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Sample records for glass forming liquids

  1. Dynamics of glass-forming liquids

    DEFF Research Database (Denmark)

    Hansen, Henriette Wase

    on alpha relaxation dynamics, and for the two van der Waals liquids, also when we have separation of timescales, i.e. the alpha relaxation is not contributing to the picosecond dynamics. The concept of isomorphs is observed to break down in two cases for the hydrogen bonding system: in density scaling......The overall theme of this work has been to experimentally test the shoving model and isomorph theory related to the dynamics of glass-forming liquids, both of which, rather than being universal explanations, are expected to work in the simplest case. We test the connection between fast and slow...... dynamics in light of the shoving model from the temperature dependence of the mean-squared displacement from neutron scattering at nanosecond timescale and the elastic modulus from shear mechanics. We find the fast dynamics to correlate with the alpha relaxation time and fragility in agreement...

  2. Binary eutectic clusters and glass formation in ideal glass-forming liquids

    International Nuclear Information System (INIS)

    Lu, Z. P.; Shen, J.; Xing, D. W.; Sun, J. F.; Liu, C. T.

    2006-01-01

    In this letter, a physical concept of binary eutectic clusters in 'ideal' glass-forming liquids is proposed based on the characteristics of most well-known bulk metallic glasses (BMGs). The authors approach also includes the treatment of binary eutectic clusters as basic units, which leads to the development of a simple but reliable method for designing BMGs more efficiently and effectively in these unique glass-forming liquids. As an example, bulk glass formers with superior glass-forming ability in the Zr-Ni-Cu-Al and Zr-Fe-Cu-Al systems were identified with the use of the strategy

  3. Glass-forming liquids: one or more "order" parameters"

    DEFF Research Database (Denmark)

    Bailey, Nicholas; Christensen, Tage Emil; Jakobsen, Bo

    2008-01-01

    We first summarize the classical arguments that the vast majority of glass-forming liquids require more than one ‘order' parameter for their description. Critiques against this conventional wisdom are then presented, and it is argued that the matter deserves to be reconsidered in the light...... that a description with a single "order" parameter applies to a good approximation whenever thermal equilibrium fluctuations of fundamental variables like energy and pressure are strongly correlated. Results from computer simulations showing that this is the case for a number of simple glass-forming liquids, as well...

  4. Glass-Forming Ability of Soda Lime Borate Liquids

    DEFF Research Database (Denmark)

    Zheng, Qiuju; Mauro, J.C.; Smedskjær, Morten Mattrup

    2012-01-01

    We investigate the composition dependence of glass-forming ability (GFA) of a series of iron-containing soda lime borate liquids by substituting Na2O for B2O3. We have characterized GFA by measuring the glass stability against crystallization using a differential scanning calorimeter (DSC......). The results show that the GFA decreases when substituting Na2O for B2O3. Moreover, we find that there is no direct link between the kinetic fragility and GFA for the soda lime borate series studied herein. We have also discovered and clarified a striking thermal history dependence of the glass stability...

  5. Measuring the Thermophysical and Structural Properties of Glass-Forming and Quasicrystal-Forming Liquids

    Science.gov (United States)

    Hyers, Robert W.; Bradshaw, Richard C.; Rogers, Jan R.; Gangopadhyay, Anup K.; Kelton, Ken F.

    2006-01-01

    The thermophysical properties of glass-forming and quasicrystal-forming alloys show many interesting features in the undercooled liquid range. Some of the features in the thermophysical property curves are expected to reflect changes in the structure and coordination of the liquid. These measurements require containerless processing such as electrostatic levitation to access the undercooled liquid regime. An overview of the state of the art in measuring the thermophysical properties and structure of undercooled liquid glass-forming and quasicrystal-forming alloys will be presented, along with the status of current measurements.

  6. Structural disorder in metallic glass-forming liquids.

    Science.gov (United States)

    Pan, Shao-Peng; Feng, Shi-Dong; Wang, Li-Min; Qiao, Jun-Wei; Niu, Xiao-Feng; Dong, Bang-Shao; Wang, Wei-Min; Qin, Jing-Yu

    2016-06-09

    We investigated structural disorder by a new structural parameter, quasi-nearest atom (QNA), in atomistic configurations of eight metallic glass-forming systems generated through molecular dynamics simulations at various temperatures. Structural analysis reveals that the scaled distribution of the number of QNA appears to be an universal property of metallic liquids and the spatial distribution of the number of QNA displays to be clearly heterogeneous. Furthermore, the new parameter can be directly correlated with potential energy and structural relaxation at the atomic level. Some straightforward relationships between QNA and other properties (per-atom potential energy and α-relaxation time) are introduced to reflect structure-property relationship in metallic liquids. We believe that the new structural parameter can well reflect structure disorder in metallic liquids and play an important role in understanding various properties in metallic liquids.

  7. Are the dynamics of silicate glasses and glass-forming liquids embedded in their elastic properties?

    DEFF Research Database (Denmark)

    Smedskjær, Morten Mattrup; Mauro, John C.

    According to the elastic theory of the glass transition, the dynamics of glasses and glass-forming liquids are controlled by the evolution of shear modulus. In particular, the elastic shoving model expresses dynamics in terms of an activation energy required to shove aside the surrounding atoms......, which is determined by the shear modulus. First, we here present an in situ high-temperature Brillouin spectroscopy test of the shoving model near the glass transition of eight aluminosilicate glass-forming systems. We find that the measured viscosity data agree qualitatively with the measured...... temperature dependence of shear moduli, as predicted by the shoving model. However, the model systematically underpredicts the values of fragility. Second, we also present a thorough test of the shoving model for predicting the low temperature dynamics of an aluminosilicate glass system. This is done...

  8. Shear viscosity of glass-forming melts in the liquid-glass transition region

    International Nuclear Information System (INIS)

    Sanditov, D. S.

    2010-01-01

    A new approach to interpreting the hole-activation model of a viscous flow of glass-forming liquids is proposed. This model underlies the development of the concept on the exponential temperature dependence of the free energy of activation of a flow within the range of the liquid-glass transition in complete agreement with available experimental data. The 'formation of a fluctuation hole' in high-heat glass-forming melts is considered as a small-scale low-activation local deformation of a structural network, i.e., the quasi-lattice necessary for the switching of the valence bond, which is the main elementary event of viscous flow of glasses and their melts. In this sense, the hole formation is a conditioned process. A drastic increase in the activation free energy of viscous flow in the liquid-glass transition region is explained by a structural transformation that is reduced to a limiting local elastic deformation of the structural network, which, in turn, originates from the excitation (critical displacement) of a bridging atom like the oxygen atom in the Si-O-Si bridge. At elevated temperatures, as a rule, a necessary amount of excited bridging atoms (locally deformed regions of the structural network) always exists, and the activation free energy of viscous flow is almost independent of temperature. The hole-activation model is closely connected with a number of well-known models describing the viscous flow of glass-forming liquids (the Avramov-Milchev, Nemilov, Ojovan, and other models).

  9. Fragility correlates thermodynamic and kinetic properties of glass forming liquids

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, C.Narayana [Maharani’s Science College for Women, Bangalore 560001 (India); Viswanatha, R.; Chethana, B.K. [Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012 (India); Gowda, V.C.Veeranna [Government First Grade College, Jayanagara, Bangalore 560070 (India); Rao, K.J., E-mail: kalyajrao@yahoo.co.in [Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012 (India)

    2015-03-15

    Graphical abstract: The suggested new fragility parameter correlates viscosity and configurational entropy. - Highlights: • A new fragility function, F=ΔT/ΔC{sub p}×C{sub p}{sup l}/T{sub g} has been proposed. • A three parameter viscosity function using the new F reproduces Angell fragility plot. • A new ΔC{sub p} function is derived which directly relates Adam–Gibbs function with the fragility based viscosity function. - Abstract: In our earlier communication we proposed a simple fragility determining function, ([NBO]/V{sub m}{sup 3}T{sub g}), which we have now used to analyze several glass systems using available thermal data. A comparison with similar fragility determining function, ΔC{sub p}/C{sub p}{sup l}, introduced by Chryssikos et al. in their investigation of lithium borate glasses has also been performed and found to be more convenient quantity for discussing fragilities. We now propose a new function which uses both ΔC{sub p} and ΔT and which gives a numerical fragility parameter, F whose value lies between 0 and 1 for glass forming liquids. F can be calculated through the use of measured thermal parameters ΔC{sub p}, C{sub p}{sup l}, T{sub g} and T{sub m}. Use of the new fragility values in reduced viscosity equation reproduces the whole range of viscosity curves of the Angell plot. The reduced viscosity equation can be directly compared with the Adam–Gibbs viscosity equation and a heat capacity function can be formulated which reproduces satisfactorily the ΔC{sub p} versus ln(T{sub r}) curves and hence the configurational entropy.

  10. Supercooled dynamics of glass-forming liquids and polymers under hydrostatic pressure

    Energy Technology Data Exchange (ETDEWEB)

    Roland, C M [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States); Hensel-Bielowka, S [Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice (Poland); Paluch, M [Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice (Poland); Casalini, R [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States); Chemistry Department, George Mason University, Fairfax, VA 22030 (United States)

    2005-06-01

    An intriguing problem in condensed matter physics is understanding the glass transition, in particular the dynamics in the equilibrium liquid close to vitrification. Recent advances have been made by using hydrostatic pressure as an experimental variable. These results are reviewed, with an emphasis in the insight provided into the mechanisms underlying the relaxation properties of glass-forming liquids and polymers.

  11. Effect of high pressure on the relaxation dynamics of glass-forming liquids

    Energy Technology Data Exchange (ETDEWEB)

    Paluch, M; Grzybowska, K; Grzybowski, A [Institute of Physics, Silesian University, ulica Uniwersytecka 4, 40-007 Katowice (Poland)

    2007-05-23

    A glass is usually formed by cooling a liquid at a rate sufficient to avoid crystallization. In the vicinity of the glass transition the structural relaxation time increases with lowering temperature in a non-Arrhenius fashion and the structural relaxation function reveals a non-Debye behaviour. However, liquid can be also vitrified by keeping it at a constant temperature and increasing the pressure. This pressure-induced transition to the glassy state is also accompanied by dramatic changes in the relaxation dynamics. Herein we discuss the behaviour of the structural relaxation times of glass-forming liquids and polymer melts under high pressure.

  12. Effect of high pressure on the relaxation dynamics of glass-forming liquids

    International Nuclear Information System (INIS)

    Paluch, M; Grzybowska, K; Grzybowski, A

    2007-01-01

    A glass is usually formed by cooling a liquid at a rate sufficient to avoid crystallization. In the vicinity of the glass transition the structural relaxation time increases with lowering temperature in a non-Arrhenius fashion and the structural relaxation function reveals a non-Debye behaviour. However, liquid can be also vitrified by keeping it at a constant temperature and increasing the pressure. This pressure-induced transition to the glassy state is also accompanied by dramatic changes in the relaxation dynamics. Herein we discuss the behaviour of the structural relaxation times of glass-forming liquids and polymer melts under high pressure

  13. Revealing the Link between Structural Relaxation and Dynamic Heterogeneity in Glass-Forming Liquids.

    Science.gov (United States)

    Wang, Lijin; Xu, Ning; Wang, W H; Guan, Pengfei

    2018-03-23

    Despite the use of glasses for thousands of years, the nature of the glass transition is still mysterious. On approaching the glass transition, the growth of dynamic heterogeneity has long been thought to play a key role in explaining the abrupt slowdown of structural relaxation. However, it still remains elusive whether there is an underlying link between structural relaxation and dynamic heterogeneity. Here, we unravel the link by introducing a characteristic time scale hiding behind an identical dynamic heterogeneity for various model glass-forming liquids. We find that the time scale corresponds to the kinetic fragility of liquids. Moreover, it leads to scaling collapse of both the structural relaxation time and dynamic heterogeneity for all liquids studied, together with a characteristic temperature associated with the same dynamic heterogeneity. Our findings imply that studying the glass transition from the viewpoint of dynamic heterogeneity is more informative than expected.

  14. Revealing the Link between Structural Relaxation and Dynamic Heterogeneity in Glass-Forming Liquids

    Science.gov (United States)

    Wang, Lijin; Xu, Ning; Wang, W. H.; Guan, Pengfei

    2018-03-01

    Despite the use of glasses for thousands of years, the nature of the glass transition is still mysterious. On approaching the glass transition, the growth of dynamic heterogeneity has long been thought to play a key role in explaining the abrupt slowdown of structural relaxation. However, it still remains elusive whether there is an underlying link between structural relaxation and dynamic heterogeneity. Here, we unravel the link by introducing a characteristic time scale hiding behind an identical dynamic heterogeneity for various model glass-forming liquids. We find that the time scale corresponds to the kinetic fragility of liquids. Moreover, it leads to scaling collapse of both the structural relaxation time and dynamic heterogeneity for all liquids studied, together with a characteristic temperature associated with the same dynamic heterogeneity. Our findings imply that studying the glass transition from the viewpoint of dynamic heterogeneity is more informative than expected.

  15. Local elastic expansion model for viscous-flow activation energies of glass-forming molecular liquids

    DEFF Research Database (Denmark)

    Dyre, Jeppe; Olsen, Niels Boye; Christensen, Tage Emil

    1996-01-01

    A model for the viscosity of glass-forming molecular liquids is proposed in which a "flow event" requires a local volume increase. The activation energy for a flow event is identified with the work done in shoving aside the surrounding liquid; this work is proportional to the high-frequency shear...

  16. Structural origin of fractional Stokes-Einstein relation in glass-forming liquids.

    Science.gov (United States)

    Pan, Shaopeng; Wu, Z W; Wang, W H; Li, M Z; Xu, Limei

    2017-01-06

    In many glass-forming liquids, fractional Stokes-Einstein relation (SER) is observed above the glass transition temperature. However, the origin of such phenomenon remains elusive. Using molecular dynamics simulations, we investigate the break- down of SER and the onset of fractional SER in a model of metallic glass-forming liquid. We find that SER breaks down when the size of the largest cluster consisting of trapped atoms starts to increase sharply at which the largest cluster spans half of the simulations box along one direction, and the fractional SER starts to follows when the largest cluster percolates the entire system and forms 3-dimentional network structures. Further analysis based on the percolation theory also confirms that percolation occurs at the onset of the fractional SER. Our results directly link the breakdown of the SER with structure inhomogeneity and onset of the fraction SER with percolation of largest clusters, thus provide a possible picture for the break- down of SER and onset of fractional SER in glass-forming liquids, which is is important for the understanding of the dynamic properties in glass-forming liquids.

  17. Diffusion in confinement as a microscopic relaxation mechanism in glass-forming liquids

    International Nuclear Information System (INIS)

    Mamontov, Eugene

    2012-01-01

    Using quasielastic neutron scattering, we compare dynamics in single-element liquids, glass-forming selenium and non glass-forming gallium. There is a single jump-diffusion process in gallium, whereas in selenium there is also a faster, spatially localized process. The fast and slow processes describe β- and α-relaxation, respectively. We then analyze an archetypical glass-former, glycerol, to show that the two-component fit, with β- and α-relaxations explicitly separated, yields the correct value for the translational diffusion coefficient and provides information on the spatial localization of the β-relaxation that is not experimentally accessible otherwise.

  18. Measurements of the Poisson ratio and fragility of glass-forming liquids

    DEFF Research Database (Denmark)

    Christensen, Tage Emil; Olsen, Niels Boye

    Recently much attention has been given to models and phenomenology of glass-forming liquids that correlates fast and slow degrees of freedom . In particular the Poisson ratio has been correlated with fragility. We present data on shear - and bulk modulus obtained by the techniques...... of the piezoelectric transducers PBG and PSG on a number of glass-forming liquids. Hereby the Poisson ratio can be found. Furthermore the PSG also gives the temperature dependence of shear viscosity and thereby the fragility. The validity of the conjectured relation is discussed...

  19. Linking structure to fragility in bulk metallic glass-forming liquids

    International Nuclear Information System (INIS)

    Wei, Shuai; Stolpe, Moritz; Gross, Oliver; Gallino, Isabella; Hembree, William; Busch, Ralf; Evenson, Zach; Bednarcik, Jozef; Kruzic, Jamie J.

    2015-01-01

    Using in-situ synchrotron X-ray scattering, we show that the structural evolution of various bulk metallic glass-forming liquids can be quantitatively connected to their viscosity behavior in the supercooled liquid near T g . The structural signature of fragility is identified as the temperature dependence of local dilatation on distinct key atomic length scales. A more fragile behavior results from a more pronounced thermally induced dilatation of the structure on a length scale of about 3 to 4 atomic diameters, coupled with shallower temperature dependence of structural changes in the nearest neighbor environment. These findings shed light on the structural origin of viscous slowdown during undercooling of bulk metallic glass-forming liquids and demonstrate the promise of predicting the properties of bulk metallic glasses from the atomic scale structure

  20. Linking structure to fragility in bulk metallic glass-forming liquids

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Shuai, E-mail: shuai.wei@asu.edu, E-mail: m.stolpe@mx.uni-saarland.de [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287 (United States); Stolpe, Moritz, E-mail: shuai.wei@asu.edu, E-mail: m.stolpe@mx.uni-saarland.de; Gross, Oliver; Gallino, Isabella; Hembree, William; Busch, Ralf [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Evenson, Zach [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und Raumfahrt (DLR), 51170 Köln (Germany); Bednarcik, Jozef [Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, D-22603 Hamburg (Germany); Kruzic, Jamie J. [Material Science, School of Mechanical, Industrial, and Manufacturing Engineering, Oregon State University, Corvallis, Oregon 97331 (United States)

    2015-05-04

    Using in-situ synchrotron X-ray scattering, we show that the structural evolution of various bulk metallic glass-forming liquids can be quantitatively connected to their viscosity behavior in the supercooled liquid near T{sub g}. The structural signature of fragility is identified as the temperature dependence of local dilatation on distinct key atomic length scales. A more fragile behavior results from a more pronounced thermally induced dilatation of the structure on a length scale of about 3 to 4 atomic diameters, coupled with shallower temperature dependence of structural changes in the nearest neighbor environment. These findings shed light on the structural origin of viscous slowdown during undercooling of bulk metallic glass-forming liquids and demonstrate the promise of predicting the properties of bulk metallic glasses from the atomic scale structure.

  1. Correlation between relaxations and plastic deformation, and elastic model of flow in metallic glasses and glass-forming liquids

    International Nuclear Information System (INIS)

    Wang Weihua

    2011-01-01

    We study the similarity and correlations between relaxations and plastic deformation in metallic glasses (MGs) and MG-forming liquids. It is shown that the microscope plastic events, the initiation and formation of shear bands, and the mechanical yield in MGs where the atomic sites are topologically unstable induced by applied stress, can be treated as the glass to supercooled liquid state transition induced by external shear stress. On the other hand, the glass transition, the primary and secondary relaxations, plastic deformation and yield can be attributed to the free volume increase induced flow, and the flow can be modeled as the activated hopping between the inherent states in the potential energy landscape. We then propose an extended elastic model to describe the flow based on the energy landscape theory. That is, the flow activation energy density is linear proportional to the instantaneous elastic moduli, and the activation energy density ρ E is determined to be a simple expression of ρ E =(10/11)G+(1/11)K. The model indicates that both shear and bulk moduli are critical parameters accounting for both the homogeneous and inhomogeneous flows in MGs and MG-forming liquids. The elastic model is experimentally certified. We show that the elastic perspectives offers a simple scenario for the flow in MGs and MG-forming liquids and are suggestive for understanding the glass transition, plastic deformation, and nature and characteristics of MGs

  2. Single-order-parameter description of glass-forming liquids

    DEFF Research Database (Denmark)

    Ellegaard, Niels Langager; Christensen, Tage Emil; Christiansen, Peder Voetmann

    2007-01-01

    Thermoviscoelastic linear-response functions are calculated from the master equation describing viscous liquid inherent dynamics. From the imaginary parts of the frequency-dependent isobaric specific heat, isothermal compressibility, and isobaric thermal expansion coefficient, we define a "linear...... dynamic Prigogine-Defay ratio" with the property that if this ratio is unity at one frequency, then it is unity at all frequencies. This happens if and only if there is a single-order-parameter description of the thermoviscoelastic linear responses via an order parameter which may be nonexponential...

  3. Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature.

    Science.gov (United States)

    Mallamace, Francesco; Branca, Caterina; Corsaro, Carmelo; Leone, Nancy; Spooren, Jeroen; Chen, Sow-Hsin; Stanley, H Eugene

    2010-12-28

    It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T. In an Arrhenius plot, ln η vs 1/T, a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel-Fulcher-Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η(×), where η(×) has the same value, η(×) ≈ 10(3) Poise, for all 84 liquids. The crossover temperature, T(×), located well above the calorimetric glass transition temperature T(g), marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T(×) to Arrhenius behavior below T(×). We also show that below T(×) the familiar Stokes-Einstein relation D/T ∼ η(-1) breaks down and is replaced by a fractional form D/T ∼ η(-ζ), with ζ ≈ 0.85.

  4. Exploring the Origin of Fragile-to-Strong Transition in Some Glass-Forming Liquids

    DEFF Research Database (Denmark)

    Yue, Yuanzheng; Hu, L. N.

    2014-01-01

    , topological and thermodynamic changes causing this transition. The theory for describing the transition has not been fully established. In this paper, we summarize our current understanding of the fragile-to-strong transition in some glass-forming liquids basedon our two published papers and recent...

  5. Molecular dynamics simulations of glycerol glass-forming liquid

    International Nuclear Information System (INIS)

    Blieck, J.; Affouard, F.; Bordat, P.; Lerbret, A.; Descamps, M.

    2005-01-01

    Structural and dynamical properties of liquid glycerol have been investigated by Molecular Dynamics simulations. An improved model based on a slight reparametrisation of the all-atoms AMBER force field used in [R. Chelli, P. Procacci, G. Cardini, R.G.D. Valle, S. Califano, Phys. Chem. Chem. Phys. 1 (1999) 871] is presented. The structure remains satisfactory, qualitatively similar to that obtained from the original model. This new model is also found to reproduce significantly better the diffusion coefficient and the correlations times as they can be deduced from neutron spin echo (NSE) experiments. Structural heterogeneities revealed as a pre-peak of the static structure factor S(Q) close to Q ∼ 0.6 A -1 are observed. Our results are also found compatible with predictions of the Mode Coupling Theory

  6. Crystallization of glass-forming liquids: Specific surface energy

    International Nuclear Information System (INIS)

    Schmelzer, Jürn W. P.; Abyzov, Alexander S.

    2016-01-01

    A generalization of the Stefan-Skapski-Turnbull relation for the melt-crystal specific interfacial energy is developed in terms of the generalized Gibbs approach extending its standard formulation to thermodynamic non-equilibrium states. With respect to crystal nucleation, this relation is required in order to determine the parameters of the critical crystal clusters being a prerequisite for the computation of the work of critical cluster formation. As one of its consequences, a relation for the dependence of the specific surface energy of critical clusters on temperature and pressure is derived applicable for small and moderate deviations from liquid-crystal macroscopic equilibrium states. Employing the Stefan-Skapski-Turnbull relation, general expressions for the size and the work of formation of critical crystal clusters are formulated. The resulting expressions are much more complex as compared to the respective relations obtained via the classical Gibbs theory. Latter relations are retained as limiting cases of these more general expressions for moderate undercoolings. By this reason, the formulated, here, general relations for the specification of the critical cluster size and the work of critical cluster formation give a key for an appropriate interpretation of a variety of crystallization phenomena occurring at large undercoolings which cannot be understood in terms of the Gibbs’ classical treatment.

  7. Fluctuations in an Inorganic Glass Forming System Capable of Liquid-Liquid Phase Separation

    Science.gov (United States)

    Bogdanov, V.; Maksimov, L.; Anan'ev, A.; Nemilov, S.; Rusan, V.

    2012-08-01

    Rayleigh and Mandel'shtam-Brillouin scattering (RMBS) spectroscopy and high temperature ultrasonic study (HTUS) are applied to PbO-Al2O3-B2O3 glass forming system characterized by over liquidus miscibility gap. Temperature dependences of ultrasonic velocity of glass melts were measured in 600-1200°C range. "Frozen-in" density fluctuations in two phase glasses were estimated from HTUS data by Macedo-Shroeder formulation. Landau-Placzek ratios were found from RMBS spectra of single phase glasses at room temperature. Results of RMBS and HTUS were compared with well-known SAXS data. It was found that contribution of "frozen-in" density fluctuations into light scattering by two-phase glasses is much smaller than the scattering on particles of the second glassy phase causing opalescence of the glasses. Abnormal "water-like" growth of ultrasonic velocity with melt temperature can be explained by coexistence of two types of packaging of structural elements.

  8. Communication: High pressure specific heat spectroscopy reveals simple relaxation behavior of glass forming molecular liquid

    DEFF Research Database (Denmark)

    Roed, Lisa Anita; Niss, Kristine; Jakobsen, Bo

    2015-01-01

    The frequency dependent specific heat has been measured under pressure for the molecular glass forming liquid 5-polyphenyl-4-ether in the viscous regime close to the glass transition. The temperature and pressure dependences of the characteristic time scale associated with the specific heat...... is compared to the equivalent time scale from dielectric spectroscopy performed under identical conditions. It is shown that the ratio between the two time scales is independent of both temperature and pressure. This observation is non-trivial and demonstrates the existence of specially simple molecular...... liquids in which different physical relaxation processes are both as function of temperature and pressure/density governed by the same underlying “inner clock.” Furthermore, the results are discussed in terms of the recent conjecture that van der Waals liquids, like the measuredliquid, comply...

  9. Anomalous Crystallization as a Signature of the Fragile-to-Strong Transition in Metallic Glass-Forming Liquids

    DEFF Research Database (Denmark)

    Yang, X.N.; Zhou, C.; Sun, Q.J.

    2014-01-01

    We study the fragile-to-strong (F−S) transition of metallic glass-forming liquids (MGFLs) by measuring the thermal response during annealing and dynamic heating of La55Al25Ni5Cu15 glass ribbons fabricated at different cooling rates. We find that the glasses fabricated in the intermediate regime o...

  10. Solvent dynamics in a glass-forming liquid from 300 K to 3 K : What photon echoes can teach us

    NARCIS (Netherlands)

    Lazonder, Kees; Pshenichnikov, Maxim S.

    2007-01-01

    The temperature dependence of the optical non-linear response of dye molecules dissolved in a glass-forming liquid over a temperature range that includes the glass transition is investigated. Cooling down to temperatures below the glass transition dramatically slows the diffusive motion of the

  11. The correlation between fragility, density, and atomic interaction in glass-forming liquids

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lijin; Guan, Pengfei, E-mail: pguan@csrc.ac.cn [Beijing Computational Science Research Center, Beijing 100193 (China); Wang, W. H. [Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China)

    2016-07-21

    The fragility that controls the temperature-dependent viscous properties of liquids as the glass transition is approached, in various glass-forming liquids with different softness of the repulsive part of atomic interactions at different densities, is investigated by molecular dynamic simulations. We show that the landscape of fragility in purely repulsive systems can be separated into three regions denoted as R{sub I,} R{sub II}, and R{sub III}, respectively, with qualitatively disparate dynamic behaviors: R{sub I} which can be described by “softness makes strong glasses,” R{sub II} where fragility is independent of softness and can only be tuned by density, and R{sub III} with constant fragility, suggesting that density plays an unexpected role for understanding the repulsive softness dependence of fragility. What is more important is that we unify the long-standing inconsistence with respect to the repulsive softness dependence of fragility by observing that a glass former can be tuned more fragile if nonperturbative attraction is added into it. Moreover, we find that the vastly dissimilar influences of attractive interaction on fragility could be estimated from the structural properties of related zero-temperature glasses.

  12. The correlation between fragility, density, and atomic interaction in glass-forming liquids

    International Nuclear Information System (INIS)

    Wang, Lijin; Guan, Pengfei; Wang, W. H.

    2016-01-01

    The fragility that controls the temperature-dependent viscous properties of liquids as the glass transition is approached, in various glass-forming liquids with different softness of the repulsive part of atomic interactions at different densities, is investigated by molecular dynamic simulations. We show that the landscape of fragility in purely repulsive systems can be separated into three regions denoted as R I, R II , and R III , respectively, with qualitatively disparate dynamic behaviors: R I which can be described by “softness makes strong glasses,” R II where fragility is independent of softness and can only be tuned by density, and R III with constant fragility, suggesting that density plays an unexpected role for understanding the repulsive softness dependence of fragility. What is more important is that we unify the long-standing inconsistence with respect to the repulsive softness dependence of fragility by observing that a glass former can be tuned more fragile if nonperturbative attraction is added into it. Moreover, we find that the vastly dissimilar influences of attractive interaction on fragility could be estimated from the structural properties of related zero-temperature glasses.

  13. The correlation between fragility, density, and atomic interaction in glass-forming liquids.

    Science.gov (United States)

    Wang, Lijin; Guan, Pengfei; Wang, W H

    2016-07-21

    The fragility that controls the temperature-dependent viscous properties of liquids as the glass transition is approached, in various glass-forming liquids with different softness of the repulsive part of atomic interactions at different densities, is investigated by molecular dynamic simulations. We show that the landscape of fragility in purely repulsive systems can be separated into three regions denoted as RI, RII, and RIII, respectively, with qualitatively disparate dynamic behaviors: RI which can be described by "softness makes strong glasses," RII where fragility is independent of softness and can only be tuned by density, and RIII with constant fragility, suggesting that density plays an unexpected role for understanding the repulsive softness dependence of fragility. What is more important is that we unify the long-standing inconsistence with respect to the repulsive softness dependence of fragility by observing that a glass former can be tuned more fragile if nonperturbative attraction is added into it. Moreover, we find that the vastly dissimilar influences of attractive interaction on fragility could be estimated from the structural properties of related zero-temperature glasses.

  14. Length scales in glass-forming liquids and related systems: a review

    International Nuclear Information System (INIS)

    Karmakar, Smarajit; Dasgupta, Chandan; Sastry, Srikanth

    2016-01-01

    The central problem in the study of glass-forming liquids and other glassy systems is the understanding of the complex structural relaxation and rapid growth of relaxation times seen on approaching the glass transition. A central conceptual question is whether one can identify one or more growing length scale(s) associated with this behavior. Given the diversity of molecular glass-formers and a vast body of experimental, computational and theoretical work addressing glassy behavior, a number of ideas and observations pertaining to growing length scales have been presented over the past few decades, but there is as yet no consensus view on this question. In this review, we will summarize the salient results and the state of our understanding of length scales associated with dynamical slow down. After a review of slow dynamics and the glass transition, pertinent theories of the glass transition will be summarized and a survey of ideas relating to length scales in glassy systems will be presented. A number of studies have focused on the emergence of preferred packing arrangements and discussed their role in glassy dynamics. More recently, a central object of attention has been the study of spatially correlated, heterogeneous dynamics and the associated length scale, studied in computer simulations and theoretical analysis such as inhomogeneous mode coupling theory. A number of static length scales have been proposed and studied recently, such as the mosaic length scale discussed in the random first-order transition theory and the related point-to-set correlation length. We will discuss these, elaborating on key results, along with a critical appraisal of the state of the art. Finally we will discuss length scales in driven soft matter, granular fluids and amorphous solids, and give a brief description of length scales in aging systems. Possible relations of these length scales with those in glass-forming liquids will be discussed. (review article)

  15. Growing correlation length on cooling below the onset of caging in a simulated glass-forming liquid

    DEFF Research Database (Denmark)

    Lačević, N.; Starr, F. W.; Schrøder, Thomas

    2002-01-01

    We present a calculation of a fourth-order, time-dependent density correlation function that measures higher-order spatiotemporal correlations of the density of a liquid. From molecular dynamics simulations of a glass-forming Lennard-Jones liquid, we find that the characteristic length scale...... of the dynamics of the liquid in the alpha-relaxation regime....

  16. Crossover to potential energy landscape dominated dynamics in a model glass-forming liquid

    DEFF Research Database (Denmark)

    Schrøder, Thomas; Sastry, S.; Dyre, Jeppe

    2000-01-01

    An equilibrated model glass-forming liquid is studied by mapping successive configurations produced by molecular dynamics simulation onto a time series of inherent structures (local minima in the potential energy). Using this "inherent dynamics" approach we find direct numerical evidence for the ......An equilibrated model glass-forming liquid is studied by mapping successive configurations produced by molecular dynamics simulation onto a time series of inherent structures (local minima in the potential energy). Using this "inherent dynamics" approach we find direct numerical evidence...... for the long held view that below a crossover temperature, Tx, the liquid's dynamics can be separated into (i) vibrations around inherent structures and (ii) transitions between inherent structures [M. Goldstein, J. Chem. Phys. 51, 3728 (1969)], i.e., the dynamics become "dominated" by the potential energy...... landscape. In agreement with previous proposals, we find that Tx is within the vicinity of the mode-coupling critical temperature Tc. We further find that near Tx, transitions between inherent structures occur via cooperative, stringlike rearrangements of groups of particles moving distances substantially...

  17. Probing heterogeneous dynamics from spatial density correlation in glass-forming liquids.

    Science.gov (United States)

    Li, Yan-Wei; Zhu, You-Liang; Sun, Zhao-Yan

    2016-12-01

    We numerically investigate the connection between spatial density correlation and dynamical heterogeneity in glass-forming liquids. We demonstrate that the cluster size defined by the spatial aggregation of densely packed particles (DPPs) can better capture the difference between the dynamics of the Lennard-Jones glass model and the Weeks-Chandler-Andersen truncation model than the commonly used pair correlation functions. More interestingly, we compare the mobility of DPPs and loosely packed particles, and we find that high local density correlates well with slow dynamics in systems with relatively hard repulsive interactions but links to mobile ones in the system with soft repulsive interactions at one relaxation time scale. Our results show clear evidence that the above model dependence behavior stems from the hopping motion of DPPs at the end of the caging stage due to the compressive nature of soft repulsive spheres, which activates the dynamics of DPPs in the α relaxation stage.

  18. Extracting energy and structure properties of glass-forming liquids from structural relaxation time.

    Science.gov (United States)

    Wang, Lianwen

    2012-04-18

    A comprehensive examination of the kinetic liquid model (Wang et al 2010 J. Phys.: Condens. Matter 22 455104) is carried out by fitting the structural relaxation time of 26 different glass-forming liquids in a wide temperature range, including most of the well-studied materials. Careful analysis of the compiled reported data reveals that experimental inaccuracies should not be overlooked in any 'benchmark test' of relating theories or models (e.g. in Lunkenheimer et al 2010 Phys. Rev. E 81 051504). The procedure, accuracy, ability, and efficiency of the kinetic liquid model are discussed in detail and in comparison with other available fitting methods. In general, the kinetic liquid model could be verified by 17 of the 26 compiled data sets and can serve as a meaningful approximative method for analyzing these liquids. Nonetheless, further experimental examinations in a wide temperature range are needed and are called for. Through fitting, the microscopic details of these liquids are extracted, namely, the enthalpy, entropy, and cooperativity in structural relaxation, which may facilitate further quantitative analysis to both the liquidus and glassy states of these materials.

  19. PREFACE: Dynamic crossover phenomena in water and other glass-forming liquids Dynamic crossover phenomena in water and other glass-forming liquids

    Science.gov (United States)

    Chen, Sow-Hsin; Baglioni, Piero

    2012-02-01

    This special section has been inspired by the workshop on Dynamic Crossover Phenomena in Water and Other Glass-Forming Liquids, held during November 11-13, 2010 at Pensione Bencistà, Fiesole, Italy, a well-preserved 14th century Italian villa tucked high in the hills overlooking Florence. The meeting, an assembly of world renowned scientists, was organized as a special occasion to celebrate the 75th birthday of Professor Sow-Hsin Chen of MIT, a pioneer in several aspects of complex fluids and soft matter physics. The workshop covered a large variety of experimental and theoretical research topics of current interest related to dynamic crossover phenomena in water and, more generally, in other glass-forming liquids. The 30 invited speakers/lecturers and approximately 60 participants were a select group of prominent physicists and chemists from the USA, Europe, Asia and Mexico, who are actively working in the field. Some highlights of this special issue include the following works. Professor Yamaguchi's group and their collaborators present a neutron spin echo study of the coherent intermediate scattering function of heavy water confined in cylindrical pores of MCM-41-C10 silica material in the temperature range 190-298 K. They clearly show that a fragile-to-strong (FTS) dynamic crossover occurs at about 225 K. They attribute the FTS dynamic crossover to the formation of a tetrahedral-like structure, which is preserved in the bulk-like water confined to the central part of the cylindrical pores. Mamontov and Kolesnikov et al study the collective excitations in an aqueous solution of lithium chloride over a temperature range of 205-270 K using neutron and x-ray Rayleigh-Brillouin (coherent) scattering. They detect both the low-frequency and the high-frequency sounds known to exist in pure bulk water above the melting temperature. They also perform neutron (incoherent) and x-ray (coherent) elastic intensity scan measurements. Clear evidence of the crossover in the

  20. High density liquid structure enhancement in glass forming aqueous solution of LiCl

    Science.gov (United States)

    Camisasca, G.; De Marzio, M.; Rovere, M.; Gallo, P.

    2018-06-01

    We investigate using molecular dynamics simulations the dynamical and structural properties of LiCl:6H2O aqueous solution upon supercooling. This ionic solution is a glass forming liquid of relevant interest in connection with the study of the anomalies of supercooled water. The LiCl:6H2O solution is easily supercooled and the liquid state can be maintained over a large decreasing temperature range. We performed simulations from ambient to 200 K in order to investigate how the presence of the salt modifies the behavior of supercooled water. The study of the relaxation time of the self-density correlation function shows that the system follows the prediction of the mode coupling theory and behaves like a fragile liquid in all the range explored. The analysis of the changes in the water structure induced by the salt shows that while the salt preserves the water hydrogen bonds in the system, it strongly affects the tetrahedral hydrogen bond network. Following the interpretation of the anomalies of water in terms of a two-state model, the modifications of the oxygen radial distribution function and the angular distribution function of the hydrogen bonds in water indicate that LiCl has the role of enhancing the high density liquid component of water with respect to the low density component. This is in agreement with recent experiments on aqueous ionic solutions.

  1. Structural predictor for nonlinear sheared dynamics in simple glass-forming liquids.

    Science.gov (United States)

    Ingebrigtsen, Trond S; Tanaka, Hajime

    2018-01-02

    Glass-forming liquids subjected to sufficiently strong shear universally exhibit striking nonlinear behavior; for example, a power-law decrease of the viscosity with increasing shear rate. This phenomenon has attracted considerable attention over the years from both fundamental and applicational viewpoints. However, the out-of-equilibrium and nonlinear nature of sheared fluids have made theoretical understanding of this phenomenon very challenging and thus slower to progress. We find here that the structural relaxation time as a function of the two-body excess entropy, calculated for the extensional axis of the shear flow, collapses onto the corresponding equilibrium curve for a wide range of pair potentials ranging from harsh repulsive to soft and finite. This two-body excess entropy collapse provides a powerful approach to predicting the dynamics of nonequilibrium liquids from their equilibrium counterparts. Furthermore, the two-body excess entropy scaling suggests that sheared dynamics is controlled purely by the liquid structure captured in the form of the two-body excess entropy along the extensional direction, shedding light on the perplexing mechanism behind shear thinning.

  2. Structural predictor for nonlinear sheared dynamics in simple glass-forming liquids

    Science.gov (United States)

    Ingebrigtsen, Trond S.; Tanaka, Hajime

    2018-01-01

    Glass-forming liquids subjected to sufficiently strong shear universally exhibit striking nonlinear behavior; for example, a power-law decrease of the viscosity with increasing shear rate. This phenomenon has attracted considerable attention over the years from both fundamental and applicational viewpoints. However, the out-of-equilibrium and nonlinear nature of sheared fluids have made theoretical understanding of this phenomenon very challenging and thus slower to progress. We find here that the structural relaxation time as a function of the two-body excess entropy, calculated for the extensional axis of the shear flow, collapses onto the corresponding equilibrium curve for a wide range of pair potentials ranging from harsh repulsive to soft and finite. This two-body excess entropy collapse provides a powerful approach to predicting the dynamics of nonequilibrium liquids from their equilibrium counterparts. Furthermore, the two-body excess entropy scaling suggests that sheared dynamics is controlled purely by the liquid structure captured in the form of the two-body excess entropy along the extensional direction, shedding light on the perplexing mechanism behind shear thinning.

  3. AC Calorimetry and Thermophysical Properties of Bulk Glass-Forming Metallic Liquids

    Science.gov (United States)

    Johnson, William L.

    2000-01-01

    Thermo-physical properties of two bulk metallic glass forming alloys, Ti34Zr11Cu47Ni8 (VIT 101) and Zr57Nb5Ni12.6Al10CU15.4 (VIT 106), were investigated in the stable and undercooled melt. Our investigation focused on measurements of the specific heat in the stable and undercooled liquid using the method of AC modulation calorimetry. The VIT 106 exhibited a maximum undercooling of 140 K in free radiative cooling. Specific heat measurements could be performed in stable melt down to an undercooling of 80 K. Analysis of the specific heat data indicate an anomaly near the equilibrium liquidus temperature. This anomaly is also observed in y the temperature dependencies of the external relaxation time, the specific volume, and the surface tension; it is tentatively attributed to a phase separation in the liquid state. The VIT 101 specimen exhibited a small undercooling of about 50 K. Specific heat measurements were performed in the stable and undercooled melt. These various results will be combined with ground based work such as the measurement of T-T-T curves in the electrostatic levitator and low temperature viscosity and specific heat measurements for modeling the nucleation kinetics of these alloys.

  4. Potential energy landscape signatures of slow dynamics in glass forming liquids

    DEFF Research Database (Denmark)

    Sastry, S.; Debenedetti, P. G.; Stillinger, F. H.

    1999-01-01

    We study the properties of local potential energy minima (‘inherent structures’) sampled by liquids at low temperatures as an approach to elucidating the mechanisms of the observed dynamical slowing down observed as the glass transition temperature is approached. This onset of slow dynamics...

  5. Connection between fragility, mean-squared displacement and shear modulus in two van der Waals bonded glass-forming liquids

    DEFF Research Database (Denmark)

    Hansen, Henriette Wase; Frick, Bernhard; Hecksher, Tina

    2017-01-01

    The temperature dependence of the high-frequency shear modulus measured in the kHz range is compared with the mean-squared displacement measured in the nanosecond range for the two van der Waals bonded glass-forming liquids cumene and 5-polyphenyl ether. This provides an experimental test for the...... for the assumption connecting two versions of the shoving model for the non-Arrhenius temperature dependence of the relaxation time in glass formers. The two versions of the model are also tested directly and both are shown to work well for these liquids....

  6. Kissinger method applied to the crystallization of glass-forming liquids: Regimes revealed by ultra-fast-heating calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Orava, J., E-mail: jo316@cam.ac.uk [Department of Materials Science & Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS (United Kingdom); WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Greer, A.L., E-mail: alg13@cam.ac.uk [Department of Materials Science & Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS (United Kingdom); WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan)

    2015-03-10

    Highlights: • Study of ultra-fast DSC applied to the crystallization of glass-forming liquids. • Numerical modeling of DSC traces at heating rates exceeding 10 orders of magnitude. • Identification of three regimes in Kissinger plots. • Elucidation of the effect of liquid fragility on the Kissinger method. • Modeling to study the regime in which crystal growth is thermodynamically limited. - Abstract: Numerical simulation of DSC traces is used to study the validity and limitations of the Kissinger method for determining the temperature dependence of the crystal-growth rate on continuous heating of glasses from the glass transition to the melting temperature. A particular interest is to use the wide range of heating rates accessible with ultra-fast DSC to study systems such as the chalcogenide Ge{sub 2}Sb{sub 2}Te{sub 5} for which fast crystallization is of practical interest in phase-change memory. Kissinger plots are found to show three regimes: (i) at low heating rates the plot is straight, (ii) at medium heating rates the plot is curved as expected from the liquid fragility, and (iii) at the highest heating rates the crystallization rate is thermodynamically limited, and the plot has curvature of the opposite sign. The relative importance of these regimes is identified for different glass-forming systems, considered in terms of the liquid fragility and the reduced glass-transition temperature. The extraction of quantitative information on fundamental crystallization kinetics from Kissinger plots is discussed.

  7. Kissinger method applied to the crystallization of glass-forming liquids: Regimes revealed by ultra-fast-heating calorimetry

    International Nuclear Information System (INIS)

    Orava, J.; Greer, A.L.

    2015-01-01

    Highlights: • Study of ultra-fast DSC applied to the crystallization of glass-forming liquids. • Numerical modeling of DSC traces at heating rates exceeding 10 orders of magnitude. • Identification of three regimes in Kissinger plots. • Elucidation of the effect of liquid fragility on the Kissinger method. • Modeling to study the regime in which crystal growth is thermodynamically limited. - Abstract: Numerical simulation of DSC traces is used to study the validity and limitations of the Kissinger method for determining the temperature dependence of the crystal-growth rate on continuous heating of glasses from the glass transition to the melting temperature. A particular interest is to use the wide range of heating rates accessible with ultra-fast DSC to study systems such as the chalcogenide Ge 2 Sb 2 Te 5 for which fast crystallization is of practical interest in phase-change memory. Kissinger plots are found to show three regimes: (i) at low heating rates the plot is straight, (ii) at medium heating rates the plot is curved as expected from the liquid fragility, and (iii) at the highest heating rates the crystallization rate is thermodynamically limited, and the plot has curvature of the opposite sign. The relative importance of these regimes is identified for different glass-forming systems, considered in terms of the liquid fragility and the reduced glass-transition temperature. The extraction of quantitative information on fundamental crystallization kinetics from Kissinger plots is discussed

  8. A comparative study of ibuprofen and ketoprofen glass-forming liquids by molecular dynamics simulations

    Science.gov (United States)

    Ottou Abe, M. T.; Correia, N. T.; Ndjaka, J. M. B.; Affouard, F.

    2015-10-01

    In this paper, structural and dynamical properties of ibuprofen and ketoprofen glass-forming liquids have been investigated by means of molecular dynamics simulations. Molecular mobility of both materials is analyzed with respect to the different inter-molecular linear/cyclic hydrogen bonding associations. For ibuprofen, the dominant organization is found to be composed of small hydrogen bonding aggregates corresponding to cyclic dimers through the carboxyl group. For ketoprofen, the propensity of cyclic dimers is significantly reduced by the formation of hydrogen bonds with the ketone oxygen of the molecule altering the hydrogen bond (HB) associating structures that can be formed and thus molecular dynamics. The issue of the presence/absence of the peculiar low frequency Debye-type process in dielectric relaxation spectroscopy (DRS) data in these materials is addressed. Results obtained from simulations confirm that the Debye process originates from the internal cis-trans conversion of the —COOH carboxyl group. It is shown that the specific intermolecular HB structures associated to a given profen control the main dynamical features of this conversion, in particular its separation from the α-process, which make it detectable or not from DRS. For ibuprofen, the possible role of the —CCCO torsion motion, more "local" than the —COOH motion since it is less influenced by the intermolecular HBs, is suggested in the microscopic origin of the quite intense secondary γ-relaxation process detected from DRS.

  9. Mean-coordination number dependence of the fragility in Ge-Se-In glass-forming liquids

    International Nuclear Information System (INIS)

    Saffarini, G.; Saiter, A.; Garda, M.R.; Saiter, J.M.

    2007-01-01

    Differential scanning calorimetry measurements have been performed on elemental Se as well as on Ge x Se 94- x In 6 (x=4, 8, and 11 at%) and on Ge y Se 88- y In 12 (y=5, 7, and 9 at%) chalcogenide glasses. From the cooling rate dependence of the fictive temperature, the apparent activation energies, Δh*, and the fragility indices, m, as defined in the strong-fragile glass-forming liquid concept, are determined. It is found that, in Ge-Se-In system, there is an evolution from strong (m=67) to fragile (m=116) glass-forming liquids. The dependence of 'm' on the mean-coordination number, Z, is also obtained. This dependence is rationalized by assuming that, in this glassy alloy system, there is a tendency for the formation of In 2 Se 3 clusters

  10. Aging of the Johari-Goldstein relaxation in the glass-forming liquids sorbitol and xylitol

    Science.gov (United States)

    Yardimci, Hasan; Leheny, Robert L.

    2006-06-01

    Employing frequency-dependent dielectric susceptibility we characterize the aging in two supercooled liquids, sorbitol and xylitol, below their calorimetric glass transition temperatures. In addition to the alpha relaxation that tracks the structural dynamics, the susceptibility of both liquids possesses a secondary Johari-Goldstein relaxation at higher frequencies. Following a quench through the glass transition, the susceptibility slowly approaches the equilibrium behavior. For both liquids, the magnitude of the Johari-Goldstein relaxation displays a dependence on the time since the quench, or aging time, that is quantitatively very similar to the age dependence of the alpha peak frequency. The Johari-Goldstein relaxation time remains constant during aging for sorbitol while it decreases slightly with age for xylitol. Hence, one cannot sensibly assign a fictive temperature to the Johari-Goldstein relaxation. This behavior contrasts with that of liquids lacking distinct Johari-Goldstein peaks for which the excess wing of the alpha peak tracks the main part of the peak during aging, enabling the assignment of a single fictive temperature to the entire spectrum. The aging behavior of the Johari-Goldstein relaxation time further calls into question the possibility that the relaxation time possesses stronger temperature dependence in equilibrium than is observed in the out-of-equilibrium state below the glass transition.

  11. Liquid -to-glass transition in bulk glass-forming Cu55-xZr45Agx alloys using molecular dynamic simulations

    Directory of Open Access Journals (Sweden)

    Celtek M.

    2011-05-01

    Full Text Available We report results from molecular dynamics (MD studies concerning the microscopic structure of the ternary, bulk metallic glass-forming Cu55-x Zr45Agx (x=0,10,20 alloys using tight-binding potentials. Understanding of the nature of Glass Forming Ability (GFA of studied alloys, GFA parameters, glass transition temperature (T-g, melting temperature (T-m, reduced glass transition temperature (T-g/T-m, the supercooled liquid region and other parameters were simulated and compared with experiments. The computed pair distribution functions reproduce well experimental x-ray data of Inoue and co-workers. Structure analysis of the Cu-Zr-Ag alloy based on MD simulation will be also presented

  12. Conventional methods fail to measure cp(omega) of glass-forming liquids

    DEFF Research Database (Denmark)

    Christensen, Tage Emil; Olsen, Niels Boye; Dyre, Jeppe

    2007-01-01

    thermal-wave method does not measure the isobaric frequency-dependent specific heat cp(omega). This method rather measures a "longitudinal" frequency-dependent specific heat, a quantity defined and detailed here that is in between cp(omega) and cV(omega). This result means that no reliable wide......-frequency measurements of cp(omega) on liquids approaching the calorimetric glass transition exist. We briefly discuss consequences for experiment....

  13. Dynamical, structural and chemical heterogeneities in a binary metallic glass-forming liquid

    Science.gov (United States)

    Puosi, F.; Jakse, N.; Pasturel, A.

    2018-04-01

    As it approaches the glass transition, particle motion in liquids becomes highly heterogeneous and regions with virtually no mobility coexist with liquid-like domains. This complex dynamic is believed to be responsible for different phenomena including non-exponential relaxation and the breakdown of the Stokes-Einstein relation. Understanding the relationships between dynamical heterogeneities and local structure in metallic liquids and glasses is a major scientific challenge. Here we use classical molecular dynamics simulations to study the atomic dynamics and microscopic structure of Cu50Zr50 alloy in the supercooling regime. Dynamical heterogeneities are identified via an isoconfigurational analysis. We demonstrate the transition from isolated to clustering low mobility with decreasing temperature. These slow clusters, whose sizes grow upon cooling, are also associated with concentration fluctuations, characterized by a Zr-enriched phase, with a composition CuZr2 . In addition, a structural analysis of slow clusters based on Voronoi tessellation evidences an increase with respect of the bulk system of the fraction of Cu atoms having a local icosahedral order. These results are in agreement with the consolidated scenario of the relevant role played by icosahedral order in the dynamic slowing-down in supercooled metal alloys.

  14. Structural evolution during fragile-to-strong transition in CuZr(Al) glass-forming liquids

    DEFF Research Database (Denmark)

    Zhou, C.; Hu, L.N.; Sun, Q.J.

    2015-01-01

    In the present work, we show experimental evidence for the dynamic fragile-to-strong (F-S) transition in a series of CuZr(Al) glass-forming liquids (GFLs). A detailed analysis of the dynamics of 98 glass-forming liquids indicates that the F-S transition occurs around Tf-s ≈ 1.36 Tg. Using...... the hyperquenching-annealing-x-ray scattering approach, we have observed a three-stage evolution pattern of medium-range ordering (MRO) structures during the F-S transition, indicating a dramatic change of the MRO clusters around Tf-s upon cooling. The F-S transition in CuZr(Al) GFLs is attributed to the competition...... among the MRO clusters composed of different locally ordering configurations. A phenomenological scenario has been proposed to explain the structural evolution from the fragile to the strong phase in the CuZr(Al) GFLs....

  15. Predicting Nanoscale Dynamics of a Glass-Forming Liquid from Its Macroscopic Bulk Behavior and Vice Versa.

    Science.gov (United States)

    Adrjanowicz, Karolina; Kaminski, Kamil; Tarnacka, Magdalena; Szklarz, Grzegorz; Paluch, Marian

    2017-02-02

    The properties of a molecular liquid confined at the nanometer length scale can be very distinct from the bulk. For that reason, the macro- and the nanoscopic behaviors of glass-forming liquids are regarded as two nonconnected realms, governed by their own rules. Here, we show that the glassy dynamics in molecular liquids confined to nanometer pores might obey the density scaling relation, ρ γ /T, just like in bulk fluids. Even more surprisingly, the same value of the scaling exponent γ superposes the α-relaxation time measured at different state points in nanoscale confinement and upon increased pressure. We report this remarkable finding for van der Waals liquids tetramethyl-tetraphenyl-trisiloxane (DC704) and polyphenyl ether (5PPE), considered as simple, single-parameter liquids. Demonstrating that the density scaling idea can be fulfilled in both environments opens an exciting possibility to predict the dynamic features of the nanoconfined system close to its glass-transition temperature from the high-pressure studies of the bulk liquid. Likewise, we can describe the viscous liquid dynamics at any given combination of temperature and pressure based on analysis of its behavior in nanopores.

  16. Entropic vs. elastic models of fragility of glass-forming liquids: Two sides of the same coin?

    Science.gov (United States)

    Sen, Sabyasachi

    2012-10-01

    The two most influential atomistic models that have been proposed in the literature to explain the temperature dependent activation energy of viscous flow of a glass-forming liquid, i.e., its fragility, are the configurational entropy model of Adam and Gibbs [J. Chem. Phys. 43, 139 (1965), 10.1063/1.1696442] and the elastic "shoving" model of Dyre et al. [J. Non-Cryst. Solids 352, 4635 (2006), 10.1016/j.jnoncrysol.2006.02.173]. Here we demonstrate a qualitative equivalence between these two models starting from the well-established general relationships between the interatomic potentials, elastic constants, structural rearrangement, and entropy in amorphous materials. The unification of these two models provides important predictions that are consistent with experimental observations and shed new light into the problem of glass transition.

  17. Changing the Tendency of Glass-Forming Liquid To Crystallize by Moving Along Different Isolines in the T-p Phase Diagram

    DEFF Research Database (Denmark)

    Adrjanowicz, Karolina; Koperwas, Kajetan; Tarnacka, Magdalena

    2016-01-01

    Controlling crystallization and glass-forming tendencies of molecular liquids is of great scientific and practical importance. In the present work, we show that a lot can be learned regarding this process by introducing temperature and pressure as thermodynamic control variables. For the glass...

  18. Study of the mixed alkali effect in lithium and sodium metaphosphate glass-forming liquids by photon correlation spectroscopy

    International Nuclear Information System (INIS)

    Changstrom, J R; Sidebottom, D L

    2008-01-01

    We report results of an extensive study of the structural relaxation occurring in mixed alkali metaphosphate liquids obtained by photon correlation spectroscopy. Values for the glass transition temperature, the fragility index, and the heterogeneity parameter (also known as the Kohlrausch exponent) are extracted from the measurements and are all shown to exhibit a mixed alkali effect wherein nonlinear variations with mixing occur. The depression in the glass transition temperature is shown to be the direct result of mechanical relaxations, present in the solid, which prematurely loosen the glass structure. A minimum in the fragility index is believed to be an artifact of the resulting depression of the glass transition temperature

  19. Low-energy excitations in a low-viscous glass-forming liquid

    Indian Academy of Sciences (India)

    Abstract. Polarized and depolarized low frequency Raman spectra of a liquid mixture, viz. 0·15LiCl–0·85H2O, has been analysed in detail in order to elucidate the temperature and polarization characteristics of quasi-elastic line and Boson peak. The employed fitting procedure shows more convincingly that the Boson peak ...

  20. An energy landscape model for glass-forming liquids in three dimensions

    DEFF Research Database (Denmark)

    Pedersen, Ulf Rørbæk; Hecksher, Tina; Dyre, Jeppe

    2006-01-01

    different densities at several temperatures. At high densities and low temperatures the model captures the important characteristics of viscous liquid dynamics. We thus observe non-exponential relaxation in the self part of the density auto-correlation function, and fragility plots of the self...

  1. Elastic models for the non-Arrhenius viscosity of glass-forming liquids

    DEFF Research Database (Denmark)

    Dyre, Jeppe; Christensen, Tage Emil; Olsen, Niels Boye

    2006-01-01

    This paper first reviews the shoving model for the non-Arrhenius viscosity of viscous liquids. According to this model the main contribution to the activation energy of a flow event is the energy needed for molecules to shove aside the surrounding, an energy which is proportional...

  2. Source of non-arrhenius average relaxation time in glass-forming liquids

    DEFF Research Database (Denmark)

    Dyre, Jeppe

    1998-01-01

    then discuss a recently proposed model according to which the activation energy of the average relaxation time is determined by the work done in shoving aside the surrounding liquid to create space needed for a "flow event". In this model, which is based on the fact that intermolecular interactions...

  3. Elastic models for the non-Arrhenius relaxation time of glass-forming liquids

    DEFF Research Database (Denmark)

    Dyre, Jeppe

    We first review the phenomenology of viscous liquids and the standard models used for explaining the non-Arrhenius average relaxation time. Then the focus is turned to the so-called elastic models, arguing that these models are all equivalent in the Einstein approximation (where the short-time...... elastic properties are all determined by just one effective, temperature-dependent force constant). We finally discuss the connection between the elastic models and two well-established research fields of condensed-matter physics: point defects in crystals and solid-state diffusion....

  4. Elastic models for the Non-Arrhenius Relaxation Time of Glass-Forming Liquids

    DEFF Research Database (Denmark)

    Dyre, J. C.

    2006-01-01

    We first review the phenomenology of viscous liquids and the standard models used for explaining the non-Arrhenius average relaxation time. Then the focus is turned to the so-called elastic models, arguing that these models are all equivalent in the Einstein approximation (where the short-time...... elastic properties are all determined by just one effective, temperature-dependent force constant). We finally discuss the connection between the elastic models and two well-established research fields of condensed-matter physics: point defects in crystals and solid-state diffusion....

  5. Unusual features of long-range density fluctuations in glass-forming organic liquids: A Rayleigh and Rayleigh-Brillouin light scattering study

    International Nuclear Information System (INIS)

    Patkowski, A.; Fischer, E. W.; Steffen, W.; Glaser, H.; Baumann, M.; Ruths, T.; Meier, G.

    2001-01-01

    A new feature of glass-forming liquids, i.e., long-range density fluctuations of the order of 100 nm, has been extensively characterized by means of static light scattering, photon correlation spectroscopy and Rayleigh-Brillouin spectroscopy in orthoterphenyl (OTP) and 1,1-di(4 # prime#-methoxy-5 # prime#methyl-phenyl)-cyclohexane (BMMPC). These long-range density fluctuations result in the following unusual features observed in a light scattering experiment, which are not described by the existing theories: (i) strong q-dependent isotropic excess Rayleigh intensity, (ii) additional slow component in the polarized photon correlation function, and (iii) high Landau-Placzek ratio. These unusual features are equilibrium properties of the glass-forming liquids and depend only on temperature, provided that the sample has been equilibrated long enough. The temperature-dependent equilibration times were measured for BMMPC and are about 11 orders of magnitude longer than the α process. It was found that the glass-forming liquid OTP may occur in two states: with and without long-range density fluctuations ('clusters'). We have characterized the two states by static and dynamic light scattering in the temperature range from T g to T g +200 K. The relaxation times of the α process as well as the parameters of the Brillouin line are identical in both OTP with and without clusters. The α process (density fluctuations) in OTP was characterized by measuring either the polarized (VV) or depolarized (VH) correlation function, which are practically identical and q-independent. This feature, which is commonly observed in glass-forming liquids, is not fully explained by the existing theories

  6. Do atmospheric aerosols form glasses?

    Directory of Open Access Journals (Sweden)

    D. A. Pedernera

    2008-09-01

    Full Text Available A new process is presented by which water soluble organics might influence ice nucleation, ice growth, chemical reactions and water uptake of aerosols in the upper troposphere: the formation of glassy aerosol particles. Glasses are disordered amorphous (non-crystalline solids that form when a liquid is cooled without crystallization until the viscosity increases exponentially and molecular diffusion practically ceases. The glass transition temperatures, Tg, homogeneous ice nucleation temperatures, Thom, and ice melting temperatures, Tm, of various aqueous inorganic, organic and multi-component solutions are investigated with a differential scanning calorimeter. The investigated solutes are: various polyols, glucose, raffinose, levoglucosan, an aromatic compound, sulfuric acid, ammonium bisulfate and mixtures of dicarboxylic acids (M5, of dicarboxylic acids and ammonium sulfate (M5AS, of two polyols, of glucose and ammonium nitrate, and of raffinose and M5AS. The results indicate that aqueous solutions of the investigated inorganic solutes show Tg values that are too low to be of atmospheric importance. In contrast, aqueous organic and multi-component solutions readily form glasses at low but atmospherically relevant temperatures (≤230 K. To apply the laboratory data to the atmospheric situation, the measured phase transition temperatures were transformed from a concentration to a water activity scale by extrapolating water activities determined between 252 K and 313 K to lower temperatures. The obtained state diagrams reveal that the higher the molar mass of the aqueous organic or multi-component solutes, the higher Tg of their respective solutions at a given water activity. To a lesser extent, Tg also depends on the hydrophilicity of the organic solutes. Therefore, aerosol particles containing larger (≳150 g mol−1 and

  7. Thermal behaviors of liquid La-based bulk metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, D. W.; Wang, X. D., E-mail: wangxd@zju.edu.cn, E-mail: jiangjz@zju.edu.cn; Lou, H. B.; Cao, Q. P.; Jiang, J. Z., E-mail: wangxd@zju.edu.cn, E-mail: jiangjz@zju.edu.cn [International Center for New-Structured Materials (ICNSM), Laboratory of New-Structured Materials, State Key Laboratory of Silicon Materials, and Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Wang, L. W. [Institute of Materials Science and Engineering, Lanzhou University, Lanzhou 730000 (China); Zhang, D. X. [State Key Laboratory of Modern Optical Instrumentation, Zhejiang University, Hangzhou 310027 (China)

    2014-12-14

    Thermal behaviors of liquid La-based bulk metallic glasses have been measured by using the dilatometer with a self-sealed sample cell. It is demonstrated that the strong glass forming liquid not only has the small thermal expansion coefficient but also shows the slow variation rate. Moreover, the strong glass former has relatively dense atomic packing and also small density change in the liquid state. The results suggest that the high glass forming ability of La-based metallic glasses would be closely related to the slow atomic rearrangements in liquid melts.

  8. Determination of Fragility in Organic Small Molecular Glass Forming Liquids: Comparison of Calorimetric and Spectroscopic Data and Commentary on Pharmaceutical Importance.

    Science.gov (United States)

    Chakravarty, Paroma; Pandya, Keyur; Nagapudi, Karthik

    2018-03-05

    The fragility index ( m) and conversely the strength parameter ( D) are widely used to categorize glass forming liquids and are used to characterize temperature dependency of viscosity and relaxation time as the supercooled liquid approaches glass transition. The currently used calorimetric methods in pharmaceutical literature lead to wide variability in measured values of m. In this work, a modulated differential scanning calorimetry (DSC) method is introduced that can directly determine m with minimal variability. Although calorimetric fragility is easy to measure due to availability and ease of use of DSC, there is no correlation between calorimetric and dielectric fragility (calculated spectroscopically from relaxation times). In addition, there is also no correlation between calorimetric fragility and the so-called "thermodynamic fragility" that can be calculated using only thermodynamic parameters. No relationship can be found between the crystallization propensity in the supercooled liquid state and D. However, the crystallization propensity shows a reasonable correlation with the Kohlrausch distribution parameter β k , which defines the breadth of the relaxation time distribution.

  9. 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

  10. Glass Forming Ability in Systems with Competing Orderings

    Science.gov (United States)

    Russo, John; Romano, Flavio; Tanaka, Hajime

    2018-04-01

    Some liquids, if cooled rapidly enough to avoid crystallization, can be frozen into a nonergodic glassy state. The tendency for a material to form a glass when quenched is called "glass-forming ability," and it is of key significance both fundamentally and for materials science applications. Here, we consider liquids with competing orderings, where an increase in the glass-forming ability is signaled by a depression of the melting temperature towards its minimum at triple or eutectic points. With simulations of two model systems where glass-forming ability can be tuned by an external parameter, we are able to interpolate between crystal-forming and glass-forming behavior. We find that the enhancement of the glass-forming ability is caused by an increase in the structural difference between liquid and crystal: stronger competition in orderings towards the melting point minimum makes a liquid structure more disordered (more complex). This increase in the liquid-crystal structure difference can be described by a single adimensional parameter, i.e., the interface energy cost scaled by the thermal energy, which we call the "thermodynamic interface penalty." Our finding may provide a general physical principle for not only controlling the glass-forming ability but also the emergence of glassy behavior of various systems with competing orderings, including orderings of structural, magnetic, electronic, charge, and dipolar origin.

  11. ESCA studies on leached glass forms

    International Nuclear Information System (INIS)

    Dawkins, B.G.

    1979-01-01

    Electron Spectroscopy for Chemical Analysis (ESCA) results for frit, obsidian, NBS standard, and Savannah River Laboratory (SRL) glass forms that have been subjected to cumulative water leachings of 36 hours show that [Na] exhibits the largest and fastest change of all the elements observed. Leaching of surface Na occurred within minutes. Surface Na depletion increased with leach time. Continuous x-ray irradiation and argon ion milling induced Na mobility, precluding semiquantitative ESCA analysis at normal operating temperatures. However, the sample stage has been equipped with a liquid nitrogen supply and alkali mobility should be eliminated in future work

  12. Apparent Violation of the Fluctuation-Dissipation Theorem due to Dynamic Heterogeneity in a Model Glass-Forming Liquid

    International Nuclear Information System (INIS)

    Kawasaki, Takeshi; Tanaka, Hajime

    2009-01-01

    Here we study the relation between the mobility and the translational diffusion in supercooled two-dimensional polydisperse colloidal liquids, using numerical simulations. We find an apparent violation of the Einstein-Smoluchowski (ES) relation D=k B Tμ (D: diffusion constant; μ: mobility; k B ; Boltzmann's constant; T: temperature). The violation is a direct consequence of the fact that it is difficult for a driven particle to enter a jammed region with high order due to its yield stress. The degree of this apparent ES violation is controlled solely by the characteristic size of slow jammed regions, ξ. Our finding implies that the characteristic time of this problem is not the structural relaxation time τ α but the lifetime of dynamic heterogeneity, τ ξ . A supercooled liquid can be regarded to be ergodic only over τ ξ , which may be the slowest intrinsic time scale of the system.

  13. Dynamic thermal expansivity of liquids near the glass transition

    DEFF Research Database (Denmark)

    Niss, Kristine; Gundermann, Ditte; Christensen, Tage Emil

    2012-01-01

    Based on previous works on polymers by Bauer et al. [ Phys. Rev. E 61 1755 (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704) in the ......Based on previous works on polymers by Bauer et al. [ Phys. Rev. E 61 1755 (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704...... the liquid contracts when cooling from room temperature down to around the glass-transition temperature, which is relevant when measuring on a molecular liquid rather than a polymer....

  14. Transition from Arrhenius to non-Arrhenius temperature dependence of structural relaxation time in glass-forming liquids: continuous versus discontinuous scenario.

    Science.gov (United States)

    Popova, V A; Surovtsev, N V

    2014-09-01

    The temperature dependences of α relaxation time τ(α)(T) of three glass-forming liquids (salol, o-terphenyl, and α-picoline) were investigated by a depolarized light scattering technique. A detailed description of τ(α)(T) near T(A), the temperature of the transition from the Arrhenius law at high temperatures to a non-Arrhenius behavior of τ(α)(T) at lower temperatures, was done. It was found that this transition is quite sharp. If the transition is described as switching from the Arrhenius law to the Vogel-Fulcher-Tammann law, it occurs within the temperature range of about 15 K or less. Most of the known expressions for τ(α)(T) cannot describe this sharp transition. Our analysis revealed that this transition can be described either as a discontinuous transition in the spirit of the frustration-limited domain theory [D. Kivelson, G. Tarjus, X. Zhao, and S. A. Kivelson, Phys. Rev. E 53, 751 (1996)], implying a phase transition, or by a phenomenological expression recently suggested [B. Schmidtke, N. Petzold, R. Kahlau, M. Hofmann, and E. A. Rössler, Phys. Rev. E 86, 041507 (2012)], where the activation energy includes the term depending exponentially on temperature.

  15. Review of glass ceramic waste forms

    International Nuclear Information System (INIS)

    Rusin, J.M.

    1981-01-01

    Glass ceramics are being considered for the immobilization of nuclear wastes to obtain a waste form with improved properties relative to glasses. Improved impact resistance, decreased thermal expansion, and increased leach resistance are possible. In addition to improved properties, the spontaneous devitrification exhibited in some waste-containing glasses can be avoided by the controlled crystallization after melting in the glass-ceramic process. The majority of the glass-ceramic development for nuclear wastes has been conducted at the Hahn-Meitner Institute (HMI) in Germany. Two of their products, a celsian-based (BaAl 3 Si 2 O 8 ) and a fresnoite-based (Ba 2 TiSi 2 O 8 ) glass ceramic, have been studied at Pacific Northwest Laboratory (PNL). A basalt-based glass ceramic primarily containing diopsidic augite (CaMgSi 2 O 6 ) has been developed at PNL. This glass ceramic is of interest since it would be in near equilibrium with a basalt repository. Studies at the Power Reactor and Nuclear Fuel Development Corporation (PNC) in Japan have favored a glass-ceramic product based upon diopside (CaMgSi 2 O 6 ). Compositions, processing conditions, and product characterization of typical commercial and nuclear waste glass ceramics are discussed. In general, glass-ceramic waste forms can offer improved strength and decreased thermal expansion. Due to typcially large residual glass phases of up to 50%, there may be little improvement in leach resistance

  16. Method and apparatus for glass solidification porcessing for radioactive liquid waste

    International Nuclear Information System (INIS)

    Torada, Shin-ichiro; Masaki, Toshio; Sakai, Akira.

    1989-01-01

    Glass material supplied to a glass melting furnace is made in the form of a glass container. Then, radioactive liquid wastes are directly injected into the glass vessel and the glass vessel injected with the radioactive liquid wastes is charged into the glass melting furnace. The glass material and the radioactive liquid wastes are supplied simultaneously to the glass melting furnace. Then, corresponding to the amount of the glass material used for the glass vessel, the amount of the radioactive liquid wastes injected to the inside thereof is controlled to thereby set the mixing ratio between the glass material and the radioactive liquid wastes. Further, by controlling the number of the glass vessels injected with the radioactive liquid wastes to be charged into the glass melting furnace, the amount of supplying the radioactive liquid wastes and the glass material is controlled. This can easily maintain constant the amount of the glass material and the radioacative liquid wastes supplied to the glass melting furnace and the mixing ratio thereof. (T.M.)

  17. Thermal conductivity of Glycerol's liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures.

    Science.gov (United States)

    Andersson, Ove; Johari, G P

    2016-02-14

    To investigate the effects of local density fluctuations on phonon propagation in a hydrogen bonded structure, we studied the thermal conductivity κ of the crystal, liquid, and glassy states of pure glycerol as a function of the temperature, T, and the pressure, p. We find that the following: (i) κcrystal is 3.6-times the κliquid value at 140 K at 0.1 MPa and 2.2-times at 290 K, and it varies with T according to 138 × T(-0.95); (ii) the ratio κliquid (p)/κliquid (0.1 MPa) is 1.45 GPa(-1) at 280 K, which, unexpectedly, is about the same as κcrystal (p)/κcrystal (0.1 MPa) of 1.42 GPa(-1) at 298 K; (iii) κglass is relatively insensitive to T but sensitive to the applied p (1.38 GPa(-1) at 150 K); (iv) κglass-T plots show an enhanced, pressure-dependent peak-like feature, which is due to the glass to liquid transition on heating; (v) continuous heating cold-crystallizes ultraviscous glycerol under pressure, at a higher T when p is high; and (vi) glycerol formed by cooling at a high p and then measured at a low p has a significantly higher κ than the glass formed by cooling at a low p. On heating at a fixed low p, its κ decreases before its glass-liquid transition range at that p is reached. We attribute this effect to thermally assisted loss of the configurational and vibrational instabilities of a glass formed at high p and recovered at low p, which is different from the usual glass-aging effect. While the heat capacity, entropy, and volume of glycerol crystal are less than those for its glass and liquid, κcrystal of glycerol, like its elastic modulus and refractive index, is higher. We discuss these findings in terms of the role of fluctuations in local density and structure, and the relations between κ and the thermodynamic quantities.

  18. Forming Glasses from Se and Te

    Directory of Open Access Journals (Sweden)

    Pierre Lucas

    2009-10-01

    Full Text Available Despite being close neighbors on the Periodic Table, selenium and tellurium present a totally different abilities to form glasses. Se is a very good glass former, and gives rise to numerous glass compositions which are popular for their transparency in the infrared range and their stability against crystallization. These glasses can be shaped into sophisticated optical devices such as optical fibers, planar guides or lenses. Nevertheless, their transparencies are limited at about 12 μm (depending on the thickness of the optical systems due to the relatively small mass of the Se element. On the other hand, tellurium is heavier and its use in substitution for Se permits to shift the IR cutoff beyond 20 μm. However, the semimetallic nature of Te limits its glass formation ability and this glass family is known to be unstable and consequently has found application as phase change material in the Digital Versatile Disk (DVD technology. In this paper, after a review of selenide glasses and their applications, it will be shown how, in a recent past, it has been possible to stabilize tellurium glasses by introducing new elements like Ga or I in their compositions.

  19. Free volume from positron lifetime and pressure-volume-temperature experiments in relation to structural relaxation of van der Waals molecular glass-forming liquids.

    Science.gov (United States)

    Dlubek, G; Shaikh, M Q; Rätzke, K; Paluch, M; Faupel, F

    2010-06-16

    Positron annihilation lifetime spectroscopy (PALS) is employed to characterize the temperature dependence of the free volume in two van der Waals liquids: 1, 1'-bis(p-methoxyphenyl)cyclohexane (BMPC) and 1, 1'-di(4-methoxy-5-methylphenyl)cyclohexane (BMMPC). From the PALS spectra analysed with the routine LifeTime9.0, the size (volume) distribution of local free volumes (subnanometer size holes), its mean, [v(h)], and mean dispersion, σ(h), were calculated. A comparison with the macroscopic volume from pressure-volume-temperature (PV T) experiments delivered the hole density and the specific hole free volume and a complete characterization of the free volume microstructure in that sense. These data are used in correlation with structural (α) relaxation data from broad-band dielectric spectroscopy (BDS) in terms of the Cohen-Grest and Cohen-Turnbull free volume models. An extension of the latter model allows us to quantify deviations between experiments and theory and an attempt to systematize these in terms of T(g) or of the fragility. The experimental data for several fragile and less fragile glass formers are involved in the final discussion. It was concluded that, for large differences in the fragility of different glass formers, the positron lifetime mirrors clearly the different character of these materials. For small differences in the fragility, additional properties like the character of bonds and chemical structure of the material may affect size, distribution and thermal behaviour of the free volume.

  20. Free volume from positron lifetime and pressure-volume-temperature experiments in relation to structural relaxation of van der Waals molecular glass-forming liquids

    Energy Technology Data Exchange (ETDEWEB)

    Dlubek, G [ITA Institute for Innovative Technologies, Koethen/Halle, Wiesenring 4, D-06120 Lieskau (Germany); Shaikh, M Q; Raetzke, K; Faupel, F [Faculty of Engineering, Institute for Materials Science, Christian-Albrechts University of Kiel, Kaiserstrasse 2, D-24143 Kiel (Germany); Paluch, M, E-mail: guenter.dlubek@gmx.d [Institute of Physics, Silesian University, Uniwersytecka 4, 40-007 Katowice (Poland)

    2010-06-16

    Positron annihilation lifetime spectroscopy (PALS) is employed to characterize the temperature dependence of the free volume in two van der Waals liquids: 1, 1'-bis(p-methoxyphenyl)cyclohexane (BMPC) and 1, 1'-di(4-methoxy-5-methylphenyl)cyclohexane (BMMPC). From the PALS spectra analysed with the routine LifeTime9.0, the size (volume) distribution of local free volumes (subnanometer size holes), its mean, (v{sub h}), and mean dispersion, {sigma}{sub h}, were calculated. A comparison with the macroscopic volume from pressure-volume-temperature (PV T) experiments delivered the hole density and the specific hole free volume and a complete characterization of the free volume microstructure in that sense. These data are used in correlation with structural ({alpha}) relaxation data from broad-band dielectric spectroscopy (BDS) in terms of the Cohen-Grest and Cohen-Turnbull free volume models. An extension of the latter model allows us to quantify deviations between experiments and theory and an attempt to systematize these in terms of T{sub g} or of the fragility. The experimental data for several fragile and less fragile glass formers are involved in the final discussion. It was concluded that, for large differences in the fragility of different glass formers, the positron lifetime mirrors clearly the different character of these materials. For small differences in the fragility, additional properties like the character of bonds and chemical structure of the material may affect size, distribution and thermal behaviour of the free volume.

  1. Undercooling Limits and Thermophysical Properties in Glass Forming Alloys

    Science.gov (United States)

    Rhim, Won-Kyu; Ohsaka, Kenichi; Spjut, R. Erik

    1999-01-01

    The primary objective of this program is to produce deeply undercooled metallic liquids and to identify factors that limit undercooling and glass formation. The main research objectives are: (1) Investigating undercooling limits in glass-forming alloys and identifying factors that affect undercooling; (2) Measuring thermophysical properties and investigating the validity of the classical nucleation theory and other existing theories in the extreme undercooled states; and (3) To investigate the limits of electrostatic levitation technology in the ground base and to identify thermophysical parameters that might require reduced-g environment.

  2. Dynamic thermal expansivity of liquids near the glass transition.

    Science.gov (United States)

    Niss, Kristine; Gundermann, Ditte; Christensen, Tage; Dyre, Jeppe C

    2012-04-01

    Based on previous works on polymers by Bauer et al. [Phys. Rev. E 61, 1755 (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704) in the ultraviscous regime. Compared to the method of Bauer et al., the dynamical range has been extended by making time-domain experiments and by making very small and fast temperature steps. The modeling of the experiment presented in this paper includes the situation in which the capacitor is not full because the liquid contracts when cooling from room temperature down to around the glass-transition temperature, which is relevant when measuring on a molecular liquid rather than a polymer.

  3. Vitrification and determination of the crystallization time scales of the bulk-metallic-glass-forming liquid Zr58.5Nb2.8Cu15.6Ni12.8Al10.3

    International Nuclear Information System (INIS)

    Hays, C. C.; Schroers, J.; Johnson, W. L.; Rathz, T. J.; Hyers, R. W.; Rogers, J. R.; Robinson, M. B.

    2001-01-01

    The crystallization kinetics of Zr 58.5 Nb 2.8 Cu 15.6 Ni 12.8 Al 10.3 were studied in an electrostatic levitation (ESL) apparatus. The measured critical cooling rate is 1.75 K/s. Zr 58.5 Nb 2.8 Cu 15.6 Ni 12.8 Al 10.3 is the first bulk-metallic-glass-forming liquid that does not contain beryllium to be vitrified by purely radiative cooling in the ESL. Furthermore, the sluggish crystallization kinetics enable the determination of the time-temperature-transformation (TTT) diagram between the liquidus and the glass transition temperatures. The shortest time to reach crystallization in an isothermal experiment; i.e., the nose of the TTT diagram is 32 s. The nose of the TTT diagram is at 900 K and positioned about 200 K below the liquidus temperature

  4. Ceramic and glass radioactive waste forms

    Energy Technology Data Exchange (ETDEWEB)

    Readey, D.W.; Cooley, C.R. (comps.)

    1977-01-01

    This report contains 14 individual presentations and 6 group reports on the subject of glass and polycrystalline ceramic radioactive waste forms. It was the general consensus that the information available on glass as a waste form provided a good basis for planning on the use of glass as an initial waste form, that crystalline ceramic forms could also be good waste forms if much more development work were completed, and that prediction of the chemical and physical stability of the waste form far into the future would be much improved if the basic synergistic effects of low temperature, radiation and long times were better understood. Continuing development of the polycrystalline ceramic forms was recommended. It was concluded that the leach rate of radioactive species from the waste form is an important criterion for evaluating its suitability, particularly for the time period before solidified waste is permanently placed in the geologic isolation of a Federal repository. Separate abstracts were prepared for 12 of the individual papers; the remaining two were previously abstracted.

  5. Glass and liquid phase diagram of a polyamorphic monatomic system

    Science.gov (United States)

    Reisman, Shaina; Giovambattista, Nicolas

    2013-02-01

    We perform out-of-equilibrium molecular dynamics (MD) simulations of a monatomic system with Fermi-Jagla (FJ) pair potential interactions. This model system exhibits polyamorphism both in the liquid and glass state. The two liquids, low-density (LDL) and high-density liquid (HDL), are accessible in equilibrium MD simulations and can form two glasses, low-density (LDA) and high-density amorphous (HDA) solid, upon isobaric cooling. The FJ model exhibits many of the anomalous properties observed in water and other polyamorphic liquids and thus, it is an excellent model system to explore qualitatively the thermodynamic properties of such substances. The liquid phase behavior of the FJ model system has been previously characterized. In this work, we focus on the glass behavior of the FJ system. Specifically, we perform systematic isothermal compression and decompression simulations of LDA and HDA at different temperatures and determine "phase diagrams" for the glass state; these phase diagrams varying with the compression/decompression rate used. We obtain the LDA-to-HDA and HDA-to-LDA transition pressure loci, PLDA-HDA(T) and PHDA-LDA(T), respectively. In addition, the compression-induced amorphization line, at which the low-pressure crystal (LPC) transforms to HDA, PLPC-HDA(T), is determined. As originally proposed by Poole et al. [Phys. Rev. E 48, 4605 (1993)], 10.1103/PhysRevE.48.4605 simulations suggest that the PLDA-HDA(T) and PHDA-LDA(T) loci are extensions of the LDL-to-HDL and HDL-to-LDL spinodal lines into the glass domain. Interestingly, our simulations indicate that the PLPC-HDA(T) locus is an extension, into the glass domain, of the LPC metastability limit relative to the liquid. We discuss the effects of compression/decompression rates on the behavior of the PLDA-HDA(T), PHDA-LDA(T), PLPC-HDA(T) loci. The competition between glass polyamorphism and crystallization is also addressed. At our "fast rate," crystallization can be partially suppressed and the

  6. Glass forming ability of calcium aluminosilicate melts

    DEFF Research Database (Denmark)

    Moesgaard, Mette; Yue, Yuanzheng

    2011-01-01

    The glass forming ability (GFA) of two series of calcium aluminosilicate melts is studied by measuring their viscous behavior and crystallization tendency. The first series consists of five compositions on the joining line between the eutectic point of anorthite-wollastonite-tridymite and that of......The glass forming ability (GFA) of two series of calcium aluminosilicate melts is studied by measuring their viscous behavior and crystallization tendency. The first series consists of five compositions on the joining line between the eutectic point of anorthite......-wollastonite-tridymite and that of anorthite-wollastonite-gehlenite. The series includes the eutectic compositions as end members. The second series consists of five compositions on a line parallel to the joining line on the alumina rich side. In the present work, GFA is described in terms of glass stability, i.e., the ability of a glass...... to resist crystallization during reheating. In addition, the fragility index (m) is derived by fitting the viscosity data with the Avramov-Milchev equation. The results show that m is inversely proportional to the glass stability for the two series of melts, implying that m is an indirect measure of GFA...

  7. Liquid phase and supercooled liquid phase welding of bulk metallic glasses

    International Nuclear Information System (INIS)

    Kawamura, Y.

    2004-01-01

    Recent progress on welding in bulk metallic glasses (BMGs) has been reviewed. BMGs have been successfully welded to BMGs or crystalline metals by liquid phase welding using explosion, pulse-current and electron-beam methods, and by supercooled liquid phase welding using friction method. Successful welding of the liquid phase methods was due to the high glass-forming ability of the BMGs and the high concentration of welding energy in these methods. In contrast, the supercooled liquid phase welding was successful due to the thermally stable supercooled liquid state of the BMGs and the superplasticity and viscous flow of the supercooled liquid. The successful welding of BMGs to BMGs and crystalline materials is promising for the future development of BMGs as engineering materials

  8. Glass forms for immobilization of Hanford wastes

    International Nuclear Information System (INIS)

    Schulz, W.W.; Dressen, A.L.; Hobbick, C.W.; Babad, H.

    1975-03-01

    Approximately 140 million liters of solid salt cake (mainly NaNO 3 ), produced by evaporation of aged alkaline high-level liquid wastes, will be stored in underground tanks when the present Hanford Waste Management Program is completed in the early 1980's. At this time also, large volumes of various other solid radioactive wastes (sludges, excavated Pu-contaminated soil, and doubly encapsulated 137 CsCl and 90 SrF 2 ) will be stored on the Hanford Reservation. All these solid wastes can be converted to immobile silicate and aluminosilicate glasses of low water leachability by melting them at 1100 0 to 1400 0 C with appropriate amounts of basalt (or sand) and other glass-formers such as B 2 O 3 or CaO. Reviewed in this paper are formulations and other melt conditions used successfully in batch tests to make glasses from actual and synthetic wastes; leachability and other properties of these glasses show them to be satisfactory vehicles for immobilization of the Hanford wastes. (U.S.)

  9. Simulation of Glass Fiber Forming Processes

    DEFF Research Database (Denmark)

    Von der Ohe, Renate

    Two glass fiber forming processes have been simulated using FEM, which are the drawing of continuous glass fibers for reinforcement purposes and the spinning of discontinuous glass fibers - stone wool for insulation. The aim of this work was to set up a numerical model for each process, and to use...... this model in finding relationships between the production conditions and the resulting fiber properties. For both processes, a free surface with large deformation and radiative and convective heat transfer must be taken into account. The continuous fiber drawing has been simulated successfully......, and parametric studies have been made. Several properties that characterize the process have been calculated, and the relationship between the fictive temperature and the cooling rate of the fibers has been found. The model for the discontinuous fiber spinning was brought to the limits of the commercial code...

  10. 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

  11. Heating-induced glass-glass and glass-liquid transformations in computer simulations of water

    Science.gov (United States)

    Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

    2014-03-01

    Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T "phase diagram" for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related

  12. Heating-induced glass-glass and glass-liquid transformations in computer simulations of water

    International Nuclear Information System (INIS)

    Chiu, Janet; Giovambattista, Nicolas; Starr, Francis W.

    2014-01-01

    Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T “phase diagram” for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related

  13. Heating-induced glass-glass and glass-liquid transformations in computer simulations of water

    Energy Technology Data Exchange (ETDEWEB)

    Chiu, Janet; Giovambattista, Nicolas [Department of Physics, Brooklyn College of the City University of New York, Brooklyn, New York 11210 (United States); Starr, Francis W. [Department of Physics, Wesleyan University, Middletown, Connecticut 06459 (United States)

    2014-03-21

    Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T “phase diagram” for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related

  14. Mechanical spectra of glass-forming liquids. II. Gigahertz-frequency longitudinal and shear acoustic dynamics in glycerol and DC704 studied by time-domain Brillouin scattering

    DEFF Research Database (Denmark)

    Klieber, Christoph; Hecksher, Tina; Pezeril, Thomas

    2013-01-01

    This paper presents and discusses the temperature and frequency dependence of the longitudinal and shear viscoelastic response at MHz and GHz frequencies of the intermediate glass former glycerol and the fragile glass former tetramethyl-tetraphenyl-trisiloxane (DC704). Measurements were performed...

  15. Mechanical spectra of glass-forming liquids. I. Low-frequency bulk and shear moduli of DC704 and 5-PPE measured by piezoceramic transducers

    DEFF Research Database (Denmark)

    Hecksher, Tina; Olsen, Niels Boye; Nelson, Keith Adam

    2013-01-01

    We present dynamic shear and bulk modulus measurements of supercooled tetraphenyl-tetramethyl-trisiloxane (DC704) and 5-phenyl-4-ether over a range of temperatures close to their glass transition. The data are analyzed and compared in terms of time-temperature superposition (TTS), the relaxation ...

  16. Forming of bulk metallic glass microcomponents

    DEFF Research Database (Denmark)

    Wert, John A.; Thomsen, Christian; Jensen, Rune Debel

    2009-01-01

    The present article considers forward extrusion, closed-die forging and backward extrusion processes for fabrication of individual microcomponents from two bulk metallic glass (BMG) compositions: Mg60Cu30Y10 and Zr44Cu40Ag8Al8. Two types of tooling were used in the present work: relatively massive...... die sets characteristic of cold forming operations for crystalline metals and lightweight die sets adapted to the special characteristics of BMGs. In addition to demonstrating that microcomponents of several geometries can be readily fabricated from BMGs, rheological properties are combined...

  17. Structure of the glass-forming metallic liquids by ab-initio and classical molecular dynamics, a case study: Quenching the Cu{sub 60}Ti{sub 20}Zr{sub 20} alloy

    Energy Technology Data Exchange (ETDEWEB)

    Amokrane, S.; Ayadim, A.; Levrel, L. [Groupe “Physique des Liquides et Milieux Complexes,” Faculté des Sciences et Technologie, Université Paris-Est (Créteil), 61 av. du Général de Gaulle, 94010 Créteil Cedex (France)

    2015-11-21

    We consider the question of the amorphization of metallic alloys by melt quenching, as predicted by molecular dynamics simulations with semi-empirical potentials. The parametrization of the potentials is discussed on the example of the ternary Cu-Ti-Zr transition metals alloy, using the ab-initio simulation as a reference. The pair structure in the amorphous state is computed from a potential of the Stillinger-Weber form. The transferability of the parameters during the quench is investigated using two parametrizations: from solid state data, as usual and from a new parametrization on the liquid structure. When the adjustment is made on the pair structure of the liquid, a satisfactory transferability is found between the pure components and their alloys. The liquid structure predicted in this way agrees well with experiment, in contrast with the one obtained using the adjustment on the solid. The final structure, after quenches down to the amorphous state, determined with the new set of parameters is shown to be very close to the ab-initio one, the latter being in excellent agreement with recent X-rays diffraction experiments. The corresponding critical temperature of the glass transition is estimated from the behavior of the heat capacity. Discussion on the consistency between the structures predicted using semi-empirical potentials and ab-initio simulation, and comparison of different experimental data underlines the question of the dependence of the final structure on the thermodynamic path followed to reach the amorphous state.

  18. A new parameter to evaluate the glass-forming ability of bulk metallic glasses

    International Nuclear Information System (INIS)

    Suo, Z.Y.; Qiu, K.Q.; Li, Q.F.; You, J.H.; Ren, Y.L.; Hu, Z.Q.

    2010-01-01

    Research highlights: → Develop a new criterion, i.e., Q=((T g +T x )/T l ).(ΔE/ΔH). → The reliability and benefits of the new criterion have been demonstrated in a wide range of BMG alloys. → It corresponds well with the critical diameter of BMGs investigated up to now. - Abstract: Based on the consideration of the liquid phase stability, the resistance to crystallization and the glass transition enthalpy, a new criterion Q, defined as ((T g + T x )/T l ).(ΔE/ΔH), where the T g , T x , T l , ΔE and ΔH are the glass transition temperature, the onset crystallization temperature, the liquidus temperature, the crystalline enthalpy and the fusion enthalpy, respectively, has been proposed for evaluating the glass-forming ability of bulk metallic glasses. The new criterion Q exhibits better correlation with the maximum cross section thickness (D m ) for glass formation compared with γ (=T x /(T l + T g )), T rg (=T g /T l ) and ΔT x (=T x - T g ) respectively. The available data from literatures and experiments have confirmed the effectiveness of the newly developed criterion.

  19. Connection between slow and fast dynamics of molecular liquids around the glass transition

    DEFF Research Database (Denmark)

    Niss, Kristine; Dalle-Ferrier, Cecile; Frick, Bernhard

    2010-01-01

    The mean-square displacement (MSD) was measured by neutron scattering at various temperatures and pressures for a number of molecular glass-forming liquids. The MSD is invariant along the glass-transition line at the pressure studied, thus establishing an “intrinsic” Lindemann criterion for any...

  20. Liquid-liquid phase transition and glass transition in a monoatomic model system.

    Science.gov (United States)

    Xu, Limei; Buldyrev, Sergey V; Giovambattista, Nicolas; Stanley, H Eugene

    2010-01-01

    We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses.

  1. Neutron- and light-scattering studies of the liquid-to-glass and glass-to-glass transitions in dense copolymer micellar solutions

    International Nuclear Information System (INIS)

    Chen Weiren; Chen Sowhsin; Mallamace, Francesco; Glinka, Charles J.; Fratini, Emiliano

    2003-01-01

    Recent mode coupling theory (MCT) calculations show that if a short-range attractive interaction is added to the pure hard sphere system, one may observe a new type of glass originating from the clustering effect (the attractive glass) as a result of the attractive interaction. This is in addition to the known glass-forming mechanism due to the cage effect in the hard sphere system (the repulsive glass). The calculations also indicate that if the range of attraction is sufficiently short compared to the diameter of the particle, within a certain interval of volume fractions where the two glass-forming mechanisms nearly balance each other, varying the external control parameter, the effective temperature, makes the glass-to-liquid-to-glass reentrance and the glass-to-glass transitions possible. Here we present experimental evidence of both transitions, obtained from small-angle neutron-scattering and photon correlation measurements taken from dense L64 copolymer micellar solutions in heavy water. Varying the temperature in certain predicted volume fraction range triggers a sharp transition between these two different types of glass. In particular, according to MCT, there is an end point (called A 3 singularity) of this glass-to-glass transition line, beyond which the long-time dynamics of the two glasses become identical. Our findings confirm this theoretical prediction. Surprisingly, although the Debye-Waller factors, the long-time limit of the coherent intermediate scattering functions, of these two glasses obtained from photon correlation measurements indeed become identical at the predicted volume fraction, they exhibit distinctly different intermediate time relaxation. Furthermore, our experimental results obtained from volume fractions beyond the end point are characterized by the same features as the repulsive glass obtained before the end point. A complete phase diagram giving the boundaries of the structural arrest transitions for L64 micellar system is

  2. Analysis of form deviation in non-isothermal glass molding

    Science.gov (United States)

    Kreilkamp, H.; Grunwald, T.; Dambon, O.; Klocke, F.

    2018-02-01

    Especially in the market of sensors, LED lighting and medical technologies, there is a growing demand for precise yet low-cost glass optics. This demand poses a major challenge for glass manufacturers who are confronted with the challenge arising from the trend towards ever-higher levels of precision combined with immense pressure on market prices. Since current manufacturing technologies especially grinding and polishing as well as Precision Glass Molding (PGM) are not able to achieve the desired production costs, glass manufacturers are looking for alternative technologies. Non-isothermal Glass Molding (NGM) has been shown to have a big potential for low-cost mass manufacturing of complex glass optics. However, the biggest drawback of this technology at the moment is the limited accuracy of the manufactured glass optics. This research is addressing the specific challenges of non-isothermal glass molding with respect to form deviation of molded glass optics. Based on empirical models, the influencing factors on form deviation in particular form accuracy, waviness and surface roughness will be discussed. A comparison with traditional isothermal glass molding processes (PGM) will point out the specific challenges of non-isothermal process conditions. Furthermore, the underlying physical principle leading to the formation of form deviations will be analyzed in detail with the help of numerical simulation. In this way, this research contributes to a better understanding of form deviations in non-isothermal glass molding and is an important step towards new applications demanding precise yet low-cost glass optics.

  3. Effect of temperature and density fluctuations on the spatially heterogeneous dynamics of glass-forming Van der Waals liquids under high pressure.

    Science.gov (United States)

    Koperwas, K; Grzybowski, A; Grzybowska, K; Wojnarowska, Z; Sokolov, A P; Paluch, M

    2013-09-20

    In this Letter, we show how temperature and density fluctuations affect the spatially heterogeneous dynamics at ambient and elevated pressures. By using high-pressure experimental data for van der Waals liquids, we examine contributions of the temperature and density fluctuations to the dynamics heterogeneity. We show that the dynamic heterogeneity decreases significantly with increasing pressure at a constant structural relaxation time (isochronal condition), while the broadening of the relaxation spectrum remains constant. This observation questions the relationship between spectral broadening and dynamic heterogeneity.

  4. Glass Transition, Crystallization of Glass-Forming Melts, and Entropy

    Directory of Open Access Journals (Sweden)

    Jürn W. P. Schmelzer

    2018-02-01

    Full Text Available A critical analysis of possible (including some newly proposed definitions of the vitreous state and the glass transition is performed and an overview of kinetic criteria of vitrification is presented. On the basis of these results, recent controversial discussions on the possible values of the residual entropy of glasses are reviewed. Our conclusion is that the treatment of vitrification as a process of continuously breaking ergodicity with entropy loss and a residual entropy tending to zero in the limit of zero absolute temperature is in disagreement with the absolute majority of experimental and theoretical investigations of this process and the nature of the vitreous state. This conclusion is illustrated by model computations. In addition to the main conclusion derived from these computations, they are employed as a test for several suggestions concerning the behavior of thermodynamic coefficients in the glass transition range. Further, a brief review is given on possible ways of resolving the Kauzmann paradox and its implications with respect to the validity of the third law of thermodynamics. It is shown that neither in its primary formulations nor in its consequences does the Kauzmann paradox result in contradictions with any basic laws of nature. Such contradictions are excluded by either crystallization (not associated with a pseudospinodal as suggested by Kauzmann or a conventional (and not an ideal glass transition. Some further so far widely unexplored directions of research on the interplay between crystallization and glass transition are anticipated, in which entropy may play—beyond the topics widely discussed and reviewed here—a major role.

  5. Metastability and thermophysical properties of metallic bulk glass forming alloys

    International Nuclear Information System (INIS)

    Wunderlich, R.K.; Fecht, H.J.

    1998-01-01

    The absence of crystallization over a wide time/temperature window can be used to produce bulk metallic glass by relatively slow cooling of the melt. For a number of alloys, including several multicomponent Zr-based alloys, the relevant thermodynamic and thermomechanical properties of the metastable glassy and undercooled liquid states have been measured below and above the glass transition temperature. These measurements include specific heat, viscosity, volume, and elastic properties as a function of temperature. As a result, it becomes obvious that the maximum undercooling for these alloys is given by an isentropic condition before an enthalpic or isochoric instability is reached. Alternatively, these glasses can also be produced by mechanical alloying, thus replacing the thermal disorder by static disorder and resulting in the same thermodynamic glass state. During heating through the undercooled liquid, a nanoscale phase separation occurs for most glasses as a precursor of crystallization

  6. Glass binder development for a glass-bonded sodalite ceramic waste form

    International Nuclear Information System (INIS)

    Riley, Brian J.; Vienna, John D.; Frank, Steven M.; Kroll, Jared O.; Peterson, Jacob A.

    2017-01-01

    This paper discusses work to develop Na_2O-B_2O_3-SiO_2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. In this paper, five new glasses with ~20 mass% Na_2O were designed to generate waste forms with high sodalite. The glasses were then used to produce ceramic waste forms with a surrogate salt waste. The waste forms made using these new glasses were formulated to generate more sodalite than those made with previous baseline glasses for this type of waste. The coefficients of thermal expansion for the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature than previous binder glasses used. Finally, these improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability.

  7. A new method locating good glass-forming compositions

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Dechuan [Department of Materials Physics and Chemistry, Northeastern University, No.3-11, Wenhua Road, Shenyang, 110819 (China); Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016 (China); Geng, Yan [Department of Materials Physics and Chemistry, Northeastern University, No.3-11, Wenhua Road, Shenyang, 110819 (China); Li, Zhengkun [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016 (China); Liu, Dingming [Department of Materials Physics and Chemistry, Northeastern University, No.3-11, Wenhua Road, Shenyang, 110819 (China); Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016 (China); Fu, Huameng; Zhu, Zhengwang [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016 (China); Qi, Yang, E-mail: qiyang@imp.neu.edu.cn [Department of Materials Physics and Chemistry, Northeastern University, No.3-11, Wenhua Road, Shenyang, 110819 (China); Zhang, Haifeng, E-mail: hfzhang@imr.ac.cn [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016 (China)

    2015-10-15

    A new method was proposed to pinpoint the compositions with good glass forming ability (GFA) by combining atomic clusters and mixing entropy. The clusters were confirmed by analyzing competing crystalline phases. The method was applied to the Zr–Al–Ni–Cu–Ag alloy system. A series of glass formers with diameter up to 20 mm were quickly detected in this system. The good glass formers were located only after trying 5 compositions around the calculated composition. The method was also effective in other multi-component systems. This method might provide a new way to understand glass formation and to quickly pinpoint compositions with high GFA. - Highlights: • A new method was proposed to quickly design glass formers with high glass forming ability. • The method of designing pentabasic Zr–Al–Ni–Cu–Ag alloys was applied. • A series of new Zr-based bulk metallic glasses with critical diameter of 20 mm were discovered.

  8. A new method locating good glass-forming compositions

    International Nuclear Information System (INIS)

    Yu, Dechuan; Geng, Yan; Li, Zhengkun; Liu, Dingming; Fu, Huameng; Zhu, Zhengwang; Qi, Yang; Zhang, Haifeng

    2015-01-01

    A new method was proposed to pinpoint the compositions with good glass forming ability (GFA) by combining atomic clusters and mixing entropy. The clusters were confirmed by analyzing competing crystalline phases. The method was applied to the Zr–Al–Ni–Cu–Ag alloy system. A series of glass formers with diameter up to 20 mm were quickly detected in this system. The good glass formers were located only after trying 5 compositions around the calculated composition. The method was also effective in other multi-component systems. This method might provide a new way to understand glass formation and to quickly pinpoint compositions with high GFA. - Highlights: • A new method was proposed to quickly design glass formers with high glass forming ability. • The method of designing pentabasic Zr–Al–Ni–Cu–Ag alloys was applied. • A series of new Zr-based bulk metallic glasses with critical diameter of 20 mm were discovered

  9. Unusual glass-forming ability induced by changes in the local atomic structure in Ti-based bulk metallic glass

    International Nuclear Information System (INIS)

    Kim, Y C; Chang, H J; Kim, D H; Kim, W T; Cha, P R

    2007-01-01

    The effect of partial replacement of Cu by Be in Ti 50 Cu 32 Ni 15 Sn 3 alloy on the thermal properties, structure, and forming ability of an amorphous phase were investigated by differential scanning calorimetry (DSC), x-ray diffraction (XRD), extended x-ray absorption fine structure (EXAFS), and high-resolution transmission electron microscopy (HRTEM). Ti 50 Cu 25 Ni 15 Sn 3 Be 7 alloy shows enhanced glass-forming ability, enabling one to fabricate a fully amorphous bulk metallic glass sample 2 mm in diameter by injection casting. With the replacement, the supercooled liquid region ΔT x (= T x -T g , where T x is the crystallization temperature and T g is the glass transition temperature) decreased from 73 to 45 K and the reduced glass transition temperature T rg (= T g /T 1 , where T 1 is the liquidus temperature) increased from 0.53 to 0.57. The amorphous Ti 50 Cu 25 Ni 15 Sn 3 Be 7 phase showed a formation of short-range-ordered clusters 1-2 nm in size, which is attributed to the strong interaction between Ti and Be. The results show that ΔT x can be used as a thermal parameter reflecting the glass-forming ability of the alloy only when the phase formed during crystallization is the same as the phase competing with the glass transition during solidification

  10. Thermalization calorimetry: A simple method for investigating glass transition and crystallization of supercooled liquids

    DEFF Research Database (Denmark)

    Jakobsen, Bo; Sanz, Alejandro; Niss, Kristine

    2016-01-01

    and their crystallization, e.g., for locating the glass transition and melting point(s), as well as for investigating the stability against crystallization and estimating the relative change in specific heat between the solid and liquid phases at the glass transition......We present a simple method for fast and cheap thermal analysis on supercooled glass-forming liquids. This “Thermalization Calorimetry” technique is based on monitoring the temperature and its rate of change during heating or cooling of a sample for which the thermal power input comes from heat...

  11. Anomalous structural evolution and liquid fragility signatures in Cu–Zr and Cu–Hf liquids and glasses

    International Nuclear Information System (INIS)

    Mauro, N.A.; Vogt, Adam J.; Johnson, Mark L.; Bendert, James C.; Soklaski, Ryan; Yang, Li; Kelton, K.F.

    2013-01-01

    The results of high energy X-ray scattering studies of equilibrium and supercooled Cu 100−x Zr x (x = 46 and 54) and Cu x Hf 100−x (x = 55 and 60.8) liquids and the corresponding glasses are presented. The liquid data were obtained in a containerless environment using the beamline electrostatic levitation (BESL) technique. The total structure factor and total pair correlation functions were measured as a function of temperature for the liquids, and for the glasses at room temperature. A developing asymmetry in the peak of the first coordination shell in the total pair correlation function suggests chemical ordering in the liquids with cooling. This asymmetry takes the form of two prominent peaks, suggesting two prominent ordering length scales. When the magnitudes of these peaks are extrapolated to the glass transition temperature a discontinuity is observed, indicating that an abrupt increase in the magnitude is required to match the observed peak heights in the glass. This suggests that the structure of the supercooled liquid orders more rapidly near the glass transition temperature, a conclusion that is supported by molecular dynamics simulations. This observed structural evolution of the liquid indicates that the concept of fragility, typically defined from the behavior of viscosity with temperature, has a measurable structural signature as well, which can be observed in X-ray diffraction studies

  12. Consolidated waste forms: glass marbles and ceramic pellets

    International Nuclear Information System (INIS)

    Treat, R.L.; Rusin, J.M.

    1982-05-01

    Glass marbles and ceramic pellets have been developed at Pacific Northwest Laboratory as part of the multibarrier concept for immobilizing high-level radioactive waste. These consolidated waste forms served as substrates for the application of various inert coatings and as ideal-sized particles for encapsulation in protective matrices. Marble and pellet formulations were based on existing defense wastes at Savannah River Plant and proposed commercial wastes. To produce marbles, glass is poured from a melter in a continuous stream into a marble-making device. Marbles were produced at PNL on a vibratory marble machine at rates as high as 60 kg/h. Other marble-making concepts were also investigated. The marble process, including a lead-encapsulation step, was judged as one of the more feasible processes for immobilizing high-level wastes. To produce ceramic pellets, a series of processing steps are required, which include: spray calcining - to dry liquid wastes to a powder; disc pelletizing - to convert waste powders to spherical pellets; sintering - to densify pellets and cause desired crystal formation. These processing steps are quite complex, and thereby render the ceramic pellet process as one of the least feasible processes for immobilizing high-level wastes

  13. Glass-solidification method for high level radioactive liquid waste

    International Nuclear Information System (INIS)

    Kawamura, Kazuhiro; Kometani, Masayuki; Sasage, Ken-ichi.

    1996-01-01

    High level liquid wastes are removed with precipitates mainly comprising Mo and Zr, thereafter, the high level liquid wastes are mixed with a glass raw material comprising a composition having a B 2 O 3 /SiO 2 ratio of not less than 0.41, a ZnO/Li 2 O ratio of not less than 1.00, and an Al 2 O 3 /Li 2 O ratio of not less than 2.58, and they are melted and solidified into glass-solidification products. The liquid waste content in the glass-solidification products can be increased up to about 45% by using the glass raw material having such a predetermined composition. In addition, deposition of a yellow phase does not occur, and a leaching rate identical with that in a conventional case can be maintained. (T.M.)

  14. Infrared spectroscopy study of structural changes in glass-forming salol.

    Science.gov (United States)

    Baran, J; Davydova, N A

    2010-03-01

    We report the investigation of glass-forming salol upon different courses of the temperature changes from liquid to glass state and back using FT-IR spectroscopy measurements in the wide spectral and temperature ranges. The formation of the ordered clusters in supercooled liquid salol has been observed at 250 K. When the temperature is decreased further to 11 K these ordered clusters become an element of the glass structure. With increasing temperature to 270 K through the glass transition noticeable evolutions of the IR spectrum occurs up till the ordered clusters are developed into crystal. So produced crystal melts in the temperature range 300-310 K, that corresponds to the melting temperature of the metastable phase (Tmelt=302 K) . Thus, the crystalline structure of the ordered clusters corresponds to the structure of metastable phase and is monoclinic.

  15. Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

    Science.gov (United States)

    Giovambattista, Nicolas

    2013-03-01

    Most liquids can form a single glass or amorphous state when cooled sufficiently fast (in order to prevent crystallization). However, there are a few substances that are relevant to scientific and technological applications which can exist in at least two different amorphous states, a property known as polyamorphism. Examples include silicon, silica, and in particular, water. In the case of water, experiments show the existence of a low-density (LDA) and high-density (HDA) amorphous ice that are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation evolves into a first-order liquid-liquid phase transition (LLPT) at temperatures above the glass transition temperature Tg. However, obtaining direct experimental evidence of the LLPT has been challenging since the LLPT occurs at conditions where water rapidly crystallizes. In this talk, I will (i) discuss the general phenomenology of polyamorphism in water and its implications, and (ii) explore the effects of a LLPT on the pressure dependence of Tg(P) for LDA and HDA. Our study is based on computer simulations of two water models - one with a LLPT (ST2 model), and one without (SPC/E model). In the absence of a LLPT, Tg(P) for all glasses nearly coincide. Instead, when there is a LLPT, different glasses exhibit dramatically different Tg(P) loci which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario that includes a LLPT (ST2 model) and hence, our results support the view that a LLPT may exist for the case of water.

  16. Predicting glass-forming compositions in the Al-La and Al-La-Ni systems

    International Nuclear Information System (INIS)

    Gargarella, P.; de Oliveira, M.F.; Kiminami, C.S.; Pauly, S.; Kuehn, U.; Bolfarini, C.; Botta, W.J.; Eckert, J.

    2011-01-01

    Research highlights: → The glass-forming ability of the Al-La and Al-La-Ni systems was studied using the λ* and the λ.Δe criteria. → Both criteria predicted with just 1% at. of error the best glass-former verified so far in the Al-La system. → Four new glass-former compositions could be predicted in the Al-La-Ni system using the λ.Δe criterion. → The best glass-former reported so far in the Al-La-Ni system was found. - Abstract: In this work, a criterion considering the topological instability (λ) and the differences in the electronegativity of the constituent elements (Δe) was applied to the Al-La and Al-Ni-La systems in order to predict the best glass-forming compositions. The results were compared with literature data and with our own experimental data for the Al-La-Ni system. The alloy described in the literature as the best glass former in the Al-La system is located near the point with local maximum for the λ.Δe criterion. A good agreement was found between the predictions of the λ.Δe criterion and literature data in the Al-La-Ni system, with the region of the best glass-forming ability (GFA) and largest supercooled liquid region (ΔT x ) coinciding with the best compositional region for amorphization indicated by the λ.Δe criterion. Four new glassy compositions were found in the Al-La-Ni system, with the best predicted composition presenting the best glass-forming ability observed so far for this system. Although the λ.Δe criterion needs further refinements for completely describe the glass-forming ability in the Al-La and Al-La-Ni systems, the results demonstrated that this criterion is a good tool to predict new glass-forming compositions.

  17. Fast and slow crystal growth kinetics in glass-forming melts

    Energy Technology Data Exchange (ETDEWEB)

    Orava, J.; Greer, A. L., E-mail: alg13@cam.ac.uk [WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan and Department of Materials Science and Metallurgy, 27 Charles Babbage Road, University of Cambridge, Cambridge CB3 0FS (United Kingdom)

    2014-06-07

    Published values of crystal growth rates are compared for supercooled glass-forming liquids undergoing congruent freezing at a planar crystal-liquid interface. For the purposes of comparison pure metals are considered to be glass-forming systems, using data from molecular-dynamics simulations. For each system, the growth rate has a maximum value U{sub max} at a temperature T{sub max} that lies between the glass-transition temperature T{sub g} and the melting temperature T{sub m}. A classification is suggested, based on the lability (specifically, the propensity for fast crystallization), of the liquid. High-lability systems show “fast” growth characterized by a high U{sub max}, a low T{sub max} / T{sub m}, and a very broad peak in U vs. T / T{sub m}. In contrast, systems showing “slow” growth have a low U{sub max}, a high T{sub max} / T{sub m}, and a sharp peak in U vs. T / T{sub m}. Despite the difference of more than 11 orders of magnitude in U{sub max} seen in pure metals and in silica, the range of glass-forming systems surveyed fit into a common pattern in which the lability increases with lower reduced glass-transition temperature (T{sub g} / T{sub m}) and higher fragility of the liquid. A single parameter, a linear combination of T{sub g} / T{sub m} and fragility, can show a good correlation with U{sub max}. For all the systems, growth at U{sub max} is coupled to the atomic/molecular mobility in the liquid. It is found that, across the diversity of glass-forming systems, T{sub max} / T{sub g} = 1.48 ± 0.15.

  18. Structural relaxation and thermal conductivity of high-pressure formed, high-density di-n-butyl phthalate glass and pressure induced departures from equilibrium state.

    Science.gov (United States)

    Johari, G P; Andersson, Ove

    2017-06-21

    We report a study of structural relaxation of high-density glasses of di-n-butyl phthalate (DBP) by measuring thermal conductivity, κ, under conditions of pressure and temperature (p,T) designed to modify both the vibrational and configurational states of a glass. Various high-density glassy states of DBP were formed by (i) cooling the liquid under a fixed high p and partially depressurizing the glass, (ii) isothermal annealing of the depressurized glass, and (iii) pressurizing the glass formed by cooling the liquid under low p. At a given low p, κ of the glass formed by cooling under high p is higher than that of the glass formed by cooling under low p, and the difference increases as glass formation p is increased. κ of the glass formed under 1 GPa is ∼20% higher at ambient p than κ of the glass formed at ambient p. On heating at low p, κ decreases until the glass to liquid transition range is reached. This is the opposite of the increase in κ observed when a glass formed under a certain p is heated under the same p. At a given high p, κ of the low-density glass formed by cooling at low p is lower than that of the high-density glass formed by cooling at that high p. On heating at high p, κ increases until the glass to liquid transition range is reached. The effects observed are due to a thermally assisted approach toward equilibrium at p different from the glass formation p. In all cases, the density, enthalpy, and entropy would change until the glasses become metastable liquids at a fixed p, thus qualitatively relating κ to variation in these properties.

  19. Radiation effects in glass and glass-ceramic waste forms for the immobilization of CANDU UO2 fuel reprocessing waste

    International Nuclear Information System (INIS)

    Tait, J.C.

    1993-05-01

    AECL has investigated three waste forms for the immobilization of high-level liquid wastes that would arise if used CANDU fuels were reprocessed at some time in the future to remove fissile materials for the fabrication of new power reactor fuel. These waste forms are borosilicate glasses, aluminosilicate glasses and titanosilicate glass-ceramics. This report discusses the potential effects of alpha, beta and gamma radiation on the releases of radionuclides from these waste forms as a result of aqueous corrosion by groundwaters that would be present in an underground waste disposal vault. The report discusses solid-state damage caused by radiation-induced atomic displacements in the waste forms as well as irradiation of groundwater solutions (radiolysis), and their potential effects on waste-form corrosion and radionuclide release. The current literature on radiation effects on borosilicate glasses and in ceramics is briefly reviewed, as are potential radiation effects on specialized waste forms for the immobilization of 129 I, 85 Kr and 14 C. (author). 104 refs., 9 tabs., 5 figs

  20. Liquid-Liquid Phase Transition and Glass Transition in a Monoatomic Model System

    Directory of Open Access Journals (Sweden)

    Nicolas Giovambattista

    2010-12-01

    Full Text Available We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses.

  1. Phenomenological description of internal friction spectra in glass-forming and glassy systems

    International Nuclear Information System (INIS)

    Lomovskij, V.A.

    1999-01-01

    Dissipative events in different by chemical nature glass-forming systems, including B 2 O 3 , are studied. It is established from the spectra of internal friction of these systems that the maxima of the energy dissipation of the external power impact are positioned both in the area of viscous flow metastable structural liquid state and in the area of solid elastic state

  2. Thermodynamics of the Gd/sub 63.2/Co/sub 36.8/ glass-forming eutectic

    International Nuclear Information System (INIS)

    Baricco, M.; Antonione, C.; Battezzati, L.

    1987-01-01

    In the last years a tendency has consolidated to investigate the properties of the liquid phase in relation to amorphization. The thermodynamic properties of glass-forming liquids show some remarkable similarities and provide a unifying picture for the understanding of glass formation. In particular the specific heat difference between liquid and crystal phases, C/sub P/, seem always positive thus enabling the liquid entropy to approach that of the solid on under-cooling towards the glass transition temperature, T/sub g/. The enthalpy of mixing in glass-forming alloys is strongly negative and depends on temperature giving rise to an excess specific heat. As the liquid and crystalline pure elements have similar specific heat and the Newmann-Kopp law is usually obeyed by solid alloys, the excess specific heat can be assimilated to G. This last quantity, therefore, determines the trend of the thermodynamic properties in the undercooling regime and ultimately the glass-forming tendency of the liquid systems. Specific heat data are available for some liquid alloys but only a few of them refer to glass-forming systems. Typical examples are Au/sub 77/Ge/sub 13.6/Si/sub 9.4/ among metal-metalloid and Mg/sub 85.5/Cu/sub 14.5/ among metal-metal systems. The authors present here a complete determination of the thermodynamic properties of the Gd/sub 63.2/Co/sub 36.8/ eutectic as an example for anthanide transition metal glass-formers. This alloy is low melting so that its liquid state is accessible by differential scanning calorimetry. It forms glasses readily by means of liquid quenching

  3. Five-fold local symmetry in metallic liquids and glasses

    International Nuclear Information System (INIS)

    Li M Z; Li F X; Zhang H P; Peng H L; Hu Y C; Wang W H

    2017-01-01

    The structure of metallic glasses has been a long-standing mystery. Owing to the disordered nature of atomic structures in metallic glasses, it is a great challenge to find a simple structural description, such as periodicity for crystals, for establishing the structure–property relationship in amorphous materials. In this paper, we briefly review the recent developments of the five-fold local symmetry in metallic liquids and glasses and the understanding of the structure–property relationship based on this parameter. Experimental evidence demonstrates that five-fold local symmetry is found to be general in metallic liquids and glasses. Comprehensive molecular dynamics simulations show that the temperature evolution of five-fold local symmetry reflects the structural evolution in glass transition in cooling process, and the structure–property relationship such as relaxation dynamics, dynamic crossover phenomena, glass transition, and mechanical deformation in metallic liquids and glasses can be well understood base on the simple and general structure parameter of five-fold local symmetry. (paper)

  4. 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)

  5. Glass Transitions in a Monatomic Liquid with Two Glassy States

    Science.gov (United States)

    Gordon, Andrew; Giovambattista, Nicolas

    2014-04-01

    We perform out-of-equilibrium molecular dynamics simulations of a monatomic liquid that exhibits liquid and glass polymorphism, with two distinct glasses, low- (LDA) and high-density (HDA) amorphous solids. By performing isobaric heating simulations of LDA and HDA at different pressures, we determine (a) the glass transition temperature of LDA and HDA, TgLDA(P) and TgHDA(P), as well as (b) the corresponding glass-glass transformation temperatures, TLDA-HDA(P) and THDA-LDA(P). It is found that TgLDA(P) is anomalous; i.e., it decreases with increasing pressure, while TgHDA(P) increases with increasing pressure. Interestingly, the TgLDA(P) and TLDA-HDA(P) loci, as well as the TgHDA(P) and THDA-LDA(P) loci, constitute smooth single lines in the P -T plane, suggesting that heating-induced glass-glass and glass transitions are related. We discuss the present results in the context of water experiments and simulations.

  6. Leaching behavior of glass ceramic nuclear waste forms

    International Nuclear Information System (INIS)

    Lokken, R.O.

    1981-11-01

    Glass ceramic waste forms have been investigated as alternatives to borosilicate glasses for the immobilization of high-level radioactive waste at Pacific Northwest Laboratory (PNL). Three glass ceramic systems were investigated, including basalt, celsian, and fresnoite, each containing 20 wt % simulated high-level waste calcine. Static leach tests were performed on seven glass ceramic materials and one parent glass (before recrystallization). Samples were leached at 90 0 C for 3 to 28 days in deionized water and silicate water. The results, expressed in normalized elemental mass loss, (g/m 2 ), show comparable releases from celsian and fresnoite glass ceramics. Basalt glass ceramics demonstrated the lowest normalized elemental losses with a nominal release less than 2 g/m 2 when leached in polypropylene containers. The releases from basalt glass ceramics when leached in silicate water were nearly identical with those in deionized water. The overall leachability of celsian and fresnoite glass ceramics was improved when silicate water was used as the leachant

  7. Thermal expansion accompanying the glass-liquid transition and crystallization

    Directory of Open Access Journals (Sweden)

    M. Q. Jiang

    2015-12-01

    Full Text Available We report the linear thermal expansion behaviors of a Zr-based (Vitreloy 1 bulk metallic glass in its as-cast, annealed and crystallized states. Accompanying the glass-liquid transition, the as-cast Vitreloy 1 shows a continuous decrease in the thermal expansivity, whereas the annealed glass shows a sudden increase. The crystallized Vitreloy 1 exhibits an almost unchanged thermal expansivity prior to its melting. Furthermore, it is demonstrated that the nucleation of crystalline phases can induce a significant thermal shrinkage of the supercooled liquid, but with the growth of these nuclei, the thermal expansion again dominates. These results are explained in the framework of the potential energy landscape, advocating that the configurational and vibrational contributions to the thermal expansion of the glass depend on both, structure and temperature.

  8. Molecular dynamics study of the ternary Cu50Ti25Zr25 bulk glass forming alloy

    Directory of Open Access Journals (Sweden)

    Celtek M.

    2011-05-01

    Full Text Available The structure and thermodynamic properties of a ternary Cu50Ti25Zr25 metallic glass forming alloy in solid-liquid to glass phases were studied using molecular dynamics (MD method based on tight-binding (TB potentials. An atomic description of the melting, glass formation and crystallization process has been analyzed using different heating and cooling rates. The computed Glass Forming Ability (GFA parameters are in good agreement with experimental data. The structure analysis of the Cu50Ti25Zr25 based on molecular dynamics simulation will be also presented and compared with available MD results. We have also discussed the crystallization transition with two different interatomic potentials used in this work

  9. Crystallization dynamics in glass-forming systems

    Energy Technology Data Exchange (ETDEWEB)

    Cullinan, Timothy Edward [Iowa State Univ., Ames, IA (United States)

    2016-02-19

    Crystallization under far-from-equilibrium conditions is investigated for two different scenarios: crystallization of the metallic glass alloy Cu50Zr50 and solidification of a transparent organic compound, o-terphenyl. For Cu50Zr50, crystallization kinetics are quanti ed through a new procedure that directly fits thermal analysis data to the commonly utilized JMAK model. The phase evolution during crystallization is quantified through in-situ measurements (HEXRD, DSC) and ex-situ microstructural analysis (TEM, HRTEM). The influence of chemical partitioning, diffusion, and crystallographic orientation on this sequence are examined. For o-terphenyl, the relationship between crystal growth velocity and interface undercooling is systematically studied via directional solidification.

  10. Predicting glass-to-glass and liquid-to-liquid phase transitions in supercooled water using classical nucleation theory

    Science.gov (United States)

    Tournier, Robert F.

    2018-01-01

    Glass-to-glass and liquid-to-liquid phase transitions are observed in bulk and confined water, with or without applied pressure. They result from the competition of two liquid phases separated by an enthalpy difference depending on temperature. The classical nucleation equation of these phases is completed by this quantity existing at all temperatures, a pressure contribution, and an enthalpy excess. This equation leads to two homogeneous nucleation temperatures in each liquid phase; the first one (Tn- below Tm) being the formation temperature of an "ordered" liquid phase and the second one corresponding to the overheating temperature (Tn+ above Tm). Thermodynamic properties, double glass transition temperatures, sharp enthalpy and volume changes are predicted in agreement with experimental results. The first-order transition line at TLL = 0.833 × Tm between fragile and strong liquids joins two critical points. Glass phase above Tg becomes "ordered" liquid phase disappearing at TLL at low pressure and at Tn+ = 1.302 × Tm at high pressure.

  11. A universal reduced glass transition temperature for liquids

    Science.gov (United States)

    Fedors, R. F.

    1979-01-01

    Data on the dependence of the glass transition temperature on the molecular structure for low-molecular-weight liquids are analyzed in order to determine whether Boyer's reduced glass transition temperature (1952) is a universal constant as proposed. It is shown that the Boyer ratio varies widely depending on the chemical nature of the molecule. It is pointed out that a characteristic temperature ratio, defined by the ratio of the sum of the melting temperature and the boiling temperature to the sum of the glass transition temperature and the boiling temperature, is a universal constant independent of the molecular structure of the liquid. The average value of the ratio obtained from data for 65 liquids is 1.15.

  12. Computational analysis of the atomic size effect in bulk metallic glasses and their liquid precursors

    International Nuclear Information System (INIS)

    Kokotin, V.; Hermann, H.

    2008-01-01

    The atomic size effect and its consequences for the ability of multicomponent liquid alloys to form bulk metallic glasses are analyzed in terms of the generalized Bernal's model for liquids, following the hypothesis that maximum density in the liquid state improves the glass-forming ability. The maximum density that can be achieved in the liquid state is studied in the 2(N-1) dimensional parameter space of N-component systems. Computer simulations reveal that the size ratio of largest to smallest atoms are most relevant for achieving the maximum packing for N = 3-5, whereas the number of components plays a minor role. At small size ratio, the maximum packing density can be achieved by different atomic size distributions, whereas for medium size ratios the maximum density is always correlated to a concave size distribution. The relationship of the results to Miracle's efficient cluster packing model is also discussed

  13. Light scattering from crystals, glasses and liquids

    International Nuclear Information System (INIS)

    Subbaswamy, K.R.

    1984-09-01

    The theory of inelastic light scattering from a model system in the crystalline, disordered and liquid phases is analyzed. The roles of disorder induced first order scattering and second order scattering are clarified in the context of the classical liquid. The correlation functions appropriate for the various contributions are identified and useful ways of processing experimental data are pointed out. (author)

  14. Thermalization calorimetry: A simple method for investigating glass transition and crystallization of supercooled liquids

    Directory of Open Access Journals (Sweden)

    Bo Jakobsen

    2016-05-01

    Full Text Available We present a simple method for fast and cheap thermal analysis on supercooled glass-forming liquids. This “Thermalization Calorimetry” technique is based on monitoring the temperature and its rate of change during heating or cooling of a sample for which the thermal power input comes from heat conduction through an insulating material, i.e., is proportional to the temperature difference between sample and surroundings. The monitored signal reflects the sample’s specific heat and is sensitive to exo- and endothermic processes. The technique is useful for studying supercooled liquids and their crystallization, e.g., for locating the glass transition and melting point(s, as well as for investigating the stability against crystallization and estimating the relative change in specific heat between the solid and liquid phases at the glass transition.

  15. Glasses

    DEFF Research Database (Denmark)

    Dyre, Jeppe

    2004-01-01

    The temperature dependence of the viscosity of most glassforming liquids is known to depart significantly from the classical Arrhenius behaviour of simple fluids. The discovery of an unexpected correlation between the extent of this departure and the Poisson ratio of the resulting glass could lead...... to new understanding of glass ageing and viscous liquid dynamics....

  16. Effect of Nb on glass forming ability and plasticity of (Ti-Cu)-based bulk metallic glasses

    International Nuclear Information System (INIS)

    Suo, Z.Y.; Qiu, K.Q.; Li, Q.F.; Ren, Y.L.; Hu, Z.Q.

    2010-01-01

    A Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 bulk metallic glass has been developed by Nb partial substitution for Zr in Ti 33 Cu 47 Zr 11 Ni 6 Sn 2 Si 1 alloy. The glass forming ability Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 alloy has been investigated using differential scanning calorimetry and X-ray diffractometry. Partial Nb substitutes for Zr promote the glass forming ability. Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 BMG with diameter of 3 mm can be fabricated by Cu-mold injection casting method. The glass forming ability of Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 alloy is enhanced by stabilizing the undercooled liquid against crystallization. The plastic strain up to 2.5% was obtained for Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 BMG compared to 0.15% for Ti 33 Cu 47 Zr 11 Ni 6 Sn 2 Si 1 BMG, which demonstrates that small amount of Nb addition can have a dramatic effect on plasticity enhancement in Ti-Cu-based BMG. The intersection and branching of the shear bands are observed. The plastic strain of the Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 BMG can be improved by the generation of nanocrystalline particles, which lead to multiple shear bands.

  17. Impact of medium-range order on the glass transition in liquid Ni-Si alloys

    Science.gov (United States)

    Lü, Y. J.; Entel, P.

    2011-09-01

    We study the thermophysical properties and structure of liquid Ni-Si alloys using molecular dynamics simulations. The liquid Ni-5% and 10%Si alloys crystallize to form the face-centered cubic (Ni) at 900 and 850 K, respectively, and the glass transitions take place in Ni-20% and 25%Si alloys at about 700 K. The temperature-dependent self-diffusion coefficients and viscosities exhibit more pronounced non-Arrhenius behavior with the increase of Si content before phase transitions, indicating the enhanced glass-forming ability. These appearances of thermodynamic properties and phase transitions are found to closely relate to the medium-range order clusters with the defective face-centered cubic structure characterized by both local translational and orientational order. This locally ordered structure tends to be destroyed by the addition of more Si atoms, resulting in a delay of nucleation and even glass transition instead.

  18. Communication: Glass transition and melting lines of an ionic liquid

    Science.gov (United States)

    Lima, Thamires A.; Faria, Luiz F. O.; Paschoal, Vitor H.; Ribeiro, Mauro C. C.

    2018-05-01

    The phase diagram of the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesufonyl)imide, [Pyrr1,4][NTf2], was explored by synchroton X-ray diffraction and Raman scattering measurements as a function of temperature and pressure. Glass transition Tg(p) and melting Tm(p) temperatures were obtained from atmospheric pressure up to ca. 2.0 GPa. We found that both the Tg(p) and Tm(p) curves follow essentially the same pressure dependence. The similarity of pressure coefficients, dTg/dp ≈ dTm/dp, is explained within the non-equilibrium thermodynamics approach for the glass transition by assuming that one of the Ehrenfest equations is appropriated for Tg(p), whereas Tm(p) follows the Clausius-Clapeyron equation valid for the first-order transitions. The results highlight that ionic liquids are excellent model systems to address fundamental questions related to the glass transition.

  19. Durability, mechanical, and thermal properties of experimental glass-ceramic forms for immobilizing ICPP high level waste

    International Nuclear Information System (INIS)

    Vinjamuri, K.

    1990-01-01

    The high-level liquid waste generated at the Idaho Chemical Processing Plant (ICPP) is routinely solidified into granular calcined high-level waste (HLW) and stored onsite. Research is being conducted at the ICPP on methods of immobilizing the HLW, including developing a durable glass-ceramic form which has the potential to significantly reduce the final waste volume by up to 60% compared to a glass form. Simulated, pilot plant, non-radioactive, calcines similar to the composition of the calcined HLW and glass forming additives are used to produce experimental glass-ceramic forms. The objective of the research reported in this paper is to study the impact of ground calcine particle size on durability and mechanical and thermal properties of experimental glass-ceramic forms

  20. Density of states of colloidal glasses and supercooled liquids

    NARCIS (Netherlands)

    Ghosh, A.; Mari, R.; Chikkadi, V.; Schall, P.; Kurchan, J.; Bonn, D.

    2010-01-01

    The glass transition is perhaps the greatest unsolved problem in condensed matter physics: the main question is how to reconcile the liquid-like structure with solid-like mechanical properties. In solids, structure and mechanics are related directly through the vibrational density of states of the

  1. Piezoelectricity of a ferroelectric liquid crystal with a glass transition.

    Science.gov (United States)

    Jákli, A; Tóth-Katona, T; Scharf, T; Schadt, M; Saupe, A

    2002-07-01

    Pressure-electric (hydrostatic piezoelectric) measurements are reported on bookshelf textures of a ferroelectric smectic-C (Sm C*) liquid crystal with a glass transition. The continuous variation of a partially fluid state to the solid glass enables one to trace how the piezoelectric effect depends on the consistency of the material. It was observed that in the Sm C* samples with poled glass the piezoelectric constants are comparable to conventional piezoelectric crystals and poled piezoelectric polymers. This implies their application possibilities. The magnitude of the piezoelectric constant in the glassy state depends very much on the poling conditions. The studies indicate that there are two counteracting effects, which cancel each other out in the Sm C* phase near the glass transition. Our analysis indicates that the pressure-induced director tilt change has a dominating effect both in the fluid and the glassy Sm C* states.

  2. Bulk glass formation and crystallization in zirconium based bulk metallic glass forming alloys

    International Nuclear Information System (INIS)

    Savalia, R.T.; Neogy, S.; Dey, G.K.; Banerjee, S.

    2002-01-01

    The microstructures of Zr based metallic glasses produced in bulk form have been described in the as-cast condition and after crystallization. Various microscopic techniques have been used to characterize the microstructures. The microstructure in the as-cast condition was found to contain isolated crystals and crystalline aggregates embedded in the amorphous matrix. Quenched-in nuclei of crystalline phases were found to be present in fully amorphous regions. These glasses after crystallization gave rise to nanocrystalline solids. (author)

  3. 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)

  4. High level waste forms: glass marbles and thermal spray coatings

    International Nuclear Information System (INIS)

    Treat, R.L.; Oma, K.H.; Slate, S.C.

    1982-01-01

    A process that converts high-level waste to glass marbles and then coats the marbles has been developed at Pacific Northwest Laboratory (PNL) under sponsorship of the US Department of Energy. The process consists of a joule-heated glass melter, a marble-making device based on a patent issued to Corning Glass Works, and a coating system that includes a plasma spray coater and a marble tumbler. The process was developed under the Alternative Waste Forms Program which strived to improve upon monolithic glass for immobilizing high-level wastes. Coated glass marbles were found to be more leach-resistant, and the marbles, before coating were found to be very homogeneous, highly impact resistant, and conductive to encapsulation in a metal matric for improved heat transfer and containment. Marbles are also ideally suited for quality assurance and recycling. However, the marble process is more complex, and marbles require a larger number of canisters for waste containment and have a higher surface area than do glass monoliths

  5. Copper oxide content dependence of crystallization behavior, glass forming ability, glass stability and fragility of lithium borate glasses

    International Nuclear Information System (INIS)

    Soliman, A.A.; Kashif, I.

    2010-01-01

    Differential thermal analysis (DTA) and X-ray diffraction (XRD) have been employed to investigate the copper oxide content dependence of the glass transition temperatures data, activation energy for the glass transition E t , glass stability GS, fragility index Fi, the glass-forming ability (GFA) and crystallization behavior of {(100-x) mol% Li 2 B 4 O 7 -x mol% CuO} glass samples, where x=0-40 mol% CuO. From the dependence of the glass transition temperature T g on the heating rate β, the fragility, F i , and the activation energy, E t , have been calculated. It is seen that F i and E t are attained their minimum values at 0 x -T g , SCL region and the GS. The GFA has been investigated on the basis of Hruby parameter K H , which is a strong indicator of GFA, and the relaxation time. Results of GFA are in good agreement with the fragility index, F i , calculations indicating that {90Li 2 B 4 O 7 .10CuO} is the best glass former. The stronger glass forming ability has decreasing the fragility index. XRD result indicates that no fully amorphous samples but a mixture of crystalline and amorphous phases are formed in the samples containing x>25 mol% CuO and below it composed of glassy phase. Increasing the CuO content above 25 mol% helps the crystallization process, and thus promotes a distinct SCL region. XRD suggests the presence of micro-crystallites of remaining residual amorphous matrix by increasing the CuO content.

  6. Investigating the atomic level influencing factors of glass forming ability in NiAl and CuZr metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Sedighi, Sina; Kirk, Donald Walter; Singh, Chandra Veer, E-mail: chandraveer.singh@utoronto.ca; Thorpe, Steven John [Department of Materials Science and Engineering, University of Toronto, Room 140, 184 College Street, Toronto, Ontario M5S 3E4 (Canada)

    2015-09-21

    Bulk metallic glasses are a relatively new class of amorphous metal alloy which possess unique mechanical and magnetic properties. The specific concentrations and combinations of alloy elements needed to prevent crystallization during melt quenching remains poorly understood. A correlation between atomic properties that can explain some of the previously identified glass forming ability (GFA) anomalies of the NiAl and CuZr systems has been identified, with these findings likely extensible to other transition metal–transition metal and transition metal–metalloid (TM–M) alloy classes as a whole. In this work, molecular dynamics simulation methods are utilized to study thermodynamic, kinetic, and structural properties of equiatomic CuZr and NiAl metallic glasses in an attempt to further understand the underlying connections between glass forming ability, nature of atomic level bonding, short and medium range ordering, and the evolution of structure and relaxation properties in the disordered phase. The anomalous breakdown of the fragility parameter as a useful GFA indicator in TM–M alloy systems is addressed through an in-depth investigation of bulk stiffness properties and the evolution of (pseudo)Gruneisen parameters over the quench domain, with the efficacy of other common glass forming ability indicators similarly being analyzed through direct computation in respective CuZr and NiAl systems. Comparison of fractional liquid-crystal density differences in the two systems revealed 2-3 times higher values for the NiAl system, providing further support for its efficacy as a general purpose GFA indicator.

  7. Transparent form-active system with structural glass

    NARCIS (Netherlands)

    Nikolaou, M.S.N.; Veer, F.A.; Eigenraam, P.

    2015-01-01

    Free-form transparent wide-span spatial structures which have being constructed so far, are based on the concept of three sets of components, the structural components, usually steel elements to ensure both compressive and tensional capacity; the glass cladding elements for expressing transparency;

  8. Thermodynamic and relative approach to compute glass-forming

    Indian Academy of Sciences (India)

    This study deals with the evaluation of glass-forming ability (GFA) of oxides and is a critical reading of Sun and Rawson thermodynamic approach to quantify this aptitude. Both approaches are adequate but ambiguous regarding the behaviour of some oxides (tendency to amorphization or crystallization). Indeed, ZrO2 and ...

  9. Thermodynamic and relative approach to compute glass-forming ...

    Indian Academy of Sciences (India)

    models) characteristic: the isobaric heat capacity (Cp) of oxides, and execute a mathematical treatment of oxides thermodynamic data. We note this coefficient as thermodynamical relative glass-forming ability (ThRGFA) and for- mulate a model to compute it. Computed values of 2nd, 3rd, 4th and 5th period metal oxides ...

  10. Inelastic scattering from liquid 4He in aerogel glass

    International Nuclear Information System (INIS)

    Snow, W.M.; Sokol, P.E.

    1988-01-01

    The physics of liquid and solid 4 He in restricted geometries has motivated a number of interesting experiments. Recent experiments include detailed measurements of the phase diagram for bulk liquid in vycor, showing a suppression of the superfluid transition and elevation of the melting pressure, and measurements of the superfluid fraction in vycor, aerogel, and zerogel glasses near the lambda point, in which critical exponents differ from the pure 4 He values have been observed. Many striking features in several of the experiments on helium in restricted geometries are poorly understood. We have performed inelastic neutron scattering measurements of liquid helium in aerogel glass above and below the superfluid transition for two samples of different porosities. The kinetic energy (KE) of the confined liquid is the same as that of the bulk liquid in the normal phase, but is clearly higher than the bulk values in the superfluid phase. The observed scattering in the superfluid phase is more peaked than in the normal phase: consistent with the presence of a Bose condensate. An estimate of the condensate fraction using a modification of a method due to Sears yields values consistent with those estimated for the bulk liquid. 7 refs., 2 figs., 1 tab

  11. Kinetic and structural fragility—a correlation between structures and dynamics in metallic liquids and glasses

    International Nuclear Information System (INIS)

    Kelton, K F

    2017-01-01

    The liquid phase remains poorly understood. In many cases, the densities of liquids and their crystallized solid phases are similar, but since they are amorphous they lack the spatial order of the solid. Their dynamical properties change remarkably over a very small temperature range. At high temperatures, near their melting temperature, liquids flow easily under shear. However, only a few hundred degrees lower flow effectively ceases, as the liquid transforms into a solid-like glass. This temperature-dependent dynamical behavior is frequently characterized by the concept of kinetic fragility (or, generally, simply fragility). Fragility is believed to be an important quantity in glass formation, making it of significant practical interest. The microscopic origin of fragility remains unclear, however, making it also of fundamental interest. It is widely (although not uniformly) believed that the dynamical behavior is linked to the atomic structure of the liquid, yet experimental studies show that although the viscosity changes by orders of magnitude with temperature, the structural change is barely perceptible. In this article the concept of fragility is discussed, building to a discussion of recent results in metallic glass-forming liquids that demonstrate the presumed connection between structural and dynamical changes. In particular, it becomes possible to define a structural fragility parameter that can be linked with the kinetic fragility. (topical review)

  12. Hybrid glasses from strong and fragile metal-organic framework liquids.

    Science.gov (United States)

    Bennett, Thomas D; Tan, Jin-Chong; Yue, Yuanzheng; Baxter, Emma; Ducati, Caterina; Terrill, Nick J; Yeung, Hamish H-M; Zhou, Zhongfu; Chen, Wenlin; Henke, Sebastian; Cheetham, Anthony K; Greaves, G Neville

    2015-08-28

    Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship between amorphization and melting has so far not been investigated. Here we show how heating MOFs of zeolitic topology first results in a low density 'perfect' glass, similar to those formed in ice, silicon and disaccharides. This order-order transition leads to a super-strong liquid of low fragility that dynamically controls collapse, before a subsequent order-disorder transition, which creates a more fragile high-density liquid. After crystallization to a dense phase, which can be remelted, subsequent quenching results in a bulk glass, virtually identical to the high-density phase. We provide evidence that the wide-ranging melting temperatures of zeolitic MOFs are related to their network topologies and opens up the possibility of 'melt-casting' MOF glasses.

  13. Linking Equilibrium and Nonequilibrium Dynamics in Glass-Forming Systems

    DEFF Research Database (Denmark)

    Mauro, John C.; Guo, Xiaoju; Smedskjær, Morten Mattrup

    , we show that the nonequilibrium glassy dynamics are intimately connected with the equilibrium liquid dynamics. This is accomplished by deriving a new functional form for the thermal history dependence of nonequilibrium viscosity, which is validated against experimental measurements of industrial...

  14. Infrared and x-ray photoelectron spectroscopic studies on sodium borosilicate glass interacted with thermally oxidized aluminides formed on alloy 690

    International Nuclear Information System (INIS)

    Yusufali, C.; Dutta, R.S.; Dey, G.K.; Kshirsagar, R.J.; Jagannath; Mishra, R.K.

    2012-01-01

    Thermally oxidized aluminides formed on Ni-Cr-Fe based superalloy 690 substrates were subjected to interaction with sodium borosilicate melt (used as matrices for immobilization of high-level radioactive liquid waste) at 1248 K for 192 hours. After the interaction, Fourier-transform infrared (FT-IR) spectroscopy analysis of glass samples indicated the incorporation of Al in the glass network. X-ray photoelectron spectroscopy (XPS) of glass specimens revealed modified glass structure. (author)

  15. Connection between slow and fast dynamics of molecular liquids around the glass transition

    International Nuclear Information System (INIS)

    Niss, Kristine; Dalle-Ferrier, Cecile; Frick, Bernhard; Russo, Daniela; Dyre, Jeppe; Alba-Simionesco, Christiane

    2010-01-01

    The mean-square displacement (MSD) was measured by neutron scattering at various temperatures and pressures for a number of molecular glass-forming liquids. The MSD is invariant along the glass-transition line at the pressure studied, thus establishing an 'intrinsic' Lindemann criterion for any given liquid. A one-to-one connection between the MSD's temperature dependence and the liquid's fragility is found when the MSD is evaluated on a time scale of ∼4 ns, but does not hold when the MSD is evaluated at shorter times. The findings are discussed in terms of the elastic model and the role of relaxations, and the correlations between slow and fast dynamics are addressed.

  16. Reversible and Irreversible Behavior of Glass-forming Materials from the Standpoint of Hierarchical Dynamical Facilitation

    Science.gov (United States)

    Keys, Aaron

    2013-03-01

    Using molecular simulation and coarse-grained lattice models, we study the dynamics of glass-forming liquids above and below the glass transition temperature. In the supercooled regime, we study the structure, statistics, and dynamics of excitations responsible for structural relaxation for several atomistic models of glass-formers. Excitations (or soft spots) are detected in terms of persistent particle displacements. At supercooled conditions, we find that excitations are associated with correlated particle motions that are sparse and localized, and the statistics and dynamics of these excitations are facilitated and hierarchical. Excitations at one point in space facilitate the birth and death of excitations at neighboring locations, and space-time excitation structures are microcosms of heterogeneous dynamics at larger scales. Excitation-energy scales grow logarithmically with the characteristic size of the excitation, giving structural-relaxation times that can be predicted quantitatively from dynamics at short time scales. We demonstrate that these same physical principles govern the dynamics of glass-forming systems driven out-of-equilibrium by time-dependent protocols. For a system cooled and re-heated through the glass transition, non-equilibrium response functions, such as heat capacities, are notably asymmetric in time, and the response to melting a glass depends markedly on the cooling protocol by which the glass was formed. We introduce a quantitative description of this behavior based on the East model, with parameters determined from reversible transport data, that agrees well with irreversible differential scanning calorimetry. We find that the observed hysteresis and asymmetric response is a signature of an underlying dynamical transition between equilibrium melts with no trivial spatial correlations and non-equilibrium glasses with correlation lengths that are both large and dependent upon the rate at which the glass is prepared. The correlation

  17. The role of the dynamic crossover temperature and the arrest in glass-forming fluids.

    Science.gov (United States)

    Mallamace, F; Corsaro, C; Stanley, H E; Chen, S-H

    2011-09-01

    We discuss the role of the dynamic glass-forming fragile-to-strong crossover (FSC) in supercooled liquids. In the FSC, significant dynamic changes such as the decoupling (the violation of the Stokes-Einstein relation) of homologous transport parameters, e.g., the density relaxation time τ and the viscosity η, occur at a characteristic temperature T(c). We study the FSC using a scaling law approach. In particular, we use both forms of the mode-coupling theory (MCT): the original (ideal) and the extended form, which explicitly describes energy hopping processes. We demonstrate that T(c) plays the most important physical role in understanding dynamic arrest processes.

  18. Glass transition memorized by the enthalpy-entropy compensation in the shear thinning of supercooled metallic liquids

    Science.gov (United States)

    Zhang, Meng; Liu, Lin

    2018-06-01

    To unravel the true nature of glass transition, broader insights into glass forming have been gained by examining the stress-driven glassy systems, where strong shear thinning, i.e. a reduced viscosity under increasing shear rate, is encountered. It is argued that arbitrarily small stress-driven shear rates would ‘melt’ the glass and erase any memory of its thermal history. In this work, we report a glass transition memorized by the enthalpy-entropy compensation in strongly shear-thinned supercooled metallic liquids, which coincides with the thermal glass transition in both the transition temperature and the activation Gibbs free energy. Our findings provide distinctive insights into both glass forming and shear thinning, and enrich current knowledge on the ubiquitous enthalpy-entropy compensation empirical law in condensed matter physics.

  19. Glass Bubbles Insulation for Liquid Hydrogen Storage Tanks

    Science.gov (United States)

    Sass, J. P.; SaintCyr, W. W.; Barrett, T. M.; Baumgartner, R. G.; Lott, J. W.; Fesmire, J. E.

    2009-01-01

    A full-scale field application of glass bubbles insulation has been demonstrated in a 218,000 L liquid hydrogen storage tank. This work is the evolution of extensive materials testing, laboratory scale testing, and system studies leading to the use of glass bubbles insulation as a cost efficient and high performance alternative in cryogenic storage tanks of any size. The tank utilized is part of a rocket propulsion test complex at the NASA Stennis Space Center and is a 1960's vintage spherical double wall tank with an evacuated annulus. The original perlite that was removed from the annulus was in pristine condition and showed no signs of deterioration or compaction. Test results show a significant reduction in liquid hydrogen boiloff when compared to recent baseline data prior to removal of the perlite insulation. The data also validates the previous laboratory scale testing (1000 L) and full-scale numerical modeling (3,200,000 L) of boiloff in spherical cryogenic storage tanks. The performance of the tank will continue to be monitored during operation of the tank over the coming years. KEYWORDS: Glass bubble, perlite, insulation, liquid hydrogen, storage tank.

  20. Low sintering temperature glass waste forms for sequestering radioactive iodine

    Science.gov (United States)

    Nenoff, Tina M.; Krumhansl, James L.; Garino, Terry J.; Ockwig, Nathan W.

    2012-09-11

    Materials and methods of making low-sintering-temperature glass waste forms that sequester radioactive iodine in a strong and durable structure. First, the iodine is captured by an adsorbant, which forms an iodine-loaded material, e.g., AgI, AgI-zeolite, AgI-mordenite, Ag-silica aerogel, ZnI.sub.2, CuI, or Bi.sub.5O.sub.7I. Next, particles of the iodine-loaded material are mixed with powdered frits of low-sintering-temperature glasses (comprising various oxides of Si, B, Bi, Pb, and Zn), and then sintered at a relatively low temperature, ranging from 425.degree. C. to 550.degree. C. The sintering converts the mixed powders into a solid block of a glassy waste form, having low iodine leaching rates. The vitrified glassy waste form can contain as much as 60 wt % AgI. A preferred glass, having a sintering temperature of 500.degree. C. (below the silver iodide sublimation temperature of 500.degree. C.) was identified that contains oxides of boron, bismuth, and zinc, while containing essentially no lead or silicon.

  1. Synthesis and devitrification of high glass-forming ability bulk metallic glasses.

    OpenAIRE

    Huang, Hong.

    2007-01-01

    In this thesis, literature on the production, microstructures and properties of bulk metallic glasses (BMG) has been reviewed with particular reference to glass forming ability (GFA) and alloys of the Fe-Zr-B and Zr-based BMG systems. The experimental procedures used in the research are presented and the results for the amorphous Fe80Zr12B8 ribbon and the Zr57Ti5Al10Cu20Ni8, Zr57Nb5Al10Cu20Ni8, Zr53Nb2Al8Cu30Ni7 BMGs are given and discussed. Wedge-shaped ingots of the Zr-based BMGs were produ...

  2. Beating Homogeneous Nucleation and Tuning Atomic Ordering in Glass-Forming Metals by Nanocalorimetry.

    Science.gov (United States)

    Zhao, Bingge; Yang, Bin; Abyzov, Alexander S; Schmelzer, Jürn W P; Rodríguez-Viejo, Javier; Zhai, Qijie; Schick, Christoph; Gao, Yulai

    2017-12-13

    In this paper, the amorphous Ce 68 Al 10 Cu 20 Co 2 (atom %) alloy was in situ prepared by nanocalorimetry. The high cooling and heating rates accessible with this technique facilitate the suppression of crystallization on cooling and the identification of homogeneous nucleation. Different from the generally accepted notion that metallic glasses form just by avoiding crystallization, the role of nucleation and growth in the crystallization behavior of amorphous alloys is specified, allowing an access to the ideal metallic glass free of nuclei. Local atomic configurations are fundamentally significant to unravel the glass forming ability (GFA) and phase transitions in metallic glasses. For this reason, isothermal annealing near T g from 0.001 s to 25,000 s following quenching becomes the strategy to tune local atomic configurations and facilitate an amorphous alloy, a mixed glassy-nanocrystalline state, and a crystalline sample successively. On the basis of the evolution of crystallization enthalpy and overall latent heat on reheating, we quantify the underlying mechanism for the isothermal nucleation and crystallization of amorphous alloys. With Johnson-Mehl-Avrami method, it is demonstrated that the coexistence of homogeneous and heterogeneous nucleation contributes to the isothermal crystallization of glass. Heterogeneous rather than homogeneous nucleation dominates the isothermal crystallization of the undercooled liquid. For the mixed glassy-nanocrystalline structure, an extraordinary kinetic stability of the residual glass is validated, which is ascribed to the denser packed interface between amorphous phase and ordered nanocrystals. Tailoring the amorphous structure by nanocalorimetry permits new insights into unraveling GFA and the mechanism that correlates local atomic configurations and phase transitions in metallic glasses.

  3. Glass phase expelling during liquid phase sintering of YSZ

    International Nuclear Information System (INIS)

    Souza, Milton Ferreira de; Souza, Dulcina Pinatti Ferreira de

    1998-01-01

    Expelling of the liquid phase during sintering of Zr O 2 -6.5 mol % Y 2 O 3 - 0.5 mol % Pr 2 O 3 ceramic was observed as a result of grain coarsening. ZrO 2 - 7.0 mol % Y 2 O 3 samples, without Pr 2 O 3 addition, do not show this effect under the same sintering conditions. The expelling process is caused by surface tension forces and attracting van der Waals forces between the grains, coupled with the existence of two glass phases on the grain boundaries. The amount of expelled glass phase increases with grain growth, but saturates above 16 μm average grain size. (author)

  4. Breaking Through the Glass Ceiling: Recent Experimental Approaches to Probe the Properties of Supercooled Liquids near the Glass Transition.

    Science.gov (United States)

    Smith, R Scott; Kay, Bruce D

    2012-03-15

    Experimental measurements of the properties of supercooled liquids at temperatures near their glass transition temperatures, Tg, are requisite for understanding the behavior of glasses and amorphous solids. Unfortunately, many supercooled molecular liquids rapidly crystallize at temperatures far above their Tg, making such measurements difficult to nearly impossible. In this Perspective, we discuss some recent alternative approaches to obtain experimental data in the temperature regime near Tg. These new approaches may yield the additional experimental data necessary to test current theoretical models of the dynamical slowdown that occurs in supercooled liquids approaching the glass transition.

  5. Quantitative model of super-Arrhenian behavior in glass forming materials

    Science.gov (United States)

    Caruthers, J. M.; Medvedev, G. A.

    2018-05-01

    The key feature of glass forming liquids is the super-Arrhenian temperature dependence of the mobility, where the mobility can increase by ten orders of magnitude or more as the temperature is decreased if crystallization does not intervene. A fundamental description of the super-Arrhenian behavior has been developed; specifically, the logarithm of the relaxation time is a linear function of 1 /U¯x , where U¯x is the independently determined excess molar internal energy and B is a material constant. This one-parameter mobility model quantitatively describes data for 21 glass forming materials, which are all the materials where there are sufficient experimental data for analysis. The effect of pressure on the loga mobility is also described using the same U¯x(T ,p ) function determined from the difference between the liquid and crystalline internal energies. It is also shown that B is well correlated with the heat of fusion. The prediction of the B /U¯x model is compared to the Adam and Gibbs 1 /T S¯x model, where the B /U¯x model is significantly better in unifying the full complement of mobility data. The implications of the B /U¯x model for the development of a fundamental description of glass are discussed.

  6. Zr-Cu-Ni-Al bulk metallic glasses with superhigh glass-forming ability

    International Nuclear Information System (INIS)

    Sun, Y.J.; Qu, D.D.; Huang, Y.J.; Liss, K.-D.; Wei, X.S.; Xing, D.W.; Shen, J.

    2009-01-01

    Zr-Cu-Ni-Al quaternary amorphous alloy compositions with varying glass-forming ability are developed by an efficient method of proportional mixing of binary eutectics. The critical diameter of the glassy sample is improved from 6 mm for Zr 53 Cu 18.7 Ni 12 Al 16.3 to 14 mm for Zr 50.7 Cu 28 Ni 9 Al 12.3 by straightforwardly adjusting the eutectic unit's coefficients. The drastic improvement in GFA is attributed to balancing the chemical affinities of the Zr, Cu, Ni and Al components in the melt prior to solidification which makes the precipitation of competing crystalline phases more difficult. As the glass-forming ability increases, the concentration of Cu in the alloys exhibits a same trend. Based on synchrotron radiation high-energy X-ray diffraction analysis and Miracle's structural model, it is envisioned that the substitution of additional Cu atoms for Zr atoms in the investigated alloys stabilizes the efficient cluster packing structure of the amorphous alloys, leading to the pronounced increase in their glass-forming ability

  7. Glass forming ability and mechanical properties of Zr50Cu42Al8 bulk metallic glass

    International Nuclear Information System (INIS)

    Xia, L; Chan, K C; Wang, G; Liu, L

    2008-01-01

    In this work, we report that Zr 50 Cu 42 Al 8 bulk metallic glass (BMG) exhibits excellent glass forming ability and mechanical properties. Zr 50 Cu 42 Al 8 glassy rods with a diameter of 3 mm were prepared using conventional copper mould suction casting. The glassy rod exhibits a modulus of about 115 GPa and a fracture strength of about 2 GPa, and, as compared with other large-scale BMGs, it has excellent room-temperature plasticity of up to 20% under compression. The fracture mechanism of the rod was investigated by microstructural investigations, and it was found that the large plasticity of the as-cast rod is closely related to the in situ formation of nano-crystalline particles embedded in the amorphous matrix.

  8. Icosahedral binary clusters of glass-forming Lennard-Jones binary alloy

    International Nuclear Information System (INIS)

    Iwamatsu, Masao

    2007-01-01

    It is widely believed that the local icosahedral structure is related to the formation of bulk metallic glasses (BMGs). Specifically the existence of 13-atom icosahedral cluster in undercooled liquid is imagined to play a key role to initiate the glass formation as the seed of amorphous structure or to block the nucleation of regular crystal as the impurity. The existence of 13-atom icosahedral clusters in one-component liquids was predicted more than half a century ago by Frank from his total energy calculation for isolated clusters. In BMG alloys, however, the situation is less clear. In this report, we present the lowest-energy structures of 13-atom Lennard-Jones binary cluster calculated from the modified space-fixed genetic algorithm. We study, in particular, the artificial Lennard-Jones potential designed by Kob and Andersen [W. Kob, H.C. Andersen, Phys. Rev. E 51 (1995) 4626] that is known to form BMG. Curiously, the lowest-energy structures of 13-atom cluster are non-icosahedral for almost all compositions. Our result suggests that the existence of the icosahedral cluster is not a necessary condition but only a sufficient condition for glass formation

  9. Microscopic Theory of Coupled Slow Activated Dynamics in Glass-Forming Binary Mixtures.

    Science.gov (United States)

    Zhang, Rui; Schweizer, Kenneth S

    2018-04-05

    The Elastically Collective Nonlinear Langevin Equation theory for one-component viscous liquids and suspensions is generalized to treat coupled slow activated relaxation and diffusion in glass-forming binary sphere mixtures of any composition, size ratio, and interparticle interactions. A trajectory-level dynamical coupling parameter concept is introduced to construct two coupled dynamic free energy functions for the smaller penetrant and larger matrix particle. A two-step dynamical picture is proposed where the first-step process involves matrix-facilitated penetrant hopping quantified in a self-consistent manner based on a temporal coincidence condition. After penetrants dynamically equilibrate, the effectively one-component matrix particle dynamics is controlled by a new dynamic free energy (second-step process). Depending on the time scales associated with the first- and second-step processes, as well as the extent of matrix-correlated facilitation, distinct physical scenarios are predicted. The theory is implemented for purely hard-core interactions, and addresses the glass transition based on variable kinetic criteria, penetrant-matrix coupled activated relaxation, self-diffusion of both species, dynamic fragility, and shear elasticity. Testable predictions are made. Motivated by the analytic ultralocal limit idea derived for pure hard sphere fluids, we identify structure-thermodynamics-dynamics relationships. As a case study for molecule-polymer thermal mixtures, the chemically matched fully miscible polystyrene-toluene system is quantitatively studied based on a predictive mapping scheme. The resulting no-adjustable-parameter results for toluene diffusivity and the mixture glass transition temperature are in good agreement with experiment. The theory provides a foundation to treat diverse dynamical problems in glass-forming mixtures, including suspensions of colloids and nanoparticles, polymer-molecule liquids, and polymer nanocomposites.

  10. Liquid nitrogen enhancement of partially annealed fission tracks in glass

    International Nuclear Information System (INIS)

    Pilione, L.J.; Gold, D.P.

    1976-01-01

    It is known that the number density of fission tracks in solids is reduced if the sample is heated before chemical etching, and the effect of annealing must be allowed for before an age can be assigned to the sample. The extent of annealing can be determined by measuring the reduction of track parameters (diameter and/or length) and comparison with unannealed tracks. Correct ages can be obtained by careful calibration studies of track density reduction against track diameter or length reduction at different annealing temperatures and times. For crystallised minerals, however, the resulting correction techniques are not generally valid. In the experimental work described glass samples were partially annealed and then immersed in liquid N 2 for various periods, and it was shown that the properties of the glass and the track parameters could be altered so as to observe tracks that would normally be erased by annealing. The results of track density measurements against liquid N 2 immersion times are shown graphically. A gain of about 40% was achieved after 760 hours immersion time. The size of the tracks was not noticeably affected by the immersion. It was thought that thermal shock might be the cause of the track enhancement, but it was found that repeated immersion for about 2 hours did not lead to an increase in track density. Other studies suggest that the mechanism that erases the tracks through annealing may be partially reversed when the temperature of the sample is significantly lowered for a sufficient length of time. Further work is under way to find whether or not the process of enhancement is a reversal of the annealing process. Similar enhancement effects using liquid N 2 have been observed for d-particle tracks in polycarbonate detectors. (U.K.)

  11. Dynamics and Geometry of Icosahedral Order in Liquid and Glassy Phases of Metallic Glasses

    Directory of Open Access Journals (Sweden)

    Masato Shimono

    2015-07-01

    Full Text Available The geometrical properties of the icosahedral ordered structure formed in liquid and glassy phases of metallic glasses are investigated by using molecular dynamics simulations. We investigate the Zr-Cu alloy system as well as a simple model for binary alloys, in which we can change the atomic size ratio between alloying components. In both cases, we found the same nature of icosahedral order in liquid and glassy phases. The icosahedral clusters are observed in liquid phases as well as in glassy phases. As the temperature approaches to the glass transition point Tg, the density of the clusters rapidly grows and the icosahedral clusters begin to connect to each other and form a medium-range network structure. By investigating the geometry of connection between clusters in the icosahedral network, we found that the dominant connecting pattern is the one sharing seven atoms which forms a pentagonal bicap with five-fold symmetry. From a geometrical point of view, we can understand the mechanism of the formation and growth of the icosahedral order by using the Regge calculus, which is originally employed to formulate a theory of gravity. The Regge calculus tells us that the distortion energy of the pentagonal bicap could be decreased by introducing an atomic size difference between alloying elements and that the icosahedral network would be stabilized by a considerably large atomic size difference.

  12. Radiation effects in glass and glass-ceramic waste forms for the immobilization of CANDU UO{sub 2} fuel reprocessing waste

    Energy Technology Data Exchange (ETDEWEB)

    Tait, J C

    1993-05-01

    AECL has investigated three waste forms for the immobilization of high-level liquid wastes that would arise if used CANDU fuels were reprocessed at some time in the future to remove fissile materials for the fabrication of new power reactor fuel. These waste forms are borosilicate glasses, aluminosilicate glasses and titanosilicate glass-ceramics. This report discusses the potential effects of alpha, beta and gamma radiation on the releases of radionuclides from these waste forms as a result of aqueous corrosion by groundwaters that would be present in an underground waste disposal vault. The report discusses solid-state damage caused by radiation-induced atomic displacements in the waste forms as well as irradiation of groundwater solutions (radiolysis), and their potential effects on waste-form corrosion and radionuclide release. The current literature on radiation effects on borosilicate glasses and in ceramics is briefly reviewed, as are potential radiation effects on specialized waste forms for the immobilization of {sup 129}I, {sup 85}Kr and {sup 14}C. (author). 104 refs., 9 tabs., 5 figs.

  13. Discontinuities of Plastic Deformation in Metallic Glasses with Different Glass Forming Ability

    Science.gov (United States)

    Hurakova, Maria; Csach, Kornel; Miskuf, Jozef; Jurikova, Alena; Demcak, Stefan; Ocelik, Vaclav; Hosson, Jeff Th. M. De

    The metallic ribbons Fe40Ni40B20, Cu47Ti35Zr11Ni6Si1 and Zr65Cu17.5Ni10Al7.5 with different microhardness and glass forming ability were studied at different loading rates from 0.05 to 100 mN/s. We describe in details the differences in elemental discontinuities on the loading curves for the studied alloys. It was found that the discontinuities began at a certain local deformation independently on the macroscopic mechanical properties of a ribbon. More developed discontinuities at higher deformations are created for the materials with lower microhardness and so lower strength.

  14. IR Sensor Synchronizing Active Shutter Glasses for 3D HDTV with Flexible Liquid Crystal Lenses

    Directory of Open Access Journals (Sweden)

    Jeong In Han

    2013-12-01

    Full Text Available IR sensor synchronizing active shutter glasses for three-dimensional high definition television (3D HDTV were developed using a flexible liquid crystal (FLC lens. The FLC lens was made on a polycarbonate (PC substrate using conventional liquid crystal display (LCD processes. The flexible liquid crystal lens displayed a maximum transmission of 32% and total response time of 2.56 ms. The transmittance, the contrast ratio and the response time of the flexible liquid crystal lens were superior to those of glass liquid crystal lenses. Microcontroller unit and drivers were developed as part of a reception module with power supply for the IR sensor synchronizing active shutter glasses with the flexible liquid crystal lens prototypes. IR sensor synchronizing active shutter glasses for 3D HDTV with flexible liquid crystal lenses produced excellent 3D images viewing characteristics.

  15. Immobilization of radwastes in glass containers and products formed thereby

    International Nuclear Information System (INIS)

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

    1982-01-01

    A mixture of glass packing and radioactive or other toxic material is placed in a solid glass container, and the container is heated to drive off volatile components and collapse and seal the container

  16. Effect of Ga substitution on the crystallization behaviour and glass forming ability of Zr-Al-Cu-Ni alloys

    International Nuclear Information System (INIS)

    Singh, Devinder; Yadav, T.P.; Mandal, R.K.; Tiwari, R.S.; Srivastava, O.N.

    2010-01-01

    The crystallization behaviour of melt spun Zr 69.5 Al 7.5-x Ga x Cu 12 Ni 11 (x = 0-7.5; in at.%) metallic glasses has been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The DSC traces showed changes in crystallization behaviour with substitution of Ga. Formation of single nano-quasicrystalline phase by controlled crystallization of glasses has been found only for 0 ≤ x ≤ 1.5. Further increase of Ga content gives rise to formation of the quasicrystals together with Zr 2 Cu type crystalline phase. In addition to this, the substitution of Ga influences the size and shape of nano-quasicrystals. The glass forming abilities (GFAs) of these metallic glasses were assessed by the recognition of glass forming ability indicators, i.e. reduced glass transition temperature (T rg ) and supercooled liquid region (ΔT x ). The glass transition temperature (T g ) has been observed for all the melt spun ribbons.

  17. Glass as a waste form for the immobilization of plutonium

    International Nuclear Information System (INIS)

    Bates, J.K.; Ellison, A.J.G.; Emery, J.W.; Hoh, J.C.

    1995-01-01

    Several alternatives for disposal of surplus plutonium are being considered. One method is incorporating Pu into glass and in this paper we discuss the development and corrosion behavior of an alkali-tin-silicate glass and update results in testing Pu doped Defense Waste Processing Facility (DWPF) reference glasses. The alkali-tin-silicate glass was engineered to accommodate a high Pu loading and to be durable under conditions likely to accelerate glass reaction. The glass dissolves about 7 wt% Pu together with the neutron absorber Gd, and under test conditions expected to accelerate the glass reaction with water, is resistant to corrosion. The Pu and the Gd are released from the glass at nearly the same rate in static corrosion tests in water, and are not segregated into surface alteration phases when the glass is reacted in water vapor. Similar results for the behavior of Pu and Gd are found for the DWPF reference glasses, although the long-term rate of reaction for the reference glasses is more rapid than for the alkali-tin-silicate glass

  18. Compressive deformation of in situ formed bulk metallic glass composites

    Energy Technology Data Exchange (ETDEWEB)

    Clausen, B. [Lujan Neutron Science Center, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Lee, S.Y. [Department of Materials Science and Engineering, Iowa State University, Ames, IA 50011 (United States); Ustuendag, E. [Department of Materials Science and Engineering, Iowa State University, Ames, IA 50011 (United States)]. E-mail: ustundag@iastate.edu; Kim, C.P. [Liquidmetal Technologies, Lake Forest, CA 92630 (United States); Brown, D.W. [Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Bourke, M.A.M. [Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2006-02-15

    A bulk metallic glass matrix composite with dendc second phase precipitates was investigated using neutron diffraction and self-consistent modeling (SCM) to ascertain its deformation mechanisms. The compressive behavior of both the composite and the second phase (in its monolithic form) were investigated. The diffraction data were compared to the predictions of a new SCM resulting in good agreement. For the first time, this model considered both amorphous and crystalline phases and allowed the calculation of single crystal elastic constants from polycrystalline diffraction data. It was shown that the ductile second phase yielded first upon loading, and this was followed by multiple shear band formation in the matrix, a process which enhanced the ductility of the composite.

  19. Compressive deformation of in situ formed bulk metallic glass composites

    International Nuclear Information System (INIS)

    Clausen, B.; Lee, S.Y.; Ustuendag, E.; Kim, C.P.; Brown, D.W.; Bourke, M.A.M.

    2006-01-01

    A bulk metallic glass matrix composite with dendritic second phase precipitates was investigated using neutron diffraction and self-consistent modeling (SCM) to ascertain its deformation mechanisms. The compressive behavior of both the composite and the second phase (in its monolithic form) were investigated. The diffraction data were compared to the predictions of a new SCM resulting in good agreement. For the first time, this model considered both amorphous and crystalline phases and allowed the calculation of single crystal elastic constants from polycrystalline diffraction data. It was shown that the ductile second phase yielded first upon loading, and this was followed by multiple shear band formation in the matrix, a process which enhanced the ductility of the composite

  20. The kinetic glass transition of the Zr46.75Ti8.25Cu7.5Ni10Be27.5 bulk metallic glass former-supercooled liquids on a long time scale

    International Nuclear Information System (INIS)

    Busch, R.; Johnson, W.L.

    1998-01-01

    Viscosity and enthalpy relaxation from the amorphous state into the supercooled liquid state was investigated in the bulk metallic glass forming Zr 46.75 Ti 8.25 Cu 7.5 Ni 10 Be 27.5 alloy below the calorimetric glass transition. At different temperatures, the viscosities relax into states that obey the same Vogel endash Fulcher endash Tammann relation as the data obtained at higher temperatures in the supercooled liquid. Enthalpy recovery experiments after relaxation in the same temperature range show that the enthalpy of the material reaches values that also corresponds to the supercooled liquid state. The glass relaxes into a metastable supercooled liquid state, if it is observed on a long time scale. Equilibration is possible far below the calorimetric glass transition and very likely even below the isentropic temperature. copyright 1998 American Institute of Physics

  1. Production of sodalite waste forms by addition of glass

    International Nuclear Information System (INIS)

    Pereira, C.

    1995-01-01

    Spent nuclear fuel can be treated in a molten salt electrorefiner for conversion into metal and mineral waste forms for geologic disposal. Sodalite is one of the mineral waste forms under study. Fission products in the molten salt are ion-exchanged into zeolite A, which is converted to sodalite and consolidated. Sodalite can be formed directly from mixtures of salt and zeolite A at temperatures above 975 K; however, nepheline is usually produced as a secondary phase. Addition of small amounts of glass frit to the mixture reduced nepheline formation significantly. Loss of fission products was not observed for reaction below 1000 K. Hot-pressing of the sodalite powders yielded dense pellets (∼2.3 g/cm 3 ) without any loss of fission product species. Normalized release rates were below 1 g/m 2 ·day for pre-washed samples in 28-day leach tests based on standard MCC-1 tests but increased with the presence of free salt on the sodalite

  2. Forms of vibration and structural changes in liquid state

    Czech Academy of Sciences Publication Activity Database

    Hlaváček, B.; Šesták, Jaroslav; Koudelka, L.; Mošner, P.; Mareš, Jiří J.

    2005-01-01

    Roč. 80, - (2005), s. 271-283 ISSN 1388-6150 Institutional research plan: CEZ:AV0Z10100521 Keywords : crossover temperature * deterministic chaos * glass transition * non-linear oscillators * solid-liquid transition Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.425, year: 2005

  3. Basaltic glasses from Iceland and the deep sea: Natural analogues to borosilicate nuclear waste-form glass

    International Nuclear Information System (INIS)

    Jercinovic, M.J.; Ewing, R.C.

    1987-12-01

    The report provides a detailed analysis of the alteration process and products for natural basaltic glasses. Information of specific applicability to the JSS project include: * The identification of typical alteration products which should be expected during the long-term corrosion process of low-silica glasses. The leached layers contain a relatively high proportion of crystalline phases, mostly in the form of smectite-type clays. Channels through the layer provide immediate access of solutions to the fresh glass/alteration layer interface. Thus, glasses are not 'protected' from further corrosion by the surface layer. * Corrosion proceeds with two rates - an initial rate in silica-undersaturated environments and a long-term rate in silica-saturated environments. This demonstrates that there is no unexpected change in corrosion rate over long periods of time. The long-term corrosion rate is consistent with that of borosilicate glasses. * Precipitation of silica-containing phases can result in increased alteration of the glass as manifested by greater alteration layer thicknesses. This emphasizes the importance of being able to predict which phases form during the reaction sequence. * For natural basaltic glasses the flow rate of water and surface area of exposed glass are critical parameters in minimizing glass alteration over long periods of time. The long-term stability of basalt glasses is enhanced when silica concentrations in solution are increased. In summary, there is considerable agreement between corrosion phenomena observed for borosilicate glasses in the laboratory and those observed for natural basalt glasses of great age. (With 121 refs.) (authors)

  4. Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

    Science.gov (United States)

    Giovambattista, Nicolas; Loerting, Thomas; Lukanov, Boris R.; Starr, Francis W.

    2012-01-01

    Water has multiple glassy states, often called amorphous ices. Low-density (LDA) and high-density (HDA) amorphous ice are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation connects to a first-order liquid-liquid phase transition (LLPT) above the glass transition temperature Tg. Direct experimental evidence of the LLPT is challenging to obtain, since the LLPT occurs at conditions where water rapidly crystallizes. In this work, we explore the implications of a LLPT on the pressure dependence of Tg(P) for LDA and HDA by performing computer simulations of two water models – one with a LLPT, and one without. In the absence of a LLPT, Tg(P) for all glasses nearly coincide. When there is a LLPT, different glasses exhibit dramatically different Tg(P) which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario including a LLPT. PMID:22550566

  5. New insight on glass-forming ability and designing Cu-based bulk metallic glasses: The solidification range perspective

    International Nuclear Information System (INIS)

    Wu, Jili; Pan, Ye; Li, Xingzhou; Wang, Xianfei

    2014-01-01

    Highlights: • The equation, T rg = T g /T l , was rotationally modified to T rg = κ(T m /T l ) + C/T l . • The newly generalized equation suggests a way for describing glass-forming ability. • Several new Cu-based bulk metallic glasses were discovered by solidification range. - Abstract: In this paper, a new equation was rationally generalized from the reduced glass transition temperature. This equation indicates that solidification range can be used for describing glass-forming ability, which can be calculated with the aid of computational thermodynamic approach. Based on this scenario, several new Cu-based bulk metallic glasses in the ternary Cu–Zr–Ti alloy system were discovered. The as-cast samples were characterized by X-ray diffraction and transmission electronic microscopy. The results indicate that as-cast samples have monolithic amorphous nature. Thermal analysis validates that the smaller solidification range is closely related to the higher glass-forming ability, which is contributed to the effect of solidification time on the formation of bulk metallic glasses. This work also suggests that solidus can influence glass formation

  6. Glass-liquid-glass reentrance in mono-component colloidal dispersions

    International Nuclear Information System (INIS)

    Ramirez-Gonzalez, P E; Medina-Noyola, M; Vizcarra-Rendon, A; Guevara-Rodriguez, F de J

    2008-01-01

    The self-consistent generalized Langevin equation (SCGLE) theory of colloid dynamics is employed to describe the ergodic-non-ergodic transition in model mono-disperse colloidal dispersions whose particles interact through hard-sphere plus short-ranged attractive forces. The ergodic-non-ergodic phase diagram in the temperature-concentration state space is determined for the hard-sphere plus attractive Yukawa model within the mean spherical approximation for the static structure factor by solving a remarkably simple equation for the localization length of the colloidal particles. Finite real values of this property signals non-ergodicity and determines the non-ergodic parameters f(k) and f s (k). The resulting phase diagram for this system, which involves the existence of reentrant (repulsive and attractive) glass states, is compared with the corresponding prediction of mode coupling theory. Although both theories coincide in the general features of this phase diagram, there are also clear qualitative differences. One of the most relevant is the SCGLE prediction that the ergodic-attractive glass transition does not preempt the gas-liquid phase transition, but always intersects the corresponding spinodal curve on its high-concentration side. We also calculate the ergodic-non-ergodic phase diagram for the sticky hard-sphere model to illustrate the dependence of the predicted SCGLE dynamic phase diagram on the choice of one important constituent element of the SCGLE theory

  7. Glass-liquid-glass reentrance in mono-component colloidal dispersions

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez-Gonzalez, P E; Medina-Noyola, M [Instituto de Fisica ' Manuel Sandoval Vallarta' , Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, 78000 San Luis Potosi, SLP (Mexico); Vizcarra-Rendon, A [Unidad Academica de Fisica, Universidad Autonoma de Zacatecas, Paseo la Bufa y Calzada Solidaridad, 98600, Zacatecas, Zac. (Mexico); Guevara-Rodriguez, F de J [Coordinacion de IngenierIa Molecular, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico, DF (Mexico)

    2008-05-21

    The self-consistent generalized Langevin equation (SCGLE) theory of colloid dynamics is employed to describe the ergodic-non-ergodic transition in model mono-disperse colloidal dispersions whose particles interact through hard-sphere plus short-ranged attractive forces. The ergodic-non-ergodic phase diagram in the temperature-concentration state space is determined for the hard-sphere plus attractive Yukawa model within the mean spherical approximation for the static structure factor by solving a remarkably simple equation for the localization length of the colloidal particles. Finite real values of this property signals non-ergodicity and determines the non-ergodic parameters f(k) and f{sub s}(k). The resulting phase diagram for this system, which involves the existence of reentrant (repulsive and attractive) glass states, is compared with the corresponding prediction of mode coupling theory. Although both theories coincide in the general features of this phase diagram, there are also clear qualitative differences. One of the most relevant is the SCGLE prediction that the ergodic-attractive glass transition does not preempt the gas-liquid phase transition, but always intersects the corresponding spinodal curve on its high-concentration side. We also calculate the ergodic-non-ergodic phase diagram for the sticky hard-sphere model to illustrate the dependence of the predicted SCGLE dynamic phase diagram on the choice of one important constituent element of the SCGLE theory.

  8. Comparison of the corrosion behaviors of the glass-bonded sodalite ceramic waste form and reference HLW glasses

    International Nuclear Information System (INIS)

    Ebert, W. L.; Lewis, M. A.

    1999-01-01

    A glass-bonded sodalite ceramic waste form is being developed for the long-term immobilization of salt wastes that are generated during spent nuclear fuel conditioning activities. A durable waste form is prepared by hot isostatic pressing (HIP) a mixture of salt-loaded zeolite powders and glass frit. A mechanistic description of the corrosion processes is being developed to support qualification of the CWF for disposal. The initial set of characterization tests included two standard tests that have been used extensively to study the corrosion behavior of high level waste (HLW) glasses: the Material Characterization Center-1 (MCC-1) Test and the Product Consistency Test (PCT). Direct comparison of the results of tests with the reference CWF and HLW glasses indicate that the corrosion behaviors of the CWF and HLW glasses are very similar

  9. Correlation between supercooled liquid relaxation and glass poisson’s ratio

    DEFF Research Database (Denmark)

    Sun, Q.J.; Hu, L.N.; Zhou, C.

    2015-01-01

    in the ratio r and this relation can be described by the empirical function v = 0.5 − A ∗ exp(−B ∗ r), where A and B are constants. This correlation might imply that glass plasticity is associated with the competition between the α and the slow β relaxations in SLs. The underlying physics of this correlation......We report on a correlation between the supercooled liquid (SL) relaxation and glass Poisson’s ratio (v) by comparing the activation energy ratio (r) of the α and the slow β relaxations and the v values for both metallic and nonmetallic glasses. Poisson’s ratio v generally increases with an increase...... lies in the heredity of the structural heterogeneity from liquid to glass. This work gives insights into both the microscopic mechanism of glass deformation through the SL dynamics and the complex structural evolution during liquid-glass transition....

  10. Candidate Low-Temperature Glass Waste Forms for Technetium-99 Recovered from Hanford Effluent Management Facility Evaporator Concentrate

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Mei [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Tang, Ming [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Rim, Jung Ho [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chamberlin, Rebecca M. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-07-24

    Alternative treatment and disposition options may exist for technetium-99 (99Tc) in secondary liquid waste from the Hanford Direct-Feed Low-Activity Waste (DFLAW) process. One approach includes development of an alternate glass waste form that is suitable for on-site disposition of technetium, including salts and other species recovered by ion exchange or precipitation from the EMF evaporator concentrate. By recovering the Tc content from the stream, and not recycling the treated concentrate, the DFLAW process can potentially be operated in a more efficient manner that lowers the cost to the Department of Energy. This report provides a survey of candidate glass formulations and glass-making processes that can potentially incorporate technetium at temperatures <700 °C to avoid volatilization. Three candidate technetium feed streams are considered: (1) dilute sodium pertechnetate loaded on a non-elutable ion exchange resin; (2) dilute sodium-bearing aqueous eluent from ion exchange recovery of pertechnetate, or (3) technetium(IV) oxide precipitate containing Sn and Cr solids in an aqueous slurry. From the technical literature, promising candidate glasses are identified based on their processing temperatures and chemical durability data. The suitability and technical risk of three low-temperature glass processing routes (vitrification, encapsulation by sintering into a glass composite material, and sol-gel chemical condensation) for the three waste streams was assessed, based on available low-temperature glass data. For a subset of candidate glasses, their long-term thermodynamic behavior with exposure to water and oxygen was modeled using Geochemist’s Workbench, with and without addition of reducing stannous ion. For further evaluation and development, encapsulation of precipitated TcO2/Sn/Cr in a glass composite material based on lead-free sealing glasses is recommended as a high priority. Vitrification of pertechnetate in aqueous anion exchange eluent solution

  11. Glass forming in La2O3-TiO2-ZrO2 ternary system by containerless processing

    Science.gov (United States)

    Kaneko, Masashi; Kentei Yu, Yu; Kumar, Vijaya; Masuno, Atsunobu; Inoue, Hiroyuki; Odawara, Osamu; Yoda, Shinichi

    The containerless processing is an appropriate method to create new glasses, because it sup-presses nucleation at the boundary between liquid and crucible during solidification and it enables molten samples to be solidified without crystallization. Recently, we have succeeded in forming BaTi2 O5 glass in the bulk state by using an aerodynamic levitation furnace. BaTi2 O5 glass includes no traditional glass network former and it possesses high electric permittivity [1, 2]. From the point of view of optical application, BaTi2 O5 glass has high refractive indices over 2.1. BaTi2 O5 glass, however, vitrify only in a small sphere, and it crystallize when its diameter exceed 1.5 mm. In order to synthesize new titanate oxide glasses which possess higher refractive indices and larger diameter than BaTi2 O5 , La and Zr can be used as substitutive components. When Ba is replaced with La, refractive indices are expected to increase because of the heavier element. The addition of a third element is thought to be effective for enhance-ment of glass formation ability and Zr can be a candidate because Ti and Zr are homologous. In this research, we have succeeded in forming new bulk glass in La2 O3 -TiO2 -ZrO2 ternary system by means of the aerodynamic levitation furnace. We investigated the glass forming region, thermal properties and optical properties of La2 O3 -TiO2 -ZrO2 glass. Glass transition temperature, crystallization temperature, density, refractive indices and transmittance spectra were varied depending on the chemical composition. Reference [1] J. Yu et al, "Fabrication of BaTi2O5 Glass-Ceramics with Unusual Dielectric Properties during Crystallization", Chem-istry of Materials, 18 (2006) 2169-2173. [2] J. Yu et al., "Comprehensive Structural Study of Glassy and Metastable Crystalline BaTi2O5", Chemistry of Materials, 21 (2009) 259-263.

  12. Isoviscosity lines and the liquid-glass transition in simple liquids.

    Science.gov (United States)

    Fomin, Yu D; Brazhkin, V V; Ryzhov, V N

    2012-07-01

    This article presents the study of the generic behavior of viscosity of liquids based on some simple theoretical models, the soft-spheres and Lennard-Jones systems. The use of these simple models allows us to investigate in detail the viscosity behavior in a wide range of temperatures and pressures including the high-temperature-high-pressure limits. Based on the simulation results, we discuss the shape of isoviscosity lines and analyze the glass transition at high temperatures and high pressures. Despite the fact that the viscosity drastically increases in the limit of high temperatures and high pressures along the melting line, the relaxation time rapidly decreases in this region, and the system becomes further from the glass transition.

  13. Waste vitrification: prediction of acceptable compositions in a lime-soda-silica glass-forming system

    International Nuclear Information System (INIS)

    Gilliam, T.M.; Jantzen, C.M.

    1996-10-01

    A model is presented based upon calculated bridging oxygens which allows the prediction of the region of acceptable glass compositions for a lime-soda-silica glass-forming system containing mixed waste. The model can be used to guide glass formulation studies (e.g., treatability studies) or assess the applicability of vitrification to candidate waste streams

  14. Evaluation of final waste forms and recommendations for baseline alternatives to group and glass

    Energy Technology Data Exchange (ETDEWEB)

    Bleier, A.

    1997-09-01

    An assessment of final waste forms was made as part of the Federal Facilities Compliance Agreement/Development, Demonstration, Testing, and Evaluation (FFCA/DDT&E) Program because supplemental waste-form technologies are needed for the hazardous, radioactive, and mixed wastes of concern to the Department of Energy and the problematic wastes on the Oak Ridge Reservation. The principal objective was to identify a primary waste-form candidate as an alternative to grout (cement) and glass. The effort principally comprised a literature search, the goal of which was to establish a knowledge base regarding four areas: (1) the waste-form technologies based on grout and glass, (2) candidate alternatives, (3) the wastes that need to be immobilized, and (4) the technical and regulatory constraints on the waste-from technologies. This report serves, in part, to meet this goal. Six families of materials emerged as relevant; inorganic, organic, vitrified, devitrified, ceramic, and metallic matrices. Multiple members of each family were assessed, emphasizing the materials-oriented factors and accounting for the fact that the two most prevalent types of wastes for the FFCA/DDT&E Program are aqueous liquids and inorganic sludges and solids. Presently, no individual matrix is sufficiently developed to permit its immediate implementation as a baseline alternative. Three thermoplastic materials, sulfur-polymer cement (inorganic), bitumen (organic), and polyethylene (organic), are the most technologically developed candidates. Each warrants further study, emphasizing the engineering and economic factors, but each also has limitations that regulate it to a status of short-term alternative. The crystallinity and flexible processing of sulfur provide sulfur-polymer cement with the highest potential for short-term success via encapsulation. Long-term immobilization demands chemical stabilization, which the thermoplastic matrices do not offer. Among the properties of the remaining

  15. Evaluation of final waste forms and recommendations for baseline alternatives to grout and glass

    International Nuclear Information System (INIS)

    Bleier, A.

    1997-09-01

    An assessment of final waste forms was made as part of the Federal Facilities Compliance Agreement/Development, Demonstration, Testing, and Evaluation (FFCA/DDT ampersand E) Program because supplemental waste-form technologies are needed for the hazardous, radioactive, and mixed wastes of concern to the Department of Energy and the problematic wastes on the Oak Ridge Reservation. The principal objective was to identify a primary waste-form candidate as an alternative to grout (cement) and glass. The effort principally comprised a literature search, the goal of which was to establish a knowledge base regarding four areas: (1) the waste-form technologies based on grout and glass, (2) candidate alternatives, (3) the wastes that need to be immobilized, and (4) the technical and regulatory constraints on the waste-from technologies. This report serves, in part, to meet this goal. Six families of materials emerged as relevant; inorganic, organic, vitrified, devitrified, ceramic, and metallic matrices. Multiple members of each family were assessed, emphasizing the materials-oriented factors and accounting for the fact that the two most prevalent types of wastes for the FFCA/DDT ampersand E Program are aqueous liquids and inorganic sludges and solids. Presently, no individual matrix is sufficiently developed to permit its immediate implementation as a baseline alternative. Three thermoplastic materials, sulfur-polymer cement (inorganic), bitumen (organic), and polyethylene (organic), are the most technologically developed candidates. Each warrants further study, emphasizing the engineering and economic factors, but each also has limitations that regulate it to a status of short-term alternative. The crystallinity and flexible processing of sulfur provide sulfur-polymer cement with the highest potential for short-term success via encapsulation. Long-term immobilization demands chemical stabilization, which the thermoplastic matrices do not offer. Among the properties of the

  16. Simulation of an Aspheric Glass Lens Forming Behavior in Progressive GMP Process

    International Nuclear Information System (INIS)

    Chang, Sung Ho; Lee, Young Min; Kang, Jeong Jin; Hong, Seok Kwan; Shin, Gwang Ho; Heo, Young Moo; Jung, Tae Sung

    2007-01-01

    Recently, GMP(Glass Molding Press) process is mainly used to produce aspheric glass lenses. Because glass lens is heated at high temperature above Tg (Transformation Temperature) for forming the glass, the quality of aspheric glass lens is deteriorated by residual stresses which are generated in a aspheric glass lens after forming. In this study, as a fundamental study to develop the mold for progressive GMP process, we conducted a aspheric glass lens forming simulation. Prior to a aspheric glass lens forming simulation, compression and thermal conductivity tests were carried out to obtain mechanical and thermal properties of K-PBK40 which is newly developed material for precision molding, and flow characteristics of K-PBK40 were obtained at high temperature. Then, using the flow characteristics obtained, compression simulation was carried out and compared with the experimental result for the purpose of verifying the obtained flow characteristics. Finally, a glass lens press simulation in progressive GMP process was carried out and we could forecast the shape of deformed glass lenses and residual stresses contribution in the structure of deformed glass lenses after forming

  17. Effects of Nb addition on icosahedral quasicrystalline phase formation and glass-forming ability of Zr--Ni--Cu--Al metallic glasses

    International Nuclear Information System (INIS)

    Fan, Cang; Li, Chunfei; Inoue, Akihisa; Haas, Volker

    2001-01-01

    This work shows that the crystallization process of Zr--Ni--Cu--Al metallic glass is greatly influenced by adding Nb as an alloying element. Based on the results of the differential scanning calorimetry experiments for metallic glasses Zr 69-x Nb x Ni 10 Cu 12 Al 9 (x=0--15at.%), the crystallization process takes place through two individual stages. For Zr 69 Ni 10 Cu 12 Al 9 (x=0), metastable hexagonal ω-Zr and a small fraction of tetragonal Zr 2 Cu are precipitated upon completion of the first exothermic reaction. Contrary to this alloy, the precipitation of a nanoquasicrystalline phase is detected when 5--10 at.% Nb is added. Furthermore, the crystallization temperature T x , supercooled liquid region ΔT x and reduced temperature T g /T L (T g is the glass transition temperature, T L the liquidus temperature) increase with increasing Nb content. These results indicate that adding Nb content to Zr--Ni--Cu--Al metallic glasses not only induces quasicrystalline phase formation, but also enhances glass-forming ability. Copyright 2001 American Institute of Physics

  18. Glass-forming ability and crystallization behavior of some binary and ternary Ni-based glassy alloys

    International Nuclear Information System (INIS)

    Louzguine-Luzgin, Dmitri V.; Louzguina-Luzgina, Larissa V.; Xie Guoqiang; Li Song; Zhang Wei; Inoue, Akihisa

    2008-01-01

    The purpose of the current paper is to study the influence of Ti, V, Nb, Al, Sn and Pd additions on the glass-forming ability, formation of a supercooled liquid region and a devitrification process of some Ni-Zr glassy alloys as well as to compare the results with those obtained for similar Cu-based alloys studied earlier. The Ni-based glassy alloys were investigated by using X-ray diffraction, differential scanning and isothermal calorimetries. Although the studied Ni-based alloys showed high values of the reduced glass-transition temperature of about 0.6, their glass-forming ability is quite low. This fact may be explained by low stability of the supercooled liquid against crystallization and formation of the equilibrium intermetallic compounds with a high growth rate compared to those observed in similar Cu-based alloys studied earlier. Relatively low thermal conductivity of Ni-based alloys is also found to be another factor limiting their glass-forming ability

  19. Transparent phosphosilicate glasses containing crystals formed during cooling of melts

    DEFF Research Database (Denmark)

    Liu, S. J.; Zhang, Yanfei; He, W.

    2011-01-01

    The effect of P2O5-SiO2 substitution on spontaneous crystallization of SiO2-Al2O3-P2O5- Na2O-MgO melts during cooling was studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and rotation viscometry. Results show that addition of P2O5 leads...... to amorphous phase separation (APS), i.e., phosphate- and silicate-rich phases. It is due to the tendency of Mg2+ to form [MgO4] linking with [SiO4]. Molar substitution of P2O5 for SiO2 enhances the network polymerization of silicate-rich phase in the melts, and thereby the spontaneous crystallization of cubic...... Na2MgSiO4 is also enhanced during cooling of the melts. In addition, the sizes of the local crystalline and separated glassy domains are smaller than the wavelength of the visible light, and this leads to the transparency of the obtained glasses containing crystals....

  20. Insight on the glass-forming ability of Al–Y–Ni–Ce bulk metallic glass

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Shih-Fan, E-mail: sfchen@ntut.edu.tw [Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei 106, Taiwan (China); Chen, Chih-Yuan, E-mail: chen6563@gmail.com [Department of Energy Engineering, National United University, Miaoli 36003, Taiwan (China); Lin, Chia-Hung [Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei 106, Taiwan (China)

    2015-07-15

    Highlights: • Adding 1 at.% cerium to Al{sub 87}Y{sub 8}Ni{sub 5} alloy causes glass transition. • A large ΔT{sub x} indicates that (Al{sub 87}Y{sub 8}Ni{sub 5}){sub 99}Ce{sub 1} is possibly a ductile amorphous alloy. • Ce is effective in improving the thermal stability of the Al–Y–Ni amorphous alloy. • The hardness of the crystallized cerium-bearing alloy was as high as 593 Hv. - Abstract: In the present study, the role of Ce in the thermal stability and glass forming ability (GFA) of (Al{sub 87}Y{sub 8}Ni{sub 5}){sub 99}Ce{sub 1} alloy ribbons produced by a single roller melt-spinning process has been investigated in an attempt to understand the influences of multiple RE elements in an Al–TM–RE (TM: transition metal, RE: rear earth metal) alloy system. Only the (Al{sub 87}Y{sub 8}Ni{sub 5}){sub 99}Ce{sub 1} alloy ribbon showed a glass transition temperature (T{sub g}) at 483.2 K, and its ΔT{sub x} value was 41.3 K. Crystallization occurred in the temperature range of 500–750 K in three exothermic reaction stages. The peak temperature for these reactions shifted toward higher temperatures at higher heating rates. XRD and SEM analysis of annealed samples revealed that nano-sized Al particles precipitated within the amorphous matrix during the first exothermic reaction. The maximum hardness was obtained for both non-cerium and cerium addition alloys after crystallization in the 550–660 K region due to numerous nano-sized precipitates randomly and homogeneously distributed in the amorphous matrix. Moreover, from observation of the fracture surface, it is found that the fracture mode transforms from ductile to brittle when the sample is annealed at a higher crystallization temperature, at which brittle intermetallic compounds appear.

  1. Evaluation of lead-iron-phosphate glass as a high-level waste form

    International Nuclear Information System (INIS)

    Chick, L.A.; Bunnell, L.R.; Strachan, D.M.; Kissinger, H.E.; Hodges, F.N.

    1986-01-01

    The lead-iron-phosphate (Pb-Fe-P) nuclear waste glass developed at Oak Ridge National Laboratory (ORNL) was evaluated for its potential as an improvement over the current reference waste form, borosilicate (B-Si) glass. Vitreous Pb-Fe-P glass appears to have substantially better chemical durability than B-Si glass. However, severe crystallization leading to deteriorated chemical durability would result if this glass were poured into large canisters, as is presently done with B-Si glass. Cesium leach rates from this crystallized material are orders of magnitude greater than those from B-Si glass. Therefore, to realize the performance advantages of the Pb-Fe-P material in a nuclear waste form, it would be necessary to process it so that it is cooled rapidly, thus retaining its vitreous structure

  2. Evaluation of lead-iron-phosphate glass as a high-level waste form

    International Nuclear Information System (INIS)

    Chick, L.A.; Bunnell, L.R.; Strachan, D.M.; Kissinger, H.E.; Hodges, F.N.

    1986-01-01

    The lead-iron-phosphate nuclear waste glass developed at Oak Ridge National Laboratory (ORNL) was evaluated for its potential as an improvement over the current reference waste form, borosilicate glass. Vitreous lead-iron-phosphate glass appears to have substantially better chemical durability than borosilicate glass. However, severe crystallization leading to deteriorated chemical durability would result if this glass were poured into large canisters as is presently done with borosilicate glass. Cesium leach rates from this crystallized material are orders of magnitude greater than those from borosilicate glass. Therefore, in order to realize the performance advantages of the lead-iron-phosphate material in a nuclear waste form, it would be necessary to process it so that it is rapidly cooled, thus retaining its vitreous structure. 22 refs., 4 figs., 4 tabs

  3. Composition Range and Glass Forming Ability of Ternary Ca-Mg-Cu Bulk Metallic Glasses (Preprint)

    National Research Council Canada - National Science Library

    Senkov, O. N; Scott, J. M; Miracle, D. B

    2006-01-01

    .... The maximum thickness at which an alloy remains fully amorphous, glass transition temperature, crystallization temperature, temperature interval of the super-cooled region, solidus and liquidus...

  4. In-situ ductile metal/bulk metallic glass matrix composites formed by chemical partitioning

    Science.gov (United States)

    Kim, Choong Paul; Hays, Charles C.; Johnson, William L.

    2004-03-23

    A composite metal object comprises ductile crystalline metal particles in an amorphous metal matrix. An alloy is heated above its liquidus temperature. Upon cooling from the high temperature melt, the alloy chemically partitions, forming dendrites in the melt. Upon cooling the remaining liquid below the glass transition temperature it freezes to the amorphous state, producing a two-phase microstructure containing crystalline particles in an amorphous metal matrix. The ductile metal particles have a size in the range of from 0.1 to 15 micrometers and spacing in the range of from 0.1 to 20 micrometers. Preferably, the particle size is in the range of from 0.5 to 8 micrometers and spacing is in the range of from 1 to 10 micrometers. The volume proportion of particles is in the range of from 5 to 50% and preferably 15 to 35%. Differential cooling can produce oriented dendrites of ductile metal phase in an amorphous matrix. Examples are given in the Zr--Ti--Cu--Ni--Be alloy bulk glass forming system with added niobium.

  5. Spinel dissolution via addition of glass forming chemicals. Results of preliminary experiments

    Energy Technology Data Exchange (ETDEWEB)

    Fox, K. M. [Savannah River Site (SRS), Aiken, SC (United States); Johnson, F. C. [Savannah River Site (SRS), Aiken, SC (United States)

    2015-11-01

    Increased loading of high level waste in glass can lead to crystallization within the glass. Some crystalline species, such as spinel, have no practical impact on the chemical durability of the glass, and therefore may be acceptable from both a processing and a product performance standpoint. In order to operate a melter with a controlled amount of crystallization, options must be developed for remediating an unacceptable accumulation of crystals. This report describes preliminary experiments designed to evaluate the ability to dissolve spinel crystals in simulated waste glass melts via the addition of glass forming chemicals (GFCs).

  6. Poor glass-forming ability of Fe-based alloys

    DEFF Research Database (Denmark)

    Zheng, H.J.; Hu, L.N.; Zhao, X.

    2017-01-01

    processes. By using the concept of fluid cluster and supercooled liquid fragility in metallic liquids, it has been found that this dynamic transition makes the Fe-based supercooled liquids become more unstable, which leads to the poor GFA of Fe-based alloys. Further, it has been found that the degree...

  7. Substrate and surfactant effects on the glass-liquid transition of thin water films.

    Science.gov (United States)

    Souda, Ryutaro

    2006-09-07

    Temperature-programmed time-of-flight secondary ion mass spectrometry (TP-TOF-SIMS) and temperature-programmed desorption (TPD) have been used to perform a detailed investigation of the adsorption, desorption, and glass-liquid transition of water on the graphite and Ni(111) surfaces in the temperature range 13-200 K. Water wets the graphite surface at 100-120 K, and the hydrogen-bonded network is formed preferentially in the first monolayer to reduce the number of nonbonding hydrogens. The strongly chemisorbed water molecules at the Ni(111) surface do not form such a network and play a role in stabilizing the film morphology up to 160 K, where dewetting occurs abruptly irrespective of the film thickness. The surface structure of the water film formed on graphite is fluctuated considerably, resulting in deweting at 150-160 K depending on the film thickness. The dewetted patches of graphite are molecularly clean, whereas the chemisorbed water remains on the Ni(111) surface even after evaporation of the film. The abrupt drop in the desorption rate of water molecules at 160 K, which has been attributed to crystallization in the previous TPD studies, is found to disappear completely when a monolayer of methanol is present on the surface. This is because the morphology of supercooled liquid water is changed by the surface tension, and it is quenched by termination of the free OH groups on the surface. The surfactant methanol desorbs above 160 K since the hydrogen bonds of the water molecules are reconstructed. The drastic change in the properties of supercooled liquid water at 160 K should be ascribed to the liquid-liquid phase transition.

  8. Glass Ceramic Waste Forms for Combined CS+LN+TM Fission Products Waste Streams

    International Nuclear Information System (INIS)

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

    2010-01-01

    In this study, glass ceramics were explored as an alternative waste form for glass, the current baseline, to be used for immobilizing alkaline/alkaline earth + lanthanide (CS+LN) or CS+LN+transition metal (TM) fission-product waste streams generated by a uranium extraction (UREX+) aqueous separations type process. Results from past work on a glass waste form for the combined CS+LN waste streams showed that as waste loading increased, large fractions of crystalline phases precipitated upon slow cooling.(1) The crystalline phases had no noticeable impact on the waste form performance by the 7-day product consistency test (PCT). These results point towards the development of a glass ceramic waste form for treating CS+LN or CS+LN+TM combined waste streams. Three main benefits for exploring glass ceramics are: (1) Glass ceramics offer increased solubility of troublesome components in crystalline phases as compared to glass, leading to increased waste loading; (2) The crystalline network formed in the glass ceramic results in higher heat tolerance than glass; and (3) These glass ceramics are designed to be processed by the same melter technology as the current baseline glass waste form. It will only require adding controlled canister cooling for crystallization into a glass ceramic waste form. Highly annealed waste form (essentially crack free) with up to 50X lower surface area than a typical High-Level Waste (HLW) glass canister. Lower surface area translates directly into increased durability. This was the first full year of exploring glass ceramics for the Option 1 and 2 combined waste stream options. This work has shown that dramatic increases in waste loading are achievable by designing a glass ceramic waste form as an alternative to glass. Table S1 shows the upper limits for heat, waste loading (based on solubility), and the decay time needed before treatment can occur for glass and glass ceramic waste forms. The improvements are significant for both combined waste

  9. Glass Ceramic Waste Forms for Combined CS+LN+TM Fission Products Waste Streams

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-09-23

    In this study, glass ceramics were explored as an alternative waste form for glass, the current baseline, to be used for immobilizing alkaline/alkaline earth + lanthanide (CS+LN) or CS+LN+transition metal (TM) fission-product waste streams generated by a uranium extraction (UREX+) aqueous separations type process. Results from past work on a glass waste form for the combined CS+LN waste streams showed that as waste loading increased, large fractions of crystalline phases precipitated upon slow cooling.[1] The crystalline phases had no noticeable impact on the waste form performance by the 7-day product consistency test (PCT). These results point towards the development of a glass ceramic waste form for treating CS+LN or CS+LN+TM combined waste streams. Three main benefits for exploring glass ceramics are: (1) Glass ceramics offer increased solubility of troublesome components in crystalline phases as compared to glass, leading to increased waste loading; (2) The crystalline network formed in the glass ceramic results in higher heat tolerance than glass; and (3) These glass ceramics are designed to be processed by the same melter technology as the current baseline glass waste form. It will only require adding controlled canister cooling for crystallization into a glass ceramic waste form. Highly annealed waste form (essentially crack free) with up to 50X lower surface area than a typical High-Level Waste (HLW) glass canister. Lower surface area translates directly into increased durability. This was the first full year of exploring glass ceramics for the Option 1 and 2 combined waste stream options. This work has shown that dramatic increases in waste loading are achievable by designing a glass ceramic waste form as an alternative to glass. Table S1 shows the upper limits for heat, waste loading (based on solubility), and the decay time needed before treatment can occur for glass and glass ceramic waste forms. The improvements are significant for both combined waste

  10. Simulation of Patterned Glass Film Formation in the Evaporating Colloidal Liquid under IR Heating

    Science.gov (United States)

    Kolegov, K. S.

    2018-02-01

    The paper theoretically studies the method of evaporative lithography in combination with external infrared heating. This method makes it possible to form solid microstructures of the required relief shape as a result of evaporation of the liquid film of the colloidal solution under the mask. The heated particles are sintered easier, so there are no cracks in the obtained structure, unlike the structure obtained employing the standard method of evaporative lithography. The paper puts forward a modification of the mathematical model which allows to describe not only heat and mass transfer at the initial stage of the process, but also the phase transition of colloidal solution into glass. Aqueous latex is taken as an example. The resulting final form of solid film is in good agreement with the experimental data of other authors.

  11. Roughened glass slides and a spectrophotometer for the detection of the wavelength-dependent refractive index of transparent liquids.

    Science.gov (United States)

    Niskanen, Ilpo; Räty, Jukka; Myllylä, Risto; Sutinen, Veijo; Matsuda, Kiyofumi; Homma, Kazuhiro; Silfsten, Pertti; Peiponen, Kai-Erik

    2012-07-01

    We describe a method to determine the wavelength-dependent refractive index of liquids by measurement of light transmittance with a spectrophotometer. The method is based on using roughened glass slides with different a priori known refractive indices and immersing the slides into the transparent liquid with unknown refractive index. Using the dispersion data on the glass material it is possible to find the index match between the liquid and the glass slide, and hence the refractive index of the liquid.

  12. Glass forming ability: Miedema approach to (Zr, Ti, Hf)-(Cu, Ni) binary and ternary alloys

    Energy Technology Data Exchange (ETDEWEB)

    Basu, Joysurya [Department of Chemical, Materials and Biomolecular Engineering, 191 Auditorium Road, University of Connecticut, Storrs 06269, CT (United States)], E-mail: jbasu@engr.uconn.edu; Murty, B.S. [Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600036 (India); Ranganathan, S. [Department of Materials Engineering, Indian Institute of Science, Bangalore 560012 (India)

    2008-10-06

    Miedema's approach has been useful in determining the glass forming composition range for a particular alloy system. The concept of mixing enthalpy and mismatch entropy can be used in order to quantify Inoue's criteria of bulk metallic glass formation. In the present study, glass forming composition range has been determined for different binary and ternary (Zr, Ti, Hf)-(Cu, Ni) alloys based on the mixing enthalpy and mismatch entropy calculations. Though copper and nickel appear next to each other in the periodic table, the glass forming ability of the copper and nickel bearing alloys is different. Thermodynamic analysis reveals that the glass forming behaviour of Zr and Hf is similar, whereas it is different from that of Ti. The smaller atomic size of Ti and the difference in the heat of mixing of Ti, Zr, Hf with Cu and Ni leads to the observed changes in the glass forming behaviour. Enthalpy contour plots can be used to distinguish the glass forming compositions on the basis of the increasing negative enthalpy of the composition. This method reveals the high glass forming ability of binary Zr-Cu, Hf-Cu, Hf-Ni systems over a narrow composition range.

  13. Atomistic approach to predict the glass-forming ability in Zr–Cu–Al ternary metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Yu, C.Y. [Center for Advanced Structural Materials, Department of Mechanical and Biomedical Engineering, College of Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong (China); Liu, X.J. [State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083 (China); Zheng, G.P. [Department of Mechanical Engineering, The Hong Kong Polytechnic University, Kowloon, Hong Kong (China); Niu, X.R. [Center for Advanced Structural Materials, Department of Mechanical and Biomedical Engineering, College of Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong (China); Liu, C.T., E-mail: chainliu@cityu.edu.hk [Center for Advanced Structural Materials, Department of Mechanical and Biomedical Engineering, College of Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong (China)

    2015-04-05

    Highlights: • An atomistic approach has been developed to predict the glass forming ability (GFA) in Zr–Cu–Al ternary alloy system. • Both of the thermodynamic and structure-dependent kinetic effects to glass formation have been taken into account. • The first-principles calculation and molecular dynamics simulation have been performed. • The approach predicts the best glass former in the model Zr–Cu–Al alloy system. • The predicted GFA is consistent with various experimental results. - Abstract: Prediction of composition-dependent glass-forming ability (GFA) remains to be a key scientific challenge in the metallic-glass community, especially in multi-component alloy systems. In the present study, we apply an atomistic approach to predict the trend of GFA effectively in the Zr–Cu–Al ternary alloy system from alloy compositions alone. This approach is derived from the first-principles calculations based on the density-functional theory and molecular dynamic (MD) simulations. By considering of both the thermodynamic and atomic-structure induced kinetic effects, the predicted GFA trend from this approach shows an excellent agreement with experimental data available in this alloy system, manifesting its capability of seeking metallic glasses with superior GFA in ternary alloy systems.

  14. Radiation-Induced Fluidity and Glass-Liquid Transition in Irradiated Amorphous Materials

    International Nuclear Information System (INIS)

    Ojovan, M.I.

    2009-01-01

    This paper describes the fluidity behaviour of continuously irradiated glasses using the Congruent Bond Lattice model in which broken bonds 'configurons' facilitate the flow. Irradiation breaks the bonds creating configurons which at high concentrations provide the transition of material from the glassy to liquid state. An explicit equation of viscosity has been derived which gives results in agreement with experimental data. This equation provides correct viscosity data for non-irradiated materials and shows a significant increase of fluidity in radiation fields. It demonstrates a decrease of activation energy of flow for irradiated glasses. A simple equation for glass-transition temperature was also obtained which shows that irradiated glasses have lower glass transition temperatures and are readily transformed from glassy to liquid state e.g. fluidized in strong radiation fields. (authors)

  15. Anomalies in the Thermophysical Properties of Undercooled Glass-Forming Alloys

    Science.gov (United States)

    Hyers, Robert W.; Rogers, Jan R.; Kelton, Kenneth F.; Gangopadhyay, Anup

    2008-01-01

    The surface tension, viscosity, and density of several bulk metallic glass-forming alloys have been measured using noncontact techniques in the electrostatic levitation facility (ESL) at NASA Marshall Space Flight Center. All three properties show unexpected behavior in the undercooled regime. Similar deviations were previously observed in titanium-based quasicrystal-forming alloys,but the deviations in the properties of the glass-forming alloys are much more pronounced. New results for anomalous thermophysical properties in undercooled glass-forming alloys will be presented and discussed.

  16. A thermodynamic approach towards glass-forming ability of ...

    Indian Academy of Sciences (India)

    A quantitative measure of the stability of a glass as compared to its corresponding crystalline state can be obtained by calculating ... The thermal stability of various alloy compositions is studied by ... corrosion resistance and attractive soft magnetic behaviour.1,2 .... The value of R2 determines the relationship between GFA.

  17. Enhanced glass forming ability and refrigerant capacity of a Gd55Ni22Mn3Al20 bulk metallic glass

    International Nuclear Information System (INIS)

    Xia, L.; Chan, K.C.; Tang, M.B.

    2011-01-01

    Highlights: → A new Gd 55 Ni 22 Mn 3 Al 20 bulk metallic glass (BMG) was synthesized by minor Mn addition. → The BMG has enhanced glass forming ability and excellent refrigerant capacity (RC). → The RC of the BMG reaches a high value of 825 J kg -1 under a field of 3979 kA/m. → Its excellent RC is related to its large effective magnetic moment. - Abstract: In this work, a small amount of Mn was added to a Gd 55 Ni 25 Al 20 glass forming alloy, as a replacement for Ni, and a Gd 55 Ni 22 Mn 3 Al 20 bulk metallic glass (BMG) was obtained by suction casting. Its glass forming ability (GFA) was characterized by X-ray diffraction and differential scanning calorimetry, and its magnetic properties were measured using a magnetic property measurement system. It is found that the minor Mn addition can significantly improve both the GFA and the magnetocaloric effect (MCE) of the alloy. The refrigerant capacity (RC) of the BMG can reach a high value of 825 J kg -1 under a field of 3979 kA/m, which is about 29% larger than that of a Gd 55 Ni 25 Al 20 BMG. The effect of the minor Mn addition on the GFA and MCE of the BMG was investigated in the study.

  18. Effects of configurational changes on electrical resistivity during glass-liquid transition of two bulk metal-alloy glasses

    Energy Technology Data Exchange (ETDEWEB)

    Aji, D. P. B.; Johari, G. P., E-mail: joharig@mcmaster.ca [Department of Materials Science and Engineering, McMaster University, Hamilton, Ontario L8S 4L7 (Canada)

    2014-12-14

    Consequences of increase in structural fluctuations on heating Pd{sub 40}Ni{sub 10}Cu{sub 30}P{sub 20} and Zr{sub 46.75}Ti{sub 8.25}Cu{sub 7.5}Ni{sub 10}Be{sub 27.5} through their glass to liquid transition range were investigated by measuring the electrical resistivity, ρ, an electron scattering property. The temperature coefficient of resistivity (TCR = (1/ρ) dρ/dT) of the liquid and glassy states is negative. The plots of their ρ against T in the T{sub g} (glass to liquid transition) range show a gradual change in the slope similar to the change observed generally for the plots of the density, elastic modulus, and refractive index. As fluctuations in the melt structure involve fewer configurations on cooling, ρ increases. In the energy landscape description, the melt's structure explores fewer minima with decrease in T, vibrational frequencies increase, and electron scattering and ρ increase. Plots of (−dρ/dT) against T resemble the plot of the specific heat of other glasses and show a sub-T{sub g} feature and a rapid rise at T near T{sub g}. Analysis shows that the magnitude of negative TCR is dominated by change in the phonon characteristics, and configurational fluctuations make it more negative. The TCR of the liquid and glassy states seems qualitatively consistent with the variation in the structure factor in Ziman's model for pure liquid metals as extended by Nagel to metal alloys and used to explain the negative TCR of a two-component metal glass.

  19. Distinct atomic structures of the Ni-Nb metallic glasses formed by ion beam mixing

    International Nuclear Information System (INIS)

    Tai, K. P.; Wang, L. T.; Liu, B. X.

    2007-01-01

    Four Ni-Nb metallic glasses are obtained by ion beam mixing and their compositions are measured to be Ni 77 Nb 23 , Ni 55 Nb 45 , Ni 31 Nb 69 , and Ni 15 Nb 85 , respectively, suggesting that a composition range of 23-85 at. % of Nb is favored for metallic glass formation in the Ni-Nb system. Interestingly, diffraction analyses show that the structure of the Nb-based Ni 31 Nb 69 metallic glass is distinctly different from the structure of the Nb-based Ni 15 Nb 85 metallic glass, as the respective amorphous halos are located at 2θ≅38 and 39 deg. To explore an atomic scale description of the Ni-Nb metallic glasses, an n-body Ni-Nb potential is first constructed with an aid of the ab initio calculations and then applied to perform the molecular dynamics simulation. Simulation results determine not only the intrinsic glass forming range of the Ni-Nb system to be within 20-85 at. % of Nb, but also the exact atomic positions in the Ni-Nb metallic glasses. Through a statistical analysis of the determined atomic positions, a new dominant local packing unit is found in the Ni 15 Nb 85 metallic glass, i.e., an icositetrahedron with a coordination number to be around 14, while in Ni 31 Nb 69 metallic glasses, the dominant local packing unit is an icosahedron with a coordination number to be around 12, which has been reported for the other metallic glasses. In fact, with increasing the irradiation dose, the Ni 31 Nb 69 metallic glasses are formed through an intermediate state of face-centered-cubic-solid solution, whereas the Ni 15 Nb 85 metallic glass is through an intermediate state of body-centered-cubic-solid solution, suggesting that the structures of the constituent metals play an important role in governing the structural characteristics of the resultant metallic glasses

  20. 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

  1. Silicate glasses

    International Nuclear Information System (INIS)

    Lutze, W.

    1988-01-01

    Vitrification of liquid high-level radioactive wastes has received the greatest attention, world-wide, compared to any other HLW solidification process. The waste form is a borosilicate-based glass. The production of phosphate-based glass has been abandoned in the western world. Only in the Soviet Union are phosphate-based glasses still being developed. Vitrification techniques, equipment and processes and their remote operation have been developed and studied for almost thirty years and have reached a high degree of technical maturity. Industrial demonstration of the vitrification process has been in progress since 1978. This chapter is a survey of world-wide research and development efforts in nuclear waste glasses and its production technology. The principal glasses considered are silicate glasses which contain boron, i.e., borosilicate glasses

  2. 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

  3. String model for the dynamics of glass-forming liquids.

    Science.gov (United States)

    Pazmiño Betancourt, Beatriz A; Douglas, Jack F; Starr, Francis W

    2014-05-28

    We test the applicability of a living polymerization theory to describe cooperative string-like particle rearrangement clusters (strings) observed in simulations of a coarse-grained polymer melt. The theory quantitatively describes the interrelation between the average string length L, configurational entropy Sconf, and the order parameter for string assembly Φ without free parameters. Combining this theory with the Adam-Gibbs model allows us to predict the relaxation time τ in a lower temperature T range than accessible by current simulations. In particular, the combined theories suggest a return to Arrhenius behavior near Tg and a low T residual entropy, thus avoiding a Kauzmann "entropy crisis."

  4. Machinable glass-ceramics forming as a restorative dental material.

    Science.gov (United States)

    Chaysuwan, Duangrudee; Sirinukunwattana, Krongkarn; Kanchanatawewat, Kanchana; Heness, Greg; Yamashita, Kimihiro

    2011-01-01

    MgO, SiO(2), Al(2)O(3), MgF(2), CaF(2), CaCO(3), SrCO(3), and P(2)O(5) were used to prepare glass-ceramics for restorative dental materials. Thermal properties, phases, microstructures and hardness were characterized by DTA, XRD, SEM and Vickers microhardness. Three-point bending strength and fracture toughness were applied by UTM according to ISO 6872: 1997(E). XRD showed that the glass crystallized at 892°C (second crystallization temperature+20°C) for 3 hrs consisted mainly of calcium-mica and fluorapatite crystalline phases. Average hardness (3.70 GPa) closely matched human enamel (3.20 GPa). The higher fracture toughness (2.04 MPa√m) combined with the hardness to give a lower brittleness index (1.81 µm(-1/2)) which indicates that they have exceptional machinability. Bending strength results (176.61 MPa) were analyzed by Weibull analysis to determine modulus value (m=17.80). Machinability of the calcium mica-fluorapatite glass-ceramic was demonstrated by fabricating with CAD/CAM.

  5. AN ALTERNATIVE HOST MATRIX BASED ON IRON PHOSPHATE GLASSES FOR THE VITRIFICATION OF SPECIALIZED WASTE FORMS

    International Nuclear Information System (INIS)

    Day, Delbert D.

    2000-01-01

    As mentioned above, the overall goal of this research project was to collect the scientific information essential to develop iron phosphate glass based nuclear wasteforms. The specific objectives of the project were: (1) Investigate the structure of binary iron phosphate glasses and it's dependence on the composition and melting atmosphere: Understand atomic arrangements and nature of the bonding. Establish structure-property relationships. Determine the compositions and melting conditions which optimize the critical properties of the base glass. (2) Understand the structure of iron phosphate wasteforms and it's dependence on the composition and melting atmosphere: Investigate how the waste elements are bonded and coordinated within the glass structure. Establish structure-property relationships for the waste glasses. Determine the compositions and melting atmosphere for which the critical properties of the waste forms would be optimum. (3) Determine the role(s) played by the valence states of iron ions and it's dependence on the composition and melting atmosphere: Understand the different roles of iron(II) and iron(III) ions in determining the critical properties of the base glass and the waste forms. Investigate how the iron valence and its significance depend on the composition and melting atmosphere. (4) Investigate glass forming and crystallization processes of the iron phosphate glasses and their waste forms: Understand the dependence of the glass forming and crystallization characteristics on overall glass composition and valence states of iron ions. Identify the products of devitrification and investigate the critical properties of these crystalline compounds which may adversely affect the chemical and physical properties of the waste forms

  6. Talc-silicon glass-ceramic waste forms for immobilization of high- level calcined waste

    International Nuclear Information System (INIS)

    Vinjamuri, K.

    1993-06-01

    Talc-silicon glass-ceramic waste forms are being evaluated as candidates for immobilization of the high level calcined waste stored onsite at the Idaho Chemical Processing Plant. These glass-ceramic waste forms were prepared by hot isostatically pressing a mixture of simulated nonradioactive high level calcined waste, talc, silicon and aluminum metal additives. The waste forms were characterized for density, chemical durability, and glass and crystalline phase compositions. The results indicate improved density and chemical durability as the silicon content is increased

  7. 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

  8. 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

  9. Evaluation of lead-iron-phosphate glass as a high-level waste form

    International Nuclear Information System (INIS)

    Chick, L.A.; Bunnell, L.R.; Strachan, D.M.; Kissinger, H.E.; Hodges, F.N.

    1986-09-01

    The lead-iron-phosphate (Pb-Fe-P) glass developed at Oak Ridge National Laboratory was evaluated for its potential as an improvement over the current reference nuclear waste form, borosilicate (B-Si) glass. The evaluation was conducted as part of the Second Generation HLW Technology Subtask of the Nuclear Waste Treatment Program at Pacific Northwest Laboratory. The purpose of this work was to investigate possible alternatives to B-Si glass as second-generation waste forms. While vitreous Pb-Fe-P glass appears to have substantially better chemical durability than B-Si glass, severe crystallization or devitrification leading to deteriorated chemical durability would result if this glass were poured into large canisters as is the procedure with B-Si glass. Cesium leach rates from this crystallized material are orders of magnitude greater than those from B-Si glass. Therefore, to realize the potential performance advantages of the Pb-Fe-P material in a nuclear waste form, the processing method would have to cool the material rapidly to retain its vitreous structure

  10. Infrared and Raman investigation of rare-earth phosphate glasses for potential use as radioactive waste forms

    International Nuclear Information System (INIS)

    Morgan, S.H.

    1989-01-01

    This project was designed to investigate the properties of the rare-earth phosphate glass systems CeO 2 -P 2 O 5 and Pr 2 O 3 -P 2 O 5 for potential use as radioactive waste glasses. The glass-forming region and optimum processing parameters of these glass systems were investigated. The structure of the host glasses and glassed loaded with simulated waste elements was investigated using Raman and infrared spectroscopy. Because of the radical differences in the spectra of the molybdenum-loaded glasses, the structure of the MoO 3 -P 2 O 5 glass system was also investigated. 29 refs., 8 figs., 2 tabs

  11. Early stage crystallization kinetics in metallic glass-forming alloys

    International Nuclear Information System (INIS)

    Louzguine-Luzgin, Dmitri V.

    2014-01-01

    Highlights: • Heterogeneous nucleation may precede the homogeneous one in an alloy. • High kinetic constants and the nucleation rate at the initial stage. • Metallic glasses have heterogeneous nucleation sites which saturate later. -- Abstract: The crystallization kinetics and structural changes of a few metallic glassy alloys were monitored using X-ray diffraction, transmission electron microscopy, differential scanning and isothermal calorimetry methods. Microstructural observations were used to estimate the nucleation and growth rates. A clear comparison of the differences in the crystallization kinetics in the metallic glassy samples is observed at the early and later crystallization stages

  12. Glass-Forming Ability and Early Crystallization Kinetics of Novel Cu-Zr-Al-Co Bulk Metallic Glasses

    Directory of Open Access Journals (Sweden)

    Xiaoliang Han

    2016-09-01

    Full Text Available In recent years, CuZr-based bulk metallic glass (BMG composites ductilized by a shape memory B2 CuZr phase have attracted great attention owing to their outstanding mechanical properties. However, the B2 CuZr phase for most CuZr-based glass-forming compositions is only stable at very high temperatures, leading to the uncontrollable formation of B2 crystals during quenching. In this work, by introducing Co (i.e., 4, 5, and 6 at. % and 10 at. % Al into CuZr-based alloys, the relatively good glass-forming ability (GFA of CuZr-based alloys still can be achieved. Meanwhile, the B2 phase can be successfully stabilized to lower temperatures than the final temperatures of crystallization upon heating CuZr-based BMGs. Unlike previous reported CuZr-based BMGs, the primary crystallization products upon heating are mainly B2 CuZr crystals but not CuZr2 and Cu10Zr7 crystals. Furthermore, the primary precipitates during solidification are still dominated by B2 crystals, whose percolation threshold is detected to lie between 10 ± 2 vol. % and 31 ± 2 vol. %. The crystallization kinetics underlying the precipitation of B2 crystals was also investigated. Our results show that the present glass-forming composites are promising candidates for the fabrication of ductile CuZr-based BMG composites.

  13. The production of advanced glass ceramic HLW forms using cold crucible induction melter

    International Nuclear Information System (INIS)

    Rutledge, V.J.; Maio, V.

    2013-01-01

    Cold Crucible Induction Melters (CCIM) will favorably change how High-Level radioactive Waste (from nuclear fuel recovery) is treated in a near future. Unlike the existing Joule-Heated Melters (JHM) currently in operation for the glass-based immobilization of High-Level Waste (HLW), CCIM offers unique material features that will increase melt temperatures, increase throughput, increase mixing, increase loading in the waste form, lower melter foot prints, eliminate melter corrosion and lower costs. These features not only enhance the technology for producing HLW forms, but also provide advantageous attributes to the waste form by allowing more durable alternatives to glass. It is concluded that glass ceramic waste forms that are tailored to immobilize fission products of HLW can be can be made from the HLW processed with the CCIM. The advantageous higher temperatures reached with the CCIM and unachievable with JHM allows the lanthanides, alkali, alkaline earths, and molybdenum to dissolve into a molten glass. Upon controlled cooling they go into targeted crystalline phases to form a glass ceramic waste form with higher waste loadings than achievable with borosilicate glass waste forms. Natural cooling proves to be too fast for the formation of all targeted crystalline phases

  14. The liquid-glass-jamming transition in disordered ionic nanoemulsions.

    Science.gov (United States)

    Braibanti, Marco; Kim, Ha Seong; Şenbil, Nesrin; Pagenkopp, Matthew J; Mason, Thomas G; Scheffold, Frank

    2017-11-08

    In quenched disordered out-of-equilibrium many-body colloidal systems, there are important distinctions between the glass transition, which is related to the onset of nonergodicity and loss of low-frequency relaxations caused by crowding, and the jamming transition, which is related to the dramatic increase in elasticity of the system caused by the deformation of constituent objects. For softer repulsive interaction potentials, these two transitions become increasingly smeared together, so measuring a clear distinction between where the glass ends and where jamming begins becomes very difficult or even impossible. Here, we investigate droplet dynamics in concentrated silicone oil-in-water nanoemulsions using light scattering. For zero or low NaCl electrolyte concentrations, interfacial repulsions are soft and longer in range, this transition sets in at lower concentrations, and the glass and the jamming regimes are smeared. However, at higher electrolyte concentrations the interactions are stiffer, and the characteristics of the glass-jamming transition resemble more closely the situation of disordered elastic spheres having sharp interfaces, so the glass and jamming regimes can be distinguished more clearly.

  15. Liquid nitrogen enhancement of partially annealed fission tracks in glass; and reply

    International Nuclear Information System (INIS)

    Wagner, G.A.; Carpenter, B.S.; Pilione, L.J.; Gold, D.P.

    1977-01-01

    Pilione and Gold (Nature 262: 773 (1976)) stated that it was possible to reveal partially annealed fission tracks in glass by immersion in liquid N 2 , and that it was possible to increase the total number of etchable tracks by increasing the immersion time. The present authors attempted to duplicate the work of the former authors using the same glass. They found no significant change in the number of etchable tracks after immersion in liquid N 2 , and they concluded that the latter has no effect on annealed tracks in glass. Any observed enhancement of partially annealed tracks is probably a surface effect and has no effect on the interior matrix of the glass. A reply by Pilione and Gold is appended. (U.K.)

  16. Density and glass forming ability in amorphous atomic alloys: The role of the particle softness

    International Nuclear Information System (INIS)

    Douglass, Ian; Hudson, Toby; Harrowell, Peter

    2016-01-01

    A key property of glass forming alloys, the anomalously small volume difference with respect to the crystal, is shown to arise as a direct consequence of the soft repulsive potentials between metals. This feature of the inter-atomic potential is demonstrated to be responsible for a significant component of the glass forming ability of alloys due to the decrease in the enthalpy of fusion and the associated depression of the freezing point.

  17. Density and glass forming ability in amorphous atomic alloys: The role of the particle softness

    Energy Technology Data Exchange (ETDEWEB)

    Douglass, Ian; Hudson, Toby; Harrowell, Peter [School of Chemistry, University of Sydney, Sydney, NSW (Australia)

    2016-04-14

    A key property of glass forming alloys, the anomalously small volume difference with respect to the crystal, is shown to arise as a direct consequence of the soft repulsive potentials between metals. This feature of the inter-atomic potential is demonstrated to be responsible for a significant component of the glass forming ability of alloys due to the decrease in the enthalpy of fusion and the associated depression of the freezing point.

  18. Role of string-like collective atomic motion on diffusion and structural relaxation in glass forming Cu-Zr alloys

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hao [International Center for New-Structured Materials (ICNSM), Zhejiang University and Laboratory of New-Structured Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4 (Canada); Zhong, Cheng; Wang, Xiaodong; Cao, Qingping; Jiang, Jian-Zhong, E-mail: jiangjz@zju.edu.cn, E-mail: jack.douglas@nist.gov [International Center for New-Structured Materials (ICNSM), Zhejiang University and Laboratory of New-Structured Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China); Douglas, Jack F., E-mail: jiangjz@zju.edu.cn, E-mail: jack.douglas@nist.gov [Materials Science and Engineering Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Zhang, Dongxian [State Key Laboratory of Modern Optical Instrumentation, Zhejiang University, Hangzhou 310027 (China)

    2015-04-28

    We investigate Cu-Zr liquid alloys using molecular dynamics simulation and well-accepted embedded atom method potentials over a wide range of chemical composition and temperature as model metallic glass-forming (GF) liquids. As with other types of GF materials, the dynamics of these complex liquids are characterized by “dynamic heterogeneity” in the form of transient polymeric clusters of highly mobile atoms that are composed in turn of atomic clusters exhibiting string-like cooperative motion. In accordance with the string model of relaxation, an extension of the Adam-Gibbs (AG) model, changes in the activation free energy ΔG{sub a} with temperature of both the Cu and Zr diffusion coefficients D, and the alpha structural relaxation time τ{sub α} can be described to a good approximation by changes in the average string length, L. In particular, we confirm that the strings are a concrete realization of the abstract “cooperatively rearranging regions” of AG. We also find coexisting clusters of relatively “immobile” atoms that exhibit predominantly icosahedral local packing rather than the low symmetry packing of “mobile” atoms. These two distinct types of dynamic heterogeneity are then associated with different fluid structural states. Glass-forming liquids are thus analogous to polycrystalline materials where the icosahedrally packed regions correspond to crystal grains, and the strings reside in the relatively disordered grain boundary-like regions exterior to these locally well-ordered regions. A dynamic equilibrium between localized (“immobile”) and wandering (“mobile”) particles exists in the liquid so that the dynamic heterogeneity can be considered to be type of self-assembly process. We also characterize changes in the local atomic free volume in the course of string-like atomic motion to better understand the initiation and propagation of these fluid excitations.

  19. Development of iodine waste forms using low-temperature sintering glass

    International Nuclear Information System (INIS)

    Krumhansl, James Lee; Nenoff, Tina Maria; Garino, Terry J.; Rademacher, David

    2010-01-01

    This presentation will describe our recent work on the use of low temperature-sintering glass powders mixed with either AgI or AgI-zeolite to produce a stable waste form. Radioactive iodine ( 129 I, half-life of 1.6 x 10 7 years) is generated in the nuclear fuel cycle and is of particular concern due to its extremely long half-life and its effects on human health. As part of the DOE/NE Advanced Fuel Cycle Initiative (AFCI), the separation of 129 I from spent fuel during fuel reprocessing is being studied. In the spent fuel reprocessing scheme under consideration, the iodine is released in gaseous form and collected using Ag-loaded zeolites, to form AgI. Although AgI has extremely low solubility in water, it has a relatively high vapor pressure at moderate temperatures (>550 C), thus limiting the thermal processing. Because of this, immobilization using borosilicate glass is not feasible. Therefore, a bismuth oxide-based glasses are being studied due to the low solubility of bismuth oxide in aqueous solution at pH > 7. These waste forms were processed at 500 C, where AgI volatility is low but the glass powder is able to first densify by viscous sintering and then crystallize. Since the glass is not melted, a more chemically stable glass can be used. The AgI-glass mixture was found to have high iodine leach resistance in these initial studies.

  20. Sputtering of silicon and glass substrates with polyatomic molecular ion beams generated from ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Takeuchi, Mitsuaki, E-mail: m-takeuchi@kuee.kyoto-u.ac.jp; Hoshide, Yuki; Ryuto, Hiromichi; Takaoka, Gikan H. [Photonics and Electronics Science and Engineering Center, Kyoto University, Kyotodaigaku-Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan)

    2016-03-15

    The effect of irradiating 1-ethyl-3-methylimidazolium positive (EMIM{sup +}) or dicyanamide negative (DCA{sup –}) ion beams using an ionic liquid ion source was characterized concerning its sputtering properties for single crystalline Si(100) and nonalkaline borosilicate glass substrates. The irradiation of the DCA{sup –} ion beam onto the Si substrate at an acceleration voltage of 4 and 6 kV exhibited detectable sputtered depths greater than a couple of nanometers with an ion fluence of only 1 × 10{sup 15} ions/cm{sup 2}, while the EMIM{sup +} ion beam produced the same depths with an ion fluence 5 × 10{sup 15} ions/cm{sup 2}. The irradiation of a 4 kV DCA{sup –} ion beam at a fluence of 1 × 10{sup 16} ions/cm{sup 2} also yields large etching depths in Si substrates, corresponding to a sputtering yield of Si/DCA{sup – }= 10, and exhibits a smoothed surface roughness of 0.05 nm. The interaction between DCA{sup –} and Si likely causes a chemical reaction that relates to the high sputtering yield and forms an amorphous C-N capping layer that results in the smooth surface. Moreover, sputtering damage by the DCA{sup –} irradiation, which was estimated by Rutherford backscattering spectroscopy with the channeling technique, was minimal compared to Ar{sup +} irradiation at the same condition. In contrast, the glass substrates exhibited no apparent change in surface roughnesses when sputtered by the DCA{sup –} irradiation compared to the unirradiated glass substrates.

  1. Liquid Film Migration in Warm Formed Aluminum Brazing Sheet

    Science.gov (United States)

    Benoit, M. J.; Whitney, M. A.; Wells, M. A.; Jin, H.; Winkler, S.

    2017-10-01

    Warm forming has previously proven to be a promising manufacturing route to improve formability of Al brazing sheets used in automotive heat exchanger production; however, the impact of warm forming on subsequent brazing has not previously been studied. In particular, the interaction between liquid clad and solid core alloys during brazing through the process of liquid film migration (LFM) requires further understanding. Al brazing sheet comprised of an AA3003 core and AA4045 clad alloy, supplied in O and H24 tempers, was stretched between 0 and 12 pct strain, at room temperature and 523K (250 °C), to simulate warm forming. Brazeability was predicted through thermal and microstructure analysis. The rate of solid-liquid interactions was quantified using thermal analysis, while microstructure analysis was used to investigate the opposing processes of LFM and core alloy recrystallization during brazing. In general, liquid clad was consumed relatively rapidly and LFM occurred in forming conditions where the core alloy did not recrystallize during brazing. The results showed that warm forming could potentially impair brazeability of O temper sheet by extending the regime over which LFM occurs during brazing. No change in microstructure or thermal data was found for H24 sheet when the forming temperature was increased, and thus warm forming was not predicted to adversely affect the brazing performance of H24 sheet.

  2. Beta relaxation of nonpolymeric liquids close to the glass transition

    DEFF Research Database (Denmark)

    Olsen, Niels Boye; Christensen, Tage Emil; Dyre, Jeppe

    2000-01-01

    Dielectric beta relaxation in a pyridine-toluene solution is studied close to the glass transition. Loss peak frequency and maximum loss both exhibit thermal hysteresis. An annealing-state-independent parameter involving loss and loss peak frequency is identified. This parameter has a simple...

  3. Corrosion behaviors of a glass-bonded sodalite ceramic waste form and its constituents

    International Nuclear Information System (INIS)

    Lewis, M. A.; Ebert, W. L.; Morss, L.

    1999-01-01

    A ceramic waste form (CWF) of glass bonded sodalite is being developed as a waste form for the long-term immobilization of fission products and transuranic elements from the U.S. Department of Energy's activities on spent nuclear fuel conditioning. A durable waste form was prepared by hot isostatic pressing (HIP) a mixture of salt-loaded zeolite powders and glass frit. During HIP the zeolite is converted to sodalite, and the resultant CWF is been completed for durations of up to 182 days. Four dissolution modes were identified: dissolution of free salt, dissolution of the aluminosilicate matrix of sodalite and the accompanying dissolution of occluded salt, dissolution of the boroaluminosilicate matrix of the glass, and ion exchange. Synergies inherent to the CWF were identified by comparing the results of the tests with pure glass and sodalite with those of the composite CWF

  4. Thermal forming of glass microsheets for x-ray telescope mirror segments

    DEFF Research Database (Denmark)

    Jimenez-Garate, M.A.; Hailey, C.J.; Craig, W.W.

    2003-01-01

    envisioned for future x-ray observatories. The glass microsheets are shaped into mirror segments at high temperature by use of a guiding mandrel, without polishing. We determine the physical properties and mechanisms that elucidate the formation process and that are crucial to improve surface quality. We......We describe a technology to mass-produce ultrathin mirror substrates for x-ray telescopes of near Wolter-I geometry. Thermal glass forming is a low-cost method to produce high-throughput, spaceborne x-ray mirrors for the 0.1-200-keV energy band. These substrates can provide the collecting area...... develop a viscodynamic model for the glass strain as the forming proceeds to find the conditions for repeatability. Thermal forming preserves the x-ray reflectance and scattering properties of the raw glass. The imaging resolution is driven by a large wavelength figure. We discuss the sources of figure...

  5. Effect of component substitution on the atomic dynamics in glass-forming binary metallic melts

    Science.gov (United States)

    Nowak, B.; Holland-Moritz, D.; Yang, F.; Voigtmann, Th.; Evenson, Z.; Hansen, T. C.; Meyer, A.

    2017-08-01

    We investigate the substitution of early transition metals (Zr, Hf, and Nb) in Ni-based binary glass-forming metallic melts and the impact on structural and dynamical properties by using a combination of neutron scattering, electrostatic levitation (ESL), and isotopic substitution. The self-diffusion coefficients measured by quasielastic neutron scattering (QENS) identify a sluggish diffusion as well as an increased activation energy by almost a factor of 2 for Hf35Ni65 compared to Zr36Ni64 . This finding can be explained by the locally higher packing density of Hf atoms in Hf35Ni65 compared to Zr atoms in Zr36Ni64 , which has been derived from interatomic distances by analyzing the measured partial structure factors. Furthermore, QENS measurements of liquid Hf35Ni65 prepared with 60Ni , which has a vanishing incoherent scattering cross section, have demonstrated that self-diffusion of Hf is slowed down compared to the concentration weighted self-diffusion of Hf and Ni. This implies a dynamical decoupling between larger Hf and smaller Ni atoms, which can be related to a saturation effect of unequal atomic nearest-neighbor pairs, that was observed recently for Ni-rich compositions in Zr-Ni metallic melts. In order to establish a structure-dynamics relation, measured partial structure factors have been used as an input for mode-coupling theory (MCT) of the glass transition to calculate self-diffusion coefficients for the different atomic components. Remarkably, MCT can reproduce the increased activation energy for Hf35Ni65 as well as the dynamical decoupling between Hf and Ni atoms.

  6. Dynamical heterogeneity in a glass-forming ideal gas.

    Science.gov (United States)

    Charbonneau, Patrick; Das, Chinmay; Frenkel, Daan

    2008-07-01

    We conduct a numerical study of the dynamical behavior of a system of three-dimensional "crosses," particles that consist of three mutually perpendicular line segments of length sigma rigidly joined at their midpoints. In an earlier study [W. van Ketel, Phys. Rev. Lett. 94, 135703 (2005)] we showed that this model has the structural properties of an ideal gas, yet the dynamical properties of a strong glass former. In the present paper we report an extensive study of the dynamical heterogeneities that appear in this system in the regime where glassy behavior sets in. On the one hand, we find that the propensity of a particle to diffuse is determined by the structure of its local environment. The local density around mobile particles is significantly less than the average density, but there is little clustering of mobile particles, and the clusters observed tend to be small. On the other hand, dynamical susceptibility results indicate that a large dynamical length scale develops even at moderate densities. This suggests that propensity and other mobility measures are an incomplete measure of the dynamical length scales in this system.

  7. Glass Forming Ability of Amorphous Drugs Investigated by Continuous Cooling and Isothermal Transformation.

    Science.gov (United States)

    Blaabjerg, Lasse I; Lindenberg, Eleanor; Löbmann, Korbinian; Grohganz, Holger; Rades, Thomas

    2016-09-06

    The aim of this study was to investigate the glass forming ability of 12 different drugs by the determination of continuous cooling and isothermal transformation diagrams in order to elucidate if an inherent differentiation between the drugs with respect to their the glass forming ability can be made. Continuous-cooling-transformation (CCT) and time-temperature-transformation (TTT) diagrams of the drugs were developed in order to predict the critical cooling rate necessary to convert the drug from the melt into an amorphous form. While TTT diagrams overestimated the actual critical cooling rate, they allowed an inherent differentiation of glass forming ability for the investigated drugs into drugs that are extremely difficult to amorphize (>750 °C/min), drugs that require modest cooling rates (>10 °C/min), and drugs that can be made amorphous even at very slow cooling rates (>2 °C/min). Thus, the glass forming ability can be predicted by the use of TTT diagrams. In contrast to TTT diagrams, CCT diagrams may not be suitable for small organic molecules due to poor separation of exothermic events, which makes it difficult to determine the zone of recrystallization. In conclusion, this study shows that glass forming ability of drugs can be predicted by TTT diagrams.

  8. 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

  9. Characterization and durability testing of a glass-bonded ceramic waste form

    International Nuclear Information System (INIS)

    Johnson, S. G.

    1998-01-01

    Argonne National Laboratory is developing a glass bonded ceramic waste form for encapsulating the fission products and transuranics from the conditioning of metallic reactor fuel. This waste form is currently being scaled to the multi-kilogram size for encapsulation of actual high level waste. This paper will present characterization and durability testing of the ceramic waste form. An emphasis on results from application of glass durability tests such as the Product Consistency Test and characterization methods such as X-ray diffraction and scanning electron microscopy. The information presented is based on a suite of tests utilized for assessing product quality during scale-up and parametric testing

  10. Polyphase ceramic and glass-ceramic forms for immobilizing ICPP high-level nuclear waste

    International Nuclear Information System (INIS)

    Harker, A.B.; Flintoff, J.F.

    1984-01-01

    Polyphase ceramic and glass-ceramic forms have been consolidated from simulated Idaho Chemical Processing Plant wastes by hot isostatic pressing calcined waste and chemical additives by 1000 0 C or less. The ceramic forms can contain over 70 wt% waste with densities ranging from 3.5 to 3.85 g/cm 3 , depending upon the formulation. Major phases are CaF 2 , CaZrTi 207 , CaTiO 3 , monoclinic ZrO 2 , and amorphous intergranular material. The relative fraction of the phases is a function of the chemical additives (TiO 2 , CaO, and SiO 2 ) and consolidation temperature. Zirconolite, the major actinide host, makes the ceramic forms extremely leach resistant for the actinide simulant U 238 . The amorphous phase controls the leach performance for Sr and Cs which is improved by the addition of SiO 2 . Glass-ceramic forms were also consolidated by HIP at waste loadings of 30 to 70 wt% with densities of 2.73 to 3.1 g/cm 3 using Exxon 127 borosilicate glass frit. The glass-ceramic forms contain crystalline CaF 2 , Al 203 , and ZrSi 04 (zircon) in a glass matrix. Natural mineral zircon is a stable host for 4+ valent actinides. 17 references, 3 figures, 5 tables

  11. Physical stability of drugs after storage above and below the glass transition temperature: Relationship to glass-forming ability.

    Science.gov (United States)

    Alhalaweh, Amjad; Alzghoul, Ahmad; Mahlin, Denny; Bergström, Christel A S

    2015-11-10

    Amorphous materials are inherently unstable and tend to crystallize upon storage. In this study, we investigated the extent to which the physical stability and inherent crystallization tendency of drugs are related to their glass-forming ability (GFA), the glass transition temperature (Tg) and thermodynamic factors. Differential scanning calorimetry was used to produce the amorphous state of 52 drugs [18 compounds crystallized upon heating (Class II) and 34 remained in the amorphous state (Class III)] and to perform in situ storage for the amorphous material for 12h at temperatures 20°C above or below the Tg. A computational model based on the support vector machine (SVM) algorithm was developed to predict the structure-property relationships. All drugs maintained their Class when stored at 20°C below the Tg. Fourteen of the Class II compounds crystallized when stored above the Tg whereas all except one of the Class III compounds remained amorphous. These results were only related to the glass-forming ability and no relationship to e.g. thermodynamic factors was found. The experimental data were used for computational modeling and a classification model was developed that correctly predicted the physical stability above the Tg. The use of a large dataset revealed that molecular features related to aromaticity and π-π interactions reduce the inherent physical stability of amorphous drugs. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100- x Al x Metallic Glasses

    Science.gov (United States)

    Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

    2018-06-01

    In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated and 13-coordinated ) and by playing a main role in the structure stability of the Ti-Al MGs.

  13. Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100-x Al x Metallic Glasses

    Science.gov (United States)

    Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

    2018-03-01

    In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated and 13-coordinated ) and by playing a main role in the structure stability of the Ti-Al MGs.

  14. Influence of minor alloying additions on the glass-forming ability of Mg-Ni-La bulk metallic glasses

    International Nuclear Information System (INIS)

    Gonzalez, S.; Figueroa, I.A.; Todd, I.

    2009-01-01

    Bulk metallic glasses of Mg 60 Ni 23.6 Y x La (16.4-x) and Mg 65 Ni 20 Y x LaMM (15-x) with 0 ≤ x ≤ 1 at.% have been produced by injection casting. For the La-containing alloy a maximum amorphous diameter of 4 mm for x = 0.5 and 0.75 was obtained. The LaMM-containing alloy showed a maximum amorphous diameter of 2 mm for x = 0 and 0.25 but decreased to 1 mm with further Y additions. The glass-forming ability of the Mg 60 Ni 23.6 La 16.4 alloy decreased when La is partially substituted by small amounts of small atoms (Si or B) or by large atoms (Y and Si).

  15. Development of a glass matrix for vitrification of sulphate bearing high level radioactive liquid waste

    International Nuclear Information System (INIS)

    Kaushik, C.P.; Mishra, R.K.; Thorat, Vidya; Ramchandran, M.; Amar Kumar; Ozarde, P.D.; Raj, Kanwar; Das, D.

    2004-07-01

    High level radioactive liquid waste (HLW) is generated during reprocessing of spent nuclear fuel. In the earlier reprocessing flow sheet ferrous sulphamate has been used for valancy adjustment of Pu from IV to III for effective separation. This has resulted in generation of HLW containing significance amount of sulphate. Internationally borosilicate glass matrix has been adopted for vitrification of HLW. The first Indian vitrification facility at Waste Immobilislition Plant (WIP), Tarapur a five component borosilicate matrix (SiO 2 :B 2 O 3 :Na 2 O : MnO : TiO 2 ) has been used for vitrification of waste. However at Trombay HLW contain significant amount of sulphate which is not compatible with standard borosilicate formulation. Extensive R and D efforts were made to develop a glass formulation which can accommodate sulphate and other constituents of HLW e.g., U, Al, Ca, etc. This report deals with development work of a glass formulations for immobilization of sulphate bearing waste. Different glass formulations were studied to evaluate the compatibility with respect to sulphate and other constituents as mentioned above. This includes sodium, lead and barium borosilicate glass matrices. Problems encountered in different glass matrices for containment of sulphate have also been addressed. A glass formulation based on barium borosilicate was found to be effective and compatible for sulphate bearing high level waste. (author)

  16. Effect of irradiation on the evolution of alteration layer formed during nuclear glass leaching

    International Nuclear Information System (INIS)

    Mougnaud, Sarah

    2016-01-01

    High-level radioactive waste (HLW) remaining after spent nuclear fuel reprocessing is immobilized within a glass matrix, eventually destined for geological disposal. Water intrusion into the repository is expected after several thousand years. The alteration of a non-radioactive surrogate for nuclear glass has been extensively studied and it has been determined that successive leaching mechanisms lead to the formation of a 'passivating' alteration layer and to the establishment of a residual rate regime in the long term. However, glass packages are submitted to the radioactivity of confined radioelements. This work focuses on the influence of irradiation on the alteration layer formed during the residual rate regime, in a structural and mechanistic point of view. Three focal areas have been selected. Non-radioactive simple glasses have been leached and externally irradiated in order to determine modifications induced by electronic effects (irradiations with electrons and alpha particles). The same type of glass samples have been previously irradiated with heavy ions and their leaching behavior have been studied in order to assess the impact of ballistic dose cumulated by the glass before water intrusion. Leaching behavior of a complex radioactive glass, doped with an alpha-emitter, has been studied to consider a more realistic situation. (author) [fr

  17. Acoustic and thermal anomalies in a liquid-glass transition of racemic S(+)-R(-) ketoprofen

    Science.gov (United States)

    Shibata, Tomohiko; Takayama, Haruki; Kim, Tae Hyun; Kojima, Seiji

    2014-01-01

    Acoustic and thermal properties of pharmaceutical racemic S(+)-R(-) ketoprofen were investigated in wide temperature range including glassy, supercooled liquid and liquid states by Brillouin scattering and temperature modulated DSC. Sound velocity and acoustic attenuation exhibited clear changes at 265 K indicating a liquid-glass transition and showed the typical structural relaxation above Tg. The high value of the fragility index m = 71 was determined by the dispersion of the complex heat capacity. New relaxation map was suggested in combination with previous study of dielectric measurement.

  18. Comprehension and modelling of chromia-forming alloys corrosion mechanisms in nuclear glasses

    International Nuclear Information System (INIS)

    Schmucker, Eric

    2016-01-01

    Nuclear wastes management consists in the confinement of the radioactive wastes in a glass matrix. This is made by inductive melting in a hot crucible at an operating temperature around 1150 C. These crucibles are constituted of nickel based superalloys with high chromium content. They are submitted to a harsh corrosion by the molten glass, eventually leading to their replacement. The protection of the crucible against corrosion is best provided by the establishment of a protective chromium oxide layer at the surface of the alloy. A binary chromia-forming alloy (Ni-30Cr) is studied in this work. Three different binary and ternary glass compositions are chosen in order to understand the influence of the glass basicity and glass viscosity on the corrosion kinetics. Besides, the de-correlation of the formation and dissolution kinetics of the oxide layer allows the modelling of the overall oxide growth in the molten glass. For that purpose, the oxide formation kinetics in molten glass media is assimilated to the oxidation kinetics of the alloy in gaseous media with oxygen partial pressure that are representative of the redox properties of the glasses. Studies of the oxidation kinetics and of the diffusion mechanisms have shown that the oxidation kinetics is independent on the oxygen pressure in the range of 10"-"1"3 up to 10"-"3 atm O_2 at 1150 C. The present work has shown that the dissolution kinetics of the oxide layer is governed by the diffusion of Cr(III) in the glass melt. This dissolution kinetics has been evaluated from the diffusion coefficient and the solubility limit of Cr(III) in the glass. Finally, the overall growth kinetics of the Cr_2O_3 layer in the glass has been successfully modelled for each glass, thanks to the knowledge of (i) the solubility limit of Cr(III), (ii) its diffusion coefficient in the glasses and (iii) the oxidation kinetics of the alloy. The presented model also allows quantifying the influence of each of these parameters on the

  19. Economic comparison of crystalline ceramic and glass waste forms for HLW disposal

    International Nuclear Information System (INIS)

    McKee, R.W.; Daling, P.M.; Wiles, L.E.

    1983-05-01

    A titanate-based, crystalline ceramic produced by hot isostatic pressing has been proposed as a potentially more stable and improved waste form for high-level nuclear waste disposal compared to the currently favored borosilicate glass waste form. This paper describes the results of a study to evaluate the relative costs for disposal of high-level waste from a 70,000 metric ton equivalent (MTE) system. The entire waste management system, including waste processing and encapsulation, transportation, and final repository disposal, was included in this analysis. The repository concept is based on the current basalt waste isolation project (BWIP) reference design. A range of design basis alternatives is considered to determine if this would influence the relative economics of the two waste forms. A thermal analysis procedure was utilized to define optimum canister sizes to assure that each waste form was compared under favorable conditions. Repository costs are found to favor the borosilicate glass waste form while transportation costs greatly favor the crystalline ceramic waste form. The determining component in the cost comparison is the waste processing cost, which strongly favors the borosilicate glass process because of its relative simplicity. A net cost advantage on the order of 12% to 15% on a waste management system basis is indicated for the glass waste form

  20. 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)

  1. Effects of partitioned enthalpy of mixing on glass-forming ability

    Energy Technology Data Exchange (ETDEWEB)

    Song, Wen-Xiong; Zhao, Shi-Jin, E-mail: shijin.zhao@shu.edu.cn [Institute of Materials Science, Shanghai University, Shanghai 200072 (China)

    2015-04-14

    We explore the inherent reason at atomic level for the glass-forming ability of alloys by molecular simulation, in which the effect of partitioned enthalpy of mixing is studied. Based on Morse potential, we divide the enthalpy of mixing into three parts: the chemical part (Δ E{sub nn}), strain part (Δ E{sub strain}), and non-bond part (Δ E{sub nnn}). We find that a large negative Δ E{sub nn} value represents strong AB chemical bonding in AB alloy and is the driving force to form a local ordered structure, meanwhile the transformed local ordered structure needs to satisfy the condition (Δ E{sub nn}/2 + Δ E{sub strain}) < 0 to be stabilized. Understanding the chemical and strain parts of enthalpy of mixing is helpful to design a new metallic glass with a good glass forming ability. Moreover, two types of metallic glasses (i.e., “strain dominant” and “chemical dominant”) are classified according to the relative importance between chemical effect and strain effect, which enriches our knowledge of the forming mechanism of metallic glass. Finally, a soft sphere model is established, different from the common hard sphere model.

  2. Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing.

    Science.gov (United States)

    Kim, Chae Un; Tate, Mark W; Gruner, Sol M

    2015-09-22

    Observation of theorized glass-to-liquid transitions between low-density amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-to-liquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-to-liquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water.

  3. Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing

    Science.gov (United States)

    Kim, Chae Un; Tate, Mark W.; Gruner, Sol M.

    2015-01-01

    Observation of theorized glass-to-liquid transitions between low-density amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-to-liquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-to-liquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water. PMID:26351671

  4. Radiation effects in glass waste forms for high-level waste and plutonium disposal

    International Nuclear Information System (INIS)

    Weber, W.J.; Ewing, R.C.

    1997-01-01

    A key challenge in the permanent disposal of high-level waste (HLW), plutonium residues/scraps, and excess weapons plutonium in glass waste forms is the development of predictive models of long-term performance that are based on a sound scientific understanding of relevant phenomena. Radiation effects from β-decay and α-decay can impact the performance of glasses for HLW and Pu disposition through the interactions of the α-particles, β-particles, recoil nuclei, and γ-rays with the atoms in the glass. Recently, a scientific panel convened under the auspices of the DOE Council on Materials Science to assess the current state of understanding, identify important scientific issues, and recommend directions for research in the area of radiation effects in glasses for HLW and Pu disposition. The overall finding of the panel was that there is a critical lack of systematic understanding on radiation effects in glasses at the atomic, microscopic, and macroscopic levels. The current state of understanding on radiation effects in glass waste forms and critical scientific issues are presented

  5. Liquid secondary waste. Waste form formulation and qualification

    Energy Technology Data Exchange (ETDEWEB)

    Cozzi, A. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Dixon, K. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hill, K. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); King, W. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Nichols, R. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-03-01

    The Hanford Site Effluent Treatment Facility (ETF) currently treats aqueous waste streams generated during Site cleanup activities. When the Hanford Tank Waste Treatment and Immobilization Plant (WTP) begins operations, a liquid secondary waste (LSW) stream from the WTP will need to be treated. The volume of effluent for treatment at the ETF will increase significantly. Washington River Protection Solutions is implementing a Secondary Liquid Waste Immobilization Technology Development Plan to address the technology needs for a waste form and solidification process to treat the increased volume of waste planned for disposal at the Integrated Disposal Facility IDF). Waste form testing to support this plan is composed of work in the near term to demonstrate the waste form will provide data as input to a performance assessment (PA) for Hanford’s IDF.

  6. A slow atomic diffusion process in high-entropy glass-forming metallic melts

    Science.gov (United States)

    Chen, Changjiu; Wong, Kaikin; Krishnan, Rithin P.; Embs, Jan P.; Chathoth, Suresh M.

    2018-04-01

    Quasi-elastic neutron scattering has been used to study atomic relaxation processes in high-entropy glass-forming metallic melts with different glass-forming ability (GFA). The momentum transfer dependence of mean relaxation time shows a highly collective atomic transport process in the alloy melts with the highest and lowest GFA. However, a jump diffusion process is the long-range atomic transport process in the intermediate GFA alloy melt. Nevertheless, atomic mobility close to the melting temperature of these alloy melts is quite similar, and the temperature dependence of the diffusion coefficient exhibits a non-Arrhenius behavior. The atomic mobility in these high-entropy melts is much slower than that of the best glass-forming melts at their respective melting temperatures.

  7. Studies of glass waste form performance at Japan Atomic Energy Research Institute

    International Nuclear Information System (INIS)

    Banba, Tsunetaka; Kamizono, Hiroshi; Nakayama, Shinichi; Tashiro, Shingo

    1989-08-01

    The recent studies of glass waste form performance at Japan Atomic Energy Research Institute can be classified into the following three categories; (1) Study on the volatilization of radionuclides from the waste glass, which is necessary to estimate the safety in relation to operation of a storage facility. (2) Study on the radiation (alpha-radiation) effects which have relation to the long-term stability of the waste glass. (3) Study on the leaching behavior of actinides under the repository conditions, which is necessary to predict the long-term release rate of radionuclides from the waste glass. In the present report, the recent results corresponding to the above categories are described. (author)

  8. Changes in glass formation and glass forming ability of Nd2Fe14B by the addition of TiC

    International Nuclear Information System (INIS)

    Branagan, D.J.; Iowa State Univ. of Science and Technology, Ames, IA; McCallum, R.W.; Iowa State Univ. of Science and Technology, Ames, IA

    1996-01-01

    The glass forming ability (GFA) of a stoichiometric Nd 2 Fe 14 B alloy modified with TiC additions was studied. Structural, magnetic, and thermal measurements of as-quenched melt-spun ribbons indicate increasing enhancement of GFA with increasing amounts of TiC addition. The limit of the glass formation range and the amount of glass formed at a particular cooling rate also increased with TiC addition. Enhanced GFA was concurrent with changes in the intrinsic properties of the glass. The crystallization temperature, as well as the transformation rate of crystallization, was raised by TiC addition. The intrinsic magnetic properties of the glass were changed with reductions in saturation magnetization and Curie temperature T c with increasing amounts of TiC addition. The intrinsic glass changes were related to changes in the local short range order of the glass and are consistent with a reduction in free volume and an increased packing efficiency. These changes in local structure of the glass increase the glass stability, which means that less undercooling is needed to prevent crystallization. Thus, at a particular cooling rate, a higher percentage of glass will be formed and the GFA is increased. (orig.)

  9. The Production of Advanced Glass Ceramic HLW Forms using Cold Crucible Induction Melter

    Energy Technology Data Exchange (ETDEWEB)

    Veronica J Rutledge; Vince Maio

    2013-10-01

    Cold Crucible Induction Melters (CCIMs) will favorably change how High-Level radioactive Waste (from nuclear fuel recovery) is treated in the 21st century. Unlike the existing Joule-Heated Melters (JHMs) currently in operation for the glass-based immobilization of High-Level Waste (HLW), CCIMs offer unique material features that will increase melt temperatures, increase throughput, increase mixing, increase loading in the waste form, lower melter foot prints, eliminate melter corrosion and lower costs. These features not only enhance the technology for producing HLW forms, but also provide advantageous attributes to the waste form by allowing more durable alternatives to glass. This paper discusses advantageous features of the CCIM, with emphasis on features that overcome the historical issues with the JHMs presently utilized, as well as the benefits of glass ceramic waste forms over borosilicate glass waste forms. These advantages are then validated based on recent INL testing to demonstrate a first-of-a-kind formulation of a non-radioactive ceramic-based waste form utilizing a CCIM.

  10. Liquid secondary waste: Waste form formulation and qualification

    Energy Technology Data Exchange (ETDEWEB)

    Cozzi, A. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Dixon, K. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hill, K. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Nichols, R. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-07-31

    The Hanford Site Effluent Treatment Facility (ETF) currently treats aqueous waste streams generated during site cleanup activities. When the Hanford Tank Waste Treatment and Immobilization Plant (WTP) begins operations, including Direct Feed Low Activity Waste (DFLAW) vitrification, a liquid secondary waste (LSW) stream from the WTP will need to be treated. The volume of effluent for treatment at the ETF will increase significantly. The powdered salt waste form produced by the ETF will be replaced by a stabilized solidified waste form for disposal in Hanford’s Integrated Disposal Facility (IDF). Washington River Protection Solutions is implementing a Secondary Liquid Waste Immobilization Technology Development Plan to address the technology needs for a waste form and solidification process to treat the increased volume of waste planned for disposal at the IDF. Waste form testing to support this plan is composed of work in the near term to provide data as input to a performance assessment (PA) for Hanford’s IDF. In 2015, three Hanford Liquid Secondary Waste simulants were developed based on existing and projected waste streams. Using these waste simulants, fourteen mixes of Hanford Liquid Secondary Waste were prepared and tested varying the waste simulant, the water-to-dry materials ratio, and the dry materials blend composition.1 In FY16, testing was performed using a simulant of the EMF process condensate blended with the caustic scrubber—from the Low Activity Waste (LAW) melter—, processed through the ETF. The initial EMF-16 simulant will be based on modeling efforts performed to determine the mass balance of the ETF for the DFLAW.2 The compressive strength of all of the mixes exceeded the target of 3.4 MPa (500 psi) to meet the requirements identified as potential IDF Waste Acceptance Criteria in Table 1 of the Secondary Liquid Waste Immobilization Technology Development Plan.3 The hydraulic properties of the waste forms tested (hydraulic conductivity

  11. Scaling parallels in the non-Debye dielectric relaxation of ionic glasses and dipolar supercooled liquids

    International Nuclear Information System (INIS)

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

    1997-01-01

    We compare the dielectric response of ionic glasses and dipolar liquids near the glass transition. Our work is divided into two parts. In the first section we examine ionic glasses and the two prominent approaches to analyzing the dielectric response. The conductivity of ion-conducting glasses displays a power law dispersion σ(ω)∝ω n , where n∼0.67, but frequently the dielectric response is analyzed using the electrical modulus M * (ω)=1/var-epsilon * (ω), where var-epsilon * (ω)=var-epsilon(ω)-iσ(ω)/ω is the complex permittivity. We reexamine two specific examples where the shape of M * (ω) changes in response to changes in (a) temperature and (b) ion concentration, to suggest fundamental changes in ion dynamics are occurring. We show, however, that these changes in the shape of M * (ω) occur in the absence of changes in the scaling properties of σ(ω), for which n remains constant. In the second part, we examine the dielectric relaxation found in dipolar liquids, for which var-epsilon * (ω) likewise exhibits changes in shape on approach to the glass transition. Guided by similarities of M * (ω) in ionic glasses and var-epsilon * (ω) in dipolar liquids, we demonstrate that a recent scaling approach proposed by Dixon and co-workers for var-epsilon * (ω) of dipolar relaxation also appears valid for M * (ω) in the ionic case. While this suggests that the Dixon scaling approach is more universal than previously recognized, we demonstrate how the dielectric response can be scaled in a linear manner using an alternative data representation. copyright 1997 The American Physical Society

  12. Glass composite waste forms for iodine confined in bismuth-embedded SBA-15

    Science.gov (United States)

    Yang, Jae Hwan; Park, Hwan Seo; Ahn, Do-Hee; Yim, Man-Sung

    2016-11-01

    The aim of this study was to stabilize bismuth-embedded SBA-15 that captured iodine gas by fabrication of monolithic waste forms. The iodine containing waste was mixed with Bi2O3 (a stabilizing additive) and low-temperature sintering glass followed by pelletizing and the sintering process to produce glass composite materials. Iodine volatility during the sintering process was significantly affected by the ratio of Bi2O3 and the glass composition. It was confirmed that BiI3, the main iodine phase within bismuth-embedded SBA-15, was effectively transformed to the mixed phases of Bi5O7I and BiOI. The initial leaching rates of iodine from the glass composite waste forms ranged 10-3-10-2 g/m2 day, showing the stability of the iodine phases encapsulated by the glassy networks. It was also observed that common groundwater anions (e.g., chloride, carbonate, sulfite, and fluoride) elevated the iodine leaching rate by anion exchange reactions. The present results suggest that the glass composite waste form of bismuth-embedded SBA-15 could be a candidate material for stable storage of 129I.

  13. Behavior of uranium and its surrogates in molten aluminosilicate glasses in contact with liquid metals

    International Nuclear Information System (INIS)

    Chevreux, Pierrick

    2016-01-01

    This study concerns an innovative process used for conditioning nuclear waste that contain metallic parts contaminated with actinides. High actinides concentrations are expected to be incorporated in the glass melt in contact with the molten metals. Among these metals, aluminum and/or stainless steel impose a strongly reducing environment to the glass melt involving redox reactions. These reactions modify actinides oxidation states and therefore change their solubilities in the glass and could also reduce them into the metallic form. In this work, we focus on the behavior of uranium and its surrogates, namely hafnium and neodymium, in aluminosilicate glasses from the Na 2 O-CaO-SiO 2 -Al 2 O 3 system melted in highly reducing conditions. The first step consists in comparing the hafnium and uranium solubilities in the glass as functions of redox conditions and glass composition. A methodology has been set up and a specific device has been used to control the oxygen fugacity and the alkali content of the glass. The results show that uranium is far less soluble in the glass than hafnium (Hf(IV)) in reducing conditions. The uranium solubility ranges from 4 to 7 wt% UO 2 for an oxygen fugacity below 10 -14 atm at 1250 C-1400 C. Uranium oxidation states have been investigated by X-ray absorption spectroscopy (XANES). It has been pointed out that U(IV) is the main form in the glass for such imposed oxygen fugacities. The second step of this work is to identify the glass-metal interaction mechanisms in order to determine the localization of uranium and its surrogates (Nd, Hf) in the glass-metal system. Mechanisms are mostly ruled by the presence of metallic aluminum and are similar for uranium, neodymium and hafnium. Glass-metal interaction kinetics demonstrate that uranium and its surrogates can temporarily be reduced into the metallic form for particular conditions. A re-oxidation occurs with time which is in good agreement with thermodynamics. Regarding uranium, the re

  14. Understanding the glass-forming ability of active pharmaceutical ingredients for designing supersaturating dosage forms.

    Science.gov (United States)

    Kawakami, Kohsaku; Usui, Toshinori; Hattori, Mitsunari

    2012-09-01

    Amorphous solid dispersions have great potential for enhancing oral absorption of poorly soluble drugs. Crystallization behavior during storage and after exposure to aqueous media must be examined in detail for designing stable and effective amorphous formulations, and it is significantly affected by the intrinsic properties of an amorphous drug. Many attempts have been made to correlate various thermodynamic parameters of pharmaceutical glasses with their crystallization behavior; however, variations in model drugs that could be used for such investigation has been limited because the amorphous characteristics of drugs possessing a high crystallization tendency are difficult to evaluate. In this study, high-speed differential scanning calorimetry, which could inhibit their crystallization using high cooling rates up to 2000°C/s, was employed for assessing such drugs. The thermodynamic parameters of the glasses, including glass transition temperature (T(g)) and fragility, were obtained to show that their crystallization tendency cannot be explained simply by the parameters, although there have been general thought that fragility may be correlated with crystallization tendency. Also investigated was correlation between the thermodynamic parameters and crystallization tendency upon contact with water, which influences in vivo efficacy of amorphous formulations. T(g) was correlated well with the crystallization tendency upon contact with water. Copyright © 2012 Wiley Periodicals, Inc.

  15. Kondo effect and non-Fermi liquid behavior in metallic glasses containing Yb, Ce, and Sm

    Science.gov (United States)

    Huang, B.; Yang, Y. F.; Wang, W. H.

    2013-04-01

    The low temperature properties of metallic glasses containing different concentrations of ytterbium, cerium, and samarium are studied. It is found that the Kondo effect caused by exchange interactions between the conduction and 4f electrons and non-Fermi liquid behavior appear in the strongly disordered alloys. We study the origins for these unique features and demonstrate that the found Kondo effect is inherited from the crystalline counterparts. The results might have significance on investigating the strong electron-electron interaction systems with structural disorder and be helpful for designing new metallic glasses with functional properties.

  16. Liquidus Temperature of SrO-Al2O3-SiO2 Glass-Forming Compositions

    DEFF Research Database (Denmark)

    Abel, Brett M.; Morgan, James M.; Mauro, John C.

    2013-01-01

    . In the composition range of interest for industrial glasses, Tliq tends to decrease with increasing strontium-to-alumina ratio. We find that cristobalite, mullite, and slawsonite are the dominant devitrification phases for the compositions with high SiO2, SiO2+Al2O3, and SrO contents, respectively. By comparison...... with the phase diagrams for CaO-Al2O3-SiO2 and MgO-Al2O3-SiO2 systems, we have found that for the highest [RO]/[Al2O3] ratios, Tliq exhibits a minimum value for R = Ca. Based on the phase diagram established here, the composition of glass materials, for example, for liquid crystal display substrates, belonging...... to the SrO-Al2O3-SiO2 family may be designed with a more exact control of the glass-forming ability by avoiding the regions of high liquidus temperature....

  17. Secondary phases formed during nuclear waste glass-water interactions: Thermodynamic and derived properties

    International Nuclear Information System (INIS)

    McKenzie, W.F.

    1992-08-01

    The thermodynamic properties of secondary phases observed to form during nuclear waste glass-water interactions are of particular interest as it is with the application of these properties together with the thermodynamic properties of other solid phases, fluid phases, and aqueous species that one may predict the environmental consequences of introducing radionuclides contained in the glass into groundwater at a high-level nuclear waste repository. The validation of these predicted consequences can be obtained from laboratory experiments and field observations at natural analogue sites. The purpose of this report is to update and expand the previous compilation (McKenzie, 1991) of thermodynamic data retrieved from the literature and/or estimated for secondary phases observed to form (and candidate phases from observed chemical compositions) during nuclear waste glass-water interactions. In addition, this report includes provisionally recommended thermodynamic data of secondary phases

  18. Cold crucible induction melter studies for making glass ceramic waste forms: A feasibility assessment

    International Nuclear Information System (INIS)

    Crum, Jarrod; Maio, Vince; McCloy, John; Scott, Clark; Riley, Brian; Benefiel, Brad; Vienna, John; Archibald, Kip; Rodriguez, Carmen; Rutledge, Veronica; Zhu, Zihua; Ryan, Joe; Olszta, Matthew

    2014-01-01

    Glass ceramics are being developed to immobilize fission products, separated from used nuclear fuel by aqueous reprocessing, into a stable waste form suitable for disposal in a geological repository. This work documents the glass ceramic formulation at bench scale and for a scaled melter test performed in a pilot-scale (∼1/4 scale) cold crucible induction melter (CCIM). Melt viscosity, electrical conductivity, and crystallization behavior upon cooling were measured on a small set of compositions to select a formulation for melter testing. Property measurements also identified a temperature range for melter operation and cooling profiles necessary to crystallize the targeted phases in the waste form. Bench scale and melter run results successfully demonstrate the processability of the glass ceramic using the CCIM melter technology

  19. Mineralogy and thermodynamic properties of magnesium phyllosilicates formed during the alteration of a simplified nuclear glass

    Energy Technology Data Exchange (ETDEWEB)

    Debure, Mathieu, E-mail: m.debure@brgm.fr [CEA, DEN, DTCD, SECM, F-30207 Bagnols-sur-Ceze (France); MINES-ParisTech, PSL Research University, Centre de Géosciences, 77305 Fontainebleau (France); De Windt, Laurent [MINES-ParisTech, PSL Research University, Centre de Géosciences, 77305 Fontainebleau (France); Frugier, Pierre; Gin, Stéphane [CEA, DEN, DTCD, SECM, F-30207 Bagnols-sur-Ceze (France); Vieillard, Philippe [IC2MP-CNRS-UMR 7285, 5 Ave. Albert Turpain TSA 51106, 86073 Poitiers Cedex 09 (France)

    2016-07-15

    The precipitation of crystallized magnesium phyllosilicates generally sustains the alteration rate of nuclear waste containment glass. However, glass alteration slows down to a residual rate as soon as Mg disappears from the solution. The identification of the phyllosilicates formed is therefore crucial for modeling the long-term behavior of nuclear glass. This study deals with batch alteration of the simplified nuclear glass ISG in presence of magnesium, and the characterization of the secondary phases. Morphological, chemical and structural analyses (MET, EDX, XRD) were performed to determine the nature and structure of the precipitated phases identified as trioctahedral smectites. Analyses conducted on the secondary phases proved the presence of Al, Na and Ca in the Mg-phyllosilicate phases. Such elements had been suspected but never quantitatively measured. The experimental results were then used to determine the thermodynamic solubility constants for each precipitated secondary phase at various temperatures. The calculated values were consistent with those available for sodium and magnesium saponites in the existing thermodynamic databases. - Highlights: • The international simple glass dissolution rate increases in presence of magnesium. • Mg added in solution combines with Si from glass to yield trioctahedral smectites. • Their calculated logK are close to smectite thermodynamic constants reported in databases. • It confirms assumptions on Mg-silicates phases made in previous geochemical modeling.

  20. Development and testing of a glass waste form for the immobilization of plutonium

    International Nuclear Information System (INIS)

    Chamberlain, D.B.; Hanchar, J.M.; Emery, J.W.; Hoh, J.C.; Wolf, S.F.; Finch, R.J.; Bates, J.K.; Ellison, A.J.G.; Dingwell, D.B.

    1996-01-01

    The United States has declared about 50 metric tons of weapons-grade Pu surplus to national security needs. The President has directed that this Pu be placed in a form that provides a high degree of proliferation resistance in which the surplus Pu is both unattractive and inaccessible for use by others [I]. Three alternatives are being evaluated for the disposal 2048 of this material: (1) use of the Pu as a fuel source for commercial reactors; (2) immobilization, where Pu is fixed in a glass or ceramic matrix that also contains or is surrounded by highly radioactive material; and (3) deep bore hole, where Pu is emplaced at depths of several kilometers. The immobilization alternative is being directed by the staff at Lawrence Livermore National Laboratory (LLNL). The staff at ANL are assisting by developing a glass for the immobilization of Pu and in the corrosion testing of glass and ceramic material prepared both at ANL and at other DOE laboratories. As part of this program, we have developed an ATS glass into which 5-7 wt percent Pu has been dissolved. The ATS glass was engineered to accommodate high Pu loading and to be durable under conditions likely to accelerate glass reactions in the geological environment during long-term storage

  1. Relating structural parameters to leachability in a glass-bonded ceramic waste form

    International Nuclear Information System (INIS)

    Frank, S. M.; Johnson, S. G.; Moschetti, T. L.

    1998-01-01

    Lattice parameters for a crystalline material can be obtained by several methods, notably by analyzing x-ray powder diffraction patterns. By utilizing a computer program to fit a pattern, one can follow the evolution or subtle changes in a structure of a crystalline species in different environments. This work involves such a study for an essential component of the ceramic waste form that is under development at Argonne National Laboratory. Zeolite 4A and zeolite 5A are used to produce two different types of waste forms: a glass-bonded sodalite and a glass-bonded zeolite, respectively. Changes in structure during production of the waste forms are discussed. Specific salt-loadings in the sodalite waste form are related to relative peak intensities of certain reflections in the XRD patterns. Structural parameters for the final waste forms will also be given and related to leachability under standard conditions

  2. Magnetic propulsion of microspheres at liquid-glass interfaces

    Science.gov (United States)

    Helgesen, Geir

    2018-02-01

    Bio-coated, magnetic microspheres have many applications in biotechnology and medical technology as a tool to separate and extract cells or molecules in a water solution by applying external strong magnetic field gradients. However, magnetic microspheres with or without attached cargo can also be separated in the liquid solution if they are exposed to alternating or rotating, relatively weak magnetic fields. Microspheres that have a higher density than the liquid will approach the bottom surface of the sample cell, and then a combination of viscous and surface frictional forces can propel the magnetic microspheres along the surface in a direction perpendicular to the axis of field rotation. Experiments demonstrating this type of magnetic propulsion are shown, and the forces active in the process are discussed. The motion of particles inside sample cells that were tilted relative to the horizontal direction was studied, and the variation of propulsion velocity as a function of tilt angle was used to find the values of different viscous and mechanical parameters of motion. Propulsion speeds of up to 5 μm/s were observed and were found to be caused by a partly rolling and partly slipping motion of rotating microspheres with a slipping coefficient near 0.6.

  3. Glass composite waste forms for iodine confined in bismuth-embedded SBA-15

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jae Hwan [Nuclear Fuel Cycle Process Development Division, Korea Atomic Energy Research Institute, 989-111 Daeduk-daero, Yuseong-gu, Daejeon, 305-353 (Korea, Republic of); Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon, 305-701 (Korea, Republic of); Park, Hwan Seo; Ahn, Do-Hee [Nuclear Fuel Cycle Process Development Division, Korea Atomic Energy Research Institute, 989-111 Daeduk-daero, Yuseong-gu, Daejeon, 305-353 (Korea, Republic of); Yim, Man-Sung, E-mail: msyim@kaist.ac.kr [Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon, 305-701 (Korea, Republic of)

    2016-11-15

    The aim of this study was to stabilize bismuth-embedded SBA-15 that captured iodine gas by fabrication of monolithic waste forms. The iodine containing waste was mixed with Bi{sub 2}O{sub 3} (a stabilizing additive) and low-temperature sintering glass followed by pelletizing and the sintering process to produce glass composite materials. Iodine volatility during the sintering process was significantly affected by the ratio of Bi{sub 2}O{sub 3} and the glass composition. It was confirmed that BiI{sub 3}, the main iodine phase within bismuth-embedded SBA-15, was effectively transformed to the mixed phases of Bi{sub 5}O{sub 7}I and BiOI. The initial leaching rates of iodine from the glass composite waste forms ranged 10{sup −3}–10{sup −2} g/m{sup 2} day, showing the stability of the iodine phases encapsulated by the glassy networks. It was also observed that common groundwater anions (e.g., chloride, carbonate, sulfite, and fluoride) elevated the iodine leaching rate by anion exchange reactions. The present results suggest that the glass composite waste form of bismuth-embedded SBA-15 could be a candidate material for stable storage of {sup 129}I. - Highlights: • Glass composite waste forms were developed to stabilize iodine confined in Bi-embedded SBA-15. • BiI{sub 3} within Bi-embedded SBA-15 was transformed to BiOI and Bi{sub 5}O{sub 7}I during sintering process. • Iodine volatility was significantly affected by glass composition and Bi{sub 2}O{sub 3} additive. • Iodine leaching rates were 10{sup −3}–10{sup −2} g/m{sup 2} day due to the stable iodine phases encapsulated by glassy networks. • Glass composite waste form of Bi-embedded SBA-15 is expected to be a candidate material for stable storage of {sup 129}I.

  4. Glass forming ability of amorphous drugs investigated by continuous cooling- and isothermal transformation

    DEFF Research Database (Denmark)

    Blaabjerg, Lasse Ingerslev; Lindenberg, Eleanor; Löbmann, Korbinian

    2016-01-01

    /min). Thus, the glass forming ability can be predicted by the use of TTT diagrams. In contrast to TTT diagrams, CCT diagrams may not be suitable for small organic molecules due to poor separation of exothermic events, which makes it difficult to determine the zone of recrystallization. In conclusion...

  5. Plan for glass waste form testing for NNWSI [Nevada Nuclear Waste Storage Investigations

    International Nuclear Information System (INIS)

    Aines, R.D.

    1987-09-01

    The purpose of glass waste form testing is to determine the rate of release of radionuclides from breached glass waste containers. This information will be used to qualify glass waste forms with respect to the release requirements. It will be the basis of the source term from glass waste for repository performance assessment modeling. This information will also serve as part of the source term in the calculation of cumulative releases after 100,000 years in the site evaluation process. It will also serve as part of the source term input for calculation of cumulative releases to the accessible environment for 10,000 years after disposal, to determine compliance with EPA regulations. This investigation will provide data to resolve information needs. Information about the waste forms which is provided by the producer will be accumulated and evaluated; the waste form will be tested, properties determined, and mechanisms of degradation determined; and models providing long-term evaluation of release rates designed and tested. 23 refs

  6. Local dynamics and deformation of glass-forming polymers : modelling and atomistic simulations

    NARCIS (Netherlands)

    Vorselaars, B.

    2008-01-01

    The research described in the present thesis is about glassy phenomena and mechanical properties in vitrifiable polymer materials. Glasses are solid materials, but, in contrast to crystals, the structure is disordered. Polymers are macromolecular chains formed by covalently linking a very large

  7. Sol-Gel synthesis of MgO-SiO2 glass compositions having stable liquid-liquid immiscibility

    Science.gov (United States)

    Bansal, Narottam P.

    1987-01-01

    MgO-SiO2 glasses containing up to 15 mol % MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol % MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol % MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol %) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

  8. Configurational entropy measurements in extremely supercooled liquids that break the glass ceiling

    Science.gov (United States)

    Berthier, Ludovic; Charbonneau, Patrick; Coslovich, Daniele; Ninarello, Andrea; Ozawa, Misaki; Yaida, Sho

    2017-10-01

    Liquids relax extremely slowly on approaching the glass state. One explanation is that an entropy crisis, because of the rarefaction of available states, makes it increasingly arduous to reach equilibrium in that regime. Validating this scenario is challenging, because experiments offer limited resolution, while numerical studies lag more than eight orders of magnitude behind experimentally relevant timescales. In this work, we not only close the colossal gap between experiments and simulations but manage to create in silico configurations that have no experimental analog yet. Deploying a range of computational tools, we obtain four estimates of their configurational entropy. These measurements consistently confirm that the steep entropy decrease observed in experiments is also found in simulations, even beyond the experimental glass transition. Our numerical results thus extend the observational window into the physics of glasses and reinforce the relevance of an entropy crisis for understanding their formation.

  9. Breaking the glass ceiling: Configurational entropy measurements in extremely supercooled liquids

    Science.gov (United States)

    Berthier, Ludovic

    Liquids relax extremely slowly on approaching the glass state. One explanation is that an entropy crisis, due to the rarefaction of available states, makes it increasingly arduous to reach equilibrium in that regime. Validating this scenario is challenging, because experiments offer limited resolution, while numerical studies lag more than eight orders of magnitude behind experimentally-relevant timescales. In this work we not only close the colossal gap between experiments and simulations but manage to create in-silico configurations that have no experimental analog yet. Deploying a range of computational tools, we obtain four independent estimates of their configurational entropy. These measurements consistently indicate that the steep entropy decrease observed in experiments is found in simulations even beyond the experimental glass transition. Our numerical results thus open a new observational window into the physics of glasses and reinforce the relevance of an entropy crisis for understanding their formation.

  10. Forty years of the Hrubý glass-forming coefficient via DTA when comparing other criteria in relation to the glass stability and vitrification ability

    Czech Academy of Sciences Publication Activity Database

    Kozmidis-Petrovic, A.; Šesták, Jaroslav

    2012-01-01

    Roč. 110, č. 2 (2012), 997-1004 ISSN 1388-6150 Institutional research plan: CEZ:AV0Z10100521 Keywords : glass transition * Hrubý criterion * glass -forming ability * DTA/DSC Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.982, year: 2012

  11. Local structure and structural signature underlying properties in metallic glasses and supercooled liquids

    Science.gov (United States)

    Ding, Jun

    Metallic glasses (MGs), discovered five decades ago as a newcomer in the family of glasses, are of current interest because of their unique structures and properties. There are also many fundamental materials science issues that remain unresolved for metallic glasses, as well as their predecessor above glass transition temperature, the supercooled liquids. In particular, it is a major challenge to characterize the local structure and unveil the structure-property relationship for these amorphous materials. This thesis presents a systematic study of the local structure of metallic glasses as well as supercooled liquids via classical and ab initio molecular dynamics simulations. Three typical MG models are chosen as representative candidate, Cu64 Zr36, Pd82Si18 and Mg65Cu 25Y10 systems, while the former is dominant with full icosahedra short-range order and the prism-type short-range order dominate for latter two. Furthermore, we move to unravel the underlying structural signature among several properties in metallic glasses. Firstly, the temperature dependence of specific heat and liquid fragility between Cu-Zr and Mg-Cu-Y (also Pd-Si) in supercooled liquids are quite distinct: gradual versus fast evolution of specific heat and viscosity/relaxation time with undercooling. Their local structural ordering are found to relate with the temperature dependence of specific heat and relaxation time. Then elastic heterogeneity has been studied to correlate with local structure in Cu-Zr MGs. Specifically, this part covers how the degree of elastic deformation correlates with the internal structure at the atomic level, how to quantitatively evaluate the local solidity/liquidity in MGs and how the network of interpenetrating connection of icosahedra determine the corresponding shear modulus. Finally, we have illustrated the structure signature of quasi-localized low-frequency vibrational normal modes, which resides the intriguing vibrational properties in MGs. Specifically, the

  12. The Knight shift in liquid gallium confined within porous glasses and opals

    International Nuclear Information System (INIS)

    Charnaya, E V; Michel, D; Tien, C; Kumzerov, Yu A; Yaskov, D

    2003-01-01

    71 Ga nuclear magnetic resonance studies were carried out for liquid gallium embedded into porous glasses with different pore sizes and into artificial opals within the temperature range from about 320 K to complete confined gallium freezing. A general decrease in the Knight shift compared to the bulk melt depending on pore sizes was observed in contrast to theoretical predictions. Correlations between alterations in the Knight shift and pore sizes were established for particular pore geometry. It was also observed that confined geometry affects the temperature dependence of the Knight shift in liquid gallium

  13. Two-dimensional optical correlation spectroscopy applied to liquid/glass dynamics

    OpenAIRE

    Lazonder, Kees; Pshenichnikov, Maxim S.; Wiersma, Douwe A.; Corkum, Paul; Jonas, David M.; Miller, R.J. Dwayne.; Weiner, Andrew M.

    2007-01-01

    Correlation spectroscopy was used to study the effects of temperature and phase changes on liquid and glass solvent dynamics. By assessing the eccentricity of the elliptic shape of a 2D optical correlation spectrum the value of the underlying frequency-frequency correlation function can be retrieved through a very simple relationship. This method yielded both intuitive clues and a quantitative measure of the dynamics of the system.

  14. Effect of Si addition on glass-forming ability and mechanical properties of Cu-Zr-Al bulk metallic glass

    International Nuclear Information System (INIS)

    Malekan, M.; Shabestari, S.G.; Zhang, W.; Seyedein, S.H.; Gholamipour, R.; Makino, A.; Inoue, A.

    2010-01-01

    Research highlights: The Cu 50 Zr 43 Al 7 alloy has a surprising GFA, and the glassy rods with diameter of 10 mm have been produced in this research. It has not been reported that the Cu-based glassy rods (Cu ≥ 50 at.%) to be produced with the critical diameter greater than 10 mm. The novelty of this research is that the glass formation has been improved and the critical diameter increased to 12 mm for the alloy having x = 1 with the addition of Si. Different criteria are used to evaluate the influence of Si content on the GFA, and the possible mechanisms involved in the achievement of this GFA are also discussed. - Abstract: The effect of Si addition on the glass-forming ability (GFA) and mechanical properties of (Cu 50 Zr 43 Al 7 ) 100-x Si x (x = 0, 0.5, 1, 1.5 and 2 at.%) alloys were investigated. The GFA of Cu 50 Zr 43 Al 7 alloy is improved by addition of a small amount of Si, and the critical diameter for glass formation increases from 10 mm for the alloy with x = 0-12 mm for the alloy with x = 1 when prepared using copper mold casting. Different criteria are used to evaluate the influence of Si content on the GFA, and the possible mechanisms involved in the achievement of this GFA are also discussed. In the uniaxial compression, the bulk glassy alloys exhibit a limited plastic strain of less than 1%, but the compressive fracture strength and Young's modulus were obtained in high values of 1969-2129 MPa and 101-144 GPa, respectively. Fracture surface and shear bands of samples were studied by using scanning electron microscopy (SEM).

  15. Effect of similar elements on improving glass-forming ability of La-Ce-based alloys

    International Nuclear Information System (INIS)

    Zhang Tao; Li Ran; Pang Shujie

    2009-01-01

    To date the effect of unlike component elements on glass-forming ability (GFA) of alloys have been studied extensively, and it is generally recognized that the main consisting elements of the alloys with high GFA usually have large difference in atomic size and atomic interaction (large negative heat of mixing) among them. In our recent work, a series of rare earth metal-based alloy compositions with superior GFA were found through the approach of coexistence of similar constituent elements. The quinary (La 0.5 Ce 0.5 ) 65 Al 10 (Co 0.6 Cu 0.4 ) 25 bulk metallic glass (BMG) in a rod form with a diameter up to 32 mm was synthesized by tilt-pour casting, for which the glass-forming ability is significantly higher than that for ternary Ln-Al-TM alloys (Ln = La or Ce; TM = Co or Cu) with critical diameters for glass-formation of several millimeters. We suggest that the strong frustration of crystallization by utilizing the coexistence of La-Ce and Co-Cu to complicate competing crystalline phases is helpful to construct BMG component with superior GFA. The results of our present work indicate that similar elements (elements with similar atomic size and chemical properties) have significant effect on GFA of alloys.

  16. Disposal costs for SRP high-level wastes in borosilicate glass and crystalline ceramic waste forms

    International Nuclear Information System (INIS)

    Rozsa, R.B.; Campbell, J.H.

    1982-01-01

    Purpose of this document is to compare and contrast the overall burial costs of the glass and ceramic waste forms, including processing, storage, transportation, packaging, and emplacement in a repository. Amount of waste will require approximately 10,300 standard (24 in. i.d. x 9-5/6 ft length) canisters of waste glass, each containing about 3260 lb of waste at 28% waste loading. The ceramic waste form requires about one-third the above number of standard canisters. Approximately $2.5 billion is required to process and dispose of this waste, and the total cost is independent of waste form (glass or ceramic). The major cost items (about 80% of the total cost) for all cases are capital and operating expenses. The capital and 20-year operating costs for the processing facility are the same order of magnitude, and their sum ranges from about one-half of the total for the reference glass case to two-thirds of the total for the ceramic cases

  17. Experimental evidence for excess entropy discontinuities in glass-forming solutions.

    Science.gov (United States)

    Lienhard, Daniel M; Zobrist, Bernhard; Zuend, Andreas; Krieger, Ulrich K; Peter, Thomas

    2012-02-21

    Glass transition temperatures T(g) are investigated in aqueous binary and multi-component solutions consisting of citric acid, calcium nitrate (Ca(NO(3))(2)), malonic acid, raffinose, and ammonium bisulfate (NH(4)HSO(4)) using a differential scanning calorimeter. Based on measured glass transition temperatures of binary aqueous mixtures and fitted binary coefficients, the T(g) of multi-component systems can be predicted using mixing rules. However, the experimentally observed T(g) in multi-component solutions show considerable deviations from two theoretical approaches considered. The deviations from these predictions are explained in terms of the molar excess mixing entropy difference between the supercooled liquid and glassy state at T(g). The multi-component mixtures involve contributions to these excess mixing entropies that the mixing rules do not take into account. © 2012 American Institute of Physics

  18. Study into the feasibility of manufacturing liquid glass using resource-saving technology

    Directory of Open Access Journals (Sweden)

    Mizyuryaev Sergey

    2017-01-01

    Full Text Available The authors’ views on the problem of resource-saving in the production of building materials are outlined, with three main modes of resource-saving indicated: the use of cheap raw materials, a reduction in the production costs, and an increase in the efficiency of the produced materials and products. The research provides information on the production and use of liquid glass in industry, including the construction industry. The theoretical substantiation of the possibility of developing a resource-saving technology for the production of liquid glass for construction purposes is given. The work provides information on promising alternative raw material components - diatomite, natural rock and black ash, industrial waste. Their properties are given as well as the justification of their effective use as raw materials. The method of preparation of the components and their mixtures, the preparation of sodium silicate through roasting, and the identification of the suitability of the obtained product for the manufacture of efficient building materials are described. Conclusions are made in regards to the feasibility of producing liquid glass using resource-saving technology.

  19. A Glass-Ceramic Waste Forms for the Immobilization of Rare Earth Oxides from the Pyroprocessing Waste salt

    International Nuclear Information System (INIS)

    Ahn, Byung-Gil; Park, Hwan-Seo; Kim, Hwan-Young; Kim, In-Tae

    2008-01-01

    The fission product of rare earth (RE) oxide wastes are generates during the pyroprocess . Borosilicate glass or some ceramic materials such as monazite, apatite or sodium zirconium phosphate (NZP) have been a prospective host matrix through lots of experimental results. Silicate glasses have long been the preferred waste form for the immobilization of HLW. In immobilization of the RE oxides, the developed process on an industrial scale involves their incorporation into a glass matrix, by melting under 1200 ∼ 1300 .deg. C. Instead of the melting process, glass powder sintering is lower temperature (∼ 900 .deg. C) required for the process which implies less demanding conditions for the equipment and a less evaporation of volatile radionuclides. This study reports the behaviors, direct vitrification of RE oxides with glass frit, glass powder sintering of REceramic with glass frit, formation of RE-apatite (or REmonazite) ceramic according to reaction temperature, and the leach resistance of the solidified waste forms

  20. Study on the leach mechanism of 90-19/U glass form in underground water of disposal site

    International Nuclear Information System (INIS)

    Sheng Jiawei; Luo Shanggeng; Tang Baolong

    1996-01-01

    The leach behavior of 90-19/U glass form in underground water (UW) of disposal site and in the deionized water (DIW) is studied. The total mass losses of glass form and the normalized element mass losses of B, Li and Si in UW are presented and compared to DIW. It is found that the ions in UW affect the leach behavior of 90-19/U glass. At the beginning of the reaction the reaction rate of the glass is smaller in UW than in DIW due to the low glass dissolution affinity in UW which is defined as (1-c/K). The rate determining step of leach reaction of 90-19/U glass in UW during the entire reaction period is the ion-exchange reaction. The apparent activation energy of glass reaction in UW is 51.6 kJ/mol

  1. Development and testing of matrices for the encapsulation of glass and ceramic nuclear waste forms

    International Nuclear Information System (INIS)

    Wald, J.W.; Brite, D.W.; Gurwell, W.E.; Buckwalter, C.Q.; Bunnell, L.R.; Gray, W.J.; Blair, H.T.; Rusin, J.M.

    1982-02-01

    This report details the results of research on the matrix encapsulation of high level wastes at PML over the past few years. The demonstrations and tests described were designed to illustrate how the waste materials are effected when encapsulated in an inert matrix. Candidate materials evaluated for potential use as matrices for encapslation of pelletized ceramics or glass marbles were categorized into four groups: metals, glasses, ceramics, and graphite. Two processing techniques, casting and hot pressing, were investigated as the most promising methods of formation or densification of the matrices. The major results reported deal with the development aspects. However, chemical durability tests (leach tests) of the matrix materials themselves and matrix-waste form composites are also reported. Matrix waste forms can provide a low porosity, waste-free barrier resulting in increased leach protection, higher impact strength and improved thermal conductivity compared to unencapsulated glass or ceramic waste materials. Glass marbles encapsulated in a lead matrix offer the most significant improvement in waste form stability of all combinations evaluated. This form represents a readily demonstrable process that provides high thermal conductivity, mechanical shock resistance, radiation shielding and increased chemical durability through both a chemical passivation mechanism and as a physical barrier. Other durable matrix waste forms evaluated, applicable primarily to ceramic pellets, involved hot-pressed titanium or TiO 2 materials. In the processing of these forms, near 100% dense matrices were obtained. The matrix materials had excellent compatibility with the waste materials and superior potential chemical durability. Cracking of the hot-pressed ceramic matrix forms, in general, prevented the realization of their optimum properties

  2. 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.

  3. The glass-forming ability of model metal-metalloid alloys

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai; Liu, Yanhui; Schroers, Jan [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Center for Research on Interface Structures and Phenomena, Yale University, New Haven, Connecticut 06520 (United States); Shattuck, Mark D. [Department of Physics and Benjamin Levich Institute, The City College of the City University of New York, New York, New York 10031 (United States); Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); O’Hern, Corey S. [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Center for Research on Interface Structures and Phenomena, Yale University, New Haven, Connecticut 06520 (United States); Department of Physics, Yale University, New Haven, Connecticut 06520 (United States); Department of Applied Physics, Yale University, New Haven, Connecticut 06520 (United States)

    2015-03-14

    Bulk metallic glasses (BMGs) are amorphous alloys with desirable mechanical properties and processing capabilities. To date, the design of new BMGs has largely employed empirical rules and trial-and-error experimental approaches. Ab initio computational methods are currently prohibitively slow to be practically used in searching the vast space of possible atomic combinations for bulk glass formers. Here, we perform molecular dynamics simulations of a coarse-grained, anisotropic potential, which mimics interatomic covalent bonding, to measure the critical cooling rates for metal-metalloid alloys as a function of the atomic size ratio σ{sub S}/σ{sub L} and number fraction x{sub S} of the metalloid species. We show that the regime in the space of σ{sub S}/σ{sub L} and x{sub S} where well-mixed, optimal glass formers occur for patchy and LJ particle mixtures, coincides with that for experimentally observed metal-metalloid glass formers. Thus, our simple computational model provides the capability to perform combinatorial searches to identify novel glass-forming alloys.

  4. Electron microprobe analysis (WDS EPMA) of Zhamanshin glass reveals the impactor and a common role of accretion in the origin of splash-form impact glass

    International Nuclear Information System (INIS)

    Vetvicka, I; Frank, J; Drtina, J

    2010-01-01

    Impact glass samples collected during expeditions to the Zhamashin and Lonar craters were subjected to a morphology survey and compared to Wabar, Henbury and Darwin impact glasses to reveal that the accretion of fibres and spherules is not exclusive for irghizites but occurs in other splash form glasses over the world. WDS EPMA and LA-ICP-MS assays of Zhamanshin and Lonar glasses enabled the definition of akmurynites as Zhamanshin glass of specific morphology, chemistry and absence of extraterrestrial contamination. However, extraterrestrial contamination in irghizites was verified and further WDS EPMA analyses led to the conclusion that the Zhamanshin crater had been formed by the impact of a primitive achondrite of Lodran chemistry.

  5. Preparation and characterization of Zr-based bulk metallic glasses in form of plate

    International Nuclear Information System (INIS)

    Pilarczyk, Wirginia

    2014-01-01

    Highlights: • Zr-based BMGs in form of plate was successful produced by die pressure casting method. • Many techniques have been used to characterize the structure of Zr 55 Cu 30 Ni 5 Al 10 alloy. • The calculated GFA parameters show that the alloy exhibits satisfactory GFA. • The studies reveal that tested as-cast Zr-based alloy is in amorphous state. - Abstract: Zr-based bulk metallic glasses present an interesting combination of physical, chemical and mechanical properties. During the last decade, intensive progress has been made and a number of applications have been suggested for these materials. In order to successfully apply these materials, it is necessary to accurately characterize their structure, thermal stability and other properties accurately. The aim of the presented work is the manufacturing, examination of the structure of selected Zr-based bulk metallic alloys and confirmation of an amorphous structure using X-ray analysis, microscopic observation and thermal analysis. In this work, the Zr-based bulk metallic glasses in form of plate was successful produced by die pressure casting method. Designed scientific station for casting zirconium based amorphous alloys in the form of plates and rods with selected dimensions is in our university a comprehensive method for achieving amorphous materials which enables us to maintain repeatability of as-cast samples with the amorphous structure and the assumed dimensions range. The diffraction pattern and exothermic reaction as well as the fracture surface morphology reveal that studied as-cast Zr-based alloy is in amorphous state. The calculated GFA parameters show that the alloy exhibits satisfactory glass-forming ability in form of studied plate. These obtained values can suggest that studied alloys are suitable materials for further planned practical application at welding process. The success of Zr-based bulk metallic glasses production in form of plate with obtained sizes is important for future

  6. Correlation between local structure and stability of supercooled liquid state in Zr-based metallic glasses

    International Nuclear Information System (INIS)

    Saida, Junji; Imafuku, Muneyuki; Sato, Shigeo; Sanada, Takashi; Matsubara, Eiichiro; Inoue, Akihisa

    2007-01-01

    The correlation between the local structure and stability of supercooled liquid state is investigated in the Zr 70 (Ni, Cu) 30 binary and Zr 70 Al 10 (Ni, Cu) 20 (numbers indicate at.%) ternary metallic glasses. The Zr 70 Ni 30 binary amorphous alloy with a low stability of supercooled liquid state has a tetragonal Zr 2 Ni-like local structure around Ni atom. Meanwhile, the Zr 70 Cu 30 binary metallic glass has a different local structure of tetragonal Zr 2 Cu, where we suggest the icosahedral local structure by the quasicrystallization behavior in addition of a very small amount of noble metals. The effect of Al addition on the local structure in the Zr-Ni alloy is also examined. We have investigated that the dominant local structure changes in the icosahedral-like structure from the tetragonal Zr 2 Ni-like local structure by the Al substitution with Ni accompanying with the significant stabilization of supercooled liquid state. It is concluded that the formation of icosahedral local structure contributes to the enhancement of stability of supercooled liquid state in the Zr-based alloys

  7. Effects of Cu substitution for Fe on the glass-forming ability and soft magnetic properties for Fe-based bulk metallic glasses

    International Nuclear Information System (INIS)

    Dou, Lintao; Liu, Haishun; Hou, Long; Xue, Lin; Yang, Weiming; Zhao, Yucheng; Chang, Chuntao

    2014-01-01

    The effects of Cu substitution for Fe on the glass-forming ability (GFA) and soft magnetic properties for Fe 72−x Cu x B 20 Si 4 Nb 4 (x=0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) bulk metallic glasses (BMGs) are investigated. It is found that the investigated BMGs exhibit large GFA as well as excellent soft magnetic properties, and proper substitution of Fe by Cu improves the saturation magnetization, coercive force, and effective permeability without obvious deterioration of the GFA. - Highlights: • Fully glassy rods of Fe 72−x Cu x B 20 Si 4 Nb 4 BMGs were produced above 1 mm in diameter. • Investigated BMGs exhibit large glass-forming ability and excellent soft magnetic properties. • Proper Cu substitution improves magnetic properties without obvious deterioration of glass-forming ability

  8. Retrofit of a high power Nd:glass laser system with liquid crystal polarizers

    International Nuclear Information System (INIS)

    Jacobs, S.D.; Cerqua, K.A.; Kessler, T.J.; Seka, W.; Bahr, R.

    1985-03-01

    The glass development laser (GDL), has been operating at the Laboratory for Laser Energetics since 1978. This Nd:phosphate glass system produces high peak power optical radiation at lambda = 1054 nm or lambda = 351 nm for use in studying the interaction physics of intense laser beams with matter. The amplifier staging incorporates the propagation of linearly and circularly polarized light in rod amplifiers which vary in diameter from 16 mm to 90 mm. Numerous quartz or mica quarter waveplates and Brewster angle dielectric thin film polarizers are required to limit accumulated phase retardation between amplification stages and to accommodate interstage Pockels' cell isolation switches. We have recently replaced most of the waveplate-dielectric polarizer combinations in GDL with liquid crystal polarizers. Comprised of 11 μm thick cholesteric fluids sandwiched between optical quality glass plates, liquid crystal polarizers provide excellent polarization properties, low insertion loss, angular insensitivity, and laser damage resistance at lambda = 1054 nm. The design, fabrication, and performance of left-handed and right-handed circular polarizers will be discussed

  9. Structural stability of Pd40Cu30Ni10P20 metallic glass in supercooled liquid region

    International Nuclear Information System (INIS)

    Jiang, J.Z.; Saksl, K.

    2004-01-01

    Phase separation of bulk and ribbon Pd 40 Cu 30 Ni 10 P 20 glasses, annealed in the supercooled liquid region at ambient pressure and high pressures, has been studied by means of differential scanning calorimetry (DSC) and X-ray diffraction techniques. DSC measurements show only one glass transition event in all annealed samples, indicating that no phase separation occurs in the alloy annealed in the supercooled liquid region. Phase analyses reveal at least six crystalline phases in the crystallized sample: monoclinic, tetragonal Cu 3 Pd-like, rhombohedral, fcc-Ni 2 Pd 2 P, fcc-(Ni, Pd) solid solution, and body-centered tetragonal (bct) Ni 3 P-like phases. Annealing treatments under external pressures in the vicinity of the glass transition temperature neither induce phase separation nor alter the glass transition temperature of the Pd 40 Cu 30 Ni 10 P 20 bulk glass

  10. Performance of borosilicate glass, Synroc and spent fuel as nuclear waste forms

    International Nuclear Information System (INIS)

    Lutze, W.; Grambow, B.; Ewing, R.C.

    1990-01-01

    Presently, there are three prominent waste forms under consideration for the disposal of high-level waste: Borosilicate glass and Synroc for high-level radioactive waste from fuel reprocessing and spent fuel as the waste form for non-reprocessed fuel. Using the present experimental data base, one may compare the performance of these three waste forms under repository relevant conditions. In low water flow regimes and at temperatures less than 100 degree C, the fractional release rates of all three waste forms are low, on the order of 10-7/d or less and may decrease with time. Under these conditions the three waste forms behave similarly. At elevated temperatures or in high flow regimes, the durability of borosilicate glass will be much less than that of Synroc, and thus, for certain disposal schemes (e.g., deep burial) Synroc is preferable. All predictions of the long-term behavior are based on the extrapolation of short term experimental data, we point out that appropriate and useful natural analogues are available for each of these waste forms and should be used in the performance assessment of each waste form's long-term behavior. 14 refs

  11. The effect of devitrification on leaching rate of glass containing simulated high level liquid waste (HLLW)

    International Nuclear Information System (INIS)

    Suryantoro; Sumarbagiono; Martono, H.

    1996-01-01

    Effect of devitrification on leaching rate of glass named G1 and G2 each contains 20 wt% and 30wt% of waste has been studied. devitrification of waste - glass has been carried out by heating those specimens at 850 o C for 10, 18, 26, 34, 42 and 50 hours respectively. The weight percentage of crystal in waste glass was determined by X-ray diffractometer and leaching rate was determined by soxhlet apparatus at 100 o C for 24 hours. The longer heating time, the more weight percentage of crystal is formed. The results show that leaching rate of G2 specimens are higher than those of G1. For G1 the leaching rate at 850 o C in 20 times than without heating, and for G2 leaching rate is 15.7 times than without heating. (author)

  12. Thermodynamic and topological instability approaches for forecasting glass-forming ability in the ternary Al-Ni-Y system

    International Nuclear Information System (INIS)

    Oliveira, M.F. de; Aliaga, L.C.R.; Bolfarini, C.; Botta, W.J.; Kiminami, C.S.

    2008-01-01

    A thermodynamic approach to predict bulk glass-forming compositions in binary metallic systems was recently proposed. In this approach, the parameter γ* = ΔH amor /(ΔH inter - ΔH amor ) indicates the glass-forming ability (GFA) from the standpoint of the driving force to form different competing phases, and ΔH amor and ΔH inter are the enthalpies for glass and intermetallic formation, respectively. Good glass-forming compositions should have a large negative enthalpy for glass formation and a very small difference for intermetallic formation, thus making the glassy phase easily reachable even under low cooling rates. The γ* parameter showed a good correlation with GFA experimental data in the Ni-Nb binary system. In this work, a simple extension of the γ* parameter is applied in the ternary Al-Ni-Y system. The calculated γ* isocontours in the ternary diagram are compared with experimental results of glass formation in that system. Despite some misfitting, the best glass formers are found quite close to the highest γ* values, leading to the conclusion that this thermodynamic approach can be extended to ternary systems, serving as a useful tool for the development of new glass-forming compositions. Finally the thermodynamic approach is compared with the topological instability criteria used to predict the thermal behavior of glassy Al alloys

  13. Effect of solute atoms on glass-forming ability for Fe–Y–B alloy: An ab initio molecular dynamics study

    International Nuclear Information System (INIS)

    Han, J.J.; Wang, W.Y.; Liu, X.J.; Wang, C.P.; Hui, X.D.; Liu, Z.K.

    2014-01-01

    The glass-forming abilities of Fe 78 B 22 , Fe 70 Y 6 B 24 , Fe 72 Y 6 B 22 and Fe 72.5 Y 3.5 B 24 alloys were characterized comprehensively using ab initio molecular dynamics simulations. The calculated results were correlated with the properties and atomic structures. It was found that the Fe 72 Y 6 B 22 alloy consists of both the most stable and the least deformed body centered cubic atomic packing structures in the supercooled liquid and glassy states. It was observed that the local compositions in the Fe 72 Y 6 B 22 alloy significantly deviate from the compositions of stable crystalline phases, indicating that the Fe 72 Y 6 B 22 alloy has the best glass-forming ability among the alloys studied. However, Fe 72 Y 6 B 22 alloy has two flaws in terms of glass-forming ability, i.e. relatively large atomic diffusivity and insufficiently close atomic packing. The best performance in these two aspects is observed in the Fe 72.5 Y 3.5 B 24 alloy. Thus, the theoretical study predicts that the best glass former for the Fe–Y–B system is within the compositional range of 22–24 at.% B and 3.5–6 at.% Y

  14. Hydrotalcite formed by alteration of R7T7 nuclear waste glass and basaltic glass in salt brine at 190 degrees C

    International Nuclear Information System (INIS)

    Abdelouas, A.; Crovisier, J.L.; Lutze, W.; Mueller, R.; Bernotat, W.

    1994-01-01

    The R7T7 and synthetic basaltic glasses were submitted to corrosion in a saline MgCl 2 dominated solution at 190 degrees C. For both glasses, the early alteration product is a hydrotalcite-like compound in which HPO 4 2- , SO 4 2- and Cl - substitutes to CO 3 2- . The measured d 003 spacing is 7.68 angstrom for the hydrotalcite formed from R7T7 glass and 7.62 angstrom for the hydrotalcite formed from basaltic glass which reflect the high aluminium content. Chemical microanalyses show that the hydrotalcite is subsequently covered by a silica-rich gel which evolves into saponite after few months

  15. The fundamental structural factor in determining the glass-forming ability and mechanical behavior in the Cu-Zr metallic glasses

    International Nuclear Information System (INIS)

    Sha, Z.D.; Feng, Y.P.; Li, Y.

    2011-01-01

    Research highlights: → A weak but significant hump in trend of the coordinate number and density was observed, respectively. → Our findings indicate our simulation is more accurate to describe the atomic structure of Cu-Zr MGs. The composition-structure-properties correlation was established. → And the effective structural unit for this correlation is the Cu-centered full icosahedra. - Abstract: Using the large-scale atomic/molecular massively parallel simulator, the quantitative composition-structure-properties (including glass-forming ability (GFA) and mechanical behavior) correlations in the Cu-Zr metallic glasses were established. The atomic-level origin of these correlations was tracked down. It was found that the Cu-centered full icosahedron is the microscopic factor that fundamentally influences both GFA and mechanical behavior. Our findings have implications for understanding the nature, forming ability and properties of metallic glasses, and for searching novel metallic glasses with unique functional properties.

  16. Ceramic transactions: Nucleation and crystallization in liquids and glasses. Volume 30

    International Nuclear Information System (INIS)

    Weinberg, M.C.

    1993-01-01

    The collection of papers presented herein were presented at the Nucleation and Crystallization symposium at the Glass and Optical Materials Division Meeting of the American Ceramic Society, held August 16-19, 1992, at Stone Mountain, Georgia. This symposium was the fourth in a series held approximately every ten years. It was similar to the third symposium in that a combination of review and research papers were presented. The three major topics of this meeting were nucleation, crystallization, and crystallized glass applications, as in the third symposium. On the other hand, the present meeting had certain distinct aspects that set it apart form previous symposia. First and foremost, there was the participation of a number of scientists and engineers from diverse disciplines, such as ceramic engineering, theoretical and experimental chemistry, metallurgy, astrophysics, and glass and polymer science. Second, the outlook was somewhat broader than in previous symposia, especially with regard to the topic of nucleation. Finally, on the last day of the meeting, a panel discussion was held on the topic of nucleation. During this session, assessments were given of the experimental and theoretical triumphs and deficiencies regarding crystal nucleation fro the melt. Papers of interest cover zirconate glasses and glasses for immobilization of radioactive wastes

  17. Forming of protective nanostructure coatings on metals and glasses and their properties investigation

    International Nuclear Information System (INIS)

    Deshkovskaya, A.; Lynkov, L.; Nagibarov, A.; Glybin, V.; Richter, E.; Pham, M.

    2013-01-01

    Transparent heat-resistant coatings of 10-30 nm thickness described by (ZrO 2 ) x •(Y 2 O 3 ) y composition are formed on the surface of metals and glasses by thermolysis technique. Produced coatings possess high adhesive strength, high corrosive and abrasive resistance. Nanocrystalline formations are revealed on samples surface, with quantity of these formations depending on basic solution concentration, formed layers number and thermal treatment mode. Ion-beam modification of obtained coatings under mixing mode enables said properties enhancing owing to zirconium oxiboride formation at substrate-coating interface as a result of ion-beam synthesis. (authors)

  18. Fracture toughness measurements on a glass bonded sodalite high-level waste form

    International Nuclear Information System (INIS)

    DiSanto, T.; Goff, K. M.; Johnson, S. G.; O'Holleran, T. P.

    1999-01-01

    The electrometallurgical treatment of metallic spent nuclear fuel produces two high-level waste streams; cladding hulls and chloride salt. Argonne National Laboratory is developing a glass bonded sodalite waste form to immobilize the salt waste stream. The waste form consists of 75 Vol.% crystalline sodalite (containing the salt) with 25 Vol.% of an ''intergranular'' glassy phase. Microindentation fracture toughness measurements were performed on representative samples of this material using a Vickers indenter. Palmqvist cracking was confirmed by post-indentation polishing of a test sample. Young's modulus was measured by an acoustic technique. Fracture toughness, microhardness, and Young's modulus values are reported, along with results from scanning electron microscopy studies

  19. Liquid Secondary Waste Grout Formulation and Waste Form Qualification

    Energy Technology Data Exchange (ETDEWEB)

    Um, Wooyong [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Williams, B. D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Snyder, Michelle M. V. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wang, Guohui [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-05-23

    This report describes the results from liquid secondary waste (LSW) grout formulation and waste form qualification tests performed at Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions (WRPS) to evaluate new formulations for preparing a grout waste form with high-sulfate secondary waste simulants and the release of key constituents from these grout monoliths. Specific objectives of the LSW grout formulation and waste form qualification tests described in this report focused on five activities: 1.preparing new formulations for the LSW grout waste form with high-sulfate LSW simulants and solid characterization of the cured LSW grout waste form; 2.conducting the U.S. Environmental Protection Agency (EPA) Method 1313 leach test (EPA 2012) on the grout prepared with the new formulations, which solidify sulfate-rich Hanford Tank Waste Treatment and Immobilization Plant (WTP) off-gas condensate secondary waste simulant, using deionized water (DIW); 3.conducting the EPA Method 1315 leach tests (EPA 2013) on the grout monoliths made with the new dry blend formulations and three LSW simulants (242-A evaporator condensate, Environmental Restoration Disposal Facility (ERDF) leachate, and WTP off-gas condensate) using two leachants, DIW and simulated Hanford Integrated Disposal Facility (IDF) Site vadose zone pore water (VZPW); 4.estimating the 99Tc desorption Kd (distribution coefficient) values for 99Tc transport in oxidizing conditions to support the IDF performance assessment (PA); 5.estimating the solubility of 99Tc(IV)-bearing solid phases for 99Tc transport in reducing conditions to support the IDF PA.

  20. Devitrification behavior and glass-forming ability of Cu-Zr-Ag alloys

    International Nuclear Information System (INIS)

    Louzguine-Luzgin, Dmitri V.; Xie, Guoqiang; Zhang, Wei; Inoue, Akihisa

    2007-01-01

    This paper presents an influence of Ag addition on the glass-forming ability and devitrification behavior of Cu-Zr glassy alloys on heating. The crystallization kinetics and structure changes in Cu 45 Zr 45 Ag 10 and Cu 35 Zr 45 Ag 20 glassy alloys on heating were studied by X-ray diffraction, transmission electron microscopy, differential scanning and isothermal calorimetry methods. Based on the results obtained one can assume that the improvement of the glass-forming ability of the Cu-Zr alloys by the addition of Ag is connected with a particular crystallization mechanism and a higher reduced glass-transition temperature of the Cu 45 Zr 45 Ag 10 ternary alloy compared to the binary Cu 55 Zr 45 counterpart. As observed in the present work crystallization of the Cu-Zr-Ag alloys is found to cause embitterment of the samples and should be avoided as these alloys are considered to be used as structural materials. The Cu 35 Zr 45 Ag 20 alloy shows possible submicron-scale phase separation upon annealing

  1. 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

  2. Glass-bonded iodosodalite waste form for immobilization of 129I

    Science.gov (United States)

    Chong, Saehwa; Peterson, Jacob A.; Riley, Brian J.; Tabada, Diana; Wall, Donald; Corkhill, Claire L.; McCloy, John S.

    2018-06-01

    Immobilization of radioiodine is an important requirement for current and future nuclear fuel cycles. Iodosodalite [Na8(AlSiO4)6I2] was synthesized hydrothermally from metakaolin, NaI, and NaOH. Dried unwashed sodalite powders were used to synthesize glass-bonded iodosodalite waste forms (glass composite materials) by heating pressed pellets at 650, 750, or 850 °C with two types of sodium borosilicate glass binders. These heat-treated specimens were characterized with X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal analysis, porosity and density measurements, neutron activation analysis, and inductively-coupled plasma mass spectrometry. For the best waste form produced (pellets mixed with 10 mass% of glass binder and heat-treated at 750 °C), the maximum possible elemental iodine loading was 19.8 mass%, but only ∼8-9 mass% waste loading of iodine was retained in the waste form after thermal processing. Other pellets with higher iodine retention either contained higher porosity or were incompletely sintered. ASTM C1308 and C1285 (product consistency test, PCT) experiments were performed to understand chemical durability under diffusive and static conditions. The C1308 test resulted in significantly higher normalized loss compared to the C1285 test, most likely because of the strong effect of neutral pH solution renewal and prevention of ion saturation in solution. Both experiments indicated that release rates of Na and Si were higher than for Al and I, probably due to a poorly durable Na-Si-O phase from the glass bonding matrix or from initial sodalite synthesis; however the C1308 test result indicated that congruent dissolution of iodosodalite occurred. The average release rates of iodine obtained from C1308 were 0.17 and 1.29 g m-2 d-1 for 80 or 8 m-1, respectively, and the C1285 analysis gave a value of 2 × 10-5 g m-2 d-1, which is comparable to or better than the durability of

  3. Expected anomalies of the neutron cross section near the liquid-glass transition

    International Nuclear Information System (INIS)

    Gotze, W.

    1987-01-01

    In the frameworks of a microscopic theory the anomalies of the neutron cross section near the liquid-glass transition are discussed. The central concept of the theory is the correlation function for density fluctuations of wave vector q and frequency ω. Its absorptive part is proportional to the dynamical structure factor S(q, ω), this is the scattering law for coherent neutron scattering. Tagged particle motion is evaluated as well and it yields the incoherent neutron scattering cross section S i (q, ω) in. The predictions of the theory for S(q, ω) and Si (q, ω) a q-ω domain are given

  4. Oriented color centres being formed in anisotropic action of optical radiation on sodium-silicate glass

    International Nuclear Information System (INIS)

    Barinova, N.A.; Glebov, L.B.; Dokuchaev, V.G.; Savel'ev, V.L.

    1992-01-01

    A study was made of anisotropy of absorption of hole colour centres appearing in sodium-silicate glass due to anisotropic action of UV radiation. In case of such action in the field of long-wave edge of their fundamental absorption oriented hole colour centres occurs with maximum of absorption bands to 2.0, 2.8, 4.1 eV. Principal direction of hole colour centres orientation in this case coincides with orientation of ionized glass matrix centres. Orientation of such kind is connected with selective ionization of disorderedly oriented centres forming edge of fundamental absorption. Value of guided dichroism of colour centres absorption is determined by hole migration

  5. Fragility of superheated melts and glass-forming ability in Pr-based alloys

    International Nuclear Information System (INIS)

    Meng, Q.G.; Zhou, J.K.; Zheng, H.X.; Li, J.G.

    2006-01-01

    The kinetic viscosity (η) of superheated melts, thermal properties (T x , T m , T L ) and X-ray diffraction analysis on the Pr-based bulk metallic glasses (BMG) are reported and discussed. A new refined concept, the superheated fragility defined as M' = E S δ x /k B , has been developed based on common solidification theory and the Arrhenius equation. The interrelationship between this kind of fragility and the glass-forming ability (GFA) is elaborated on and evaluated in Pr-based BMG and Al-based amorphous ribbon alloys. Using viscosity data of superheated melts, it is shown, theoretically and experimentally, that the fragility parameter M' may be used as a GFA indicator for metallic alloys

  6. Preparation and characterization of Zr-based bulk metallic glasses in form of plate

    Energy Technology Data Exchange (ETDEWEB)

    Pilarczyk, Wirginia, E-mail: wirginia.pilarczyk@polsl.pl

    2014-12-05

    Highlights: • Zr-based BMGs in form of plate was successful produced by die pressure casting method. • Many techniques have been used to characterize the structure of Zr{sub 55}Cu{sub 30}Ni{sub 5}Al{sub 10} alloy. • The calculated GFA parameters show that the alloy exhibits satisfactory GFA. • The studies reveal that tested as-cast Zr-based alloy is in amorphous state. - Abstract: Zr-based bulk metallic glasses present an interesting combination of physical, chemical and mechanical properties. During the last decade, intensive progress has been made and a number of applications have been suggested for these materials. In order to successfully apply these materials, it is necessary to accurately characterize their structure, thermal stability and other properties accurately. The aim of the presented work is the manufacturing, examination of the structure of selected Zr-based bulk metallic alloys and confirmation of an amorphous structure using X-ray analysis, microscopic observation and thermal analysis. In this work, the Zr-based bulk metallic glasses in form of plate was successful produced by die pressure casting method. Designed scientific station for casting zirconium based amorphous alloys in the form of plates and rods with selected dimensions is in our university a comprehensive method for achieving amorphous materials which enables us to maintain repeatability of as-cast samples with the amorphous structure and the assumed dimensions range. The diffraction pattern and exothermic reaction as well as the fracture surface morphology reveal that studied as-cast Zr-based alloy is in amorphous state. The calculated GFA parameters show that the alloy exhibits satisfactory glass-forming ability in form of studied plate. These obtained values can suggest that studied alloys are suitable materials for further planned practical application at welding process. The success of Zr-based bulk metallic glasses production in form of plate with obtained sizes is

  7. Comparison of SRP high-level waste disposal costs for borosilicate glass and crystalline ceramic waste forms

    International Nuclear Information System (INIS)

    McDonell, W.R.

    1982-04-01

    An evaluation of costs for the immobilization and repository disposal of SRP high-level wastes indicates that the borosilicate glass waste form is less costly than the crystalline ceramic waste form. The wastes were assumed immobilized as glass with 28% waste loading in 10,300 reference 24-in.-diameter canisters or as crystalline ceramic with 65% waste loading in either 3400 24-in.-diameter canisters or 5900 18-in.-diameter canisters. After an interim period of onsite storage, the canisters would be transported to the federal repository for burial. Total costs in undiscounted 1981 dollars of the waste disposal operations, excluding salt processing for which costs are not yet well defined, were about $2500 million for the borosilicate glass form in reference 24-in.-diameter canisters, compared to about $2900 million for the crystalline ceramic form in 24-in.-diameter canisters and about $3100 million for the crystalline ceramic form in 18-in.-diameter canisters. No large differences in salt processing costs for the borosilicate glass and crystalline ceramic forms are expected. Discounting to present values, because of a projected 2-year delay in startup of the DWPF for the crystalline ceramic form, preserved the overall cost advantage of the borosilicate glass form. The waste immobilization operations for the glass form were much less costly than for the crystalline ceramic form. The waste disposal operations, in contrast, were less costly for the crystalline ceramic form, due to fewer canisters requiring disposal; however, this advantage was not sufficient to offset the higher development and processing costs of the crystalline ceramic form. Changes in proposed Nuclear Regulatory Commission regulations to permit lower cost repository packages for defense high-level wastes would decrease the waste disposal costs of the more numerous borosilicate glass forms relative to the crystalline ceramic forms

  8. Recent advances on glass-forming systems driven far from equilibrium. Special issue marking the completion of the Research Unit FOR 1394 `Nonlinear response to probe vitrification'

    Science.gov (United States)

    Fuchs, Matthias

    2017-08-01

    The nature of the glass transition is one of the frontier questions in Statistical Physics and Materials Science. Highly cooperative structural processes develop in glass-forming melts exhibiting relaxational dynamics which is spread out over many decades in time. While considerable progress has been made in recent decades towards understanding dynamical slowing-down in quiescent systems, the interplay of glassy dynamics with external fields reveals a wealth of novel phenomena yet to be explored. This special issue focuses on recent results obtained by the Research Unit FOR 1394 `Nonlinear response to probe vitrification' which was funded by the German Science Foundation (DFG). In the projects of the research unit, strong external fields were used in order to gain insights into the complex structural and transport phenomena at the glass transition under far-from-equilibrium conditions. This aimed inter alia to test theories of the glass transition developed for quiescent systems by pushing them beyond their original regime. Combining experimental, simulational, and theoretical efforts, the eight projects within the FOR 1394 measured and determined aspects of the nonlinear response of supercooled metallic, polymeric, and silica melts, of colloidal dispersions, and of ionic liquids. Applied fields included electric and mechanic fields, and forced active probing (`micro-rheology'), where a single probe is forced through the glass-forming host. Nonlinear stress-strain and force-velocity relations as well as nonlinear dielectric susceptibilities and conductivities were observed. While the physical manipulation of melts and glasses is interesting in its own right, especially technologically, the investigations performed by the FOR 1394 suggest to use the response to strong homogeneous and inhomogeneous fields as technique to explore on the microscopic level the cooperative mechanisms in dense melts of strongly interacting constituents. Questions considered concern the

  9. Photoluminescence at room temperature of liquid-phase crystallized silicon on glass

    Directory of Open Access Journals (Sweden)

    Michael Vetter

    2016-12-01

    Full Text Available The room temperature photoluminescence (PL spectrum due band-to-band recombination in an only 8 μm thick liquid-phase crystallized silicon on glass solar cell absorber is measured over 3 orders of magnitude with a thin 400 μm thick optical fiber directly coupled to the spectrometer. High PL signal is achieved by the possibility to capture the PL spectrum very near to the silicon surface. The spectra measured within microcrystals of the absorber present the same features as spectra of crystalline silicon wafers without showing defect luminescence indicating the high electronic material quality of the liquid-phase multi-crystalline layer after hydrogen plasma treatment.

  10. Simulation of bulk phases formed by polyphilic liquid crystal dendrimers

    Directory of Open Access Journals (Sweden)

    J.M. Ilnytskyi

    2010-01-01

    Full Text Available A coarse-grained simulation model for a third generation liquid crystalline dendrimer (LCDr is presented. It allows, for the first time, for a successful molecular simulation study of a relation between the shape of a polyphilic macromolecular mesogen and the symmetry of a macroscopic phase. The model dendrimer consists of a soft central sphere and 32 grafted chains each terminated by a mesogen group. The mesogenic pair interactions are modelled by the recently proposed soft core spherocylinder model of Lintuvuori and Wilson [J. Chem. Phys, 128, 044906, (2008]. Coarse-grained (CG molecular dynamics (MD simulations are performed on a melt of 100 molecules in the anisotropic-isobaric ensemble. The model LCDr shows conformational bistability, with both rod-like and disc-like conformations stable at lower temperatures. Each conformation can be induced by an external aligning field of appropriate symmetry that acts on the mesogens (uniaxial for rod-like and planar for disc-like, leading to formation of a monodomain smectic A (SmA or a columnar (Col phase, respectively. Both phases are stable for approximately the same temperature range and both exhibit a sharp transition to an isotropic cubic-like phase upon heating. We observe a very strong coupling between the conformation of the LCDr and the symmetry of a bulk phase, as suggested previously by theory. The study reveals rich potential in terms of the application of this form of CG modelling to the study of molecular self-assembly of liquid crystalline macromolecules.

  11. On the dynamics of liquids in their viscous regime approaching the glass transition.

    Science.gov (United States)

    Chen, Z; Angell, C A; Richert, R

    2012-07-01

    Recently, Mallamace et al. (Eur. Phys. J. E 34, 94 (2011)) proposed a crossover temperature, T(×), and claimed that the dynamics of many supercooled liquids follow an Arrhenius-type temperature dependence between T(×) and the glass transition temperature T(g). The opposite, namely super-Arrhenius behavior in this viscous regime, has been demonstrated repeatedly for molecular glass-former, for polymers, and for the majority of the exhaustively studied inorganic glasses of technological interest. Therefore, we subject the molecular systems of the Mallamace et al. study to a "residuals" analysis and include not only viscosity data but also the more precise data available from dielectric relaxation experiments over the same temperature range. Although many viscosity data sets are inconclusive due to their noise level, we find that Arrhenius behavior is not a general feature of viscosity in the T(g) to T(×) range. Moreover, the residuals of dielectric relaxation times with respect to an Arrhenius law clearly reveal systematic curvature consistent with super-Arrhenius behavior being an endemic feature of transport properties in this viscous regime. We also observe a common pattern of how dielectric relaxation times decouple slightly from viscosity.

  12. Effects of waste content of glass waste forms on Savannah River high-level waste disposal costs

    International Nuclear Information System (INIS)

    McDonell, W.R.; Jantzen, C.M.

    1985-01-01

    Effects of the waste content of glass waste forms of Savannah River high-level waste disposal costs are evaluated by their impact on the number of waste canisters produced. Changes in waste content affect onsite Defense Waste Processing Facility (DWPF) costs as well as offsite shipping and repository emplacement charges. A nominal 1% increase over the 28 wt % waste loading of DWPF glass would reduce disposal costs by about $50 million for Savannah River wastes generated to the year 2000. Waste form modifications under current study include adjustments of glass frit content to compensate for added salt decontamination residues and increased sludge loadings in the DWPF glass. Projected cost reductions demonstrate significant incentives for continued optimization of the glass waste loadings. 13 refs., 3 figs., 3 tabs

  13. Investigation of crystallization kinetics and deformation behavior in supercooled liquid region of CuZr-based bulk metallic glass

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ke; Fan, Xinhui; Li, Bing; Li, Yanhong; Wang, Xin; Xu, Xuanxuan [Xi' an Technological Univ. (China). School of Material and Chemical Engineering

    2017-08-15

    In this paper, a systematic study of crystallization kinetics and deformation behavior is presented for (Cu{sub 50}Zr{sub 50}){sub 94}Al{sub 6} bulk metallic glass in the supercooled liquid region. Crystallization results showed that the activation energy for (Cu{sub 50}Zr{sub 50}){sub 94}Al{sub 6} was calculated using the Arrhenius equation in isothermal mode and the Kissinger-Akahira-Sunose method in non-isothermal mode. The activation energy was quite high compared with other bulk metallic glasses. Based on isothermal transformation kinetics described by the Johson-Mehl-Avrami model, the average Avrami exponent of about 3.05 implies a mainly diffusion controlled three-dimensional growth with an increasing nucleation rate during the crystallization. For warm deformation, the results showed that deformation behavior, composed of homogeneous and inhomogeneous deformation, is strongly dependent on strain rate and temperature. The homogeneous deformation transformed from non-Newtonian flow to Newtonian flow with a decrease in strain rate and an increase in temperature. It was found that the crystallization during high temperature deformation is induced by heating. The appropriate working temperature/strain rate combination for the alloy forming, without in-situ crystallization, was deduced by constructing an empirical deformation map. The optimum process condition for (Cu{sub 50}Zr{sub 50}){sub 94}Al{sub 6} can be expressed as T∝733 K and ∝ ε 10{sup -3} s{sup -1}.

  14. Barium borosilicate glass - a potential matrix for immobilization of sulfate bearing high-level radioactive liquid waste

    International Nuclear Information System (INIS)

    Kaushik, C.P.; Mishra, R.K.; Sengupta, P.; Kumar, Amar; Das, D.; Kale, G.B.; Raj, Kanwar

    2006-01-01

    Borosilicate glass formulations adopted worldwide for immobilization of high-level radioactive liquid waste (HLW) is not suitable for sulphate bearing HLW, because of its low solubility in such glass. A suitable glass matrix based on barium borosilicate has been developed for immobilization of sulphate bearing HLW. Various compositions based on different glass formulations were made to examine compatibility with waste oxide with around 10 wt% sulfate content. The vitrified waste product obtained from barium borosilicate glass matrix was extensively evaluated for its characteristic properties like homogeneity, chemical durability, glass transition temperature, thermal conductivity, impact strength, etc. using appropriate techniques. Process parameters like melt viscosity and pour temperature were also determined. It is found that SB-44 glass composition (SiO 2 : 30.5 wt%, B 2 O 3 : 20.0 wt%, Na 2 O: 9.5 wt% and BaO: 19.0 wt%) can be safely loaded with 21 wt% waste oxide without any phase separation. The other product qualities of SB-44 waste glass are also found to be on a par with internationally adopted waste glass matrices. This formulation has been successfully implemented in plant scale

  15. Cerium, uranium, and plutonium behavior in glass-bonded sodalite, a ceramic nuclear waste form

    International Nuclear Information System (INIS)

    Lewis, M. A.; Lexa, D.; Morss, L. R.; Richmann, M. K.

    1999-01-01

    Glass-bonded sodalite is being developed as a ceramic waste form (CWF) to immobilize radioactive fission products, actinides, and salt residues from electrometallurgical treatment of spent nuclear reactor fuel. The CWF consists of about 75 mass % sodalite, 25 mass % glass, and small amounts of other phases. This paper presents some results and interpretation of physical measurements to characterize the CWF structure, and dissolution tests to measure the release of matrix components and radionuclides from the waste form. Tests have been carried out with specimens of the CWF that contain rare earths at concentrations similar to those expected in the waste form. Parallel tests have been carried out on specimens that have uranium or plutonium as well as the rare earths at concentrations similar to those expected in the waste forms; in these specimens UCl 3 forms UO 2 and PuCl 3 forms PuO 2 . The normalized releases of rare earths in dissolution tests were found to be much lower than those of matrix elements (B, Si, Al, Na). When there is no uranium in the CWF, the release of cerium is two to ten times lower than the release of the other rare earths. The low release of cerium may be due to its tetravalent state in uranium-free CWF. However, when there is uranium in the CWF, the release of cerium is similar to that of the other rare earths. This trivalent behavior of cerium is attributed to charge transfer or covalent interactions among cerium, uranium, and oxygen in (U,Ce)O 2

  16. Lap shear strength of selected adhesives (epoxy, varnish, B-stage glass cloth) in liquid nitrogen and at room temperature

    International Nuclear Information System (INIS)

    Froelich, K.J.; Fitzpatrick, C.M.

    1976-12-01

    The adhesives included several epoxy resins, a varnish, and a B-stage glass cloth (a partially cured resin in a fiberglass cloth matrix). Several parameters critical to bond strength were varied: adhesive and adherend differences, surface preparation, coupling agents, glass cloth, epoxy thickness, fillers, and bonding pressure and temperature. The highest lap shear strengths were obtained with the B-shear glass cloth at both liquid nitrogen and room temperatures with values of approximately 20 MPa (3000 psi) and approximately 25.5 MPa (3700 psi) respectively

  17. Y and Er minor addition effect on glass forming ability of a Ni–Nb–Zr alloy

    International Nuclear Information System (INIS)

    Deo, L.P.; Oliveira, M.F. de

    2015-01-01

    Highlights: • A theoretical selection criterion to predict the GFA was used for Ni–Nb–Zr–RE alloys. • The prediction agrees very well with thermal parameter gm used to evaluate experimentally the GFA. • RE doped alloys showed higher GFA than the base alloy. • Y and Er elements showed similar effects to improve the GFA of the base alloy. - Abstract: Since the discovering of amorphous alloys in 1960, the actual causes of why some alloys can be easily formed into glasses while others cannot, are not clearly known, thus there is no universal theory to predict the glass forming ability in metallic systems. It is well known that the minor amount addition of proper rare-earth elements can greatly enhance the glass forming ability of some glass-forming alloys. In the present study, a selection criterion was successfully used to predict the glass forming ability improvement of Ni 67.3 Nb 28.4 Zr 4.3 alloy with minor additions of Y or Er. The actual glass forming ability of the base alloy and rare-earth doped alloys were evaluated by the thermal parameter γ m and the results agree very well with the tendency predicted by the calculation. The amorphous nature of alloys was mainly analyzed by X-ray diffraction and differential scanning calorimetry. This work also presents a brief and complementary consideration about oxygen contamination quantified by the inert gas fusion method

  18. The study of diffusion mechanism in network-forming liquid: Silica liquid

    Directory of Open Access Journals (Sweden)

    P. K. Hung

    2016-12-01

    Full Text Available Molecular dynamics simulation is employed to investigate the diffusion mechanism in silica melt, a typical network-forming liquid. From the analysis of SiOx→SiOx±1 and OSiy→OSiy±1 reactions we reveal two moving modes: fast hopping and slow collective moving. Accordingly the atoms diffuse in the melt by simple hopping or through displacing of super-molecule (SM. A cluster analysis is performed for several of atom sets. It is shown that the melt exhibits non-uniform spatial distribution of reaction which causes the dynamics heterogeneity (DH. Further, the network structure of the melt consists of main subnet and large defective subnets. These subnets differ strongly in local environment, chemical composition and atomic density. This result evidences two distinct phases, the structure heterogeneity in silica melt and supports the polymorphism of network-forming liquid. We also find out that the node transformation spreads non-uniformly through the network structure. It takes place mainly in large defective subnet. The strong localization of node transformation is responsible for dynamical slowdown.

  19. Elastic properties of Pd40Cu30Ni10P20 bulk glass in supercooled liquid region

    DEFF Research Database (Denmark)

    Nishiyama, N.; Inoue, A.; Jiang, Jianzhong

    2001-01-01

    In situ ultrasonic measurements for the Pd40Cu30Ni10P20 bulk glass in three states: Glassy solid, supercooled liquid, and crystalline, have been performed. It is found that velocities of both longitudinal and transverse waves and elastic moduli (shear modulus, bulk modulus, Young's modulus......, and Lame parameter), together with Debye temperature, gradually decrease with increasing temperature through the glass transition temperature as the Poisson's ratio increases. The behavior of the velocity of transverse wave vs. temperature in the supercooled liquid region could be explained by viscosity...

  20. Improvement of corrosion resistance in NaOH solution and glass forming ability of as-cast Mg-based bulk metallic glasses by microalloying

    Directory of Open Access Journals (Sweden)

    Peng Hao

    2011-02-01

    Full Text Available The influences of the addition of Ag on the glass forming ability (GFA and corrosion behavior were investigated in the Mg-Ni-based alloy system by X-ray diffraction (XRD and electrochemical polarization in 0.1 mol/L NaOH solution. Results shows that the GFA of the Mg-Ni-based BMGs can be improved dramatically by the addition of an appropriate amount of Ag; and the addition element Ag can improve the corrosion resistance of Mg-Ni-based bulk metallic glass. The large difference in atomic size and large negative mixing enthalpy in alloy system can contribute to the high GFA. The addition element Ag improves the forming speed and the stability of the passive film, which is helpful to decrease the passivation current density and to improve the corrosion resistance of Mg-Ni-based bulk metallic glass.

  1. Beyond packing of hard spheres: The effects of core softness, non-additivity, intermediate-range repulsion, and many-body interactions on the glass-forming ability of bulk metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai; Fan, Meng; Liu, Yanhui; Schroers, Jan [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Center for Research on Interface Structures and Phenomena, Yale University, New Haven, Connecticut 06520 (United States); Shattuck, Mark D. [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Department of Physics and Benjamin Levich Institute, The City College of the City University of New York, New York, New York 10031 (United States); O’Hern, Corey S. [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Center for Research on Interface Structures and Phenomena, Yale University, New Haven, Connecticut 06520 (United States); Department of Physics, Yale University, New Haven, Connecticut 06520 (United States); Department of Applied Physics, Yale University, New Haven, Connecticut 06520 (United States)

    2015-11-14

    When a liquid is cooled well below its melting temperature at a rate that exceeds the critical cooling rate R{sub c}, the crystalline state is bypassed and a metastable, amorphous glassy state forms instead. R{sub c} (or the corresponding critical casting thickness d{sub c}) characterizes the glass-forming ability (GFA) of each material. While silica is an excellent glass-former with small R{sub c} < 10{sup −2} K/s, pure metals and most alloys are typically poor glass-formers with large R{sub c} > 10{sup 10} K/s. Only in the past thirty years have bulk metallic glasses (BMGs) been identified with R{sub c} approaching that for silica. Recent simulations have shown that simple, hard-sphere models are able to identify the atomic size ratio and number fraction regime where BMGs exist with critical cooling rates more than 13 orders of magnitude smaller than those for pure metals. However, there are a number of other features of interatomic potentials beyond hard-core interactions. How do these other features affect the glass-forming ability of BMGs? In this manuscript, we perform molecular dynamics simulations to determine how variations in the softness and non-additivity of the repulsive core and form of the interatomic pair potential at intermediate distances affect the GFA of binary alloys. These variations in the interatomic pair potential allow us to introduce geometric frustration and change the crystal phases that compete with glass formation. We also investigate the effect of tuning the strength of the many-body interactions from zero to the full embedded atom model on the GFA for pure metals. We then employ the full embedded atom model for binary BMGs and show that hard-core interactions play the dominant role in setting the GFA of alloys, while other features of the interatomic potential only change the GFA by one to two orders of magnitude. Despite their perturbative effect, understanding the detailed form of the intermetallic potential is important for

  2. Evolution of short range order in Ar: Liquid to glass and solid transitions-A computational study

    Science.gov (United States)

    Shor, Stanislav; Yahel, Eyal; Makov, Guy

    2018-04-01

    The evolution of the short range order (SRO) as a function of temperature in a Lennard-Jones model liquid with Ar parameters was determined and juxtaposed with thermodynamic and kinetic properties obtained as the liquid was cooled (heated) and transformed between crystalline solid or glassy states and an undercooled liquid. The Lennard-Jones system was studied by non-equilibrium molecular dynamics simulations of large supercells (approximately 20000 atoms) rapidly cooled or heated at selected quenching rates and at constant pressure. The liquid to solid transition was identified by discontinuities in the atomic volume and molar enthalpy; the glass transition temperature range was identified from the temperature dependence of the self-diffusion. The SRO was studied within the quasi-crystalline model (QCM) framework and compared with the Steinhardt bond order parameters. Within the QCM it was found that the SRO evolves from a bcc-like order in the liquid through a bct-like short range order (c/a=1.2) in the supercooled liquid which persists into the glass and finally to a fcc-like ordering in the crystalline solid. The variation of the SRO that results from the QCM compares well with that obtained with Steinhardt's bond order parameters. The hypothesis of icosahedral order in liquids and glasses is not supported by our results.

  3. Collective dynamics of glass-forming polymers at intermediate length scales

    International Nuclear Information System (INIS)

    Colmenero, J.; Alvarez, F.; Arbe, A.

    2015-01-01

    Deep understanding of the complex dynamics taking place in glass-forming systems could potentially be gained by exploiting the information provided by the collective response monitored by coherent neutron scattering. We have revisited the question of the characterization of the collective response of polyisobutylene at intermediate length scales observed by neutron spin echo (NSE) experiments. The model, generalized for sub-linear diffusion - as it is the case of glass-forming polymers - has been successfully applied by using the information on the total self-motions available from MD-simulations properly validated by direct comparison with experimental results. From the fits of the coherent NSE data, the collective time at Q → 0 has been extracted that agrees very well with compiled results from different experimental techniques directly accessing such relaxation time. We show that a unique temperature dependence governs both, the Q → 0 and Q → ∞ asymptotic characteristic times. The generalized model also gives account for the modulation of the apparent activation energy of the collective times with the static structure factor. It mainly results from changes of the short-range order at inter-molecular length scales

  4. Using 20-million-year-old amber to test the super-Arrhenius behaviour of glass-forming systems

    Science.gov (United States)

    Zhao, Jing; Simon, Sindee L.; McKenna, Gregory B.

    2013-04-01

    Fossil amber offers the opportunity to investigate the dynamics of glass-forming materials far below the nominal glass transition temperature. This is important in the context of classical theory, as well as some new theories that challenge the idea of an ‘ideal’ glass transition. Here we report results from calorimetric and stress relaxation experiments using a 20-million-year-old Dominican amber. By performing the stress relaxation experiments in a step-wise fashion, we measured the relaxation time at each temperature and, above the fictive temperature of this 20-million-year-old glass, this is an upper bound to the equilibrium relaxation time. The results deviate dramatically from the expectation of classical theory and are consistent with some modern ideas, in which the diverging timescale signature of complex fluids disappears below the glass transition temperature.

  5. Simulated glass-forming polymer melts: dynamic scattering functions, chain length effects, and mode-coupling theory analysis.

    Science.gov (United States)

    Frey, S; Weysser, F; Meyer, H; Farago, J; Fuchs, M; Baschnagel, J

    2015-02-01

    We present molecular-dynamics simulations for a fully flexible model of polymer melts with different chain length N ranging from short oligomers (N = 4) to values near the entanglement length (N = 64). For these systems we explore the structural relaxation of the supercooled melt near the critical temperature T c of mode-coupling theory (MCT). Coherent and incoherent scattering functions are analyzed in terms of the idealized MCT. For temperatures T > T c we provide evidence for the space-time factorization property of the β relaxation and for the time-temperature superposition principle (TTSP) of the α relaxation, and we also discuss deviations from these predictions for T ≈ T c. For T larger than the smallest temperature where the TTSP holds we perform a quantitative analysis of the dynamics with the asymptotic MCT predictions for the late β regime. Within MCT a key quantity, in addition to T c, is the exponent parameter λ. For the fully flexible polymer models studied we find that λ is independent of N and has a value (λ = 0.735 ) typical of simple glass-forming liquids. On the other hand, the critical temperature increases with chain length toward an asymptotic value T c (∞) . This increase can be described by T c (∞) - T c(N) ∼ 1/N and may be interpreted in terms of the N dependence of the monomer density ρ, if we assume that the MCT glass transition is ruled by a soft-sphere-like constant coupling parameter Γ c = ρ c T c (-1/4), where ρ c is the monomer density at T c. In addition, we also estimate T c from a Hansen-Verlet-like criterion and MCT calculations based on structural input from the simulation. For our polymer model both the Hansen-Verlet criterion and the MCT calculations suggest T c to decrease with increasing chain length, in contrast to the direct analysis of the simulation data.

  6. Thermal stability and glass-forming ability of amorphous Nd-Al-TM (TM=Fe, Co, Ni or Cu) alloys

    International Nuclear Information System (INIS)

    Inoue, A.; Zhang Tao

    1997-01-01

    Bulk amorphous alloys were prepared for Nd 70 Al 10 TM 20 and Nd 60 Al 10 TM 30 (TM=Fe or Co) alloys by copper mold casting. The maximum sample thickness for glass formation reaches 15 mm for the Nd-Al-Fe alloys and 5 mm for the Nd-Al-Co alloys. A significant difference in the phase transition upon heating is recognized between the Fe- and Co-containing alloys. No glass transition before crystallization is observed for the Nd-Al-Fe alloys, but the Nd-Al-Co alloys exhibit the glass transition. The ΔT x (=T x -T g ) and T g /T m are 40-55 K and 0.65-0.67, respectively, for the latter alloys. The absence of supercooled liquid for the former alloys is different from those for all bulk amorphous alloys reported up to date. The T x /T m and ΔT m (=T m -T x ) are 0.85-0.89 and 88-137 K, respectively, for the Nd-Al-Fe alloys and, hence, the large glass-forming ability is presumably due to the high T x /T m and small ΔT m values. (orig.)

  7. Glass forming ability of Al–Ni–La alloys with Si addition

    Energy Technology Data Exchange (ETDEWEB)

    Yi, J.J.; Xiong, X.Z. [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Inoue, A. [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); WPI-Advanced Institute for Material Research, Tohoku University, Sendai 980-8577 (Japan); Kong, L.T. [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Li, J.F., E-mail: jfli@sjtu.edu.cn [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China)

    2015-11-25

    (Al{sub 85.5}Ni{sub 9.5}La{sub 5}){sub 100−x}Si{sub x}, (Al{sub 86}Ni{sub 9}La{sub 5}){sub 100−x}Si{sub x}, (Al{sub 86}Ni{sub 9.5}La{sub 4.5}){sub 100−x}Si{sub x}, (Al{sub 86}Ni{sub 10}La{sub 4}){sub 100−x}Si{sub x} and (Al{sub 86}Ni{sub 10.5}La{sub 3.5}){sub 100−x}Si{sub x} alloys, where x = 0.0, 0.2, 0.5, 1.0, 1.5 and 2.0, were cast under the same suction casting conditions into a wedge-shaped copper mold for investigating the effect of Si addition on the glass-forming ability (GFA). The GFA of the Al–Ni–La base alloys, except for the optimal glass former (Al{sub 85.5}Ni{sub 9.5}La{sub 5}), is enhanced when a proper content of Si is added. The largest content of Si up to which GFA can be enhanced changes in the following order of the base alloys: Al{sub 86}Ni{sub 9}La{sub 5}, Al{sub 86}Ni{sub 9.5}La{sub 4.5}, Al{sub 86}Ni{sub 10}La{sub 4} and Al{sub 86}Ni{sub 10.5}La{sub 3.5}. The enhancement of GFA due to Si addition becomes more significant as the La content decreases. This is presumably because more free Al atoms are present in the base alloy. - Highlights: • 0.2–2.0 at. % Si was added to each ternary base alloy. • Wedge-shaped samples were suction cast to obtain the glass-forming ability (GFA). • The GFA of the ternary non-optimal glass formers can be enhanced by Si addition. • The number of free-Al atoms dominates the best Si addition.

  8. Glass forming ability of Al–Ni–La alloys with Si addition

    International Nuclear Information System (INIS)

    Yi, J.J.; Xiong, X.Z.; Inoue, A.; Kong, L.T.; Li, J.F.

    2015-01-01

    (Al_8_5_._5Ni_9_._5La_5)_1_0_0_−_xSi_x, (Al_8_6Ni_9La_5)_1_0_0_−_xSi_x, (Al_8_6Ni_9_._5La_4_._5)_1_0_0_−_xSi_x, (Al_8_6Ni_1_0La_4)_1_0_0_−_xSi_x and (Al_8_6Ni_1_0_._5La_3_._5)_1_0_0_−_xSi_x alloys, where x = 0.0, 0.2, 0.5, 1.0, 1.5 and 2.0, were cast under the same suction casting conditions into a wedge-shaped copper mold for investigating the effect of Si addition on the glass-forming ability (GFA). The GFA of the Al–Ni–La base alloys, except for the optimal glass former (Al_8_5_._5Ni_9_._5La_5), is enhanced when a proper content of Si is added. The largest content of Si up to which GFA can be enhanced changes in the following order of the base alloys: Al_8_6Ni_9La_5, Al_8_6Ni_9_._5La_4_._5, Al_8_6Ni_1_0La_4 and Al_8_6Ni_1_0_._5La_3_._5. The enhancement of GFA due to Si addition becomes more significant as the La content decreases. This is presumably because more free Al atoms are present in the base alloy. - Highlights: • 0.2–2.0 at. % Si was added to each ternary base alloy. • Wedge-shaped samples were suction cast to obtain the glass-forming ability (GFA). • The GFA of the ternary non-optimal glass formers can be enhanced by Si addition. • The number of free-Al atoms dominates the best Si addition.

  9. Glass-bonded iodosodalite waste form for immobilization of 129 I

    Energy Technology Data Exchange (ETDEWEB)

    Chong, Saehwa; Peterson, Jacob A.; Riley, Brian J.; Tabada, Diana; Wall, Donald; Corkhill, Claire L.; McCloy, John S.

    2018-06-01

    Immobilization of radioiodine (e.g., 129I, 131I) is an important need for current and future nuclear fuel cycles. For the current work, iodosodalite [Na8(AlSiO4)6I2] was synthesized hydrothermally from metakaolin, NaI, and NaOH. Following hydrothermal treatment, dried unwashed powders were used to make glass-bonded iodosodalite waste forms by heating pressed pellets at 650, 750, or 850 °C with two different types of sodium borosilicate glass binders, i.e., NBS-4 and SA-800. These heat-treated specimens were characterized with X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal analysis, porosity and density measurements, neutron activation analysis, and inductively-coupled plasma mass spectrometry. The pellets mixed with 10 mass% of NBS-4 or SA-800 and heat-treated at 750 °C contained relatively high percentage iodine retention (~44-47 % of the maximum iodine loading) with relatively low porosities, while other pellets with higher percentages iodine retention either contained higher porosity or were not completely sintered. ASTM C1308 chemical durability tests of monolithic specimens showed a large initial release of Na, Al, Si, and I on the first day, possibly from water-soluble salt crystals or non-durable amorphous phases. Release rates of Na and Si were higher than for Al and I, probably due to a poorly durable Na-Si-O phase from the glass bonding matrix. The cumulative normalized release of iodine was 12.5 g m-2 for the first 10 1-d exchanges, suggestive of coherent dissolution. The average release rate from 10-24 days during the 7-d exchange intervals was 0.2336 g m-2 d-1.

  10. Influence of granulometry in the Hurst exponent of air liquid interfaces formed during capillary rising in a granular media

    Directory of Open Access Journals (Sweden)

    Gontijo Guilherme L.

    2017-01-01

    Full Text Available We report results concerning the fractal dimension of a air/fluid interface formed during the capillary rising of a fluid into a dense granular media. The system consists in a modified Hele-Shaw cell filled with grains at different granulometries and confined in a narrow gap between the glass plates. The system is then placed onto a water reservoir, and the liquid penetrates the medium due to capillary forces. We measure the Hurst exponent of the liquid/air interface with help of image processing, and follow the temporal evolution of the profiles. We observe that the Hurst exponent can be related with the granulometry, but the range of values are odd to the predicted values from models or theory.

  11. Microcolumn high pressure liquid chromatography with a glass-frit nebulizer interface for plasma emission detection

    International Nuclear Information System (INIS)

    Ibrahim, M.; Nisamaneepong, W.; Caruso, J.

    1985-01-01

    Microcolumn high pressure liquid chromatography (micro-HPLC) is rapidly gaining recognition as a practical separation tool for organometallic compounds. The use of the inductively coupled plasma (ICP) as a detector for micro-HPLC is studied. Several miniaturized glass-frit nebulizers are investigated as interfaces between the output of the microbore column and the ICP torch. Their performance with aqueous and methanolic solutions is evaluated by direct nebulization and flow injection analysis. The most efficient of these nebulizers is used in the micro-HPLC/ICP study of some Cd, Pb, and Zn organometallic compounds. Detection limits of 1.92 ng of Pb for tetramethyllead and 5.01 ng of Pb for tetraethyllead are obtained and compared with regular HPLC/ICP of these same compounds. Approximately equivalent detection limits were obtained when using a microwave induced plasma as an alternate plasma source

  12. Experimental results from a large volume active target made of glass capillaries and liquid scintillator

    International Nuclear Information System (INIS)

    Annis, P.; Buontempo, S.; Brunner, J.; De Jong, M.; Fabre, J.P.; Frenkel, A.; Galeazzi, F.; Golovkin, S.; Gregoire, G.; Hoepfner, K.; Konijn, J.; Kozarenko, E.; Kreslo, I.; Kushnirenko, A.; Martellotti, G.; Mazzoni, M.A.; Medvedkov, A.; Michel, L.; Mondardini, M.R.; Panman, J.; Penso, G.; Petukhov, Y.; Riccardi, F.; Siegmund, W.P.; Strack, R.; Tyukov, V.; Vasilchenko, V.; Vilain, P.; Wilquet, G.; Winter, K.; Wong, H.; Zymin, K.

    1995-01-01

    We are investigating the feasibility of high-resolution tracking with an active target made of glass capillaries filled with organic liquid scintillator. This technique allows real time detection of short-lived particle decays. In this paper, we report on experimental results obtained from an active target having 2 x 2 cm 2 cross section and 180 cm length, installed in front of the CHORUS detector and exposed to the CERN Wide Band Neutrino Beam. The detector consists of 5.1 x 10 5 capillaries with 20 μm inner diameter, read out by a single optoelectronic chain and a Megapixel CCD. Details on tests in the neutrino beam will be reported. First neutrino interactions have been detected. (orig.)

  13. Combined PIXE and SEM study of the behaviour of trace elements in gel formed around implant coated with bioactive glass

    Science.gov (United States)

    Oudadesse, H.; Irigaray, J. L.; Barbotteau, Y.; Brun, V.; Moretto, Ph.

    2002-05-01

    Bioactive glasses are used as coating biomaterials to facilitate anchorage of metallic prostheses implanted into the body. The aim of this work is to study the behavior of gel formed in contact with alloys and BVA and BVH bioactive glasses implanted. Cylinders of metallic implants composed by Ti, Al and V, are coated with bioactive glass. Three sheep were implanted for different time length: 3, 6 and 12 months in the femoral epiphysis. Results obtained with particle induced X-ray emission and scanning electron microscopy show that BVA coating induces a better contact between the metallic implant and bone. On the other hand, BVH coating prevents corrosion from the metallic implant.

  14. Does an electron form a bubble in liquid neon?

    International Nuclear Information System (INIS)

    Storchak, V.G.; Brewer, J.H.; Morris, G.D.

    1997-01-01

    Muon spin relaxation measurements in liquid neon in electric fields up to 35 kV/cm reveal the existence of a delocalized electron state which is responsible for delayed muonium atom formation. Other fraction of radiolysis electrons created in the positive muon's ionization track is believed to be localized inside bubbles and therefore possesses low mobility. Bubble formation in liquid neon is discussed in detail

  15. A simple criterion to predict the glass forming ability of metallic alloys

    International Nuclear Information System (INIS)

    Falcao de Oliveira, Marcelo

    2012-01-01

    A new and simple criterion with which to quantitatively predict the glass forming ability (GFA) of metallic alloys is proposed. It was found that the critical cooling rate for glass formation (R C ) correlates well with a proper combination of two factors, the minimum topological instability (λ min ) and the Δh parameter, which depends on the average work function difference (Δφ) and the average electron density difference (Δn ws 1/3 ) among the constituent elements of the alloy. A correlation coefficient (R 2 ) of 0.76 was found between R c and the new criterion for 68 alloys in 30 different metallic systems. The new criterion and the Uhlmann's approach were used to estimate the critical amorphous thickness (Z C ) of alloys in the Cu-Zr system. The new criterion underestimated R C in the Cu-Zr system, producing predicted Z C values larger than those observed experimentally. However, when considering a scale factor, a remarkable similarity was observed between the predicted and the experimental behavior of the GFA in the binary Cu-Zr. When using the same scale factor and performing the calculation for the ternary Zr-Cu-Al, good agreement was found between the predicted and the actual best GFA region, as well as between the expected and the observed critical amorphous thickness.

  16. 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

  17. Effect of Yttrium Addition on Glass-Forming Ability and Magnetic Properties of Fe–Co–B–Si–Nb Bulk Metallic Glass

    Directory of Open Access Journals (Sweden)

    Teruo Bitoh

    2015-06-01

    Full Text Available The glass-forming ability (GFA and the magnetic properties of the [(Fe0.5Co0.50.75B0.20Si0.05]96Nb4−xYx bulk metallic glasses (BMGs have been studied. The partial replacement of Nb by Y improves the thermal stability of the glass against crystallization. The saturation mass magnetization (σs exhibits a maximum around 2 at. % Y, and the value of σs of the alloy with 2 at. % Y is 6.5% larger than that of the Y-free alloy. The coercivity shows a tendency to decrease with increasing Y content. These results indicate that the partial replacement of Nb by Y in the Fe–Co–B–Si–Nb BMGs is useful to simultaneous achievement of high GFA, high σs, and good soft magnetic properties.

  18. Casting of organic glass by radiation-induced polymerization of glass-forming monomers at low temperature. II. Optical strain of remaining stress type

    International Nuclear Information System (INIS)

    Okubo, H.; Yoshii, F.; Kaetsu, I.; Honda, S.

    1978-01-01

    Previously it was found that casting could be carried out efficiently without strain formation by radiation-induced polymerization of glass-forming monomers. Two types of strain were observed in casting: thermal stream type, which was studied previously, and remained stress type. In this report, the effect of various factors on the formation of remaining stress-type strain in radiation-induced casting polymerization was studied. It was found that the molecular weight of prepolymer did not affect strain formation, while prepolymer concentration and viscosity of the system had a serious influence on strain formation. It could be deduced that this type of strain formed as a result of remaining inner stress due to poor relaxation of the shrinking stress. It was realized that less volume shrinkage of glass-forming monomers accompanying casting polymerization reduced the strain formation of this type in radiation-induced casting polymerization at low temperatures

  19. Simple Theory for the Dynamics of Mean-Field-Like Models of Glass-Forming Fluids

    Science.gov (United States)

    Szamel, Grzegorz

    2017-10-01

    We propose a simple theory for the dynamics of model glass-forming fluids, which should be solvable using a mean-field-like approach. The theory is based on transparent physical assumptions, which can be tested in computer simulations. The theory predicts an ergodicity-breaking transition that is identical to the so-called dynamic transition predicted within the replica approach. Thus, it can provide the missing dynamic component of the random first order transition framework. In the large-dimensional limit the theory reproduces the result of a recent exact calculation of Maimbourg et al. [Phys. Rev. Lett. 116, 015902 (2016), 10.1103/PhysRevLett.116.015902]. Our approach provides an alternative, physically motivated derivation of this result.

  20. The Monte Carlo dynamics of a binary Lennard-Jones glass-forming mixture

    International Nuclear Information System (INIS)

    Berthier, L; Kob, W

    2007-01-01

    We use a standard Monte Carlo algorithm to study the slow dynamics of a binary Lennard-Jones glass-forming mixture at low temperature. We find that the Monte Carlo approach is by far the most efficient way to simulate a stochastic dynamics since the relaxation is about 10 times faster than in Brownian dynamics and about 30 times faster than in stochastic dynamics. Moreover, the average dynamical behaviour of the system is in quantitative agreement with that obtained using Newtonian dynamics, apart from at very short times where thermal vibrations are suppressed. We show, however, that dynamic fluctuations quantified by four-point dynamic susceptibilities do retain a dependence on the microscopic dynamics, as recently predicted theoretically

  1. Ductile Bulk Aluminum-Based Alloy with Good Glass-Forming Ability and High Strength

    International Nuclear Information System (INIS)

    Long-Chao, Zhuo; Shu-Jie, Pang; Hui, Wang; Tao, Zhang

    2009-01-01

    Based on a new approach for designing glassy alloy compositions, bulk Al-based alloys with good glass-forming ability (GFA) are synthesized. The cast Al 86 Si 0.5 Ni 4.06 Co 2.94 Y 6 Sc 0.5 rod with a diameter of 1 mm shows almost fully amorphous structure besides about 5% fcc-Al nucleated in the center of the rod. The bulk alloy with high Al concentration exhibits an ultrahigh yield strength of 1.18 GPa and maximum strength of 1.27 GPa as well as an obvious plastic strain of about 2.4% during compressive deformation. This light Al-based alloy with good GFA and mechanical properties is promising as a new high specific strength material with good deformability. (condensed matter: structure, mechanical and thermal properties)

  2. Crystal phases of a glass-forming Lennard-Jones mixture

    International Nuclear Information System (INIS)

    Fernandez, Julian R.; Harrowell, Peter

    2003-01-01

    We compare the potential energy at zero temperature of a range of crystal structures for a glass-forming binary mixture of Lennard-Jones particles. The lowest-energy ordered state consists of coexisting phases of a single component face centered cubic structure and an equimolar cesium chloride structure. An infinite number of layered crystal structures are identified with energies close to this ground state. We demonstrate that the finite size increase of the energy of the coexisting crystal with incoherent interfaces is sufficient to destabilize this ordered phase in simulations of typical size. Two specific local coordination structures are identified as of possible structural significance in the amorphous state. We observe rapid crystal growth in the equimolar mixture

  3. Immobilization of enzymes by radiation-induced polymerization of glass-forming monomers

    International Nuclear Information System (INIS)

    Yoshida, M.; Kumakura, M.; Kaetsu, I.

    1979-01-01

    The effect of cooling rate of a monomeric system on the porosity and activity of an immobilized enzyme prepared by radiation-induced polymerization of 2-hydroxyethyl methacrylate at low temperatures has been studied. Slow cooling gave the same effect on porosity of the polymer as decreasing the monomer concentration. A glass-forming solvent such as diethylene glycol was added to water to study the effect of the supercooling tendency of the solvent. Addition of diethylene glycol decreased porosity and also enzymic activity. Water was replaced by the miscible solvent p-dioxane and the immiscible solvent n-decane in order to clarify the effect of solvent. p-Dioxane had a similar effect to water on the relation between the monomer concentration, porosity and activity. On the other hand, polymer prepared from the system containing n-decane showed different immobilization properties owing to the presence of independent pores in the matrix. (author)

  4. Liquid composition having ammonia borane and decomposing to form hydrogen and liquid reaction product

    Science.gov (United States)

    Davis, Benjamin L; Rekken, Brian D

    2014-04-01

    Liquid compositions of ammonia borane and a suitably chosen amine borane material were prepared and subjected to conditions suitable for their thermal decomposition in a closed system that resulted in hydrogen and a liquid reaction product.

  5. Osteoconductive properties of two different bioactive glass forms (powder and fiber) combined with collagen

    Science.gov (United States)

    Magri, Angela Maria Paiva; Fernandes, Kelly Rossetti; Ueno, Fabio Roberto; Kido, Hueliton Wilian; da Silva, Antonio Carlos; Braga, Francisco José Correa; Granito, Renata Neves; Gabbai-Armelin, Paulo Roberto; Rennó, Ana Claudia Muniz

    2017-11-01

    Bioactive Glasses (BG) is a group of synthetic silica-based materials with the unique ability to bond to living bone and can be used in bone repair. Although the osteogenic potential of BG, this material may have not present sufficient osteoconductive and osteoinductive properties to allow bone regeneration, especially in compromised situations. In order to overcome this limitation, it was proposed the combination the BG in two forms (powder and fiber) combined with collagen type I (COL-1). The aim of this study was to evaluate the BG/COL-based materials in terms of morphological characteristics, physicochemical features and mineralization. Additionally, the second objective was to investigate and compare the osteoconductive properties of two different bioactive glass forms (powder and fiber) enriched or not with collagen using a tibial bone defect model in rats. For this, four different formulations (BG powder - BGp, BG powder enriched with collagen - BGp/Col, BG fibers - BGf and BGp fibers enriched with collagen - BGf/Col) were developed. The physicochemical and morphological modifications were analyzed by SEM, FTIR, calcium assay and pH measurement. For in vivo evaluations, histopathology, morphometrical and immunohistochemistry were performed in a tibial defect in rats. The FTIR analysis indicated that BGp and BGf maintained the characteristic peaks for this class of material. Furthermore, the calcium assay showed an increased Ca uptake in the BG fibers. The pH measurements revealed that BGp (with or without collagen) presented higher pH values compared to BGf. In addition, the histological analysis demonstrated no inflammation for all groups at the site of the injury, besides a faster material degradation and higher bone ingrowth for groups with collagen. The immunohistochemistry analysis demonstrated Runx-2 and Rank-L expression for all the groups. Those findings support that BGp with collagen can be a promising alternative for treating fracture of difficult

  6. Mean shear resistance at steady-state for wet glass beads impact of liquid content and particle size

    Science.gov (United States)

    Louati, Haithem; Oulahna, Driss; de Ryck, Alain

    2017-06-01

    The flow behaviour of a granular media is due to their weight, frictional contact forces between them, and external forces exerted by the walls. If their size is lower than 50 microns, the Van-der-Waals forces between them may also influence their flowability. When adding some wetting liquid, we introduce attractive forces between the particles, whose order of magnitude may overcome the particle weight and V-d-W interactions. This leads to a cohesive behaviour. The shear stress to start the flow is greater than in the dry case but the steady-state flow is also perturbed by the presence of liquid bridges. This later phenomenon has been recently quantitatively studied for 70-110 μm glass beads with a non-volatile liquid, with experimental results for different normal stresses (up to 12 kPa) and liquid content (up to 20 % in volume). These results have been compared to a heuristic model, based on the model for capillary bridges and the simplest hypothesis for the granular bed texture depending on the stresses applied. We extend this study with new results concerning smaller glass beads 12-40 μm in diameter and larger liquid fraction for 70-110 μm glass beads using experimental and theoretical approaches.

  7. Characteristics of borosilicate waste glass form for high-level radioactive waste

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seung Soo; Chun, Kwan Sik; Choi, Jong Won; Kang, Chul Hyung

    2001-03-01

    Basic data, required for the design and the performance assessment of a repository of HLW, suchas the chemical composition and the characteristics of the borosilicate waste glass have been identified according to the burn-ups of spent PWR fuels. The diemnsion of waste canister is 430mm in diameter and 1135mm in length, and the canister should hold less than 2kwatts of heat from their decay of radionuclides contained in the HLW. Based on the reprocessing of 5 years-cooled spent fuel, one canister could hold about 11.5wt.% and 10.8wt.% of oxidized HLW corresponding to their burn-ups of 45,000MWD/MTU and 55,000MWD/MTU, respectively. These waste forms have been recommanded as the reference waste forms of HLW. The characteristics of these wastes as a function of decay time been evaluated. However, after a specific waste form and a specific site for the disposal would be selected, the characteristics of the waste should be reevaluated under the consideration of solidification period, loaded waste, storage condition and duration, site circumstances for the repository system and its performance assessment.

  8. Estimates of radionuclide release from glass waste forms in a tuff repository and the effects on regulatory compliance

    International Nuclear Information System (INIS)

    Aines, R.D.

    1986-04-01

    This paper discusses preliminary estimates of the release of radionuclides from waste packages containing glass-based waste forms under the expected conditions at Yucca Mountain. These estimates can be used to evaluate the contribution of waste package performance toward meeting repository regulatory restrictions on radionuclide release. Glass waste will be held in double stainless steel canisters. After failure of the container sometime after the 300 to 1000 year containment period, the open headspace in these cans will provide the only area where standing water can accumulate and react with the glass. A maximum release rate of 0.177 g/m 2 x year or 1.3 grams per year was obtained. Normalized loss of 1.3 grams per year corresponds to 0.08 parts in 100,000 per year of the 1660 kg reference weight of DWPF glass

  9. Glass composition development for plasma processing of Hanford high sodium content low-level radioactive liquid waste

    International Nuclear Information System (INIS)

    Marra, J.C.

    1995-02-01

    To assess the acceptability of prospective compositions, response criteria based on durability, homogeneity, viscosity and volatility were defined. Response variables were weighted: durability 35%, homogeneity 25%, viscosity 25%, volatility 15%. A Plackett-Burman experimental design was used to define the first twelve glass formulations. Glass former additives included Al2O3, B2O3, CaO, Li2O, ZrO2 and SiO2. Lithia was added to facilitate fritting of the additives. The additives were normalized to silica content to ease experimental matrix definition and glass formulation. Preset high and low values of these ratios were determined for the initial twelve melts. Based on rankings of initial compositions, new formulations for testing were developed based on a simplex algorithm. Rating and ranking of subsequent compositions continued until no apparent improvement in glass quality was achieved in newly developed formulations. An optimized composition was determined by averaging the additive component values of the final best performing compositions. The glass former contents to form the optimized glass were: 16.1 wt % Al2O3, 12.3 wt % B2O3, 5.5 wt % CaO, 1.7 wt % Li2O, 3.3 wt % ZrO2, 61.1 wt % SiO2. An optimized composition resulted after only 25 trials despite studying six glass additives. A vitrification campaign was completed using a small-scale Joule heated melter. 80 lbs of glass was produced over 96 hours of continuous operation. Several salt compounds formed and deposited on melter components during the run and likely caused the failure of several pour chamber heaters. In an attempt to minimize sodium volatility, several low or no boron glasses were formulated. One composition containing no boron produced a homogeneous glass worthy of additional testing

  10. Study of the confined solutions properties: case of gel formed during nuclear glass alteration

    International Nuclear Information System (INIS)

    Matar-Briman, I.

    2012-01-01

    In this study, we have investigated the thermodynamic properties, the structure and the dynamics of confined solutions in model gels and in a gel coming from glass alteration. The first step was to determine the structure and the dynamics of pure confined water in porous materials by using nuclear magnetic resonance and neutron scattering. Meso-porous silica was elaborated and grafted by sol-gel route to decrease the pore sizes from 2.7 to 2 nm and to modify pore surfaces to have Si-OH, Zr-OH and Al-OH. The second step involved determining the dynamics of water in leachate confined in the model gels and in the gel of altered glass by using neutron scattering. In the model gels and at a 10 -12 -10 -9 second timescale, two kinds of waters were highlighted: first, an interfacial water linked to the pore surfaces and second, a free water in the pore core. Their ratio depends on the pore size and pore surface composition. Whatever the pore surface, when the pore size decreases the free water ratio in the pore center also decreases. For pores smaller than 2.3 nm and pore surfaces with Zr-OH or Al-OH surfaces, water is strongly linked to the surface and few water molecules are mobile. This is due to the ability of alumina and zirconia to immobilize water molecules through chemical coordination bonds stronger than the physical bonds established between silica and water. The result also highlight that pore surface composition could be the predominant parameter affecting the fixed proton content. Moreover, the mobility of water confined in a leachate is not modified. The study of the water dynamics in a gel formed during alteration of glass constituted of SiO 2 , Al 2 O 3 and CaO, and having a porosity between 2 and 7 nm showed the same behavior as water confined in pores presenting an Al-OH surface. (author) [fr

  11. Preparation and characterization of Fe-based bulk metallic glasses in plate form

    International Nuclear Information System (INIS)

    Lavorato, G.C.; Fiore, G.; Castellero, A.; Baricco, M.; Moya, J.A.

    2012-01-01

    Amorphous alloys with composition (at%) Fe 48 Cr 15 Mo 14 C 15 B 6 Gd 2 (alloy A) and Fe 48 Cr 15 Mo 14 C 15 B 6 Y 2 (alloy B) were prepared either using pure elements (A and B1) and a commercial AISI430 steel as a base material (B2). When prepared from pure elements both alloys (A and B1) could be cast in plate form with a fixed thickness of 2 mm and variable lengths between 10 and 20 mm by means of copper-mold injection in air atmosphere. In the case of alloy B2, prepared using commercial grade raw materials, rods of 2 mm diameter were obtained. X-ray diffraction and scanning electron microscopy observations confirmed that an amorphous structure was obtained in all the as-cast samples. A minor fraction of crystalline phases (oxides and carbides) was detected on the as-cast surface. Differential scanning calorimetry measurements showed a glass transition temperature at 856 K for alloy A and 841 K for alloy B1, and an onset crystallization temperature of 887 K for alloy A and 885 K for alloy B1. In the case of alloy B2 a slightly different crystallization sequence was observed. Values of hardness (∼13 GPa) and the Young modulus (∼180 GPa) were measured by nanoindentation for both the alloys. The effects of adverse casting conditions (such as air atmosphere, non-conventional injection copper mold casting and partial replacement of pure elements with commercial grade raw materials) on the glass formation and properties of the alloy are discussed.

  12. Preparation and characterization of Fe-based bulk metallic glasses in plate form

    Energy Technology Data Exchange (ETDEWEB)

    Lavorato, G.C. [INTECIN (FIUBA-CONICET), Paseo Colon 850, Capital Federal (Argentina); Dipartimento di Chimica IFM and NIS, Universita di Torino, Torino (Italy); Fiore, G.; Castellero, A.; Baricco, M. [Dipartimento di Chimica IFM and NIS, Universita di Torino, Torino (Italy); Moya, J.A., E-mail: jmoya.fi.uba@gmail.com [IESIING, Facultad de Ingenieria e Informatica, UCASAL, Salta (Argentina); CONICET (Argentina)

    2012-08-15

    Amorphous alloys with composition (at%) Fe{sub 48}Cr{sub 15}Mo{sub 14}C{sub 15}B{sub 6}Gd{sub 2} (alloy A) and Fe{sub 48}Cr{sub 15}Mo{sub 14}C{sub 15}B{sub 6}Y{sub 2} (alloy B) were prepared either using pure elements (A and B1) and a commercial AISI430 steel as a base material (B2). When prepared from pure elements both alloys (A and B1) could be cast in plate form with a fixed thickness of 2 mm and variable lengths between 10 and 20 mm by means of copper-mold injection in air atmosphere. In the case of alloy B2, prepared using commercial grade raw materials, rods of 2 mm diameter were obtained. X-ray diffraction and scanning electron microscopy observations confirmed that an amorphous structure was obtained in all the as-cast samples. A minor fraction of crystalline phases (oxides and carbides) was detected on the as-cast surface. Differential scanning calorimetry measurements showed a glass transition temperature at 856 K for alloy A and 841 K for alloy B1, and an onset crystallization temperature of 887 K for alloy A and 885 K for alloy B1. In the case of alloy B2 a slightly different crystallization sequence was observed. Values of hardness ({approx}13 GPa) and the Young modulus ({approx}180 GPa) were measured by nanoindentation for both the alloys. The effects of adverse casting conditions (such as air atmosphere, non-conventional injection copper mold casting and partial replacement of pure elements with commercial grade raw materials) on the glass formation and properties of the alloy are discussed.

  13. In-plane spectroscopy with optical fibers and liquid-filled APEX™ glass microcuvettes

    International Nuclear Information System (INIS)

    Gaillard, William R; Tantawi, Khalid Hasan; Williams, John D; Waddell, Emanuel; Fedorov, Vladimir

    2013-01-01

    Chemical etching and laser drilling of microstructural glass results in opaque or translucent sidewalls, limiting the optical analysis of glass microfluidic devices to top down or non-planar topologies. These non-planar observation topologies prevent each layer of a multilayered device from being independently optically addressed. However, novel photosensitive glass processing techniques in APEX™ have resulted in microfabricated glass structures with transparent sidewalls. Toward the goal of a transparent multilayered glass microfluidic device, this study demonstrates the ability to perform spectroscopy with optical fibers and microcuvettes fabricated in photosensitive APEX™ glass. (technical note)

  14. Magnetic nanoparticles formed in glasses co-doped with iron and larger radius elements

    OpenAIRE

    Edelman , Irina; Ivanova , Oxana; Ivantsov , Ruslan; Velikanov , D.; Zabluda , V.; Zubavichus , Y.; Veligzhanin , A.; Zaikovskiy , V.; Stepanov , S.; Artemenko , Alla; Curély , Jacques; Kliava , Janis

    2012-01-01

    International audience; A new type of nanoparticle-containing glasses based on borate glasses co-doped with low contents of iron and larger radius elements, Dy, Tb, Gd, Ho, Er, Y, and Bi, is studied. Heat treatment of these glasses results in formation of magnetic nanoparticles, radically changing their physical properties. Transmission electron microscopy and synchrotron radiation-based techniques: x-ray diffraction, extended x-ray absorption fine structure, x-ray absorption near-edge struct...

  15. Cesium Hydroxide Fusion Dissolution of Analytical Reference Glass-1 in Both Powder and Shard Form

    International Nuclear Information System (INIS)

    Coleman, C.J.; Spencer, W.A.

    1998-04-01

    CsOH has been shown to be an effective and convenient dissolution reagent for Analytical Reference Glass-1 (ARG-1). This glass standard was prepared from nonradioactive DWPF Start-up Glass. Therefore, its composition is similar to DWPF product glass and many of the glass matrices prepared at SRTC.The principal advantage of the CsOH fusion dissolution is that the reagent does not add the alkali metals Li, Na, and K usually needed by SRS customers. Commercially available CsOH is quite pure so that alkali metals can be measured accurately, often without blank corrections. CsOH fusions provide a single dissolution method for applicable glass to replace multiple dissolution schemes used by most laboratories. For example, SRTC glass samples are most commonly dissolved with a Na 2 O 2 -NaOH fusion (ref.1) and a microwave- assisted acid dissolution with HNO 3 -HF-H 3 BO 3 -HCl (ref.2). Othe laboratories use fusion methods based on KOH, LiBO 2 , and Na 2 CO 3 CsOH fusion approach reduces by half not only the work in the dissolution laboratory, but also in the spectroscopy laboratories that must analyze each solution.Experiments also revealed that glass shards or pellets are rapidly attacked if the flux temperature is raised considerably above the glass softening point. The softening point of ARG-1 glass is near 650 degrees C. Fusions performed at 750 degrees C provided complete dissolutions and accurate elemental analyses of shards. Successful dissolution of glass shards was demonstrated with CsOH, Na 2 O 2 , NaOH, KOH, and RbOH. Ability to dissolve glass shards is of considerable practical importance. Crushing glass to a fine powder is a slow and tedious task, especially for radioactive glasses dissolved in shielded cells. CsOH fusion of glass powder or shards is a convenient, cost-effective dissolution scheme applicable in SRTC, the DWPF, and the commercial glass industry

  16. Effect of Mo-Fe substitution on glass forming ability, thermal stability, and hardness of Fe-C-B-Mo-Cr-W bulk amorphous alloys

    Energy Technology Data Exchange (ETDEWEB)

    Khalifa, Hesham E.; Cheney, Justin L. [University of California, San Diego Materials Science and Engineering Program, 9500 Gilman Drive, La Jolla, CA 92093-0411 (United States); Vecchio, Kenneth S. [University of California, San Diego Department of NanoEngineering, 9500 Gilman Drive, La Jolla, CA 92093-0411 (United States)], E-mail: kvecchio@ucsd.edu

    2008-08-25

    Amorphous Fe{sub 67-x}C{sub 10}B{sub 9}Mo{sub 7+x}Cr{sub 4}W{sub 3} (x = 1-7 at.%) plates with 640 {mu}m thickness were prepared by copper mold casting. The thermal properties and microstructural development during heat treatments were investigated by a combination of differential scanning calorimetry (DSC), differential thermal analysis, and X-ray diffractometry (XRD). The glass forming ability (GFA) and activation energy for crystallization have a distinct dependence on Mo content. Fe{sub 62}C{sub 10}B{sub 9}Mo{sub 12}Cr{sub 4}W{sub 3} is the best glass former in this study, demonstrating a supercooled liquid region, {delta}T{sub x} = 51 K, and an activation energy for crystallization, Q = 453 kJ/mol. The GFA of alloys in this system was governed by elastic strain optimization resulting directly from the variation in Mo content. Heat treatments were performed to demonstrate resistance to crystallization under typical processing conditions. Alloys in this system exhibited a three-phase evolution during crystallization. A second set of heat treatments was performed to identify each phase. Hardness data was collected at each of the heat treatment conditions, and a bulk metallic glasses (BMG)-derived composite containing a Mo-rich phase exhibited Vickers Hardness in excess of 2000. The fully amorphous alloys had an average hardness approaching 1500.

  17. Thermo-physical characterization of the Fe_6_7Mo_6Ni_3_._5Cr_3_._5P_1_2C_5_._5B_2_._5 bulk metallic glass forming alloy

    International Nuclear Information System (INIS)

    Bochtler, Benedikt; Gross, Oliver; Gallino, Isabella; Busch, Ralf

    2016-01-01

    The iron-phosphorus based bulk metallic glass forming alloy Fe_6_7Mo_6Ni_3_._5Cr_3_._5P_1_2C_5_._5B_2_._5 is characterized with respect to its thermophysical properties, crystallization and relaxation behavior, as well as its viscosity. The alloy provides a high critical casting thickness of 13 mm, thus allowing for the casting of amorphous parts with a considerable size. Calorimetric measurements reveal the characteristic transformation temperatures, transformation enthalpies, and the specific heat capacity. The analyses show that no stable supercooled liquid region exists upon heating. The specific heat capacity data are used to calculate the enthalpy, entropy, and Gibbs free energy differences between the crystalline and the supercooled liquid state. The crystallization behavior of amorphous samples upon heating is analyzed by differential scanning calorimetry and X-ray diffraction, and a time-temperature-transformation diagram is constructed. Dilatometry is used to determine the thermal expansion behavior. The equilibrium viscosity below the glass transition as well as volume relaxation behavior are measured by three-point beam bending and dilatometry, respectively, to assess the kinetic fragility. With a kinetic fragility parameter of D* = 21.3, the alloy displays a rather strong liquid behavior. Viscosity above the melting point is determined using electromagnetic levitation in microgravity on a reduced gravity aircraft in cooperation with the German Aerospace Center (DLR). These high-temperature viscosity data are compared with the low-temperature three-point beam bending measurements. The alloy displays a strong liquid behavior at low temperatures and a fragile behavior at high temperatures. These results are analogous to the ones observed in several Zr-based bulk metallic glass forming liquids, indicating a strong to fragile liquid-liquid transition in the undercooled liquid, which is obscured by crystallization.

  18. A New Vogel-Like Law: Ionic Conductivity, Dielectric Relaxation and Viscosity Near the Glass Transition

    National Research Council Canada - National Science Library

    Bendler, John

    2001-01-01

    A model, based on defect diffusion, is developed that describes temperature and pressure dependence of dielectric relaxation, ionic conductivity and viscosity of glass-forming liquids near the glass...

  19. Structural Origin of the Enhanced Glass-Forming Ability Induced by Microalloying Y in the ZrCuAl Alloy

    Directory of Open Access Journals (Sweden)

    Gu-Qing Guo

    2016-03-01

    Full Text Available In this work, the structural origin of the enhanced glass-forming ability induced by microalloying Y in a ZrCuAl multicomponent system is studied by performing synchrotron radiation experiments combined with simulations. It is revealed that the addition of Y leads to the optimization of local structures, including: (1 more Zr-centered and Y-centered icosahedral-like clusters occur in the microstructure; (2 the atomic packing efficiency inside clusters and the regularity of clusters are both enhanced. These structural optimizations help to stabilize the amorphous structure in the ZrCuAlY system, and lead to a high glass-forming ability (GFA. The present work provides an understanding of GFAs in multicomponent alloys and will shed light on the development of more metallic glasses with high GFAs.

  20. Strong composition-dependence on glass-forming ability in Ni-(Ti,Zr)-Si pseudo-ternary alloys

    International Nuclear Information System (INIS)

    Yang, H.; Wang, J.Q.; Li, Y.

    2006-01-01

    The glass formation in Ni-(Ti,Zr)-Si pseudo-ternary alloys was studied. For suction casting, by carefully adjusting the alloy composition and studying the microstructure changes, the best glass-forming alloy with a 2 mm diameter is pinpointed in a narrow composition region of 57.5-58.5 at.% Ni, 36.5-38.5 at.% (Ti + Zr) and 5-5.5 at.% Si. The main competing crystalline phases, identified by XRD and SEM, were Ni 10 (Zr,Ti) 7 , Ni(Ti,Zr) and an unidentified Si-containing phase. Our results indicate a clear need for monitoring the microstructure change in the cross section of the ingots to locate the best glass-forming alloys

  1. Experimental Study on Ice Forming Process of Cryogenic Liquid Releasing underwater

    Science.gov (United States)

    Zhang, Bin; Wu, Wanqing; Zhang, Xingdong; Zhang, Yi; Zhang, Chuanlin; Zhang, Haoran; Wang, Peng

    2017-11-01

    Cryogenic liquid releasing into water would be a process combines hyperactive boiling with ice forming. There are still few researches on the experimental study on the environmental conditions for deciding ice forming speed and liquid surviving state. In this paper, to advance our understanding of ice forming deciding factors in the process of LN2 releasing underwater, a visualization experimental system is built. The results show that the pressure difference significantly influences the ice forming speed and liquid surviving distance, which is observed by the experiment and theoretically analysed by Kelvin-Helmholtz instability. Adding nucleating agent is helpful to provide ice nucleus which can accelerate the ice forming speed. Water flowing has some effect on changing pressure difference, which can affect the ice forming speed and liquid surviving distance.

  2. Crystal growth nucleation and Fermi energy equalization of intrinsic spherical nuclei in glass-forming melts

    Directory of Open Access Journals (Sweden)

    Robert F Tournier

    2009-01-01

    Full Text Available The energy saving resulting from the equalization of Fermi energies of a crystal and its melt is added to the Gibbs free-energy change ΔG2ls associated with a crystal formation in glass-forming melts. This negative contribution being a fraction ε ls(T of the fusion heat is created by the electrostatic potential energy −U0 resulting from the electron transfer from the crystal to the melt and is maximum at the melting temperature Tm in agreement with a thermodynamics constraint. The homogeneous nucleation critical temperature T2, the nucleation critical barrier ΔG2ls*/kBT and the critical radius R*2ls are determined as functions of εls(T. In bulk metallic glass forming melts, εls(T and T2 only depend on the free-volume disappearance temperature T0l, and εls(Tm is larger than 1 (T0l>Tm/3; in conventional undercooled melts εls(Tm is smaller than 1 (T0l>Tm/3. Unmelted intrinsic crystals act as growth nuclei reducing ΔG2ls*/kBT and the nucleation time. The temperature-time transformation diagrams of Mg65Y10 Cu25, Zr41.2Ti13.8 Cu12.5Ni10Be22.5, Pd43Cu27 Ni10P20, Fe83B17 and Ni melts are predicted using classic nucleation models including time lags in transient nucleation, by varying the intrinsic nucleus contribution to the reduction of ΔG2ls*/kBT. The energy-saving coefficient ε nm(T of an unmelted crystal of radius Rnm is reduced when Rnm LtR*2ls; εnm is quantified and corresponds to the first energy level of one s-electron moving in vacuum in the same spherical attractive potential −U0 despite the fact that the charge screening is built by many-body effects.

  3. Relationships between biomass composition and liquid products formed via pyrolysis

    Directory of Open Access Journals (Sweden)

    Fan eLin

    2015-10-01

    Full Text Available Thermal conversion of biomass is a rapid, low-cost way to produce a dense liquid product, known as bio-oil, that can be refined to transportation fuels. However, utilization of bio-oil is challenging due to its chemical complexity, acidity, and instability—all results of the intricate nature of biomass. A clear understanding of how biomass properties impact yield and composition of thermal products will provide guidance to optimize both biomass and conditions for thermal conversion. To aid elucidation of these associations, we first describe biomass polymers, including phenolics, polysaccharides, acetyl groups, and inorganic ions, and the chemical interactions among them. We then discuss evidence for three roles (i.e., models for biomass components in formation of liquid pyrolysis products: (1 as direct sources, (2 as catalysts, and (3 as indirect factors whereby chemical interactions among components and/or cell wall structural features impact thermal conversion products. We highlight associations that might be utilized to optimize biomass content prior to pyrolysis, though a more detailed characterization is required to understand indirect effects. In combination with high-throughput biomass characterization techniques this knowledge will enable identification of biomass particularly suited for biofuel production and can also guide genetic engineering of bioenergy crops to improve biomass features.

  4. Relationships between Biomass Composition and Liquid Products Formed via Pyrolysis

    International Nuclear Information System (INIS)

    Lin, Fan; Waters, Christopher L.; Mallinson, Richard G.; Lobban, Lance L.; Bartley, Laura E.

    2015-01-01

    Thermal conversion of biomass is a rapid, low-cost way to produce a dense liquid product, known as bio-oil, that can be refined to transportation fuels. However, utilization of bio-oil is challenging due to its chemical complexity, acidity, and instability – all results of the intricate nature of biomass. A clear understanding of how biomass properties impact yield and composition of thermal products will provide guidance to optimize both biomass and conditions for thermal conversion. To aid elucidation of these associations, we first describe biomass polymers, including phenolics, polysaccharides, acetyl groups, and inorganic ions, and the chemical interactions among them. We then discuss evidence for three roles (i.e., models) for biomass components in the formation of liquid pyrolysis products: (1) as direct sources, (2) as catalysts, and (3) as indirect factors whereby chemical interactions among components and/or cell wall structural features impact thermal conversion products. We highlight associations that might be utilized to optimize biomass content prior to pyrolysis, though a more detailed characterization is required to understand indirect effects. In combination with high-throughput biomass characterization techniques, this knowledge will enable identification of biomass particularly suited for biofuel production and can also guide genetic engineering of bioenergy crops to improve biomass features.

  5. Hybrid Glasses from Strong and Fragile Metal-Organic Framework Liquids

    DEFF Research Database (Denmark)

    Bennett, T.D.; Tan, J.C.; Yue, Yuanzheng

    2015-01-01

    Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship betwee...

  6. Applications of High Energy Ion Beam Techniques in Environmental Science: Investigation Associated with Glass and Ceramic Waste Forms

    Energy Technology Data Exchange (ETDEWEB)

    Thevuthasan, Suntharampillai; Shutthanandan, V; Zhang, Yanwen

    2006-02-01

    High energy ion beam capabilities including Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA) have been very effectively used in environmental science to investigate the ion exchange mechanisms in glass waste forms and the effects of irradiation in glass and ceramic waste forms in the past. In this study, RBS and NRA along with SIMNRA simulations were used to monitor the Na depletion and D and 18O uptake in alumina silicate glasses, respectively, after the glass coupons were exposed to aqueous solution. These results show that the formation of a reaction layer and an establishment of a region where diffusion limited ion exchange occur in these glasses during exposure to silica-saturated solutions. Different regions including reaction and diffusion regions were identified on the basis of the depth distributions of these elements. In the case of ceramics, damage accumulation was studied as a function of ion dose at different irradiation temperatures. A sigmoidal dependence of relative disorder on the ion dose was observed. The defect dechanneling factors were calculated for two irradiated regions in SrTiO? using the critical angles determined from the angular yield curves. The dependence of defect dechanneling parameter on the incident energy was investigated and it was observed that the generated defects are mostly interstitial atoms and amorphous clusters. Thermal recovery experiments were performed to study the damage recovery processes up to a maximum temperature of 870 K.

  7. Effect of low dose electron beam irradiation on the alteration layer formed during nuclear glass leaching

    Energy Technology Data Exchange (ETDEWEB)

    Mougnaud, S., E-mail: sarah.mougnaud@gmail.com [CEA Marcoule, DEN, DTCD, SECM, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Tribet, M. [CEA Marcoule, DEN, DTCD, SECM, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Renault, J.-P. [NIMBE, CNRS, CEA, Université Paris Saclay, CEA Saclay, 91191 Gif-sur-Yvette cedex (France); Jollivet, P. [CEA Marcoule, DEN, DTCD, SECM, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Panczer, G. [Institut Lumière Matière, UMR 5306, Université Lyon 1-CNRS, Université de Lyon, 69622 Villeurbanne cedex (France); Charpentier, T. [NIMBE, CNRS, CEA, Université Paris Saclay, CEA Saclay, 91191 Gif-sur-Yvette cedex (France); Jégou, C. [CEA Marcoule, DEN, DTCD, SECM, BP 17171, 30207 Bagnols-sur-Cèze cedex (France)

    2016-12-15

    This investigation concerns borosilicate glass leaching mechanisms and the evolution of alteration layer under electron beam irradiation. A simple glass doped with rare earth elements was selected in order to access mechanistic and structural information and better evaluate the effects of irradiation. It was fully leached in initially pure water at 90 °C and at high glass surface area to solution volume ratio (S/V = 20 000 m{sup −1}) in static conditions. Under these conditions, the system quickly reaches the residual alteration rate regime. A small particle size fraction (2–5 μm) was sampled in order to obtain a fairly homogeneous altered material enabling the use of bulk characterization methods. External irradiations with 10 MeV electrons up to a dose of 10 MGy were performed either before or after leaching, to investigate respectively the effect of initial glass irradiation on its alteration behavior and the irradiation stability of the alteration layer. Glass dissolution rate was analyzed by regular leachate samplings and the alteration layer structure was characterized by Raman, luminescence (continuous or time-resolved), and {sup 29}Si MAS NMR and EPR spectroscopy. It was shown that the small initial glass evolutions under irradiation did not induce any modification of the leaching kinetic nor of the structure of the alteration layer. The alteration process seemed to “smooth over” the created defects. Otherwise, the alteration layer and initial glass appeared to have different behaviors under irradiation. No Eu{sup 3+} reduction was detected in the alteration layer after irradiation and the defect creation efficiency was much lower than for initial glass. This can possibly be explained by the protective role of pore water contained in the altered material (∼20%). Moreover, a slight depolymerization of the silicon network of the altered glass under irradiation with electrons was evidenced, whereas in the initial glass it typically

  8. GLAD: The IPNS (Intense Pulsed Neutron Source) Glass, Liquid, and Amorphous materials Diffractometer

    International Nuclear Information System (INIS)

    Crawford, R.K.; Price, D.L.; Haumann, J.R.; Kleb, R.; Montague, D.G.; Carpenter, J.M.; Susman, S.; Dejus, R.J.

    1989-01-01

    A number of years of experience in diffraction from amorphous materials has now been accumulated at various pulsed neutron sources. Workshops t IPNS and elsewhere have distilled some of this experience to provide a set of criteria for a new diffractometer dedicated to an optimized for structural studies of amorphous materials. This paper discusses the instrument GLAD (Glass, Liquid, and Amorphous Materials Diffractometer) which has been designed to meet these criteria and is now being built at IPNS. This instrument involves the use of relatively short-wavelength neutrons and a sophisticated neutron detection and acquisition system. A preliminary, simplified version of the instrument has been constructed while the final version is still under design, in order to develop the data acquisition and analysis techniques and to develop methods for collection of data with adequate quality (low background) at short wavelengths. This paper will briefly outline the final instrument envisioned and its calculated performance, but will focus mostly on the details of the detection/acquisition system and the calibration and data collection procedures which have been developed. The brief operating experience which has been gained to data with the preliminary instrument version will also be summarized. 6 refs., 12 figs

  9. Bulk metallic glass matrix composites

    International Nuclear Information System (INIS)

    Choi-Yim, H.; Johnson, W.L.

    1997-01-01

    Composites with a bulk metallic glass matrix were synthesized and characterized. This was made possible by the recent development of bulk metallic glasses that exhibit high resistance to crystallization in the undercooled liquid state. In this letter, experimental methods for processing metallic glass composites are introduced. Three different bulk metallic glass forming alloys were used as the matrix materials. Both ceramics and metals were introduced as reinforcement into the metallic glass. The metallic glass matrix remained amorphous after adding up to a 30 vol% fraction of particles or short wires. X-ray diffraction patterns of the composites show only peaks from the second phase particles superimposed on the broad diffuse maxima from the amorphous phase. Optical micrographs reveal uniformly distributed particles in the matrix. The glass transition of the amorphous matrix and the crystallization behavior of the composites were studied by calorimetric methods. copyright 1997 American Institute of Physics

  10. Radiation-induced polymerization of glass-forming systems. VII. Polymerization in supercooled state under high pressure

    International Nuclear Information System (INIS)

    Kaetsu, I.; Yoshii, F.; Watanabe, Y.

    1978-01-01

    Radiation-induced polymerization of glass-forming monomers such as 2-hydroxyethyl methacrylate and glycidyl methacrylate under high pressure was studied. The glass transition temperature of these monomers was heightened by increased pressure. The temperature dependence of polymerizability showed a characteristic relation, similar to those in supercooled-phase polymerization under normal pressure, that had a maximum at T/sub ν/ which shifted to higher levels of temperature as well as to T/sub g/ under high pressure. Polymerizability in the supercooled state also increased under increased pressure

  11. Research of decreasing of the cesium radionuclides discharge in the course pouring of the liquid glass from furnace EhP-500/1

    International Nuclear Information System (INIS)

    Sadovskij, B.F.; Borisov, N.B.; Dzekun, E.G.; Skobtsov, A.S.

    1996-01-01

    Cesium radionuclides discharge from the furnace liquid-glass discharge unit are studied and estimates of cesium emission from the glass melt by the stream flow-out and filling the waste storage capacity are performed. The ways for decreasing cesium discharges are indicated and new additional aerosol protection system for high-active glass discharge, providing for high protection efficiency is proposed. 10 refs., 1 fig., 1 tab

  12. Development of new waste form for treatment and disposal of concentrated liquid radioactive waste

    International Nuclear Information System (INIS)

    Kwak, Kyung Kil; Ji, Young Yong

    2010-12-01

    The radioactive waste form should be meet the waste acceptance criteria of national regulation and disposal site specification. We carried out a characterization of rad waste form, especially the characteristics of radioactivity, mechanical and physical-chemical properties in various rad waste forms. But asphalt products is not acceptable waste form at disposal site. Thus we are change the product materials. We select the development of the new process or new materials. The asphalt process is treatment of concentrated liquid and spent-resin and that we decide the Development of new waste form for treatment and disposal of concentrated liquid radioactive waste

  13. Solution exchange corrosion testing with the glass-zeolite ceramic waste form in demineralized water at 900C

    International Nuclear Information System (INIS)

    Simpson, L. J.

    1998-01-01

    A ceramic waste form of glass-bonded zeolite is being developed for the long-term disposition of fission products and transuranic elements in wastes from the U.S. Department of Energy's spent nuclear fuel conditioning activities. Solution exchange corrosion tests were performed on the ceramic waste form and its potential base constituents of glass, zeolite 5A, and sodalite as part of an effort to qualify the ceramic waste form for acceptance into the Civilian Radioactive Waste Management System. Solution exchange tests were performed at 90 C by replacing 80 to 90% of the leachate with fresh demineralized water after set time intervals. The results from these tests provide information about corrosion mechanisms and the ability of the ceramic waste form and its constituent materials to retain waste components. The results from solution exchange tests indicate that radionuclides will be preferentially retained in the zeolites without the glass matrix and in the ceramic waste form, with respect to cations like Li, K, and Na. Release results have been compared for simulated waste from candidate ceramic waste forms with zeolite 5A and its constituent materials to determine the corrosion behavior of each component

  14. Parallel Object Oriented MD Simulation Program for Long Time Simulations of Metallic Glasses and Undercooled Liquids

    Science.gov (United States)

    Böddeker, B.; Teichler, H.

    The MD simulation program TABB is motivated by the need of long time simulations for the investigation of slow processes near the glass transition of glass forming alloys. TABB is written in C++ with a high degree of flexibility: TABB allows the use of any short ranged pair potentials or EAM potentials, by generating and using a spline representation of all functions and their derivatives. TABB supports several numerical integration algorithms like the Runge-Kotta or the modified Gear-predictor-corrector algorithm of order five. The boundary conditions can be chosen to resemble the geometry of bulk materials or films. The simulation box length or the pressure can be fixed for each dimension separately. TABB may be used in isokinetic, isoenergeric or canonic (with random forces) mode. TABB contains a simple instruction interpreter to easily control the parameters and options during the simulation. The same source code can be compiled either for workstations or for parallel computers. The main optimization goal of TABB is to allow long time simulations of medium or small sized systems. To make this possible, much attention is spent on the optimized communication between the nodes. TABB uses a domain decomposition procedure. To use many nodes with a small system, the domain size has to be small compared to the range of particle interactions. In the limit of many nodes for only few atoms, the bottle neck of communication is the latency time. TABB minimizes the number of pairs of domains containing atoms that interact between these domains. This procedure minimizes the need of communication calls between pairs of nodes. TABB decides automatically, to how many, and to which directions the decomposition shall be applied. E.g., in the case of one dimensional domain decomposition, the simulation box is only split into "slabs" along a selected direction. The three dimensional domain decomposition is best with respect to the number of interacting domains only for simulations

  15. Apollo 12 ropy glasses revisited

    Science.gov (United States)

    Wentworth, S. J.; Mckay, D. S.; Lindstrom, D. J.; Basu, A.; Martinez, R. R.; Bogard, D. D.; Garrison, D. H.

    1994-01-01

    We analyzed ropy glasses from Apollo 12 soils 12032 and 12033 by a variety of techniques including SEM/EDX, electron microprobe analysis, INAA, and Ar-39-Ar-40 age dating. The ropy glasses have potassium rare earth elements phosphorous (KREEP)-like compositions different from those of local Apollo 12 mare soils; it is likely that the ropy glasses are of exotic origin. Mixing calculations indicate that the ropy glasses formed from a liquid enriched in KREEP and that the ropy glass liquid also contained a significant amount of mare material. The presence of solar Ar and a trace of regolith-derived glass within the ropy glasses are evidence that the ropy glasses contain a small regolith component. Anorthosite and crystalline breccia (KREEP) clasts occur in some ropy glasses. We also found within these glasses clasts of felsite (fine-grained granitic fragments) very similar in texture and composition to the larger Apollo 12 felsites, which have a Ar-39-Ar-40 degassing age of 800 +/- 15 Ma. Measurements of 39-Ar-40-Ar in 12032 ropy glass indicate that it was degassed at the same time as the large felsite although the ropy glass was not completely degassed. The ropy glasses and felsites, therefore, probably came from the same source. Most early investigators suggested that the Apollo 12 ropy glasses were part of the ejecta deposited at the Apollo 12 site from the Copernicus impact. Our new data reinforce this model. If these ropy glasses are from Copernicus, they provide new clues to the nature of the target material at the Copernicus site, a part of the Moon that has not been sampled directly.

  16. Crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics for immobilization of simulated sulfate bearing high-level liquid waste

    Science.gov (United States)

    Wu, Lang; Xiao, Jizong; Wang, Xin; Teng, Yuancheng; Li, Yuxiang; Liao, Qilong

    2018-01-01

    The crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics with different content (0-30 wt %) of simulated sulfate bearing high-level liquid waste (HLLW) were evaluated. The sulfate phase segregation in vitrification process was also investigated. The results show that the glass-ceramics with 0-20 wt% of HLLW possess mainly zirconolite phase along with a small amount baddeleyite phase. The amount of perovskite crystals increases while the amount of zirconolite crystals decreases when the HLLW content increases from 20 to 30 wt%. For the samples with 20-30 wt% HLLW, yellow phase was observed during the vitrification process and it disappeared after melting at 1150 °C for 2 h. The viscosity of the sample with 16 wt% HLLW (HLLW-16) is about 27 dPa·s at 1150 °C. The addition of a certain amount (≤20 wt %) of HLLW has no significant change on the aqueous stability of glass-ceramic waste forms. After 28 days, the 90 °C PCT-type normalized leaching rates of Na, B, Si, and La of the sample HLLW-16 are 7.23 × 10-3, 1.57 × 10-3, 8.06 × 10-4, and 1.23 × 10-4 g·m-2·d-1, respectively.

  17. Platinum catalyst formed on carbon nanotube by the in-liquid plasma method for fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Show, Yoshiyuki; Hirai, Akira; Almowarai, Anas; Ueno, Yutaro

    2015-12-01

    In-liquid plasma was generated in the carbon nanotube (CNT) dispersion fluid using platinum electrodes. The generated plasma spattered the surface of the platinum electrodes and dispersed platinum particles into the CNT dispersion. Therefore, the platinum nanoparticles were successfully formed on the CNT surface in the dispersion. The platinum nanoparticles were applied to the proton exchange membrane fuel cell (PEMFC) as a catalyst. The electrical power of 108 mW/cm{sup 2} was observed from the fuel cell which was assembled with the platinum catalyst formed on the CNT by the in-liquid plasma method. - Highlights: • The platinum catalyst was successfully formed on the CNT surface in the dispersion by the in-liquid plasma method. • The electrical power of 108 mW/cm{sup 2} was observed from the fuel cell which was assembled with the platinum catalyst formed on the CNT by the in-liquid plasma method.

  18. Study of the environment and optical properties of Ti3+ ions formed under ionizing irradiations in oxide glasses

    International Nuclear Information System (INIS)

    Lombard, Pierre

    2009-10-01

    We studied by Electron Paramagnetic Resonance (EPR), by EPR simulation, by Raman spectroscopy and by photoluminescence the Ti 3+ ions formed under β-irradiation from 3, 37 * 10 5 to 1, 68 * 10 9 Gy in SiO 2 - Na 2 O - TiO 2 and SiO 2 - Al 2 0 3 - B 2 O 3 - Na 2 O - TiO 2 glasses. We demonstrate the existence of three different Ti 3+ sites in silicate glasses and three other Ti 3+ sites in alumino-borosilicate glasses. One of theses sites is common to both kind of glasses. Moreover, we associate theses sites to three different titanium environment: (VI)Ti 3+ (octahedral), (V)Ti 3+ square pyramid and may be (V)Ti 3+ trigonal bi - pyramid. The existence of theses sites is determined by the total integrated dose and by the [Na]/[Ti] ratio. We propose a definition of this ratio in the special case of SiO 2 - Al 2 O 3 - B 2 O 3 - Na 2 O - TiO 2 glasses. Last, under 266 nm excitation, we observe at room temperature an emission band at 500 nm attributed to Ti 4+ ions. Under a 532 nm excitation, we observe an emission band at 590 nm with a short lifetime (hundred of ns) attributed either to Ti 3+ ions or to an irradiation defect formed near a Ti 4+ ion. Our study demonstrate that is possible to control by the chemical composition and the integrated dose the Ti 3+ environment and the emission properties of this ion in an oxide glass. (author)

  19. Electronic-structure origin of the glass-forming ability and magnetic properties in Fe–RE–B–Nb bulk metallic glasses

    International Nuclear Information System (INIS)

    Li, J.W.; Estévez, D.; Jiang, K.M.; Yang, W.M.; Man, Q.K.; Chang, C.T.; Wang, X.M.

    2014-01-01

    Highlights: • Relation between GFA and electronic structure of RE doped BMGs is investigated. • Tm enhances RE–B bonds and decreases the density of states near the Fermi level. • Magnetic properties of the alloys are related to the electronic structure of RE. - Abstract: (Fe 0.71 RE 0.05 B 0.24 ) 96 Nb 4 (RE = Gd, Tb, Ho, Er, Tm) bulk metallic glasses (BMGs) were found exhibiting excellent glass-forming ability (GFA) with critical diameters ranging from 3.5 to 6.5 mm, and high compressive fracture strength larger than 4300 MPa. Moreover, they displayed good soft-magnetic properties with saturation magnetic flux density of 0.71–0.87 T, coercive force of 1.23–39.76 A/m and effective permeability of 1500–12,740 at 1 kHz. X-ray photoelectron spectroscopy was performed to clarify the origin of the excellent GFA from the viewpoint of electronic structure. It was found that the Tm doped alloy displayed unique electronic structure including the deepest core-level binding energy, the most numerous RE–B bonds and the minimum density of states near the Fermi level, making this alloy the best glass former. The various trends noticed in the magnetic properties were ascribed mainly to the differences in the magnetic anisotropy and magnetic moment of RE elements

  20. Thermoplastic forming of bulk metallic glasses for precision robotics components, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Demand for novel manufacturing methods for space systems brings unique properties of bulk metallic glasses (BMG) into the spotlight. In addition to superior...

  1. Characterization of surface layers formed under natural environmental conditions on medieval glass from Siponto (Southern Italy)

    International Nuclear Information System (INIS)

    Genga, Alessandra; Siciliano, Maria; Fama, Lia; Filippo, Emanuela; Siciliano, Tiziana; Mangone, Annarosa; Traini, Angela; Laganara, Caterina

    2008-01-01

    In this paper a low-vacuum scanning electron microscope (SEM) coupled with an energy-dispersive X-ray spectrometer (EDX) was used to investigate the alteration processes that occur on silica-soda-lime glass exposed to soil materials and dated from XI to second half of XIII sec. The chemical data were collected for altered glass gel and fresh glass. In order to study the influence of chemical composition on weathering process, 16 glasses have been selected on the basis of the chemical characterization and on the basis of the different corrosion processes present on the fragments. Six selected samples had been produced with the use of natron as fluxer and 10 samples with the use of plant ash as fluxer. The analysed pieces come from Siponto excavations (Foggia, Italy) and they include feet and rims of chalices, fragments of lamps and of globular bottles

  2. Contribution of electron microscopy to the study of alteration layers formed on the surface of glasses

    International Nuclear Information System (INIS)

    Crovisier, J.L.; Eberhart, J.P.

    1985-01-01

    In order to understand the whole process of glass corrosion in aqueous solutions, the analysis of the reagent must be completed by a study of the actual alteration layers on the glass surface. Transmission electron microscopy on ultramicrotomic thin sections turns out to be a most suitable tool to achieve this. It enables to supplement the conventional methods of surface investigation, such as A.E.S., ESCA, IRRS, SIMS. Two examples are given. The first deals with a (SiO 2 -CaO-Na 2 O-P 2 O 5 )- glass leached in a buffer solution of tris-hydromethyl-aminomethane at 40 0 C. The major feature is ion exchange within a residual porous glass, followed by the precipitation of hydroxyapatite. In the second example, a basaltic glass is altered in sea-water at 50 0 C. The glass constituents are dissolved simultaneously and the alteration layer is a precipitate of crystalline and amorphous phases which have reached their saturation level [fr

  3. A unified in vitro evaluation for apatite-forming ability of bioactive glasses and their variants.

    Science.gov (United States)

    Maçon, Anthony L B; Kim, Taek B; Valliant, Esther M; Goetschius, Kathryn; Brow, Richard K; Day, Delbert E; Hoppe, Alexander; Boccaccini, Aldo R; Kim, Ill Yong; Ohtsuki, Chikara; Kokubo, Tadashi; Osaka, Akiyoshi; Vallet-Regí, Maria; Arcos, Daniel; Fraile, Leandro; Salinas, Antonio J; Teixeira, Alexandra V; Vueva, Yuliya; Almeida, Rui M; Miola, Marta; Vitale-Brovarone, Chiara; Verné, Enrica; Höland, Wolfram; Jones, Julian R

    2015-02-01

    The aim of this study was to propose and validate a new unified method for testing dissolution rates of bioactive glasses and their variants, and the formation of calcium phosphate layer formation on their surface, which is an indicator of bioactivity. At present, comparison in the literature is difficult as many groups use different testing protocols. An ISO standard covers the use of simulated body fluid on standard shape materials but it does not take into account that bioactive glasses can have very different specific surface areas, as for glass powders. Validation of the proposed modified test was through round robin testing and comparison to the ISO standard where appropriate. The proposed test uses fixed mass per solution volume ratio and agitated solution. The round robin study showed differences in hydroxyapatite nucleation on glasses of different composition and between glasses of the same composition but different particle size. The results were reproducible between research facilities. Researchers should use this method when testing new glasses, or their variants, to enable comparison between the literature in the future.

  4. Glass forming ability and magnetic properties of Co(40.2−x)Fe(20.1+x)Ni6.7B22.7Si5.3Nb5 (x=0–10) bulk metallic glasses produced by suction casting

    International Nuclear Information System (INIS)

    Sarlar, Kagan; Kucuk, Ilker

    2015-01-01

    The effect of Fe concentration on the glass forming ability (GFA) and magnetic properties in Co (40.2−x) Fe (20.1+x) Ni 6.7 B 22.7 Si 5.3 Nb 5 (x=0–10) bulk metallic glasses were investigated. By suction casting method, the bulk metallic glasses with diameters up to 2 mm were produced. We try to find out which Fe concentration makes an influence on Co based system's magnetic properties and glass forming ability. The curves of thermal analysis, obtained using differential scanning calorimetry (DSC), show that the Co (40.2−x) Fe (20.1+x) Ni 6.7 B 22.7 Si 5.3 Nb 5 (x=0–10) have a supercooled liquid region (∆T x ) of about 44 K. The saturation magnetizations (J s ) for as-cast BMG alloys were in the range of 0.62 T−0.81 T. - Highlights: • The effect of Fe concentration on the glass forming ability. • The substitution of an appropriate amount of Fe can enhance the GFA. • The substitution of Fe for Co also improves soft magnetic properties of the BMGs. • The high of J s 0.62−0.81 T with a low H c of 2−289 A/m of the alloys

  5. Fe-based bulk metallic glasses with a larger supercooled liquid region and high ductility

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, K.Q. [School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110178 (China)], E-mail: kqqiu@yahoo.com.cn; Pang, J.; Ren, Y.L.; Zhang, H.B. [School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110178 (China); Ma, C.L.; Zhang, T. [School of Materials Science and Engineering, Beijing University of Aeronautics and Astronautics, Beijing 100083 (China)

    2008-12-20

    Bulk metallic glasses (BMGs) with compositions of Fe{sub 61.5-x}Co{sub 3}Mo{sub 14}C{sub 15}B{sub 6}Er{sub 0.5}M{sub x} (x = 2, 3; M = Ni, Nb) were fabricated by copper mold casting using raw industrial materials. The X-ray diffraction (XRD), differential scanning calorimetry (DSC), mechanical tester and scanning electron microscope (SEM) were employed to check the phase constituent, the thermal stability, the mechanical properties and the fracture surfaces of as-cast samples. The results indicate that the BMGs with diameters of 1.5-3 mm were fabricated for the alloys investigated. The largest supercooled liquid region (SLR) up to 76 K was found for Fe{sub 58.5}Co{sub 3}Mo{sub 14}C{sub 15}B{sub 6}Er{sub 0.5}Ni{sub 3} BMG. The BMGs with Ni addition exhibit not only high fracture strengths reaching 3770 MPa for x = 2 and 3980 MPa for x = 3 alloys, respectively, but also apparently plastic strains up to 0.67% and 0.93%, respectively. The fracture surfaces of the Fe{sub 61.5-x}Co{sub 3}Mo{sub 14}C{sub 15}B{sub 6}Er{sub 0.5}Ni{sub x} (x = 2, 3) alloys with plasticity show narrow ridges characteristic of venous patterns combining with tearing flow between the ridges. While the Nb containing alloys show not only a lower SLR below 60 K but also a lower stress below 2400 MPa, as well as almost no plastic strain before fracture.

  6. 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

  7. Determination of the Structure of Vitrified Hydroceramic/CBC Waste Form Glasses Manufactured from DOE Reprocessing Waste

    International Nuclear Information System (INIS)

    Scheetz, B.E.; White, W. B.; Chesleigh, M.; Portanova, A.; Olanrewaju, J.

    2005-01-01

    The selection of a glass-making option for the solidification of nuclear waste has dominated DOE waste form programs since the early 1980's. Both West Valley and Savannah River are routinely manufacturing glass logs from the high level waste inventory in tank sludges. However, for some wastes, direct conversion to glass is clearly not the optimum strategy for immobilization. INEEL, for example, has approximately 4400 m 3 of calcined high level waste with an activity that produces approximately 45 watts/m 3 , a rather low concentration of radioactive constituents. For these wastes, there is value in seeking alternatives to glass. An alternative approach has been developed and the efficacy of the process demonstrated that offers a significant savings in both human health and safety exposures and also a lower cost relative to the vitrification option. The alternative approach utilizes the intrinsic chemical reactivity of the highly alkaline waste with the addition of aluminosilicate admixtures in the appropriate proportions to form zeolites. The process is one in which a chemically bonded ceramic is produced. The driving force for reaction is derived from the chemical system itself at very modest temperatures and yet forms predominantly crystalline phases. Because the chemically bonded ceramic requires an aqueous medium to serve as a vehicle for the chemical reaction, the proposed zeolite-containing waste form can more adequately be described as a hydroceramic. The hydrated crystalline materials are then subject to hot isostatic pressing (HIP) which partially melts the material to form a glass ceramic. The scientific advantages of the hydroceramic/CBC approach are: (1) Low temperature processing; (2) High waste loading and thus only modest volumetric bulking from the addition of admixtures; (3) Ability to immobilize sodium; (4) Ability to handle low levels of nitrate (2-3% NO 3 - ); (5) The flexibility of a vitrifiable waste; and (6) A process that is based on an

  8. Calculation of glass forming ranges in Al-Ni-RE (Ce, La, Y) ternary alloys and their sub-binaries based on Miedema's model

    International Nuclear Information System (INIS)

    Sun, S.P.; Yi, D.Q.; Liu, H.Q.; Zang, B.; Jiang, Y.

    2010-01-01

    Research highlights: → A method based on semi-empirical Miedema's and Toop's model for predicting glass forming range of ternary alloy system has been systematically described. → The method is superior to conventional models by considering the effect of the thermodynamic asymmetric component when dealing with a ternary alloy system. → The glass forming ranges of Al-Ni-RE (Al-Ni-Ce, Al-Ni-Y and Al-Ni-La) systems and their sub-binaries have been successfully calculated. → The present calculations using the method are in well agreement with experiments. → This model is especially useful for predicting the glass forming range of ternary alloy system because the calculations do not require experimental data. - Abstract: A method based on the semi-empirical Miedema's and Toop's model for calculating the glass forming range of a ternary alloy system was systematically described. The method is superior to conventional models by considering the effect of the thermodynamic asymmetric component when dealing with a ternary alloy system. Using this method, the glass forming ranges of Al-Ni-RE (Ce, La, Y) systems and their sub-binaries were successfully predicted. The mixing enthalpy and mismatch entropy were calculated, and their effects on the glass forming abilities of Al-Ni-RE (Ce, La, Y) systems were also discussed. The glass forming abilities of Al-Ni-Ce, Al-Ni-La and Al-Ni-Y are found to be close. The calculated glass forming ranges agree with experiments well. Meanwhile, the enthalpy change from amorphous phase to solid solution in the glass forming ranges was calculated, and the results suggest that those alloys close to the Ni-RE sub-binary system have higher glass forming abilities.

  9. Glass forming tendencies of chalcogenides of the system (As2Se3)sub(1-x):(T12Se)sub(x)

    International Nuclear Information System (INIS)

    Majid, C.A.

    1982-07-01

    In this paper glass forming capabilities of chalcogenide glasses based on As 2 Se 3 with T1 2 Se concentrations are discussed. The studies were made using the differential thermal analysis (DTA) technique. These studies show that the glass forming tendency of As 2 Se 3 decreases as the concentrations of T1 2 Se molecules are increased. Also these studies show that with addition of T1 2 Se, the glass transition temperature Tsub(g) of As 2 Se 3 decreases, suggesting a tendency for weaker bonding and hence less stability of T1-rich compositions. (author)

  10. Glass transition behaviour of the quaternary ammonium type ionic liquid, {[DEME][I] + H2O} mixtures

    International Nuclear Information System (INIS)

    Imai, Yusuke; Abe, Hiroshi; Matsumoto, Hitoshi; Shimada, Osamu; Hanasaki, Tomonori; Yoshimura, Yukihiro

    2011-01-01

    By a simple DTA system, the glass transition temperatures of the quaternary ammonium type ionic liquid, {N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium iodide, [DEME][I] + H 2 O} mixtures after quick pre-cooling were measured as a function of water concentration (x mol% H 2 O). Results were compared with the previous results of {[DEME][BF 4 ] + H 2 O} mixtures in which double glass transitions were observed in the water concentration region of (16.5 to 30.0) mol% H 2 O. Remarkably, we observed the double glass transition phenomenon in {[DEME][I] + H 2 O} mixtures too, but the two-T g s regions lie towards the water-rich side of (77.5 to 85.0) mol% H 2 O. These clearly reflect the difference in the anionic effect between BF 4 - and I - on the water structure. The end of the glass-formation region of {[DEME][I] + H 2 O} mixtures is around x = 95.0 mol% H 2 O, and this is comparable to that of {[DEME][BF 4 ] + H 2 O} mixtures (x = 96.0 mol% H 2 O).

  11. Microstructural Control via Copious Nucleation Manipulated by In Situ Formed Nucleants: Large-Sized and Ductile Metallic Glass Composites.

    Science.gov (United States)

    Song, Wenli; Wu, Yuan; Wang, Hui; Liu, Xiongjun; Chen, Houwen; Guo, Zhenxi; Lu, Zhaoping

    2016-10-01

    A novel strategy to control the precipitation behavior of the austenitic phase, and to obtain large-sized, transformation-induced, plasticity-reinforced bulk metallic glass matrix composites, with good tensile properties, is proposed. By inducing heterogeneous nucleation of the transformable reinforcement via potent nucleants formed in situ, the characteristics of the austenitic phase are well manipulated. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Preparation of glass-forming materials from granulated blast furnace slag

    Science.gov (United States)

    Alonso, M.; Sáinz, E.; Lopez, F. A.

    1996-10-01

    Glass precursor materials, to be used for the vitrification of hazardous wastes, have been prepared from blast furnace slag powder through a sol-gel route. The slag is initially reacted with a mixture of alcohol (ethanol or methanol) and mineral acid (HNO3 or H2SO4) to give a sol principally consisting of Si, Ca, Al, and Mg alkoxides. Gelation is carried out with variable amounts of either ammonia or water. The gelation rate can be made as fast as desired by adding excess hydrolizing agent or else by distilling the excess alcohol out of the alkoxide solution. The resulting gel is first dried at low temperature and ground. The powder thus obtained is then heat treated at several temperatures. The intermediate and final materials are characterized by thermal analysis, infrared (IR) spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), and chemical analysis. From the results, the operating conditions yielding a variety of glass precursors differing in their composition are established. The method, in comparison with direct vitrification of slag, presents a number of advantages: (1) the glass precursor obtained devitrifies at higher temperatures; (2) it enables the adjustment, to a certain extent, of the chemical composition of the glass precursor; and (3) it permits recovering marketable materials at different stages of the process.

  13. Volume and enthalpy recovery of glass-forming polymers and the predictions controlled by internal energy

    Czech Academy of Sciences Publication Activity Database

    Říha, Pavel; Slobodian, P.; Kubát, J.

    2009-01-01

    Roč. 54, č. 1 (2009), s. 59-71 ISSN 0001-7043 R&D Projects: GA AV ČR IAA200600803 Institutional research plan: CEZ:AV0Z20600510 Keywords : a-PMMA * Glass transition * Aging * Cooperative relaxation model Subject RIV: BK - Fluid Dynamics

  14. Enhanced 99 Tc retention in glass waste form using Tc(IV)-incorporated Fe minerals

    Energy Technology Data Exchange (ETDEWEB)

    Um, Wooyong; Luksic, Steven A.; Wang, Guohui; Saslow, Sarah; Kim, Dong-Sang; Schweiger, Michael J.; Soderquist, Chuck Z.; Bowden, Mark E.; Lukens, Wayne W.; Kruger, Albert A.

    2017-11-01

    Technetium (99Tc) immobilization by doping into iron oxide mineral phases may alleviate the problems with Tc volatility during vitrification of nuclear waste. Reduced Tc, Tc(IV), substitutes for Fe(III) in the crystal structure by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation of Fe oxide minerals. Two Tc-incorporated Fe minerals (Tc-goethite and Tc-magnetite/maghemite) were prepared and tested for Tc retention in glass melt samples at temperatures between 600 – 1,000 oC. After being cooled, the solid glass specimens prepared at different temperatures were analyzed for Tc oxidation state using Tc K-edge XANES. In most samples, Tc was partially oxidized from Tc(IV) to Tc(VII) as the melt temperature increased. However, Tc retention in glass melt samples prepared using Tc-incorporated Fe minerals were moderately higher than in glass prepared using KTcO4 because of limited and delayed Tc volatilization.

  15. Mobility of supercooled liquid toluene, ethylbenzene, and benzene near their glass transition temperatures investigated using inert gas permeation.

    Science.gov (United States)

    May, R Alan; Smith, R Scott; Kay, Bruce D

    2013-11-21

    We investigate the mobility of supercooled liquid toluene, ethylbenzene, and benzene near their respective glass transition temperatures (Tg). The permeation rate of Ar, Kr, and Xe through the supercooled liquid created when initially amorphous overlayers are heated above their glass transition temperature is used to determine the diffusivity. Amorphous benzene crystallizes at temperatures well below its Tg, and as a result, the inert gas underlayer remains trapped until the onset of benzene desorption. In contrast, for toluene and ethylbenzene the onset of inert gas permeation is observed at temperatues near Tg. The inert gas desorption peak temperature as a function of the heating rate and overlayer thickness is used to quantify the diffusivity of supercooled liquid toluene and ethylbenzene from 115 to 135 K. In this temperature range, diffusivities are found to vary across 5 orders of magnitude (∼10(-14) to 10(-9) cm(2)/s). The diffusivity data are compared to viscosity measurements and reveal a breakdown in the Stokes-Einstein relationship at low temperatures. However, the data are well fit by the fractional Stokes-Einstein equation with an exponent of 0.66. Efforts to determine the diffusivity of a mixture of benzene and ethylbenzene are detailed, and the effect of mixing these materials on benzene crystallization is explored using infrared spectroscopy.

  16. Forming of film surface of very viscous liquid flowing with gas in pipes

    Directory of Open Access Journals (Sweden)

    Czernek Krystian

    2017-01-01

    Full Text Available The study presents the possible use of optoelectronic system for the measurement of the values, which are specific for hydrodynamics of two-phase gas liquid flow in vertical pipes, where a very-high-viscosity liquid forms a falling film in a pipe. The experimental method was provided, and the findings were presented and analysed for selected values, which characterize the two-phase flow. Attempt was also made to evaluate the effects of flow parameters and properties of the liquid on the gas-liquid interface value, which is decisive for the conditions of heat exchange and mass transfer in falling film equipment. The nature and form of created waves at various velocities were also described.

  17. Thermomechanical and calorimetric behaviours of supported glass-forming films: A study based on thermodynamics with internal variables

    International Nuclear Information System (INIS)

    Lion, Alexander; Engelhard, Marco; Johlitz, Michael

    2012-01-01

    In order to understand the temperature-dependent response behaviour of thin thermoviscoelastic films which are deposited on relative stiff but thermally deformable substrates it is important to consider the lateral geometric constraints. They are generated by differences in the thermal expansion properties between the substrate and the film and provoke internal stresses. Since glass-forming materials exhibit distinct temperature history-dependent thermal expansion and calorimetric properties, primarily in the vicinity of the glass transition, the situation is rather complicated. In this article, a recently developed three-dimensional model of thermodynamics with internal variables is applied and adapted to simulate this type of behaviour. Explicit relations are obtained for the specific heat of the film, the normal strain and the lateral stresses. Numerical simulations demonstrate that the magnitude of the internal stress at temperatures below the glass transition depends strongly on the cooling rate. It is also shown that the specific heat of the supported film is principally different from the isobaric specific heat of the bulk material: the glassy limit of the specific heat of the film is reduced but the glass transition temperature is almost uninfluenced. The simulated behaviour is in accordance with experimental observations from literature. - Highlights: ► For the specific heat, stress and strain of the film, explicit equations were derived. ► The constraints of the substrate reduce the glassy limit of specific heat of the film. ► Glass transition temperatures of free bulk material and supported film are equal. ► Simulations are in good agreement with experimental observations from literature.

  18. Thermomechanical and calorimetric behaviours of supported glass-forming films: A study based on thermodynamics with internal variables

    Energy Technology Data Exchange (ETDEWEB)

    Lion, Alexander, E-mail: alexander.lion@unibw.de; Engelhard, Marco; Johlitz, Michael

    2012-11-01

    In order to understand the temperature-dependent response behaviour of thin thermoviscoelastic films which are deposited on relative stiff but thermally deformable substrates it is important to consider the lateral geometric constraints. They are generated by differences in the thermal expansion properties between the substrate and the film and provoke internal stresses. Since glass-forming materials exhibit distinct temperature history-dependent thermal expansion and calorimetric properties, primarily in the vicinity of the glass transition, the situation is rather complicated. In this article, a recently developed three-dimensional model of thermodynamics with internal variables is applied and adapted to simulate this type of behaviour. Explicit relations are obtained for the specific heat of the film, the normal strain and the lateral stresses. Numerical simulations demonstrate that the magnitude of the internal stress at temperatures below the glass transition depends strongly on the cooling rate. It is also shown that the specific heat of the supported film is principally different from the isobaric specific heat of the bulk material: the glassy limit of the specific heat of the film is reduced but the glass transition temperature is almost uninfluenced. The simulated behaviour is in accordance with experimental observations from literature. - Highlights: Black-Right-Pointing-Pointer For the specific heat, stress and strain of the film, explicit equations were derived. Black-Right-Pointing-Pointer The constraints of the substrate reduce the glassy limit of specific heat of the film. Black-Right-Pointing-Pointer Glass transition temperatures of free bulk material and supported film are equal. Black-Right-Pointing-Pointer Simulations are in good agreement with experimental observations from literature.

  19. PREFACE: Proceedings of the International Workshop on Current Challenges in Liquid and Glass Science, (The Cosener's House, Abingdon 10 12 January 2007)

    Science.gov (United States)

    Hannon, Alex C.; Salmon, Philip S.; Soper, Alan K.

    2007-10-01

    The workshop was held to discuss current experimental and theoretical challenges in liquid and glass science and to honour the contribution made by Spencer Howells (ISIS, UK) to the field of neutron scattering from liquids and glasses. The meeting was attended by 70 experimentalists, theorists and computer simulators from Europe, Japan and North America and comprised 34 oral presentations together with two lively poster sessions. Three major themes were discussed, namely (i) the glass transition and properties of liquids and glasses under extreme conditions; (ii) the complementarity of neutron and x-ray scattering techniques with other experimental methods; and (iii) the modelling of liquid and glass structure. These themes served to highlight (a) recent advances in neutron and x-ray instrumentation used to investigate liquid and glassy materials under extreme conditions; (b) the relationship between the results obtained from different experimental and theoretical/computational methods; and (c) the modern methods used to interpret experimental results. The presentations ranged from polyamorphism in liquids and glasses to protein folding in aqueous solution and included the dynamics of fresh and freeze-dried strawberries and red onions. The properties of liquid phosphorus were also memorably demonstrated! The formal highlight was the 'Spencerfest' dinner where Neil Cowlam (Sheffield, UK) gave an excellent after dinner speech. The organisation of the workshop benefited tremendously from the secretarial skills of Carole Denning (ISIS, UK). The financial support of the Council for the Central Laboratory of the Research Councils (CCLRC), the Liquids and Complex Fluids Group of the Institute of Physics, The ISIS Disordered Materials Group, the CCLRC Centre for Materials Physics and Chemistry and the CCLRC Centre for Molecular Structure and Dynamics is gratefully acknowledged. Finally, it is a pleasure to thank all the workshop participants whose lively contributions led

  20. A new Ti-Zr-Hf-Cu-Ni-Si-Sn bulk amorphous alloy with high glass-forming ability

    International Nuclear Information System (INIS)

    Huang, Y.J.; Shen, J.; Sun, J.F.; Yu, X.B.

    2007-01-01

    The effect of Sn substitution for Cu on the glass-forming ability was investigated in Ti 41.5 Zr 2.5 Hf 5 Cu 42.5-x Ni 7.5 Si 1 Sn x (x = 0, 1, 3, 5, 7) alloys by using differential scanning calorimetry (DSC) and X-ray diffractometry. The alloy containing 5% Sn shows the highest glass-forming ability (GFA) among the Ti-Zr-Hf-Cu-Ni-Si-Sn system. Fully amorphous rod sample with diameters up to 6 mm could be successfully fabricated by the copper mold casting Ti 41.5 Zr 2.5 Hf 5 Cu 37.5 Ni 7.5 Si 1 Sn 5 alloy. The activation energies for glass transition and crystallization for Ti 41.5 Zr 2.5 Hf 5 Cu 37.5 Ni 7.5 Si 1 Sn 5 amorphous alloy are both larger than those values for the Sn-free alloy. The enhancement in GFA and thermal stability after the partial replacement of Cu by Sn may be contributed to the strong atomic bonding nature between Ti and Sn and the increasing of atomic packing density. The amorphous Ti 41.5 Zr 2.5 Hf 5 Cu 37.5 Ni 7.5 Si 1 Sn 5 alloy also possesses superior mechanical properties

  1. Linking rigidity transitions with enthalpic changes at the glass transition and fragility: insight from a simple oscillator model.

    Science.gov (United States)

    Micoulaut, Matthieu

    2010-07-21

    A low temperature Monte Carlo dynamics of a Keating-like oscillator model is used to study the relationship between the nature of network glasses from the viewpoint of rigidity, the thermal reversibility during the glass transition and the strong-fragile behaviour of glass-forming liquids. The model shows that a Phillips optimal glass formation with minimal enthalpic changes is obtained under a cooling/annealing cycle when the system is optimally constrained by the harmonic interactions, i.e. when it is isostatically rigid. For these peculiar systems with a nearly reversible glass transition, the computed activation energy for relaxation time shows also a minimum, which demonstrates that isostatically rigid glasses are strong (Arrhenius-like) glass-forming liquids. Experiments on chalcogenide and oxide glass-forming liquids are discussed under this new perspective and confirm the theoretical prediction for chalcogenide network glasses whereas limitations of the approach appear for weakly interacting (non-covalent, ionic) systems.

  2. Optical and morphological characterizations of pyronin dye-poly (vinyl alcohol) thin films formed on glass substrates

    International Nuclear Information System (INIS)

    Meral, Kadem; Arik, Mustafa; Onganer, Yavuz

    2016-01-01

    Thin films of pyronin dye mixed with poly(vinyl alcohol) (PVA) on glass substrate were prepared by using spin-coating technique. The optical and morphological properties of the thin films were studied by UV-Vis., steady-state fluorescence spectroscopies and atomic force microscopy (AFM). The thin films on glass substrate were fabricated at various [PVA]/[dye] (P/D) ratios. Hence, the monomeric and H-aggregates thin films of pyronin dye mixed with PVA were formed as a function of the dye and PVA concentration. It was determined that while the monomeric thin films showed strong fluorescence, the formation of H-aggregates in the thin film caused to decreasing the fluorescence intensity. AFM studies demonstrated that the morphology of the thin film was drastically varied with changing the optical property of the thin film such as monomeric and H-aggregates thin films.

  3. Optical and morphological characterizations of pyronin dye-poly (vinyl alcohol) thin films formed on glass substrates

    Energy Technology Data Exchange (ETDEWEB)

    Meral, Kadem, E-mail: kademm@atauni.edu.tr; Arik, Mustafa, E-mail: marik@tatauni.edu.tr; Onganer, Yavuz, E-mail: yonganer@atauni.edu.tr [Department of Chemistry, Faculty of Sciences, Atatürk University, 25240 Erzurum (Turkey)

    2016-04-18

    Thin films of pyronin dye mixed with poly(vinyl alcohol) (PVA) on glass substrate were prepared by using spin-coating technique. The optical and morphological properties of the thin films were studied by UV-Vis., steady-state fluorescence spectroscopies and atomic force microscopy (AFM). The thin films on glass substrate were fabricated at various [PVA]/[dye] (P/D) ratios. Hence, the monomeric and H-aggregates thin films of pyronin dye mixed with PVA were formed as a function of the dye and PVA concentration. It was determined that while the monomeric thin films showed strong fluorescence, the formation of H-aggregates in the thin film caused to decreasing the fluorescence intensity. AFM studies demonstrated that the morphology of the thin film was drastically varied with changing the optical property of the thin film such as monomeric and H-aggregates thin films.

  4. Magnetic nanoparticles formed in glasses co-doped with iron and larger radius elements

    Energy Technology Data Exchange (ETDEWEB)

    Edelman, I.; Ivanova, O.; Ivantsov, R.; Velikanov, D.; Zabluda, V. [L.V. Kirensky Institute of Physics SB RAS, 660036 Krasnoyarsk (Russian Federation); Zubavichus, Y.; Veligzhanin, A. [NRC ' Kurchatov Institute,' 123182 Moscow (Russian Federation); Zaikovskiy, V. [Boreskov Institute of Catalysis, Siberian Branch of RAS, 630090 Novosibirsk (Russian Federation); Stepanov, S. [S.I. Vavilov State Optical Institute, St. Petersburg (Russian Federation); Artemenko, A. [ICMCB, UPR CNRS 9048, 33608 Pessac cedex (France); Curely, J.; Kliava, J. [LOMA, UMR 5798 Universite Bordeaux 1-CNRS, 33405 Talence cedex (France)

    2012-10-15

    A new type of nanoparticle-containing glasses based on borate glasses co-doped with low contents of iron and larger radius elements, Dy, Tb, Gd, Ho, Er, Y, and Bi, is studied. Heat treatment of these glasses results in formation of magnetic nanoparticles, radically changing their physical properties. Transmission electron microscopy and synchrotron radiation-based techniques: x-ray diffraction, extended x-ray absorption fine structure, x-ray absorption near-edge structure, and small-angle x-ray scattering, show a broad distribution of nanoparticle sizes with characteristics depending on the treatment regime; a crystalline structure of these nanoparticles is detected in heat treated samples. Magnetic circular dichroism (MCD) studies of samples subjected to heat treatment as well as of maghemite, magnetite, and iron garnet allow to unambiguously assign the nanoparticle structure to maghemite, independently of co-dopant nature and of heat treatment regime used. Different features observed in the MCD spectra are related to different electron transitions in Fe{sup 3+} ions gathered in the nanoparticles. The static magnetization in heat treated samples has non-linear dependence on the magnetizing field with hysteresis. Zero-field cooled magnetization curves show that at higher temperatures the nanoparticles occur in superparamagnetic state with blocking temperatures above 100 K. Below ca. 20 K, a considerable contribution to both zero field-cooled and field-cooled magnetizations occurs from diluted paramagnetic ions. Variable-temperature electron magnetic resonance (EMR) studies unambiguously show that in as-prepared glasses paramagnetic ions are in diluted state and confirm the formation of magnetic nanoparticles already at earlier stages of heat treatment. Computer simulations of the EMR spectra corroborate the broad distribution of nanoparticle sizes found by 'direct' techniques as well as superparamagnetic nanoparticle behaviour demonstrated in the

  5. Magnetic nanoparticles formed in glasses co-doped with iron and larger radius elements

    International Nuclear Information System (INIS)

    Edelman, I.; Ivanova, O.; Ivantsov, R.; Velikanov, D.; Zabluda, V.; Zubavichus, Y.; Veligzhanin, A.; Zaikovskiy, V.; Stepanov, S.; Artemenko, A.; Curély, J.; Kliava, J.

    2012-01-01

    A new type of nanoparticle-containing glasses based on borate glasses co-doped with low contents of iron and larger radius elements, Dy, Tb, Gd, Ho, Er, Y, and Bi, is studied. Heat treatment of these glasses results in formation of magnetic nanoparticles, radically changing their physical properties. Transmission electron microscopy and synchrotron radiation-based techniques: x-ray diffraction, extended x-ray absorption fine structure, x-ray absorption near-edge structure, and small-angle x-ray scattering, show a broad distribution of nanoparticle sizes with characteristics depending on the treatment regime; a crystalline structure of these nanoparticles is detected in heat treated samples. Magnetic circular dichroism (MCD) studies of samples subjected to heat treatment as well as of maghemite, magnetite, and iron garnet allow to unambiguously assign the nanoparticle structure to maghemite, independently of co-dopant nature and of heat treatment regime used. Different features observed in the MCD spectra are related to different electron transitions in Fe 3+ ions gathered in the nanoparticles. The static magnetization in heat treated samples has non-linear dependence on the magnetizing field with hysteresis. Zero-field cooled magnetization curves show that at higher temperatures the nanoparticles occur in superparamagnetic state with blocking temperatures above 100 K. Below ca. 20 K, a considerable contribution to both zero field-cooled and field-cooled magnetizations occurs from diluted paramagnetic ions. Variable-temperature electron magnetic resonance (EMR) studies unambiguously show that in as-prepared glasses paramagnetic ions are in diluted state and confirm the formation of magnetic nanoparticles already at earlier stages of heat treatment. Computer simulations of the EMR spectra corroborate the broad distribution of nanoparticle sizes found by “direct” techniques as well as superparamagnetic nanoparticle behaviour demonstrated in the magnetization

  6. Magnetic nanoparticles formed in glasses co-doped with iron and larger radius elements

    Science.gov (United States)

    Edelman, I.; Ivanova, O.; Ivantsov, R.; Velikanov, D.; Zabluda, V.; Zubavichus, Y.; Veligzhanin, A.; Zaikovskiy, V.; Stepanov, S.; Artemenko, A.; Curély, J.; Kliava, J.

    2012-10-01

    A new type of nanoparticle-containing glasses based on borate glasses co-doped with low contents of iron and larger radius elements, Dy, Tb, Gd, Ho, Er, Y, and Bi, is studied. Heat treatment of these glasses results in formation of magnetic nanoparticles, radically changing their physical properties. Transmission electron microscopy and synchrotron radiation-based techniques: x-ray diffraction, extended x-ray absorption fine structure, x-ray absorption near-edge structure, and small-angle x-ray scattering, show a broad distribution of nanoparticle sizes with characteristics depending on the treatment regime; a crystalline structure of these nanoparticles is detected in heat treated samples. Magnetic circular dichroism (MCD) studies of samples subjected to heat treatment as well as of maghemite, magnetite, and iron garnet allow to unambiguously assign the nanoparticle structure to maghemite, independently of co-dopant nature and of heat treatment regime used. Different features observed in the MCD spectra are related to different electron transitions in Fe3+ ions gathered in the nanoparticles. The static magnetization in heat treated samples has non-linear dependence on the magnetizing field with hysteresis. Zero-field cooled magnetization curves show that at higher temperatures the nanoparticles occur in superparamagnetic state with blocking temperatures above 100 K. Below ca. 20 K, a considerable contribution to both zero field-cooled and field-cooled magnetizations occurs from diluted paramagnetic ions. Variable-temperature electron magnetic resonance (EMR) studies unambiguously show that in as-prepared glasses paramagnetic ions are in diluted state and confirm the formation of magnetic nanoparticles already at earlier stages of heat treatment. Computer simulations of the EMR spectra corroborate the broad distribution of nanoparticle sizes found by "direct" techniques as well as superparamagnetic nanoparticle behaviour demonstrated in the magnetization studies.

  7. Local dynamics of glass-forming polystyrene thin films from atomistic simulation

    Science.gov (United States)

    Zhou, Yuxing; Milner, Scott

    Despite a wide technological application ranging from protective coatings to organic solar cells, there still no consensus on the mechanism for the glass transition in polymer thin films a manifestation of the infamous glass problem under confinement. Many experimental and computational studies have observed a large deviation of nanoscale dynamical properties in thin films from the corresponding properties in bulk. In this work, we perform extensive united-atom simulations on atactic polystyrene free-standing thin films near the glass transition temperature and focus on the effect of free surface on the local dynamics. We study the segmental dynamics as a function of distance from the surface for different temperatures, from which relaxation time and thereby local Tg is obtained for each layer. We find the dynamics near free surface is not only enhanced but becomes less strongly temperature dependent as Tg is approached compared to the bulk. We find an increasing length scale associated with mobility propagation from the free surface as temperature decreases, but no correlation between local structure and enhanced relaxation rates near the surface, consistent with studies on bead-spring chains.

  8. Detection of structural heterogeneity of glass melts

    DEFF Research Database (Denmark)

    Yue, Yuanzheng

    2004-01-01

    The structural heterogeneity of both supercooled liquid and molten states of silicate has been studied using calorimetric method. The objects of this study are basaltic glasses and liquids. Two experimental approaches are taken to detect the structural heterogeneity of the liquids. One is the hyp......The structural heterogeneity of both supercooled liquid and molten states of silicate has been studied using calorimetric method. The objects of this study are basaltic glasses and liquids. Two experimental approaches are taken to detect the structural heterogeneity of the liquids. One...... is the hyperquench-anneal-calorimetric scan approach, by which the structural information of a basaltic supercooled liquid and three binary silicate liquids is acquired. Another is the calorimetrically repeated up- and downscanning approach, by which the structural heterogeneity, the intermediate range order...... is discussed. The ordered structure of glass melts above the liquidus temperature is indirectly characterized by use of X-ray diffraction method. The new approaches are of importance for monitoring the glass melting and forming process and for improving the physical properties of glasses and glass fibers....

  9. Density-driven structural transformations in network forming glasses: a high-pressure neutron diffraction study of GeO2 glass up to 17.5 GPa

    International Nuclear Information System (INIS)

    Salmon, Philip S; Drewitt, James W E; Whittaker, Dean A J; Zeidler, Anita; Wezka, Kamil; Bull, Craig L; Tucker, Matthew G; Wilding, Martin C; Guthrie, Malcolm; Marrocchelli, Dario

    2012-01-01

    The structure of GeO 2 glass was investigated at pressures up to 17.5(5) GPa using in situ time-of-flight neutron diffraction with a Paris-Edinburgh press employing sintered diamond anvils. A new methodology and data correction procedure were developed, enabling a reliable measurement of structure factors that are largely free from diamond Bragg peaks. Calibration curves, which are important for neutron diffraction work on disordered materials, were constructed for pressure as a function of applied load for both single and double toroid anvil geometries. The diffraction data are compared to new molecular-dynamics simulations made using transferrable interaction potentials that include dipole-polarization effects. The results, when taken together with those from other experimental methods, are consistent with four densification mechanisms. The first, at pressures up to ≃ 5 GPa, is associated with a reorganization of GeO 4 units. The second, extending over the range from ≃ 5 to 10 GPa, corresponds to a regime where GeO 4 units are replaced predominantly by GeO 5 units. In the third, as the pressure increases beyond ∼10 GPa, appreciable concentrations of GeO 6 units begin to form and there is a decrease in the rate of change of the intermediate-range order as measured by the pressure dependence of the position of the first sharp diffraction peak. In the fourth, at about 30 GPa, the transformation to a predominantly octahedral glass is achieved and further densification proceeds via compression of the Ge-O bonds. The observed changes in the measured diffraction patterns for GeO 2 occur at similar dimensionless number densities to those found for SiO 2 , indicating similar densification mechanisms for both glasses. This implies a regime from about 15 to 24 GPa where SiO 4 units are replaced predominantly by SiO 5 units, and a regime beyond ∼24 GPa where appreciable concentrations of SiO 6 units begin to form.

  10. Liquid culture enhances diagnosis of patients with milder forms of non-tuberculous mycobacterial lung disease.

    Science.gov (United States)

    Lee, H; Han, J-H; Park, H Y; Jeon, K; Huh, H J; Ki, C-S; Lee, N Y; Koh, W-J

    2017-03-01

    To evaluate the proportion and clinical characteristics of patients with non-tuberculous mycobacteria (NTM) lung disease diagnosed based on positive culture results in liquid medium only. We reviewed the medical records of 978 patients diagnosed with NTM lung disease. All clinical samples were cultured in both solid and liquid media. Of the 978 patients, 111 (11.3%) were culture-positive in liquid medium only (liquid culture group), and 867 (88.7%) (solid culture group) on solid medium, regardless of the culture results in liquid medium. At the time of diagnosis, the liquid culture group was less likely than the solid culture group to have haemoptysis (11.7% vs. 20.0%, P = 0.04), positive sputum smear for acid-fast bacilli (14.4% vs. 50.2%, P disease (3.6% vs. 14.6%, P = 0.001). During the median follow-up period of 28.9 months (interquartile range 19.1-41.6), the proportion of patients requiring antibiotic treatment was lower in the liquid culture group than in the solid culture group (44.1% vs. 61.6%, P culture is helpful in the diagnosis of patients with less severe forms of NTM lung disease.

  11. Sol-Gel Glasses

    Science.gov (United States)

    Mukherjee, S. P.

    1985-01-01

    Multicomponent homogeneous, ultrapure noncrystalline gels/gel derived glasses are promising batch materials for the containerless glass melting experiments in microgravity. Hence, ultrapure, homogeneous gel precursors could be used to: (1) investigate the effect of the container induced nucleation on the glass forming ability of marginally glass forming compositions; and (2) investigate the influence of gravity on the phase separation and coarsening behavior of gel derived glasses in the liquid-liquid immiscibility zone of the nonsilicate systems having a high density phase. The structure and crystallization behavior of gels in the SiO2-GeO2 as a function of gel chemistry and thermal treatment were investigated. As are the chemical principles involved in the distribution of a second network former in silica gel matrix being investigated. The procedures for synthesizing noncrystalline gels/gel-monoliths in the SiO2-GeO2, GeO2-PbO systems were developed. Preliminary investigations on the levitation and thermal treatment of germania silicate gel-monoliths in the Pressure Facility Acoustic Levitator were done.

  12. Peculiar thermal points during B2O3 transition from liquid to glass-like state

    International Nuclear Information System (INIS)

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

    1992-01-01

    Relaxation transitions in glass-like B 2 O 3 were studied by dynamic methods in vacuum in the temperature range of 70-1070 K and frequency range of 10 -4 -1.2·10 6 Hz. The standard temperature of glass formation is T g =493 K and it corresponds to the standard frequency 5.3·10 -4 Hz. Above T g two special temperature points - T K and T F , position of which does not depend on the frequency, are observed

  13. Short- and long-range correlated motion observed in colloidal glasses and liquids

    International Nuclear Information System (INIS)

    Weeks, Eric R; Crocker, John C; Weitz, D A

    2007-01-01

    We use a confocal microscope to examine the motion of individual particles in a dense colloidal suspension. Close to the glass transition, particle motion is strongly spatially correlated. The correlations decay exponentially with particle separation, yielding a dynamic length scale of O(2-3σ) (in terms of particle diameter σ). This length scale grows modestly as the glass transition is approached. Further, the correlated motion exhibits a strong spatial dependence on the pair correlation function g(r). Motion within glassy samples is weakly correlated, but with a larger spatial scale for this correlation

  14. Superductile bulk metallic glass

    International Nuclear Information System (INIS)

    Yao, K.F.; Ruan, F.; Yang, Y.Q.; Chen, N.

    2006-01-01

    Usually, monolithic bulk metallic glasses undergo inhomogeneous plastic deformation and exhibit poor ductility (<2%) at room temperature. We report a newly developed Pd-Si binary bulk metallic glass, which exhibits a uniform plastic deformation and a large plastic engineering strain of 82% and a plastic true strain of 170%, together with initial strain hardening, slight strain softening and final strain hardening characteristics. The uniform shear deformation and the ultrahigh plasticity are mainly attributed to strain hardening, which results from the nanoscale inhomogeneity due to liquid phase separation. The formed nanoscale inhomogeneity will hinder, deflect, and bifurcate the propagation of shear bands

  15. Determination of chemical forms of C-14 in liquid discharges from nuclear power plants

    Czech Academy of Sciences Publication Activity Database

    Světlík, Ivo; Fejgl, M.; Povinec, P. P.; Kořínková, Tereza; Tomášková, Lenka; Pospíchal, J.; Kurfiřt, M.; Striegler, R.; Kaufmanová, M.

    2017-01-01

    Roč. 177, OCT (2017), s. 256-260 ISSN 0265-931X Institutional support: RVO:61389005 Keywords : analytical routines * dissolved organic forms of C-14 (DIC) * dissolved inorganic forms of C-14 (DOC) * Nuclear power plant (NPP) * liquid releases Subject RIV: DL - Nuclear Waste, Radioactive Pollution ; Quality OBOR OECD: Environment al sciences (social aspects to be 5.7) Impact factor: 2.310, year: 2016

  16. Apatite and sodalite based glass-bonded waste forms for immobilization of 129I and mixed halide radioactive wastes

    Energy Technology Data Exchange (ETDEWEB)

    Goel, Ashutosh [Rutgers Univ., New Brunswick, NJ (United States); McCloy, John S. [Washington State Univ., Pullman, WA (United States); Riley, Brian J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Matyas, Josef [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2017-12-30

    The goal of the project was to utilize the knowledge accumulated by the team, in working with minerals for chloride wastes and biological apatites, toward the development of advanced waste forms for immobilizing 129I and mixed-halide wastes. Based on our knowledge, experience, and thorough literature review, we had selected two minerals with different crystal structures and potential for high chemical durability, sodalite and CaP/PbV-apatite, to form the basis of this project. The focus of the proposed effort was towards: (i) low temperature synthesis of proposed minerals (iodine containing sodalite and apatite) leading to the development of monolithic waste forms, (ii) development of a fundamental understanding of the atomic-scale to meso-scale mechanisms of radionuclide incorporation in them, and (iii) understanding of the mechanism of their chemical corrosion, alteration mechanism, and rates. The proposed work was divided into four broad sections. deliverables. 1. Synthesis of materials 2. Materials structural and thermal characterization 3. Design of glass compositions and synthesis glass-bonded minerals, and 4. Chemical durability testing of materials.

  17. Mineralogical textural and compositional data on the alteration of basaltic glass from Kilauea, Hawaii to 300 degrees C: Insights to the corrosion of a borosilicate glass waste-form

    International Nuclear Information System (INIS)

    Smith, D.K.

    1990-01-01

    Mineralogical, textural and compositional data accompanying greenschist facies metamorphism (to 300 degrees C) of basalts of the East Rift Zone (ERZ), Kilauea, Hawaii may be evaluated relative to published and experimental results for the surface corrosion of borosilicate glass. The ERZ alteration sequence is dominated by intermittent palagonite, interlayered smectite-chlorite, chlorite, and actinolite-epidote-anhydrite. Alteration is best developed in fractures and vesicles where surface reaction layers root on the glass matrix forming rinds in excess of 100 microns thick. Fractures control fluid circulation and the alteration sequence. Proximal to the glass surface, palagonite, Fe-Ti oxides and clays replace fresh glass as the surface reaction layer migrates inwards; away from the surface, amphibole, anhydrite, quartz and calcite crystallize from hydrothermal fluids in contact with the glass. The texture and composition of basaltic glass surfaces are similar to those of a SRL-165 glass leached statically for sixty days at 150 degrees C. While the ERZ reservoir is a complex open system, conservative comparisons between the alteration of ERZ and synthetic borosilicate glass are warranted. 31 refs., 2 figs

  18. Reorientational dynamics in molecular liquids as revealed by dynamic light scattering: from boiling point to glass transition temperature.

    Science.gov (United States)

    Schmidtke, B; Petzold, N; Kahlau, R; Rössler, E A

    2013-08-28

    We determine the reorientational correlation time τ of a series of molecular liquids by performing depolarized light scattering experiments (double monochromator, Fabry-Perot interferometry, and photon correlation spectroscopy). Correlation times in the range 10(-12) s-100 s are compiled, i.e., the full temperature interval between the boiling point and the glass transition temperature T(g) is covered. We focus on low-T(g) liquids for which the high-temperature limit τ ≅ 10(-12) s is easily accessed by standard spectroscopic equipment (up to 440 K). Regarding the temperature dependence three interpolation formulae of τ(T) with three parameters each are tested: (i) Vogel-Fulcher-Tammann equation, (ii) the approach recently discussed by Mauro et al. [Proc. Natl. Acad. Sci. U.S.A. 106, 19780 (2009)], and (iii) our approach decomposing the activation energy E(T) in a constant high temperature value E∞ and a "cooperative part" E(coop)(T) depending exponentially on temperature [Schmidtke et al., Phys. Rev. E 86, 041507 (2012)]. On the basis of the present data, approaches (i) and (ii) are insufficient as they do not provide the correct crossover to the high-temperature Arrhenius law clearly identified in the experimental data while approach (iii) reproduces the salient features of τ(T). It allows to discuss the temperature dependence of the liquid's dynamics in terms of a E(coop)(T)/E∞ vs. T/E∞ plot and suggests that E∞ controls the energy scale of the glass transition phenomenon.

  19. Spheroidization of glass powders for glass ionomer cements.

    Science.gov (United States)

    Gu, Y W; Yap, A U J; Cheang, P; Kumar, R

    2004-08-01

    Commercial angular glass powders were spheroidized using both the flame spraying and inductively coupled radio frequency plasma spraying techniques. Spherical powders with different particle size distributions were obtained after spheroidization. The effects of spherical glass powders on the mechanical properties of glass ionomer cements (GICs) were investigated. Results showed that the particle size distribution of the glass powders had a significant influence on the mechanical properties of GICs. Powders with a bimodal particle size distribution ensured a high packing density of glass ionomer cements, giving relatively high mechanical properties of GICs. GICs prepared by flame-spheroidized powders showed low strength values due to the loss of fine particles during flame spraying, leading to a low packing density and few metal ions reacting with polyacrylic acid to form cross-linking. GICs prepared by the nano-sized powders showed low strength because of the low bulk density of the nano-sized powders and hence low powder/liquid ratio of GICs.

  20. Fragile-to-fragile liquid transition at Tg and stable-glass phase nucleation rate maximum at the Kauzmann temperature TK

    International Nuclear Information System (INIS)

    Tournier, Robert F.

    2014-01-01

    An undercooled liquid is unstable. The driving force of the glass transition at T g is a change of the undercooled-liquid Gibbs free energy. The classical Gibbs free energy change for a crystal formation is completed including an enthalpy saving. The crystal growth critical nucleus is used as a probe to observe the Laplace pressure change Δp accompanying the enthalpy change −V m ×Δp at T g where V m is the molar volume. A stable glass–liquid transition model predicts the specific heat jump of fragile liquids at T≤T g , the Kauzmann temperature T K where the liquid entropy excess with regard to crystal goes to zero, the equilibrium enthalpy between T K and T g , the maximum nucleation rate at T K of superclusters containing magic atom numbers, and the equilibrium latent heats at T g and T K . Strong-to-fragile and strong-to-strong liquid transitions at T g are also described and all their thermodynamic parameters are determined from their specific heat jumps. The existence of fragile liquids quenched in the amorphous state, which do not undergo liquid–liquid transition during heating preceding their crystallization, is predicted. Long ageing times leading to the formation at T K of a stable glass composed of superclusters containing up to 147 atom, touching and interpenetrating, are evaluated from nucleation rates. A fragile-to-fragile liquid transition occurs at T g without stable-glass formation while a strong glass is stable after transition

  1. Applying a new criterion to predict glass forming alloys in the Zr–Ni–Cu ternary system

    Energy Technology Data Exchange (ETDEWEB)

    Déo, L.P., E-mail: leonardopratavieira@gmail.com [Universidade de São Paulo, EESC, SMM - Av. Trabalhador São Carlense, 400 – São Carlos, SP 13566-590 (Brazil); Mendes, M.A.B., E-mail: marcio.andreato@gmail.com [Universidade Federal de São Carlos, DEMa - Rod. Washington Luiz, Km 235 – São Carlos, SP 13565-905 (Brazil); Costa, A.M.S., E-mail: alexmatos1980@gmail.com [Universidade de São Paulo, DEMAR, EEL – Polo Urbo-Industrial Gleba AI-6, s/n – Lorena, SP 12600-970 (Brazil); Campos Neto, N.D., E-mail: nelsonddcn@gmail.com [Universidade de São Paulo, EESC, SMM - Av. Trabalhador São Carlense, 400 – São Carlos, SP 13566-590 (Brazil); Oliveira, M.F. de, E-mail: falcao@sc.usp.br [Universidade de São Paulo, EESC, SMM - Av. Trabalhador São Carlense, 400 – São Carlos, SP 13566-590 (Brazil)

    2013-03-15

    Highlights: ► Calculation to predict and select the glass forming ability (GFA) of metallic alloys in Zr–Ni–Cu system. ► Good correlation between theoretical and experimental GFA samples. ► Combination of X-ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques mainly to characterize the samples. ► Oxygen impurity dramatically reduced the GFA. ► The selection criterion used opens the possibility to obtain new amorphous alloys, reducing the experimental procedures of trial and error. -- Abstract: A new criterion has been recently proposed to predict and select the glass forming ability (GFA) of metallic alloys. It was found that the critical cooling rate for glass formation (R{sub c}) correlates well with a proper combination of two factors, the minimum topological instability (λ{sub min}) and the thermodynamic parameter (Δh). The (λ{sub min}) criterion is based on the concept of topological instability of stable crystalline structures and (Δh) depends on the average work function difference (Δϕ) and the average electron density difference Δn{sub ws}{sup 1/3} among the constituent elements of the alloy. In the present work, the selection criterion was applied in the Zr–Ni–Cu system and its predictability was analyzed experimentally. Ribbon-shaped and splat-shaped samples were produced by melt-spinning and splat-cooling techniques respectively. The crystallization content and behavior were analyzed by X-ray diffraction (XRD) and differential scanning calorimetry (DSC), respectively. The results showed a good correlation between the theoretical GFA values and the amorphous phase percentages found in different alloy compositions.

  2. A new Ti-Zr-Hf-Cu-Ni-Si-Sn bulk amorphous alloy with high glass-forming ability

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Y.J. [School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001 (China); Shen, J. [School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001 (China)]. E-mail: junshen@hit.edu.cn; Sun, J.F. [School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001 (China); Yu, X.B. [Lab of Energy Science and Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China)]. E-mail: yuxuebin@hotmail.com

    2007-01-16

    The effect of Sn substitution for Cu on the glass-forming ability was investigated in Ti{sub 41.5}Zr{sub 2.5}Hf{sub 5}Cu{sub 42.5-x}Ni{sub 7.5}Si{sub 1}Sn {sub x} (x = 0, 1, 3, 5, 7) alloys by using differential scanning calorimetry (DSC) and X-ray diffractometry. The alloy containing 5% Sn shows the highest glass-forming ability (GFA) among the Ti-Zr-Hf-Cu-Ni-Si-Sn system. Fully amorphous rod sample with diameters up to 6 mm could be successfully fabricated by the copper mold casting Ti{sub 41.5}Zr{sub 2.5}Hf{sub 5}Cu{sub 37.5}Ni{sub 7.5}Si{sub 1}Sn{sub 5} alloy. The activation energies for glass transition and crystallization for Ti{sub 41.5}Zr{sub 2.5}Hf{sub 5}Cu{sub 37.5}Ni{sub 7.5}Si{sub 1}Sn{sub 5} amorphous alloy are both larger than those values for the Sn-free alloy. The enhancement in GFA and thermal stability after the partial replacement of Cu by Sn may be contributed to the strong atomic bonding nature between Ti and Sn and the increasing of atomic packing density. The amorphous Ti{sub 41.5}Zr{sub 2.5}Hf{sub 5}Cu{sub 37.5}Ni{sub 7.5}Si{sub 1}Sn{sub 5} alloy also possesses superior mechanical properties.

  3. Universal divergenceless scaling between structural relaxation and caged dynamics in glass-forming systems.

    Science.gov (United States)

    Ottochian, A; De Michele, C; Leporini, D

    2009-12-14

    On approaching the glass transition, the microscopic kinetic unit spends increasing time rattling in the cage of the first neighbors, whereas its average escape time, the structural relaxation time tau(alpha), increases from a few picoseconds up to thousands of seconds. A thorough study of the correlation between tau(alpha) and the rattling amplitude, expressed by the Debye-Waller factor, was carried out. Molecular-dynamics simulations of both a model polymer system and a binary mixture were performed by varying the temperature, the density rho, the potential and the polymer length to consider the structural relaxation as well as both the rotational and the translation diffusion. The present simulations, together with MD studies on other glassformers, evidence the scaling between the structural relaxation and the caged dynamics. An analytic model of the master curve is developed in terms of two characteristic length scales a(2) (1/2) and sigma(a(2) ) (1/2), pertaining to the distance to be covered by the kinetic unit to reach a transition state. The model does not imply tau(alpha) divergences. The comparison with the experiments supports the numerical evidence over a range of relaxation times as wide as about eighteen orders of magnitude. A comparison with other scaling and correlation procedures is presented. In particular, the density scaling of the length scales a(2) (1/2), sigma(a(2) ) (1/2) proportional to rho(-1/3) is shown to be not supported by the present simulations. The study suggests that the equilibrium and the moderately supercooled states of the glassformers possess key information on the huge slowing-down of their relaxation close to the glass transition. The latter, according to the present simulations, exhibits features consistent with the Lindemann melting criterion and the free-volume model.

  4. Evaluation of liquid fragility and thermal stability of Al-based metallic glasses by equivalent structure parameter

    International Nuclear Information System (INIS)

    Li Xuelian; Bian Xiufang; Hu Lina

    2010-01-01

    Based on extended Ideal-Atomic-Packing model, we propose an equivalent structure parameter '6x+11y' to evaluate fragility and thermal stability of Al-TM-RE metallic glasses, where x and y are composition concentrations of transition metal (TM) and rare earth (RE), respectively. Experimental results show that glass forming compositions with '6x+11y' near 100 have the smallest fragility parameter and best structure stability. In addition, '6x+11y' parameter has a positive relationship with onset-crystallization temperature, T x . Al-TM-RE glassy alloys with (6x+11y)≤100 undergo primary crystallization of fcc-Al nanocrystals, while alloys with (6x+11y)>100 exhibit nanoglassy or glassy crystallization behavior.

  5. Glass-forming ability and stability of ternary Ni-early transition metal (Ti/Zr/Hf) alloys

    Energy Technology Data Exchange (ETDEWEB)

    Basu, Joysurya [Department of Metallurgy, Indian Institute of Science, Bangalore 560 012 (India); Ranganathan, S. [Department of Metallurgy, Indian Institute of Science, Bangalore 560 012 (India)]. E-mail: rangu@met.iisc.ernet.in

    2006-08-15

    Four Ni-bearing Ti, Zr and Hf ternary alloys of nominal composition Zr{sub 41.5}Ti{sub 41.5}Ni{sub 17}, Zr{sub 25}Ti{sub 25}Ni{sub 50}, Zr{sub 41.5}Hf{sub 41.5}Ni{sub 17} and Ti{sub 41.5}Hf{sub 41.5}Ni{sub 17} were rapidly solidified in order to produce ribbons. The Zr-Ti-Ni and Ti-Hf-Ni alloys become amorphous, whereas the Zr-Hf-Ni alloy shows precipitation of a cubic phase. The devitrification of all three alloys was followed and the relative tendency to form nanoquasicrystals and cF96 phases analysed. The relative glass-forming ability of the alloys can be explained by taking into account their atomic size difference. Addition of Ni often leads to quasicrystallisation or quasicrystal-related phases. This can be explained by the atomic radius and heat of mixing of the constituent elements. The phases precipitated at the initial stages of crystallisation indicate the possible presence of Frank-Kasper polyhedral structure in the amorphous alloys. Structural analysis reveals that the Laves and the anti-Laves phases have the same polyhedral structural unit, which is similar to the structural characteristics of glass.

  6. Glassy slag: A complementary waste form to homogeneous glass for the implementation of MAWS in treating DOE low level/mixed wastes

    International Nuclear Information System (INIS)

    Feng, X.; Ordaz, G.; Krumrine, P.

    1994-01-01

    Glassy slag waste forms are being developed to complement glass waste forms in implementing the Minimum Additive Waste Stabilization (MAWS) Program for supporting DOE's environmental restoration efforts. These glassy slags are composed of various metal oxide crystalline phases embedded in an alumino-silicate glass phase. The slags are appropriate final waste forms for waste streams that contain large amounts of scrap metals and elements with low solubilities in glass, and that have low-flux contents. Homogeneous glass waste forms are appropriate for wastes with sufficient fluxes and low metal contents. Therefore, utilization of both glass and glassy slag waste forms will make vitrification technology applicable to the treatment of a much larger range of radioactive and mixed wastes. The MAWS approach was a plied to glassy slags by blending multiple waste streams to produce the final waste form, minimizing overall waste form volume and reducing costs. The crystalline oxide phases formed in the glassy slags can be specially formulated so that they are very durable and contain hazardous and radioactive elements in their lattice structures. The Structural Bond Strength (SBS) Model was used to predict the chemical durability of the product from the slag composition so that optimized slag compositions could be obtain with a limited number of crucible melts and testing

  7. Expected behavior of HLW glass in storage

    International Nuclear Information System (INIS)

    McElroy, J.L.

    1975-01-01

    Glass produced by solidification of high-level radioactive liquid waste is studied. Conditions to which the waste form will be exposed in a typical handling sequence representative of current U. S. planning are tabulated. The reference matrix for waste form characterization is discussed, and some of the properties of high-level waste glass are described: physical properties, leachability, fracturing, vaporization, and containment in canister. 12 fig, 5 tables

  8. COOPERATIVITY, CAGE EFFECT AND HOPPING DIFFUSION IN SUPERCOOLED LIQUIDS AND GLASSES

    Directory of Open Access Journals (Sweden)

    A.S.Bakai

    2003-01-01

    Full Text Available Molecular dynamic simulations of structure, thermodynamic and kinetic properties of model metallic Ag-Cu alloy are performed to elucidate its behavior at glass transition. In spite of small variations of inherent structure of the alloy the relaxation kinetics undergo dramatic changes at the glass transition. The time dependences of the mean square displacements and the non-Gaussianity parameter show the signs of anomalous diffusion in an intermediate time region. The analysis of time evolution of van Hove correlation function indicates the existence of both jump displacements and short-range cooperative atomic rearrangements. Below Tg these cooperative rearrangements do not contribute to a long-range diffusion but they still dominate the relaxation at short time.

  9. Updated Liquid Secondary Waste Grout Formulation and Preliminary Waste Form Qualification

    Energy Technology Data Exchange (ETDEWEB)

    Saslow, Sarah A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Um, Wooyong [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Russell, Renee L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wang, Guohui [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Asmussen, Robert M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sahajpal, Rahul [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2017-07-01

    This report describes the results from liquid secondary waste grout (LSWG) formulation and cementitious waste form qualification tests performed by Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions, LLC (WRPS). New formulations for preparing a cementitious waste form from a high-sulfate liquid secondary waste stream simulant, developed for Effluent Management Facility (EMF) process condensates merged with low activity waste (LAW) caustic scrubber, and the release of key constituents (e.g. 99Tc and 129I) from these monoliths were evaluated. This work supports a technology development program to address the technology needs for Hanford Site Effluent Treatment Facility (ETF) liquid secondary waste (LSW) solidification and supports future Direct Feed Low-Activity Waste (DFLAW) operations. High-priority activities included simulant development, LSWG formulation, and waste form qualification. The work contained within this report relates to waste form development and testing and does not directly support the 2017 integrated disposal facility (IDF) performance assessment (PA). However, this work contains valuable information for use in PA maintenance past FY17, and for future waste form development efforts. The provided data should be used by (i) cementitious waste form scientists to further understanding of cementitious dissolution behavior, (ii) IDF PA modelers who use quantified constituent leachability, effective diffusivity, and partitioning coefficients to advance PA modeling efforts, and (iii) the U.S. Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program. The results obtained help fill existing data gaps, support final selection of a LSWG waste form, and improve the technical defensibility of long-term waste form performance estimates.

  10. Influence of Y, Gd and Sm on the glass forming ability and thermal crystallization of aluminum based alloy

    International Nuclear Information System (INIS)

    Aliaga, L.C.R.; Bolfarini, C.; Kiminami, C.S.; Botta Filho, W.J.; Danez, G.P.

    2010-01-01

    Al-based amorphous alloys represent an important family of metals and a great scientific activity has been devoted to determine the main features of both glass forming ability (GFA) and crystallization behavior in order to have a comprehensive framework aimed at potential technological applications. Nowadays, it is well known that the best Al-based amorphous alloys are formed in ternary systems such as Al- RE-TM, where RE is a rare earth and TM a transition metal. This paper presents results of research in Al 85 Ni 10 RE 5 alloys (RE = Y, Gd and Sm). Amorphous ribbons were processed by melt-spinning under the same conditions and subsequently characterized by x-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results show appreciable micro structural differences as function of the rare earth, thus crystal is obtained for Y, nano-glassy for Gd and, fully amorphous structure for Sm. (author)

  11. [Influence of La2O3 and Li2O on glass powder for infiltrating ZTA all-ceramic dental material formed by gel-casting].

    Science.gov (United States)

    Jin, Qiong; Wang, Xiao-fei; Yang, Zheng-yu; Tong, Yi-ping; Zhu, Li; Ma, Jian-feng

    2012-10-01

    The influence of La2O3 and Li2O on glass powder was studied in this paper, which is to infiltrate ZTA all-ceramic dental material formed by gel-casting. The performance of different component was analyzed to optimize glass formula. Six groups of glass powder were designed and prepared by conventional melt-quenching method. ZTA ceramic blocks were covered with glass paste, which were formed by gel-casting and sintered in 1200 degrees centigrade, then infiltrated in 1150 degrees centigrade for twice to make glass/ZTA ceramic composites. By detecting differential thermal analysis and melting range of infiltration glass power, as well as flexural strength, linear shrinkage, SEM and EDS of glass/ZTA ceramic composites, the optimized glass group was determined out. Statistical analysis was performed using SPSS 13.0 software package by means of paired t test or one way ANOVA. The bending strength of group Li1 was (291.2±27.9) MPa, significantly higher than group Li2 and group La2(Pglass of group Li1 can lubricate ZTA ceramics well, their structure was compact and had a few small pores. Intergranular fracture existed on cross surface as well as transgranular fracture. The results showed that Li1(30%La2O3-15%Al2O3-15%SiO2-15%B2O3-5%Li2O) glass infiltrated ZTA ceramic composite had the best capability. Glass/ZTA composite material can be prepared by gel-casting and infiltrating way, and this process is simple and economically suitable for general dental laboratory.

  12. Glass forming ability and magnetic properties of Co{sub (40.2−x)}Fe{sub (20.1+x)}Ni{sub 6.7}B{sub 22.7}Si{sub 5.3}Nb{sub 5} (x=0–10) bulk metallic glasses produced by suction casting

    Energy Technology Data Exchange (ETDEWEB)

    Sarlar, Kagan [Physics Department, Faculty of Arts and Sciences, Uludag University, Gorukle Campus, 16059 Bursa (Turkey); Physics Department, Kamil Ozdag Faculty of Sciences, Karamanoglu Mehmetbey University, YunusEmre Campus, 70100 Karaman (Turkey); Kucuk, Ilker, E-mail: ikucuk@uludag.edu.tr [Physics Department, Faculty of Arts and Sciences, Uludag University, Gorukle Campus, 16059 Bursa (Turkey)

    2015-01-15

    The effect of Fe concentration on the glass forming ability (GFA) and magnetic properties in Co{sub (40.2−x)}Fe{sub (20.1+x)}Ni{sub 6.7}B{sub 22.7}Si{sub 5.3}Nb{sub 5} (x=0–10) bulk metallic glasses were investigated. By suction casting method, the bulk metallic glasses with diameters up to 2 mm were produced. We try to find out which Fe concentration makes an influence on Co based system's magnetic properties and glass forming ability. The curves of thermal analysis, obtained using differential scanning calorimetry (DSC), show that the Co{sub (40.2−x)}Fe{sub (20.1+x)}Ni{sub 6.7}B{sub 22.7}Si{sub 5.3}Nb{sub 5} (x=0–10) have a supercooled liquid region (∆T{sub x}) of about 44 K. The saturation magnetizations (J{sub s}) for as-cast BMG alloys were in the range of 0.62 T−0.81 T. - Highlights: • The effect of Fe concentration on the glass forming ability. • The substitution of an appropriate amount of Fe can enhance the GFA. • The substitution of Fe for Co also improves soft magnetic properties of the BMGs. • The high of J{sub s} 0.62−0.81 T with a low H{sub c} of 2−289 A/m of the alloys.

  13. Breakup characteristics of power-law liquid sheets formed by two impinging jets

    International Nuclear Information System (INIS)

    Bai, Fuqiang; Diao, Hai; Chang, Qing; Wang, Endong; Du, Qing; Zhang, Mengzheng

    2014-01-01

    The breakup characteristics of the shear-thinning power-law liquid sheets formed by two impinging jets have been investigated with the shadowgraph technique. This paper focuses on the effects of spray parameters (jet velocity), physical parameters (viscosity) and geometry parameters (impinging angle and nozzle cross-sectional shape) on the breakup behaviors of liquid sheets. The breakup mode, sheet length and expansion angle of the sheet are extracted from the spray images obtained by a high speed camera. Impinging angle and Weber number play the similar roles in promoting the breakup of liquid sheets. With the increase of jet velocity, five different breakup modes are observed and the expansion angle increases consistently after the closed-rim mode while the sheet length first increases and then decreases. But there exists a concave consisting of a fierce drop and a second rising process on the sheet length curve for the fluid with smaller viscosity. Different nozzle cross-sectional shapes emphasize significant effects on the sheet length and expansion angle of liquid sheets. At a fixed Weber number, the liquid sheet with greater viscosity has a greater sheet length and a smaller expansion angle due to the damping effect of viscosity. (papers)

  14. Sub-micrometre Particulate Matter is Primarily in Liquid Form over Amazon Rainforests

    Energy Technology Data Exchange (ETDEWEB)

    Bateman, Adam P.; Gong, Z. H.; Liu, Pengfei; Sato, Bruno; Cirino, Glauber; Zhang, Yue; Artaxo, Paulo; Bertram, Allan K.; Manzi, A.; Rizzo, L. V.; Souza, Rodrigo A.; Zaveri, Rahul A.; Martin, Scot T.

    2016-01-01

    Particulate matter (PM) occurs in the Earth’s atmosphere both in liquid and non-liquid forms. The physical state affects the available physical and chemical mechanisms of growth and reactivity, ultimately affecting the number, size, and composition of the atmospheric particle population. Herein, the physical state, including the response to relative humidity (RH), was investigated on-line and in real time for PM (< 1 μm) over the tropical rain forest of central Amazonia during both the wet and dry seasons of 2013. The results show that the PM was liquid for RH > 80% across 296 to 300 K. These results, in conjunction with the distributions of RH and temperature in Amazonia, imply that near-surface submicron PM in Amazonia is liquid most of the time. The observations are consistent with laboratory experiments showing that PM produced by isoprene photo-oxidation is liquid across these meteorological conditions. The findings have implications for the mechanisms of new particle production in Amazonia, the growth of submicron particles and hence dynamics of the cloud life cycle, and the sensitivity of these processes to anthropogenic activities. An approach for inclusion of particle physical state in chemical transport models is presented.

  15. Non-Fermi liquid and spin-glass behavior of the Sc1-xUxPd3 system

    International Nuclear Information System (INIS)

    Gajewski, D.A.; Allenspach, P.; Seaman, C.L.; Maple, M.B.

    1994-01-01

    Previous electrical resistivity ρ(T), magnetic susceptibility χ(T), and specific heat C(T) measurements on the Y 1-x U x Pd 3 system have revealed Kondo behavior for 0 K , where T K is the Kondo temperature: ρ(T)/ρ(0)∼1-T/(aT K ) and C(T)/T∼-(1/T K )ln T with evidence for a finite T=0 residual entropy S(0)=(R/2)ln(2). We report measurements of ρ(T), χ(T), and C(T) on the Sc 1-x U x Pd 3 system which reveal similar Kondo, non-Fermi liquid, and spin-glass behaviors. ((orig.))

  16. A thermodynamic approach to the quantitative evaluation of the metallic melts glass-forming ability

    International Nuclear Information System (INIS)

    Zajtsev, A.I.

    2004-01-01

    The outlook for development of quantitative criteria of the tendency of metallic melt to render amorphous is shown with taking into account specific features of chemical interaction between components. With the use of statistical physics methods and thermodynamics as well as concepts of association the techniques are devised for quantitative separation of contributions to liquid alloy thermodynamic functions conditioned by various types of chemical interaction between components. The results Knudsen mass-spectroscopic comprehensive thermodynamic study of a wide range of systems with various tendency to vitrification are summarized. It is shown that excessive (configurational) entropy and specific heat of the liquid are key features predetermining thermodynamic and kinetic stimuli of amorphization. Their values are completely determined by a covalent constituent of chemical interaction on entropic term of association reaction. The possibility of construction of quantitative amorphization criteria on the basis of this feature and the outlook for the use of the approach proposed to predict physicochemical and mechanical properties of solid amorphous materials are illustrated [ru

  17. Electrochemical determination of the glass transition temperature of thin polyelectrolyte brushes at solid-liquid interfaces by impedance spectroscopy.

    Science.gov (United States)

    Alonso-García, Teodoro; Rodríguez-Presa, María José; Gervasi, Claudio; Moya, Sergio; Azzaroni, Omar

    2013-07-16

    Devising strategies to assess the glass transition temperature (Tg) of polyelectrolyte assemblies at solid-electrolyte interfaces is very important to understand and rationalize the temperature-dependent behavior of polyelectrolyte films in a wide range of settings. Despite the evolving perception of the importance of measuring Tg under aqueous conditions in thin film configurations, its straightforward measurement poses a challenging situation that still remains elusive in polymer and materials science. Here, we describe a new method based on electrochemical impedance spectroscopy (EIS) to estimate the glass transition temperature of planar polyelectrolyte brushes at solid-liquid interfaces. To measure Tg, the charge transfer resistance (Rct) of a redox probe diffusing through the polyelectrolyte brush was measured, and the temperature corresponding to the discontinuous change in Rct was identified as Tg. Furthermore, we demonstrate that impedance measurements not only facilitate the estimation of Tg but also enable a reliable evaluation of the transport properties of the polymeric interface, i.e., determination of diffusion coefficients, close to the thermal transition. We consider that this approach bridges the gap between electrochemistry and the traditional tools used in polymer science and offers new opportunities to characterize the thermal behavior of complex polymeric interfaces and macromolecular assemblies.

  18. Evaluation of interim and final waste forms for the newly generated liquid low-level waste flowsheet

    International Nuclear Information System (INIS)

    Abotsi, G.M.K.; Bostick, D.T.; Beck, D.E.

    1996-05-01

    The purpose of this review is to evaluate the final forms that have been proposed for radioactive-containing solid wastes and to determine their application to the solid wastes that will result from the treatment of newly generated liquid low-level waste (NGLLLW) and Melton Valley Storage Tank (MVST) supernate at the Oak Ridge National Laboratory (ORNL). Since cesium and strontium are the predominant radionuclides in NGLLLW and MVST supernate, this review is focused on the stabilization and solidification of solid wastes containing these radionuclides in cement, glass, and polymeric materials-the principal waste forms that have been tested with these types of wastes. Several studies have shown that both cesium and strontium are leached by distilled water from solidified cement, although the leachabilities of cesium are generally higher than those of strontium under similar conditions. The situation is exacerbated by the presence of sulfates in the solution, as manifested by cracking of the grout. Additives such as bentonite, blast-furnace slag, fly ash, montmorillonite, pottery clay, silica, and zeolites generally decrease the cesium and strontium release rates. Longer cement curing times (>28 d) and high ionic strengths of the leachates, such as those that occur in seawater, also decrease the leach rates of these radionuclides. Lower cesium leach rates are observed from vitrified wastes than from grout waste forms. However, significant quantities of cesium are volatilized due to the elevated temperatures required to vitrify the waste. Hence, vitrification will generally require the use of cleanup systems for the off-gases to prevent their release into the atmosphere

  19. Low temperature synthesis of CaO-SiO2 glasses having stable liquid-liquid immiscibility by sol-gel process

    Science.gov (United States)

    Bansal, Narottam P.

    1990-01-01

    Calcium silicate glass compositions lying within the liquid-liquid immiscibility dome of the phase diagram, which could not have been prepared by the conventional melting method, were synthesized by the sol-gel process. Hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) solutions containing up to 20 mol percent calcium nitrate resulted in the formation of clear and transparent gels. The gel formation time decreased with increase in water:TEOS mole ratio, calcium content, and the reaction temperature. Smaller values of gel times in the presence of calcium nitrate are probably caused by lowering of the ionic charge on the sol particles by the salt present. The gelation activation energy, E(sub gel), was evaluated from temperature dependence of the gel time. Presence of Ca(2+) ions or the water:TEOS mole ratio did not have an appreciable effect on the value of E(sub gel). Presence of glycerol in the solution helped in the formation of crack-free monolithic gel specimens. Chemical and structural changes occurring in the gels, as a function of the heat treatments, have been monitored using DTA, TGA, IR-spectroscopy, x ray diffraction, surface area and pore size distribution measurements.

  20. Low temperature synthesis of CaO-SiO2 glasses having stable liquid-liquid immiscibility by the sol-gel process

    Science.gov (United States)

    Bansal, N. P.

    1992-01-01

    Calcium silicate glass compositions lying within the liquid-liquid immiscibility dome of the phase diagram, which could not have been prepared by the conventional melting method, were synthesized by the sol-gel process. Hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) solutions containing up to 20 mol percent calcium nitrate resulted in the formation of clear and transparent gels. The gel formation time decreased with increase in water: TEOS mole ratio, calcium content, and the reaction temperature. Smaller values of gel times in the presence of calcium nitrate are probably caused by lowering of the ionic charge on the sol particles by the salt present. The gelation activation energy, E(sub gel), was evaluated from temperature dependence of the gel time. Presence of Ca(2+) ions or the water:TEOS mole ratio did not have an appreciable effect on the value of E(sub gel). Presence of glycerol in the solution helped in the formation of crack-free monolithic gel specimens. Chemical and structural changes occurring in the gels, as a function of the heat treatments, have been monitored using DTA, TGA, IR-spectroscopy, X-ray diffraction, surface area and pore size distribution measurements.

  1. Experimental study of the form of "hot" steel particles on the ignition characteristics of liquid fuels

    Science.gov (United States)

    Zakharevich, Arkadiy V.

    2015-01-01

    The results of an experimental study of laws governing the ignition of liquid propellants (kerosene, diesel fuel and petroleum residue) by the single spherical steel particle heated to high temperatures are presented. Is carried out the comparison of the ignition delay times of the investigated flammable substances by the particles in the sphere and disk forms. It is established that the particle shape does not exert a substantial influence on the ignition process characteristics.

  2. Mechanical Properties of Stable Glasses Using Nanoindentation

    Science.gov (United States)

    Wolf, Sarah; Liu, Tianyi; Jiang, Yijie; Ablajan, Keyume; Zhang, Yue; Walsh, Patrick; Turner, Kevin; Fakhraai, Zahra

    Glasses with enhanced stability over ordinary, liquid quenched glasses have been formed via the process of Physical Vapor Deposition (PVD) by using a sufficiently slow deposition rate and a substrate temperature slightly below the glass transition temperature. These stable glasses have been shown to exhibit higher density, lower enthalpy, and better kinetic stability over ordinary glass, and are typically optically birefringent, due to packing and orientational anisotropy. Given these exceptional properties, it is of interest to further investigate how the properties of stable glasses compare to those of ordinary glass. In particular, the mechanical properties of stable glasses remain relatively under-investigated. While the speed of sound and elastic moduli have been shown to increase with increased stability, little is known about their hardness and fracture toughness compared to ordinary glasses. In this study, glasses of 9-(3,5-di(naphthalen-1-yl)phenyl)anthracene were deposited at varying temperatures relative to their glass transition temperature, and their mechanical properties measured by nanoindentation. Hardness and elastic modulus of the glasses were compared across substrate temperatures. After indentation, the topography of these films were studied using Atomic Force Microscopy (AFM) in order to further compare the relationship between thermodynamic and kinetic stability and mechanical failure. Z.F. and P.W. acknowledge funding from NSF(DMREF-1628407).

  3. Dependence of glass-forming ability on starting compositions in Y2O3–Al2O3–SiO2 system

    OpenAIRE

    Yixiang Chen; Zengchao Yang; Bin He; Guanghua Liu; Jiangtao Li; Liang Wu

    2011-01-01

    The dependence of glass-forming ability on starting compositions in Y2O3–Al2O3–SiO2 (YAS) system has been investigated by melting experiment. Transparent YAS glasses have been prepared under the condition of furnace cooling instead of quenching. It is found that, in the YAS ternary phase diagram, the compositions on the Y3Al5O12–SiO2 line and with 52-68 mol% SiO2 have a higher glass-forming ability to produce pure glass. For the compositions with too much or less SiO2 or with Y/Al = 5/3, 1/1,...

  4. Laser ablation of toluene liquid for surface micro-structuring of silica glass

    International Nuclear Information System (INIS)

    Niino, H.; Kawaguchi, Y.; Sato, T.; Narazaki, A.; Gumpenberger, T.; Kurosaki, R.

    2006-01-01

    Microstructures with well-defined micropatterns were fabricated on the surfaces of silica glass using a laser-induced backside wet etching (LIBWE) method by diode-pumped solid state (DPSS) UV laser at the repetition rate of 10 kHz. For a demonstration of flexible rapid prototyping as mask-less exposure system, the focused laser beam was directed to the sample by galvanometer-based point scanning system. Additionally, a diagnostics study of plume propagation in the ablated products of toluene solid film was carried out with an intensified CCD (ICCD) camera

  5. The solidification of high-level liquid wastes in glass and ceramics

    International Nuclear Information System (INIS)

    Krause, H.

    1989-01-01

    In spent nuclear fuel reprocessing a highly radioactive waste solution is produced. It must be converted into a solid product, which binds the radionuclides, be hydrolytic as well as radiation and temperature resistant. Borosilicate glasses fulfil these requirements and, jointly with the barriers of a repository, they prevent inadmissible amounts of radionuclides from escaping into the biocycle. Two techniques were developed for industrial-scale vitrification: a rotary kiln calciner combined with an induction heated metallic melter and the electrode heated ceramic melters. Both techniques were already demonstrated on an industrial scale and under radioactive conditions. (AVM, Marcoule and PAMELA, Mol). (orig./MM) [de

  6. Obtaining of lysozyme spherulitic forms at ambient temperature using pyrrolidinium octanoat as ionic liquid additive

    Directory of Open Access Journals (Sweden)

    Claudia Simona ŞTEFAN

    2012-12-01

    Full Text Available Pyrrolidinium octanoate carboxylate (Py+CnH2n+1COO-; PyO in abbreviation was used as additive for advanced crystallization of Lysozyme protein, to investigate the impact of protic ionic liquid on the protein crystal morphology. The ionic liquid was synthesized by acidic-base Brönsted neutralization, and its purity was checked by HPLC. The protein crystallization was made through the method of vapour diffusion with hanging drops. Crystallization experiments of Lysozyme with the addition of PyO were performed at 0.4 M PyO and respectively 1.6 M. The morphological of spherulitic forms of Lysozyme in aqueous solutions of PyO protic ionic liquid was investigated by optical microscopy after trials were incubated at ambient temperature (18-20°C, in various growth periods (3 days and 1 week. Hanging-drop vapour diffusion crystallization experiments with the addition of 0.4 M of PyO show that Lysozyme crystallized in type I spherulitic form. This is assumed to be a result of heterogeneous nucleation, with thin needles radially growing outwardfrom a more or less spherical particle. Hanging-drop vapour diffusioncrystallization experiments revealed that the addition of 1.6 M of PyO led to a second type of spherulitic form of the Lysozyme.

  7. Non-monotonic variations of the nucleation free energy in a glass-forming ultra-soft particles fluid.

    Science.gov (United States)

    Desgranges, Caroline; Delhommelle, Jerome

    2018-06-18

    Using molecular dynamics simulation, we study the impact of the degree of supercooling on the crystal nucleation of ultra-soft particles, modeled with the Gaussian core potential. Focusing on systems with a high number density, our simulations reveal dramatically different behaviors as the degree of supercooling is varied. In the moderate supercooling regime, crystal nucleation proceeds as expected from classical nucleation theory, with a decrease in the free energy of nucleation, as well as in the size of the critical nucleus, as supercooling is increased. On the other hand, in the large supercooling regime, we observe an unusual reversal of behavior with an increase in the free energy of nucleation and in the critical size, as supercooling is increased. This unexpected result is analyzed in terms of the interplay between the glass transition and the crystal nucleation process. Specifically, medium range order crystal-like domains, with structural features different from that of the crystal nucleus, are found to form throughout the system when the supercooling is very large. These, in turn, play a pivotal role in the increase in the free energy of nucleation, as well as in the critical size, as the temperature gets closer to the glass transition.

  8. Effect of Si addition on the glass-forming ability of a NiTiZrAlCu alloy

    International Nuclear Information System (INIS)

    Liang, W.Z.; Shen, J.; Sun, J.F.

    2006-01-01

    The effect of Si addition on the glass-forming ability (GFA) of a NiTiZrAlCu alloy was investigated by using differential scanning calorimetry (DSC), differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The maximum diameter of glassy rods increased from 0.5 mm for the Ni 42 Ti 20 Zr 25 Al 8 Cu 5 alloy (the base alloy) to 2.5 mm for the Ni 42 Ti 20 Zr 21.5 Al 8 Cu 5 Si 3.5 alloy and to 3 mm for the Ni 42 Ti 19 Zr 22.5 Al 8 Cu 5 Si 3.5 alloy, when prepared by using the copper mould casting. The GFA of the alloys can be assessed by the reduced glass transition temperature T rg (=T g /T l ) and a newly proposed parameter, δ(=T x /T l - T g ). An addition of a proper amount of Si and a minor substitution of Ti with Zr can enhance the GFA of the base alloy by suppressing the formation of primary Ni(TiZr) and (TiZr)(CuAl) 2 phases and inducing the composition close to eutectic

  9. Analysis of the Glass-Forming Ability of Fe-Er Alloys, Based on Thermodynamic Modeling

    Science.gov (United States)

    Arutyunyan, N. A.; Zaitsev, A. I.; Dunaev, S. F.; Kalmykov, K. B.; El'nyakov, D. D.; Shaposhnikov, N. G.

    2018-05-01

    The Fe-Er phase diagram and thermodynamic properties of all its phases are assessed by means of self-consistent analysis. To refine the data on phase equilibria in the Fe-Er system, an investigation is performed in the 10-40 at % range of Er concentrations. The temperature-concentration dependences of the thermodynamic properties of a melt are presented using the model of ideal associated solutions. Thermodynamic parameters of each phase are obtained, and the calculated results are in agreement with available experimental data. The correlation between the thermodynamic properties of liquid Fe-Er alloys and their tendency toward amorphization are studied. It is shown that compositions of amorphous alloys prepared by melt quenching coincide with the ranges of concentration with the predominance of Fe3Er and FeEr2 associative groups that have large negative entropies of formation.

  10. Equilibrium and out-of-equilibrium thermodynamics in supercooled liquids and glasses

    International Nuclear Information System (INIS)

    Mossa, S; Nave, E La; Tartaglia, P; Sciortino, F

    2003-01-01

    We review the inherent structure thermodynamical formalism and the formulation of an equation of state (EOS) for liquids in equilibrium based on the (volume) derivatives of the statistical properties of the potential energy surface. We also show that, under the hypothesis that during ageing the system explores states associated with equilibrium configurations, it is possible to generalize the proposed EOS to out-of-equilibrium (OOE) conditions. The proposed formulation is based on the introduction of one additional parameter which, in the chosen thermodynamic formalism, can be chosen as the local minimum where the slowly relaxing OOE liquid is trapped

  11. Alignment engineering in liquid crystalline elastomers: Free-form microstructures with multiple functionalities

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Hao; Cerretti, Giacomo; Wiersma, Diederik S., E-mail: camilla.parmeggiani@lens.unifi.it, E-mail: wiersma@lens.unifi.it [European Laboratory for Non Linear Spectroscopy (LENS), University of Florence, via Nello Carrara 1, 50019 Sesto Fiorentino (Italy); Wasylczyk, Piotr [European Laboratory for Non Linear Spectroscopy (LENS), University of Florence, via Nello Carrara 1, 50019 Sesto Fiorentino (Italy); Faculty of Physics, Institute of Experimental Physics, University of Warsaw, ul. Hoza 69, Warszawa 00-681 (Poland); Martella, Daniele [European Laboratory for Non Linear Spectroscopy (LENS), University of Florence, via Nello Carrara 1, 50019 Sesto Fiorentino (Italy); Dipartimento di Chimica “Ugo Schiff,” University of Florence, via della Lastruccia 3-13, 50019 Sesto Fiorentino (Italy); Parmeggiani, Camilla, E-mail: camilla.parmeggiani@lens.unifi.it, E-mail: wiersma@lens.unifi.it [European Laboratory for Non Linear Spectroscopy (LENS), University of Florence, via Nello Carrara 1, 50019 Sesto Fiorentino (Italy); CNR-INO, via Nello Carrara 1, 50019 Sesto Fiorentino (Italy)

    2015-03-16

    We report a method to fabricate polymer microstructures with local control over the molecular orientation. Alignment control is achieved on molecular level in a structure of arbitrary form that can be from 1 to 100 μm in size, by fixing the local boundary conditions with micro-grating patterns. The method makes use of two-photon polymerization (Direct Laser Writing) and is demonstrated specifically in liquid-crystalline elastomers. This concept allows for the realization of free-form polymeric structures with multiple functionalities which are not possible to realize with existing techniques and which can be locally controlled by light in the micrometer scale.

  12. An alternative host matrix based on iron phosphate glasses for the vitrification of specialized nuclear waste forms. Annual progress report, September 15, 1996 - September 14, 1997

    International Nuclear Information System (INIS)

    Day, D.E.; Marasinghe, K.; Ray, C.S.

    1997-01-01

    'Objectives of this project are to: (1) investigate the glass composition and processing conditions that yield optimum properties for iron phosphate glasses for vitrifying radioactive waste, (2) determine the atomic structure of iron phosphate glasses and the structure-property relationships, (3) determine how the physical and structural properties of iron phosphate glasses are affected by the addition of simulated high level nuclear waste components, and (4) investigate the process and products of devitrification of iron phosphate waste forms. The glass forming ability of about 125 iron phosphate melts has been investigated in different oxidizing to reducing atmospheres using various iron oxide raw materials such as Fe 2 O 3 , FeO, Fe 3 O 4 , and FeC 2 O 4 2H 2 O. The chemical durability, redox equilibria between Fe(II) and Fe(III), crystallization behavior and structural features for these glasses and their crystalline forms have been investigated using a variety of techniques including Mossbauer spectroscopy, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), Extended x-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) analysis, differential thermal and thermogravimetric analysis (DTA/TGA), and X-ray and neutron diffraction.'

  13. Effect of glass-forming biopreservatives on head group rotational dynamics in freeze-dried phospholipid bilayers: A 31P NMR study

    Science.gov (United States)

    Jain, P.; Sen, S.; Risbud, S. H.

    2009-07-01

    P31 NMR spectroscopy has been used to elucidate the role of glass-forming sugars in the preservation of dipalmitoylphosphatidylcholine (DPPC) lipid bilayers. P31 wideline NMR spectra of freeze-dried pure DPPC, DPPC/trehalose, DPPC/glucose, and DPPC/hydroxyethyl starch (HES) mixtures collected in the temperature range of 25-80 °C have been simulated to obtain quantitative information about rotational dynamics and orientation of the lipid head groups in these media. In the case of pure DPPC, DPPC/glucose, and DPPC/HES, the gel-to-liquid crystalline phase transition of DPPC bilayer is characterized by a sudden increase in the rate of rotational diffusion of the PO4 head groups near 40 °C. The corresponding rotational jump frequency increases from a few kilohertz in the gel phase to at least several megahertz in the liquid crystalline phase. On the other hand, in the case of DPPC/trehalose mixture the temperature of this onset of rapid head group dynamics is increased by ˜10 °C. Trehalose reduces the lipid head group motions most effectively in the temperature range of T ≤50 °C relevant for biopreservation. Additionally, and possibly more importantly, trehalose is found to strongly restrict any change in the orientation of the diffusion axis of the PO4 head groups during the phase transformation. This unique ability of trehalose to maintain the dynamical and orientational rigidity of lipid head groups is likely to be responsible for its superior ability in biopreservation.

  14. Composition dependency of the glass forming ability (GFA) in Mg-Ni-Si system by mechanical alloying

    International Nuclear Information System (INIS)

    Xie Haowen; Lin Jianguo; Li Yuncang; Hodgson, Peter D.; Wen Cuie

    2007-01-01

    The pure elemental powder mixtures with the compositions of Mg 65 Ni x Si 35-x (x = 10, 20, 25, 33 at.%) were subject to high-energy ball mill, and the structures of the mixtures at different intervals of milling were characterised by X-ray diffraction (XRD). The compositional dependency of the glass forming ability (GFA) in Mg-Ni-Si system was evaluated based on the experimental results and the theoretical calculation. The compositional dependency of GFA in Mg-Ni-Si system can be understood well by comparing the enthalpies of the crystalline and amorphous phases based on the Miedema's theory for the formation enthalpy of alloys. Increasing the Ni/Mg ratio and/or decreasing Si content can improve the amorphous formability. The calculation results might be of great help in optimising the composition with high GFA in Mg-Ni-Si system

  15. Dynamics and thermodynamics of polymer glasses.

    Science.gov (United States)

    Cangialosi, D

    2014-04-16

    The fate of matter when decreasing the temperature at constant pressure is that of passing from gas to liquid and, subsequently, from liquid to crystal. However, a class of materials can exist in an amorphous phase below the melting temperature. On cooling such materials, a glass is formed; that is, a material with the rigidity of a solid but exhibiting no long-range order. The study of the thermodynamics and dynamics of glass-forming systems is the subject of continuous research. Within the wide variety of glass formers, an important sub-class is represented by glass forming polymers. The presence of chain connectivity and, in some cases, conformational disorder are unfavourable factors from the point of view of crystallization. Furthermore, many of them, such as amorphous thermoplastics, thermosets and rubbers, are widely employed in many applications. In this review, the peculiarities of the thermodynamics and dynamics of glass-forming polymers are discussed, with particular emphasis on those topics currently the subject of debate. In particular, the following aspects will be reviewed in the present work: (i) the connection between the pronounced slowing down of glassy dynamics on cooling towards the glass transition temperature (Tg) and the thermodynamics; and, (ii) the fate of the dynamics and thermodynamics below Tg. Both aspects are reviewed in light of the possible presence of a singularity at a finite temperature with diverging relaxation time and zero configurational entropy. In this context, the specificity of glass-forming polymers is emphasized.

  16. Glass: a candidate engineered material for management of high level nuclear waste

    International Nuclear Information System (INIS)

    Mishra, R.K.; Kaushik, C.P.

    2011-01-01

    While the commercial importance of glass is generally recognized, a few people are aware of extremely wide range of glass formulations that can be made and of the versatility of this engineered material. Some of the recent developments in the field of glass leading to various technological applications include glass fiber reinforcement of cement to give new building materials, substrates for microelectronics circuitry in form of semiconducting glasses, nuclear waste immobilization and specific medical applications. The present paper covers fundamental understanding of glass structure and its application for immobilization of high level radioactive liquid waste. High level radioactive liquid waste (HLW) arising during reprocessing of spent fuel are immobilized in sodium borosilicate glass matrix developed indigenously. Glass compositions are modified according to the composition of HLW to meet the criteria of desirable properties in terms. These glass matrices have been characterized for different properties like homogeneity, chemical durability, thermal stability and radiation stability. (author)

  17. A Microsystem Based on Porous Silicon-Glass Anodic Bonding for Gas and Liquid Optical Sensing

    Directory of Open Access Journals (Sweden)

    Ivo Rendina

    2006-06-01

    Full Text Available We have recently presented an integrated silicon-glass opto-chemical sensor forlab-on-chip applications, based on porous silicon and anodic bonding technologies. In thiswork, we have optically characterized the sensor response on exposure to vapors of severalorganic compounds by means of reflectivity measurements. The interaction between theporous silicon, which acts as transducer layer, and the organic vapors fluxed into the glasssealed microchamber, is preserved by the fabrication process, resulting in optical pathincrease, due to the capillary condensation of the vapors into the pores. Using theBruggemann theory, we have calculated the filled pores volume for each substance. Thesensor dynamic has been described by time-resolved measurements: due to the analysischamber miniaturization, the response time is only of 2 s. All these results have beencompared with data acquired on the same PSi structure before the anodic bonding process.

  18. 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

  19. Characterization of a glass-bonded ceramic waste form loaded with U and Pu

    International Nuclear Information System (INIS)

    Sinkler, W.; O'Holleran, T. P.; Frank, S. M.; Richmann, M. K.; Johnson, S. G.

    1999-01-01

    This paper presents microscopic characterization of four samples of a ceramic waste form (CWF) developed for disposal of actinide-containing electrorefiner salts. The four samples were prepared to investigate the influence of water content and the Pu:U ratio on CWF microstructure and performance. While the overall phase content is not strongly influenced by either variable, the presence of water in the initial zeolite has a detectable effect on CWF microstructure. It is found to influence the distribution of the major actinide host phase, a (U,Pu)O 2 mixed oxide

  20. Impulsive Stimulated Light Scattering Studies of the Liquid-Glass Transition: on the Experimental Verification of Mode-Coupling Theory Predictions.

    Science.gov (United States)

    Halalay, Ion C.

    A study of the structural glass transition trough impulsive stimulated light scattering experiments has been carried out in concentrated aqueous lithium chloride solutions, at temperatures ranging from ambient to cryogenic. A specially designed sample cell made it possible to cover the whole temperature interval from simple liquid, to viscoelastic supercooled liquid, to glass. It is shown that a phenomenological description of the results of these experiments in terms of a spectrum of relaxation times through the use of a Kohlrausch-Williams-Watts relaxation function is inadequate. Based on predictions of mode-coupling theory of the liquid-glass transition, an alternative approach to data interpretation is proposed. It is shown that for an aqueous lithium chloride solution, the prediction of simple scaling and identical scaling for mechanical and electrical susceptibilities seems to be valid. However, another prediction of theory is called into question: instead of a power-law behavior on temperature difference, it is found experimentally that the behavior of the susceptibility spectrum minimum is exponential. Similar disagreements are found for other two materials, triphenyl phosphite and polypropylene oxide. The causes for these discrepancies are discussed and it is concluded that additional experimentation is necessary to verify theoretical claims. Experiments are proposed which can test these predictions and serve as guide for the construction of theoretical models for the glass transition in real systems. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617 -253-5668; Fax 617-253-1690.).

  1. Unveiling the relationships among the viscosity equations of glass liquids and colloidal suspensions for obtaining universal equations with the generic free volume concept.

    Science.gov (United States)

    Hao, Tian

    2015-09-14

    The underlying relationships among viscosity equations of glass liquids and colloidal suspensions are explored with the aid of free volume concept. Viscosity equations of glass liquids available in literature are focused and found to have a same physical basis but different mathematical expressions for the free volume. The glass transitions induced by temperatures in glass liquids and the percolation transition induced by particle volume fractions in colloidal suspensions essentially are a second order phase transition: both those two transitions could induce the free volume changes, which in turn determines how the viscosities are going to change with temperatures and/or particle volume fractions. Unified correlations of the free volume to both temperatures and particle volume fractions are thus proposed. The resulted viscosity equations are reducible to many popular viscosity equations currently widely used in literature; those equations should be able to cover many different types of materials over a wide temperature range. For demonstration purpose, one of the simplified versions of those newly developed equations is compared with popular viscosity equations and the experimental data: it can well fit the experimental data over a wide temperature range. The current work reveals common physical grounds among various viscosity equations, deepening our understanding on viscosity and unifying the free volume theory across many different systems.

  2. Glasses and ceramics for immobilisation of radioactive wastes for disposal

    International Nuclear Information System (INIS)

    Johnson, K.D.B.; Marples, J.A.C.

    1979-05-01

    The U.K. Research Programme on Radioactive Waste Management includes the development of processes for the conversion of high level liquid reprocessing wastes from thermal and fast reactors to borosilicate glasses. The properties of these glasses and their behaviour under storage and disposal conditions have been examined. Methods for immobilising activity from other wastes by conversion to glass or ceramic forms is described. The U.K. philosophy of final solutions to waste management and disposal is presented. (author)

  3. Comparative risk assessments for the production and interim storage of glass and ceramic waste forms: defense waste processing facility

    International Nuclear Information System (INIS)

    Huang, J.C.; Wright, W.V.

    1982-04-01

    The Defense Waste Processing Facility (DWPF) for immobilizing nuclear high level waste (HLW) is scheduled to be built at the Savannah River Plant (SRP). High level waste is produced when SRP reactor components are subjected to chemical separation operations. Two candidates for immobilizing this HLW are borosilicate glass and crystalline ceramic, either being contained in weld-sealed stainless steel canisters. A number of technical analyses are being conducted to support a selection between these two waste forms. The present document compares the risks associated with the manufacture and interim storage of these two forms in the DWPF. Process information used in the risk analysis was taken primarily from a DWPF processibility analysis. The DWPF environmental analysis provided much of the necessary environmental information. To perform the comparative risk assessments, consequences of the postulated accidents are calculated in terms of: (1) the maximum dose to an off-site individual; and (2) the dose to off-site population within 80 kilometers of the DWPF, both taken in terms of the 50-year inhalation dose commitment. The consequences are then multiplied by the estimated accident probabilities to obtain the risks. The analyses indicate that the maximum exposure risk to an individual resulting from the accidents postulated for both the production and interim storage of either waste form represents only an insignificant fraction of the natural background radiation of about 90 mrem per year per person in the local area. They also show that there is no disaster potential to the off-site population. Therefore, the risks from abnormal events in the production and the interim storage of the DWPF waste forms should not be considered as a dominant factor in the selection of the final waste form

  4. Making MgO/SiO2 Glasses By The Sol-Gel Process

    Science.gov (United States)

    Bansal, Narottam P.

    1989-01-01

    Silicon dioxide glasses containing 15 mole percent magnesium oxide prepared by sol-gel process. Not made by conventional melting because ingredients immiscible liquids. Synthesis of MgO/SiO2 glass starts with mixing of magnesium nitrate hexahydrate with silicon tetraethoxide, both in alcohol. Water added, and transparent gel forms. Subsequent processing converts gel into glass. Besides producing glasses of new composition at lower processing temperatures, sol-gel method leads to improved homogeneity and higher purity.

  5. Theoretical predictions for glass flow into an evacuated canister

    International Nuclear Information System (INIS)

    Routt, K.R.; Crow, K.R.

    1983-01-01

    Radioactive waste currently stored at the Savannah River Plant in liquid form is to be immobilized by incorporating it into a borosilicate glass. The glass melter for this process will consist of a refractory lined, steel vessel operated at a glass temperature of 1150 0 C. At the end of a two-year projected melter lifetime, the glass inside the melter is to be drained prior to disposition of the melter vessel. One proposed technique for accomplishing this drainage is by sucking the glass into an evacuated canister. The theoretical bases for design of an evacuated canister for draining a glass melter have been developed and tested. The theoretical equations governing transient and steady-state flow were substantiated with both a silicone glass simulant and molten glass

  6. Separation coefficients of liquid-vapor in systems formed by yttrium chloride with some impurities

    International Nuclear Information System (INIS)

    Volkov, V.T.; Nikiforova, T.V.; Nisel'son, L.A.; Telegin, G.F.

    1990-01-01

    Using equilibrium Rayleigh distillation in the 800-950 deg C temperature range, separation coefficients of liquid-vapor for systems, formed by yttrium chloride with Co, Cr, Ni, Mn, Fe, Cu, Na, K, Mg, Ca, Li impurities are determined. The impurity concentration lies within 0.02-0.4 mass. % limits of each impurity, and total impurity concentration does not exceed 1 mass. %. The tested impurities, except for calcium, are more volatile than the base, yttrium trichloride. In most systems negative deviation from the Raoult's law is observed

  7. CRYSTALLIZATION IN MULTICOMPONENT GLASSES

    Energy Technology Data Exchange (ETDEWEB)

    KRUGER AA; HRMA PR

    2009-10-08

    In glass processing situations involving glass crystallization, various crystalline forms nucleate, grow, and dissolve, typically in a nonuniform temperature field of molten glass subjected to convection. Nuclear waste glasses are remarkable examples of multicomponent vitrified mixtures involving partial crystallization. In the glass melter, crystals form and dissolve during batch-to-glass conversion, melter processing, and product cooling. Crystals often agglomerate and sink, and they may settle at the melter bottom. Within the body of cooling glass, multiple phases crystallize in a non-uniform time-dependent temperature field. Self-organizing periodic distribution (the Liesegnang effect) is common. Various crystallization phenomena that occur in glass making are reviewed.

  8. Crystallization In Multicomponent Glasses

    International Nuclear Information System (INIS)

    Kruger, A.A.; Hrma, P.R.

    2009-01-01

    In glass processing situations involving glass crystallization, various crystalline forms nucleate, grow, and dissolve, typically in a nonuniform temperature field of molten glass subjected to convection. Nuclear waste glasses are remarkable examples of multicomponent vitrified mixtures involving partial crystallization. In the glass melter, crystals form and dissolve during batch-to-glass conversion, melter processing, and product cooling. Crystals often agglomerate and sink, and they may settle at the melter bottom. Within the body of cooling glass, multiple phases crystallize in a non-uniform time-dependent temperature field. Self-organizing periodic distribution (the Liesegnang effect) is common. Various crystallization phenomena that occur in glass making are reviewed.

  9. Study on glass-forming ability and hydrogen storage properties of amorphous Mg60Ni30La10−xCox (x = 0, 4) alloys

    International Nuclear Information System (INIS)

    Lv, Peng; Wang, Zhong-min; Zhang, Huai-gang; Balogun, Muhammad-Sadeeq; Ji, Zi-jun; Deng, Jian-qiu; Zhou, Huai-ying

    2013-01-01

    Mg 60 Ni 30 La 10−x Co x (x = 0, 4) amorphous alloys were prepared by rapid solidification, using a melt-spinning technique. X-ray diffraction and differential scanning calorimetry analysis were employed to measure their microstructure, thermal stability and glass-forming ability, and hydrogen storage properties were studied by means of PCTPro2000. Based on differential scanning calorimetry results, their glass-forming ability and thermal stability were investigated by Kissinger method, Lasocka curves and atomic cluster model, respectively. The results indicate that glass-forming ability, thermal properties and hydrogen storage properties in the Mg-rich corner of Mg–Ni–La–Co system alloys were enhanced by Co substitution for La. It can be found that the smaller activation energy (ΔΕ) and frequency factor (υ 0 ), the bigger value of B (glass transition point in Lasocka curves), and higher glass-forming ability of Mg–Ni–La–Co alloys would be followed. In addition, atomic structure parameter (λ), deduced from atomic cluster model is valuable in the design of Mg–Ni–La–Co system alloys with good glass-forming ability. With an increase of Co content from 0 to 4, the hydrogen desorption capacity within 4000 s rises from 2.25 to 2.85 wt.% at 573 K. - Highlights: • Amorphous Mg 60 Ni 30 La 10−x Co x (x = 0 and 4) alloys were produced by melt spinning. • The GFA and hydrogen storage properties were enhanced by Co substitution for La. • With an increase of Co content, the hydrogen desorption capacity rises at 573 K

  10. A review of the toxicity of biomass pyrolysis liquids formed at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Diebold, J P [Thermalchemie, Inc., Lakewood, CO (United States)

    1997-04-01

    The scaleup of biomass fast pyrolysis systems to large pilot and commercial scales will expose an increasingly large number of personnel to potential health hazards, especially during the evaluation of the commercial use of the pyrolysis condensates. Although the concept of fast pyrolysis to optimize liquid products is relatively new, low-temperature pyrolysis processes have been used over the aeons to produce charcoal and liquid by-products, e.g., smoky food flavors, food preservatives, and aerosols containing narcotics, e.g., nicotine. There are a number of studies in the historical literature that concern the hazards of acute and long-term exposure to smoke and to the historical pyrolysis liquids formed at low temperatures. The reported toxicity of smoke, smoke food flavors, and fast pyrolysis oils is reviewed. The data found for these complex mixtures suggest that the toxicity may be less than that of the individual components. It is speculated that there may be chemical reactions that take place that serve to reduce the toxicity during aging. 81 refs.

  11. The study of diffusion in network-forming liquids under pressure and temperature

    Energy Technology Data Exchange (ETDEWEB)

    Hung, P.K. [Department of Computational Physics, Hanoi University of Technology, 1Dai Co Viet, Hanoi (Viet Nam); Kien, P.H., E-mail: phkien80@gmail.com [Department of Physics, Thainguyen University of Education, 20 Luong Ngoc Quyen, Thainguyen (Viet Nam); San, L.T.; Hong, N.V. [Department of Computational Physics, Hanoi University of Technology, 1Dai Co Viet, Hanoi (Viet Nam)

    2016-11-15

    In this paper, the molecular dynamics simulation is applied to investigate the diffusion in silica liquids under different temperature and pressure. We show that the diffusion is controlled by the rate of effective SiO{sub x}→SiO{sub x±1} and OSi{sub y}→OSi{sub y±1} reaction. With increasing the pressure, the rate of reaction increases and the Si–O bond is weaker. Moreover, the reactions are not uniformly distributed in the space, but instead they happen frequently or rarely in separate regions. We also reveal two motion types: free and correlation motion. The correlation motion concerns the moving of a group of atoms which is similar to that of the diffusion of a super-molecule in the liquid. A detailed analysis of the movement of atoms from specified set shows the clustering of them which indicates structure and dynamics heterogeneity. Further, we find that the correlation motion is very important for the diffusion in network-forming liquid. The observed phenomena such as diffusion anomaly, dynamics heterogeneity and dynamical slowdown are originated from the correlation motion of atom.

  12. Solidification of intermediate level liquid waste - ILLW, CEMEX waste form qualification

    International Nuclear Information System (INIS)

    D'Andrea, V.; Guerra, M.; Pancotti, F.; Maio, V.

    2015-01-01

    In the Sogin EUREX Facility about 125 m 3 of intermediate level radioactive waste and about 113 m 3 of low level radioactive waste, produced during the re-processing of MTR and CANDU fuel, are stored. Solidification of these wastes is planned in order to fulfill the specific requirements established by the Safety Authority, taking into account the criteria set up in a Technical Guide on the issue of radioactive waste management. The design of a cementation plant (CEMEX) of all liquid radioactive wastes is currently ongoing. The process requires that the liquid waste is neutralized with NaOH (NaOH 19 M) and metered into 440 liter drum together with the cement, while the mixture is stirred by a lost paddle ('in drum mixing process'). The qualification of the Waste Form consists of all the activities demonstrating that the final cemented product has the minimum requirements (mechanical, chemical and physical characteristics) compliant with all the subsequent management phases: long-term interim storage, transport and long-term disposal of the waste. All tests performed to qualify the conditioning process for immobilizing first extraction cycle (MTR and CANDU) and second extraction cycle liquid wastes, gave results in compliance with the minimum requirements established for disposal

  13. The polymer–polymorphoid nature of glass aging process

    Directory of Open Access Journals (Sweden)

    Victor S. Minaev

    2015-12-01

    Full Text Available Based on the concept of polymeric–polymorphous structure of glass and glass-forming liquid experimental data have been analyzed revealing the nature of glass aging. We show that the glass forming substance is a copolymer consisting of structural nano-fragments (polymorphoids in different polymorphous modifications (PM of the material having no translational symmetry (long-range order. The study revealed that the process and degree of glass aging influences the properties of glasses, including a change in enthalpy, manifested in the exothermic and endothermic effects observed in thermograms of differential scanning calorimetry of heated and cooled glasses. We have shown that the physicochemical essence of aging is the transformation of polymorphoids from high-temperature PM (HTPM to low-temperature PM (LTPM which results, under certain conditions, in LTPM crystallization.

  14. Thermal Predictions of the Cooling of Waste Glass Canisters

    Energy Technology Data Exchange (ETDEWEB)

    Donna Post Guillen

    2014-11-01

    Radioactive liquid waste from five decades of weapons production is slated for vitrification at the Hanford site. The waste will be mixed with glass forming additives and heated to a high temperature, then poured into canisters within a pour cave where the glass will cool and solidify into a stable waste form for disposal. Computer simulations were performed to predict the heat rejected from the canisters and the temperatures within the glass during cooling. Four different waste glass compositions with different thermophysical properties were evaluated. Canister centerline temperatures and the total amount of heat transfer from the canisters to the surrounding air are reported.

  15. Glass-forming ability and structure of ZnO-MoO.sub.3./sub.-P.sub.2./sub.O.sub.5./sub. glasses

    Czech Academy of Sciences Publication Activity Database

    Šubčík, J.; Koudelka, L.; Mošner, P.; Montagne, L.; Tricot, G.; Delevoye, L.; Gregora, Ivan

    2010-01-01

    Roč. 356, 44-49 (2010), 2509-2516 ISSN 0022-3093 R&D Projects: GA AV ČR KAN301370701 Institutional research plan: CEZ:AV0Z10100520 Keywords : phosphate glass es * structure * MAS NMR spectra * Raman spectra Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.483, year: 2010

  16. Hydrothermal alteration of the glass R7T7. Glass dissolution kinetics at 150 and 2500, role of neo-formed phases

    International Nuclear Information System (INIS)

    Caurel, J.

    1990-01-01

    The glass R7T7 is chosen in France for vitrification of solution from reprocessing. Safety requires the knowledge of R7T7 long term behavior in deep geologic formations. Temperature dependence of leaching between 50 and 300 0 C is studied by static tests for 7 days. An activation energy of 30kJ/Mole is calculated between 50; 75 or 100 0 C and 250 0 C. Results suggest similar corrosion mechanisms between 90-100 and 250 0 C by a complete change between 250 and 275 0 C. Glass corrosion kinetics at 150 0 C and 250 0 C between 1 day and 1 year evidence the precipitation of aluminosilicates and formation of thick amorphous gels progressively enriched with silica. Glass dissolution at 150 0 C and 250 0 C is simulated with the geochemical DISSOL code. Results suggest that dissolution kinetics are controlled by activity of H 4 SiO 4 in solution only. Silica contained into the gel controls corrosion kinetics different from 0. Even if the nature of dissolution mechanisms does not seem modified between 150 and 250 0 C, sample cracking at 250 0 C induces an increase of dissolved glass that does not allow a direct comparison of corrosion kinetics between 150 and 250 0 C [fr

  17. Glass-forming ability and structure of glasses in the ZnO-WO.sub.3./sub.-P.sub.2./sub.O.sub.5./sub. system

    Czech Academy of Sciences Publication Activity Database

    Koudelka, L.; Šubčík, J.; Mošner, P.; Gregora, Ivan; Montagne, L.; Delevoye, L.

    2012-01-01

    Roč. 53, č. 3 (2012), s. 79-85 ISSN 1753-3562 R&D Projects: GA AV ČR KAN301370701 Institutional research plan: CEZ:AV0Z10100520 Keywords : glasses * ternary systems * Raman spectra * NMR Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.764, year: 2012

  18. Formation of Ti--Zr--Cu--Ni bulk metallic glasses

    International Nuclear Information System (INIS)

    Lin, X.H.; Johnson, W.L.

    1995-01-01

    Formation of bulk metallic glass in quaternary Ti--Zr--Cu--Ni alloys by relatively slow cooling from the melt is reported. Thick strips of metallic glass were obtained by the method of metal mold casting. The glass forming ability of the quaternary alloys exceeds that of binary or ternary alloys containing the same elements due to the complexity of the system. The best glass forming alloys such as Ti 34 Zr 11 Cu 47 Ni 8 can be cast to at least 4-mm-thick amorphous strips. The critical cooling rate for glass formation is of the order of 250 K/s or less, at least two orders of magnitude lower than that of the best ternary alloys. The glass transition, crystallization, and melting behavior of the alloys were studied by differential scanning calorimetry. The amorphous alloys exhibit a significant undercooled liquid region between the glass transition and first crystallization event. The glass forming ability of these alloys, as determined by the critical cooling rate, exceeds what is expected based on the reduced glass transition temperature. It is also found that the glass forming ability for alloys of similar reduced glass transition temperature can differ by two orders of magnitude as defined by critical cooling rates. The origins of the difference in glass forming ability of the alloys are discussed. It is found that when large composition redistribution accompanies crystallization, glass formation is enhanced. The excellent glass forming ability of alloys such as Ti 34 Zr 11 Cu 47 Ni 8 is a result of simultaneously minimizing the nucleation rate of the competing crystalline phases. The ternary/quaternary Laves phase (MgZn 2 type) shows the greatest ease of nucleation and plays a key role in determining the optimum compositions for glass formation. copyright 1995 American Institute of Physics

  19. Research on Liquid Forming Process of Nickel Superalloys Thin Sheet Metals

    Directory of Open Access Journals (Sweden)

    Hyrcza-Michalska M.

    2017-12-01

    Full Text Available The paper presents the study of drawability of thin sheet metals made of a nickel superalloy Inconel type. The manufacturing process of axisymmetric cup – cone and a closed section profile in the form of a circular tube were designed and analyzed. In both cases, working fluid-oil was used in place of the rigid tools. The process of forming liquid is currently the only alternative method for obtaining complex shapes, coatings, and especially if we do it with high-strength materials. In the case of nickel superalloys the search for efficient methods to manufacture of the shaped shell is one of the most considerable problems in aircraft industry [1-5]. However, the automotive industries have the same problem with so-called advanced high-strength steels (AHSS. Due to this, both industrial problems have been examined and the emphasis have been put on the process of liquid forming (hydroforming. The study includes physical tests and the corresponding numerical simulations performed, using the software Eta/Dynaform 5.9. Numerical analysis of the qualitative and quantitative forecasting enables the formability of materials with complex and unusual characteristics of the mechanical properties and forming technology. It has been found that only the computer aided design based on physical and numerical modeling, makes efficient plastic processing possible using a method of hydroforming. Drawability evaluation based on the determination of the mechanical properties of complex characteristics is an indispensable element of this design in the best practice of industrial manufacturing products made of thin sheet metals.

  20. Structural aspects of fish skin collagen which forms ordered arrays via liquid crystalline states.

    Science.gov (United States)

    Giraud-Guille, M M; Besseau, L; Chopin, C; Durand, P; Herbage, D

    2000-05-01

    The ability of acid-soluble type I collagen extracts from Soleidae flat fish to form ordered arrays in condensed phases has been compared with data for calf skin collagen. Liquid crystalline assemblies in vitro are optimized by preliminary treatment of the molecular population with ultrasounds. This treatment requires the stability of the fish collagen triple helicity to be controlled by X-ray diffraction and differential scanning calorimetry and the effect of sonication to be evaluated by viscosity measurements and gel electrophoresis. The collagen solution in concentrations of at least 40 mg ml(-1) showed in polarized light microscopy birefringent patterns typical of precholesteric phases indicating long-range order within the fluid collagen phase. Ultrastructural data, obtained after stabilization of the liquid crystalline collagen into a gelated matrix, showed that neutralized acid-soluble fish collagen forms cross-striated fibrils, typical of type I collagen, following sine wave-like undulations in precholesteric domains. These ordered geometries, approximating in vivo situations, give interesting mechanical properties to the material.