

OpenAIRE

Malasics, Attila; Gillespie, Dirk; Nonner, Wolfgang; Henderson, Douglas; Eisenberg, Bob; Boda, Dezső

2009-01-01

Calcium channels have highly charged selectivity filters (4 COO− groups) that attract cations in to balance this charge and minimize free energy, forcing the cations (Na+ and Ca2+) to compete for space in the filter. A reduced model was developed to better understand the mechanism of ion selectivity in calcium channels. The charge/space competition (CSC) mechanism implies that Ca2+ is more efficient in balancing the charge of the filter because it provides twice the charge as Na+ while occupy...

Nanosecond (ns) laser transfer of silver nanoparticles from silver-exchanged soda-lime glass to transparent soda-lime glass and shock waves formation

International Nuclear Information System (INIS)

Sow, Mohamed Chérif; Blondeau, Jean-Philippe; Sagot, Nadine; Ollier, Nadège; Tite, Teddy

2015-01-01

Highlights: • Silver nanoparticles growth by nanosecond laser irradiation of silver exchanged soda-lime glasses. • Silver nanoparticles transfer. • Nanosecond laser induced shock waves formation on glass. - Abstract: In this contribution, we showed for the first time in our knowledge a single-step process for silver clusters and nanoparticles growth and transfer from silver-exchanged soda-lime glass to un-exchanged soda-lime glass (transparent glass in visible and NIR domain) by nanosecond (ns) laser irradiation. The transferred silver nanoparticles in transparent glass are strongly linked to the glass surface. In addition, we point out the formation of shock waves, with selective silver clustering on the top wave. This technique provides an alternative and simple way to obtain metallic nanoparticles in different media which can be traversed by laser wavelength used. Moreover, this experiment is made at room temperature and air environment. It is worth noting that our technique requires a glass previously doped with the corresponding silver ions

Aluminosilicate melts and glasses at 1 to 3 GPa: Temperature and pressure effects on recovered structural and density changes

Science.gov (United States)

Bista, S; Stebbins, Jonathan; Hankins, William B.; Sisson, Thomas W.

2015-01-01

In the pressure range in the Earth’s mantle where many basaltic magmas are generated (1 to 3 GPa) (Stolper et al. 1981), increases in the coordination numbers of the network-forming cations in aluminosilicate melts have generally been considered to be minor, although effects on silicon and particularly on aluminum coordination in non-bridging oxygen-rich glasses from the higher, 5 to 12 GPa range, are now well known. Most high-precision measurements of network cation coordination in such samples have been made by spectroscopy (notably 27Al and 29Si NMR) on glasses quenched from high-temperature, high-pressure melts synthesized in solid-media apparatuses and decompressed to room temperature and 1 bar pressure. There are several effects that could lead to the underestimation of the extent of actual structural (and density) changes in high-pressure/temperature melts from such data. For non-bridging oxygen-rich sodium and calcium aluminosilicate compositions in the 1 to 3 GPa range, we show here that glasses annealed near to their glass transition temperatures systematically record higher recovered increases in aluminum coordination and in density than samples quenched from high-temperature melts. In the piston-cylinder apparatus used, rates of cooling through the glass transition are measured as very similar for both higher and lower initial temperatures, indicating that fictive temperature effects are not the likely explanation of these differences. Instead, transient decreases in melt pressure during thermal quenching, which may be especially large for high initial run temperatures, of as much as 0.5 to 1 GPa, may be responsible. As a result, the equilibrium proportion of high-coordinated Al in this pressure range may be 50 to 90% greater than previously estimated, reaching mean coordination numbers (e.g., 4.5) that are probably high enough to significantly affect melt properties. New data on jadeite (NaAlSi2O6) glass confirm that aluminum coordination increase

Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses.

Science.gov (United States)

Brehault, Antoine; Patil, Deepak; Kamat, Hrishikesh; Youngman, Randall E; Thirion, Lynn M; Mauro, John C; Corkhill, Claire L; McCloy, John S; Goel, Ashutosh

2018-02-08

Molybdenum oxides are an integral component of the high-level waste streams being generated from the nuclear reactors in several countries. Although borosilicate glass has been chosen as the baseline waste form by most of the countries to immobilize these waste streams, molybdate oxyanions (MoO 4 2- ) exhibit very low solubility (∼1 mol %) in these glass matrices. In the past three to four decades, several studies describing the compositional and structural dependence of molybdate anions in borosilicate and aluminoborosilicate glasses have been reported in the literature, providing a basis for our understanding of fundamental science that governs the solubility and retention of these species in the nuclear waste glasses. However, there are still several open questions that need to be answered to gain an in-depth understanding of the mechanisms that control the solubility and retention of these oxyanions in glassy waste forms. This article is focused on finding answers to two such questions: (1) What are the solubility and retention limits of MoO 3 in aluminoborosilicate glasses as a function of chemical composition? (2) Why is there a considerable increase in the solubility of MoO 3 with incorporation of rare-earth oxides (for example, Nd 2 O 3 ) in aluminoborosilicate glasses? Accordingly, three different series of aluminoborosilicate glasses (compositional complexity being added in a tiered approach) with varying MoO 3 concentrations have been synthesized and characterized for their ability to accommodate molybdate ions in their structure (solubility) and as a glass-ceramic (retention). The contradictory viewpoints (between different research groups) pertaining to the impact of rare-earth cations on the structure of aluminoborosilicate glasses are discussed, and their implications on the solubility of MoO 3 in these glasses are evaluated. A novel hypothesis explaining the mechanism governing the solubility of MoO 3 in rare-earth containing aluminoborosilicate

Glass packages in interim storage

International Nuclear Information System (INIS)

Jacquet-Francillon, N.

1994-10-01

This report summarize the current state of knowledge concerning the behavior of type C waste packages consisting of vitrified high-level solutions produced by reprocessing spent fuel. The composition and the physical and chemical properties of the feed solutions are reviewed, and the vitrification process is described. Sodium alumino-borosilicate glass compositions are generally employed - the glass used at la Hague for LWR fuel solutions, for example, contains 45 % SiO 2 . The major physical, chemical, mechanical and thermal properties of the glass are reviewed. In order to allow their thermal power to diminish, the 3630 glass packages produced (as of January 1993) in the vitrification facilities at Marcoule and La Hague are placed in interim storage for several decades. The actual interim storage period has not been defined, as it is closely related to the concept and organization selected for the final destination of the packages: a geological repository. The glass behavior under irradiation is described. Considerable basic and applied research has been conducted to assess the aqueous leaching behavior of nuclear containment glass. The effects of various repository parameters (temperature, flow rate, nature of the environmental materials) have been investigated. The experimental findings have been used to specify a model describing the kinetics of aqueous corrosion of the glass. More generally all the ''source term'' models developed in France by the CEA or by ANDRA are summarized. (author). 152 refs., 33 figs

Synthesis of glass-ceramics using glass cullet and vitrified industrial by-products

Energy Technology Data Exchange (ETDEWEB)

Karamberi, A.; Orkopoulos, K.; Moutsatsou, A. [National Technical University of Athens, Athens (Greece)

2007-07-01

This study concerns the recycling of inorganic waste materials for the production of glass-ceramics and the evaluation of the developed physical properties. Four industrial by-products were selected due to their mass production: (I) two high calcium lignite fly ashes, (ii) slag derived from the production of Fe-Ni and, (iii) steel slag. In order to examine the role of the SiO{sub 2} in the crystallization process, glass cullet and Egyptian sand were added. Thermal treatment, at 1450{sup o}C, enables the production of glasses using mixtures of these materials at appropriate proportions. The crystallization was achieved by heating at 900, 950 and 1000{sup o}C. The produced materials were examined concerning their structure by X-ray diffraction and scanning electron microscopy (SEM-EDS). The results showed that the crystalline phase is greatly depending on the structure of the raw material and the thermal process, influencing accordingly the hardness of the final products.

Mechanical, degradation and cytocompatibility properties of magnesium coated phosphate glass fibre reinforced polycaprolactone composites.

Science.gov (United States)

Liu, Xiaoling; Hasan, Muhammad S; Grant, David M; Harper, Lee T; Parsons, Andrew J; Palmer, Graham; Rudd, Chris D; Ahmed, Ifty

2014-11-01

Retention of mechanical properties of phosphate glass fibre reinforced degradable polyesters such as polycaprolactone and polylactic acid in aqueous media has been shown to be strongly influenced by the integrity of the fibre/polymer interface. A previous study utilising 'single fibre' fragmentation tests found that coating with magnesium improved the fibre and matrix interfacial shear strength. Therefore, the aim of this study was to investigate the effects of a magnesium coating on the manufacture and characterisation of a random chopped fibre reinforced polycaprolactone composite. Short chopped strand non-woven phosphate glass fibre mats were sputter coated with degradable magnesium to manufacture phosphate glass fibre/polycaprolactone composites. The degradation behaviour (water uptake, mass loss and pH change of the media) of these polycaprolactone composites as well as of pure polycaprolactone was investigated in phosphate buffered saline. The Mg coated fibre reinforced composites revealed less water uptake and mass loss during degradation compared to the non-coated composites. The cations released were also explored and a lower ion release profile for all three cations investigated (namely Na(+), Mg(2+) and Ca(2+)) was seen for the Mg coated composite samples. An increase of 17% in tensile strength and 47% in tensile modulus was obtained for the Mg coated composite samples. Both flexural and tensile properties were investigated and a higher retention of mechanical properties was obtained for the Mg coated fibre reinforced composite samples up to 10 days immersion in PBS. Cytocompatibility study showed both composite samples (coated and non-coated) had good cytocompatibility with human osteosarcoma cell line. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Magnetic and bioactivity evaluation of ferrimagnetic ZnFe 2O 4 containing glass ceramics for the hyperthermia treatment of cancer

Science.gov (United States)

Shah, Saqlain A.; Hashmi, M. U.; Alam, S.; Shamim, A.

2010-02-01

Glass ceramics of the composition xZnO·25Fe 2O 3·(40- x)SiO 2·25CaO·7P 2O 5·3Na 2O were prepared by the melt-quench method using oxy-acetylene flame. Glass-powder compacts were sintered at 1100 °C for 3 h and then rapidly cooled at -10 °C. X-ray diffraction (XRD) revealed 3 prominent crystalline phases: ZnFe 2O 4, CaSiO 3 and Ca 10(PO 4) 6(OH) 2. Vibrating sample magnetometer (VSM) data at 10 KOe and 500 Oe showed that saturation magnetization, coercivity and hence hysteresis area increased with the increase in ZnO content. Nano-sized ZnFe 2O 4 crystallites were of pseudo-single domain structure and thus coercivity increased with the increase in crystallite size. ZnFe 2O 4 exhibited ferrimagnetism due to the random distribution of Zn 2+ and Fe 3+ cations at tetrahedral A sites and octahedral B sites. This inversion/random distribution of cations was probably due to the surface effects of nano-ZnFe 2O 4 and rapid cooling of the material from 1100 °C (thus preserving the high temperature state of the random distribution of cations). Calorimetric measurements were carried out using magnetic induction furnace at 500 Oe magnetic field and 400 KHz frequency. The data showed that maximum specific power loss and temperature increase after 2 min were 26 W/g and 37 °C, respectively for the sample containing 10% ZnO. The samples were immersed in simulated body fluid (SBF) for 3 weeks. Scanning electron microscope (SEM), energy dispersive spectroscopy (EDX) and XRD results confirmed the growth of precipitated hydroxyapatite phase after immersion in SBF, suggesting that the ferrimagnetic glass ceramics were bioactive and could bond to the living tissues in physiological environment.

Magnetic and bioactivity evaluation of ferrimagnetic ZnFe2O4 containing glass ceramics for the hyperthermia treatment of cancer

International Nuclear Information System (INIS)

Shah, Saqlain A.; Hashmi, M.U.; Alam, S.; Shamim, A.

2010-01-01

Glass ceramics of the composition xZnO.25Fe 2 O 3 .(40-x)SiO 2 .25CaO.7P 2 O 5 .3Na 2 O were prepared by the melt-quench method using oxy-acetylene flame. Glass-powder compacts were sintered at 1100 deg. C for 3 h and then rapidly cooled at -10 deg. C. X-ray diffraction (XRD) revealed 3 prominent crystalline phases: ZnFe 2 O 4 , CaSiO 3 and Ca 10 (PO 4 ) 6 (OH) 2 . Vibrating sample magnetometer (VSM) data at 10 KOe and 500 Oe showed that saturation magnetization, coercivity and hence hysteresis area increased with the increase in ZnO content. Nano-sized ZnFe 2 O 4 crystallites were of pseudo-single domain structure and thus coercivity increased with the increase in crystallite size. ZnFe 2 O 4 exhibited ferrimagnetism due to the random distribution of Zn 2+ and Fe 3+ cations at tetrahedral A sites and octahedral B sites. This inversion/random distribution of cations was probably due to the surface effects of nano-ZnFe 2 O 4 and rapid cooling of the material from 1100 deg. C (thus preserving the high temperature state of the random distribution of cations). Calorimetric measurements were carried out using magnetic induction furnace at 500 Oe magnetic field and 400 KHz frequency. The data showed that maximum specific power loss and temperature increase after 2 min were 26 W/g and 37 deg. C, respectively for the sample containing 10% ZnO. The samples were immersed in simulated body fluid (SBF) for 3 weeks. Scanning electron microscope (SEM), energy dispersive spectroscopy (EDX) and XRD results confirmed the growth of precipitated hydroxyapatite phase after immersion in SBF, suggesting that the ferrimagnetic glass ceramics were bioactive and could bond to the living tissues in physiological environment.

Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

International Nuclear Information System (INIS)

Barnabas, M.V.; Trifunac, A.D.

1994-01-01

Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

Infrared spectroscopic and theoretical study of the HC2n+1O+ (n = 2-5) cations

Science.gov (United States)

Jin, Jiaye; Li, Wei; Liu, Yuhong; Wang, Guanjun; Zhou, Mingfei

2017-06-01

The carbon chain cations, HC2n+1O+ (n = 2-5), are produced via pulsed laser vaporization of a graphite target in supersonic expansions containing carbon monoxide and hydrogen. The infrared spectra are measured via mass-selected infrared photodissociation spectroscopy of the CO "tagged" [HC2n+1O.CO]+ cation complexes in the 1600-3500 cm-1 region. The geometries and electronic ground states of these cation complexes are determined by their infrared spectra compared to the predications of theoretical calculations. All of the HC2n+1O+ (n = 2-5) core cations are characterized to be linear carbon chain derivatives terminated by hydrogen and oxygen, which have the closed-shell singlet ground states with polyyne-like carbon chain structures.

Alkali-free bioactive glasses for bone regeneration =

Science.gov (United States)

Kapoor, Saurabh

Bioactive glasses and glass-ceramics are a class of third generation biomaterials which elicit a special response on their surface when in contact with biological fluids, leading to strong bonding to living tissues. The purpose of the present study was to develop diopside based alkali-free bioactive glasses in order to achieve good sintering behaviour, high bioactivity, and a dissolution/ degradation rates compatible with the target applications in bone regeneration and tissue engineering. Another aim was to understand the structure-property relationships in the investigated bioactive glasses. In this quest, various glass compositions within the Diopside (CaMgSi2O6) - Fluorapatite (Ca5(PO4)3F) - Tricalcium phosphate (3CaO•P2O5) system have been investigated. All the glasses were prepared by melt-quenching technique and characterized by a wide array of complementary characterization techniques. The glass-ceramics were produced by sintering of glass powders compacts followed by a suitable heat treatment to promote the nucleation and crystallization phenomena. Furthermore, selected parent glass compositions were doped with several functional ions and an attempt to understand their effects on the glass structure, sintering ability and on the in vitro bio-degradation and biomineralization behaviours of the glasses was made. The effects of the same variables on the devitrification (nucleation and crystallization) behaviour of glasses to form bioactive glass-ceramics were also investigated. Some of the glasses exhibited high bio-mineralization rates, expressed by the formation of a surface hydroxyapatite layer within 1-12 h of immersion in a simulated body fluid (SBF) solution. All the glasses showed relatively lower degradation rates in comparison to that of 45S5 Bioglass. Some of the glasses showed very good in vitro behaviour and the glasses co-doped with zinc and strontium showed an in vitro dose dependent behaviour. The as-designed bioactive glasses and glass

Sinter recrystalization and properties evaluation of glass-ceramic from waste glass bottle and magnesite for extended application

Directory of Open Access Journals (Sweden)

As'mau Ibrahim Gebi

2016-12-01

Full Text Available In a bid to address environmental challenges associated with the management of waste Coca cola glass bottle, this study set out to develop glass ceramic materials using waste coca cola glass bottles and magnesite from Sakatsimta in Adamawa state. A reagent grade chrome (coloring agent were used to modify the composition of the coca cola glass bottle;  X-ray fluorescence(XRF, X-ray diffraction (XRD and Thermo gravimetric analysis (TGA were used to characterize raw materials, four batches GC-1= Coca cola glass frit +1%Cr2O3, GC-2=97% Coca cola glass frit+ 2% magnesite+1%Cr2O3, GC-3=95% Coca cola glass frit+ 4%magnesite+1%Cr2O3, GC-4=93%Coca cola glass frit+ 6%magnesite+ 1%Cr2O3 were formulated and prepared. Thermal Gradient Analysis (TGA results were used as a guide in selection of three temperatures (7000C, 7500C and 8000C used for the study, three particle sizes -106+75, -75+53, -53µm and 2 hr sintering time were also used, the sinter crystallization route of glass ceramic production was adopted. The samples were characterized by X-ray diffraction (XRD and Scanning Electron Microscope (SEM, the density, porosity, hardness and flexural strength of the resulting glass ceramics were also measured. The resulting glass ceramic materials composed mainly of wollastonite, diopside and anorthite phases depending on composition as indicated by XRD and SEM, the density of the samples increased with increasing sintering temperature and decreasing particle size. The porosity is minimal and it decreases with increasing sintering temperature and decreasing particle size. The obtained glass ceramic materials possess appreciable hardness and flexural strength with GC-3 and GC-4 having the best combination of both properties.

Neutral glycoconjugated amide-based calix[4]arenes: complexation of alkali metal cations in water.

Science.gov (United States)

Cindro, Nikola; Požar, Josip; Barišić, Dajana; Bregović, Nikola; Pičuljan, Katarina; Tomaš, Renato; Frkanec, Leo; Tomišić, Vladislav

2018-02-07

Cation complexation in water presents a unique challenge in calixarene chemistry, mostly due to the fact that a vast majority of calixarene-based cation receptors is not soluble in water or their solubility has been achieved by introducing functionalities capable of (de)protonation. Such an approach inevitably involves the presence of counterions which compete with target cations for the calixarene binding site, and also rather often requires the use of ion-containing buffer solutions in order to control the pH. Herein we devised a new strategy towards the solution of this problem, based on introducing carbohydrate units at the lower or upper rim of calix[4]arenes which comprise efficient cation binding sites. In this context, we prepared neutral, water-soluble receptors with secondary or tertiary amide coordinating groups, and studied their complexation with alkali metal cations in aqueous and methanol (for the comparison purpose) solutions. Complexation thermodynamics was quantitatively characterized by UV spectrometry and isothermal titration calorimetry, revealing that one of the prepared tertiary amide derivatives is capable of remarkably efficient (log K ≈ 5) and selective binding of sodium cations among alkali metal cations in water. Given the ease of the synthetic procedure used, and thus the variety of accessible analogues, this study can serve as a platform for the development of reagents for diverse purposes in aqueous media.

Synthesis, activity, and structure--activity relationship studies of novel cationic lipids for DNA transfer.

Science.gov (United States)

Byk, G; Dubertret, C; Escriou, V; Frederic, M; Jaslin, G; Rangara, R; Pitard, B; Crouzet, J; Wils, P; Schwartz, B; Scherman, D

1998-01-15

We have designed and synthesized original cationic lipids for gene delivery. A synthetic method on solid support allowed easy access to unsymmetrically monofunctionalized polyamine building blocks of variable geometries. These polyamine building blocks were introduced into cationic lipids. To optimize the transfection efficiency in the novel series, we have carried out structure-activity relationship studies by introduction of variable-length lipids, of variable-length linkers between lipid and cationic moiety, and of substituted linkers. We introduce the concept of using the linkers within cationic lipids molecules as carriers of side groups harboring various functionalities (side chain entity), as assessed by the introduction of a library composed of cationic entities, additional lipid chains, targeting groups, and finally the molecular probes rhodamine and biotin for cellular traffic studies. The transfection activity of the products was assayed in vitro on Hela carcinoma, on NIH3T3, and on CV1 fibroblasts and in vivo on the Lewis Lung carcinoma model. Products from the series displayed high transfection activities. Results indicated that the introduction of a targeting side chain moiety into the cationic lipid is permitted. A primary physicochemical characterization of the DNA/lipid complexes was demonstrated with this leading compound. Selected products from the series are currently being developed for preclinical studies, and the labeled lipopolyamines can be used to study the intracellular traffic of DNA/cationic lipid complexes.

Role of oxygen on the optical properties of borate glass doped with ZnO

International Nuclear Information System (INIS)

Abdel-Baki, Manal; El-Diasty, Fouad

2011-01-01

Lithium tungsten borate glass (0.56-x)B 2 O 3 -0.4Li 2 O-xZnO-0.04WO 3 (0≤x≤0.1 mol%) is prepared by the melt quenching technique for photonic applications. Small relative values of ZnO are used to improve the glass optical dispersion and to probe as well the role of oxygen electronic polarizability on its optical characteristics. The spectroscopic properties of the glass are determined in a wide spectrum range (200-2500 nm) using a Fresnel-based spectrophotometric technique. Based on the Lorentz-Lorenz theory, as ZnO content increases on the expense of B 2 O 3 the glass molar polarizability increased due to an enhanced unshared oxide ion 2p electron density, which increases ionicity of the chemical bonds of glass. The role of oxide ion polarizability is explained in accordance with advanced measures and theories such as optical basicity, O 1s binding energy, the outer most cation binding energy in Yamashita-Kurosawa's interionic interaction parameter and Sun's average single bond strength. FT-IR measurements confirm an increase in bridging oxygen bonds, as a result of replacement of ZnO by B 2 O 3 , which increase the UV glass transmission window and transmittance. - Graphical abstract: O1s, Yamashita-Kurosawa's parameter and average single bond strength of charge overlapping between electronic shells are used to explain enhanced oxide ion 2p electron density, which increases refractive index of glasses. Highlights: → New borate glass for photonic application is prepared. → The dispersion property of the glass is effectively controlled using small amounts of ZnO. → ZnO is used to probe the glass structure and investigate the role of oxygen on the obtained optical properties of the glasses. → Modern theories are used to explain enhanced unshared oxide ion 2p electron density, which increases ionicity of chemical bonds of the glass.

DWPF GLASS BEADS AND GLASS FRIT TRANSPORT DEMONSTRATION

Energy Technology Data Exchange (ETDEWEB)

Adamson, D; Bradley Pickenheim, B

2008-11-24

DWPF is considering replacing irregularly shaped glass frit with spherical glass beads in the Slurry Mix Evaporator (SME) process to decrease the yield stress of the melter feed (a non-Newtonian Bingham Plastic). Pilot-scale testing was conducted on spherical glass beads and glass frit to determine how well the glass beads would transfer when compared to the glass frit. Process Engineering Development designed and constructed the test apparatus to aid in the understanding and impacts that spherical glass beads may have on the existing DWPF Frit Transfer System. Testing was conducted to determine if the lines would plug with the glass beads and the glass frit slurry and what is required to unplug the lines. The flow loop consisted of vertical and horizontal runs of clear PVC piping, similar in geometry to the existing system. Two different batches of glass slurry were tested: a batch of 50 wt% spherical glass beads and a batch of 50 wt% glass frit in process water. No chemicals such as formic acid was used in slurry, only water and glass formers. The glass beads used for this testing were commercially available borosilicate glass of mesh size -100+200. The glass frit was Frit 418 obtained from DWPF and is nominally -45+200 mesh. The spherical glass beads did not have a negative impact on the frit transfer system. The transferring of the spherical glass beads was much easier than the glass frit. It was difficult to create a plug with glass bead slurry in the pilot transfer system. When a small plug occurred from setting overnight with the spherical glass beads, the plug was easy to displace using only the pump. In the case of creating a man made plug in a vertical line, by filling the line with spherical glass beads and allowing the slurry to settle for days, the plug was easy to remove by using flush water. The glass frit proved to be much more difficult to transfer when compared to the spherical glass beads. The glass frit impacted the transfer system to the point

DWPF GLASS BEADS AND GLASS FRIT TRANSPORT DEMONSTRATION

International Nuclear Information System (INIS)

Adamson, D.; Pickenheim, Bradley

2008-01-01

DWPF is considering replacing irregularly shaped glass frit with spherical glass beads in the Slurry Mix Evaporator (SME) process to decrease the yield stress of the melter feed (a non-Newtonian Bingham Plastic). Pilot-scale testing was conducted on spherical glass beads and glass frit to determine how well the glass beads would transfer when compared to the glass frit. Process Engineering Development designed and constructed the test apparatus to aid in the understanding and impacts that spherical glass beads may have on the existing DWPF Frit Transfer System. Testing was conducted to determine if the lines would plug with the glass beads and the glass frit slurry and what is required to unplug the lines. The flow loop consisted of vertical and horizontal runs of clear PVC piping, similar in geometry to the existing system. Two different batches of glass slurry were tested: a batch of 50 wt% spherical glass beads and a batch of 50 wt% glass frit in process water. No chemicals such as formic acid was used in slurry, only water and glass formers. The glass beads used for this testing were commercially available borosilicate glass of mesh size -100+200. The glass frit was Frit 418 obtained from DWPF and is nominally -45+200 mesh. The spherical glass beads did not have a negative impact on the frit transfer system. The transferring of the spherical glass beads was much easier than the glass frit. It was difficult to create a plug with glass bead slurry in the pilot transfer system. When a small plug occurred from setting overnight with the spherical glass beads, the plug was easy to displace using only the pump. In the case of creating a man made plug in a vertical line, by filling the line with spherical glass beads and allowing the slurry to settle for days, the plug was easy to remove by using flush water. The glass frit proved to be much more difficult to transfer when compared to the spherical glass beads. The glass frit impacted the transfer system to the point

Viscosity calculations of simulated ion-exchange resin waste glasses

International Nuclear Information System (INIS)

Kim, Cheon Woo; Park, Jong Kil; Lee, Kyung Ho; Lee, Myung Chan; Song, Myung Jae; BRUNELOT, Pierre

2000-01-01

An induction cold crucible melter (CCM) located in the NETEC-KEPCO has been used to vitrify simulated ion-exchange resin. During vitrification, the CCM operations were tightly constrained by glass viscosity as an important process parameter. Understanding the role of viscosity and quantifying viscosity is highly required in the determination of optimized feed formulations and in the selection of the processing temperature. Therefore, existing process models of glass viscosity based on a relationship between the glass composition, its structure polymerization, and the temperature were searched and adapted to our borosilicate glass systems. Calculated data using a viscosity model based on calculation of non-bridging oxygen (NBO) were in good agreement with the measured viscosity data of benchmark glasses

Study on the adsorption of 233Pa in glass

International Nuclear Information System (INIS)

Natsumi, R.R.; Saiki, M.; Lima, F.W. de.

1982-08-01

It is intended to examine the adsorption of protactinium on glass in relation to pH, presence of complexing agents concentration and type of electrolytes. The study was made by using carrier-free 233 Pa solution and Pyrex glass tube was selected as adsorbent glass material surface. The adsorption curve of protactinium on glass surface as a function of the pH of the tracer solution showed the existence of two pronounced adsorption regions. It was found that this adsorption can be reduced by using electrolytes or complexing agents. Desorption of protactinium previously adsorbed on the Pyrex glass tube was also studied. Hidrochloric, oxalic and hydrofluoric acid solutions were used for the desorption experiments. (Author) [pt

Effect of different glasses in glass bonded zeolite

International Nuclear Information System (INIS)

Lewis, M.A.; Ackerman, J.P.; Verma, S.

1995-01-01

A mineral waste form has been developed for chloride waste salt generated during the pyrochemical treatment of spent nuclear fuel. The waste form consists of salt-occluded zeolite powders bound within a glass matrix. The zeolite contains the salt and immobilizes the fission products. The zeolite powders are hot pressed to form a mechanically stable, durable glass bonded zeolite. Further development of glass bonded zeolite as a waste form requires an understanding of the interaction between the glass and the zeolite. Properties of the glass that enhance binding and durability of the glass bonded zeolite need to be identified. Three types of glass, boroaluminosilicate, soda-lime silicate, and high silica glasses, have a range of properties and are now being investigated. Each glass was hot pressed by itself and with an equal amount of zeolite. MCC-1 leach tests were run on both. Soda-lime silicate and high silica glasses did not give a durable glass bonded zeolite. Boroaluminosilicate glasses rich in alkaline earths did bind the zeolite and gave a durable glass bonded zeolite. Scanning electron micrographs suggest that the boroaluminosilicate glasses wetted the zeolite powders better than the other glasses. Development of the glass bonded zeolite as a waste form for chloride waste salt is continuing

Preparation and characterization of electrically conducting polypyrrole Sn(IV phosphate cation-exchanger and its application as Mn(II ion selective membrane electrode

Directory of Open Access Journals (Sweden)

A.A. Khan

2011-10-01

Full Text Available Polypyrrole Sn(IV phosphate, an organic–inorganic composite cation-exchanger was synthesized via sol-gel mixing of an organic polymer, polypyrrole, into the matrices of the inorganic precipitate of Sn(IV phosphate. The physico-chemical properties of the material were determined using Atomic Absorption Spectrometry (AAS, CHN elemental analysis (inductively coupled plasma mass spectrometry, ICP-MS, UV–VIS spectrophotometry, FTIR (Fourier Transform Infra-Red, SEM (Scanning Electron Microscopy, TGA–DTA (Thermogravimetric Analysis–Differential Thermal Analysis, and XRD (X-ray diffraction. Ion-exchange behavior was observed to characterize the material. On the basis of distribution studies, the material was found to be highly selective for toxic heavy metal ion Mn2+. Due to its selective nature, the material was used as an electroactive component for the construction of an ion-selective membrane electrode. The proposed electrode shows fairly good discrimination of mercury ion over several other inorganic ions. The analytical utility of this electrode was established by employing it as an indicator electrode in electrometric titrations for Mn(II in water.

Molecular glasses for nuclear waste encapsulation

International Nuclear Information System (INIS)

Ropp, R.C.

1982-01-01

The use of a molecular glass based upon a polymerized phosphate of aluminum (PAP), indium or gallium overcomes all of the prior objections to use of glass as a high-level nuclear waste (HLW) encapsulation agent. This HLW glass product could not be made to devitrify, dissolved all of the oxides found in calcine, including the difficultly soluble ones, did not form microcrystallites in the melt or subsequent glass-casting, and possessed a hydrolytic etching rate to boiling water even lower than that of HLW-ZBS glass. A precursor compound, M(H 2 PO 4 ) 3 , is prepared, where M is a trivalent metal selected from the group consisting of aluminum, indium and gallium. The impurity level is carefully controlled so as not to exceed 300 ppm total. The precursor crystals may be washed to remove excess phosphoric acid as desired. HLW is added to the crystals and the mixture is then heated at a controlled heating rate to induce solid state polymerization and to form a melt at 1350 degrees C in which the HLW oxides dissolve rapidly

Converting Hg-1212 to Tl-2212 via Tl-Hg cation exchange in combination with Tl cation intercalation

International Nuclear Information System (INIS)

Zhao Hua; Wu, Judy Z

2007-01-01

In a cation exchange process developed recently for epitaxy of HgBa 2 CaCu 2 O 6 (Hg-1212) thin films, TlBa 2 CaCu 2 O 7 (Tl-1212) or Tl 2 Ba 2 CaCu 2 O 9 (Tl-2212) precursor films were employed as the precursor matrices and Hg-1212 was obtained by replacing Tl cations on the precursor lattice with Hg cations. The reversibility of the cation exchange dictates directly the underlying mechanism. Following our recent success in demonstrating a complete reversibility within '1212' structure, we show the conversion from Hg-1212 to Tl-2212 can be achieved via two steps: conversion from Hg-1212 to Tl-1212 followed by Tl intercalation to form double Tl-O plans in each unit cell. The demonstrated reversibility of the cation exchange process has confirmed the process is a thermal perturbation of weakly bonded cations on the lattice and the direction of the process is determined by the population ratio between the replacing cations and that to be replaced

Comparison of glass surfaces as a countertop material to existing surfaces

Energy Technology Data Exchange (ETDEWEB)

Turo, Laura A.; Winschell, Abigail E.

2011-09-01

Gleen Glass, a small production glass company that creates countertops, was selected for the Technology Assistance Program through Pacific Northwest National Laboratory. Gleen Glass was seeking material property analysis comparing glass as a countertop material to current surfaces (i.e. marble, granite and engineered stone). With samples provided from Gleen Glass, testing was done on granite, marble, and 3 different glass surfaces ('Journey,' 'Pebble,' and 'Gleen'). Results showed the glass surfaces have a lower density, lower water absorption, and are stronger in compressive and flexural tests as compared to granite and marble. Thermal shock tests showed the glass failed when objects with a high thermal mass are placed directly on them, whereas marble and granite did not fracture under these conditions.

New double-cation borohydrides

Energy Technology Data Exchange (ETDEWEB)

Lindemann, Inge; Domenech Ferrer, Roger; Schultz, Ludwig; Gutfleisch, Oliver [IFW Dresden, Institute for Metallic Materials, P.O. Box 270016, 01171 Dresden (Germany); Filinchuk, Yaroslav [Swiss-Norwegian Beam Lines at ESRF, BP-220, 38043 Grenoble (France); Hagemann, Hans; Cerny, Radovan [Department of Physical Chemistry and Crystallography, University of Geneva, 1211 Geneva (Switzerland)

2011-07-01

Complex hydrides are under consideration for on-board hydrogen storage due to their high hydrogen density. However, up to now conventional borohydrides are either too stable or unstable for applications as in PEM fuel cells (60-120 C). Recently, double-cation borohydride systems have attracted great interest. The desorption temperature of the borohydrides decreases with increasing electronegativity of the cation. Consequently, it is possible to tailor a feasible on-board hydrogen storage material by the combination of appropriate cations. The stability was found to be intermediate between the single-cation borohydride systems. Two combinations were sucessfully synthesised by metathesis reaction via high energy ball milling. Al-Li-borohydride shows desorption at about 70 C combined with a very high hydrogen density (17.2 wt.%) and the Na-Al-borohydride (14.2 wt.%) decomposes around 90 C. Both desorption temperatures are in the target range for applications. The decomposition pathways were observed by in-situ-Raman spectroscopy, DSC (Differential Scanning Calorimetry), TG (Thermogravimetry) and thermal desorption measurements.

Stereodynamic insight into the thermal history effects on poly(vinyl chloride) calorimetric sub-glass and glass transitions as a fragile glass model.

Science.gov (United States)

Pin, Jean-Mathieu; Behazin, Ehsan; Misra, Manjusri; Mohanty, Amar

2018-05-02

The dynamic thermal history impact of poly(vinyl chloride) (PVC) has been explored for a wide range of pre-cooling rates, from 1 to 30 °C min-1. A first macroscopic insight into the dynamic thermal history influence has been highlighted through a decrease in the apparent activation energy (Eapp) in the first stage of the glass transition. The overall glass transition Eapp surface was successfully modeled in a polynomial fashion regarding the pre-cooling range. Raman scattering was used to associate the Eapp variations along the glass transition conversion with the stereochemistry evolution during the polymeric relaxation. Herein, the selection of atactic PVC as the polymer model permits us to monitor the glassy polymer segment stereodynamics during the heating ramp through the C-Cl stretching. The intermolecular H-Cl dipole interactions, as well as intramolecular conformational reorganizations among syndiotactic, isotactic and heterotactic polymer sequences, have been associated with non-cooperative and cooperative motions, i.e. the β- and α-process, respectively. The fruitful comparison of the two extreme values of the pre-cooling rates permits us to propose a thermokinetic scenario that explains the occurrence, intensity, and inter-dependence of β- and α-processes in the glassy state and during the glass transition. This scenario could potentially be generalized to all the other polymeric glass-formers.

Decontamination processes for waste glass canisters

International Nuclear Information System (INIS)

Rankin, W.N.

1982-01-01

A Defense Waste Processing Facility (DWPF) is currently being designed to convert Savannah River Plant liquid, high-level radioactive waste into a solid form, such as borosilicate glass. To prevent the spread of radioactivity, the outside of the canisters of waste glass must have very low levels of smearable radioactive contamination before they are removed from the DWPF. Several techniques were considered for canister decontamination: high-pressure water spray, electropolishing, chemical dissolution, and abrasive blasting. An abrasive blasting technique using a glass frit slurry has been selected for use in the DWPF. No additional equipment is needed to process waste generated from decontamination. Frit used as the abrasive will be mixed with the waste and fed to the glass melter. In contrast, chemical and electrochemical techniques require more space in the DWPF, and produce large amounts of contaminated by-products, which are difficult to immobilize by vitrification

Preparation and studies on surface modifications of calcium-silico-phosphate ferrimagnetic glass-ceramics in simulated body fluid

International Nuclear Information System (INIS)

Sharma, K.; Dixit, A.; Singh, Sher; Jagannath,; Bhattacharya, S.; Prajapat, C.L.; Sharma, P.K.; Yusuf, S.M.; Tyagi, A.K.; Kothiyal, G.P.

2009-01-01

The structure and magnetic behaviour of 34SiO 2 -(45 - x) CaO-16P 2 O 5 -4.5 MgO-0.5 CaF 2 - x Fe 2 O 3 (where x = 5, 10, 15, 20 wt.%) glasses have been investigated. Ferrimagnetic glass-ceramics are prepared by melt quench followed by controlled crystallization. The surface modification and dissolution behaviour of these glass-ceramics in simulated body fluid (SBF) have also been studied. Phase formation and magnetic behaviour have been studied using XRD and SQUID magnetometer. The room temperature Moessbauer study has been done to monitor the local environment around Fe cations and valence state of Fe ions. X-ray photoelectron spectroscopy (XPS) was used to study the surface modification in glass-ceramics when immersed in simulated body fluid. Formation of bioactive layer in SBF has been ascertained using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The SBF solutions were analyzed using an absorption spectrophotometer. The magnetic measurements indicated that all these glasses possess paramagnetic character and the [Fe 2+ /Fe 3+ ] ions ratio depends on the composition of glass and varied with Fe 2 O 3 concentration in glass matrix. In glass-ceramics saturation magnetization increases with increase in amount of Fe 2 O 3 . The nanostructure of hematite and magnetite is formed in the glass-ceramics with 15 and 20 wt.% Fe 2 O 3 , which is responsible for the magnetic property of these glass-ceramics. Introduction of Fe 2 O 3 induces several modifications at the glass-ceramics surface when immersed in SBF solution and thereby affecting the surface dissolution and the formation of the bioactive layer.

Devitrification kinetics and phase selection mechanisms in Cu-Zr metallic glasses

Energy Technology Data Exchange (ETDEWEB)

Kalay, Ilkay [Iowa State Univ., Ames, IA (United States)

2010-01-01

Metallic glasses have been a promising class of materials since their discovery in the 1960s. Indeed, remarkable chemical, mechanical and physical properties have attracted considerable attention, and several excellent reviews are available. Moreover, the special group of glass forming alloys known as the bulk metallic glasses (BMG) become amorphous solids even at relatively low cooling rates, allowing them to be cast in large cross sections, opening the scope of potential applications to include bulk forms and net shape structural applications. Recent studies have been reported for new bulk metallic glasses produced with lower cooling rates, from 0.1 to several hundred K/s. Some of the application products of BMGs include sporting goods, high performance springs and medical devices. Several rapid solidification techniques, including melt-spinning, atomization and surface melting have been developed to produce amorphous alloys. The aim of all these methods is to solidify the liquid phase rapidly enough to suppress the nucleation and growth of crystalline phases. Furthermore, the production of amorphous/crystalline composite (ACC) materials by partial crystallization of amorphous precursor has recently given rise to materials that provide better mechanical and magnetic properties than the monolithic amorphous or crystalline alloys. In addition, these advances illustrate the broad untapped potential of using the glassy state as an intermediate stage in the processing of new materials and nanostructures. These advances underlie the necessity of investigations on prediction and control of phase stability and microstructural dynamics during both solidification and devitrification processes. This research presented in this dissertation is mainly focused on Cu-Zr and Cu-Zr-Al alloy systems. The Cu-Zr binary system has high glass forming ability in a wide compositional range (35-70 at.% Cu). Thereby, Cu-Zr based alloys have attracted much attention according to fundamental

R7T7 nuclear waste glass behavior in moist clay: role of the clay mass/glass surface area ratio

International Nuclear Information System (INIS)

Godon, N.; Vernaz, E.

1989-01-01

R7T7 glass alteration was investigated in the presence of various moist clays. In contact with smectite 4a, selected in France as a potential engineered barrier material, the glass was significantly corroded: after 6 months the glass corrosion rate was practically the same as the initial alteration rate in double-distilled water. Substantially lower alteration was observed in contact with bentonite 6 activated by sodium carbonate. Smectite 4a consumes silicon released by glass corrosion, and thus retards the rise to high silicon concentrations in solution at which the glass corrosion rate diminishes. Glass can therefore in some cases be altered as much in moist clay as in water with high renewal rates. Other experiments with smaller quantities of smectite 4a showed that the phenomenon becomes less important in time: its duration is proportional to the ratio between the clay mass (C) and the glass surface area (SA). Comparing the results of studies at different C/SA ratios indicates that low glass corrosion rates are obtained more slowly at higher C/SA ratios. Tests with 239 Pu-doped R7T7 glass also showed that the radionuclide retention factor in the alteration film at the glass surface is only 6, compared with a factor of nearly 50 in double-distilled water

Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers.

Science.gov (United States)

Lutter, Jacob C; Wu, Tsung-yu; Zhang, Yanjie

2013-09-05

This work reports results from the interactions of a series of monovalent and divalent cations with a triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO). Phase transition temperatures of the polymer in the presence of chloride salts with six monovalent and eight divalent cations were measured using an automated melting point apparatus. The polymer undergoes a two-step phase transition, consisting of micellization of the polymer followed by aggregation of the micelles, in the presence of all the salts studied herein. The results suggest that hydration of cations plays a key role in determining the interactions between the cations and the polymer. The modulation of the phase transition temperature of the polymer by cations can be explained as a balance between three interactions: direct binding of cations to the oxygen in the polymer chains, cations sharing one water molecule with the polymer in their hydration layer, and cations interacting with the polymer via two water molecules. Monovalent cations Na(+), K(+), Rb(+), and Cs(+) do not bind to the polymer, while Li(+) and NH4(+) and all the divalent cations investigated including Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+) bind to the polymer. The effects of the cations correlate well with their hydration thermodynamic properties. Mechanisms for cation-polymer interactions are discussed.

Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism.

Science.gov (United States)

Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

2016-06-01

We have analyzed the structure and bonding of gas-phase Cl-X and [HCl-X](+) complexes for X(+)= H(+), CH3 (+), Li(+), and Na(+), using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl(-) and HCl for the various cations. The Cl-X bond becomes longer and weaker along X(+) = H(+), CH3 (+), Li(+), and Na(+). Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn-Sham molecular orbital (KS-MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities.

Automated characterization of glass microspheres used for laser fusion experiments

International Nuclear Information System (INIS)

Tajima, Tsuyoshi; Norimatsu, Takayoshi; Izawa, Yasukazu; Yamanaka, Chiyoe.

1985-01-01

In laser fusion experiments glass microspheres of 100 to 1000 μm in diameter and 1 to 20 μm in wall thickness are most commonly used as fuel containers. The glass microspheres should be characterized precisely to meet stringent experimental requirements. Much time is consumed to characterize and select good quality spheres among thousands of spheres. We have developed an automated system to characterize and select glass microspheres. The system consists of charger, quadrupole rail, image processing and X-Y stage control with micro-computer. Total processing time primarily depends on the time required for image analysis, which should be compromised with the accuracy of characterization. The time for simple characterization requires about 10 sec. at present. (author)

Ligand-controlled reactivity, selectivity, and mechanism of cationic ruthenium-catalyzed hydrosilylations of alkynes, ketones, and nitriles: a theoretical study.

Science.gov (United States)

Yang, Yun-Fang; Chung, Lung Wa; Zhang, Xinhao; Houk, K N; Wu, Yun-Dong

2014-09-19

Density functional theory calculations with the M06 functional have been performed on the reactivity, selectivity, and mechanism of hydrosilylations of alkynes, ketones, and nitriles catalyzed by cationic ruthenium complexes [CpRu(L)(MeCN)2](+), with L = P(i)Pr3 or MeCN. The hydrosilylation of alkynes with L = P(i)Pr3 involves an initial silyl migration mechanism to generate the anti-Markovnikov product, in contrast to the Markovnikov product obtained with L = MeCN. The bulky phosphine ligand directs the silyl group to migrate to Cβ of the alkyne. This explains the anti-Markovnikov selectivity of the catalyst with L = P(i)Pr3. By contrast, the silane additions to either ketone or nitrile proceed through an ionic SN2-Si outer-sphere mechanism, in which the substrate attacks the Si center. The P(i)Pr3 ligand facilitates the activation of the Si-H bond to furnish a η(2)-silane complex, whereas a η(1)-silane complex is formed for the MeCN ligand. This property of the phosphine ligand enables the catalytic hydrosilylation of ketones and nitriles in addition to that of alkynes.

Composition effects on chemical durability and viscosity of nuclear waste glasses - systematic studies and structural thermodynamic models

International Nuclear Information System (INIS)

Feng, X.

1988-01-01

Two of the primary criteria for the acceptability of nuclear waste glasses are their durability, i.e. chemical resistance to aqueous attack for 10 4 to 10 5 years, and processability, which requires their viscosity at the desired melt temperature to be sufficiently low. Chapter 3 presents the results of systematic composition variation studies around the preliminary reference glass composition WV205 and an atomistic interpretation of the effects of individual oxides. Chapter 4 is concerned with modifications of the Jantzen-Plodinec hydration model which takes into account formation of complex aluminosilicate compounds in the glass. Chapter 5 is devoted to the development and validation of the structural-thermodynamic model for both durability and viscosity. This model assumes the strength of bonds between atoms to be the controlling factor in the composition dependence of these glass properties. The binding strengths are derived from the known heats of formation and the structural roles of constituent oxides. Since the coordination state of various oxides in the glass is temperature dependent and cation size has opposite effects on the two properties, the correlation between melt viscosity and rate of corrosion at low temperature is not simply linear. Chapter 6 surveys the effects of aqueous phase composition on the leach behavior of glasses. These studies provide a comprehensive view of the effects of both glass composition and leachant composition on leaching. The models developed correlate both durability and viscosity with glass composition. A major implication is that these findings can be used in the systematic optimization of the properties of complex oxide glasses

A molecular dynamics study of the atomic structure of (CaO)x(SiO2)1-x glasses.

Science.gov (United States)

Mead, Robert N; Mountjoy, Gavin

2006-07-27

The local atomic environment of Ca in (CaO)x(SiO2)1-x glasses is of interest because of the role of Ca in soda-lime glass, the application of calcium silicate glasses as biomaterials, and the previous experimental measurement of the Ca-Ca correlation in CaSiO(3) glass. Molecular dynamics has been used to obtain models of (CaO)x(SiO2)1-x glasses with x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5, and with approximately 1000 atoms and size approximately 25 A. As expected, the models contain a tetrahedral silica network, the connectivity of which decreases as x increases. In the glass-forming region, i.e., x = 0.4 and 0.5, Ca has a mixture of 6- and 7-fold coordination. Bridging oxygen makes an important contribution to the coordination of Ca, with most bridging oxygens coordinated to 2 Si plus 1 Ca. The x = 0.5 model is in reasonable agreement with previous experimental studies, and does not substantiate the previous theory of cation ordering, which predicted Ca arranged in sheets. In the phase-separated region, i.e., x = 0.1 and 0.2, there is marked clustering of Ca.

Characterization of yellow and colorless decorative glasses from the Temple of the Emerald Buddha, Bangkok, Thailand

Science.gov (United States)

Klysubun, Wantana; Ravel, Bruce; Klysubun, Prapong; Sombunchoo, Panidtha; Deenan, Weeraya

2013-06-01

Yellow and colorless ancient glasses, which were once used to decorate the Temple of the Emerald Buddha, Bangkok, Thailand, around 150 years ago, are studied to unravel the long-lost glass-making recipes and manufacturing techniques. Analyses of chemical compositions, using synchrotron x-ray fluorescence (SRXRF), indicate that the Thai ancient glasses are soda lime silica glasses (60 % SiO2; 10 % Na2O; 10 % CaO) bearing lead oxide between 2-16 %. Iron (1.5-9.4 % Fe2O3) and manganese (1.7 % MnO) are present in larger abundance than the other 3 d transition metals detected (0.04-0.2 %). K-edge x-ray absorption near edge spectroscopy (XANES) and extended x-ray absorption fine structure spectroscopy (EXAFS) provide conclusive evidence on the oxidation states of Fe being 3+ and Mn being 2+ and on short-length tetrahedral structures around the cations. This suggests that iron is used as a yellow colorant with manganese as a decolorant. L 3-edge XANES results reveal the oxidation states of lead as 2+. The results from this work provide information crucial for replicating these decorative glasses for the future restoration of the Temple of the Emerald Buddha.

The structure of phosphate glass biomaterials from neutron diffraction and 31P nuclear magnetic resonance data

International Nuclear Information System (INIS)

Pickup, D M; Ahmed, I; Guerry, P; Knowles, J C; Smith, M E; Newport, R J

2007-01-01

Neutron diffraction and 31 P nuclear magnetic resonance spectroscopy were used to probe the structure of phosphate glass biomaterials of general composition (CaO) 0.5-x (Na 2 O) x (P 2 O 5 ) 0.5 (x = 0, 0.1 and 0.5). The results suggest that all three glasses have structures based on chains of Q 2 phosphate groups. Clear structural differences are observed between the glasses containing Na 2 O and CaO. The P-O bonds to bridging and non-bridging oxygens are less well resolved in the neutron data from the samples containing CaO, suggesting a change in the nature of the bonding as the field strength of the cation increases Na + → Ca 2+ . In the (CaO) 0.5 (P 2 O 5 ) 0.5 glass most of the Ca 2+ ions are present in isolated CaO x polyhedra whereas in the (Na 2 O) 0.5 (P 2 O 5 ) 0.5 glass the NaO x polyhedra share edges leading to a Na-Na correlation. The results of the structural study are related to the properties of the (CaO) 0.4 (Na 2 O) 0.1 (P 2 O 5 ) 0.5 biomaterial

NMR study of glasses in the PbO-B/sub 2/O/sub 3/-PbF/sub 2/-AlF/sub 3/ system

Energy Technology Data Exchange (ETDEWEB)

Vopilov, V.A.; Bogdanov, V.L.; Buznik, V.M.; Karapetyan, A.K.; Matsulev, A.N.

1986-01-01

The NMR method has been successfully used in the study of the structure of oxide glasses and in lithium glasses. Using steady-state and pulse methods of B-11 and F-19 NMR, the authors have studied borate glasses in the PbO-B/sub 2/O/sub 3/-PbF/sub 2/-AlF/sub 3/ system. Lead fluoride was added to the composition of the experimental glasses. A small amount of PbF2 has a weak effect on the electrical conductivity, and it is only in the specimen with the maximum values of the PbF/sub 2/ concentration that conductivity becomes significant. In glasses of the PbO X B/sub 2/O/sub 3/ X AlF/sub 3/ compositions, there is an exchange of the oxygen and fluoride modifier anions and as a result the F ions are incorporated into the first coordination sphere of the lead cations.

Evaluation of the cationic trypsinogen gene for potential mutations in miniature schnauzers with pancreatitis.

Science.gov (United States)

Bishop, Micah A; Steiner, Jörg M; Moore, Lisa E; Williams, David A

2004-10-01

The purpose of this study was to evaluate the cationic trypsinogen gene in miniature schnauzers for possible mutations. Genetic mutations have been linked with hereditary pancreatitis in humans. Four miniature schnauzers were selected on the basis of a clinical history of pancreatitis. One healthy miniature schnauzer and 1 healthy mixed breed canine were enrolled as controls. DNA was extracted from these canines using a commercial kit. Primers were designed to amplify the entire canine cationic trypsinogen cDNA sequence. A polymerase chain reaction (PCR) was performed and products were purified and sequenced. All sequences were then compared. The healthy control canine, a healthy miniature schnauzer, and the 4 miniature schnauzers with pancreatitis showed identical sequences of the cationic trypsinogen gene to the published sequence. We conclude that, in contrast to humans with hereditary pancreatitis, mutations of the cationic trypsinogen gene do not play a major role in the genesis of pancreatitis in the miniature schnauzer.

Influence of rare-earth ions on SiO{sub 2}-Na{sub 2}O-RE{sub 2}O{sub 3} glass structure

Energy Technology Data Exchange (ETDEWEB)

Johnson, J A [Department of Materials Science and Engineering, University of Tennessee Space Institute, Tullahoma, TN 37388 (United States); Benmore, C J [X-ray Science Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Holland, D [Department of Physics, University of Warwick, CV4 7AL (United Kingdom); Du, J [Department of Material Science and Engineering, University of North Texas, Denton, TX 76203 (United States); Beuneu, B [Laboratoire Leon Brillouin, CEA-CNRS, CEA/Saclay, F-91191 Gif-sur-Yvette (France); Mekki, A, E-mail: jjohnson@utsi.edu [Department of Physics, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia)

2011-02-16

Praseodymium and europium sodium silicate glasses of nominal composition (SiO{sub 2}){sub 0.70-x}(Na{sub 2}O){sub 0.30}(RE{sub 2}O{sub 3}){sub x}, where RE is the rare earth and 0 {<=} x {<=} 0.10, were studied by neutron and high-energy x-ray scattering and classical molecular dynamics simulations. The observation of a significant x-ray intensity in doped as compared to un-doped glasses is indicative of RE-RE correlations at a distance of {approx} 3.7-3.9 A, much shorter than would be expected for a homogeneous distribution, suggesting that clustering of the rare-earth cations occurs in both these glass systems at low concentrations. Above x = 0.075 (nominal), minimal changes in this region indicate that the RE atoms are incorporated much more randomly into the glass structure. The molecular dynamics simulations suggest that the rare-earth ions enter the sodium-rich regions in the sodium silicate glasses and act as modifiers. A cluster analysis performed on the model systems indicates that the tendency for clustering is higher in praseodymium-containing glasses than in the europium glasses.

Bio-active glass air-abrasion has the potential to remove resin composite restorative material selectively

International Nuclear Information System (INIS)

Milly, Hussam; Andiappan, Manoharan; Thompson, Ian; Banerjee, Avijit

2014-01-01

The aims of this study were to assess: (a) the chemistry, morphology and bioactivity of bio-active glass (BAG) air-abrasive powder, (b) the effect of three air-abrasion operating parameters: air pressure, powder flow rate (PFR) and the abrasive powder itself, on the selective removal of resin composite and (c) the required “time taken”. BAG abrasive particles were characterised using scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX) and Fourier-transform infrared spectroscopy (FTIR). Standardised resin composite restorations created within an enamel analogue block (Macor™) in vitro, were removed using air-abrasion undersimulated clinical conditions. 90 standardised cavities were scanned before and after resin composite removal using laser profilometry and the volume of the resulting 3D images calculated. Multilevel linear model was used to identify the significant factors affecting Macor™ removal. BAG powder removed resin composite more selectively than conventional air-abrasion alumina powder using the same operating parameters (p < 0.001) and the effect of altering the unit's operating parameters was significant (p < 0.001). In conclusion, BAG powder is more efficient than alumina in the selective removal of resin composite particularly under specific operating parameters, and therefore may be recommended clinically as a method of preserving sound enamel structure when repairing and removing defective resin composite restorations.

Cation-exchanged SAPO-34 for adsorption-based hydrocarbon separations: predictions from dispersion-corrected DFT calculations.

Science.gov (United States)

Fischer, Michael; Bell, Robert G

2014-10-21

The influence of the nature of the cation on the interaction of the silicoaluminophosphate SAPO-34 with small hydrocarbons (ethane, ethylene, acetylene, propane, propylene) is investigated using periodic density-functional theory calculations including a semi-empirical dispersion correction (DFT-D). Initial calculations are used to evaluate which of the guest-accessible cation sites in the chabazite-type structure is energetically preferred for a set of ten cations, which comprises four alkali metals (Li(+), Na(+), K(+), Rb(+)), three alkaline earth metals (Mg(2+), Ca(2+), Sr(2+)), and three transition metals (Cu(+), Ag(+), Fe(2+)). All eight cations that are likely to be found at the SII site (centre of a six-ring) are then included in the following investigation, which studies the interaction with the hydrocarbon guest molecules. In addition to the interaction energies, some trends and peculiarities regarding the adsorption geometries are analysed, and electron density difference plots obtained from the calculations are used to gain insights into the dominant interaction types. In addition to dispersion interactions, electrostatic and polarisation effects dominate for the main group cations, whereas significant orbital interactions are observed for unsaturated hydrocarbons interacting with transition metal (TM) cations. The differences between the interaction energies obtained for pairs of hydrocarbons of interest (such as ethylene-ethane and propylene-propane) deliver some qualitative insights: if this energy difference is large, it can be expected that the material will exhibit a high selectivity in the adsorption-based separation of alkene-alkane mixtures, which constitutes a problem of considerable industrial relevance. While the calculations show that TM-exchanged SAPO-34 materials are likely to exhibit a very high preference for alkenes over alkanes, the strong interaction may render an application in industrial processes impractical due to the large amount

Cationic Antimicrobial Polymers and Their Assemblies

Science.gov (United States)

Carmona-Ribeiro, Ana Maria; de Melo Carrasco, Letícia Dias

2013-01-01

Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs). The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications. PMID:23665898

Cationic Antimicrobial Polymers and Their Assemblies

Directory of Open Access Journals (Sweden)

Ana Maria Carmona-Ribeiro

2013-05-01

Full Text Available Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs. The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications.

Binding properties of oxacalix[4]arenes derivatives toward metal cations; Interactions entre cations metalliques et derives des oxacalix[4]arenes

Energy Technology Data Exchange (ETDEWEB)

Mellah, B

2006-11-15

The objective of this work was to establish the binding properties of oxacalix[4]arene derivatives with different numbers of the oxa bridges, functional groups (ketones, pyridine, ester, amide and methoxy) and conformations. Their interactions with alkali and alkaline-earth, heavy and transition metal cations have been evaluated according to different approaches: (i) extraction of corresponding picrates from an aqueous phase into dichloromethane; (ii) determination of the thermodynamic parameters of complexation in methanol and/or acetonitrile by UV-spectrophotometry and micro-calorimetry; (iii) determination of the stoichiometry of the complexes by ESI-MS; (iv) {sup 1}H-NMR titrations allowing to localize the metal ions in the ligand cavity. In a first part dealing on homo-oxacalix[4]arenes, selectivities for Na{sup +}, K{sup +}, Ca{sup 2+}, Pb{sup 2+} and Mn{sup 2+} of ketones derivatives was shown. The presence of oxa bridge in these derivatives increases their efficiency while decreasing their selectivity with respect to related calixarenes. The pyridine derivative prefers transition and heavy metal cations, in agreement with the presence of the soft nitrogen atoms. In the second part, di-oxacalix[4]arene ester and secondary amide derivatives were shown to be less effective than tertiary amide counterparts but to present high selectivities for Li{sup +}, Ba{sup 2+}, Zn{sup 2+} and Hg{sup 2+}. A third part devoted to the octa-homo-tetra-oxacalix[4]arene tetra-methoxy shows that the 1:1 metal complexes formed are generally more stable than those of calixarenes, suggesting the participation of the oxygen atoms of the bridge in the complexation. Selectivity for Cs{sup +}, Ba{sup 2+}, Cu{sup 2+} and Hg{sup 2+} were noted. (author)

Conduction mechanism in bismuth silicate glasses containing titanium

International Nuclear Information System (INIS)

Dult, Meenakshi; Kundu, R.S.; Murugavel, S.; Punia, R.; Kishore, N.

2014-01-01

Bismuth silicate glasses mixed with different concentrations of titanium dioxide having compositions xTiO 2 –(60−x)Bi 2 O 3 –40SiO 2 with x=0, 5, 10, 15 and 20 were prepared by the normal melt quench technique. The frequency dependence of the ac electrical conductivity of different compositions of titanium bismuth silicate glasses has been studied in the frequency range 10 −1 Hz to 10 MHz and in the temperature range 623–703 K. The temperature and frequency dependent conductivity is found to obey Jonscher's universal power law for all the compositions of titanium bismuth silicate glass system. The dc conductivity (σ dc ), so called crossover frequency (ω H ), and frequency exponent (s) have been estimated from the fitting of experimental data of ac conductivity with Jonscher's universal power law. Enthalpy to dissociate the cation from its original site next to a charge compensating center (H f ) and enthalpy of migration (H m ) have also been estimated. The conductivity data have been analyzed in terms of different theoretical models to determine the possible conduction mechanism. Analysis of the conductivity data and the frequency exponent shows that the correlated barrier hopping of electrons between Ti 3+ and Ti 4+ ions in the glasses is the most favorable mechanism for ac conduction. The temperature dependent dc conductivity has been analyzed in the framework of theoretical variable range hopping model (VRH) proposed by Mott which describe the hopping conduction in disordered semiconducting systems. The various polaron hopping parameters have also been deduced. Mott's VRH model is found to be in good agreement with experimental data and the values of inverse localization length of s-like wave function (α) obtained by this model with modifications suggested by Punia et al. are close to the ones reported for a number of oxide glasses

[Noncovalent cation-π interactions--their role in nature].

Science.gov (United States)

Fink, Krzysztof; Boratyński, Janusz

2014-11-07

Non-covalent interactions play an extremely important role in organisms. The main non-covalent interactions in nature are: ion-ion interactions, dipole-dipole interactions, hydrogen bonds, and van der Waals interactions. A new kind of intermolecular interactions--cation-π interactions--is gaining increasing attention. These interactions occur between a cation and a π system. The main contributors to cation-π interactions are electrostatic, polarization and, to a lesser extent, dispersion interactions. At first, cation-π interactions were studied in a gas phase, with metal cation-aromatic system complexes. The characteristics of these complexes are as follows: an increase of cation atomic number leads to a decrease of interaction energy, and an increase of cation charge leads to an increase of interaction energy. Aromatic amino acids bind with metal cations mainly through interactions with their main chain. Nevertheless, cation-π interaction with a hydrophobic side chain significantly enhances binding energy. In water solutions most cations preferentially interact with water molecules rather than aromatic systems. Cation-π interactions occur in environments with lower accessibility to a polar solvent. Cation-π interactions can have a stabilizing role on the secondary, tertiary and quaternary structure of proteins. These interactions play an important role in substrate or ligand binding sites in many proteins, which should be taken into consideration when the screening of effective inhibitors for these proteins is carried out. Cation-π interactions are abundant and play an important role in many biological processes.

Stressor states and the cation crossroads.

Science.gov (United States)

Weber, Karl T; Bhattacharya, Syamal K; Newman, Kevin P; Soberman, Judith E; Ramanathan, Kodangudi B; McGee, Jesse E; Malik, Kafait U; Hickerson, William L

2010-12-01

Neurohormonal activation involving the hypothalamic-pituitary-adrenal axis and adrenergic nervous and renin-angiotensin-aldosterone systems is integral to stressor state-mediated homeostatic responses. The levels of effector hormones, depending upon the degree of stress, orchestrate the concordant appearance of hypokalemia, ionized hypocalcemia and hypomagnesemia, hypozincemia, and hyposelenemia. Seemingly contradictory to homeostatic responses wherein the constancy of extracellular fluid would be preserved, upregulation of cognate-binding proteins promotes coordinated translocation of cations to injured tissues, where they participate in wound healing. Associated catecholamine-mediated intracellular cation shifts regulate the equilibrium between pro-oxidants and antioxidant defenses, a critical determinant of cell survival. These acute and chronic stressor-induced iterations in extracellular and intracellular cations are collectively referred to as the cation crossroads. Intracellular cation shifts, particularly excessive accumulation of Ca2+, converge on mitochondria to induce oxidative stress and raise the opening potential of their inner membrane permeability transition pores (mPTPs). The ensuing loss of cationic homeostasis and adenosine triphosphate (ATP) production, together with osmotic swelling, leads to organellar degeneration and cellular necrosis. The overall impact of iterations in extracellular and intracellular cations and their influence on cardiac redox state, cardiomyocyte survival, and myocardial structure and function are addressed herein.

Cationic electrodepositable coating composition comprising lignin

Science.gov (United States)

Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

2013-07-30

A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

A theoretical study of complexes formed between cations and curved aromatic systems: electrostatics does not always control cation-π interaction.

Science.gov (United States)

Carrazana-García, Jorge A; Cabaleiro-Lago, Enrique M; Rodríguez-Otero, Jesús

2017-04-19

The present work studies the interaction of two extended curved π-systems (corannulene and sumanene) with various cations (sodium, potassium, ammonium, tetramethylammonium, guanidinium and imidazolium). Polyatomic cations are models of groups found in important biomolecules in which cation-π interaction plays a fundamental role. The results indicate an important size effect: with extended π systems and cations of the size of potassium and larger, dispersion is much more important than has been generally recognized for cation-π interactions. In most of the systems studied here, the stability of the cation-π complexes is the result of a balanced combination of electrostatic, induction and dispersion contributions. None of the systems studied here owes its stability to the electrostatic interaction more than 42%. Induction dominates stabilization in complexes with sodium, and in some of the potassium and ammonium complexes. In complexes with large cations and with flat cations dispersion is the major stabilizing contribution and can provide more than 50% of the stabilization energy. This implies that theoretical studies of the cation-π interaction involving large or even medium-size fragments require a level of calculation capable of properly modelling dispersion. The separation between the cation and the π system is another important factor to take into account, especially when the fragments of the cation-π complex are bound (for example, to a protein backbone) and cannot interact at the most favourable distance.

Calixarenes synthesized for seducing and trapping cations

International Nuclear Information System (INIS)

Dozol, J.F.

1997-01-01

Calixarenes are known to be selective extractants for cesium radioactive cations. This liquid-liquid extraction is still to be studied and would allow to reduce the volume of years living radioactive wastes before they were stored and perhaps to remove then the cesium by transmutation. Calixarenes are macrocycles with phenolic units bridged by methylene groups. They have the important property to have a flexible structure. On this basic structure, all kinds of chemical functions can be branched. They thus confer particular properties to the molecule. A computerized virtual construction phase of molecules is actually studied in order to optimize the extraction. It is currently known that with small modifications it will be possible to selectively extract heavy metals (Hg, Cd..) coming from industrial pollution. (O.M.)

Modification of the glass surface induced by redox reactions and internal diffusion processes

DEFF Research Database (Denmark)

Smedskjær, Morten Mattrup; Deubener, Joachim; Yue, Yuanzheng

In this paper we report a novel way to modify the glass surface in favor of some physical performances. The main step is to perform iso-thermal treatments on the selected silicate glasses containing transition metal at temperatures near the glass transition temperature for various durations under...

Hollow porous-wall glass microspheres for hydrogen storage

Science.gov (United States)

Heung, Leung K.; Schumacher, Ray F.; Wicks, George G.

2010-02-23

A porous wall hollow glass microsphere is provided having a diameter range of between 1 to 200 microns, a density of between 1.0 to 2.0 gm/cc, a porous-wall structure having wall openings defining an average pore size of between 10 to 1000 angstroms, and which contains therein a hydrogen storage material. The porous-wall structure facilitates the introduction of a hydrogen storage material into the interior of the porous wall hollow glass microsphere. In this manner, the resulting hollow glass microsphere can provide a membrane for the selective transport of hydrogen through the porous walls of the microsphere, the small pore size preventing gaseous or liquid contaminants from entering the interior of the hollow glass microsphere.

Formation of radical cations of diaryloxadiazoles

International Nuclear Information System (INIS)

Helmstreit, W.

1988-01-01

The nature of the formation of the radical cation of the 2,5-bis-(p-diethylaminophenyl)-1,3,4-oxadiazole (PC) in liquid n-butyl chloride and acetonitrile has been investigated by observing excited state fluorescence and transient absorption using nanosecond pulse radiolysis and laser flash photolysis. The formation of solute oxonium ions has also been observed. At concentrations -4 mol dm -3 the growth time at which the transient absorption of the radical cation reaches the maximum follows the rise time of the electron pulse ( 2 laser yields the solute radical cation in an acetonitrile solution of 2 x 10 -4 mol dm -3 PC via an electronically excited state. Here, the generation time was smaller than 5 ns. The yield of the cation is increased by addition of CCl 4 . A reaction mechanism is proposed that explains the fast cation formation in terms of an exciplex formed by interaction between an electronically excited state of diaryloxadiazole and the ground state of the solvent. This exciplex yields the solute radical cation. (author)

Characterization of glass and glass ceramic nuclear waste forms

International Nuclear Information System (INIS)

Lutze, W.; Borchardt, J.; De, A.K.

1979-01-01

Characteristics of solidified nuclear waste forms, glass and glass ceramic compositions and the properties (composition, thermal stability, crystallization, phase behavior, chemical stability, mechanical stability, and radiation effects) of glasses and glass ceramics are discussed. The preparation of glass ceramics may be an optional step for proposed vitrification plants if tailored glasses are used. Glass ceramics exhibit some improved properties with respect to glasses. The overall leach resistance is similar to that of glasses. An increased leach resistance may become effective for single radionuclides being hosted in highly insoluble crystal phases mainly when higher melting temperatures are applicable in order to get more leach resistant residual glass phases. The development of glass ceramic is going on. The technological feasibility is still to be demonstrated. The potential gain of stability when using glass ceramics qualifies the material as an alternative nuclear waste form

Chemistry and kinetics of size-selected cobalt cluster cations at thermal energies. I. Reactions with CO

Science.gov (United States)

Guo, B. C.; Kerns, K. P.; Castleman, A. W., Jr.

1992-06-01

The chemistry and kinetics of size-selected Co+n cluster-ion (n=2-8) reactions with CO are studied using a selected ion drift tube affixed with a laser vaporization source operated under well-defined thermal conditions. All reactions studied in the present work are found to be association reactions. Their absolute rate constants, which are determined quantitatively, are found to have a strong dependence on cluster size. Similar to the cases of reactions with many other reactants such as H2 and CH4, Co+4 and Co+5 display a higher reactivity toward the CO molecule than do clusters of neighboring size. The multiple-collision conditions employed in the present work have enabled a determination of the maximum coordination number of CO molecules bound onto each Co+n cluster. It is found that the tetramer tends to bond 12 CO molecules, the pentamer 14 CO, hexamer 16 CO, and so on. The results are interpreted in terms of Lauher's calculation and the polyhedral skeletal electron pair theory. All the measured maximum coordination numbers correlate extremely well with the predictions of these theories, except for the trimer where the measured number is one CO less than the predicted value. The good agreement between experiment and theory enables one to gain some insight into the geometric structure of the clusters. Based on the present findings, the cobalt tetramer cation is interpreted to have a tetrahedral structure, the pentamer a trigonal bipyramid, and the hexamer an octahedral structure. Other cluster structures are also discussed.

Crafting glass vessels: current research on the ancient glass collections in the Freer Gallery of Art, Washington, D.C.

Science.gov (United States)

Nagel, Alexander; McCarthy, Blythe; Bowe, Stacy

Our knowledge of glass production in ancient Egypt has been well augmented by the publication of recently excavated materials and glass workshops, but also by more recent materials analysis, and experiments of modern glass-makers attempting to reconstruct the production process of thin-walled coreformed glass vessels. From the mounting of a prefabricated core to the final glass product our understanding of this profession has much improved. The small but well preserved glass collection of the Freer Gallery of Art in Washington, D.C. is a valid tool for examining and studying the technology and production of ancient Egyptian core formed glass vessels. Charles Lang Freer (1854-1919) acquired most of the material from Giovanni Dattari in Cairo in 1909. Previously the glass had received only limited discussion, suggesting that most of these vessels were produced in the 18th Dynasty in the 15th and 14th centuries BCE, while others date from the Hellenistic period and later. In an ongoing project we conducted computed radiography in conjunction with qualitative x-ray fluorescence analysis on a selected group of vessels to understand further aspects of the ancient production process. This paper will provide an overview of our recent research and present our data-gathering process and preliminary results. How can the examinations of core formed glass vessels in the Freer Gallery contribute to our understanding of ancient glass production and technology? By focusing on new ways of looking at old assumptions using the Freer Gallery glass collections, we hope to increase understanding of the challenges of the production process of core-vessel technology as represented by these vessels.

Cationic polymers and porous materials

KAUST Repository

Han, Yu

2017-04-27

According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

Cationic polymers and porous materials

KAUST Repository

Han, Yu; Tian, Qiwei; Dong, Xinglong; Liu, Zhaohui; Basset, Jean-Marie; Saih, Youssef; Sun, Miao; Xu, Wei; Shaikh, Sohel

2017-01-01

According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

Radiation induced in-situ cationic polymerization of polystyrene organogel for selective absorption of cholorophenols from petrochemical wastewater.

Science.gov (United States)

Ghobashy, Mohamed M; Younis, Sherif A; Elhady, Mohamed A; Serp, Philippe

2018-03-15

A new in-situ cationic polymerization was performed to synthesize a cross-linked (91%) polystyrene (PS) organogel through tetrachloroethylene radiolysis assisted by 60 Co gamma rays. Hoernschemeyer diagram and swelling capacity test show a better selectivity of PS organogel to chlorinated molecules compared to ester, hydrocarbons and alcohols organic molecules by 80-184 folds. Response surface modeling (RSM) of CPs (2,4,6-trichlorophenol) sorption from artificial wastewater confirm superiority of PS organogel to absorb 1746 μmol CPs/g (∼345 mg CPs/g) at broad pH (4-10) and temperature (25-45 °C). Based on ANOVA statistic, simulated CPs absorption model onto PS organogel was successfully developed, with accuracy of prediction of R 2 ≈ R Adj 2 of 0.991-0.995 and lower coefficient of variation of 2.73% with F model of 611.4 at p 99%) by non-covalent and/or dispersive interaction mechanisms with a well-term reusability and good stability up to 5 cycles. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ion-Exchange Processes and Mechanisms in Glasses

International Nuclear Information System (INIS)

McGrail, B.P.; Icenhower, J.P.; Darab, J.G.; Shuh, D.K.; Baer, D.R.; Shutthanandan, V.; Thevuthasan, S.; Engelhard, M.H.; Steele, J.L.; Rodriguez, E.A.; Liu, P.; Ivanov, K.E.; Booth, C.H.; Nachimuthu, P.

2001-01-01

Leaching of alkalis from glass is widely recognized as an important mechanism in the initial stages of glass-water interactions. Pioneering experimental studies [1-3] nearly thirty-five years ago established that alkali (designated as M + ) are lost to solution more rapidly than network-forming cations. The overall chemical reaction describing the process can be written as: (triple b ond)Si-O-M + H + → (triple b ond)Si-OH + M + (1) or (triple b ond)Si-O-M + H 3 O + → (triple b ond)Si-OH + M + + H 2 O. (2) Doremus and coworkers [4-7] fashioned a quantitative model where M + ions in the glass are exchanged for counter-diffusing H 3 O + or H + . Subsequent investigations [8], which have relied heavily on reaction layer analysis, recognized the role of H 2 O molecules in the alkali-exchange process, without minimizing the importance of charged hydrogen species. Beginning in the 1980s, however, interest in M + -H + exchange reactions in silicate glasses diminished considerably because important experimental observations showed that network hydrolysis and dissolution rates were principally controlled by the chemical potential difference between the glass and solution (chemical affinity) [9]. For nuclear waste glasses, formation of alteration products or secondary phases that remove important elements from solution, particularly Si, was found to have very large impacts on glass dissolution rates [10,11]. Consequently, recent work on glass/water interactions has focused on understanding this process and incorporating it into models [12]. The ion-exchange process has been largely ignored because it has been thought to be a short duration, secondary or tertiary process that had little or no bearing on long-term corrosion or radionuclide release rates from glasses [13]. The only significant effect identified in the literature that is attributed to alkali ion exchange is an increase in solution pH in static laboratory tests conducted at high surface area-to-volume ratios

Impact of the associated cation on chloride binding of Portland cement paste

International Nuclear Information System (INIS)

De Weerdt, K.; Colombo, A.; Coppola, L.; Justnes, H.; Geiker, M.R.

2015-01-01

Well hydrated cement paste was exposed to MgCl 2 , CaCl 2 and NaCl solutions at 20 °C. The chloride binding isotherms for free chloride concentrations ranging up to 1.5 mol/l were determined experimentally. More chlorides were found to be bound when the associated cation was Mg 2 + or Ca 2 + compared to Na + . The chloride binding capacity of the paste appeared to be related to the pH of the exposure solution. In order to explain the cation dependency of the chloride binding a selection of samples was investigated in detail using experimental techniques such as TG, XRD and SEM–EDS to identify the phases binding the chlorides. The experimentally obtained data were compared with the calculations of a thermodynamic model, GEMS. It was concluded that the measured change in chloride binding depending on the cation was mainly governed by the pH of the exposure solution and thereby the binding capacity of the C-S-H

Machine Learning Approach for Prediction and Understanding of Glass-Forming Ability.

Science.gov (United States)

Sun, Y T; Bai, H Y; Li, M Z; Wang, W H

2017-07-20

The prediction of the glass-forming ability (GFA) by varying the composition of alloys is a challenging problem in glass physics, as well as a problem for industry, with enormous financial ramifications. Although different empirical guides for the prediction of GFA were established over decades, a comprehensive model or approach that is able to deal with as many variables as possible simultaneously for efficiently predicting good glass formers is still highly desirable. Here, by applying the support vector classification method, we develop models for predicting the GFA of binary metallic alloys from random compositions. The effect of different input descriptors on GFA were evaluated, and the best prediction model was selected, which shows that the information related to liquidus temperatures plays a key role in the GFA of alloys. On the basis of this model, good glass formers can be predicted with high efficiency. The prediction efficiency can be further enhanced by improving larger database and refined input descriptor selection. Our findings suggest that machine learning is very powerful and efficient and has great potential for discovering new metallic glasses with good GFA.

Synthesis and different optical properties of Gd2O3 doped sodium zinc tellurite glasses

Science.gov (United States)

Samanta, Buddhadev; Dutta, Dibakar; Ghosh, Subhankar

2017-06-01

A series of Gd2O3 doped sodium zinc tellurite [xGd2O3-(0.8-x) TeO2-0.1Na2O-0.1ZnO] glasses are prepared by the conventional melt quenching method and their optical properties have been studied. UV-vis spectrophotometric studies within the wavelength range from 230 nm-800 nm are carried out in the integrating sphere mode to study the effect of Gd2O3 doping on the optical band gap (Eg), refractive index (n), dielectric constant (εr) and susceptibility (χ). Other physical properties like molar volume, molar refraction, polarizability, metallization criterion, number density of rare-earth ions (N), polaron radius (rp), inter ionic distance (ri), molar cation polarizability (∑αi), number of oxide ions in chemical composition (NO2-), optical band gap based electronic oxide ion polarizability (αO2-) and optical basicity (Λ) of glass samples have been studied on the basis of UV-vis spectra and density profile of the different glasses.

Cation-π interaction of the univalent sodium cation with [2.2.2]paracyclophane: Experimental and theoretical study

Science.gov (United States)

Makrlík, Emanuel; Sýkora, David; Böhm, Stanislav; Vaňura, Petr

2018-02-01

By employing electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent sodium cation (Na+) forms with [2.2.2]paracyclophane (C24H24) the cationic complex [Na(C24H24)]+. Further, applying quantum chemical DFT calculations, the most probable structure of the [Na(C24H24)]+ complex was derived. In the resulting complex with a symmetry very close to C3, the "central" cation Na+, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation-π interaction. Finally, the interaction energy, E(int), of the considered cation-π complex [Na(C24H24)]+ was found to be -267.3 kJ/mol, confirming the formation of this fascinating complex species as well.

Activation of a Ca2+-dependent cation conductance with properties of TRPM2 by reactive oxygen species in lens epithelial cells.

Science.gov (United States)

Keckeis, Susanne; Wernecke, Laura; Salchow, Daniel J; Reichhart, Nadine; Strauß, Olaf

2017-08-01

Ion channels are crucial for maintenance of ion homeostasis and transparency of the lens. The lens epithelium is the metabolically and electrophysiologically active cell type providing nutrients, ions and water to the lens fiber cells. Ca 2+ -dependent non-selective ion channels seem to play an important role for ion homeostasis. The aim of the study was to identify and characterize Ca 2+ - and reactive oxygen species (ROS)-dependent non-selective cation channels in human lens epithelial cells. RT-PCR revealed gene expression of the Ca 2+ -activated non-selective cation channels TRPC3, TRPM2, TRPM4 and Ano6 in both primary lens epithelial cells and the cell line HLE-B3, whereas TRPM5 mRNA was only found in HLE-B3 cells. Using whole-cell patch-clamp technique, ionomycin evoked non-selective cation currents with linear current-voltage relationship in both cell types. The current was decreased by flufenamic acid (FFA), 2-APB, 9-phenanthrol and miconazole, but insensitive to DIDS, ruthenium red, and intracellularly applied spermine. H 2 O 2 evoked a comparable current, abolished by FFA. TRPM2 protein expression in HLE-B3 cells was confirmed by means of immunocytochemistry and western blot. In summary, we conclude that lens epithelial cells functionally express Ca 2+ - and H 2 O 2 -activated non-selective cation channels with properties of TRPM2. Copyright © 2017. Published by Elsevier Ltd.

Sealing glasses for titanium and titanium alloys

Science.gov (United States)

Brow, Richard K.; McCollister, Howard L.; Phifer, Carol C.; Day, Delbert E.

1997-01-01

Barium lanthanoborate sealing-glass compositions are provided comprising various combinations (in terms of mole-%) of boron oxide (B.sub.2 O.sub.3), barium oxide (BaO), lanthanum oxide (La.sub.2 O.sub.3), and at least one other oxide selected from the group consisting of aluminum oxide (Al.sub.2 O.sub.3), calcium oxide (CaO), lithium oxide (Li.sub.2 O), sodium oxide (Na.sub.2 O), silicon dioxide (SiO.sub.2), or titanium dioxide (TiO.sub.2). These sealing-glass compositions are useful for forming hermetic glass-to-metal seals with titanium and titanium alloys having an improved aqueous durability and favorable sealing characteristics. Examples of the sealing-glass compositions are provided having coefficients of thermal expansion about that of titanium or titanium alloys, and with sealing temperatures less than about 900.degree. C., and generally about 700.degree.-800.degree. C. The barium lanthanoborate sealing-glass compositions are useful for components and devices requiring prolonged exposure to moisture or water, and for implanted biomedical devices (e.g. batteries, pacemakers, defibrillators, pumps).

A new cationic porphyrin derivative (TMPipEOPP with large side arm substituents: a highly selective G-quadruplex optical probe.

Directory of Open Access Journals (Sweden)

Li-Na Zhu

Full Text Available The discovery of uncommon DNA structures and speculation about their potential functions in genes has brought attention to specific DNA structure recognition. G-quadruplexes are four-stranded nucleic acid structures formed by G-rich DNA (or RNA sequences. G-rich sequences with a high potential to form G-quadruplexes have been found in many important genomic regions. Porphyrin derivatives with cationic side arm substituents are important G-quadruplex-binding ligands. For example, 5,10,15,20-Tetrakis(N-methylpyridinium-4-yl-21H,23H-porphyrin (TMPyP4, interacts strongly with G-quadruplexes, but has poor selectivity for G-quadruplex versus duplex DNA. To increase the G-quadruplex recognition specificity, a new cationic porphyrin derivative, 5,10,15,20-tetra-{4-[2-(1-methyl-1-piperidinylethoxy]phenyl} porphyrin (TMPipEOPP, with large side arm substituents was synthesized, and the interactions between TMPipEOPP and different DNA structures were compared. The results show that G-quadruplexes cause large changes in the UV-Vis absorption and fluorescence spectra of TMPipEOPP, but duplex and single-stranded DNAs do not, indicating that TMPipEOPP can be developed as a highly specific optical probe for discriminating G-quadruplex from duplex and single-stranded DNA. Visual discrimination is also possible. Job plot and Scatchard analysis suggest that a complicated binding interaction occurs between TMPipEOPP and G-quadruplexes. At a low [G-quadruplex]/[TMPipEOPP] ratio, one G-quadruplex binds two TMPipEOPP molecules by end-stacking and outside binding modes. At a high [G-quadruplex]/[TMPipEOPP] ratio, two G-quadruplexes bind to one TMPipEOPP molecule in a sandwich-like end-stacking mode.

A new cationic porphyrin derivative (TMPipEOPP) with large side arm substituents: a highly selective G-quadruplex optical probe.

Science.gov (United States)

Zhu, Li-Na; Zhao, Shu-Juan; Wu, Bin; Li, Xiao-Zeng; Kong, De-Ming

2012-01-01

The discovery of uncommon DNA structures and speculation about their potential functions in genes has brought attention to specific DNA structure recognition. G-quadruplexes are four-stranded nucleic acid structures formed by G-rich DNA (or RNA) sequences. G-rich sequences with a high potential to form G-quadruplexes have been found in many important genomic regions. Porphyrin derivatives with cationic side arm substituents are important G-quadruplex-binding ligands. For example, 5,10,15,20-Tetrakis(N-methylpyridinium-4-yl)-21H,23H-porphyrin (TMPyP4), interacts strongly with G-quadruplexes, but has poor selectivity for G-quadruplex versus duplex DNA. To increase the G-quadruplex recognition specificity, a new cationic porphyrin derivative, 5,10,15,20-tetra-{4-[2-(1-methyl-1-piperidinyl)ethoxy]phenyl} porphyrin (TMPipEOPP), with large side arm substituents was synthesized, and the interactions between TMPipEOPP and different DNA structures were compared. The results show that G-quadruplexes cause large changes in the UV-Vis absorption and fluorescence spectra of TMPipEOPP, but duplex and single-stranded DNAs do not, indicating that TMPipEOPP can be developed as a highly specific optical probe for discriminating G-quadruplex from duplex and single-stranded DNA. Visual discrimination is also possible. Job plot and Scatchard analysis suggest that a complicated binding interaction occurs between TMPipEOPP and G-quadruplexes. At a low [G-quadruplex]/[TMPipEOPP] ratio, one G-quadruplex binds two TMPipEOPP molecules by end-stacking and outside binding modes. At a high [G-quadruplex]/[TMPipEOPP] ratio, two G-quadruplexes bind to one TMPipEOPP molecule in a sandwich-like end-stacking mode.

Infrared spectroscopy of the acetyl cation and its protonated ketene isomer

Science.gov (United States)

Mosley, J. D.; Young, J. W.; Duncan, M. A.

2014-07-01

[C2,H3,O]+ ions are generated with a pulsed discharge in a supersonic expansion containing methyl acetate or acetone. These ions are mass selected and their infrared spectra are recorded via laser photodissociation and the method of argon tagging. Computational chemistry is employed to investigate structural isomers and their spectra. The acetyl cation (CH3CO+) is the global minimum and protonated ketene (CH2COH+) is the next lowest energy isomer (+176.2 kJ/mol). When methyl acetate is employed as the precursor, the infrared spectrum reveals that only the acetyl cation is formed. Partially resolved rotational structure reveals rotation about the C3 axis. When acetone is used as the precursor, acetyl is still the most abundant cation, but there is also a minor component of protonated ketene. Computations reveal a significant barrier to interconversion between the two isomers (+221 kJ/mol), indicating that protonated ketene must be obtained via kinetic trapping. Both isomers may be present in interstellar environments, and their implications for astrochemistry are discussed.

Enhanced LAW Glass Correlation - Phase 1

Energy Technology Data Exchange (ETDEWEB)

Muller, Isabelle S. [The Catholic Univ. of America, Washington, DC (United States). Vitreous State Lab.; Matlack, Keith S. [The Catholic Univ. of America, Washington, DC (United States). Vitreous State Lab.; Pegg, Ian L. [The Catholic Univ. of America, Washington, DC (United States). Vitreous State Lab.; Joseph, Innocent [Atkins Energy Federal EPC, Inc., Columbia, MD (United States)

2016-12-01

About 50 million gallons of high-level mixed waste is currently stored in underground tanks at the United States Department of Energy’s (DOE’s) Hanford site in the State of Washington. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) will provide DOE’s Office of River Protection (ORP) with a means of treating this waste by vitrification for subsequent disposal. The tank waste will be separated into low- and high-activity waste fractions, which will then be vitrified respectively into Immobilized Low Activity Waste (ILAW) and Immobilized High Level Waste (IHLW) products. The ILAW product will be disposed in an engineered facility on the Hanford site while the IHLW product is designed for acceptance into a national deep geological disposal facility for high-level nuclear waste. The ILAW and IHLW products must meet a variety of requirements with respect to protection of the environment before they can be accepted for disposal. Acceptable glass formulations for vitrification of Hanford low activity waste (LAW) must meet a variety of product quality, processability, and waste loading requirements. To this end, The Vitreous State Laboratory (VSL) at The Catholic University of America (CUA) developed and tested a number of glass formulations during Part A, Part B1 and Part B2 of the WTP development program. The testing resulted in the selection of target glass compositions for the processing of eight of the Phase I LAW tanks. The selected glass compositions were tested at the crucible scale to confirm their compliance with ILAW performance requirements. Duramelter 100 (DM100) and LAW Pilot Melter tests were then conducted to demonstrate the viability of these glass compositions for LAW vitrification at high processing rates.

A Ferrocene-Quinoxaline Derivative as a Highly Selective Probe for Colorimetric and Redox Sensing of Toxic Mercury(II Cations

Directory of Open Access Journals (Sweden)

Antonio Caballero

2010-12-01

Full Text Available A new chemosensor molecule 3 based on a ferrocene-quinoxaline dyad recognizes mercury (II cations in acetonitrile solution. Upon recognition, an anodic shift of the ferrocene/ferrocenium oxidation peaks and a progressive red-shift (Δλ = 140 nm of the low-energy band, are observed in its absorption spectrum. This change in the absorption spectrum is accompanied by a colour change from orange to deep green, which can be used for a “naked-eye” detection of this metal cation.

Ion sieving in graphene oxide membranes via cationic control of interlayer spacing

Science.gov (United States)

Chen, Liang; Shi, Guosheng; Shen, Jie; Peng, Bingquan; Zhang, Bowu; Wang, Yuzhu; Bian, Fenggang; Wang, Jiajun; Li, Deyuan; Qian, Zhe; Xu, Gang; Liu, Gongping; Zeng, Jianrong; Zhang, Lijuan; Yang, Yizhou; Zhou, Guoquan; Wu, Minghong; Jin, Wanqin; Li, Jingye; Fang, Haiping

2017-10-01

Graphene oxide membranes—partially oxidized, stacked sheets of graphene—can provide ultrathin, high-flux and energy-efficient membranes for precise ionic and molecular sieving in aqueous solution. These materials have shown potential in a variety of applications, including water desalination and purification, gas and ion separation, biosensors, proton conductors, lithium-based batteries and super-capacitors. Unlike the pores of carbon nanotube membranes, which have fixed sizes, the pores of graphene oxide membranes—that is, the interlayer spacing between graphene oxide sheets (a sheet is a single flake inside the membrane)—are of variable size. Furthermore, it is difficult to reduce the interlayer spacing sufficiently to exclude small ions and to maintain this spacing against the tendency of graphene oxide membranes to swell when immersed in aqueous solution. These challenges hinder the potential ion filtration applications of graphene oxide membranes. Here we demonstrate cationic control of the interlayer spacing of graphene oxide membranes with ångström precision using K+, Na+, Ca2+, Li+ or Mg2+ ions. Moreover, membrane spacings controlled by one type of cation can efficiently and selectively exclude other cations that have larger hydrated volumes. First-principles calculations and ultraviolet absorption spectroscopy reveal that the location of the most stable cation adsorption is where oxide groups and aromatic rings coexist. Previous density functional theory computations show that other cations (Fe2+, Co2+, Cu2+, Cd2+, Cr2+ and Pb2+) should have a much stronger cation-π interaction with the graphene sheet than Na+ has, suggesting that other ions could be used to produce a wider range of interlayer spacings.

Glass formulation for phase 1 high-level waste vitrification

International Nuclear Information System (INIS)

Vienna, J.D.; Hrma, P.R.

1996-04-01

The purpose of this study is to provide potential glass formulations for prospective Phase 1 High-Level Waste (HLW) vitrification at Hanford. The results reported here will be used to aid in developing a Phase 1 HLW vitrification request for proposal (RFP) and facilitate the evaluation of ensuing proposals. The following factors were considered in the glass formulation effort: impact on total glass volume of requiring the vendor to process each of the tank compositions independently versus as a blend; effects of imposing typical values of B 2 O 3 content and waste loading in HLW borosilicate glasses as restrictions on the vendors (according to WAPS 1995, the typical values are 5--10 wt% B 2 O 3 and 20--40 wt% waste oxide loading); impacts of restricting the processing temperature to 1,150 C on eventual glass volume; and effects of caustic washing on any of the selected tank wastes relative to glass volume

Glass formulation for phase 1 high-level waste vitrification

Energy Technology Data Exchange (ETDEWEB)

Vienna, J.D.; Hrma, P.R.

1996-04-01

The purpose of this study is to provide potential glass formulations for prospective Phase 1 High-Level Waste (HLW) vitrification at Hanford. The results reported here will be used to aid in developing a Phase 1 HLW vitrification request for proposal (RFP) and facilitate the evaluation of ensuing proposals. The following factors were considered in the glass formulation effort: impact on total glass volume of requiring the vendor to process each of the tank compositions independently versus as a blend; effects of imposing typical values of B{sub 2}O{sub 3} content and waste loading in HLW borosilicate glasses as restrictions on the vendors (according to WAPS 1995, the typical values are 5--10 wt% B{sub 2}O{sub 3} and 20--40 wt% waste oxide loading); impacts of restricting the processing temperature to 1,150 C on eventual glass volume; and effects of caustic washing on any of the selected tank wastes relative to glass volume.

Effect of platinoids on French LWR reference glass properties

International Nuclear Information System (INIS)

Pacaud, F.; Fillet, C.; Jacquet-Francillon, N.

1991-01-01

Nine samples of the 'R7T7' glass composition selected to vitrify fission product solutions in France were prepared with added platinoid elements (ruthenium, rhodium and palladium) in soluble form and as insoluble metal particles in solution, and their major properties were measured. Regardless of the initial form when added to the glass the platinoids always formed the same heterogeneous inclusions in the final glass: RuO 2 precipitates which were often found as aggregates, and polymetallic (Pd, Rh and Te) inclusions. The particles tended to settle in the molten glass. The viscosity increased by about 20% at 1100 deg C. The mechanical properties and short-term leach rates were not significantly affected. Crystallization increased by a factor of 2 or 3 in heat-treated glass specimens but did not exceed a few volume percent. However, as the short-term leach rate did not significantly increase, the glass properties were very satisfactory

Isomerization of propargyl cation to cyclopropenyl cation ...

Indian Academy of Sciences (India)

step) for isomeri- zation of the linear propargyl cation to ..... C3, C4 and C5. The ZPE corrections in each case are derived from the. B3LYP calculations. ..... the converse of which gives the relative capacity of the. LPD's to stabilize TS6 with respect ...

Investigation on Compressive Strength of Special Concrete made with Crushed Waste Glass

Directory of Open Access Journals (Sweden)

Mohd Sani Mohd Syahrul Hisyam

2015-01-01

Full Text Available Special concrete is the type of concrete that produced by using waste material or using unusual techniques/method of preparation. Special concrete made with waste material is becoming popular in a construction site. This is because the special concrete is selected due to quality, integrity, economic factor and environmental factor. The waste glass is selected as an additional material to provide a good in compressive strength value. The compressive strength is the importance of mechanical properties of concrete and typically the concrete is sustained and stiffed in compression load. The significant issue to utilize the waste glass from the automotive windscreen is to improve the strength of concrete. The waste glass is crushed to become 5 mm size and recognised as crushed waste glass that be used in concrete as additional material. The main objective of the study is to determine the appropriate percentage of crushed waste glass in concrete grade, 30 in order to enhance the compressive strength. There are four mixes of concrete that contained of crushed waste glass with percentage of 2 %, 4 %, 6 % and 8 % and one control mix with 0 % of crushed waste glass. As the result, crushed waste glass with an additional 4 % in concrete is reported having a higher value of compressive strength in early and mature stage. In addition, if the percentage of crushed glass wastes in concrete increases and it leads to a reduction in the workability of concrete.

Atomic layer deposition of alternative glass microchannel plates

Energy Technology Data Exchange (ETDEWEB)

O' Mahony, Aileen, E-mail: aom@incomusa.com; Craven, Christopher A.; Minot, Michael J.; Popecki, Mark A.; Renaud, Joseph M.; Bennis, Daniel C.; Bond, Justin L.; Stochaj, Michael E.; Foley, Michael R.; Adams, Bernhard W. [Incom, Inc., 294 Southbridge Road, Charlton, Massachusetts 01507 (United States); Mane, Anil U.; Elam, Jeffrey W. [Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439 (United States); Ertley, Camden; Siegmund, Oswald H. W. [Space Sciences Laboratory, University of California, 7 Gauss Way, Berkeley, California 94720 (United States)

2016-01-15

The technique of atomic layer deposition (ALD) has enabled the development of alternative glass microchannel plates (MCPs) with independently tunable resistive and emissive layers, resulting in excellent thickness uniformity across the large area (20 × 20 cm), high aspect ratio (60:1 L/d) glass substrates. Furthermore, the use of ALD to deposit functional layers allows the optimal substrate material to be selected, such as borosilicate glass, which has many benefits compared to the lead-oxide glass used in conventional MCPs, including increased stability and lifetime, low background noise, mechanical robustness, and larger area (at present up to 400 cm{sup 2}). Resistively stable, high gain MCPs are demonstrated due to the deposition of uniform ALD resistive and emissive layers on alternative glass microcapillary substrates. The MCP performance characteristics reported include increased stability and lifetime, low background noise (0.04 events cm{sup −2} s{sup −1}), and low gain variation (±5%)

Effects of solar radiation on glass

Science.gov (United States)

Tucker, Dennis S.; Kinser, Donald L.

1991-01-01

The effects of solar radiation of selected glasses are reported. Optical property degradation is studied using UV-Vis spectrophotometry. Strength changes are measured using a concentric ring bend test. Direct fracture toughness measurements using an indentation test are planned.

Bio-active glass air-abrasion has the potential to remove resin composite restorative material selectively

Energy Technology Data Exchange (ETDEWEB)

Milly, Hussam [Biomaterials, Biomimetics and Biophotonics Research Group, Kings College London Dental Institute at Guy' s Hospital, King' s Health Partners, London (United Kingdom); Andiappan, Manoharan [Unit of Dental Public Health, Kings College London Dental Institute at Guy' s Hospital, King' s Health Partners, London (United Kingdom); Thompson, Ian [Biomaterials, Biomimetics and Biophotonics Research Group, Kings College London Dental Institute at Guy' s Hospital, King' s Health Partners, London (United Kingdom); Banerjee, Avijit, E-mail: avijit.banerjee@kcl.ac.uk [Biomaterials, Biomimetics and Biophotonics Research Group, Kings College London Dental Institute at Guy' s Hospital, King' s Health Partners, London (United Kingdom); Unit of Conservative Dentistry, King' s College London Dental Institute at Guy' s Hospital, King' s Health Partners, London (United Kingdom)

2014-06-01

The aims of this study were to assess: (a) the chemistry, morphology and bioactivity of bio-active glass (BAG) air-abrasive powder, (b) the effect of three air-abrasion operating parameters: air pressure, powder flow rate (PFR) and the abrasive powder itself, on the selective removal of resin composite and (c) the required “time taken”. BAG abrasive particles were characterised using scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX) and Fourier-transform infrared spectroscopy (FTIR). Standardised resin composite restorations created within an enamel analogue block (Macor™) in vitro, were removed using air-abrasion undersimulated clinical conditions. 90 standardised cavities were scanned before and after resin composite removal using laser profilometry and the volume of the resulting 3D images calculated. Multilevel linear model was used to identify the significant factors affecting Macor™ removal. BAG powder removed resin composite more selectively than conventional air-abrasion alumina powder using the same operating parameters (p < 0.001) and the effect of altering the unit's operating parameters was significant (p < 0.001). In conclusion, BAG powder is more efficient than alumina in the selective removal of resin composite particularly under specific operating parameters, and therefore may be recommended clinically as a method of preserving sound enamel structure when repairing and removing defective resin composite restorations.

IMPACTS OF SMALL COLUMN ION EXCHANGE STREAMS ON DWPF GLASS FORMULATION: KT01, KT02, KT03, AND KT04-SERIES GLASS COMPOSITIONS

Energy Technology Data Exchange (ETDEWEB)

Fox, K.; Edwards, T.

2010-11-01

Four series of glass compositions were selected, fabricated, and characterized as part of a study to determine the impacts of the addition of Crystalline Silicotitanate (CST) and Monosodium Titanate (MST) from the Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) glass waste form and the applicability of the DWPF process control models. The KT01 and KT02-series of glasses were chosen to allow for the identification of the influence of the concentrations of major components of the glass on the retention of TiO{sub 2}. The KT03 series of glasses was chosen to allow for the identification of these influences when higher Nb{sub 2}O{sub 5} and ZrO{sub 2} concentrations are included along with TiO2. The KT04 series of glasses was chosen to investigate the properties and performance of glasses based on the best available projections of actual compositions to be processed at the DWPF (i.e., future sludge batches including the SCIX streams).

Evaluation of shielding parameters for heavy metal fluoride based tellurite-rich glasses for gamma ray shielding applications

Science.gov (United States)

Sayyed, M. I.; Lakshminarayana, G.; Kityk, I. V.; Mahdi, M. A.

2017-10-01

In this work, we have evaluated the γ-ray shielding parameters such as mass attenuation coefficient (μ/ρ), effective atomic number (Zeff), half value layer (HVL), mean free path (MFP) and exposure buildup factors (EBF) for heavy metal fluoride (PbF2) based tellurite-rich glasses. In addition, neutron total macroscopic cross sections (∑R) for these glasses were also calculated. The maximum value for μ/ρ, Zeff and ∑R was found for heavy metal (Bi2O3) oxide introduced glass. The results of the selected glasses have been compared, in terms of MFP with different glass systems. The shielding effectiveness of the selected glasses is found comparable or better than of common ones, which indicates that these glasses with suitable oxides could be developed for gamma ray shielding applications.

Final Report. Baseline LAW Glass Formulation Testing, VSL-03R3460-1, Rev. 0

Energy Technology Data Exchange (ETDEWEB)

Muller, Isabelle S. [The Catholic University of America, Washington, DC (United States); Pegg, Ian L. [The Catholic University of America, Washington, DC (United States); Gan, Hao [The Catholic University of America, Washington, DC (United States); Buechele, Andrew [The Catholic University of America, Washington, DC (United States); Rielley, Elizabeth [The Catholic University of America, Washington, DC (United States); Bazemore, Gina [The Catholic University of America, Washington, DC (United States); Cecil, Richard [The Catholic University of America, Washington, DC (United States); Hight, Kenneth [The Catholic University of America, Washington, DC (United States); Mooers, Cavin [The Catholic University of America, Washington, DC (United States); Lai, Shan-Tao T. [The Catholic University of America, Washington, DC (United States); Kruger, Albert A. [The Catholic University of America, Washington, DC (United States)

2015-06-18

The major objective of the baseline glass formulation work was to develop and select glass formulations that are compliant with contractual and processing requirements for each of the LAW waste streams. Other objectives of the work included preparation and characterization of glasses with respect to the properties of interest, optimization of sulfate loading in the glasses, evaluation of ability to achieve waste loading limits, testing to demonstrate compatibility of glass melts with melter materials of construction, development of glass formulations to support ILAW qualification activities, and identification of glass formulation issues with respect to contract specifications and processing requirements.

Electrochromic Glasses.

Science.gov (United States)

1980-07-31

this glass and that dipole-dipole correlations contribute to the "ferroelectric-like" character of this amorphous system. The TeO2 -W03 glasses can only...shows the dielectric constant and Fig. I(b) glass from pure TeO2 ot pure WO. In addition, glass the tan 8 of the WO glass as a function of temperature... glasses containing WO, in various glass forming nitworks of LifO-B1O0, Na:O-BzO,, and TeO2 were prepared from reagent grade oxides at 800 C - 9SO C in

Development of a low-permeability glass--ceramic to seal to molybdenum

International Nuclear Information System (INIS)

Eagan, R.J.

1975-03-01

This report describes the development of low-permeability glass-ceramics which can be sealed directly to molybdenum for the purpose of producing long-life vacuum tubes. Low permeability to helium and thermal expansion match to molybdenum are the bases upon which particular glass-ceramic compositions were selected and developed. The fabrication of tube envelopes using glass-ceramics is simplified when compared to conventional ceramic/metal tubes and these melting and sealing techniques are presented

Luminescent sulfides of monovalent and trivalent cations

International Nuclear Information System (INIS)

1975-01-01

The invention discloses a family of luminescent materials or phosphors having a rhombohedral crystal structure and consisting essentially of a mixed host sulfide of at least one monovalent host cation and at least one trivalent host cation, and containing, for each mole of phosphor, 0.0005 to 0.05 mole of at least one activating cation. The monovalent host cations may be Na, K or Rb and Cs. The trivalent host cations may be Gd, La, Lu, Sc and Y. The activating cations may be one or more of trivalent As, Bi, Ce, Dy, Er, Pr, Sb, Sm, Tb and Tm; divalent Lu, Mn, Pb and Sn; and monovalent Ag, Cu and Tl. The novel phosphors may be used in devices to convert electron-beam, ultraviolet or x-ray energy to light in the visible spectrum. Such energy conversion can be employed for example in fluoroscopic screens, and in viewing screens of cathode-ray tubes and other electron tubes

Application of ABTS radical cation for selective on-line detection of radical scavengers in HPLC eluates

NARCIS (Netherlands)

Koleva, [No Value; Niederlander, HAG; van Beek, TA

2001-01-01

The radical cation 2,2 ' -azinobis-(3 -ethylbenzothiazoline-6-sulfonate), (ABTS(.+)) was utilized in an on-line HPLC method for the detection of radical scavengers in complex matrixes. The HPLC-separated analytes react postcolumn with the preformed ABTS(.+), and the induced bleaching is detected as

Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light.

Science.gov (United States)

Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

2015-04-28

Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe(3+)>Al(3+)>Cu(2+)>Ca(2+)>K(+)>Na(+), which is consistent with the binding energy of cation-π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation-π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na(+)-smectite and K(+)-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe(3+), Al(3+), and Cu(2+) are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O2(-) , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

Antibacterial effects and dissolution behavior of six bioactive glasses.

Science.gov (United States)

Zhang, Di; Leppäranta, Outi; Munukka, Eveliina; Ylänen, Heimo; Viljanen, Matti K; Eerola, Erkki; Hupa, Mikko; Hupa, Leena

2010-05-01

Dissolution behavior of six bioactive glasses was correlated with the antibacterial effects of the same glasses against sixteen clinically important bacterial species. Powdered glasses (<45 microm) were immersed in simulated body fluid (SBF) for 48 h. The pH in the solution inside the glass powder was measured in situ with a microelectrode. After 2, 4, 27, and 48 h, the pH and concentration of ions after removing the particles and mixing the SBF were measured with a normal glass pH electrode and ICP-OES. The bacteria were cultured in broth with the glass powder for up to 4 days, after which the viability of the bacteria was determined. The antibacterial effect of the glasses increased with increasing pH and concentration of alkali ions and thus with increased dissolution tendency of the glasses, but it also depended on the bacterium type. The changes in the concentrations of Si, Ca, Mg, P, and B ions in SBF did not show statistically significant influence on the antibacterial property. Bioactive glasses showed strong antibacterial effects for a wide selection of aerobic bacteria at a high sample concentration (100 mg/mL). The antibacterial effects increased with glass concentration and a concentration of 50 mg/mL (SA/V 185 cm(-1)) was required to generate the bactericidal effects. Understanding the dissolution mechanisms of bioactive glasses is essential when assessing their antibacterial effects. Copyright 2009 Wiley Periodicals, Inc.

Calix[6]arenes functionalized with malondiamides at the upper rim as possible extractants for lanthanide and actinide cations

International Nuclear Information System (INIS)

Almaraz, M.; Esperanza, S.; Magrans, O.; Mendoza, J. de; Pradus, P.

2001-01-01

Lipophilic malondiamides have been recently employed successfully as extractants for lanthanide and actinide cations from strongly acidic media. Many complexes between malondiamides and lanthanide-actinides cations have been studied by different techniques. For many of these complexes it has been observed that more than one malondiamide ligand participates in the complexation of each metallic cation. Incorporation of two or three malondiamide moieties into a calixarene platform would probably improve both extraction and selectivity with respect to the already tested malondiamides. According to CPK examination, a calix[6]arene substituted at the upper rim with two or three malondiamide moieties should constitute a promising ligand for lanthanide and actinide cations due to co-operative complexation with the malondiamides. Based on these considerations, we synthesised calix[6]arenes functionalized with malonic acid derivatives. (author)

Radiochemical study of isomerization of free butyl cations

International Nuclear Information System (INIS)

Sinotova, E.N.; Nefedov, V.D.; Skorokhodov, S.S.; Arkhipov, Yu.M.

1987-01-01

Ion-molecular reactions of free butyl cations, generated by nuclear chemical method, with carbon monoxide containing small quantities of ethanol vapors are studied. Carbon monoxide was used to fix instable butyl cations in the form of corresponding acyl ions. Ester of α-methyl-butyric acid appears to be the only product of free butyl cation interaction with carbon monoxide in the presence of ethanol vapors. That means, that up to the moment of butyl cation reaction with carbon monoxide, the primary butyl cations are almost completely isomerized into secondary in agreement with results of previous investigations. This allows one to study free butyl cation isomerization process according to ion-molecular reaction product isomeric composition

Gas phase chemistry of N-benzylbenzamides with silver(I) cations: characterization of benzylsilver cation.

Science.gov (United States)

Sun, Hezhi; Jin, Zhe; Quan, Hong; Sun, Cuirong; Pan, Yuanjiang

2015-03-07

The benzylsilver cation which emerges from the collisional dissociation of silver(I)-N-benzylbenzamide complexes was characterized by deuterium-labeling experiments, theoretical calculations, breakdown curves and substituent effects. The nucleophilic attack of the carbonyl oxygen on an α-hydrogen results in the generation of the benzylsilver cation, which is competitive to the AgH loss with the α-hydrogen.

X-ray absorption and Raman spectroscopy studies of molybdenum environments in borosilicate waste glasses

Science.gov (United States)

McKeown, David A.; Gan, Hao; Pegg, Ian L.

2017-05-01

Mo-containing high-level nuclear waste borosilicate glasses were investigated as part of an effort to improve Mo loading while avoiding yellow phase crystallization. Previous work showed that additions of vanadium decrease yellow phase formation and increases Mo solubility. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to characterize Mo environments in HLW borosilicate glasses and to investigate possible structural relationships between Mo and V. Mo XAS spectra for the glasses indicate isolated tetrahedral Mo6+O4 with Mo-O distances near 1.75 Å. V XANES indicate tetrahedral V5+O4 as the dominant species. Raman spectra show composition dependent trends, where Mo-O symmetrical stretch mode frequencies (ν1) are sensitive to the mix of alkali and alkaline earth cations, decreasing by up to 10 cm-1 for glasses that change from Li+ to Na+ as the dominant network-modifying species. This indicates that MoO4 tetrahedra are isolated from the borosilicate network and are surrounded, at least partly, by Na+ and Li+. Secondary ν1 frequency effects, with changes up to 7 cm-1, were also observed with increasing V2O5 and MoO3 content. These secondary trends may indicate MoO4-MoO4 and MoO4-VO4 clustering, suggesting that V additions may stabilize Mo in the matrix with respect to yellow phase formation.

Fiscal 1976 Sunshine Project result report. R and D on solar cooling/heating and hot water supply system (R and D on glass system materials); 1976 nendo taiyo reidanbo oyobi kyuto system no kenkyu kaihatsu seika hokokusho. Glass kei zairyo no kenkyu kaihatsu

Energy Technology Data Exchange (ETDEWEB)

NONE

1977-03-01

This report describes the fiscal 1976 research result on solar heat collectors using glass system materials. In fiscal 1976, study was made on improvement of selective transmission films by vacuum deposition and large prototype films, prototype coated glass by chemical treatment and its quality stability, prototype full-scale honeycomb collector, practical heat collection property, and evaluation of some problems. As the study result, characteristics of this selective transmission glass were equivalent to those of the other selective transmission films with a transmissivity of 0.90 and a reflectivity of 0.10. As the study result of production cost by vacuum deposition and resistance heating, the film treatment cost was estimated to be 2,300yen/m{sup 2}. 40 prototype coated glass plates of 1,000 x 1,000 x 3mm, and 300 prototype coated glass pipes of 16mm diameter, 870mm long and 0.6mm thick were prepared for prototype collectors. Two kinds of full-scale collectors prepared by using these selective absorption heat collection plates and coated glass showed favorable performance in heat collection experiment. (NEDO)

Sulphate solubility and sulphate diffusion in oxide glasses: implications for the containment of sulphate-bearing nuclear wastes; Solubilite et cinetiques de diffusion des sulfates dans differents verres d'oxydes: application au conditionnement des dechets nucleaires sulfates

Energy Technology Data Exchange (ETDEWEB)

Lenoir, M.

2009-09-15

The thesis deals with sulphate solubility and sulphate diffusion in oxide glasses, in order to control sulphate incorporation and sulphate volatilization in nuclear waste glasses. It was conducted on simplified compositions, in the SiO{sub 2}-B{sub 2}O{sub 3}-R{sub 2}O (R = Li, Na, K, Cs), SiO{sub 2}-B{sub 2}O{sub 3}-BaO and V{sub 2}O{sub 5}-B{sub 2}O{sub 3}-BaO systems. These compositions allowed us to study the influence of the nature of network-modifying ions (Li{sup +}, Na{sup +}, K{sup +}, Cs{sup +} or Ba{sup 2+}) and also of former elements (Si, B, V), on structure and properties of glasses. Sulphate volatility is studied in sodium borosilicate melts using an innovative technique of sulphate quantitation with Raman spectroscopy. This technique is useful to obtain kinetic curves of sulphate volatilization. The establishment of a model to fit these curves leads to the determination of diffusion coefficients of sulphate. These diffusion coefficients can thus be compared to diffusion coefficients of other species, determined by other techniques and presented in the literature. They are also linked to diffusion coefficients in relation with the viscosity of the melts. Concerning sulphate solubility in glasses, it depends on glass composition and on the nature of sulphate incorporated. Sulphate incorporation in alkali borosilicate glasses leads to the formation of a sulphate layer floating on top of the melt. Sulphate incorporation in barium borosilicate and boro-vanadate glasses leads to the crystallization of sulphate species inside the vitreous matrix. Moreover, sulphate solubility is higher in these glasses than in alkali borosilicates. Finally, exchanges between cations present in glasses and cations present in the sulphate phase are also studied. (author)

Relaxations in spin glasses: Similarities and differences from ordinary glasses

International Nuclear Information System (INIS)

Ngai, K.L.; Rajagopal, A.K.; Huang, C.Y.

1984-01-01

Relaxation phenomena have become a major concern in the physics of spin glasses. There are certain resemblances of these relaxation properties to those of ordinary glasses. In this work, we compare the relaxation properties of spin glasses near the freezing temperature with those of glasses near the glass transition temperature. There are similarities between the two types of glasses. Moreover, the relaxation properties of many glasses and spin glasses are in conformity with two coupled ''universality'' relations predicted by a recent model of relaxations in condensed matter

Cation-Dependent Gold Recovery with α-Cyclodextrin Facilitated by Second-Sphere Coordination.

Science.gov (United States)

Liu, Zhichang; Samanta, Avik; Lei, Juying; Sun, Junling; Wang, Yuping; Stoddart, J Fraser

2016-09-14

Herein, we report an alkali metal cation-dependent approach to gold recovery, facilitated by second-sphere coordination with eco-friendly α-cyclodextrin (α-CD). Upon mixing eight salts composed of Na(+), K(+), Rb(+), or Cs(+) cations and [AuX4](-) (X = Cl/Br) anions with α-, β-, or γ-CD in water, co-precipitates form selectively from the three (out of 24) aqueous solutions containing α-CD with KAuBr4, RbAuBr4, and CsAuBr4, from which the combination of α-CD and KAuBr4 affords the highest yield. Single-crystal X-ray analyses reveal that in 20 of the 24 adducts CD and [AuX4](-) anions form 2:1 sandwich-type second-sphere adducts driven partially by [C-H···X-Au] interactions between [AuX4](-) anions and the primary faces of two neighboring CDs. In the adduct formed between α-CD and KAuBr4, a [K(OH2)6](+) cation is encapsulated inside the cavity between the secondary faces of two α-CDs, leading to highly efficient precipitation owing to the formation of a cation/anion alternating ion wire residing inside a continuous α-CD nanotube. By contrast, in the other 19 adducts, the cations are coordinated by OH groups and glucopyranosyl ring O atoms in CDs. The strong coordination of Rb(+) and Cs(+) cations by these ligands, in conjunction with the stereoelectronically favorable binding of [AuBr4](-) anions with two α-CDs, facilitates the co-precipitation of the two adducts formed between α-CD with RbAuBr4 and CsAuBr4. In order to develop an efficient process for green gold recovery, the co-precipitation yield of α-CD and KAuBr4 has been optimized regarding both the temperature and the molar ratio of α-CD to KAuBr4.

Towards green buildings: Glass as a building element-the use and misuse in the gulf region

Energy Technology Data Exchange (ETDEWEB)

Aboulnaga, Mohsen M. [College of Design and Applied Arts, Dubai University College, Dubai P.O. Box 14143 (United Arab Emirates)

2006-04-15

The recent economic growth in the Gulf region notably in Dubai, United Arab Emirates (UAE) has led to a colossal number of buildings that has been constructed in the past 5 years. In the last decade, a total glazed building's facades became the icon of Dubai. This large area of glazing in each facade needs protection against overheating and sun glare in summer. According to leader in energy and environmental design (LEED) glass selection becomes a main element in this equation to contribute towards achieving a green building. The aim of this paper is to investigate the problems associated with misuse of glass, as a building element in UAE particularly in Dubai. Inadequate design with ill-selected glass/glazing type may lead not only to poor daylighting in building interiors but also contribute significantly to fatigue, insomnia, seasonal affective disorder (SAD) and above all increase CO{sub 2} emission. The purpose of the study is to specify the required improvements to permit natural, 'free' daylight to filter through the building facade into interior space, especially with the right type of glass. This paper examines the status of buildings in Dubai in terms of glass type, visible light transmittance, reflection (out/in) and relative heat gain. A quantitative analysis is conducted to assess the impact of glass on the building users' performance in terms of daylight environment. A recent built high-rise office building was selected in the investigation to asses whether selected glass provide the recommended daylight factor (DF) and daylight level (DL) according to IES standards. The results revealed that most the glass/glazing was misused in 70% of buildings in intermediate and low performance groups. The DF and DD in the selected office building were unexpectedly tremendous and found far beyond the recommended level due to the use of spectrally selective glazing (clear on both sides). [Author].

Comparison of the Amount of Fluoride Release from Nanofilled Resin Modified Glass Ionomer Conventional and Resin Modified Glass Ionomer Cements

Directory of Open Access Journals (Sweden)

Sumitha Upadhyay

2013-01-01

Full Text Available Objective: To investigate and compare the amount of fluoride release of conventional, resin modified and nanofilled resin modified glass ionomer cements.Materials and Methods: Tablets of glass-ionomer cements were immersed in deionized water and incubated at 37◦C. After 1, 2, 7, 15 and 30 days, fluoride ion was measured under normal atmospheric conditions by fluoride ion selective electrode. Buffer (TISAB II was used to decomplex the fluoride ion and to provide a constant background ionic strength and to maintain the pH of water between 5.0 and 5.5 as the fluoride electrode is sensitive to changes in pH. Statistical evaluation was carried out by one way ANOVA (Analysis of Variance using SPSS 11.0. The significance level was set at p< 0.05.Results: The release of fluoride was highest on day 1 and there was a sudden fall on day 2 in all three groups. Initially fluoride release from conven-tional glass-ionomer cement was highest compared to the other two glass-ionomer cements, but the amount drastically reduced over the period. Although the amount of fluoride release was less than both the resin modified and nanofilled resin modified glass-ionomer cement, the release was sustained consistently for 30 daysConclusion: The cumulative fluoride release of nanofilled resin modified glass ionomer cement was very less compared to the conventional and resin modified glass ionomer cements and Nanofilled resin modified glass ionomer cement released less but steady fluoride as compared to other resin modified glass ionomer cements.

Cationic uremic toxins affect human renal proximal tubule cell functioning through interaction with the organic cation transporter.

Science.gov (United States)

Schophuizen, Carolien M S; Wilmer, Martijn J; Jansen, Jitske; Gustavsson, Lena; Hilgendorf, Constanze; Hoenderop, Joost G J; van den Heuvel, Lambert P; Masereeuw, Rosalinde

2013-12-01

Several organic cations, such as guanidino compounds and polyamines, have been found to accumulate in plasma of patients with kidney failure due to inadequate renal clearance. Here, we studied the interaction of cationic uremic toxins with renal organic cation transport in a conditionally immortalized human proximal tubule epithelial cell line (ciPTEC). Transporter activity was measured and validated in cell suspensions by studying uptake of the fluorescent substrate 4-(4-(dimethylamino)styryl)-N-methylpyridinium-iodide (ASP(+)). Subsequently, the inhibitory potencies of the cationic uremic toxins, cadaverine, putrescine, spermine and spermidine (polyamines), acrolein (polyamine breakdown product), guanidine, and methylguanidine (guanidino compounds) were determined. Concentration-dependent inhibition of ASP(+) uptake by TPA, cimetidine, quinidine, and metformin confirmed functional endogenous organic cation transporter 2 (OCT2) expression in ciPTEC. All uremic toxins tested inhibited ASP(+) uptake, of which acrolein required the lowest concentration to provoke a half-maximal inhibition (IC50 = 44 ± 2 μM). A Dixon plot was constructed for acrolein using three independent inhibition curves with 10, 20, or 30 μM ASP(+), which demonstrated competitive or mixed type of interaction (K i = 93 ± 16 μM). Exposing the cells to a mixture of cationic uremic toxins resulted in a more potent and biphasic inhibitory response curve, indicating complex interactions between the toxins and ASP(+) uptake. In conclusion, ciPTEC proves a suitable model to study cationic xenobiotic interactions. Inhibition of cellular uptake transport was demonstrated for several uremic toxins, which might indicate a possible role in kidney disease progression during uremia.

Preliminary Testing For Anionic, Cationic and Non-ionic

Directory of Open Access Journals (Sweden)

Bokic, Lj.

2007-11-01

Full Text Available Detergents present a major environmental problem due to large quantities of surfactants released from laundries. For this reason, it is important to apply an appropriate analytical method for their determination. In this work, we propose two simple, fast and inexpensive analytical methods for anionic, cationic and non-ionic surfactant determination: thin layer chromatography (TLC separation for qualitative screening and quantitative potentiometric determination with ion-selective electrodes. These methods have been chosen because of their many advantages: rapidity, ease of operation, low cost of analysis and a wide variety of TLC application possibilities. The advantage of potentiometric titration is its very high degree of automation and very low detection limits obtained with different ion-selective electrodes applied for different surfactants.

Electronic spectra of astrophysically interesting cations

Energy Technology Data Exchange (ETDEWEB)

Maier, John P., E-mail: j.p.maier@unibas.ch; Rice, Corey A., E-mail: j.p.maier@unibas.ch; Mazzotti, Fabio J., E-mail: j.p.maier@unibas.ch; Johnson, Anatoly, E-mail: j.p.maier@unibas.ch [Department of Chemistry, University of Basel, Klingelbergstr. 80, CH-4056 Basel (Switzerland)

2015-01-22

The electronic spectra of polyacetylene cations were recorded at 20K in the laboratory in an ion trap instrument. These can then be compared with diffuse interstellar band (DIB) absorptions. Examination of recently published data shows that the attribution of a weak DIB at ∼506.9 nm to diacetylene cation is not justified. Study of the higher excited electronic states of polyacetylene cations shows that their widths can still be sufficiently narrow for consideration as DIB carriers.

How the cation-cation π-π stacking occurs: A theoretical investigation into ionic clusters of imidazolium.

Science.gov (United States)

Gao, Wei; Tian, Yong; Xuan, Xiaopeng

2015-07-01

The cation-cation π-π stacking is uncommon but it is essential for the understanding of some supramolecular structures. We explore theoretically the nature of non-covalent interaction occurring in the stacked structure within modeled clusters of 1,3-dimethylimidazolium and halide. The evidences of the energy decomposition analysis (EDA) and reduced density gradient (RDG) approach are different from those of common π-π interaction. Isosurfaces with RDG also illustrate the strength of the titled π-π interaction and their region. Additionally, we find that the occurrence of this interaction is attributed to a few C-H···X interactions, as depicted using atom in molecule (AIM) method. This work presents a clear picture of the typical cation-cation π-π interaction and can serve to advance the understanding of this uncommon interaction. Copyright © 2015 Elsevier Inc. All rights reserved.

Influence of the substitution of β-cyclodextrins by cationic groups on the complexation of organic anions

International Nuclear Information System (INIS)

Hbaieb, S.; Kalfat, R.; Chevalier, Y.; Amdouni, N.; Parrot-Lopez, H.

2008-01-01

The inclusion complexation of the organic anion, dansyl-acid, by cationic derivatives of β-cyclodextrin has been investigated. A series of cationic β-cyclodextrins with various positive charge has been synthesized by selective functionalization of the primary face of β-cyclodextrin with amino groups. The complexes were of the 1:1 stoichiometry; the stability constants (K 11 ) have been evaluated from UV-Vis measurements by application of the Benesi-Hildebrand equation. The presence of amino groups increased the complexation ability. β-cyclodextrin fully substituted at the primary face with amino groups showed the strongest inclusion binding ability towards the dansyl-acid guest. The enhanced complexation for anions was ascribed to the cationic amino groups. A simple thermodynamic model of the electrostatic contribution to the complexation is presented

Glass science tutorial: Lecture No. 7, Waste glass technology for Hanford

International Nuclear Information System (INIS)

Kruger, A.A.

1995-07-01

This paper presents the details of the waste glass tutorial session that was held to promote knowledge of waste glass technology and how this can be used at the Hanford Reservation. Topics discussed include: glass properties; statistical approach to glass development; processing properties of nuclear waste glass; glass composition and the effects of composition on durability; model comparisons of free energy of hydration; LLW glass structure; glass crystallization; amorphous phase separation; corrosion of refractories and electrodes in waste glass melters; and glass formulation for maximum waste loading

Complementary methods to study glasses and melts at large scale facilities

International Nuclear Information System (INIS)

Leydier, M.

2010-01-01

In this work, large scale facilities (neutron and synchrotron sources) were used for studying the structure and dynamic of disordered materials (liquids and glasses). In particular, three studies are presented. The first is a structural study of Ln 2 O 3 -Al 2 O 3 -SiO 2 glasses where Ln represents the cations Sc, Y and La. We combined the results obtained from x-ray and neutron diffraction and x-ray absorption experiments. This work is focused on the determination of the interatomic distances and coordination numbers for the three pairs Si-O, Al-O and Ln-O. The second is a study of the iron oxide FeO in the liquid state. Photoemission experiments at the iron absorption edge were associated with x-ray and neutron diffraction measurements. The results obtained made it possible to define a consistent structural model for liquid FeO. The third is a study of the dynamics in CaAl 2 O 4 melts. From inelastic x-ray scattering experiments, it was possible to determine the apparent and isothermal sound velocities as well as the longitudinal viscosity. These measurements were complemented by quasielastic neutron scattering experiments from which atomic diffusion coefficients were determined. This work shows the interest of combining various experimental techniques for studying glasses and melts and points out the need to associate also modelling techniques such as molecular dynamics simulations. (author)

Effect of different glass and zeolite A compositions on the leach resistance of ceramic waste forms

International Nuclear Information System (INIS)

Lewis, M.A.; Hash, M.; Glandorf, D.

1996-01-01

A ceramic waste form is being developed for waste generated during electrometallurgical treatment of spent nuclear fuel. The waste is generated when fission products are removed from the electrolyte, LiCl-KCl eutectic. The waste form is a composite fabricated by hot isostatic pressing a mixture of glass frit and zeolite occluded with fission products and salt. Normalized release rate is less than 1 g/m 2 d for all elements in MCC-1 leach test run for 28 days in deionized water at 90 C. This leach resistance is comparable to that of early Savannah River glasses. We are investigating how leach resistance is affected by changes in cationic form of zeolite and in glass composition. Composites were made with 3 forms of zeolite A and 6 glasses. We used 3-day ASTM C1220-92 (formerly MCC-1) leach tests to screen samples for development purposes only. The leach test results show that the glass composites of zeolites 5A and 4A retain fission products equally well. Loss of Cs is small (0.1-0.5 wt%), while the loss of divalent and trivalent fission products is one or more orders of magnitude smaller. Composites of 5A retain chloride ion better in these short-term screens than 4A and 3A. The more leach resistant composites were made with durable glasses rich in silica and poor in alkaline earth oxides. XRD show that a salt phase was absent in the leach resistant composites of 5A and the better glasses but was present in the other composites with poorer leach performance. Thus, absence of salt phase corresponds to improved leach resistance. Interactions between zeolite and glass depend on composition of both