First-order dissolution rate law and the role of surface layers in glass performance assessment

Science.gov (United States)

Grambow, B.; Müller, R.

2001-09-01

The first-order dissolution rate law is used for nuclear waste glass performance predictions since 1984. A first discussion of the role of saturation effects was initiated at the MRS conference that year. In paper (1) it was stated that "For glass dissolution A* (the reaction affinity) cannot become zero since saturation only involves the reacting surface while soluble elements still might be extracted from the glass" [B. Grambow, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 15]. Saturation of silica at the surface and condensation of surface silanol groups was considered as being responsible for the slow down of reaction rates by as much as a factor of 1000. Precipitation of Si containing secondary phases such as quartz was invoked as a mechanism for keeping final dissolution affinities higher than zero. Another (2) paper [A.B. Barkatt, P.B. Macedo, B.C. Gibson, C.J. Montrose, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 3] stated that "… under repository conditions the extent of glass dissolution will be moderate due to saturation with respect to certain major elements (in particular, Si, Al and Ca). Consequently, the concentration levels of the more soluble glass constituents in the aqueous medium are expected to fall appreciable below their solubility limit." The formation of dense surface layers was considered responsible for explaining the saturation effect. The mathematical model assumed stop of reaction in closed systems, once solubility limits were achieved. For more than 15 years the question of the correctness of one or the other concept has seldom been posed and has not yet been resolved. The need of repository performance assessment for validated rate laws demands a solution, particularly since the consequences of the two concepts and research requirements for the long-term glass behavior are quite different. In concept (1) the stability of the `equilibrium surface region' is not relevant because, by definition, this region is stable chemically and after a

Thermokinetic model of borosilicate glass dissolution: contextual affinity

International Nuclear Information System (INIS)

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

1989-01-01

Short and long-term geochemical interactions of R7T7 nuclear glass with water at 100 0 C were simulated with the DISSOL thermokinetic computer code. Both the dissolved glass quantity and the resulting water composition, saturation states and mineral quantities produced were calculated as a function of time. The rate equation used in the simulation was first proposed by Aagaard and Helgeson. It simulates a gradually diminishing dissolution rate as the reaction affinity diminishes. The best agreement with 1-year experimental data was obtained with a reaction affinity calculated from silica activity (Grambow's hypothesis) rather than taking into account the activity of all the glass components as proposed by Jantzen and Plodinec. The concept of residual affinity was introduced by Grambow to express the fact that the glass dissolution rate does not cease. We prefer to replace the term residual affinity by contextual affinity, which expresses the influence on the dissolution rate of three factors: the solution chemistry, the metastability of SiO 2 (m), and the possible precipitation of certain aluminosilicates such as zeolites. 19 refs

Attenuation of glass dissolution in the presence of natural additives

Energy Technology Data Exchange (ETDEWEB)

Sang, Jing C.; Barkatt, Aaron [Department of Chemistry, The Catholic University of America, Washington, DC (United States); O`Keefe, John A. [National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, MD (United States)

1996-11-01

The dissolution kinetics of silicate glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase are reported. The results demonstrate the possibility of a dramatic decrease in the rate of dissolution of silicate glass in the presence of certain varieties of olivine-based materials. This decrease in dissolution rate was shown to be due to the fact that these additives consist mostly of Mg-based material but also contain minor amounts of Al and Ca. The combined presence of Mg with these minor species affected the corrosion rate of the glass as a whole, including its most soluble components such as boron. This study has potentially important implications to the durability of glasses exposed to natural environments. The results may be relevant to the use of active backfill materials in burial sites for nuclear waste glasses, as well as to better understanding of the environmental degradation of natural and ancient glasses.

Thermokinetic model of borosilicate glass dissolution: Contextual affinity

International Nuclear Information System (INIS)

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

1990-01-01

Short and long-term geochemical interactions of R7T7 nuclear glass with water at 100C were simulated with the DISSOL thermokinetic computer code. Both the dissolved glass quantity and the resulting water composition, saturation states and mineral quantities produced were calculated as a function of time. The rate equation used in the simulation was first proposed by Aagaard and Hegelson: v = k + · S · a( H + ) -n · (1 - e -(A/RT) ). It simulates a gradually diminishing dissolution rate as the reaction affinity diminishes. The best agreement with 1-year experimental data was obtained with a reaction affinity calculated from silica activity (Grambow's hypothesis) rather than taking into account the activity of all the glass components as proposed by Jantzen and Plodinec. The concept of residual affinity was introduced by Grambow to express the fact that the glass dissolution rate does not cease. The authors prefer to replace the term residual affinity by contextual affinity, which expresses the influence on the dissolution rate of three factors: the solution chemistry, the metastability of SiO 2 (m), and the possible precipitation of certain aluminosilicates such as zeolites

Thermodynamic and structural models compared with the initial dissolution rates of open-quotes SONclose quotes glass samples

International Nuclear Information System (INIS)

Tovena, I.; Advocat, T.; Ghaleb, D.; Vernaz, E.; Larche, F.

1994-01-01

The experimentally determined initial dissolution rate R 0 of nuclear glass was correlated with thermodynamic parameters and structural parameters. The initial corrosion rates of six open-quotes R7T7close quotes glass samples measured at 100 degrees C in a Soxhlet device were correlated with the glass free hydration energy and the glass formation enthalpy. These correlations were then tested with a group of 26 SON glasses selected for their wide diversity of compositions. The thermodynamic models provided a satisfactory approximation of the initial dissolution rate determined under Soxhlet conditions for SON glass samples that include up to 15 wt% of boron and some alumina. Conversely, these models are inaccurate if the boron concentration exceeds 15 wt% and the glass contains no alumina. Possible correlations between R 0 and structural parameters, such as the boron coordination number and the number of nonbridging oxygen atoms, were also investigated. The authors show that R 0 varies inversely with the number of 4-coordinate boron atoms; conversely, the results do not substantiate published reports of a correlation between R 0 and the number of nonbridging oxygen atoms

Glass composition and solution speciation effects on stage III dissolution

International Nuclear Information System (INIS)

Trivelpiece, Cory L.; Rice, Jarret A.; Pantano, Carlo G.

2017-01-01

To understand and mitigate the onset of Stage III corrosion of multicomponent oxides waste glasses. Stage III refers to a resumption of the high initial rate of glass dissolution in some glass samples that have otherwise exhibited dissolution at the much lower residual rate for a long time (Stage II). Although the onset of Stage III is known to occur concurrently with the precipitation of particular alteration products, the root cause of the transition is still unknown. Certain glass compositions (notably AFCI) and high pH environmental conditions are also associated with this observed transition.

Glass composition and solution speciation effects on stage III dissolution

Energy Technology Data Exchange (ETDEWEB)

Trivelpiece, Cory L. [Pennsylvania State Univ., University Park, PA (United States); Rice, Jarret A. [Pennsylvania State Univ., University Park, PA (United States); Pantano, Carlo G. [Pennsylvania State Univ., University Park, PA (United States)

2017-10-03

To understand and mitigate the onset of Stage III corrosion of multicomponent oxides waste glasses. Stage III refers to a resumption of the high initial rate of glass dissolution in some glass samples that have otherwise exhibited dissolution at the much lower residual rate for a long time (Stage II). Although the onset of Stage III is known to occur concurrently with the precipitation of particular alteration products, the root cause of the transition is still unknown. Certain glass compositions (notably AFCI) and high pH environmental conditions are also associated with this observed transition.

The Dissolution Behavior of Borosilicate Glasses in Far-From Equilibrium Conditions

Energy Technology Data Exchange (ETDEWEB)

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin PG; Ryan, Joseph V.; Asmussen, Robert M.

2018-02-10

In far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this paper is to study effects of these variables on three model waste glasses (SON68, ISG, AFCI). To do this, experiments were conducted at temperatures of 23, 40, 70, and 90 °C and pH(RT) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. The results from these tests were then used to parameterize a kinetic rate model based on transition state theory. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Discrepancies in the absolute dissolution rates as compared to those obtained using other test methods are discussed. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies. The results were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), which is capable of providing a robust uncertainty analysis. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, the effect of glass composition on the rate parameter values could possibly be obtained. This would allow for the possibility of predicting the forward dissolution rate of glass based solely on composition

Improvement of database on glass dissolution

International Nuclear Information System (INIS)

Hayashi, Maki; Sasamoto, Hiroshi; Yoshikawa, Hideki

2008-03-01

In geological disposal system, high-level radioactive waste (HLW) glass is expected to retain radionuclide for the long term as the first barrier to prevent radionuclide release. The advancement of its performance assessment technology leads to the reliability improvement of the safety assessment of entire geological disposal system. For this purpose, phenomenological studies for improvement of scientific understanding of dissolution/alteration mechanisms, and development of robust dissolution/alteration model based on the study outcomes are indispensable. The database on glass dissolution has been developed for supporting these studies. This report describes improvement of the prototype glass database. Also, this report gives an example of the application of the database for reliability assessment of glass dissolution model. (author)

Dissolution patterns of biocompatible glasses in 2-amino-2-hydroxymethyl-propane-1,3-diol (Tris) buffer.

Science.gov (United States)

Fagerlund, S; Hupa, L; Hupa, M

2013-02-01

A continuous flow measurement system with sensitive on-line ion analysis has been applied to study the initial dissolution behaviour of biocompatible glasses in Tris. Altogether 16 glasses with widely varying compositions were studied. The measurement system allowed for quantitative determination of the time-dependent rates of dissolution of sodium, potassium, calcium, magnesium, silicon and phosphorus during the first 10-15 min in contact with Tris solution. The dissolution rates of the different ions showed significant glass to glass variations, but all glasses studied showed one of four distinct dissolution patterns. The ion dissolution rates after an exposure of 1000 s, expressed as the normalized surface-specific mass loss rates, were compared with the in vitro and in vivo reactivity of the glasses as predicted by models in the literature. The results showed a clear correlation between the dissolution rates of the glasses in Tris and their reactivity as measured by other different methods. Consequently, the measured short-term dissolution patterns could be used to determine which glasses are suitable as bioactive, biodegradable, or inert biomaterials for medical devices. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The effect of clay on the dissolution of nuclear waste glass

Science.gov (United States)

Lemmens, K.

2001-09-01

In a nuclear waste repository, the waste glass can interact with metals, backfill materials (if present) and natural host rock. Of the various host rocks considered, clays are often reported to delay the onset of the apparent glass saturation, where the glass dissolution rate becomes very small. This effect is ascribed to the sorption of silica or other glass components on the clay. This can have two consequences: (1) the decrease of the silica concentration in solution increases the driving force for further dissolution of glass silica, and (2) the transfer of relatively insoluble glass components (mainly silica) from the glass surface to the clay makes the alteration layer less protective. In recent literature, the latter explanation has gained credibility. The impact of the environmental materials on the glass surface layers is however not well understood. Although the glass dissolution can initially be enhanced by clay, there are arguments to assume that it will decrease to very low values after a long time. Whether this will indeed be the case, depends on the fate of the released glass components in the clay. If they are sorbed on specific sites, it is likely that saturation of the clay will occur. If however the released glass components are removed by precipitation (growth of pre-existing or new secondary phases), saturation of the clay is less likely, and the process can continue until exhaustion of one of the system components. There are indications that the latter mechanism can occur for varying glass compositions in Boom Clay and FoCa clay. If sorption or precipitation prevents the formation of protective surface layers, the glass dissolution can in principle proceed at a high rate. High silica concentrations are assumed to decrease the dissolution rate (by a solution saturation effect or by the impact on the properties of the glass alteration layer). In glass corrosion tests at high clay concentrations, silica concentrations are, however, often higher

The effect of clay on the dissolution of nuclear waste glass

International Nuclear Information System (INIS)

Lemmens, K.

2001-01-01

In a nuclear waste repository, the waste glass can interact with metals, backfill materials (if present) and natural host rock. Of the various host rocks considered, clays are often reported to delay the onset of the apparent glass saturation, where the glass dissolution rate becomes very small. This effect is ascribed to the sorption of silica or other glass components on the clay. This can have two consequences: (1) the decrease of the silica concentration in solution increases the driving force for further dissolution of glass silica, and (2) the transfer of relatively insoluble glass components (mainly silica) from the glass surface to the clay makes the alteration layer less protective. In recent literature, the latter explanation has gained credibility. The impact of the environmental materials on the glass surface layers is however not well understood. Although the glass dissolution can initially be enhanced by clay, there are arguments to assume that it will decrease to very low values after a long time. Whether this will indeed be the case, depends on the fate of the released glass components in the clay. If they are sorbed on specific sites, it is likely that saturation of the clay will occur. If however the released glass components are removed by precipitation (growth of pre-existing or new secondary phases), saturation of the clay is less likely, and the process can continue until exhaustion of one of the system components. There are indications that the latter mechanism can occur for varying glass compositions in Boom Clay and FoCa clay. If sorption or precipitation prevents the formation of protective surface layers, the glass dissolution can in principle proceed at a high rate. High silica concentrations are assumed to decrease the dissolution rate (by a solution saturation effect or by the impact on the properties of the glass alteration layer). In glass corrosion tests at high clay concentrations, silica concentrations are, however, often higher

Plutonium dioxide dissolution in glass

International Nuclear Information System (INIS)

Vienna, J.D.; Alexander, D.L.; Li, Hong

1996-09-01

In the aftermath of the Cold War, the U.S. Department of Energy's (DOE) Office of Fissile Materials Disposition (OFMD) is charged with providing technical support for evaluation of disposition options for excess fissile materials manufactured for the nation's defense. One option being considered for the disposition of excess plutonium (Pu) is immobilization by vitrification. The vitrification option entails immobilizing Pu in a host glass and waste package that are criticality-safe (immune to nuclear criticality), proliferation-resistant, and environmentally acceptable for long-term storage or disposal. To prove the technical and economic feasibility of candidate vitrification options it is necessary to demonstrate that PuO 2 feedstock can be dissolved in glass in sufficient quantity. The OFMD immobilization program has set a Pu solubility goal of 10 wt% in glass. The life cycle cost of the vitrification options are strongly influenced by the rate at which PUO 2 dissolves in glass. The total number of process lines needed for vitrification of 50 t of Pu in 10 years is directly dependent upon the time required for Pu dissolution in glass. The objective of this joint Pacific Northwest National Laboratory (PNNL) - Savannah River Technology Center (SRTC) study was to demonstrate a high Pu solubility in glass and to identify on a rough scale the time required for Pu dissolution in the glass. This study was conducted using a lanthanide borosilicate (LaBS) glass composition designed at the SRTC for the vitrification of actinides

Plutonium dioxide dissolution in glass

Energy Technology Data Exchange (ETDEWEB)

Vienna, J.D.; Alexander, D.L.; Li, Hong [and others

1996-09-01

In the aftermath of the Cold War, the U.S. Department of Energy`s (DOE) Office of Fissile Materials Disposition (OFMD) is charged with providing technical support for evaluation of disposition options for excess fissile materials manufactured for the nation`s defense. One option being considered for the disposition of excess plutonium (Pu) is immobilization by vitrification. The vitrification option entails immobilizing Pu in a host glass and waste package that are criticality-safe (immune to nuclear criticality), proliferation-resistant, and environmentally acceptable for long-term storage or disposal. To prove the technical and economic feasibility of candidate vitrification options it is necessary to demonstrate that PuO{sub 2} feedstock can be dissolved in glass in sufficient quantity. The OFMD immobilization program has set a Pu solubility goal of 10 wt% in glass. The life cycle cost of the vitrification options are strongly influenced by the rate at which PUO{sub 2} dissolves in glass. The total number of process lines needed for vitrification of 50 t of Pu in 10 years is directly dependent upon the time required for Pu dissolution in glass. The objective of this joint Pacific Northwest National Laboratory (PNNL) - Savannah River Technology Center (SRTC) study was to demonstrate a high Pu solubility in glass and to identify on a rough scale the time required for Pu dissolution in the glass. This study was conducted using a lanthanide borosilicate (LaBS) glass composition designed at the SRTC for the vitrification of actinides.

Predicting the dissolution kinetics of silicate glasses using machine learning

Science.gov (United States)

Anoop Krishnan, N. M.; Mangalathu, Sujith; Smedskjaer, Morten M.; Tandia, Adama; Burton, Henry; Bauchy, Mathieu

2018-05-01

Predicting the dissolution rates of silicate glasses in aqueous conditions is a complex task as the underlying mechanism(s) remain poorly understood and the dissolution kinetics can depend on a large number of intrinsic and extrinsic factors. Here, we assess the potential of data-driven models based on machine learning to predict the dissolution rates of various aluminosilicate glasses exposed to a wide range of solution pH values, from acidic to caustic conditions. Four classes of machine learning methods are investigated, namely, linear regression, support vector machine regression, random forest, and artificial neural network. We observe that, although linear methods all fail to describe the dissolution kinetics, the artificial neural network approach offers excellent predictions, thanks to its inherent ability to handle non-linear data. Overall, we suggest that a more extensive use of machine learning approaches could significantly accelerate the design of novel glasses with tailored properties.

The dissolution rate of silicate glasses and minerals: an alternative model based on several activated complexes

International Nuclear Information System (INIS)

Berger, G.

1997-01-01

Most of the mineral reactions in natural water-rock systems progress at conditions close to the chemical equilibrium. The kinetics of these reactions, in particular the dissolution rate of the primary minerals, is a major constrain for the numerical modelling of diagenetic and hydrothermal processes. In the case of silicates, recent experimental studies have pointed out the necessity to better understand the elementary reactions which control the dissolution process. This article presents several models that have been proposed to account for the observed dissolution rate/chemical affinity relationships. The case of glasses (R7T7), feldspars and clays, in water, in near neutral pH aqueous solutions and in acid/basic media, are reviewed. (A.C.)

Toward a consistent model for glass dissolution

International Nuclear Information System (INIS)

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

1994-01-01

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

Enhancement of the glass corrosion in the presence of clay minerals: testing experimental results with an integrated glass dissolution model

International Nuclear Information System (INIS)

Godon, N.; Vernaz, E.Y.

1992-01-01

Recent glass dissolution experiments, conducted at 90 deg C in the presence of potential backfill materials, indicate remarkably faster glass corrosion in the presence of clay, compared to tests where the glass is leached either alone or with alternative backfill materials. This effect correlates with the clay content in the backfill, and may be attributed to the removal of silica from solution. Scorpion, or dissolution with reprecipitation of a silica-rich clay, have been proposed as possible mechanisms for the silica consumption. The results of some experiments have been tested against a glass dissolution model, in which a widely used kinetic equation for glass corrosion is coupled with diffusive silica transport through a single porosity, linearly sorbing medium, which represents the backfilling. Because the glass corrosion rates imposed by the kinetic equation are inversely proportional to the silicic acid concentration of the leachant contacting the glass, the model predicts enhanced glass dissolution if silica is sorbed by the porous medium. The experimental data proved to be consistent with the predicted enhancement of the glass dissolution. Moreover, the model-estimated distribution coefficients for silica sorption (K d ) fall within the range of values extracted from available literature data, thus supporting the hypothesis that the observed high corrosion rates are due to sorption of silica on the clay mineral surfaces. (author)

Effect of Callovo-Oxfordian clay rock on the dissolution rate of the SON68 simulated nuclear waste glass

Energy Technology Data Exchange (ETDEWEB)

Neeway, James J., E-mail: James.Neeway@pnnl.gov [SUBATECH, Unité Mixte de Recherche 6457, École des Mines de Nantes, CNRS/IN2P3, Université de Nantes, BP 20722, 44307 Nantes cedex 3 (France); Abdelouas, Abdesselam; Ribet, Solange; El Mendili, Yassine [SUBATECH, Unité Mixte de Recherche 6457, École des Mines de Nantes, CNRS/IN2P3, Université de Nantes, BP 20722, 44307 Nantes cedex 3 (France); Schumacher, Stéphan [ANDRA, Parc de la Croix Blanche, 1/7 rue Jean Monnet, 92298 Châtenay-Malabry (France); Grambow, Bernd [SUBATECH, Unité Mixte de Recherche 6457, École des Mines de Nantes, CNRS/IN2P3, Université de Nantes, BP 20722, 44307 Nantes cedex 3 (France)

2015-04-15

Long-term storage of high-level nuclear waste glass in France is expected to occur in an engineered barrier system (EBS) located in a subsurface Callovo-Oxfordian (COx) clay rock formation in the Paris Basin in northeastern France. Understanding the behavior of glass dissolution in the complex system is critical to be able to reliably model the performance of the glass in this complex environment. To simulate this multi-barrier repository scenario in the laboratory, several tests have been performed to measure glass dissolution rates of the simulated high-level nuclear waste glass, SON68, in the presence of COx claystone at 90 °C. Experiments utilized a High-Performance Liquid Chromatography (HPLC) pump to pass simulated Bure site COx pore water through a reaction cell containing SON68 placed between two COx claystone cores for durations up to 200 days. Silicon concentrations at the outlet were similar in all experiments, even the blank experiment with only the COx claystone (∼4 mg/L at 25 °C and ∼15 mg/L at 90 °C). The steady-state pH of the effluent, measured at room temperature, was roughly 7.1 for the blank and 7.3–7.6 for the glass-containing experiments demonstrating the pH buffering capacity of the COx claystone. Dissolution rates for SON68 in the presence of the claystone were elevated compared to those obtained from flow-through experiments conducted with SON68 without claystone in silica-saturated solutions at the same temperature and similar pH values. Additionally, through surface examination of the monoliths, the side of the monolith in direct contact with the claystone was seen to have a corrosion thickness 2.5× greater than the side in contact with the bulk glass powder. Results from one experiment containing {sup 32}Si-doped SON68 also suggest that the movement of Si through the claystone is controlled by a chemically coupled transport with a Si retention factor, K{sub d}, of 900 mL/g.

Dissolution rate enhancement of piroxicam by ordered mixing.

Science.gov (United States)

Saharan, Vikas Anand; Choudhury, Pratim Kumar

2012-07-01

Micronized piroxicam was mixed with lactose, mannitol, sorbitol, maltitol and sodium chloride to produce ordered mixture in a glass vial by manual hand shaking method. The effect of excipients, surfactant, superdisintegrant, drug concentration and carrier particle size on dissolution rate was investigated. Dissolution rate studies of the prepared ordered mixtures revealed that all water soluble excipients increased the dissolution rate of piroxicam when compared to the dissolution rate of piroxicam or its suspension. Ordered mixture formulation PLF4, consisting of lactose as water soluble excipient, SSG (8% w/s) and SLS (1% w/w), released piroxcam at a very fast rate so much so that about 90% of the composition had passed into solution within 2 min. The order of the dissolution rate enhancement for ordered mixtures of various water soluble excipients was: lactose > mannitol > maltitol > sorbitol > sodium chloride. Carrier granules of size 355-710 µm were most effective in increasing the dissolution rate of drug from ordered mixtures. Decreasing the carrier particle size reduced drug dissolution from ordered mixtures. The dissolution rate of ordered mixtures consisting of 1-5% w/w piroxicam was superior to dissolution rate of piroxicam suspension. The dissolution data fitting and the resulting regression parameters indicated Hixson Crowell, cube root law, as the best fit to drug release data of ordered mixtures.

Numerical modelling of glass dissolution: gel layer morphology

Energy Technology Data Exchange (ETDEWEB)

Devreux, F. E-mail: fd@pmc.polytechnique.fr; Barboux, P

2001-09-01

Numerical simulations of glass dissolution are presented. The glass is modelized as a random binary mixture composed of two species representing silica and soluble oxides, such as boron and alkali oxides. The soluble species are dissolved immediately when they are in contact with the solution. For the species which represents silica, one introduces dissolution and condensation probabilities. It is shown that the morphology and the thickness of the surface hydration layer (the gel) are highly dependent on the dissolution model, especially on the parameter which controls the surface tension. Simulations with different glass surface area to solution volume ratio (S/V) show that this experimental parameter has important effects on both the shrinkage and the gel layer thickness.

Impact of iron chelators on short-term dissolution of basaltic glass

Science.gov (United States)

Perez, Anne; Rossano, Stéphanie; Trcera, Nicolas; Verney-Carron, Aurélie; Huguenot, David; van Hullebusch, Eric D.; Catillon, Gilles; Razafitianamaharavo, Angelina; Guyot, François

2015-08-01

Although microorganisms seem to play an important role in the alteration processes of basaltic glasses in solution, the elementary mechanisms involved remain unclear in particular with regard to the role of organic ligands excreted by the cells. Two glasses, one with Fe and one without Fe were synthesized to model basaltic glass compositions. Fe in the glass was mostly Fe(III) for enhancing interaction with siderophores, yet with small but significant amounts of Fe(II) (between 10% and 30% of iron). The prepared samples were submitted to abiotic alteration experiments in buffered (pH 6.4) diluted solutions of metal-specific ligands, namely oxalic acid (OA, 10 mM), desferrioxamine (DFA, 1 mM) or 2,2‧-bipyridyl (BPI, 1 mM). Element release from the glass into the solution after short term alteration (maximum 1 week) was measured by ICP-OES, and normalized mass losses and relative release ratios (with respect to Si) were evaluated for each element in each experimental condition. The presence of organic ligands had a significant effect on the dissolution of both glasses. Trivalent metals chelators (OA, DFA) impacted on the release of Fe3+ and Al3+, and thus on the global dissolution of both glasses, enhancing all release rates and dissolution stoichiometry (release rates were increased up to 7 times for Al or Fe). As expected, the mostly divalent metal chelator BPI interacted preferentially with Ca2+, Mg2+ and Fe2+. This study thus allows to highlight the central roles of iron and aluminium in interaction with some organic ligands in the alteration processes of basaltic glasses. It thus provides a step toward understanding the biological contribution of this fundamental geological process.

Progress toward bridging from atomistic to continuum modeling to predict nuclear waste glass dissolution.

Energy Technology Data Exchange (ETDEWEB)

Zapol, Peter (Argonne National Laboratory, Argonne, IL); Bourg, Ian (Lawrence Berkeley National Laboratories, Berkeley, CA); Criscenti, Louise Jacqueline; Steefel, Carl I. (Lawrence Berkeley National Laboratories, Berkeley, CA); Schultz, Peter Andrew

2011-10-01

This report summarizes research performed for the Nuclear Energy Advanced Modeling and Simulation (NEAMS) Subcontinuum and Upscaling Task. The work conducted focused on developing a roadmap to include molecular scale, mechanistic information in continuum-scale models of nuclear waste glass dissolution. This information is derived from molecular-scale modeling efforts that are validated through comparison with experimental data. In addition to developing a master plan to incorporate a subcontinuum mechanistic understanding of glass dissolution into continuum models, methods were developed to generate constitutive dissolution rate expressions from quantum calculations, force field models were selected to generate multicomponent glass structures and gel layers, classical molecular modeling was used to study diffusion through nanopores analogous to those in the interfacial gel layer, and a micro-continuum model (K{mu}C) was developed to study coupled diffusion and reaction at the glass-gel-solution interface.

Results of testing the Grambow rate law for use in HWVP glass durability correlations

International Nuclear Information System (INIS)

Kuhn, W.L.; Bunnell, L.R.

1996-03-01

A theory based on Grambow's work on hydration of glass as linear function of solution composition was evaluated. Use of Grambow's linear rate law for correlation of durability with glass composition is not recommended. Dissolution rate of the glass was determined using the rate of release of sodium with an ion selective electrode. This method was tested first applying it to initial dissolution rate of several glasses at several temperatures with zero initial concentration of silicic acid. HW39-2, HW39-4, and SRL-202 from Savannah River were tested; there was significant scatter in the data, with the dissolution rates of HW39 glasses and the SRL glass being comparable within this scatter. The dissolution rate of SRL-202 at 80 C and pH 7 for silicic acid concentrations 0, 25, 50, and 100% saturation, was found to decrease dramatically at only 25% of the saturated silicic acid concentration, which does not conform to the linear theory

Modeling surface area to volume effects on borosilicate glass dissolution

International Nuclear Information System (INIS)

Bourcier, W.L.; Ebert, W.L.; Feng, X.

1992-11-01

We simulated the reaction of SRL-131 glass with equilibrated J-13 water in order to investigate the effects of surface area to volume ratio (SA/V) on glass dissolution. We show that glass-fluid ion exchange causes solution pH to rise to progressively higher values as SA/V increases. Because the ion exchange is rapid relative to the duration of the glass dissolution experiment, the pH effect does not scale with (SA/V)*time. Experiments compared at the same (SA/V)*time value therefore have different pHs, with higher pHs at higher SA/V ratios. Both experimental data and our simulation results show similar trends of increasing reaction rate as a function of SA/V ratio when scaled to (SA/V)*time. Glasses which react in systems of differing SA/V ratio therefore follow different reaction paths and high SA/V ratios cannot be used to generate data which accurately scales to long time periods unless the ion exchange effect is taken into account. We suggest some simple test designs which enable more reliable high. SA/V accelerated tests

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

International Nuclear Information System (INIS)

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

1991-01-01

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

Antibacterial effects and dissolution behavior of six bioactive glasses.

Science.gov (United States)

Zhang, Di; Leppäranta, Outi; Munukka, Eveliina; Ylänen, Heimo; Viljanen, Matti K; Eerola, Erkki; Hupa, Mikko; Hupa, Leena

2010-05-01

Dissolution behavior of six bioactive glasses was correlated with the antibacterial effects of the same glasses against sixteen clinically important bacterial species. Powdered glasses (<45 microm) were immersed in simulated body fluid (SBF) for 48 h. The pH in the solution inside the glass powder was measured in situ with a microelectrode. After 2, 4, 27, and 48 h, the pH and concentration of ions after removing the particles and mixing the SBF were measured with a normal glass pH electrode and ICP-OES. The bacteria were cultured in broth with the glass powder for up to 4 days, after which the viability of the bacteria was determined. The antibacterial effect of the glasses increased with increasing pH and concentration of alkali ions and thus with increased dissolution tendency of the glasses, but it also depended on the bacterium type. The changes in the concentrations of Si, Ca, Mg, P, and B ions in SBF did not show statistically significant influence on the antibacterial property. Bioactive glasses showed strong antibacterial effects for a wide selection of aerobic bacteria at a high sample concentration (100 mg/mL). The antibacterial effects increased with glass concentration and a concentration of 50 mg/mL (SA/V 185 cm(-1)) was required to generate the bactericidal effects. Understanding the dissolution mechanisms of bioactive glasses is essential when assessing their antibacterial effects. Copyright 2009 Wiley Periodicals, Inc.

SON68 nuclear glass dissolution kinetics: Current state of knowledge and basis of the new GRAAL model

Energy Technology Data Exchange (ETDEWEB)

Frugier, P. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France)], E-mail: pierre.frugier@cea.fr; Gin, S.; Minet, Y.; Chave, T. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France); Bonin, B. [CEA Saclay, DEN/DIR/DS, 91191 Gif-sur-Yvette cedex (France); Godon, N.; Lartigue, J.-E.; Jollivet, P. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France); Ayral, A. [IEM/CNRS-ENSCM Universite Montpellier 2, CC 047, Place Eugene Bataillon, 34095 Montpellier cedex 5 (France); De Windt, L. [ENSMP, CG, 35 rue St Honore, 77305 Fontainebleau cedex (France); Santarini, G. [CEA Saclay HC/CAB, 91191 Gif-sur-Yvette cedex (France)

2008-10-15

This article summarizes the present state of knowledge concerning aqueous alteration of R7T7-type nuclear containment glasses, represented mainly by the inactive reference glass designated SON68. Based on this review, we propose to describe the glass alteration kinetics up to and including the final residual rate regime by means of a new mechanistic model known as GRAAL (glassreactivitywithallowanceforthealterationlayer). Phenomenological analysis findings are reviewed for the various glass alteration regimes: interdiffusion, initial rate, rate drop, residual rate and, under very particular circumstances, resumption of alteration. These alteration regimes are associated with predominant mechanisms. Published work interpreting and modeling these mechanisms was examined in detail. There is a broad consensus on the general mechanisms of the initial rate and even the interdiffusion regime, whereas the mechanisms controlling the rate drop remain a subject of dispute not only with regard to nuclear glasses but also for the dissolution of silicate minerals. The reaction affinity responsible for the rate drop is expressed differently by different authors and depending on the underlying theories. The disagreement concerns the nature of the phase (glass or gel) or the activated complex controlling the rate drop, which in turn determines the elements that must be taken into account in the overall affinity term. Progress in recent years, especially in identifying the mechanisms responsible for the residual rate, has shed new light on these issues, allowing us to propose new theoretical foundations for modeling the different kinetic regimes of SON68 nuclear glass dissolution. The GRAAL model considers that water diffusion in the passivating reaction zone (the gel formed under saturation conditions) is a rate-limiting step in the overall glass dissolution kinetics. Moreover, this passivation zone is a soluble phase whose stability is directly dependent on the nature of the

Study of the surface crystallization and resistance to dissolution of niobium phosphate glasses for nuclear waste immobilization

International Nuclear Information System (INIS)

Vieira, Heveline

2008-01-01

The surface crystallization and the dissolution rate of three phosphate glass compositions containing different amounts of niobium oxide were studied. The glasses were named Nb30, Nb37, and Nb44 according to the nominal content of niobium oxide in the glass composition. The three compositions were evaluated keeping the P 2 O 5 /K 2 O ratio constant and varying the amount of Nb 2 O 5 . These glasses were produced by melting appropriate chemical compounds at 1500 deg C for 0.5 hour. The crystalline phases which were nucleated on the glass surface after heat treatment were determined by X-ray diffraction. The crystalline structures depend on the amount of niobium oxide in the glass composition. The crystal morphologies were observed by using an optical microscope, and their characteristics are specific for each kind of crystalline phase. The crystal growth rate and the surface nuclei density were determined for each glass composition, and they depend on each crystalline phase nucleated on the surface. From the differential thermal analysis curves it was determined that the Nb44 glass containing 46.5 mol por cent of niobium oxide is the most thermally stable against crystallization when compared to the Nb30 and Nb37 glasses. According to the activation energies determined for crystal growth on the surface of each glass type, the Nb44 glass can also be considered the most resistant one against crystallization. The dissolution rate for the Nb44 glass after 14 days immersed in an aqueous solution with pH equals to 7 at 90 deg C is the lowest (9.0 x 10 -7 g. cm -2 . day -1 ) when compared to the other two glass compositions. The dissolution rates in acidic and neutral solutions of all studied glasses meet the international standards for materials which can be used in the immobilization of nuclear wastes. (author)

Initial dissolution rate of a Japanese simulated high-level waste glass P0798 as a function of pH and temperature measured by using micro-channel flow-through test method

International Nuclear Information System (INIS)

Inagaki, Yaohiro; Makigaki, Hikaru; Idemitsu, Kazuya; Arima, Tatsumi; Mitsui, Sei-ichiro; Noshita, Kenji

2012-01-01

Aqueous dissolution tests were performed for a Japanese type of simulated high-level waste (HLW) glass P0798 by using a newly developed test method of micro-channel flow-through (MCFT) method, and the initial dissolution rate of glass matrix, r 0 , was measured as a function of solution pH (3-11) and temperature (25-90degC) precisely and consistently for systematic evaluation of the dissolution kinetics. The MCFT method using a micro-channel reactor with a coupon shaped glass specimen has the following features to provide precise and consistent data on the glass dissolution rate: (1) any controlled constant solution condition can be provided over the test duration; (2) the glass surface area actually reacting with solution can be determined accurately; and (3) direct and totally quantitative analyses of the reacted glass surface can be performed for confirming consistency of the test results. The present test results indicated that the r 0 shows a 'V-shaped' pH dependence with a minimum at around pH 6 at 25degC, but it changes to a 'U-shaped' one with a flat bottom at neutral pH at elevated temperatures of up to 90degC. The present results also indicated that the r 0 increases with temperature according to an Arrhenius law at any pH, and the apparent activation energy evaluated from Arrhenius relation increases with pH from 54 kJ/mol at pH 3 to 76 kJ/mol at pH 10, which suggests that the dissolution mechanism changes depending on pH. (author)

Theoretical consideration on the application of the Aagaard-Helgeson rate law to the dissolution of silicate minerals and glasses

International Nuclear Information System (INIS)

Gin, S.; Jegou, C.; Frugier, P.; Minet, Y.

2008-01-01

The kinetic laws derived from the work of Aagaard and Helgeson are discussed, notably those applied to aluminosilicate or borosilicate glasses. Aagaard and Helgeson extended the kinetic formalism of an elementary reaction in a homogeneous medium to overall alteration processes in heterogeneous media by assuming they consist of a series of elementary steps. The dissolution rate of a mineral phase can thus be expressed as follows: r φ = k φ Π(i)a i -n ij (1-exp(-A/σRT)) (1) where k φ is the kinetic constant of hydrolysis of the mineral φ, a i the activity of the reactants i in the limiting elementary step j, n ij the stoichiometric coefficient for reactant i in the limiting reaction j, A the chemical affinity of the overall dissolution reaction, σ the average stoichiometric number of the overall reaction, R the ideal gas constant and T the temperature. We first illustrate the relation between transition state theory and a kinetic law such as Eq. (1) initially associated with an elementary reaction, using the simple example of hydriodic acid synthesis. We then discuss the extension of Eq. (1) to overall processes, showing that there is no obvious relation between the elementary limiting step and the contents of the affinity function and that this reflects a problem of scale in the Aagaard-Helgeson law between the kinetic constant (based on microscopic theories) and the affinity term (a macroscopic entity derived from classical thermodynamics). The discussion shows the difficulties encountered in attempting to determine the activity of the reactants in the elementary limiting step, particularly in the case of surface groups, and highlights the limited validity of extending a chemical affinity law of the type (1-exp(-ΔG/RT))- which is theoretically valid for an elementary reaction near equilibrium for an overall process. Our article then reviews Grambow's reasoning and the difficulties he encountered in applying the Aagaard-Helgeson law to the dissolution of

Modeling the dissolution behavior of defense waste glass in a salt repository environment

International Nuclear Information System (INIS)

McGrain, B.P.

1988-02-01

A mechanistic model describing a dynamic mass balance between the production and consumption of dissolved silica was found to describe the dissolution behavior of SRL-165 defense waste glass in a high-magnesium brine (PBB3) at a temperature of 90 0 C. The synergistic effect of the waste package container on the glass dissolution rate was found to depend on a precipitation reaction for a ferrous silicate mineral. The model predicted that the ferrous silicate precipitate should be variable in composition where the iron/silica stoichiometry depended on the metal/glass surface area ratio used in the experiment. This prediction was confirmed experimentally by the variable iron/silica ratios observed in filtered leachates. However, the interaction between dissolved silica and iron corrosion products needs to be much better understood before the model can be used with confidence in predicting radionuclide release rates for a salt repository. 25 refs., 4 figs., 1 tab

Effect of clayey groundwater on the dissolution rate of SON68 simulated nuclear waste glass at 70 °C

Science.gov (United States)

De Echave, T.; Tribet, M.; Jollivet, P.; Marques, C.; Gin, S.; Jégou, C.

2018-05-01

To predict the long-term behavior of high-level radioactive waste glass, it is necessary to study aqueous dissolution of the glass matrix under geological repository conditions. The present article focuses on SON68 (an inactive surrogate of the R7T7 glass) glass alteration in synthetic clayey groundwater at 70 °C. Experiments in deionized water as reference were also performed in the same conditions. Results are in agreement with those of previous studies showing that magnesium present in the solution is responsible for higher glass alteration. This effect is transient and pH-dependent: Once all the magnesium is consumed, the glass alteration rate diminishes. Precipitation of magnesium silicate of the smectite group seems to be the main factor for the increased glass alteration. A pH threshold of 7.5-7.8 was found, above which precipitation of these magnesium silicates at 70 °C is possible. TEM observations reveal that magnesium silicates grow at the expense of the passivating gel, which partly dissolves, forming large pores which increase mass transfer between the reacting glass surface and the bulk solution.

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

Kinetic model for quartz and spinel dissolution during melting of high-level-waste glass batch

International Nuclear Information System (INIS)

Pokorny, Richard; Rice, Jarrett A.; Crum, Jarrod V.; Schweiger, Michael J.; Hrma, Pavel

2013-01-01

The dissolution of quartz particles and the growth and dissolution of crystalline phases during the conversion of batch to glass potentially affects both the glass melting process and product quality. Crystals of spinel exiting the cold cap to molten glass below can be troublesome during the vitrification of iron-containing high-level wastes. To estimate the distribution of quartz and spinel fractions within the cold cap, we used kinetic models that relate fractions of these phases to temperature and heating rate. Fitting the model equations to data showed that the heating rate, apart from affecting quartz and spinel behavior directly, also affects them indirectly via concurrent processes, such as the formation and motion of bubbles. Because of these indirect effects, it was necessary to allow one kinetic parameter (the pre-exponential factor) to vary with the heating rate. The resulting kinetic equations are sufficiently simple for the detailed modeling of batch-to-glass conversion as it occurs in glass melters. The estimated fractions and sizes of quartz and spinel particles as they leave the cold cap, determined in this study, will provide the source terms needed for modeling the behavior of these solid particles within the flow of molten glass in the melter

A general model for the dissolution of nuclear waste glasses in salt brine

International Nuclear Information System (INIS)

McGrail, B.P.; Strachan, D.M.

1988-07-01

A mechanistic model describing a dynamic mass balance between the production and consumption of dissolved silica was found to describe the dissolution of SRL-165 defense waste glass in a high-magnesium (PBB3) brine at a temperature of 90/degree/C. The synergetic effect of the waste package container on the glass dissolution rate was found to depend on a precipitation reaction for a ferrous silicate mineral. The model predicted that the ferrous silicate precipitate should be variable in composition where the iron-silica ratio depended on the metal-to-glass surface area ratio used in the experiment. This prediction was confirmed experimentally by the variable iron-silica ratios observed in filtered leachates. However, the interaction between dissolved silica and iron corrosion products needs to be much better understood before the model could be used with confidence in predicting radionuclide release rates for a salt repository. If the deleterious effects of the iron corrosion products can be shown to be transient, and the fracturing of the glass can be minimized, it appears that the performance of SRL-165 defense waste glass will be near the NRC regulatory criterion for fraction release of one part in 100,000 in PBB3 brine at 90/degree/C under silica-saturated conditions. 47 refs., 6 figs., 1 tab

Use of fission track for deciphering the dissolution mechanism of silicates glasses

International Nuclear Information System (INIS)

Petit, J.C.; Brousse, C.

1985-09-01

Polished sections of silicate glasses containing latent or pre-etched fission tracks have been subjected to corrosion in deionized water or NaCl brines at 20, 50 and 100 0 C. The evolution of glass surface helps deciphering among reported dissolution models. We show that ion-exchange is dominant in simple glasses while in complex ones, dissolution involves several steps including an in-situ transformation of the pristine material and a reprecipitation of dissolved species

Feldspar dissolution rates in the Topopah Spring Tuff, Yucca Mountain, Nevada

Science.gov (United States)

Bryan, C.R.; Helean, K.B.; Marshall, B.D.; Brady, P.V.

2009-01-01

Two different field-based methods are used here to calculate feldspar dissolution rates in the Topopah Spring Tuff, the host rock for the proposed nuclear waste repository at Yucca Mountain, Nevada. The center of the tuff is a high silica rhyolite, consisting largely of alkali feldspar (???60 wt%) and quartz polymorphs (???35 wt%) that formed by devitrification of rhyolitic glass as the tuff cooled. First, the abundance of secondary aluminosilicates is used to estimate the cumulative amount of feldspar dissolution over the history of the tuff, and an ambient dissolution rate is calculated by using the estimated thermal history. Second, the feldspar dissolution rate is calculated by using measured Sr isotope compositions for the pore water and rock. Pore waters display systematic changes in Sr isotopic composition with depth that are caused by feldspar dissolution. The range in dissolution rates determined from secondary mineral abundances varies from 10-16 to 10-17 mol s-1 kg tuff-1 with the largest uncertainty being the effect of the early thermal history of the tuff. Dissolution rates based on pore water Sr isotopic data were calculated by treating percolation flux parametrically, and vary from 10-15 to 10-16 mol s-1 kg tuff-1 for percolation fluxes of 15 mm a-1 and 1 mm a-1, respectively. Reconciling the rates from the two methods requires that percolation fluxes at the sampled locations be a few mm a-1 or less. The calculated feldspar dissolution rates are low relative to other measured field-based feldspar dissolution rates, possibly due to the age (12.8 Ma) of the unsaturated system at Yucca Mountain; because oxidizing and organic-poor conditions limit biological activity; and/or because elevated silica concentrations in the pore waters (???50 mg L-1) may inhibit feldspar dissolution. ?? 2009 Elsevier Ltd. All rights reserved.

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

International Nuclear Information System (INIS)

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

1996-01-01

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

Long-term leach rates of glasses containing actual waste

International Nuclear Information System (INIS)

Wiley, J.R.; LeRoy, J.H.

1979-01-01

Leach rates of borosilicate glasses that contained actual Savannah River Plant waste were measured. Leaching was done by water and by buffer solutions of pH 4, 7, and 9. Leach rates were then determined from the amount of 137 Cs, 90 Sr, and Pu released into the leach solutions. The cumulative fractions leached were fit to a mathematical model that included leaching by diffusion and glass dissolution

Biologically mediated dissolution of volcanic glass in seawater

NARCIS (Netherlands)

Staudigel, H; Yayanos, A; Chastain, R; Davies, G.T.; Verdurmen, E.A Th; Schiffmann, P; Bourcier, R; de Baar, H.J.W.

1998-01-01

We studied the effects of biological mediation on the dissolution of basaltic glass in seawater. Experiments with typical seawater microbial populations were contrasted with a sterile control, and reactions were monitored chemically and isotopically. Biologically mediated experiments produce twice

Long-term leach rates of glasses containing actual waste

International Nuclear Information System (INIS)

Wiley, J.R.; LeRoy, J.H.

1979-01-01

Leach rates of borosilicate glasses that contained actual Savannah River Plant waste were measured. Leaching was done by water and by buffer solutions of pH 4, 7, and 9. Leach rates were then determined from the amount of 137 Cs, 90 Sr, and plutonium released into the leach solutions. The cumulative fractions leached were fit to a mathematical model that included leaching by diffusion and glass dissolution. 5 figures, 3 tables

Haw-glass dissolution and radionuclide release: mechanism - modelling - source term

Energy Technology Data Exchange (ETDEWEB)

Grambow, B [Forschungszentrum Karlsruhe, Institut fur Nukleare, Karlsruhe (Germany)

1997-07-01

Important release controlling processes are: 1) kinetics of glass matrix dissolution (leaching), 2) formation of secondary alteration products (controlling thermodynamic solubility), 3) sorption on surfaces in the engineered barrier system and 4) formation of mobile species. Quantification of these processes requires assessment of the energetics and dynamics of the various reversible and irreversible processes within an overall open non-equilibrium system. Corrosion/dissolution of the waste matrices is not necessarily associated with a proportional release of radionuclides. The formation of new secondary phases, such as silicates, molybdates, uranates, carbonates... establishes a new geochemical barrier for re-immobilization of radionuclides dissolved from the waste matrices. The presence of iron (corroding canisters during glass alteration) reduces the solution concentration of redox sensitive radionuclides. Consequently, the container, after being corroded, constitutes an important geochemical barrier for radionuclide re-immobilization. Geochemical modelling of the long-term behaviour of glasses must be performed in an integrated way, considering simultaneous reactions of the glass, of container corrosion, of repository rock and of backfill material. Until now, only few attempts were made for integral systems modelling. (A.C.)

water alteration processes and kinetics of basaltic glasses, natural analogue of nuclear glasses

International Nuclear Information System (INIS)

Techer, I.; Advocat, Th.; Vernaz, E.; Lancelot, J.R.; Liotard, J.M.

1997-01-01

Dissolution experiments of a basaltic glass were carried out at 90 deg C for different reaction progresses. The initial dissolution rate was compared with values obtained for rhyolitic glass and the R7T7 nuclear glass. The activation energy was also determined by computing literature data. The results provide similar reactional mechanism for basaltic and nuclear glasses. Dissolution rates measured under saturation conditions were compared to theoretical dissolution rates. These ones were calculated using two kinetic models: the first rate equation is the Grambow's law which only takes into account ortho-silica acid activity; the second rate equation was proposed by Daux et al., where silica and aluminum are combined to formulate the affinity. The comparison between experimental and theoretical results point out that these two models are not appropriate to describe the alteration kinetic of basaltic glasses. (authors)

Anomalous dissolution behaviour of tablets prepared from sugar glass-based solid dispersions

NARCIS (Netherlands)

Van Drooge, D.J.; Hinrichs, W.L.J.; Frijlink, H.W.

2004-01-01

In this study, anomalous dissolution behaviour of tablets consisting of sugar glass dispersions was investigated. The poorly aqueous soluble diazepam was used as a lipophilic model drug. The release of diazepam and sugar carrier was determined to study the mechanisms governing dissolution behaviour.

Progress in development of a source term for sphene glass-ceramic dissolution under vault conditions

International Nuclear Information System (INIS)

Hayward, P.J.; Tait, J.C.; George, I.M.; Carmichael, A.A.; Ross, J.M.P.

1986-01-01

This report describes the results of ongoing leaching experiments, involving aluminosilicate glass and sphene (CaTiSiO/sub 5/) ceramics, doped with /sup 22/Na or /sup 45/Ca, and leached in a simulated Ca-NA-Cl brine at 25 0 or 100 0 C. The experiments are designed to aid development of separate models for the dissolution of the glass and the ceramic phase in a sphene glass-ceramic, and to help evaluate a composite model for the dissolution of the glass-ceramic

DEFENSE HIGH LEVEL WASTE GLASS DEGRADATION

International Nuclear Information System (INIS)

Ebert, W.

2001-01-01

The purpose of this Analysis/Model Report (AMR) is to document the analyses that were done to develop models for radionuclide release from high-level waste (HLW) glass dissolution that can be integrated into performance assessment (PA) calculations conducted to support site recommendation and license application for the Yucca Mountain site. This report was developed in accordance with the ''Technical Work Plan for Waste Form Degradation Process Model Report for SR'' (CRWMS M andO 2000a). It specifically addresses the item, ''Defense High Level Waste Glass Degradation'', of the product technical work plan. The AP-3.15Q Attachment 1 screening criteria determines the importance for its intended use of the HLW glass model derived herein to be in the category ''Other Factors for the Postclosure Safety Case-Waste Form Performance'', and thus indicates that this factor does not contribute significantly to the postclosure safety strategy. Because the release of radionuclides from the glass will depend on the prior dissolution of the glass, the dissolution rate of the glass imposes an upper bound on the radionuclide release rate. The approach taken to provide a bound for the radionuclide release is to develop models that can be used to calculate the dissolution rate of waste glass when contacted by water in the disposal site. The release rate of a particular radionuclide can then be calculated by multiplying the glass dissolution rate by the mass fraction of that radionuclide in the glass and by the surface area of glass contacted by water. The scope includes consideration of the three modes by which water may contact waste glass in the disposal system: contact by humid air, dripping water, and immersion. The models for glass dissolution under these contact modes are all based on the rate expression for aqueous dissolution of borosilicate glasses. The mechanism and rate expression for aqueous dissolution are adequately understood; the analyses in this AMR were conducted to

GLAMOR - Or How We Achieved A Common Understanding On The Decrease Of Glass Dissolution Kinetics Through International Cooperation

International Nuclear Information System (INIS)

Van Iseghem, Pierre; Aerstens, Marc; Gin, Stephane; Grambow, Bernd; Strachan, Denis M.; McGrail, B. Peter; Wicks, George G.; McMenamin, Thomas

2011-01-01

The objective of the EC funded GLAMOR project was to achieve a common understanding of the processes that control the decrease of the dissolution rate of high-level waste glass in water when silica becomes saturated. Is affinity control or a protective layer dominating? The following steps were taken: (1) review of the literature, (2) selection ofselect an experimental dataset, and selection of the models r(t) and GM2003, and (3) application apply by the GLAMOR partners of the models to the datasets. The main focus has beenwas on dissolution tests in pure water at different values of surface-to-volume and pH. Some of the main conclusions were: (1) both affinity and protective layer concepts must be considered in the interpretation of the rate decreasing stage, (2) the residual dissolution rate observed beyond the silica saturation stage is far more important in view of the long-term performance of the glass, and deserves more attention in future R and D. In the GLAMOR final report, we also discussed in detail the modeling parameters, such as the silica saturation concentration, the silica diffusion coefficient, the silica retention factor in the reaction layer, and the water diffusion coefficient.

UO2 dissolution rates: A review

International Nuclear Information System (INIS)

McKenzie, W.F.

1992-09-01

This report reviews literature data on UO 2 dissolution kinetics and provides a framework for guiding future experimental studies as well as theoretical modeling studies. Under oxidizing conditions, UO 2 dissolution involves formation of an oxidized surface layer which is then dissolved by formation of aqueous complexes. Higher oxygen pressures or other oxidants are required at higher temperatures to have dissolution rates independent of oxygen pressure. At high oxygen pressures (1-5 atm, 25-70 C), the dissolution rate has a one-half order dependence on oxygen pressure, whereas at oxygen pressures below 0.2 atm, Grandstaff (1976), but nobody else, observed a first-order dependence on dissolution rate. Most people found a first-order dependence on carbonate concentration; Posey-Dowty (1987) found independence of carbonate at pH 7 to 8.2. Dissolution rates increase with temperature except in experiments involving granitic groundwater. Dissolution rates were generally greater under acid or basic conditions than near neutral pH

Hydrolysis of R7T7 nuclear waste glass in dilute media: mechanisms and rate as a function of pH

International Nuclear Information System (INIS)

Advocat, T.; Vernaz, E.; Charpentier, H.; Crovisier, J.L.; Ehret, G.

1990-01-01

R7T7 nuclear waste glass dissolution in highly dilute aqueous media under static conditions at 90 0 C occurs according to two different mechanisms depending on the solution acidity. In acid media (pH 4.8 and 5.5), preferential extraction of glass network modifiers results in the formation of an alkali metal-depleted surface region on which amorphous and crystallized (phosphate) compounds rich in transition elements precipitate. Steady-state dissolution conditions are not reached, as attested by variable normalized Si, B and Na mass losses. Glass dissolution is stoichiometric in basic media (pH 7 to 10): the strong bonds of the silicated network are broken at a rate that increases with the pH: the glass dissolution rate increases by a factor of 15 between pH 7 and 10. Under these conditions, alteration products at the glass/solution interface do not constitute a short-term kinetic barrier against the release of the major glass components

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

International Nuclear Information System (INIS)

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

1996-01-01

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

Effect of the size of nanoparticles on their dissolution within metal-glass nanocomposites under sustained irradiation

Energy Technology Data Exchange (ETDEWEB)

Vu, T. H. Y., E-mail: thi-hai-yen.vu@polytechnique.edu; Ramjauny, Y.; Rizza, G.; Hayoun, M. [Laboratoire des Solides Irradiés, École Polytechnique, CNRS, CEA, Université Paris-Saclay, F-91128 Palaiseau (France)

2016-01-21

We investigate the dissolution law of metallic nanoparticles (NPs) under sustained irradiation. The system is composed of isolated spherical gold NPs (4–100 nm) embedded in an amorphous silica host matrix. Samples are irradiated at room temperature in the nuclear stopping power regime with 4 MeV Au ions for fluences up to 8 × 10{sup 16 }cm{sup −2}. Experimentally, the dependence of the dissolution kinetics on the irradiation fluence is linear for large NPs (45–100 nm) and exponential for small NPs (4–25 nm). A lattice-based kinetic Monte Carlo (KMC) code, which includes atomic diffusion and ballistic displacement events, is used to simulate the dynamical competition between irradiation effects and thermal healing. The KMC simulations allow for a qualitative description of the NP dissolution in two main stages, in good agreement with the experiment. Moreover, the perfect correlation obtained between the evolution of the simulated flux of ejected atoms and the dissolution rate in two stages implies that there exists an effect of the size of NPs on their dissolution and a critical size for the transition between the two stages. The Frost-Russell model providing an analytical solution for the dissolution rate, accounts well for the first dissolution stage but fails in reproducing the data for the second stage. An improved model obtained by including a size-dependent recoil generation rate permits fully describing the dissolution for any NP size. This proves, in particular, that the size effect on the generation rate is the principal reason for the existence of two regimes. Finally, our results also demonstrate that it is justified to use a unidirectional approximation to describe the dissolution of the NP under irradiation, because the solute concentration is particularly low in metal-glass nanocomposites.

JSS project phase 4: Experimental and modelling studies of HLW glass dissolution in repository environments

International Nuclear Information System (INIS)

1987-10-01

A goal of the JSS project was to develop a scientific basis for understanding the effects of waste package components, groundwater chemistry, and other repository conditions on glass dissolution behaviour, and to develop and refine a model for the processes governing glass dissolution. The fourth phase of the project, which was performed by the Hahn-Meitner-Institut, Berlin, FRG, dealt specifically with model development and application. Phase 4 also adressed whether basaltic glasses could serve as natural analogues for nuclear waste glasses, thus providing a means to test the capability of the model for long-term predictions. Additional experiments were performed in order to complete the data base necessary to model interactions between the glass and bentonite and between glass and steel corrosion products. More data on temperature, S/V, and pH dependence of the glass/water reaction were also collected. In this report, the data acquired during phase 4 are presented and discussed. (orig./DG)

Dissolution rate of BTEX contaminants in water

International Nuclear Information System (INIS)

Njobuenwu, D.O.; Amadi, S.A.; Ukpaka, P.C.

2005-01-01

Benzene, toluene, ethylbenzene and xylenes (BTEX) and substituted benzenes are the most common aromatic compounds in petroleum. BTEX components are the most soluble and mobile fraction of crude oil and many petroleum products, and frequently enter soil, sediments and aquatic environments because of accidental spills, leaks and improper oil waste disposal practices. The mass transfer process of hydrocarbons in aquatic mediums has received considerable attention in the literature. This paper focused on the molecular mass transfer rate of BTEX in water, with the aim of understanding and predicting contaminant fate and transport. A comprehensive model was developed to simulate the molecular dissolution rate of BTEX in a natural water stream. The model considered the physicochemical properties of the BTEX compounds and physical processes relevant to the spreading of contaminants in the sea. The dissolution rate was a function of oil slick area, dissolution mass transferability and oil solubility in water. The total dissolution rate N was calculated and the dissolution mass transfer coefficient K was given as the point value of mass transfer coefficient. Results for the dissolution rate based on the solubility of the components in the water were compared with analytical solutions from previous studies and showed good agreement. The model showed that benzene had the largest dissolution rate, while o-xylene had the lowest rate because of its lower fraction. Benzene dissolution rate was approximately 2.6, which was 20.6 times that of toluene and ethylbenzene. It was concluded that the model is useful in predicting and monitoring the dissolution rate of BTEX contaminants in soil and water systems. 22 refs., 2 tabs., 3 figs

Glass Dissolution Parameters: Update for Entsorgungsnachweis

International Nuclear Information System (INIS)

Curti, E.

2003-11-01

This document provides updated long-term corrosion rates for borosilicate glasses used in Switzerland as a matrix for high-level radioactive waste. The new rates are based on long-term leaching experiments conducted at PSI and are corroborated by recent investigations. The asymptotic rates have been determined through weighted linear regressions of the normalised mass losses, directly calculated from B and Li concentrations in the leaching solutions. Special attention was given to the determination of the analytical uncertainty of the mass losses. The sensitivity of the corrosion rates to analytical uncertainties and to other criteria (e.g. the choice of data points for the regressions) was also studied. A major finding was that the uncertainty of the corrosion rate mainly depends on the uncertainty of the specific glass surface area. The reference rates proposed for safety assessment calculations are 1.5 mg m -2 d -1 for BNFL glasses and 0.2 mg m -2 d -1 for Cogema glasses. The relevance of the proposed corrosion rates for repository conditions is shown based on the analysis of processes and parameters currently known to affect the long-term kinetics of silicate glasses. Specifically, recent studies indicate that potentially detrimental effects, notably the removal of silica from solution through adsorption on clay minerals, are transitory and will not affect the long-term corrosion rate of the Swiss reference glasses. Iron corrosion products are also known to bind silica, but present data are not sufficient to quantify their influence on the long-term rate. (author)

Jarosite dissolution rates in perchlorate brine

Science.gov (United States)

Legett, Carey; Pritchett, Brittany N.; Elwood Madden, Andrew S.; Phillips-Lander, Charity M.; Elwood Madden, Megan E.

2018-02-01

Perchlorate salts and the ferric sulfate mineral jarosite have been detected at multiple locations on Mars by both landed instruments and orbiting spectrometers. Many perchlorate brines have eutectic temperatures bearing rocks and sediments may have been altered by perchlorate brines. Here we measured jarosite dissolution rates in 2 M sodium perchlorate brine as well as dilute water at 298 K to determine the effects of perchlorate anions on jarosite dissolution rates and potential reaction products. We developed a simple method for determining aqueous iron concentrations in high salinity perchlorate solutions using ultraviolet-visible spectrophotometry that eliminates the risk of rapid oxidation reactions during analyses. Jarosite dissolution rates in 2 M perchlorate brine determined by iron release rate (2.87 × 10-12 ±0.85 × 10-12 mol m-2 s-1) were slightly slower than the jarosite dissolution rate measured in ultrapure (18.2 MΩ cm-1) water (5.06 × 10-12 mol m-2 s-1) using identical methods. No additional secondary phases were observed in XRD analyses of the reaction products. The observed decrease in dissolution rate may be due to lower activity of water (ɑH2O = 0.9) in the 2 M NaClO4 brine compared with ultrapure water (ɑH2O = 1). This suggests that the perchlorate anion does not facilitate iron release, unlike chloride anions which accelerated Fe release rates in previously reported jarosite and hematite dissolution experiments. Since dissolution rates are slower in perchlorate-rich solutions, jarosite is expected to persist longer in perchlorate brines than in dilute waters or chloride-rich brines. Therefore, if perchlorate brines dominate aqueous fluids on the surface of Mars, jarosite may remain preserved over extended periods of time, despite active aqueous processes.

Physical heterogeneity control on effective mineral dissolution rates

Science.gov (United States)

Jung, Heewon; Navarre-Sitchler, Alexis

2018-04-01

Hydrologic heterogeneity may be an important factor contributing to the discrepancy in laboratory and field measured dissolution rates, but the governing factors influencing mineral dissolution rates among various representations of physical heterogeneity remain poorly understood. Here, we present multiple reactive transport simulations of anorthite dissolution in 2D latticed random permeability fields and link the information from local grid scale (1 cm or 4 m) dissolution rates to domain-scale (1m or 400 m) effective dissolution rates measured by the flux-weighted average of an ensemble of flow paths. We compare results of homogeneous models to heterogeneous models with different structure and layered permeability distributions within the model domain. Chemistry is simplified to a single dissolving primary mineral (anorthite) distributed homogeneously throughout the domain and a single secondary mineral (kaolinite) that is allowed to dissolve or precipitate. Results show that increasing size in correlation structure (i.e. long integral scales) and high variance in permeability distribution are two important factors inducing a reduction in effective mineral dissolution rates compared to homogeneous permeability domains. Larger correlation structures produce larger zones of low permeability where diffusion is an important transport mechanism. Due to the increased residence time under slow diffusive transport, the saturation state of a solute with respect to a reacting mineral approaches equilibrium and reduces the reaction rate. High variance in permeability distribution favorably develops large low permeability zones that intensifies the reduction in mixing and effective dissolution rate. However, the degree of reduction in effective dissolution rate observed in 1 m × 1 m domains is too small (equilibrium conditions reduce the effective dissolution rate by increasing the saturation state. However, in large domains where less- or non-reactive zones develop, higher

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

Kinetic Rate Law Parameter Measurements on a Borosilicate Waste Glass: Effect of Temperature, pH, and Solution Composition on Alkali Ion Exchange

International Nuclear Information System (INIS)

Pierce, Eric M.; McGrail, B PETER.; Icenhower, J P.; Rodriguez, Elsa A.; Steele, Jackie L.; Baum, Steven R.

2004-01-01

The reaction kinetics of glass is controlled by matrix dissolution and ion exchange (IEX). Dissolution of an alkali-rich simulated borosilicate waste glass was investigated using single-pass flow-through (SPFT) experiments. Experiments were conducted as a function of temperature, pH, and solution composition by varying the SiO 2 (aq) activity in the influent solution. Results showed that under dilute conditions matrix dissolution increased with increasing pH and temperature, and decreased with increasing SiO 2 (aq) activity. IEX rates decreased with increasing pH and temperature, and increased with increasing SiO 2 (aq) activity. Over the solution composition range interrogated in this study the dominant dissolution mechanism changed from matrix dissolution to IEX. These results suggest that ''secondary'' reactions may become dominant under certain environmental conditions and emphasize the need to incorporate these reactions into dissolution rate models

Effects of glass composition on the residual rate of alteration and modelling parameters

International Nuclear Information System (INIS)

Fleury, Benjamin

2013-01-01

This PhD thesis deals with the long-term behavior of the French nuclear glasses R7T7. An experiment plan (based on 27 glass compositions) is developed for studying the effect of glass composition on the residual rate of alteration. The impact of Mg-phase precipitation on glass alteration is also studied and several modelling exercises are performed. There is one order of magnitude between the different measurements (rate or pH...) associated with the different glass compositions. The statistical treatment of these measurements results in predictive equations and several observable trends are valid for all materials with a composition complying with the experiment plan conditions. The effect of Si, Na, B and Al on alteration (.i.e, gel and secondary phase's formation, pH) is confirmed, the influence of Zn, Zr and Ni-Co is evidenced. The role of Cr has to be clarified. Experiments show that glass alteration rate in underground water, which contains high level of Ca and Mg, is one order of magnitude higher than in the case of pure water. The glass composition plays the same role for the alteration in the two types of solution. During alteration, the late addition of Mg introduces a time lag in the resumption response because silicon is first provided from partial dissolution of the previously-formed alteration gel. The nucleation process does not limit Mg-silicate precipitation whereas a pH above 8-8.5 is necessary for Mg-silicate precipitation. The glass alteration rate can be a limiting factor if the quantity of Mg supplied to the reaction is enough. The Mg silicate phase seems to have systematically a molar ratio Mg/Si between 0.2 and 0.4. It is also shown that the air tightness of the reactor influences the rate of dissolution of CO 2 in the solution leading to a decrease of pH. Finally, modelling exercises with GRAAL show promising results. Such modelling is required in order to extend the prediction of the long-term alteration behavior to different glass

Critical review of glass performance modeling

International Nuclear Information System (INIS)

Bourcier, W.L.

1994-07-01

Borosilicate glass is to be used for permanent disposal of high-level nuclear waste in a geologic repository. Mechanistic chemical models are used to predict the rate at which radionuclides will be released from the glass under repository conditions. The most successful and useful of these models link reaction path geochemical modeling programs with a glass dissolution rate law that is consistent with transition state theory. These models have been used to simulate several types of short-term laboratory tests of glass dissolution and to predict the long-term performance of the glass in a repository. Although mechanistically based, the current models are limited by a lack of unambiguous experimental support for some of their assumptions. The most severe problem of this type is the lack of an existing validated mechanism that controls long-term glass dissolution rates. Current models can be improved by performing carefully designed experiments and using the experimental results to validate the rate-controlling mechanisms implicit in the models. These models should be supported with long-term experiments to be used for model validation. The mechanistic basis of the models should be explored by using modern molecular simulations such as molecular orbital and molecular dynamics to investigate both the glass structure and its dissolution process

Critical review of glass performance modeling

Energy Technology Data Exchange (ETDEWEB)

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

1994-07-01

Borosilicate glass is to be used for permanent disposal of high-level nuclear waste in a geologic repository. Mechanistic chemical models are used to predict the rate at which radionuclides will be released from the glass under repository conditions. The most successful and useful of these models link reaction path geochemical modeling programs with a glass dissolution rate law that is consistent with transition state theory. These models have been used to simulate several types of short-term laboratory tests of glass dissolution and to predict the long-term performance of the glass in a repository. Although mechanistically based, the current models are limited by a lack of unambiguous experimental support for some of their assumptions. The most severe problem of this type is the lack of an existing validated mechanism that controls long-term glass dissolution rates. Current models can be improved by performing carefully designed experiments and using the experimental results to validate the rate-controlling mechanisms implicit in the models. These models should be supported with long-term experiments to be used for model validation. The mechanistic basis of the models should be explored by using modern molecular simulations such as molecular orbital and molecular dynamics to investigate both the glass structure and its dissolution process.

Investigation of gamma ray shielding, structural and dissolution rate properties of Bi2O3-BaO-B2O3-Na2O glass system

Science.gov (United States)

Dogra, Mridula; Singh, K. J.; Kaur, Kulwinder; Anand, Vikas; Kaur, Parminder; Singh, Prabhjot; Bajwa, B. S.

2018-03-01

In the present study, quaternary system of the composition (0.45 + x) Bi2O3-(0.25 - x) BaO-0.15 B2O3-0.15 Na2O (where 0 ≤ x ≤ 0.2 mol fraction) has been prepared by using melt-quenching technique for investigation of gamma ray shielding properties. Mass attenuation coefficients and half value layer parameters have been determined experimentally at 662 keV by using 137Cs source. It has been found that experimental results of these parameters hold good agreement with theoretical values. The density, molar volume, XRD, FTIR, Raman and UV-visible studies have been used to determine structural properties of the prepared glass samples. Dissolution rate of the samples has also been measured to check their utility as long term durable glasses.

Sodium tetraphenylborate solubility and dissolution rates

International Nuclear Information System (INIS)

Barnes, M.J.; Peterson, R.A.; Swingle, R.F.; Reeves, C.T.

1995-01-01

The rate of solid sodium tetraphenylborate (NaTPB) dissolution in In-Tank Precipitation salt solutions has been experimentally determined. The data indicates that the dissolution rate of solid NaTPB is a minor contributor the lag time experienced in the 1983 Salt Decontamination Demonstration Test and should not be considered as the rate determining step. Current analytical models for predicting the time to reach the composite lower flammability limit assume that the lag time is not more than 6 hours, and the data supports this assumption (i.e., dissolution by itself requires much less than 6 hours). The data suggests that another step--such as mass transport, the reaction of a benzene precursor or the mixing behavior--is the rate determining factor for benzene release to the vapor space in Tank 48H. In addition, preliminary results from this program show that the degree of agitation employed is not a significant parameter in determining the rate of NaTPB dissolution. As a result of this study, an improved equation for predicting equilibrium tetraphenylborate solubility with respect to temperature and sodium ion concentration has been determined

Modelling aqueous corrosion of nuclear waste phosphate glass

Energy Technology Data Exchange (ETDEWEB)

Poluektov, Pavel P.; Schmidt, Olga V.; Kascheev, Vladimir A. [Bochvar All-Russian Scientific Research Institute for Inorganic Materials (VNIINM), Moscow (Russian Federation); Ojovan, Michael I., E-mail: m.ojovan@sheffield.ac.uk [Immobilisation Science Laboratory, Department of Materials Science and Engineering, University of Sheffield, Mappin Street, Sheffield, S1 3JD (United Kingdom)

2017-02-15

A model is presented on nuclear sodium alumina phosphate (NAP) glass aqueous corrosion accounting for dissolution of radioactive glass and formation of corrosion products surface layer on the glass contacting ground water of a disposal environment. Modelling is used to process available experimental data demonstrating the generic inhibiting role of corrosion products on the NAP glass surface. - Highlights: • The radionuclides yield is determined by the transport from the glass through the surface corrosion layer. • Formation of the surface layer is due to the dissolution of the glass network and the formation of insoluble compounds. • The model proposed accounts for glass dissolution, formation of corrosion layer, specie diffusion and chemical reactions. • Analytical solutions are found for corrosion layer growth rate and glass components component leaching rates.

Corrosion behavior of environmental assessment glass in product consistency tests of extended duration

International Nuclear Information System (INIS)

Bates, J.K.; Buck, E.C.; Ebert, W.L.; Luo, J.S.; Tam, S.W.

1998-01-01

We have conducted static dissolution tests to study the corrosion behavior of the Environmental Assessment (EA) glass, which is the benchmark glass for high-level waste glasses being produced at US Department of Energy facilities. These tests were conducted to evaluate the behavior of the EA glass under the same long-term and accelerated test conditions that are being used to evaluate the corrosion of waste glasses. Tests were conducted at 90 C in a tuff groundwater solution at glass surface area/solution volume (WV) ratios of about 2000 and 20,000 m -1 . The glass dissolved at three distinct dissolution rates in tests conducted at 2000 m -1 . Based on the release of boron, dissolution within the first seven days occurred at a rate of about 0.65 g/(m 2 · d). The rate between seven and 70 days decreased to 0.009 g/(m 2 · d). An increase in the dissolution rate occurred at longer times after the precipitation of zeolite phases analcime, gmelinite, and an aluminum silicate base. The dissolution rate after phase formation was about 0.18 g/(m 2 · d). The formation of the same zeolite alteration phases occurred after about 20 days in tests at 20,000 m - . The average dissolution rate over the first 20 days was 0.5 g/(m 2 · d) and the rate after phase formation was about 0.20 g/(m 2 · d). An intermediate stage with a lower rate was not observed in tests at 20,000 m -1 . The corrosion behavior of EA glass is similar to that observed for other high-level waste glasses reacted under the same test conditions. The dissolution rate of EA glass is higher than that of other high-level waste glasses both in 7-day tests and after alteration phases form

Surface controlled dissolution rates of gypsum in aqueous solutions exhibit nonlinear dissolution kinetics

Science.gov (United States)

Jeschke, Alexander A.; Vosbeck, Katrin; Dreybrodt, Wolfgang

2001-01-01

The effective dissolution rates of gypsum are determined by mixed kinetics, where the rate constants of dissolution at the surface and the transport constant of molecular diffusion of dissolved material are similar. To obtain the surface reaction rate law it is necessary to know the transport constant. We have determined the surface rate law for monocrystalline selenite by using a rotating disc set-up, where the transport coefficients are well known. As a result, up to a calcium concentration of 0.6 · ceq, we find a nearly linear rate law Rs = ksl (1- cs/ ceq) n1, where cs is the total calcium concentration at the surface and ceq the equilibrium concentration with respect to gypsum, n1 = 1.2 ± 0.2, and ksl = 1.1 · 10 -4 mmol cm -2 s -1 ± 15%. We also employed batch-experiments for selenite, alabaster and gypsum rock samples. The result of these experiments were interpreted by using a transport constant determined by NaCl dissolution experiments under similar physical conditions. The batch experiments reveal a dissolution rate law Rs = ksl (1- cs/ ceq) n1, ksl = 1.3 · 10 -4 mmol · cm -2 s -1, n1 = 1.2 ± 0.2 for c ≤ 0.94 · ceq. Close to equilibrium a nonlinear rate law, Rs = ks2 (1- cs/ ceq) n2, is observed, where ks2 is in the order of 10 mmol · cm -2 s -1 and n2 ≈ 4.5. The experimentally observed gypsum dissolution rates from the batch experiments could be accurately fitted, with only minor variations of the surface reaction constant obtained from the rotating disk experiment and the transport coefficient from the NaCl dissolution batch experiment. Batch experiments on pure synthetic gypsum, reveal a linear rate law up to equilibrium. This indicates inhibition of dissolution in natural samples close to equilibrium, as is known also for calcite minerals.

A comparison of the performance of nuclear waste glasses by modeling

International Nuclear Information System (INIS)

Grambow, B.; Strachan, D.M.

1988-12-01

Through a combination of data collection and computer modeling, the dissolution mechanism of nuclear waste glasses has been investigated and more clearly defined. Glass dissolution can be described as a dissolution/precipitation process in which glass dissolves in aqueous solution and solids precipitate as the solubility products are exceeded. The dissolution process is controlled by activity of the rate-limiting specie H 4 SiO 4 . As a concentration of H 4 SiO 4 increases, the rate of dissolution decreases until a final reaction rate is reached. Between the forward reaction rate (early time) and final reaction rate (very long time), glasses may exhibit an intermediate root time dependence caused by a transport resistance for the diffusion of H 4 SiO 4 within the gel layer on the glass surface. In this report, three glasses are studied: JSS-A, PNL 76-68, and SRL-131. Data from static and dynamic leach tests are assembled, plotted, and successfully modeled. The kinetic parameters for these glasses are reported. With four parameters derived from experiments for each glass, the model can be used to calculate the effects of changes in the initial composition of the water contacting the glass. The effects of convective flow can also be modeled. Furthermore, glasses of different compositions can be readily compared. 49 refs., 27 figs., 5 tabs

Chrysotile dissolution rates: Implications for carbon sequestration

International Nuclear Information System (INIS)

Thom, James G.M.; Dipple, Gregory M.; Power, Ian M.; Harrison, Anna L.

2013-01-01

Highlights: • Uncertainties in serpentine dissolution kinetics hinder carbon sequestration models. • A pH dependent, far from equilibrium dissolution rate law for chrysotile. • F chrysotile (mol/m 2 /s) = 10 −0.21pH−10.57 at 22 °C over pH 2–10. • Laboratory dissolution rates consistent with mine waste weathering observations. • Potential for carbon sequestration in mine tailings and aquifers is assessed. - Abstract: Serpentine minerals (e.g., chrysotile) are a potentially important medium for sequestration of CO 2 via carbonation reactions. The goals of this study are to report a steady-state, far from equilibrium chrysotile dissolution rate law and to better define what role serpentine dissolution kinetics will have in constraining rates of carbon sequestration via serpentine carbonation. The steady-state dissolution rate of chrysotile in 0.1 m NaCl solutions was measured at 22 °C and pH ranging from 2 to 8. Dissolution experiments were performed in a continuously stirred flow-through reactor with the input solutions pre-equilibrated with atmospheric CO 2 . Both Mg and Si steady-state fluxes from the chrysotile surface, and the overall chrysotile flux were regressed and the following empirical relationships were obtained: F Mg =-0.22pH-10.02;F Si =-0.19pH-10.37;F chrysotile =-0.21pH-10.57 where F Mg , F Si , and F chrysotile are the log 10 Mg, Si, and molar chrysotile fluxes in mol/m 2 /s, respectively. Element fluxes were used in reaction-path calculations to constrain the rate of CO 2 sequestration in two geological environments that have been proposed as potential sinks for anthropogenic CO 2 . Carbon sequestration in chrysotile tailings at 10 °C is approximately an order of magnitude faster than carbon sequestration in a serpentinite-hosted aquifer at 60 °C on a per kilogram of water basis. A serpentinite-hosted aquifer, however, provides a larger sequestration capacity. The chrysotile dissolution rate law determined in this study has

Experimental Determination of the Effect of the Ratio of B/Al on Glass Dissolution along the Nepheline (NaAlSiO₄) – Malinkoite (NaBSiO₄) Join

Energy Technology Data Exchange (ETDEWEB)

Pierce, Eric M; Reed, Lunde R; Shaw, Wendy J; McGrail, B Peter; Icenhower, Jonathan P; Windisch, Charles F; Cordova, Elsa A; Broady, Johnathan W

2010-03-27

The dissolution kinetics of five glasses along the NaAlSiO₄-NaBSiO₄ join were used to evaluate how the structural variations associated with boron-aluminum substitution affect the rate of dissolution. The composition of each glass varied inversely in mol% of Al₂O₃ (5 to 25 mol%) and B₂O₃ (20 to 0 mol%) with Na₂O (25 mol%) and SiO₂ (50 mol%) making up the remaining amount, in every case Na/(Al+B) = 1.0. Single-pass flow-through experiments (SPFT) were conducted under dilute conditions as a function of solution pH (from 7.0 to 12.0) and temperature (from 23° to 90°C). Analysis by ²⁷Al and ²⁹Si MAS-NMR suggests Al (~98% ^[4]Al) and Si atoms (~100% ^[4]Si) occupy a tetrahedral coordination whereas, B atoms occupy both tetrahedral ([4]B) and trigonal (^[3]B) coordination. The distribution of [3]B fractionated between ^[3]B(ring) and ^[3]B(non-ring) moieties, with the ^[3]B(ring)/^[3]B(non-ring) ratio increases with the B/Al ratio. The MAS-NMR results also indicated an increase in the fraction of ^[4]B with an increase in the B/Al ratio. But despite the changes in the B/Al ratio and B coordination, the ²⁹Si spectra maintain a chemical shift between -88 to -84 ppm for each glass. Unlike the ²⁹Si spectra, the ²⁷Al resonances shift to more positive values with an increase in the B/Al ratio which suggests mixing between the ^[4]Al and ^[3]B sites, assuming avoidance between tetrahedral trivalent cations (^[4]Al-O-^[4]B avoidance). Raman spectroscopy was use to augment the results collected from MAS-NMR and demonstrated that NeB4 (glass sample with the highest B content) was glass-glass phase separated (e.g., heterogeneous glass). Results from SPFT experiments suggest a forward rate of reaction and pH power law

Aqueous solutions/nuclear glasses interactions

International Nuclear Information System (INIS)

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

1991-01-01

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

Development of basic data for modelling the residual alteration rate in aqueous media of AVM nuclear glasses

International Nuclear Information System (INIS)

Thien, B.

2010-01-01

During their aqueous alteration, AVM French nuclear glasses exhibit a large range of behaviour, in spite of a small range of composition. AVM glasses alteration rates are controlled by two phenomena: (i) precipitation of secondary phases, mostly aluminous hectorites, and (ii) diffusion of water across a more or less protective gel. The magnesium contained in these glasses increases the precipitation of these secondary phases, leading to a partial or total dissolution of the gel layer. This dissolution increases the glass alteration rates. On the other hand, Mg also incorporates in the gel, increasing his passivation properties. The predominance of one of these two phenomena depends on the initial composition of the glass, the pH of the solution, and the alteration conditions. In presence of Bure geological disposal site water (Mg and Ca rich), AVM glasses undergo less alteration than in initially pure water, in spite of larger amounts of secondary phase precipitates. This results from incorporation of calcium in the gel instead of sodium and magnesium, improving its passivating properties. We have adapted the geochemical GRAAL model for AVM glasses. In spite of its limitations, this model allows us to describe the differences of behaviour between these glasses, in function of their composition. Moreover, GRAAL can be proposed as a basis of a future operational model for predicting the alteration of AVM glasses. (author) [fr

Assessing the effect of dissolved organic ligands on mineral dissolution rates: An example from calcite dissolution

International Nuclear Information System (INIS)

DeMaio, T.; Grandstaff, D.E.

1997-01-01

Experiments suggest that dissolved organic ligands may primarily modify mineral dissolution rates by three mechanisms: (1) metal-ligand (M-L) complex formation in solution, which increases the degree of undersaturation, (2) formation of surface M-L complexes that attack the surface, and (3) formation of surface complexes which passivate or protect the surface. Mechanisms (1) and (2) increase the dissolution rate and the third decreases it compared with organic-free solutions. The types and importance of these mechanisms may be assessed from plots of dissolution rate versus degree of undersaturation. To illustrate this technique, calcite, a common repository cementing and vein-filling mineral, was dissolved at pH 7.8 and 22 C in Na-Ca-HCO 3 -Cl solutions with low concentrations of three organic ligands. Low citrate concentrations (50 microM) increased the dissolution rate consistent with mechanism (1). Oxalate decreased the rate, consistent with mechanism (3). Low phthalate concentration (<50 microM) decreased calcite dissolution rates; however, higher concentrations increased the dissolution rates, which became faster than in inorganic solutions. Thus, phthalate exhibits both mechanisms (2) and (3) at different concentrations. In such cases linear extrapolations of dissolution rates from high organic ligand concentrations may not be valid

A mechanistic model for long-term nuclear waste glass dissolution integrating chemical affinity and interfacial diffusion barrier

Energy Technology Data Exchange (ETDEWEB)

Ma, Teqi [Northwest Institute of Nuclear Technology, No.28 Pingyu Road, Baqiao District, Xi' an,Shaanxi, 710024 (China); Mechanics and Physics of Solids Research Group, Modelling and Simulation Centre, The University of Manchester, Oxford Road, Manchester, M13 9PL (United Kingdom); Jivkov, Andrey P., E-mail: andrey.jivkov@manchester.ac.uk [Mechanics and Physics of Solids Research Group, Modelling and Simulation Centre, The University of Manchester, Oxford Road, Manchester, M13 9PL (United Kingdom); Li, Weiping; Liang, Wei; Wang, Yu; Xu, Hui [Northwest Institute of Nuclear Technology, No.28 Pingyu Road, Baqiao District, Xi' an,Shaanxi, 710024 (China); Han, Xiaoyuan, E-mail: xyhan_nint@sina.cn [Northwest Institute of Nuclear Technology, No.28 Pingyu Road, Baqiao District, Xi' an,Shaanxi, 710024 (China)

2017-04-01

Understanding the alteration of nuclear waste glass in geological repository conditions is critical element of the analysis of repository retention function. Experimental observations of glass alterations provide a general agreement on the following regimes: inter-diffusion, hydrolysis process, rate drop, residual rate and, under very particular conditions, resumption of alteration. Of these, the mechanisms controlling the rate drop and the residual rate remain a subject of dispute. This paper offers a critical review of the two most competitive models related to these regimes: affinity–limited dissolution and diffusion barrier. The limitations of these models are highlighted by comparison of their predictions with available experimental evidence. Based on the comprehensive discussion of the existing models, a new mechanistic model is proposed as a combination of the chemical affinity and diffusion barrier concepts. It is demonstrated how the model can explain experimental phenomena and data, for which the existing models are shown to be not fully adequate.

Understanding the structural drivers governing glass-water interactions in borosilicate based model bioactive glasses.

Science.gov (United States)

Stone-Weiss, Nicholas; Pierce, Eric M; Youngman, Randall E; Gulbiten, Ozgur; Smith, Nicholas J; Du, Jincheng; Goel, Ashutosh

2018-01-01

The past decade has witnessed a significant upsurge in the development of borate and borosilicate based resorbable bioactive glasses owing to their faster degradation rate in comparison to their silicate counterparts. However, due to our lack of understanding about the fundamental science governing the aqueous corrosion of these glasses, most of the borate/borosilicate based bioactive glasses reported in the literature have been designed by "trial-and-error" approach. With an ever-increasing demand for their application in treating a broad spectrum of non-skeletal health problems, it is becoming increasingly difficult to design advanced glass formulations using the same conventional approach. Therefore, a paradigm shift from the "trial-and-error" approach to "materials-by-design" approach is required to develop new-generations of bioactive glasses with controlled release of functional ions tailored for specific patients and disease states, whereby material functions and properties can be predicted from first principles. Realizing this goal, however, requires a thorough understanding of the complex sequence of reactions that control the dissolution kinetics of bioactive glasses and the structural drivers that govern them. While there is a considerable amount of literature published on chemical dissolution behavior and apatite-forming ability of potentially bioactive glasses, the majority of this literature has been produced on silicate glass chemistries using different experimental and measurement protocols. It follows that inter-comparison of different datasets reveals inconsistencies between experimental groups. There are also some major experimental challenges or choices that need to be carefully navigated to unearth the mechanisms governing the chemical degradation behavior and kinetics of boron-containing bioactive glasses, and to accurately determine the composition-structure-property relationships. In order to address these challenges, a simplified

Glass leaching performance

International Nuclear Information System (INIS)

Chick, L.A.; Turcotte, R.P.

1983-05-01

Current understanding of the leaching performance of high-level nuclear waste (HLW) glass is summarized. The empirical model of waste glass leaching behavior developed shows that at high water flow rates the glass leach rate is kinetically limited to a maximum value. At intermediate water flow rates, leaching is limited by the solution concentration of silica and decreases with decreasing water flow rates. Release of soluble elements is controlled by silica dissolution because silica forms the binding network of the glass. At low water flow rates, mass loss rates reach values controlled by formation rates of alteration minerals, or by diffusion of dissolution products through essentially stagnant water. The parameters reviewed with respect to their quantifiable influence on leaching behavior include temperature, pH, leachant composition, glass composition, thermal history, and radiation. Of these, temperature is most important since the rate of mass loss approximately doubles with each 10 0 C increase in dilute solutions. The pH has small effects within the 4 to 10 range. The chemical composition of the leachant is most important with regard to its influence on alteration product formation. Glass composition exhibits the largest effects at high flow rates where improved glasses leach from ten to thirty times slower than glass 76 to 68. The effects of the thermal history (devitrification) of the glass are not likely to be significant. Radiation effects are important primarily in that radiolysis can potentially drive pH values to less than 4. Radiation damage to the glass causes insignificant changes in leaching performance

Aqueous dissolution rates of uranium oxides

International Nuclear Information System (INIS)

Steward, S.A.; Mones, E.T.

1994-10-01

An understanding of the long-term dissolution of waste forms in groundwater is required for the safe disposal of high level nuclear waste in an underground repository. The main routes by which radionuclides could be released from a geological repository are the dissolution and transport processes in groundwater flow. Because uranium dioxide is the primary constituent of spent nuclear fuel, the dissolution of its matrix in spent fuel is considered the rate-limiting step for release of radioactive fission products. The purpose of our work has been to measure the intrinsic dissolution rates of uranium oxides under a variety of well-controlled conditions that are relevant to a repository and allow for modeling. The intermediate oxide phase U 3 O 8 , triuranium octaoxide, is quite stable and known to be present in oxidized spent fuel. The trioxide, UO 3 , has been shown to exist in drip tests on spent fuel. Here we compare the results of essentially identical dissolution experiments performed on depleted U 3 O 8 and dehyrated schoepite or uranium trioxide monohydrate (UO 3 ·H 2 O). These are compared with earlier work on spent fuel and UO 2 under similar conditions

Glass Durability Modeling, Activated Complex Theory (ACT)

International Nuclear Information System (INIS)

CAROL, JANTZEN

2005-01-01

The most important requirement for high-level waste glass acceptance for disposal in a geological repository is the chemical durability, expressed as a glass dissolution rate. During the early stages of glass dissolution in near static conditions that represent a repository disposal environment, a gel layer resembling a membrane forms on the glass surface through which ions exchange between the glass and the leachant. The hydrated gel layer exhibits acid/base properties which are manifested as the pH dependence of the thickness and nature of the gel layer. The gel layer has been found to age into either clay mineral assemblages or zeolite mineral assemblages. The formation of one phase preferentially over the other has been experimentally related to changes in the pH of the leachant and related to the relative amounts of Al +3 and Fe +3 in a glass. The formation of clay mineral assemblages on the leached glass surface layers ,lower pH and Fe +3 rich glasses, causes the dissolution rate to slow to a long-term steady state rate. The formation of zeolite mineral assemblages ,higher pH and Al +3 rich glasses, on leached glass surface layers causes the dissolution rate to increase and return to the initial high forward rate. The return to the forward dissolution rate is undesirable for long-term performance of glass in a disposal environment. An investigation into the role of glass stoichiometry, in terms of the quasi-crystalline mineral species in a glass, has shown that the chemistry and structure in the parent glass appear to control the activated surface complexes that form in the leached layers, and these mineral complexes ,some Fe +3 rich and some Al +3 rich, play a role in whether or not clays or zeolites are the dominant species formed on the leached glass surface. The chemistry and structure, in terms of Q distributions of the parent glass, are well represented by the atomic ratios of the glass forming components. Thus, glass dissolution modeling using simple

Waste glass corrosion modeling: Comparison with experimental results

International Nuclear Information System (INIS)

Bourcier, W.L.

1993-11-01

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

Surface chemistry and durability of borosilicate glass

International Nuclear Information System (INIS)

Carroll, S.A.; Bourcier, W.L.; Phillips, B.L.

1994-01-01

Important glass-water interactions are poorly understood for borosilicate glass radioactive waste forms. Preliminary results show that glass durability is dependent on reactions occurring at the glass-solution interface. CSG glass (18.2 wt. % Na 2 O, 5.97 wt. % CaO, 11.68 wt. % Al 2 O 3 , 8.43 wt. % B 2 O 3 , and 55.73 wt. % SiO 2 ) dissolution and net surface H + and OH - adsorption are minimal at near neutral pH. In the acid and alkaline pH regions, CSG glass dissolution rates are proportional to [H + ] adsorbed 2 and [OH - ] adsorbed 0.8 , respectively. In contrast, silica gel dissolution and net H + and OH - adsorption are minimal and independent of pH in acid to neutral solutions. In the alkaline pH region, silica gel dissolution is proportional to [OH - ] adsorbed 0.9 adsorbed . Although Na adsorption is significant for CSG glass and silica gel in the alkaline pH regions, it is not clear if it enhances dissolution, or is an artifact of depolymerization of the framework bonds

Waste glass corrosion modeling: Comparison with experimental results

International Nuclear Information System (INIS)

Bourcier, W.L.

1994-01-01

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

Quantifying Silica Reactivity in Subsurface Environments: Reaction Affinity and Solute Matrix Controls on Quartz and SiO2 Glass Dissolution Kinetics

International Nuclear Information System (INIS)

Dove, Patricia M.

1999-01-01

Our goal is to develop a quantitative and mechanistic understanding of amorphous silica, SiO2(am), dissolution kinetics in aqueous solutions. A knowledge of fundamental controls on the reactivity of simple Si-O bonded phases is the baseline of behavior for understanding highly complex silica phases. In the Earth, silicate minerals comprise >70% of the crust and dominate virtually every subsurface system. More importantly for the objectives of this EMSP project, the silicates are important because compositionally complex glasses will become the front line of defense in containing radioactive wastes in the nation's long term and interim storage strategies. To date, the behavior of SiO2(am) is largely inferred from studies of the better known crystalline polymorphs (e.g. alpha-quartz). In the first step towards constructing a general model for amorphous silica reactivity in the complex fluid compositions of natural waters, we are determining the dissolution behavior as a function of temperature, solution pH and cation concentration. With these data we are determining relationships between SiO2 glass structure and dissolution rates in aqueous solutions, as described below

Dissolution model for a glass having an adherent insoluble surface layer

International Nuclear Information System (INIS)

Harvey, K.B.; Larocque, C.A.B.

1990-01-01

Waste form glasses that contain substantial quantities of iron, manganese, and aluminum oxides, such as the Savannah River SRL TDS-131 glass, form a thick, hydrated surface layer when placed in contact with water. The dissolution of such a glass has been modeled with the Savannah River Model. The authors showed previously that the equations of the Savannah River Model could be fitted to published experimental data if a time-dependent diffusion coefficient was assumed for species of diffusing through the surface layer. The Savannah River Model assumes that all of the material dissolved from the glass enters solution, whereas it was observed that substantial quantities of material were retained in the surface layer. An alternative model, presented contains a mass balance equation that allows material either to enter solution or to be retained in the surface layer. It is shown that the equations derived using this model can be fitted to the published experimental data assuming a constant diffusion coefficient for species diffusing through the surface layer

Study of the surface crystallization and resistance to dissolution of niobium phosphate glasses for nuclear waste immobilization; Estudo da cristalizacao superficial e da resistencia a dissolucao de vidros niobofosfatos visando a imobilizacao de rejeitos radioativos

Energy Technology Data Exchange (ETDEWEB)

Vieira, Heveline

2008-07-01

The surface crystallization and the dissolution rate of three phosphate glass compositions containing different amounts of niobium oxide were studied. The glasses were named Nb30, Nb37, and Nb44 according to the nominal content of niobium oxide in the glass composition. The three compositions were evaluated keeping the P{sub 2}O{sub 5}/K{sub 2}O ratio constant and varying the amount of Nb{sub 2}O{sub 5}. These glasses were produced by melting appropriate chemical compounds at 1500 deg C for 0.5 hour. The crystalline phases which were nucleated on the glass surface after heat treatment were determined by X-ray diffraction. The crystalline structures depend on the amount of niobium oxide in the glass composition. The crystal morphologies were observed by using an optical microscope, and their characteristics are specific for each kind of crystalline phase. The crystal growth rate and the surface nuclei density were determined for each glass composition, and they depend on each crystalline phase nucleated on the surface. From the differential thermal analysis curves it was determined that the Nb44 glass containing 46.5 mol por cent of niobium oxide is the most thermally stable against crystallization when compared to the Nb30 and Nb37 glasses. According to the activation energies determined for crystal growth on the surface of each glass type, the Nb44 glass can also be considered the most resistant one against crystallization. The dissolution rate for the Nb44 glass after 14 days immersed in an aqueous solution with pH equals to 7 at 90 deg C is the lowest (9.0 x 10{sup -7} g. cm{sup -2} . day{sup -1}) when compared to the other two glass compositions. The dissolution rates in acidic and neutral solutions of all studied glasses meet the international standards for materials which can be used in the immobilization of nuclear wastes. (author)

CALCIUM CARBONATE DISSOLUTION RATE IN LIMESTONE CONTACTORS

Science.gov (United States)

The rate of carbonate mineral dissolution from limestone was studied using a rotating disk apparatus and samples of limestone of varied composition. The purpose of this study was to determine the effect of limestone composition on the kinetics of carbonate mineral dissolution. Th...

Cooling rate and size effects on the medium-range structure of multicomponent oxide glasses simulated by molecular dynamics

Energy Technology Data Exchange (ETDEWEB)

Tilocca, Antonio [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)

2013-09-21

A set of molecular dynamics simulations were performed to investigate the effect of cooling rate and system size on the medium-range structure of melt-derived multicomponent silicate glasses, represented by the quaternary 45S5 Bioglass composition. Given the significant impact of the glass degradation on applications of these materials in biomedicine and nuclear waste disposal, bulk structural features which directly affect the glass dissolution process are of particular interest. Connectivity of the silicate matrix, ion clustering and nanosegregation, distribution of ring and chain structural patterns represent critical features in this context, which can be directly extracted from the models. A key issue is represented by the effect of the computational approach on the corresponding glass models, especially in light of recent indications questioning the suitability of conventional MD approaches (that is, involving melt-and-quench of systems containing ∼10{sup 3} atoms at cooling rates of 5-10 K/ps) when applied to model these glasses. The analysis presented here compares MD models obtained with conventional and nonconventional cooling rates and system sizes, highlighting the trend and range of convergence of specific structural features in the medium range. The present results show that time-consuming computational approaches involving much lower cooling rates and/or significantly larger system sizes are in most cases not necessary in order to obtain a reliable description of the medium-range structure of multicomponent glasses. We identify the convergence range for specific properties and use them to discuss models of several glass compositions for which a possible influence of cooling-rate or size effects had been previously hypothesized. The trends highlighted here represent an important reference to obtain reliable models of multicomponent glasses and extract converged medium-range structural features which affect the glass degradation and thus their

Cooling rate and size effects on the medium-range structure of multicomponent oxide glasses simulated by molecular dynamics

International Nuclear Information System (INIS)

Tilocca, Antonio

2013-01-01

A set of molecular dynamics simulations were performed to investigate the effect of cooling rate and system size on the medium-range structure of melt-derived multicomponent silicate glasses, represented by the quaternary 45S5 Bioglass composition. Given the significant impact of the glass degradation on applications of these materials in biomedicine and nuclear waste disposal, bulk structural features which directly affect the glass dissolution process are of particular interest. Connectivity of the silicate matrix, ion clustering and nanosegregation, distribution of ring and chain structural patterns represent critical features in this context, which can be directly extracted from the models. A key issue is represented by the effect of the computational approach on the corresponding glass models, especially in light of recent indications questioning the suitability of conventional MD approaches (that is, involving melt-and-quench of systems containing ∼10 3 atoms at cooling rates of 5-10 K/ps) when applied to model these glasses. The analysis presented here compares MD models obtained with conventional and nonconventional cooling rates and system sizes, highlighting the trend and range of convergence of specific structural features in the medium range. The present results show that time-consuming computational approaches involving much lower cooling rates and/or significantly larger system sizes are in most cases not necessary in order to obtain a reliable description of the medium-range structure of multicomponent glasses. We identify the convergence range for specific properties and use them to discuss models of several glass compositions for which a possible influence of cooling-rate or size effects had been previously hypothesized. The trends highlighted here represent an important reference to obtain reliable models of multicomponent glasses and extract converged medium-range structural features which affect the glass degradation and thus their application

Chemical durability of simulated nuclear glasses containing water

International Nuclear Information System (INIS)

Li, H.; Tomozawa, M.

1995-04-01

The chemical durability of simulated nuclear waste glasses having different water contents was studied. Results from the product consistency test (PCT) showed that glass dissolution increased with water content in the glass. This trend was not observed during MCC-1 testing. This difference was attributed to the differences in reactions between glass and water. In the PCT, the glass network dissolution controlled the elemental releases, and water in the glass accelerated the reaction rate. On the other hand, alkali ion exchange with hydronium played an important role in the MCC-1. For the latter, the amount of water introduced into a leached layer from ion-exchange was found to be much greater than that of initially incorporated water in the glass. Hence, the initial water content has no effect on glass dissolution as measured by the MCC-1 test

Natural glass analogues to alteration of nuclear waste glass: A review and recommendations for further study

International Nuclear Information System (INIS)

McKenzie, W.F.

1990-01-01

The purpose of this report is to review previous work on the weathering of natural glasses; and to make recommendations for further work with respect to studying the alteration of natural glasses as it relates quantifying rates of dissolution. the first task was greatly simplified by the published papers of Jercinovic and Ewing (1987) and Byers, Jercinovic, and Ewing (1987). The second task is obviously the more difficult of the two and the author makes no claim of completeness in this regard. Glasses weather in the natural environment by reacting with aqueous solutions producing a rind of secondary solid phases. It had been proposed by some workers that the thickness of this rind is a function of the age of the glass and thus could be used to estimate glass dissolution rates. However, Jercinovic and Ewing (1987) point out that in general the rind thickness does not correlate with the age of the glass owing to the differences in time of contact with the solution compared to the actual age of the sample. It should be noted that the rate of glass dissolution is also a function of the composition of both the glass and the solution, and the temperature. Quantification of the effects of these parameters (as well as time of contact with the aqueous phase and flow rates) would thus permit a prediction of the consequences of glass-fluid interactions under varying environmental conditions. Defense high- level nuclear waste (DHLW), consisting primarily of liquid and sludge, will be encapsulated by and dispersed in a borosilicate glass before permanent storage in a HLW repository. This glass containing the DHLW serves to dilute the radionuclides and to retard their dispersion into the environment. 318 refs

Natural glass analogues to alteration of nuclear waste glass: A review and recommendations for further study

Energy Technology Data Exchange (ETDEWEB)

McKenzie, W.F.

1990-01-01

The purpose of this report is to review previous work on the weathering of natural glasses; and to make recommendations for further work with respect to studying the alteration of natural glasses as it relates quantifying rates of dissolution. the first task was greatly simplified by the published papers of Jercinovic and Ewing (1987) and Byers, Jercinovic, and Ewing (1987). The second task is obviously the more difficult of the two and the author makes no claim of completeness in this regard. Glasses weather in the natural environment by reacting with aqueous solutions producing a rind of secondary solid phases. It had been proposed by some workers that the thickness of this rind is a function of the age of the glass and thus could be used to estimate glass dissolution rates. However, Jercinovic and Ewing (1987) point out that in general the rind thickness does not correlate with the age of the glass owing to the differences in time of contact with the solution compared to the actual age of the sample. It should be noted that the rate of glass dissolution is also a function of the composition of both the glass and the solution, and the temperature. Quantification of the effects of these parameters (as well as time of contact with the aqueous phase and flow rates) would thus permit a prediction of the consequences of glass-fluid interactions under varying environmental conditions. Defense high- level nuclear waste (DHLW), consisting primarily of liquid and sludge, will be encapsulated by and dispersed in a borosilicate glass before permanent storage in a HLW repository. This glass containing the DHLW serves to dilute the radionuclides and to retard their dispersion into the environment. 318 refs.

Modeling of solution renewal with the Kindis code: example of R7T7 glass dissolution at 90 deg C

International Nuclear Information System (INIS)

Advocat, T.; Vernaz, E.; Crovisier, J.L.; Clement, A.; Gerard, F.

1994-01-01

The deep underground environment that would correspond to a geological repository is a system open to fluid flow. It is therefore necessary to investigate the effects of solution renewal on the long-term behavior of glass in contact with water. These effects can now be simulated using the new version of the geochemical KINDIS model (thermodynamic and kinetic model). We tested the model at 90 deg C with an SA/V ratio of 400 m -1 at twelve renewal rates of pure water ranging from 200 to 0 vol% per day. With renewal rates between 200 and 0.065 vol% per day, steady-state conditions were obtained in the reaction system: i.e. the glass corrosion rate remained constant as did the concentrations of the dissolved species in solution (although at different values depending on the renewal rate). The ionic strength never exceeded 1 (the validity limit for the DEBYE-HUCKEL law) and long term predictions of the dissolved glass mass, the solution composition and the potential secondary mineral sequence are possible. For simulated renewal rates of less than 0.065 vol% per day (27% per year), the ionic strength rose above 1 (as in a closed system) before steady-state conditions were reached, making it critical to calculate long-term rates; A constant and empirical long-term rate, derived from laboratory measurement, have to be extrapolated. These calculations were based on a first order equation to describe the glass dissolution kinetic. The results obtained with the KINDIS code show discrepancies with some major experimental kinetic data (the long term rate must decrease with the ''glass-water'' reaction progress, under silica saturation conditions). This clearly indicates that a more refine kinetic relation is needed for the glass matrix. (authors). 16 refs., 4 figs., 4 tabs

Corrosion of glass-bonded sodalite as a function of pH and temperature

International Nuclear Information System (INIS)

Morss, L. R.; Stanley, M.; Tatko, C.; Ebert, W. L.

1999-01-01

This paper reports the results of corrosion tests with monoliths of sodalite, binder glass, and glass-bonded sodalite, a ceramic waste form (CWF) that is being developed to immobilize radioactive electrorefiner salt used to condition spent sodium-bonded nuclear fuel. These tests were performed with dilute pH-buffered solutions in the pH range of 5-10 at temperatures of 70 and 90 C. The pH dependence of the forward dissolution rates of the CWF and its components have been determined. The pH dependence of the dissolution rates of sodalite, binder glass, and glass-bonded sodalite are similar to the pH dependence of dissolution rate of borosilicate nuclear waste glasses, with a negative pH dependence in the acidic region and a positive pH dependence in the basic region. Our results on the forward dissolution rates and their temperature and pH dependence will be used as components of a waste form degradation model to predict the long-term behavior of the CWF in a nuclear waste repository

Influence of cell culture medium composition on in vitro dissolution behavior of a fluoride-containing bioactive glass.

Science.gov (United States)

Shah, Furqan A; Brauer, Delia S; Wilson, Rory M; Hill, Robert G; Hing, Karin A

2014-03-01

Bioactive glasses are used clinically for bone regeneration, and their bioactivity and cell compatibility are often characterized in vitro, using physiologically relevant test solutions. The aim of this study was to show the influence of varying medium characteristics (pH, composition, presence of proteins) on glass dissolution and apatite formation. The dissolution behavior of a fluoride-containing bioactive glass (BG) was investigated over a period of one week in Eagle's Minimal Essential Medium with Earle's Salts (MEM), supplemented with either, (a) acetate buffer, (b) 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer, (c) HEPES + carbonate, or (d) HEPES + carbonate + fetal bovine serum. Results show pronounced differences in pH, ion release, and apatite formation over 1 week: Despite its acidic pH (pH 5.8 after BG immersion, as compared to pH 7.4-8.3 for HEPES-containing media), apatite formation was fastest in acetate buffered (HEPES-free) MEM. Presence of carbonate resulted in formation of calcite (calcium carbonate). Presence of serum proteins, on the other hand, delayed apatite formation significantly. These results confirm that the composition and properties of a tissue culture medium are important factors during in vitro experiments and need to be taken into consideration when interpreting results from dissolution or cell culture studies. Copyright © 2013 Wiley Periodicals, Inc.

Revisiting classical silicate dissolution rate laws under hydrothermal conditions

Science.gov (United States)

Pollet-Villard, Marion; Daval, Damien; Saldi, Giuseppe; Knauss, Kevin; Wild, Bastien; Fritz, Bertrand

2015-04-01

In the context of geothermal energy, the relative intensities of primary mineral leaching and secondary mineral precipitation can affect porosity and permeability of the reservoir, thereby influencing its hydraulic performance and the efficiency of the geothermal power station. That is why the prediction of reaction kinetics of fluid/rock interactions represents a critical issue in this context. Moreover, in several geothermal systems such as the one of Soultz-sous-Forêts (Alsace, France), the circulation of aqueous fluids induces only modest modifications of their chemical composition. Therefore, fluid-rock interactions take place at close-to-equilibrium conditions, where the rate-affinity relations are poorly known and intensively debated [1]. To describe more precisely the dissolution processes, our strategy consists in investigating the dissolution of the main cleavages of K-spar minerals (one of the prevalent primary minerals in the reservoir of Soultz-sous-Forêts geothermal system) over a wide range of Gibbs free energy (ΔG) conditions. The aims are to decipher the impact of crystallographic orientation and microstructural surface modifications on the dissolution kinetics and to propose a relation between K-spar dissolution rate and ΔG. Our experimental work relies on a coupled approach which combines classical experiments of K-spar dissolution monitored by aqueous chemical analyses (ICP-AES) and innovative techniques of nm- to μm-scale characterization of solid surface (SEM, AFM, VSI) [2]. Our results confirm that K-spar dissolution is an anisotropic process: we measure a tenfold factor between the slowest and the fastest-dissolving surfaces. Moreover, the formation of etch pits on surfaces during their alteration has been evidenced on all of the different faces that have been studied. This complex evolution of the surface topography casts doubt of the relevance of a surface model based on shrinking particles and represents a possible cause of an

Risk-informed assessment of radionuclide release from dissolution of spent nuclear fuel and high-level waste glass

Energy Technology Data Exchange (ETDEWEB)

Ahn, Tae M., E-mail: tae.ahn@nrc.gov

2017-06-15

Highlights: • Dissolution of HLW waste form was assessed with long-term risk informed approach. • The radionuclide release rate decreases with time from the initial release rate. • Fast release radionuclides can be dispersed with discrete container failure time. • Fast release radionuclides can be restricted by container opening area. • Dissolved radionuclides may be further sequestered by sorption or others means. - Abstract: This paper aims to detail the different parameters to be considered for use in an assessment of radionuclide release. The dissolution of spent nuclear fuel and high-level nuclear waste glass was considered for risk and performance insights in a generic disposal system for more than 100,000 years. The probabilistic performance assessment includes the waste form, container, geology, and hydrology. Based on the author’s previous extended work and data from the literature, this paper presents more detailed specific cases of (1) the time dependence of radionuclide release, (2) radionuclide release coupled with container failure (rate-limiting process), (3) radionuclide release through the opening area of the container and cladding, and (4) sequestration of radionuclides in the near field after container failure. These cases are better understood for risk and performance insights. The dissolved amount of waste form is not linear with time but is higher at first. The radionuclide release rate from waste form dissolution can be constrained by container failure time. The partial opening area of the container surface may decrease radionuclide release. Radionuclides sequestered by various chemical reactions in the near field of a failed container may become stable with time as the radiation level decreases with time.

The Influence of Pressure on the Intrinsic Dissolution Rate of Amorphous Indomethacin

Directory of Open Access Journals (Sweden)

Korbinian Löbmann

2014-08-01

Full Text Available New drug candidates increasingly tend to be poorly water soluble. One approach to increase their solubility is to convert the crystalline form of a drug into the amorphous form. Intrinsic dissolution testing is an efficient standard method to determine the intrinsic dissolution rate (IDR of a drug and to test the potential dissolution advantage of the amorphous form. However, neither the United States Pharmacopeia (USP nor the European Pharmacopeia (Ph.Eur state specific limitations for the compression pressure in order to obtain compacts for the IDR determination. In this study, the influence of different compression pressures on the IDR was determined from powder compacts of amorphous (ball-milling indomethacin (IND, a glass solution of IND and poly(vinylpyrrolidone (PVP and crystalline IND. Solid state properties were analyzed with X-ray powder diffraction (XRPD and the final compacts were visually observed to study the effects of compaction pressure on their surface properties. It was found that there is no significant correlation between IDR and compression pressure for crystalline IND and IND–PVP. This was in line with the observation of similar surface properties of the compacts. However, compression pressure had an impact on the IDR of pure amorphous IND compacts. Above a critical compression pressure, amorphous particles sintered to form a single compact with dissolution properties similar to quench-cooled disc and crystalline IND compacts. In such a case, the apparent dissolution advantage of the amorphous form might be underestimated. It is thus suggested that for a reasonable interpretation of the IDR, surface properties of the different analyzed samples should be investigated and for amorphous samples the IDR should be measured also as a function of the compression pressure used to prepare the solid sample for IDR testing.

The long-term acceleration of waste glass corrosion: A preliminary review

International Nuclear Information System (INIS)

Kielpinski, A.L.

1995-07-01

Whereas a prior conception of glass dissolution assumed a relatively rapid initial dissolution which then slowed to a smaller, fairly constant longer-term rate, some recent work suggests that these two stages are followed by a third phase of dissolution, in which the dissolution rate is accelerated with respect to what had previously been thought of as the final long-term rate. The goals of the present study are to compile experimental data which may have a bearing on this phenomena, and to provide an initial assessment of these data. The Savannah River Technology Center (SRTC) is contracted to develop glass formulation models for vitrification of Hanford low-level waste (LLW), in support of the Hanford Tank Waste Remediation System Technology Development Program. The phenomenon of an increase in corrosion rate, following a period characterized by a low corrosion rate, has been observed by a number of researchers on a number of waste glass compositions. Despite inherent ambiguities arising from SA/V (glass surface area to solution volume ratio) and other effects, valid comparisons can be made in which accelerated corrosion was observed in one test, but not in another. Some glass compositions do not appear to attain a plateau region; it may be that the observation of continued, non-negligible corrosion in these glasses represents a passage from the initial rate to the accelerated rate. The long-term corrosion is a function of the interaction between the glass and its environment, including the leaching solution and the surrounding materials. Reaction path modeling and stability field considerations have been used with some success to predict the changes in corrosion rate over time, due to these interactions. The accelerated corrosion phenomenon highlights the need for such integrated corrosion modeling and the scenario-specific nature of a particular glass composition's durability

Unexpected differences in dissolution behavior of tablets prepared from solid dispersions with a surfactant physically mixed or incorporated

NARCIS (Netherlands)

de Waard, H.; Hinrichs, W.L.J.; Visser, M.R.; Bologna, C.; Frijlink, H.W.

2008-01-01

In a previous study, it was shown that the incorporation of poorly soluble drugs (BCS class II) in sugar glasses could largely increase the drug's dissolution rate [van Drooge, D.J., Hinrichs, W.L.J., Frijlink, H.W., 20041). Anomalous dissolution behaviour of tablets prepared from sugar glass-based

Modelling the dissolution of borosilicate glasses for radioactive waste disposal with the PHREEQE/GLASSOL code: theory and practice

International Nuclear Information System (INIS)

Curti, E.

1991-02-01

A model describing the corrosion kinetics of silicate glasses has been developed by Grambow in recent years. In this report, the theoretical background of the model is thoroughly discussed, and its practical use demonstrated. The main objectives were: 1) to test the validity of the basic assumptions on which the model relies, and 2) to assess whether it can be applied to the safety analysis of a Swiss final repository for high-level radioactive waste. Transition State Theory, a tool based on quantum mechanical principles, has been used by Grambow to derive a general kinetic equation for the corrosion of silicate glasses. This equation predicts successfully the observed dependence of the corrosion rate on the silicic acid concentration in solution according to a first order kinetics law. However, some parameters required by this equation are determined on the base of questionable assumptions. In particular, the simplistic surface complexation model used for the calculation of the free energy of the glass-water reaction yields, for the protonation of silicon on the glass surface, results which are not consistent with the experimental findings. Further, although the model predicts a unique value, common to all silicate glasses, for the activation energy of the rate-determining elementary reaction, leaching experiments conducted on a wide variety of glasses suggest that this quantity may vary by a factor 2. In its present form, the model is judged to be unsuitable for the safety analysis of the Swiss final repository. The reasons include: 1) the model neglects the potential effects of diffusive transport and silica sorption in a bentonite backfill on the glass corrosion kinetics, 2) the release of radionuclides can be only modelled assuming congruent dissolution, and 3) the magnitude of the final rates of corrosion, the parameter defining the maximal lifetime of the glass matrix, is still not known with sufficient precision. (author) figs., tabs., 27 refs

Neural network analysis of nuclear waste glass composition vs durability

International Nuclear Information System (INIS)

Seibel, C.K.

1994-01-01

The relationship between the chemical composition of oxide glasses and their physical properties is poorly understood, but it is becoming more important as vitrification (transformation into glass) of high-level nuclear waste becomes the favored method for long-term storage. The vitrified waste will be stored deep in geologic repositories where it must remain intact for at least 10,000 years. A strong resistance to groundwater exposure; i.c. a slow rate of glass dissolution, is of great importance. This project deals specifically with glass samples developed and tested for the nuclear fuel reprocessing facility near West Valley, New York. This facility needs to dispose of approximately 2.2 million liters of high-level radioactive liquid waste currently stored in stainless steel tanks. A self-organizing, artificial neural network was used to analyze the trends in the glass dissolution data for the effects of composition and the resulting durability of borosilicate glasses in an aqueous environment. This durability data can be used to systematically optimize the properties of the complex nuclear glasses and slow the dissolution rate of radionuclides into the environment

Measurement of soluble nuclide dissolution rates from spent fuel

International Nuclear Information System (INIS)

Wilson, C.N.; Gray, W.J.

1990-01-01

Gaining a better understanding of the potential release behavior of water-soluble radionuclides is the focus of new laboratory spent fuel dissolution studies being planned in support of the Yucca Mountain Project. Previous studies have suggested that maximum release rates for actinide nuclides, which account for most of the long-term radioactivity in spent fuel, should be solubility-limited and should not depend on the characteristics or durability of the spent fuel waste form. Maximum actinide concentrations should be sufficiently low to meet the NRC (Nuclear Regulatory Commission) annual release limits. Potential release rates for soluble nuclides such as 99 Tc, 135 Cs, 14 C and 129 I, which account for about 1-2% of the activity in spent fuel at 1,000 years, are less certain and may depend on processes such as oxidation of the fuel in the repository air environment. Dissolution rates for several soluble nuclides have been measured from spent fuel specimens using static and semi-static methods. However, such tests do not provide a direct measurement of fuel matrix dissolution rates that may ultimately control soluble-nuclide release rates. Flow-through tests are being developed as a potential supplemental method for determining the matrix component of soluble-nuclide dissolution. Advantages and disadvantages of both semi-static and flow-through methods are discussed. Tests with fuel specimens representing a range of potential fuel states that may occur in the repository, including oxidized fuel, are proposed. Preliminary results from flow-through tests with unirradiated UO 2 suggesting that matrix dissolution rates are very sensitive to water composition are also presented

Nuclear waste glass corrosion mechanisms

International Nuclear Information System (INIS)

Jantzen, C.M.

1987-04-01

Dissolution of nuclear waste glass occurs by corrosion mechanisms similar to those of other solids, e.g., metallurgical and mineralogic systems. Metallurgical phenomena such as active corrosion, passivation and immunity have been observed to be a function of the glass composition and the solution pH. Hydration thermodynamics was used to quantify the role of glass composition and its effect on the solution pH during dissolution. A wide compositional range of natural, lunar, medieval, and nuclear waste glasses, as well as some glass-ceramics were investigated. The factors observed to affect dissolution in deionized water are pertinent to the dissolution of glass in natural environments such as the groundwaters anticipated to interact with nuclear waste glass in a geologic repository. The effects of imposed pH and oxidation potential (Eh) conditions existing in natural environments on glass dissolution is described in the context of Pourbaix diagrams, pH potential diagrams, for glass

DISSOLUTION BEHAVIOR OF BIOACTIVE GLASS CERAMICS WITH DIFFERENT CaO/MgO RATIOS

Directory of Open Access Journals (Sweden)

MUHAMMAD USMAN HASHMI

2010-03-01

Full Text Available In this work, powders of three different compositions, each having 34 SiO2-14.5 P2O5-1 CaF2-0.5 MgF (% wt and ratio of CaO/MgO varying from 11.5:1 to 1:11.5 were thoroughly mixed and melted under oxy-acetylene flame in a fire clay crucible that made the glass formation cheaper in time and cost. The melt of each composition was quenched in water to form three different glasses. Every glass was sintered at 950°C to form three glass ceramics named G1, G2 and G3 respectively. To study the dissolution behavior, each sample was immersed in a simulated body fluid (SBF for 2, 5, 10, 20 and 25 days at room temperature. Thin film XRD analysis revealed that the samples with larger CaO/MgO ratio exhibited better bioactivity. pH of SBF increased efficiently in case of G1 whereas in case of G2 and G3, this increase was slower due to greater amount of MgO. The concentrations of Ca, P, Mg and Si ions were measured by Atomic Absorption Spectroscopy. EDS analysis showed the increase in P and Ca ions and presence of C in G1 after 5 days immersion and after 10 days, in case of G2 indicating the higher formation rate of hydroxycarbonate Apatite layer in G1 as compared to G2 due to greater CaO/MgO ratio whereas in G3 Mg-hydroxycarbonate apatite (Ca(Mg5(CO3(PO43(OH (heneuite layer was recognized after 20 days showing the least bioactivity due to very large amount of Mg and the least CaO/MgO ratio.

Dissolution rate effect upon lyolumenescence of irradiated potassium chloride

International Nuclear Information System (INIS)

Leshchinskij, B.L.; Dzelme, Yu.R.; Tiliks, Yu.E.; Bugaenko, L.T.

1985-01-01

The paper is aimed at studying dissolution rate effect and concentration of electron acceptor upon lyoluminescence (LL) that occurs during dissolution of solids with radiation defects. For investigation gamma-irradiated potassium chloride monocrystalline disks were used. As a solvent 3x10sup(-6) M solution of C(RH) hodamine in 2.7 KCl aqueous solution is used. It is shown that LL occurs as a result of recombination of radiation defects with the solution and between themselves in two different regions of subsurface layer of the solid. Investigated dependences of LL intensty on dissolution rate are the efficient method of studying the structure of solids-aqueous solution interface and LL mechanism

Magnesite dissolution and precipitation rates at hydrothermal conditions

International Nuclear Information System (INIS)

Saldi, Giuseppe

2009-01-01

Magnesite (MgCO 3 ) is the stable anhydrous member of a series of Mg-carbonates with different degrees of hydration. Despite its relative scarcity in the natural environments, it constitutes an important mineral phase for the permanent sequestration of CO 2 as carbonate minerals. Experimental determination of magnesite precipitation and dissolution rates at conditions representative of the storage sites is therefore fundamental for the assessment of magnesite sequestration potential in basaltic and ultramafic rocks and the optimization of the techniques of CO 2 storage. Magnesite precipitation rates have been measured using mixed-flow and batch reactors as a function of temperature (100 ≤ T ≤ 200 deg. C), solution composition and CO 2 partial pressure (up to 30 bar). Rates were found to be independent of aqueous solution ionic strength at 0.1 M 3 2- activity at pH > 8. All rates obtained from mixed flow reactor experiments were found to be consistent with the model of Pokrovsky et al. (1999) where magnesite precipitation rates are proportional to the concentration of the >MgOH 2 + surface species. The study of magnesite crystallization using hydrothermal atomic force microscopy (HAFM) demonstrated the consistency of the rates derived from microscopic measurements with those obtained from bulk experiments and showed that these rates are also consistent with a spiral growth mechanism. According to AFM observations this mechanism controls magnesite growth over a wide range of temperatures and saturation states (15≤ Ω ≤200 for 80 ≤T 2 to accelerate the rate of the overall carbonation process, avoiding the inhibiting effect of carbonate ions on magnesite precipitation and increasing the rates of Mg-silicate dissolution via acidification of reacting solutions. Determination of magnesite dissolution rates by mixed flow reactor at 150 and 200 deg. C and at neutral to alkaline conditions allowed us to improve and extend to high temperatures the surface

Surface layer effects on waste glass corrosion

International Nuclear Information System (INIS)

Feng, X.

1993-01-01

Water contact subjects waste glass to chemical attack that results in the formation of surface alteration layers. Two principal hypotheses have been advanced concerning the effect of surface alteration layers on continued glass corrosion: (1) they act as a mass transport barrier and (2) they influence the chemical affinity of the glass reaction. In general, transport barrier effects have been found to be less important than affinity effects in the corrosion of most high-level nuclear waste glasses. However, they can be important under some circumstances, for example, in a very alkaline solution, in leachants containing Mg ions, or under conditions where the matrix dissolution rate is very low. The latter suggests that physical barrier effect may affect the long-term glass dissolution rate. Surface layers influence glass reaction affinity through the effects of the altered glass and secondary phases on the solution chemistry. The reaction affinity may be controlled by various precipitates and crystalline phases, amorphous silica phases, gel layer, or all the components of the glass. The surface alteration layers influence radionuclide release mainly through colloid formation, crystalline phase incorporation, and gel layer retention. This paper reviews current understanding and uncertainties

Aqueous corrosion mechanisms of the nuclear glass R7T7. Experimental approach. Kinetics and thermodynamic simulation

International Nuclear Information System (INIS)

Advocat, T.

1991-01-01

An inactive borosilicate glass made of about 30 oxides is studied. The composition was developed by the CEA for encapsulation of calcinated fission product solutions from reprocessing. Hydration energy of glass is first calculated for 8 glasses and results are compared to experimental data. Dissolution of R7T7 glass is examined at 90 0 C in a large range of pH and S/V ratios (glass surface/solution volume). In dilute media (S/V = 0.1 cm -1 ) dissolution is selective at acid pH and stoichiometric at basic pH. In alkaline media dissolution rate increases with pH. Corrosion products, generally amorphous or badly crystallized are observed on glass surface. For high S/V ratios (4, 20, 80 and 200 cm -1 ) the very low dissolution rate is explained by saturation. Orthosilic acid controls corrosion kinetics. A kinetic equation is proposed taking into account pH, S/V ratio and dissolved silica concentration. Geochemical consequences of R7T7 dissolution are modelled at 100 0 C and 90 0 C. Affinity of dissolution reaction depends upon many factors (pH, silica concentration, nature and crystallinity of secondary phases. Reaction affinity is not constant for the long-term [fr

Experimental investigation of the effects of aqueous species on the dissolution kinetics of R7T7 glass; Etude experimentale de l`influence d`especes aqueuses sur la cinetique de dissolution du verre nucleaire R7T7

Energy Technology Data Exchange (ETDEWEB)

Gin, S

1994-10-01

This contribution to the study of aqueous corrosion of the French ``R7T7`` reference nuclear containment glass includes a bibliographic survey of prior investigations, highlighting the problems encountered in interpreting the interactions in systems containing clay materials in contact with the glass. An experimental methodology is proposed to investigate the effects of inorganic aqueous species separately from those of a few organic acids on the dissolution mechanisms and kinetics of R7T7 glass at 90 deg. C. The experimental results discussed support the idea that several glass network forming elements may have a kinetically limiting role. The most likely hypothesis to account for the absence of saturation conditions with respect to the glass in certain clay media involves the formation of complexes with kinetically limiting metallic elements such as aluminum released by glass corrosion. This work contributes to a better understanding of the basic mechanisms of nuclear glass dissolution in a geological repository environment. It facilitates the interpretation of glass alteration studies in realistic or actual solutions and may contribute to specifying near field chemical barriers in the form of additives (amorphous silica, aluminum hydroxides or phosphates) around the glass disposal package to enhance the stability of the glass matrix. (author). 148 refs., 40 figs., 32 tabs., 1 append.

Dissolution rate of alpha-doped UO2 in natural groundwater

International Nuclear Information System (INIS)

Ollila, Kaija; Myllykylä, Emmi; Tanhua-Tyrkkö, Merja; Lavonen, Tiina

2013-01-01

The objective of this work is to determine whether the presence of trace elements in natural groundwaters affects the dissolution rate of uranium dioxide in the presence of alpha radiation that causes radiolysis of water. The study is a part of the project Reducing Uncertainty in Performance Prediction (REDUPP) under the Seventh Framework Programme of the European Atomic Energy Community (EURATOM). The project aims to reduce uncertainties related to the extrapolation of the results of laboratory experiments to the conditions expected under geologic disposal. Thus far, synthetic groundwater has been normally used in the experiments. The synthetic groundwaters used do not contain all of the chemical elements that occur in natural groundwaters. Three natural groundwaters were chosen for the dissolution experiments with 0%, 5%, and 10% 233 U-doped UO 2 samples. These include a brackish groundwater, a saline groundwater and a low ionic strength groundwater. At the time of writing this paper, the dissolution experiments have been finished in the first groundwater, which was a moderately saline, brackish groundwater. The groundwater samples for the experiments were taken from a borehole in the Olkiluoto site in Finland. The measurements for dissolution rates were conducted under reducing conditions established using metallic iron in solution and an argon atmosphere in the glove box. The isotope dilution method was used to decrease uncertainties due to precipitation and sorption effects. The resulting dissolution rates in OL-KR6 natural groundwater were generally somewhat higher than the rates measured previously in synthetic groundwaters under similar redox conditions. No clear effect of alpha radiolysis could be seen for tests with lower SA/V, while those for higher SA/V indicated that the dissolution rate was higher for the 10% 233 U-doped UO 2 , suggesting the effect of alpha radiolysis under these conditions

A statistical approach to determine the effects of nuclear glass components on the short and long term glass alteration

International Nuclear Information System (INIS)

Advocat, Th.; Tovena, I.; Vernaz, E.; Larche, F.; Phan Tan Luu, R.

1997-01-01

The experimentation plan methodology may be a powerful tool to design statistical models able to calculate quantitative leach rates as a function of glass compositions. The investigation discussed here implemented an experimentation plan methodology covering a wide range of glass composition variations with two major objectives: - identify the effects of the main component oxides of R7T7 glass (SiO 2 , B 2 O 3 , Al 2 O 3 , Na 2 O+Li 2 O, additive oxides, Fission Products oxides, actinide oxides) on the dissolution rates far and close to equilibrium; - and develop a statistical model relating the measured initial dissolution rate with the selected oxide compositions. A second-degree silica-based model was developed to express the initial dissolution rates at 100 deg C according to the oxide weight percentage of 6 major oxides or oxide groups. The model is qualified by comparison with independent experimental results. For the short term, far from saturation conditions (confined media), plotting the effects of the oxides clearly showed that SiO 2 , Al 2 O 3 and the additive oxides enhanced glass durability at 100 deg C, while B 2 O 3 and Na 2 O+Li 2 O diminished the initial corrosion resistance. For the long term, plotting the effects of the oxides showed that additive oxides, Al 2 O 3 and SiO 2 enhanced glass durability at 90 deg C, in that order, while Na 2 O+Li 2 O still diminished the corrosion resistance. The fission products and actinide oxides and ZrO 2 have apparently a slight beneficial effect on the glass durability, under saturation conditions (long term). (author)

Crystal modifications and dissolution rate of piroxicam.

Science.gov (United States)

Lyn, Lim Yee; Sze, Huan Wen; Rajendran, Adhiyaman; Adinarayana, Gorajana; Dua, Kamal; Garg, Sanjay

2011-12-01

Piroxicam is a nonsteroidal anti-inflammatory drug with low aqueous solubility which exhibits polymorphism. The present study was carried out to develop polymorphs of piroxicam with enhanced solubility and dissolution rate by the crystal modification technique using different solvent mixtures prepared with PEG 4000 and PVP K30. Physicochemical characteristics of the modified crystal forms of piroxicam were investigated by X-ray powder diffractometry, FT-IR spectrophotometry and differential scanning calorimetry. Dissolution and solubility profiles of each modified crystal form were studied and compared with pure piroxicam. Solvent evaporation method (method I) produced both needle and cubic shaped crystals. Slow crystallization from ethanol with addition of PEG 4000 or PVP K30 at room temperature (method II) produced cubic crystal forms. Needle forms produced by method I improved dissolution but not solubility. Cubic crystals produced by method I had a dissolution profile similar to that of untreated piroxicam but showed better solubility than untreated piroxicam. Cubic shaped crystals produced by method II showed improved dissolution, without a significant change in solubility. Based on the XRPD results, modified piroxicam crystals obtained by method I from acetone/benzene were cube shaped, which correlates well with the FTIR spectrum; modified needle forms obtained from ethanol/methanol and ethanol/acetone showed a slight shift of FTIR peak that may be attributed to differences in the internal structure or conformation.

Origin and evolution of cup-shaped structures on leached nuclear waste containment glass surfaces

International Nuclear Information System (INIS)

Dubois, C.; Villa, F.; Chambaudet, A.; Vernaz, E.

1994-01-01

A three-dimensional surface microanalysis system equipped with a sensitive topographical probe was used to quantify the evolution of cup-shaped structures formed by aqueous leaching of nuclear waste containment glass. A model of the dissolution phenomenon provides satisfactory correlation between calculated and measured cup radius and depth. Dissolution cups form from cracks on the initially cut glass surface. Large cracks control the phenomenon by forming the largest cups, which gradually absorb smaller ones. The evolution of the size and shape of the dissolution cups was described by a model that assumes a constant dissolution rate on the surface, diminishing with crack depth. The best fit with the experimental data was obtained with a dissolution rate one hundred times lower at the bottom of the crack than at the surface. Moreover, it is predictable that all the cups will gradually disappear as they grow larger and flatter over a leaching period of some 2 years, for the glass composition and experimental leaching procedures used in this work

Comparison of uranium dissolution rates from spent fuel and uranium dioxide

International Nuclear Information System (INIS)

Steward, S.A.; Gray, W.J.

1994-01-01

Two similar sets of dissolution experiments, resulting from a statistical experimental design were performed in order to examine systematically the effects of temperature (25--75 degree C), dissolved oxygen (0.002-0.2 atm overpressure), pH (8--10) and carbonate concentrations (2--200 x 10 -4 molar) on aqueous dissolution of UO 2 and spent fuel. The average dissolution rate was 8.6 mg/m 2 ·day for UO 2 and 3.1 mg/m 2 ·day for spent fuel. This is considered to be an insignificant difference; thus, unirradiated UO 2 and irradiated spent fuel dissolved at about the same rate. Moreover, regression analyses indicated that the dissolution rates of UO 2 and spent fuel responded similarly to changes in pH, temperature, and carbonate concentration. However, the two materials responded very differently to dissolved oxygen concentration. Approximately half-order reaction rates with respect to oxygen concentration were found for UO 2 at all conditions tested. At room temperature, spent fuel dissolution (reaction) rates were nearly independent of oxygen concentration. At 75 degree C, reaction orders of 0.35 and 0.73 were observed for spent fuel, and there was some indication that the reaction order with respect to oxygen concentration might be dependent on pH and/or carbonate concentration as well as on temperature

A Study of Analytical Solution for the Special Dissolution Rate Model of Rock Salt

Directory of Open Access Journals (Sweden)

Xin Yang

2017-01-01

Full Text Available By calculating the concentration distributions of rock salt solutions at the boundary layer, an ordinary differential equation for describing a special dissolution rate model of rock salt under the assumption of an instantaneous diffusion process was established to investigate the dissolution mechanism of rock salt under transient but stable conditions. The ordinary differential equation was then solved mathematically to give an analytical solution and related expressions for the dissolved radius and solution concentration. Thereafter, the analytical solution was fitted with transient dissolution test data of rock salt to provide the dissolution parameters at different flow rates, and the physical meaning of the analytical formula was also discussed. Finally, the influential factors of the analytical formula were investigated. There was approximately a linear relationship between the dissolution parameters and the flow rate. The effects of the dissolution area and initial volume of the solution on the dissolution rate equation of rock salt were computationally investigated. The results showed that the present analytical solution gives a good description of the dissolution mechanism of rock salt under some special conditions, which may provide a primary theoretical basis and an analytical way to investigate the dissolution characteristics of rock salt.

Dissolution rates of over-the-counter painkillers: a comparison among formulations.

Science.gov (United States)

Alemanni, Matteo; Gatoulis, Sergio C; Voelker, Michael

2016-06-01

We wanted to compare the dissolution profile of several over-the-counter analgesics to understand whether the different formulation techniques employed to enhance absorption were associated with variations in the dissolution rate, a parameter known to affect drug absorption. We considered 5 formulations currently marketed in Italy: aspirin tablets (Aspirina Dolore e Infiammazione®), ibuprofen tablets and liquid capsules (Moment®), ibuprofen lysine tablets (Nurofenimmedia®) and dexketoprofen trometamol tablets (Enantyum®). Dissolution tests were performed according to the current USP/NF monograph dissolution procedure. Drug dissolution was evaluated at 1, 3, 6, 15, and 30 minutes since the start of the test. Dissolution was evaluated at three different pH: 1.2, 4.5 and 6.8. Every test was repeated 12 times. The aspirin formulation was by far the most rapid dissolving formulation, among those tested, with more than 80% of the tablet dissolved at 6 minutes for every pH considered. At pH 1.2 and 4.5, only the dexketoprofen formulation was able to reach the dissolution level of aspirin at 30 minutes, but had lower levels of dissolution at the previous time points. Instead, at pH 6.8, most of the formulations approached aspirin dissolution level, but only after 15 minutes. Ibuprofen capsules had the slowest kinetics, with a lag phase the first 6 minutes. Different formulation strategies can lead to great differences in the dissolution rates even among drugs of the same class, suggesting that enhancements in the formulation of painkillers can lead to improvements in drug absorption, and thus in the onset of analgesia.

Effects of acid deposition on dissolution of carbonate stone during summer storms in the Adirondack Mountains, New York, 1987-89

Science.gov (United States)

Schuster, Paul F.; Reddy, Michael M.; Sherwood, S.I.

1994-01-01

This study is part of a long-term research program designed to identify and quantify acid rain damage to carbonate stone. Acidic deposition accelerates the dissolution of carbonate-stone monuments and building materials. Sequential sampling of runoff from carbonate-stone (marble) and glass (reference) microcatchments in the Adirondack Mountains in New York State provided a detailed record of the episodic fluctuations in rain rate and runoff chemistry during individual summer storms. Rain rate and chemical concentrations from carbonate-stone and glass runoff fluctuated three to tenfold during storms. Net calcium-ion concentrations from the carbonatestone runoff, a measure of stone dissolution, typically fluctuated twofold during these storms. High net sulfate and net calcium concentrations in the first effective runoff at the start of a storm indicated that atmospheric pollutants deposited on the stone surface during dry periods formed calcium sulfate minerals, an important process in carbonate stone dissolution. Dissolution of the carbonate stone generally increased up to twofold during coincident episodes of low rain rate (less than 5 millimeters per hour) and decreased rainfall (glass runoff) pH (less than 4.0); episodes of high rain rate (cloudbursts) were coincident with a rapid increase in rainfall pH and also a rapid decrease in the dissolution of carbonate-stone. During a storm, it seems the most important factors causing increased dissolution of carbonate stone are coincident periods of low rain rate and decreased rainfall pH. Dissolution of the carbonate stone decreased slightly as the rain rate exceeded about 5 millimeters per hour, probably in response to rapidly increasing rainfall pH during episodes of high rain rate and shorter contact time between the runoff and the stone surface. High runoff rates resulting from cloudbursts remove calcium sulfate minerals formed during dry periods prior to storms and also remove dissolution products formed in large

A statistical approach to determine the effects of nuclear glass components on the short and long term glass alteration

Energy Technology Data Exchange (ETDEWEB)

Advocat, Th; Tovena, I; Vernaz, E [CEA Valrho, Dir. de l' Energie Nucleaire, DEN, 30 - Marcoule (France); Larche, F [Montpellier-2 Univ., 34 (France); Phan Tan Luu, R [Faculte de St Jerome, 13 - Marseille (France)

1997-07-01

The experimentation plan methodology may be a powerful tool to design statistical models able to calculate quantitative leach rates as a function of glass compositions. The investigation discussed here implemented an experimentation plan methodology covering a wide range of glass composition variations with two major objectives: - identify the effects of the main component oxides of R7T7 glass (SiO{sub 2}, B{sub 2}O{sub 3}, Al{sub 2}O{sub 3}, Na{sub 2}O+Li{sub 2}O, additive oxides, Fission Products oxides, actinide oxides) on the dissolution rates far and close to equilibrium; - and develop a statistical model relating the measured initial dissolution rate with the selected oxide compositions. A second-degree silica-based model was developed to express the initial dissolution rates at 100 deg C according to the oxide weight percentage of 6 major oxides or oxide groups. The model is qualified by comparison with independent experimental results. For the short term, far from saturation conditions (confined media), plotting the effects of the oxides clearly showed that SiO{sub 2}, Al{sub 2}O{sub 3} and the additive oxides enhanced glass durability at 100 deg C, while B{sub 2}O{sub 3} and Na{sub 2}O+Li{sub 2}O diminished the initial corrosion resistance. For the long term, plotting the effects of the oxides showed that additive oxides, Al{sub 2}O{sub 3} and SiO{sub 2} enhanced glass durability at 90 deg C, in that order, while Na{sub 2}O+Li{sub 2}O still diminished the corrosion resistance. The fission products and actinide oxides and ZrO{sub 2} have apparently a slight beneficial effect on the glass durability, under saturation conditions (long term). (author)

The Use of Artificial Neural Network for Prediction of Dissolution Kinetics

Directory of Open Access Journals (Sweden)

H. Elçiçek

2014-01-01

Full Text Available Colemanite is a preferred boron mineral in industry, such as boric acid production, fabrication of heat resistant glass, and cleaning agents. Dissolution of the mineral is one of the most important processes for these industries. In this study, dissolution of colemanite was examined in water saturated with carbon dioxide solutions. Also, prediction of dissolution rate was determined using artificial neural networks (ANNs which are based on the multilayered perceptron. Reaction temperature, total pressure, stirring speed, solid/liquid ratio, particle size, and reaction time were selected as input parameters to predict the dissolution rate. Experimental dataset was used to train multilayer perceptron (MLP networks to allow for prediction of dissolution kinetics. Developing ANNs has provided highly accurate predictions in comparison with an obtained mathematical model used through regression method. We conclude that ANNs may be a preferred alternative approach instead of conventional statistical methods for prediction of boron minerals.

Geochemical modelling of the long-term dissolution behaviour of the French nuclear glass R7T7

International Nuclear Information System (INIS)

Michaux, L.; Mouche, E.; Petit, J.-C.; Fritz, B.

1992-01-01

The long-term dissolution behaviour of the French nuclear reference glass R7T7 was studied by means of the geochemical code DISSOL. New experimental data which support some of the assumptions of DISSOL are presented: namely, that the dissolution is congruent and that the altered layer can be considered as an assemblage of secondary phases. At 100 o C the main results of modelling are that the altered layer is essentially formed of a pure siliceous phase (amorphous silica or chalcedony) associated with smectites and zeolites. This sequence of secondary minerals is closely linked to the chemical composition of the glass. For high degrees of reaction, corresponding to high B concentration, the ionic strength reaches 1 and the pH varies from 9 to 10 depending on the CO 2 fugacity; B,Li and Na are essentially found in solution and their concentrations depend on the amount of dissolved glass. By contrast Fe,Al and Zn have low solution concentrations which are controlled by solubility products of secondary minerals. Silicon and Ca have an intermediate behaviour which depends on the choice of selected secondary minerals. The total volume of the secondary phases is always lower than that of the corresponding dissolved glass. The results of modelling compared to static leaching experimental results show only minor differences which can be explained by kinetic control or colloid formation. It is concluded that the altered layer is not a barrier to diffusion. The consequences of this work for actinide solubility are also discussed. (author)

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

Science.gov (United States)

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

2014-07-01

We investigated the structure-property relationships in a series of alkali-free phosphosilicate glass compositions co-doped with Zn(2+) and Sr(2+). The emphasis was laid on understanding the structural role of Sr(2+) and Zn(2+) co-doping on the chemical dissolution behavior of glasses and its impact on their in vitro bioactivity. The structure of glasses was studied using molecular dynamics simulations in combination with solid state nuclear magnetic resonance spectroscopy. The relevant structural properties are then linked to the observed degradation behavior, in vitro bioactivity, osteoblast proliferation and oxidative stress levels. The apatite-forming ability of glasses has been investigated by X-ray diffraction, infrared spectroscopy and scanning electron microscopy-energy-dispersive spectroscopy after immersion of glass powders/bulk in simulated body fluid (SBF) for time durations varying between 1h and 14 days, while their chemical degradation has been studied in Tris-HCl in accordance with ISO 10993-14. All the glasses exhibit hydroxyapatite formation on their surface within 1-3h of their immersion in SBF. The cellular responses were observed in vitro on bulk glass samples using human osteosarcoma MG63 cell line. The dose-dependent cytoprotective effect of glasses with respect to the concentration of zinc and strontium released from the glasses is also discussed. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Durable Glass For Thousands Of Years

International Nuclear Information System (INIS)

Jantzen, C.

2009-01-01

The durability of natural glasses on geological time scales and ancient glasses for thousands of years is well documented. The necessity to predict the durability of high level nuclear waste (HLW) glasses on extended time scales has led to various thermodynamic and kinetic approaches. Advances in the measurement of medium range order (MRO) in glasses has led to the understanding that the molecular structure of a glass, and thus the glass composition, controls the glass durability by establishing the distribution of ion exchange sites, hydrolysis sites, and the access of water to those sites. During the early stages of glass dissolution, a 'gel' layer resembling a membrane forms through which ions exchange between the glass and the leachant. The hydrated gel layer exhibits acid/base properties which are manifested as the pH dependence of the thickness and nature of the gel layer. The gel layer ages into clay or zeolite minerals by Ostwald ripening. Zeolite mineral assemblages (higher pH and Al 3+ rich glasses) may cause the dissolution rate to increase which is undesirable for long-term performance of glass in the environment. Thermodynamic and structural approaches to the prediction of glass durability are compared versus Ostwald ripening.

DURABLE GLASS FOR THOUSANDS OF YEARS

Energy Technology Data Exchange (ETDEWEB)

Jantzen, C.

2009-12-04

The durability of natural glasses on geological time scales and ancient glasses for thousands of years is well documented. The necessity to predict the durability of high level nuclear waste (HLW) glasses on extended time scales has led to various thermodynamic and kinetic approaches. Advances in the measurement of medium range order (MRO) in glasses has led to the understanding that the molecular structure of a glass, and thus the glass composition, controls the glass durability by establishing the distribution of ion exchange sites, hydrolysis sites, and the access of water to those sites. During the early stages of glass dissolution, a 'gel' layer resembling a membrane forms through which ions exchange between the glass and the leachant. The hydrated gel layer exhibits acid/base properties which are manifested as the pH dependence of the thickness and nature of the gel layer. The gel layer ages into clay or zeolite minerals by Ostwald ripening. Zeolite mineral assemblages (higher pH and Al{sup 3+} rich glasses) may cause the dissolution rate to increase which is undesirable for long-term performance of glass in the environment. Thermodynamic and structural approaches to the prediction of glass durability are compared versus Ostwald ripening.

Study of glass alteration mechanisms in cement waters

International Nuclear Information System (INIS)

Depierre, S.

2012-01-01

In the French deep geological repository concept, intermediate-level vitrified waste packages could be disposed of concrete medium. Chemical composition and pH of the interstitial leaching water are expected to influence the chemical durability of glass. Investigations have thus been carried out to study glass dissolution mechanisms and kinetics in contact with cement waters. Three cement pore waters were studied: the first two correspond to two stages of the Portland cement aging and the third corresponds to equilibrium with a low pH concrete. The S/V ratio (glass-surface-area-to-solution-volume ratio) and the chemistry of cement waters are the two main parameters that control glass alteration mechanisms. If the leaching flow from the glass allows a degree of supersaturation to be reached and maintained which leads to nucleation of secondary phases, then precipitation of these phases drives glass dissolution. At a very low S/V ratio, the calcium uptake into the alteration layer increases its passivating properties. Conversely, at a high S/V ratio, the calcium precipitates as cementitious phases consuming elements which form the alteration layer. The glass dissolution is maintained at a high rate. This study contributes to highlighting the beneficial role of low pH cement in glass alteration, and is a first step towards understanding the mechanisms between the glass and the cement medium. (author) [fr

Calculation methods for dissolution rate of multicomponent alloys during electrochemical machining

International Nuclear Information System (INIS)

Dikusar, A.I.; Petrenko, V.I.; Dikusar, G.K.; Ehngel'gardt, G.R.; Michukova, N.Yu.

1981-01-01

The possibility of theoretical calculation of metal dissolution rate during electrochemical mashining is considered. Two calculation techniques are compared at the example of two-component W-Re, Ni-W, Mo-Re alloys, namely: ''charge superposition'' and ''weight percents''. It is concluded that the technique of ''charge superposition'' is the only grounded calculation technique of specific rates of dissolution for alloys [ru

Remaining uncertainties in predicting long-term performance of nuclear waste glass from experiments

International Nuclear Information System (INIS)

Grambow, B.

1994-01-01

The current knowledge on the glass dissolution mechanism and the representation of glass dissolution concepts within overall repository performance assessment models are briefly summarized and uncertainties related to mechanism, radionuclide chemistry and parameters are discussed. Understanding of the major glass dissolution processes has been significantly increased in recent years. Long-term glass stability is related to the long-term maintenance of silica saturated conditions. The behavior of individual radionuclides in the presence of a dissolving glass has not been sufficiently and results do no yet allow meaningful predictions. Conserving long-term predictions of glass matrix dissolution as upper limit for radionuclide release can be made with sufficient confidence, however these estimations generally result in a situation where the barrier function of the glass is masked by the efficiency of the geologic barrier. Realistic long-term predictions may show that the borosilicate waste glass contributes to overall repository safety to a much larger extent than indicated by overconservatism. Today realistic predictions remain highly uncertain and much more research work is necessary. In particular, the long-term rate under silica saturated conditions needs to be understood and the behavior of individual radionuclides in the presence of a dissolving glass deserves more systematic investigations

Corrosion testing of a plutonium-loaded lanthanide borosilicate glass made with Frit B.

Energy Technology Data Exchange (ETDEWEB)

Ebert, W. L.; Chemical Engineering

2006-09-30

Laboratory tests were conducted with a lanthanide borosilicate (LaBS) glass made with Frit B and added PuO2 (the glass is referred to herein as Pu LaBS-B glass) to measure the dependence of the glass dissolution rate on pH and temperature. These results are compared with the dependencies used in the Defense HLW Glass Degradation Model that was developed to account for HLW glasses in total system performance assessment (TSPA) calculations for the Yucca Mountain repository to determine if that model can also be used to represent the release of radionuclides from disposed Pu LaBS glass by using either the same parameter values that are used for HLW glasses or parameter values specific for Pu LaBS glass. Tests were conducted by immersing monolithic specimens of Pu LaBS-B glass in six solutions that imposed pH values between about pH 3.5 and pH 11, and then measuring the amounts of glass components released into solution. Tests were conducted at 40, 70, and 90 C for 1, 2, 3, 4, and 5 days at low glass-surface-area-to-solution volume ratios. As intended, these test conditions maintained sufficiently dilute solutions that the impacts of solution feedback effects on the dissolution rates were negligible in most tests. The glass dissolution rates were determined from the concentrations of Si and B measured in the test solutions. The dissolution rates determined from the releases of Si and B were consistent with the 'V' shaped pH dependence that is commonly seen for borosilicate glasses and is included in the Defense HLW Glass Degradation Model. The rate equation in that model (using the coefficients determined for HLW glasses) provides values that are higher than the Pu LaBS-B glass dissolution rates that were measured over the range of pH and temperature values that were studied (i.e., an upper bound). Separate coefficients for the rate expression in acidic and alkaline solutions were also determined from the test results to model Pu LaBS-B glass dissolution

A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling

Science.gov (United States)

2004-03-01

Eggleston C. M. (2002) Dissolution kinetics of magnesite in acidic solutions: A hydrothermal atomic force microscopy study assessing step kinetics and...glass dissolution: I. An experimental study of the dissolution rates of basaltic glass as a function of aqueous Al, Si and oxalic acid concentration at...Stillings L. L., Drever J. I., Brantley S. L., Sun Y., and Oxburgh R. (1996) Rates of feldspar dissolution at pH 3-7 with 0-8mM oxalic acid . Chem

Cooling Rates of Lunar Volcanic Glass Beads

Science.gov (United States)

Hui, Hejiu; Hess, Kai-Uwe; Zhang, Youxue; Peslier, Anne; Lange, Rebecca; Dingwell, Donald; Neal, Clive

2016-01-01

It is widely accepted that the Apollo 15 green and Apollo 17 orange glass beads are of volcanic origin. The diffusion profiles of volatiles in these glass beads are believed to be due to degassing during eruption (Saal et al., 2008). The degree of degassing depends on the initial temperature and cooling rate. Therefore, the estimations of volatiles in parental magmas of lunar pyroclastic deposits depend on melt cooling rates. Furthermore, lunar glass beads may have cooled in volcanic environments on the moon. Therefore, the cooling rates may be used to assess the atmospheric condition in an early moon, when volcanic activities were common. The cooling rates of glasses can be inferred from direct heat capacity measurements on the glasses themselves (Wilding et al., 1995, 1996a,b). This method does not require knowledge of glass cooling environments and has been applied to calculate the cooling rates of natural silicate glasses formed in different terrestrial environments. We have carried out heat capacity measurements on hand-picked lunar glass beads using a Netzsch DSC 404C Pegasus differential scanning calorimeter at University of Munich. Our preliminary results suggest that the cooling rate of Apollo 17 orange glass beads may be 12 K/min, based on the correlation between temperature of the heat capacity curve peak in the glass transition range and glass cooling rate. The results imply that the parental magmas of lunar pyroclastic deposits may have contained more water initially than the early estimations (Saal et al., 2008), which used higher cooling rates, 60-180 K/min in the modeling. Furthermore, lunar volcanic glass beads could have been cooled in a hot gaseous medium released from volcanic eruptions, not during free flight. Therefore, our results may shed light on atmospheric condition in an early moon.

Alkali-free bioactive glasses for bone regeneration

OpenAIRE

Kapoor, Saurabh

2014-01-01

Bioactive glasses and glass-ceramics are a class of third generation biomaterials which elicit a special response on their surface when in contact with biological fluids, leading to strong bonding to living tissues. The purpose of the present study was to develop diopside based alkali-free bioactive glasses in order to achieve good sintering behaviour, high bioactivity, and a dissolution/ degradation rates compatible with the target applications in bone regeneration and tiss...

Diurnal variation in rates of calcification and carbonate sediment dissolution in Florida Bay

Science.gov (United States)

Yates, K.K.; Halley, R.B.

2006-01-01

Water quality and circulation in Florida Bay (a shallow, subtropical estuary in south Florida) are highly dependent upon the development and evolution of carbonate mud banks distributed throughout the Bay. Predicting the effect of natural and anthropogenic perturbations on carbonate sedimentation requires an understanding of annual, seasonal, and daily variations in the biogenic and inorganic processes affecting carbonate sediment precipitation and dissolution. In this study, net calcification rates were measured over diurnal cycles on 27 d during summer and winter from 1999 to 2003 on mud banks and four representative substrate types located within basins between mud banks. Substrate types that were measured in basins include seagrass beds of sparse and intermediate density Thalassia sp., mud bottom, and hard bottom communities. Changes in total alkalinity were used as a proxy for calcification and dissolution. On 22 d (81%), diurnal variation in rates of net calcification was observed. The highest rates of net carbonate sediment production (or lowest rates of net dissolution) generally occurred during daylight hours and ranged from 2.900 to -0.410 g CaCO3 m-2 d-1. The lowest rates of carbonate sediment production (or net sediment dissolution) occurred at night and ranged from 0.210 to -1.900 g CaCO3 m -2 night-1. During typical diurnal cycles, dissolution during the night consumed an average of 29% of sediment produced during the day on banks and 68% of sediment produced during the day in basins. Net sediment dissolution also occurred during daylight, but only when there was total cloud cover, high turbidity, or hypersalinity. Diurnal variation in calcification and dissolution in surface waters and surface sediments of Florida Bay is linked to cycling of carbon dioxide through photosynthesis and respiration. Estimation of long-term sediment accumulation rates from diurnal rates of carbonate sediment production measured in this study indicates an overall average

Enhancement of solubility and dissolution rate of atorvastatin ...

African Journals Online (AJOL)

solvent evaporation method using methanol. ... crystal significantly increases in solubility with a dissolution rate 2 - 3 times faster than that of ... considered one of the most effective synthetic .... temperature of 37 ± 0.5 °C. The test was carried.

Glass properties in the yttria-alumina-silica system

Science.gov (United States)

Hyatt, M. J.; Day, D. E.

1987-01-01

The glass formation region in the yttria-alumina-silica system was investigated. Properties of glasses containing 25 to 55 wt pct yttria were measured and the effect of the composition was determined. The density, refractive index, thermal-expansion coefficient, and microhardness increased with increasing yttria content. The dissolution rate in 1N HCl increased with increasing yttria content and temperature. These glasses were also found to have high electrical resistivity.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-05-15

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

Performance of surrogate high-level waste glass in the presence of iron corrosion products

International Nuclear Information System (INIS)

Jain, V.; Pan, Y.M.

2004-01-01

Radionuclide release from a waste package (WP) is a series of processes that depend upon the composition and flux of groundwater contacting the waste-forms (WF); the corrosion rate of WP containers and internal components made of Alloy 22, 316L SS, 304L SS and carbon steel; the dissolution rate of high-level radioactive waste (HLW) glass and spent nuclear fuel (SNF); the solubility of radionuclides; and the retention of radionuclides in secondary mineral phases. In this study, forward reaction rate measurements were made on a surrogate HLW glass in the presence of FeCl 3 species. Results indicate that the forward reaction rate increases with an increase in the FeCl 3 concentration. The addition of FeCl 3 causes the drop in the pH due to hydrolysis of Fe 3+ ions in the solution. Results based on the radionuclide concentrations and dissolution rates for HLW glass and SNF indicate that the contribution from glass is similar to SNF at 75 deg C. (authors)

Direct Measurement of Surface Dissolution Rates in Potential Nuclear Waste Forms: The Example of Pyrochlore.

Science.gov (United States)

Fischer, Cornelius; Finkeldei, Sarah; Brandt, Felix; Bosbach, Dirk; Luttge, Andreas

2015-08-19

The long-term stability of ceramic materials that are considered as potential nuclear waste forms is governed by heterogeneous surface reactivity. Thus, instead of a mean rate, the identification of one or more dominant contributors to the overall dissolution rate is the key to predict the stability of waste forms quantitatively. Direct surface measurements by vertical scanning interferometry (VSI) and their analysis via material flux maps and resulting dissolution rate spectra provide data about dominant rate contributors and their variability over time. Using pyrochlore (Nd2Zr2O7) pellet dissolution under acidic conditions as an example, we demonstrate the identification and quantification of dissolution rate contributors, based on VSI data and rate spectrum analysis. Heterogeneous surface alteration of pyrochlore varies by a factor of about 5 and additional material loss by chemo-mechanical grain pull-out within the uppermost grain layer. We identified four different rate contributors that are responsible for the observed dissolution rate range of single grains. Our new concept offers the opportunity to increase our mechanistic understanding and to predict quantitatively the alteration of ceramic waste forms.

Improving the API dissolution rate during pharmaceutical hot-melt extrusion I: Effect of the API particle size, and the co-rotating, twin-screw extruder screw configuration on the API dissolution rate.

Science.gov (United States)

Li, Meng; Gogos, Costas G; Ioannidis, Nicolas

2015-01-15

The dissolution rate of the active pharmaceutical ingredients in pharmaceutical hot-melt extrusion is the most critical elementary step during the extrusion of amorphous solid solutions - total dissolution has to be achieved within the short residence time in the extruder. Dissolution and dissolution rates are affected by process, material and equipment variables. In this work, we examine the effect of one of the material variables and one of the equipment variables, namely, the API particle size and extruder screw configuration on the API dissolution rate, in a co-rotating, twin-screw extruder. By rapidly removing the extruder screws from the barrel after achieving a steady state, we collected samples along the length of the extruder screws that were characterized by polarized optical microscopy (POM) and differential scanning calorimetry (DSC) to determine the amount of undissolved API. Analyses of samples indicate that reduction of particle size of the API and appropriate selection of screw design can markedly improve the dissolution rate of the API during extrusion. In addition, angle of repose measurements and light microscopy images show that the reduction of particle size of the API can improve the flowability of the physical mixture feed and the adhesiveness between its components, respectively, through dry coating of the polymer particles by the API particles. Copyright © 2014. Published by Elsevier B.V.

FY2016 ILAW Glass Corrosion Testing with the Single-Pass Flow-Through Method

Energy Technology Data Exchange (ETDEWEB)

Neeway, James J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Asmussen, Robert M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Parruzot, Benjamin PG [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cordova, Elsa [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Williams, Benjamin D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Leavy, Ian I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Stephenson, John R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McElroy, Erin M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2017-04-21

The inventory of immobilized low-activity waste (ILAW) produced at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) will be disposed of at the near-surface, on-site Integrated Disposal Facility (IDF). When groundwater comes into contact with the waste form, the glass will corrode and radionuclides will be released into the near-field environment. Because the release of the radionuclides is dependent on the dissolution rate of the glass, it is important that the performance assessment (PA) model accounts for the dissolution rate of the glass as a function of various chemical conditions. To accomplish this, an IDF PA model based on Transition State Theory (TST) can be employed. The model is able to account for changes in temperature, exposed surface area, and pH of the contacting solution as well as the effect of silicon concentrations in solution, specifically the activity of orthosilicic acid (H4SiO4), whose concentration is directly linked to the glass dissolution rate. In addition, the IDF PA model accounts for the alkali-ion exchange process as sodium is leached from the glass and into solution. The effect of temperature, pH, H4SiO4 activity, and the rate of ion-exchange can be parameterized and implemented directly into the PA rate law model. The rate law parameters are derived from laboratory tests with the single-pass flow-through (SPFT) method. To date, rate law parameters have been determined for seven ILAW glass compositions, thus additional rate law parameters on a wider range of compositions will supplement the existing body of data for PA maintenance activities. The data provided in this report can be used by ILAW glass scientists to further the understanding of ILAW glass behavior, by IDF PA modelers to use the rate law parameters in PA modeling efforts, and by Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program.

Structural and physico-chemical analysis of calcium/strontium substituted, near-invert phosphate based glasses for biomedical applications.

Science.gov (United States)

Patel, U; Moss, R M; Hossain, K M Z; Kennedy, A R; Barney, E R; Ahmed, I; Hannon, A C

2017-09-15

Neutron diffraction, 23 Na and 31 P NMR, and FTIR spectroscopy have been used to investigate the structural effects of substituting CaO with SrO in a 40P 2 O 5 ·(16-x)CaO·20Na 2 O·24MgO·xSrO glass, where x is 0, 4, 8, 12 and 16mol%. The 31 P solid-state NMR results showed similar amounts of Q 1 and Q 2 units for all of the multicomponent glasses investigated, showing that the substitution of Sr for Ca has no effect on the phosphate network. The M-O coordinations (M=Mg, Ca, Sr, Na) were determined for binary alkali and alkaline earth metaphosphates using neutron diffraction and broad asymmetric distributions of bond length were observed, with coordination numbers that were smaller and bond lengths that were shorter than in corresponding crystals. The Mg-O coordination number was determined most reliably as 5.0(2). The neutron diffraction results for the multicomponent glasses are consistent with a structural model in which the coordination of Ca, Sr and Na is the same as in the binary metaphosphate glass, whereas there is a definite shift of Mg-O bonds to longer distance. There is also a small but consistent increase in the Mg-O coordination number and the width of the distribution of Mg-O bond lengths, as Sr substitutes for Ca. Functional properties, including glass transition temperatures, thermal processing windows, dissolution rates and ion release profiles were also investigated. Dissolution studies showed a decrease in dissolution rate with initial addition of 4mol% SrO, but further addition of SrO showed little change. The ion release profiles followed a similar trend to the observed dissolution rates. The limited changes in structure and dissolution rates observed for substitution of Ca with Sr in these fixed 40mol% P 2 O 5 glasses were attributed to their similarities in terms of ionic size and charge. Phosphate based glasses are extremely well suited for the delivery of therapeutic ions in biomedical applications, and in particular strontium plays an

The dual effect of Mg on the long-term alteration rate of AVM nuclear waste glasses

Energy Technology Data Exchange (ETDEWEB)

Thien, Bruno M.J., E-mail: bruno.thien@psi.ch [Commissariat a l' Energie Atomique (CEA), Laboratoire d' Etude du Comportement a Long Terme des Materiaux, DTCD/DEN, Marcoule, 30207 Bagnols sur Ceze (France); Godon, Nicole; Ballestero, Anthony; Gin, Stephane [Commissariat a l' Energie Atomique (CEA), Laboratoire d' Etude du Comportement a Long Terme des Materiaux, DTCD/DEN, Marcoule, 30207 Bagnols sur Ceze (France); Ayral, Andre [Institut Europeen des Membranes, Universite de Montpellier, cc. 047, Place Eugene Bataillon, 34095 Montpellier (France)

2012-08-15

Inactive Mg-containing nuclear waste glasses simulating actual HLW glasses produced at the AVM facility since 1995 (Marcoule, France), were leached in aqueous solution in order to assess their long term behaviour. The focus was on the effect of Mg. Our findings show that the distribution of Mg between the gel and the secondary crystalline phases strongly influences the glass dissolution rate. The glasses were leached in initially pure water (T = 50 Degree-Sign C, surface/volume ratio (S/V) = 55 cm{sup -1}) with and without addition of Mg{sup 2+} in the solution. 'Mg-free' AVM glasses were also leached in initially pure water (50 Degree-Sign C, 200 cm{sup -1}) with and without addition of Mg{sup 2+} in the solution. Accurate identification of Mg-smectite secondary phases and gel composition calculations enable us to explain the different observed behaviours. Glass AVM 10 was the less altered glass in pure water. Its gel is more protective than the other probably because it is mainly balanced by Mg{sup 2+}. The addition of Mg{sup 2+} in the solution triggers the precipitation of smectite (not observed in pure water experiments), which consumes silicon from the gel, leading finally to a significant increase of the glass alteration. We also focused on the AVM 6 glass which was the most altered glass in pure water of available AVM glasses. Contrary to AVM 10, the gel of AVM 6 is mainly balanced by Na{sup +}. The addition of Mg{sup 2+} in the solution allows the replacement of Na by Mg within the gel. This reaction clearly improves the gel properties and allows the rate to decrease more rapidly, in spite of the precipitation of smectite (also observed in pure water experiments). Finally, the two glasses were altered in synthetic groundwater (SGW) with a high Mg-Ca content. As expected from the previous observations, AVM 10 was insensitive to the presence of alkaline earths in the leaching solution whereas AVM 6 glass exhibited a lower rate than in pure water

A comparison of the performance of nuclear waste glasses by modeling

International Nuclear Information System (INIS)

Grambow, B.; Strachan, D.M.

1988-01-01

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

Long-term product consistency test of simulated 90-19/Nd HLW glass

International Nuclear Information System (INIS)

Gan, X.Y.; Zhang, Z.T.; Yuan, W.Y.; Wang, L.; Bai, Y.; Ma, H.

2011-01-01

Chemical durability of 90-19/Nd glass, a simulated high-level waste (HLW) glass in contact with the groundwater was investigated with a long-term product consistency test (PCT). Generally, it is difficult to observe the long term property of HLW glass due to the slow corrosion rate in a mild condition. In order to overcome this problem, increased contacting surface (S/V = 6000 m -1 ) and elevated temperature (150 o C) were employed to accelerate the glass corrosion evolution. The micro-morphological characteristics of the glass surface and the secondary minerals formed after the glass alteration were analyzed by SEM-EDS and XRD, and concentrations of elements in the leaching solution were determined by ICP-AES. In our experiments, two types of minerals, which have great impact on glass dissolution, were found to form on 90-19/Nd HLW glass surface when it was subjected to a long-term leaching in the groundwater. One is Mg-Fe-rich phyllosilicates with honeycomb structure; the other is aluminosilicates (zeolites). Mg and Fe in the leaching solution participated in the formation of phyllosilicates. The main components of phyllosilicates in alteration products of 90-19/Nd HLW glass are nontronite (Na 0.3 Fe 2 Si 4 O 10 (OH) 2 .4H 2 O) and montmorillonite (Ca 0.2 (Al,Mg) 2 Si 4 O 10 (OH) 2 .4H 2 O), and those of aluminosilicates are mordenite ((Na 2 ,K 2 ,Ca)Al 2 Si 10 O 24 .7H 2 O)) and clinoptilolite ((Na,K,Ca) 5 Al 6 Si 30 O 72 .18H 2 O). Minerals like Ca(Mg)SO 4 and CaCO 3 with low solubility limits are prone to form precipitant on the glass surface. Appearance of the phyllosilicates and aluminosilicates result in the dissolution rate of 90-19/Nd HLW glass resumed, which is increased by several times over the stable rate. As further dissolution of the glass, both B and Na in the glass were found to leach out in borax form.

Exploration and Modeling of Structural changes in Waste Glass Under Corrosion

Energy Technology Data Exchange (ETDEWEB)

Pantano, Carlos; Ryan, Joseph; Strachan, Denis

2013-11-10

Vitrification is currently the world-wide treatment of choice for the disposition of high-level nuclear wastes. In glasses, radionuclides are atomistically bonded into the solid, resulting in a highly durable product, with borosilicate glasses exhibiting particularly excellent durability in water. Considering that waste glass is designed to retain the radionuclides within the waste form for long periods, it is important to understand the long-term stability of these materials when they react in the environment, especially in the presence of water. Based on a number of previous studies, there is general consensus regarding the mechanisms controlling the initial rate of nuclear waste glass dissolution. Agreement regarding the cause of the observed decrease in dissolution rate at extended times, however, has been elusive. Two general models have been proposed to explain this behavior, and it has been concluded that both concepts are valid and must be taken into account when considering the decrease in dissolution rate. Furthermore, other processes such as water diffusion, ion exchange, and precipitation of mineral phases onto the glass surface may occur in parallel with dissolution of the glass and can influence long-term performance. Our proposed research will address these issues through a combination of aqueous-phase dissolution/reaction experiments and probing of the resulting surface layers with state-of-the-art analytical methods. These methods include solid-state nuclear magnetic resonance (SSNMR) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The resulting datasets will then be coupled with computational chemistry and reaction-rate modeling to address the most persistent uncertainties in the understanding of glass corrosion, which indeed have limited the performance of the best corrosion models to date. With an improved understanding of corrosion mechanisms, models can be developed and improved that, while still conservative, take advantage of

Enhancement of solubility and dissolution rate of atorvastatin ...

African Journals Online (AJOL)

Purpose: To investigate the formation of atorvastatin calcium (AC) co-crystal to improve its solubility and dissolution rate. Method: Co-crystallization of AC in equimolar ratio with isonicotinamide (INA) was carried out by slow solvent evaporation method using methanol. The solid obtained was characterized by powder x-ray ...

Controlled precipitation for enhanced dissolution rate of flurbiprofen: development of rapidly disintegrating tablets.

Science.gov (United States)

Essa, Ebtessam A; Elmarakby, Amira O; Donia, Ahmed M A; El Maghraby, Gamal M

2017-09-01

The aim of this work was to investigate the potential of controlled precipitation of flurbiprofen on solid surface, in the presence or absence of hydrophilic polymers, as a tool for enhanced dissolution rate of the drug. The work was extended to develop rapidly disintegrated tablets. This strategy provides simple technique for dissolution enhancement of slowly dissolving drugs with high scaling up potential. Aerosil was dispersed in ethanolic solution of flurbiprofen in the presence and absence of hydrophilic polymers. Acidified water was added as antisolvent to produce controlled precipitation. The resultant particles were centrifuged and dried at ambient temperature before monitoring the dissolution pattern. The particles were also subjected to FTIR spectroscopic, X-ray diffraction and thermal analyses. The FTIR spectroscopy excluded any interaction between flurbiprofen and excipients. The thermal analysis reflected possible change in the crystalline structure and or crystal size of the drug after controlled precipitation in the presence of hydrophilic polymers. This was further confirmed by X-ray diffraction. The modulation in the crystalline structure and size was associated with a significant enhancement in the dissolution rate of flurbiprofen. Optimum formulations were successfully formulated as rapidly disintegrating tablet with subsequent fast dissolution. Precipitation on a large solid surface area is a promising strategy for enhanced dissolution rate with the presence of hydrophilic polymers during precipitation process improving the efficiency.

Carbonate dissolution rates in high salinity brines: Implications for post-Noachian chemical weathering on Mars

Science.gov (United States)

Phillips-Lander, Charity M.; Parnell, S. R.; McGraw, L. E.; Elwood Madden, M. E.

2018-06-01

A diverse suite of carbonate minerals including calcite (CaCO3) and magnesite (MgCO3) have been observed on the martian surface and in meteorites. Terrestrial carbonates usually form via aqueous processes and often record information about the environment in which they formed, including chemical and textural biosignatures. In addition, terrestrial carbonates are often found in association with evaporite deposits on Earth. Similar high salinity environments and processes were likely active on Mars and some areas may contain active high salinity brines today. In this study, we directly compare calcite and magnesite dissolution in ultrapure water, dilute sulfate and chloride solutions, as well as near-saturated sulfate and chloride brines with known activity of water (aH2O) to determine how dissolution rates vary with mineralogy and aH2O, as well as aqueous cation and anion chemistry to better understand how high salinity fluids may have altered carbonate deposits on Mars. We measured both calcite and magnesite initial dissolution rates at 298 K and near neutral pH (6-8) in unbuffered solutions containing ultrapure water (18 MΩ cm-1 UPW; aH2O = 1), dilute (0.1 mol kg-1; aH2O = 1) and near-saturated Na2SO4 (2.5 mol kg-1, aH2O = 0.92), dilute (0.1 mol kg-1, aH2O = 1) and near-saturated NaCl (5.7 mol kg-1, aH2O = 0.75). Calcite dissolution rates were also measured in dilute and near-saturated MgSO4 (0.1 mol kg-1, aH2O = 1 and 2.7 mol kg-1, aH2O = 0.92, respectively) and MgCl2 (0.1 mol kg-1, aH2O = 1 and 3 mol kg-1, aH2O = 0.73, respectively), while magnesite dissolution rates were measured in dilute and near-saturated CaCl2 (0.1 mol kg-1, aH2O = 1 and 9 mol kg-1, aH2O = 0.35). Initial calcite dissolution rates were fastest in near-saturated MgCl2 brine, while magnesite dissolution rates were fastest in dilute (0.1 mol kg-1) NaCl and CaCl2 solutions. Calcite dissolution rates in near-saturated Na2SO4 were similar to those observed in the dilute solutions (-8.00 ± 0

Influence of pH and temperature on alunite dissolution rates and products

Science.gov (United States)

Acero, Patricia; Hudson-Edwards, Karen

2015-04-01

Aluminium is one of the main elements in most mining-affected environments, where it may influence the mobility of other elements and play a key role on pH buffering. Moreover, high concentrations of Al can have severe effects on ecosystems and humans; Al intake, for example, has been implicated in neurological pathologies (e.g., Alzheimer's disease; Flaten, 2001). The behaviour of Al in mining-affected environments is commonly determined, at least partially, by the dissolution of Al sulphate minerals and particularly by the dissolution of alunite (KAl3(SO4)2(OH)6), which is one of the most important and ubiquitous Al sulphates in mining-affected environments (Nordstrom, 2011). The presence of alunite has been described in other acid sulphate environments, including some soils (Prietzel & Hirsch, 1998) and on the surface of Mars (Swayze et al., 2008). Despite the important role of alunite, its dissolution rates and products, and their controlling factors under conditions similar to those found in these environments, remain largely unknown. In this work, batch dissolution experiments have been carried out in order to shed light on the rates, products and controlling factors of alunite dissolution under different pH conditions (between 3 and 8) and temperatures (between 279 and 313K) similar to those encountered in natural systems. The obtained initial dissolution rates using synthetic alunite, based on the evolution of K concentrations, are between 10-9.7 and 10-10.9 mol-m-2-s-1, with the lowest rates obtained at around pH 4.8, and increases in the rates recorded with both increases and decreases in pH. Increases of temperature in the studied range also cause increases in the dissolution rates. The dissolution of alunite dissolution is incongruent, as has been reported for jarosite (isostructural with alunite) by Welch et al. (2008). Compared with the stoichiometric ratio in the bulk alunite (Al/K=3), K tends to be released to the solution preferentially over Al

Glass dissolution at 20, 40, 70 and 90 C: Short-term effects of solution chemistry and long-term Na release

International Nuclear Information System (INIS)

Bakel, A.J.; Ebert, W.L.; Strachan, D.M.

1996-01-01

The corrosion behavior of a borosilicate glass containing 20 mass 5 Na 2 O was assessed using static dissolution tests. This glass (LD6-5412) is representative of high Na glasses that may be used to stabilize Hanford low-level radioactive waste. The normalized mass loss (NL) decreases as NL(Na) ∼ NL(B) > NL(Si) in 20 and 40 C for tests conducted at glass surface area to leachant volume (S/V) ratio of 10 m -1 , and decreases as NL(Na) > NL(B) ∼ NL(Si) in 90 C tests conducted at 10 m -1 and in all tests conducted at higher S/V. The difference in the corrosion behavior is probably caused by the influence of dissolved glass components in the leachates. The NL(Na) is greater than the NL(B) or NL(Si) in all the tests conducted. Results from long-term tests at 2,000 m -1 show that the preferential release of Na persists for longer than one year at all temperatures and indicate that Na is released from this glass by an ion exchange process

Examining the Conservatisms in Dissolution Rates of Commercial Spent Nuclear Fuel

International Nuclear Information System (INIS)

Hanson, Brady D.

2008-01-01

Most models for commercial spent nuclear fuel dissolution are based on data obtained from single-pass flow-through tests. These tests are designed to have a high water volume to fuel surface area ratio so that the concentration of radionuclides in solution are below solubility limits and thus back reactions and the formation of alteration products are minimized. While this method is ideal for determining the dependence of the dissolution rate on various parameters, it is important to examine the differences between these tests and the realistic scenarios that will exist in a geologic repository. Many of the inherent conservatisms that are part of the models are examined. These conservatisms include: limited water, short-term vs. long-term rates, groundwater effects, non-congruent release, radiolysis, and fuel chemistry effects. Each of these conservatisms has the potential to decrease the currently modeled dissolution rates by between a factor of 2 and 200. The combined effects are unknown, but, if quantified, could significantly improve the waste form performance relative to current models.

Effects of ocean acidification on the dissolution rates of reef-coral skeletons

Directory of Open Access Journals (Sweden)

Robert van Woesik

2013-11-01

Full Text Available Ocean acidification threatens the foundation of tropical coral reefs. This study investigated three aspects of ocean acidification: (i the rates at which perforate and imperforate coral-colony skeletons passively dissolve when pH is 7.8, which is predicted to occur globally by 2100, (ii the rates of passive dissolution of corals with respect to coral-colony surface areas, and (iii the comparative rates of a vertical reef-growth model, incorporating passive dissolution rates, and predicted sea-level rise. By 2100, when the ocean pH is expected to be 7.8, perforate Montipora coral skeletons will lose on average 15 kg CaCO3 m−2 y−1, which is approximately −10.5 mm of vertical reduction of reef framework per year. This rate of passive dissolution is higher than the average rate of reef growth over the last several millennia and suggests that reefs composed of perforate Montipora coral skeletons will have trouble keeping up with sea-level rise under ocean acidification. Reefs composed of primarily imperforate coral skeletons will not likely dissolve as rapidly, but our model shows they will also have trouble keeping up with sea-level rise by 2050.

Leaching Tc-99 from SRP glass in simulated tuff and salt groundwaters

International Nuclear Information System (INIS)

Bibler, N.E.; Jurgensen, A.R.

1987-01-01

Results of leach tests with Tc-99 doped SRP borosilicate waste glass are presented. The glass was prepared by melting a mixture of SRP 165 powdered frit doped with a carrier free solution of Tc-99 at 1150 0 C. Dissolution of portions of the resulting glass indicated that the Tc-99 was distributed homogeneously throughout the glass. Static leach tests up to 90 days were performed at 90 0 C in J-13 tuff groundwater or WIPP brine A at a SA/V of 100m -1 . Normalized mass losses were calculated for Tc-99 as well as all the major elements in the glass. Results indicated that under ambient oxidizing conditions Tc-99 leached no faster than the glass-forming elements of the glass. In J-13 water, Tc-99 leached congruently with B. In WIPP brine A, it leached congruently with Si. Leach rates for Li were higher in both groundwaters, probably due to a contribution from an ion exchange mechanism. Leach tests were performed under reducing conditions in J-13 water by adding Zn/Hg amalgam to the leachate. In these tests the pH increased significantly, probably because of the reaction of the amalgam with the water. In a 21-day test, the pH increased to 13 and leach rates for the glass were very high. Even though there was signifcant dissolution of the glass, the normalized mass loss based on Tc-99 was only 0.02g/m 2 . This result and the fact that reducing conditions at normal pH values do not significantly affect the dissolution of the glass, indicate that the low concentrations for Tc-99 obtained under reducing conditions are due to is solubility and not due to an increased durability of the glass. 14 refs., 2 figs., 5 tabs

Controlled evaluation of silver nanoparticle dissolution using atomic force microscopy.

Science.gov (United States)

Kent, Ronald D; Vikesland, Peter J

2012-07-03

Incorporation of silver nanoparticles (AgNPs) into an increasing number of consumer products has led to concern over the potential ecological impacts of their unintended release to the environment. Dissolution is an important environmental transformation that affects the form and concentration of AgNPs in natural waters; however, studies on AgNP dissolution kinetics are complicated by nanoparticle aggregation. Herein, nanosphere lithography (NSL) was used to fabricate uniform arrays of AgNPs immobilized on glass substrates. Nanoparticle immobilization enabled controlled evaluation of AgNP dissolution in an air-saturated phosphate buffer (pH 7.0, 25 °C) under variable NaCl concentrations in the absence of aggregation. Atomic force microscopy (AFM) was used to monitor changes in particle morphology and dissolution. Over the first day of exposure to ≥10 mM NaCl, the in-plane AgNP shape changed from triangular to circular, the sidewalls steepened, the in-plane radius decreased by 5-11 nm, and the height increased by 6-12 nm. Subsequently, particle height and in-plane radius decreased at a constant rate over a 2-week period. Dissolution rates varied linearly from 0.4 to 2.2 nm/d over the 10-550 mM NaCl concentration range tested. NaCl-catalyzed dissolution of AgNPs may play an important role in AgNP fate in saline waters and biological media. This study demonstrates the utility of NSL and AFM for the direct investigation of unaggregated AgNP dissolution.

Ion-Exchange Processes and Mechanisms in Glasses

International Nuclear Information System (INIS)

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

2001-01-01

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

From laboratory experiments to a geological disposal vault: calculation of used nuclear fuel dissolution rates

International Nuclear Information System (INIS)

Sunder, S.; Shoesmith, D.W.; Kolar, M.; Leneveu, D.M.

1998-01-01

Calculation of used nuclear fuel dissolution rates in a geological disposal vault requires a knowledge of the redox conditions in the vault. For redox conditions less oxidizing than those causing UO 2 oxidation to the U 3 O 7 , stage, a thermodynamically-based model is appropriate. For more oxidizing redox conditions a kinetic or an electrochemical model is needed to calculate these rates. The redox conditions in a disposal vault will be affected by the radiolysis of groundwater by the ionizing radiation associated with the fuel. Therefore, we have calculated the alpha-, beta- and gamma-dose rates in water in contact with the reference used fuel in the Canadian Nuclear Fuel Waste Management Program (CNFWMP) as a function of cooling time. Also, we have determined dissolution rates of UO 2 fuel as a function of alpha and gamma dose rates from our electrochemical measurements. These room-temperature rates are used to calculate the dissolution rates of used fuel at 100 o C, the highest temperature expected in a container in the CNFWMP, as a function of time since emplacement. It is shown that beta radiolysis of water will be the main cause of oxidation of used CANDU fuel in a failed container. The use of a kinetic or an electrochemical corrosion model, to calculate fuel dissolution rates, is required for a period of ∼1000 a following emplacement of copper containers in the geologic disposal vault envisaged in the CNFWMP. Beyond this time period a thermodynamically-based model adequately predicts the fuel dissolution rates. The results presented in this paper can be adopted to calculate used fuel dissolution rates for other used UO 2 fuels in other waste management programs. (author)

Dissolution of lanthanide alumino-silicate oxynitride glasses

Science.gov (United States)

Bois, L.; Barré, N.; Guillopé, S.; Guittet, M. J.; Gautier-Soyer, M.; Duraud, J. P.; Trocellier, P.; Verdier, P.; Laurent, Y.

2000-01-01

The aqueous corrosion behavior of lanthanide aluminosilicate glasses has been studied under static conditions ( T=96°C, duration=1 and 3 months, glass surface area/leachate volume, S/ V=0.3 cm -1) by means of solution and solid analyses. It was found that these glasses exhibit a high chemical durability. The influence of yttrium, magnesium and nitrogen, which are supposed to improve the mechanical properties, on the chemical durability, has been investigated. After a one-month experiment, lanthanum and yttrium releases were found to be about 10 -7 mol l -1, while silicon and aluminum releases were about 10 -5 mol l -1. Yttrium seems to improve the chemical durability. The presence of nitrogen does not seem to modify the glass constituents releases, but seems to improve the surface state of the altered glass. XPS experiments reveal that lanthanum and yttrium are more concentrated near the surface (20-30 Å) of the glass after the leaching test.

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

Science.gov (United States)

Shaharyar, Yaqoot

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

Chitosan and chitosan chlorhydrate based various approaches for enhancement of dissolution rate of carvedilol

Directory of Open Access Journals (Sweden)

Shete Amol S

2012-12-01

Full Text Available Abstract Background and the purpose of the study Carvedilol nonselective β-adrenoreceptor blocker, chemically (±-1-(Carbazol-4-yloxy-3-[[2-(o-methoxypHenoxy ethyl] amino]-2-propanol, slightly soluble in ethyl ether; and practically insoluble in water, gastric fluid (simulated, TS, pH 1.1, and intestinal fluid (simulated, TS without pancreatin, pH 7.5 Compounds with aqueous solubility less than 1% W/V often represents dissolution rate limited absorption. There is need to enhance the dissolution rate of carvedilol. The objective of our present investigation was to compare chitosan and chitosan chlorhydrate based various approaches for enhancement of dissolution rate of carvedilol. Methods The different formulations were prepared by different methods like solvent change approach to prepare hydrosols, solvent evaporation technique to form solid dispersions and cogrind mixtures. The prepared formulations were characterized in terms of saturation solubility, drug content, infrared spectroscopy (FTIR, differential scanning calorimetry (DSC, powder X-ray diffraction (PXRD, electron microscopy, in vitro dissolution studies and stability studies. Results The practical yield in case of hydrosols was ranged from 59.76 to 92.32%. The drug content was found to uniform among the different batches of hydrosols, cogrind mixture and solid dispersions ranged from 98.24 to 99.89%. There was significant improvement in dissolution rate of carvedilol with chitosan chlorhdyrate as compare to chitosan and explanation to this behavior was found in the differences in the wetting, solubilities and swelling capacity of the chitosan and chitosan salts, chitosan chlorhydrate rapidly wet and dissolve upon its incorporation into the dissolution medium, whereas the chitosan base, less water soluble, would take more time to dissolve. Conclusion This technique is scalable and valuable in manufacturing process in future for enhancement of dissolution of poorly water soluble

Influence of nuclear glasses composition on their liability to deterioration

International Nuclear Information System (INIS)

Tovena, I.

1995-01-01

The aim of this thesis is to contribute to the study of the nuclear glasses composition influence on their liability to deterioration. The methodology of the experimental research used has lead to define between the thirty oxides which form the reference glass light water, six oxides of interest. For each of these oxides, a composition variation area has been defined. A matrix of twenty glass compositions has then been defined. The preparation of materials of these compositions has sometimes lead to materials weakly heterogeneous which have been characterized before deterioration. This study has been completed by those of three glasses in a composition variation area narrower of the light water nuclear glass : the R7T7 and two glasses at limits having respectively an initial dissolution velocity at 100 degrees Celsius theoretically maximum and minimum. Some deterioration parameters in pure water have been experimentally measured on the twenty three glasses : 1) an initial dissolution velocity at 100 degrees (Vo 1 00) Celsius and another one at 90 degrees Celsius (Vo 9 0) 2) a dissolution velocity in conditions near the saturation at 90 degrees Celsius 3) an apparent solubility of glass based on the ortho silicic acid activity 4) the evolution of the dissolution kinetics at 90 degrees Celsius in sub-saturated medium towards saturated medium 5) the alteration films nature developed at the glasses surface during these last alteration tests. Some thermodynamic and structural models have been studied in order to predict Vo 9 0 and Vo 1 00. The dissolution kinetic law developed from reference glass dissolution results has been studied with the calculation code LIXIVER. It has not been able to be used for most of the glasses compositions studied. As a consequence, the glasses dissolution control by a surface reaction which are itself controlled by the only dissolved silica is an hypothesis which is not verified for the greater part of the glasses. (O.L.). refs., figs

Calcination/dissolution residue treatment

International Nuclear Information System (INIS)

Knight, R.C.; Creed, R.F.; Patello, G.K.; Hollenberg, G.W.; Buehler, M.F.; O'Rourke, S.M.; Visnapuu, A.; McLaughlin, D.F.

1994-09-01

Currently, high-level wastes are stored underground in steel-lined tanks at the Hanford site. Current plans call for the chemical pretreatment of these wastes before their immobilization in stable glass waste forms. One candidate pretreatment approach, calcination/dissolution, performs an alkaline fusion of the waste and creates a high-level/low-level partition based on the aqueous solubilities of the components of the product calcine. Literature and laboratory studies were conducted with the goal of finding a residue treatment technology that would decrease the quantity of high-level waste glass required following calcination/dissolution waste processing. Four elements, Fe, Ni, Bi, and U, postulated to be present in the high-level residue fraction were identified as being key to the quantity of high-level glass formed. Laboratory tests of the candidate technologies with simulant high-level residues showed reductive roasting followed by carbonyl volatilization to be successful in removing Fe, Ni, and Bi. Subsequent bench-scale tests on residues from calcination/dissolution processing of genuine Hanford Site tank waste showed Fe was separated with radioelement decontamination factors of 70 to 1,000 times with respect to total alpha activity. Thermodynamic analyses of the calcination of five typical Hanford Site tank waste compositions also were performed. The analyses showed sodium hydroxide to be the sole molten component in the waste calcine and emphasized the requirement for waste blending if fluid calcines are to be achieved. Other calcine phases identified in the thermodynamic analysis indicate the significant thermal reconstitution accomplished in calcination

Mechanisms that control aqueous leaching of nuclear waste glass

International Nuclear Information System (INIS)

Simmons, J.H.; Barkatt, A.; Macedo, P.B.

1982-01-01

The development of predictive models and risk calculations for the time evolution of radioactive isotope leaching from fixation solids depends on many factors, including measurement accuracy, measurement relevance, a complete understanding of possible dissolution mechanisms, and the ability to project worst case conditions for all appropriate mechanisms. Some of the mechanisms observed and understood at present are the mechanisms of dissolution of glasses in neutral unbuffered water, the effects of structural disintegration of the glass protective layer, the effects of slowly flowing bath waters and possibly, the mechanisms of leach-rate reduction by solution saturation. The mechanisms that control radiation and temperature effects including alpha particle emission and nuclear transmutations are as yet little understood or investigated

Calcite Dissolution Kinetics

Science.gov (United States)

Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.

2016-12-01

A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations 500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics of dissolution. The interplay of mineral

The properties and structure of Sn---Ca---P---O---F glasses

International Nuclear Information System (INIS)

Ding, J.Y.; Shih, P.Y.; Yung, S.W.; Hsu, K.L.; Chin, T.S.

2003-01-01

Low melting modified calcium stannous fluorophosphate glasses based on a basic composition 40P 2 O 5 -25SnO-30SnF 2 -5CaF 2 (in mol%) with glass transition temperature T g ranging 220-240 deg. C have been prepared. The effect of Al(OH) 3 or SiO 2 addition on the properties of these glasses has also been determined. Aluminum and silicon compounds decrease the dissolution rate in water and thermal expansion coefficient while increase the density, T g and softening temperature. The effect of Al(OH) 3 addition on the increase of chemical durability is better for these glasses, due to the partial crystallization effect in stannous calcium silicofluorophosphate glasses. With an addition of 4 wt.% Al(OH) 3 , the dissolution rate of the glass in 30 deg. C water decreases from 1.0x10 -5 to 1.3x10 -7 g cm -2 min. The structure of Al(OH) 3 added glasses was studied by 27 Al and 31 P MAS NMR and Fourier transform IR (FTIR) spectroscopies to explain the relationship between glass properties and composition. The 27 Al spectra show three different aluminum environments [Al(OP) 6 , Al(OP) 5 and Al(OP) 4 ], and Al(OP) 6 species seem to be predominant in these glasses. The formation of P---O-Al covalent bond and more strongly ionic bonds increase the strength of the glass network in stannous calcium aluminofluorophosphate glasses. FTIR spectra indicate the presence of P--F bond in the short range glass structure

Prediction of waste glass melt rates

International Nuclear Information System (INIS)

Lee, L.

1987-01-01

Under contract to the Department of Energy, the Du Pont Company has begun construction of a Defense Waste Processing Facility to immobilize radioactive wastes now stored as liquids at the Department of Energy's Savannah River Plant. The immobilization process solidifies waste sludge by vitrification into a leach-resistant borosilicate glass. Development of this process has been the responsibility of the Savannah River Laboratory. As part of the development, a simple model was developed to predict the melt rates for the waste glass melter. This model is based on an energy balance for the cold cap and gives very good agreement with melt rate data obtained from experimental campaigns in smaller scale waste glass melters

Reexamining the Dissolution of Spent Fuel: A Comparison of Different Methods for Calculating Rates

International Nuclear Information System (INIS)

Hanson, Brady D.; Stout, Ray B.

2004-01-01

Dissolution rates for spent fuel have typically been reported in terms of a rate normalized to the surface area of the specimen. Recent evidence has shown that neither the geometric surface area nor that measured with BET accurately predicts the effective surface area of spent fuel. Dissolution rates calculated from results obtained by flowthrough tests were reexamined comparing the cumulative releases and surface area normalized rates. While initial surface area is important for comparison of different rates, it appears that normalizing to the surface area introduces unnecessary uncertainty compared to using cumulative or fractional release rates. Discrepancies in past data analyses are mitigated using this alternative method

Spent fuel dissolution rates as a function of burnup and water chemistry

International Nuclear Information System (INIS)

Gray, W.J.

1998-06-01

To help provide a source term for performance-assessment calculations, dissolution studies on light-water-reactor (LWR) spent fuel have been conducted over the past few years at Pacific Northwest National Laboratory in support of the Yucca Mountain Site Characterization Project. This report describes that work for fiscal years 1996 through mid-1998 and includes summaries of some results from previous years for completeness. The following conclusions were based on the results of various flowthrough dissolution rate tests and on tests designed to measure the inventories of 129 I located within the fuel/cladding gap region of different spent fuels: (1) Spent fuels with burnups in the range 30 to 50 MWd/kgM all dissolved at about the same rate over the conditions tested. To help determine whether the lack of burnup dependence extends to higher and lower values, tests are in progress or planned for spent fuels with burnups of 13 and ∼ 65 MWd/kgM. (2) Oxidation of spent fuel up to the U 4 O 9+x stage does not have a large effect on intrinsic dissolution rates. However, this degree of oxidation could increase the dissolution rates of relatively intact fuel by opening the grain boundaries, thereby increasing the effective surface area that is available for contact by water. From a disposal viewpoint, this is a potentially more important consideration than the effect on intrinsic rates. (3) The gap inventories of 129 I were found to be smaller than the fission gas release (FGR) for the same fuel rod with the exception of the rod with the highest FGR. Several additional fuels would have to be tested to determine whether a generalized relationship exists between FGR and 129 I gap inventory for US LWR fuels

The Influence of Cooling Rates on Paleointensity of Volcanic Glasses: an Experimental Approach on Synthetic Glass

Science.gov (United States)

von Aulock, F. W.; Ferk, A.; Leonhardt, R.; Hess, K.-U.; Dingwell, D. B.

2009-04-01

The suitability of volcanic glass for paleointensity determinations has been proposed in many studies throughout the last years. Besides the mainly single domain magnetic remanence carriers and the pristine character of the volcanic glass, this was also reasoned by the possibility to correct paleointensity data for cooling rate dependency using relaxation geospeedometry. This method gives the cooling rate of a glass at the glass transition interval which marks the change of a ductile supercooled liquid to a brittle glass. In this study the cooling rate correction as carried out for example by Leonhardt et al. 2006 is tested on synthetic volcanic glass. In order to obtain a stable multicomponent glass with ideal magnetic properties, a natural phonolithic glass from Tenerife (Spain) was melted to avoid heterogeneity and degassing. Further it was tempered for 5 hours at 900 °C to yield a sufficient concentration of magnetic remanence carriers. To exclude nucleation or crystallisation 7 samples were then heated to about 50 °C above the glass transition temperature at around 720 °C and quenched at different rates from 0.1 to 15 K/min. After carrying out a paleointensity experiment using a modified Thellier method, which incorporated alteration, additivity and tail checks, the dependence of the thermoremance on cooling rate was investigated. Using the original cooling rates we corrected the data and obtained paleointensities of around 46 T, which is a good approximation of the ambient field of 48 T. Taking into account that the uncorrected mean paleointensity is about 57 T, this suggests that cooling rate correction is not only working, but also a necessary tool to yield the true field value. R. Leonhardt , J. Matzka, A.R.L. Nichols , D.B. Dingwell Cooling rate correction of paleointensity determination for volcanic glasses by relaxation geospeedometry; Earth and Planetary Science Letters 243 (2006) 282-292

Effect of Phosphate, Fluoride, and Nitrate on Gibbsite Dissolution Rate and Solubility

International Nuclear Information System (INIS)

Herting, Daniel L.

2014-01-01

Laboratory tests have been completed with simulated tank waste samples to investigate the effects of phosphate, fluoride, and nitrate on the dissolution rate and equilibrium solubility of gibbsite in sodium hydroxide solution at 22 and 40 deg C. Results are compared to relevant literature data and to computer model predictions. The presence of sodium nitrate (3 M) caused a reduction in the rate of gibbsite dissolution in NaOH, but a modest increase in the equilibrium solubility of aluminum. The increase in solubility was not as large, though, as the increase predicted by the computer model. The presence of phosphate, either as sodium phosphate or sodium fluoride phosphate, had a negligible effect on the rate of gibbsite dissolution, but caused a slight increase in aluminum solubility. The magnitude of the increased solubility, relative to the increase caused by sodium nitrate, suggests that the increase is due to ionic strength (or water activity) effects, rather than being associated with the specific ion involved. The computer model predicted that phosphate would cause a slight decrease in aluminum solubility, suggesting some Al-PO4 interaction. No evidence was found of such an interaction

Solubility limits on radionuclide dissolution

Energy Technology Data Exchange (ETDEWEB)

Kerrisk, J.F.

1984-12-31

This paper examines the effects of solubility in limiting dissolution rates of a number of important radionuclides from spent fuel and high-level waste. Two simple dissolution models were used for calculations that would be characteristics of a Yucca Mountain repository. A saturation-limited dissolution model, in which the water flowing through the repository is assumed to be saturated with each waste element, is very conservative in that it overestimates dissolution rates. A diffusion-limited dissolution model, in which element-dissolution rates are limited by diffusion of waste elements into water flowing past the waste, is more realistic, but it is subject to some uncertainty at this time. Dissolution rates of some elements (Pu, Am, Sn, Th, Zr, Sm) are always limited by solubility. Dissolution rates of other elements (Cs, Tc, Np, Sr, C, I) are never solubility limited; their release would be limited by dissolution of the bulk waste form. Still other elements (U, Cm, Ni, Ra) show solubility-limited dissolution under some conditions. 9 references, 3 tables.

Use of the liquisolid compact technique for improvement of the dissolution rate of valsartan

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Naveen Chella

2012-10-01

Full Text Available The aim of this study was to improve the dissolution rate of the poorly soluble drug valsartan by delivering the drug as a liquisolid compact. Liquisolid compacts were prepared using propylene glycol as solvent, Avicel PH102 as carrier, and Aerosil 200 as the coating material. The crystallinity of the newly formulated drug and the interaction between excipients was examined by X-ray powder diffraction and Fourier-transform infrared spectroscopy, respectively. The dissolution studies for the liquisolid formulation and the marketed product were carried out at different pH values. The results showed no change in the crystallinity of the drug and no interaction between excipients. The dissolution efficiency of valsartan at 15 min was increased from 4.02% for plain drug and 13.58% for marketed product to 29.47% for the liquisolid formulation. The increase in the dissolution rate was also found to be significant compared to the marketed product at lower pH values, simulating the gastric environment where valsartan is largely absorbed. The liquisolid technique appears to be a promising approach for improving the dissolution of poorly soluble drugs like valsartan.

Analysis for silicon in solution in high level waste glass durability studies

International Nuclear Information System (INIS)

Lewis, R.A.; Smart, R.St.C.; Dale, L.S.; Levins, D.M.

1982-01-01

In comparative studies of the durability of HLW glasses, the measurement of the dissolution of the silicate network, in terms of both rate and extent, is of prime importance. To achieve this, analytical techniques such as colorimetry, flame atomic absorption spectrometry and inductively-coupled plasma emission spectrometry are used. The reliability of these analytical techniques for determination of silicon concentration in dissolution of HLW glasses, is examined. At high concentrations both FAA and ICP are accurate but colorimetry, even with HF pretreatment or NaOH digestion, does not give agreement with ICP. At concentrations below 40 mg l -1 all three methods are reliable. (Auth.)

Factors affecting the differences in reactivity and dissolution rates between UO2 and spent nuclear fuel

International Nuclear Information System (INIS)

Shoesmith, D.W.; Tait, J.C.; Sunder, S.; Steward, S.; Russo, R.E.; Rudnicki, J.D.

1996-08-01

Strategies for the permanent disposal of spent nuclear fuel are being investigated by the U.S. Department of Energy at the Yucca Mountain site and by Atomic Energy of Canada Limited (AECL) in plutonic rock formations in the Canadian Shield. Uranium dioxide is the primary constituent of spent nuclear fuel and dissolution of the matrix is regarded as a necessary step for the release of radionuclides to repository groundwaters. In order to develop models to describe the dissolution of the U0 2 fuel matrix and subsequent release of radionuclides, it is necessary to understand both chemical and oxidative dissolution processes and how they can be affected by parameters such as groundwater composition, pH, temperature, surface area, radiolysis and redox potential. This report summarizes both published and on-going dissolution studies of U0 2 and both LWR and CANDU spent fuels being conducted at the Pacific Northwest Laboratory, Lawrence Livermore National Laboratory and Lawrence Berkeley Laboratory in the U.S. and at AECL's Whiteshell Laboratories in Canada. The studies include both dissolution tests and electrochemical experiments to measure uranium dissolution rates. The report focuses on identifying differences in reactivity towards aqueous dissolution between U0 2 and spent fuel samples as well as estimating bounding values for uranium dissolution rates. This review also outlines the basic tenets for the development of a dissolution model that is based on electrochemical principles. (author). 49 refs., 2 tabs., 11 figs

Development and characterization of solid dispersion of piroxicam for improvement of dissolution rate using hydrophilic carriers

Directory of Open Access Journals (Sweden)

Mohammad Barzegar-jalali

2014-09-01

Full Text Available Introduction: The main objective of this study was preparation and characterization of solid dispersion of piroxicam to enhance its dissolution rate. Methods: Solid dispersion formulations with different carriers including crospovidone, microcrystalline cellulose and Elaeagnus angustifolia fruit powder and with different drug: carrier ratios were prepared employing cogrinding method. Dissolution study of the piroxicam powders, physical mixtures and solid dispersions was performed in simulated gastric fluid and simulated intestinal fluid using USP Apparatus type II. The physical characterization of formulations were analyzed using powder X ray diffraction (PXRD, particle size analyzer and differential scanning calorimetry (DSC. Interactions between the drug and carriers were evaluated by Fourier transform infrared (FT-IR spectroscopic method. Results: It was revealed that all of three carriers increase the dissolution rate of piroxicam from physical mixtures and especially in solid dispersions compared to piroxicam pure and treated powders. PXRD and DSC results were confirmed the reduction of crystalline form of piroxicam. FT-IR analysis did not show any physicochemical interaction between drug and carriers in the solid dispersion formulations. Conclusion: Dissolution rate was dependent on the type and ratio of drug: carrier as well as pH of dissolution medium. Dissolution data of formulations were fitted well in to the linear Weibull as well as non-linear logistic and a suggested models.

Determination of the free enthalpies of formation of borosilicate glasses

International Nuclear Information System (INIS)

Linard, Y.

2000-01-01

This work contributes to the study of the thermochemical properties of nuclear waste glasses. Results are used to discuss mechanisms and parameters integrated in alteration models of conditioning materials. Glass is a disordered material defined thermodynamically as a non-equilibrium state. Taking into account one order parameter to characterise its configurational state, the metastable equilibrium for the glass was considered and the main thermochemical properties were determined. Calorimetric techniques were used to measure heat capacities and formation enthalpies of borosilicate glasses (from 3 to 8 constitutive oxides). Formation Entropies were measured too, using the entropy theory of relaxation processes proposed by Adam and Gibbs (1965). The configurational entropy contribution were determined from viscosity measurements. This set of data has allowed the calculation of Gibb's free energies of dissolution of glasses in pure water. By comparison with leaching experiments, it has been demonstrated that the decreasing of the dissolution rate at high reaction progress cannot be associated to the approach of an equilibrium between the sound glass and the aqueous solution. The composition changes of the reaction area at the glass surface need to be considered too. To achieve a complete description of the thermodynamic stability, the equilibrium between hydrated de-alkalinized glass and/or the gel layer with the aqueous solution should also be evaluated. (author)

Comparison of two lung clearance models based on the dissolution rates of oxidized depleted uranium

Energy Technology Data Exchange (ETDEWEB)

Crist, K.C.

1984-10-01

An in-vitro dissolution study was conducted on two respirable oxidized depleted uranium samples. The dissolution rates generated from this study were then utilized in the International Commission on Radiological Protection Task Group lung clearance model and a lung clearance model proposed by Cuddihy. Predictions from both models based on the dissolution rates of the amount of oxidized depleted uranium that would be cleared to blood from the pulmonary region following an inhalation exposure were compared. It was found that the predictions made by both models differed considerably. The difference between the predictions was attributed to the differences in the way each model perceives the clearance from the pulmonary region. 33 references, 11 figures, 9 tables.

Comparison of two lung clearance models based on the dissolution rates of oxidized depleted uranium

International Nuclear Information System (INIS)

Crist, K.C.

1984-10-01

An in-vitro dissolution study was conducted on two respirable oxidized depleted uranium samples. The dissolution rates generated from this study were then utilized in the International Commission on Radiological Protection Task Group lung clearance model and a lung clearance model proposed by Cuddihy. Predictions from both models based on the dissolution rates of the amount of oxidized depleted uranium that would be cleared to blood from the pulmonary region following an inhalation exposure were compared. It was found that the predictions made by both models differed considerably. The difference between the predictions was attributed to the differences in the way each model perceives the clearance from the pulmonary region. 33 references, 11 figures, 9 tables

Effects of MgO on short and long term stabilities in water of R7T7 and M7 nuclear waste glasses

Energy Technology Data Exchange (ETDEWEB)

Advocat, T; Vernaz, E; Dussossoy, J [CEA Centre d` Etudes de la Vallee du Rhone, 30 - Marcoule (France). Dept. des Procedes de Retraitement; Crovisier, J L [Centre National de la Recherche Scientifique (CNRS), 67 - Strasbourg (France)

1993-12-31

Magnesium oxide was added to the standard R7T7 and M7 glass compositions developed for containment of fission product solutions. M7 differs from the R7T7 reference glass mainly by a larger proportion of network modifier elements and a correspondingly lower proportion of glass network forming elements. The percentage of fission products, simulated in this study by inactive elements, was the same in both cases. Increasing the MgO content of the glass compositions by 2 to 5 wt% resulted in significant variations in the aqueous leaching resistance at 90 and 100 deg C. Experimental findings demonstrated that the initial dissolution rate measured at 100 deg C in a Soxhlet apparatus was proportional to the MgO content and inversely proportional to the network former content (mainly SiO2). This was confirmed by a glass hydration model based on the thermodynamic stability of the glass matrix components. Aqueous corrosion tests were also conducted at 90 deg C under static conditions at various SA/V ratios to simulate the progress of the reaction. Under these conditions, the glass dissolution rate diminished more slowly in time when the initial magnesium content was high and the network former content was low. This may be due primarily to a variation in the glass silica solubility limit related to the glass composition; it may also be related to the formation of secondary silica and magnesia alteration products controlling the glass dissolution reaction affinity.

Dissolution of aluminium

International Nuclear Information System (INIS)

Uriarte Hueda, A.; Berberana Eizmendi, M.; Pereira Sanchez, G.

1968-01-01

The dissolution of aluminum with acid solutions ( nitric acid-mercuric nitrate) and alkaline solutions (sodium hydroxide-sodium nitrate) has been studied. The instantaneous dissolution rate (IDR) has been studied in function of the concentration of the used reagents and the dissolution temperature. The complete dissolution has been included in the second part of this report, to know the total dissolution time, the consume of reagents and the stability of the resultant solutions. (Author)

PREPARATION OF ZEOLITE X COATINGS ON SODA-LIME TYPE GLASS PLATES

Directory of Open Access Journals (Sweden)

M. Tatlier

Full Text Available Abstract The dissolution of glass in highly alkaline reaction mixtures and the impact of this phenomenon on zeolite coating formation were investigated. Coating samples were prepared and characterized by X-ray diffraction (XRD, field emission gun scanning electron microscopy (FEGSEM and thermogravimetry (TG. It was demonstrated that zeolite X coatings might be prepared on soda-lime glass. Glass dissolved to some degree, up to 2% of its original mass, in the reaction mixtures for the conditions investigated. This dissolution affected the zeolite synthesis taking place on the glass surface, resulting in phases different from those obtained on inert metal surfaces in some cases, especially for the use of reaction mixtures with relatively high Si/Al ratios. The percentage of dissolution of glass plates increased with their decreasing thickness, indicating a surface phenomenon for the dissolution. The stabilities of the coatings, which varied with the synthesis conditions, benefited from the addition of extra thin layers of polyacrylic acid.

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

Aqueous corrosion of silicate glasses. Analogy between volcanic glasses and the French nuclear waste glass R7T7

International Nuclear Information System (INIS)

Goldschmidt, F.

1991-01-01

The behaviour of borosilicate glasses upon aqueous corrosion is controlled for long periods of time (>10,000 years) by processes which are not directly accessible by means of laboratory experiments. The analogical approach consists here to compare leaching performances between the french nuclear waste glass R7T7 and natural volcanic glasses, basaltic and rhyolitic ones. The three glasses were leached in the same conditions; open system, 90 deg C, initial pH of 9.7. Basaltic and R7T7 glasses having the same kinetic of dissolution, the basaltic glass was chosen as the best analogue. (author). refs., figs., tabs

The dissolution rate constant of magnetite in water at different temperatures and pH conditions

International Nuclear Information System (INIS)

Mohajery, Khatereh; Deydier de Pierrefeu, Laurent; Lister, Derek H.

2012-09-01

Under the nominal conditions of power system coolants, the corrosion of components made of carbon steel is limited by the magnetite films that develop on surfaces. In some situations, the magnetite film loses much of its protective ability and corrosion and loss of iron to the system are exacerbated. Common examples of such situations occur when the system is non-isothermal so that temperature gradients cause differences in magnetite solubility around the circuit; the resulting areas of under-saturation in iron give rise to dissolution of normally protective films. Condensing steam in two-phase systems may also promote oxide dissolution. When the turbulence in the system is high, oxide degradation is aggravated and flow-accelerated corrosion (FAC) results. The subsequent increased loading of systems with iron leads to fouling of flow passages and heat transfer surfaces and in reactor primary coolants to rising radiation fields, while FAC can have disastrous results in terms of pipe wall thinning and eventual rupture. Magnetite dissolution is clearly a key contributor to these processes. Thus, the conventional mechanistic description of FAC postulates magnetite dissolution in series with mass transfer of iron from the film to the bulk coolant. In the resulting equations, if the dissolution rate constant is considerably less than the mass transfer coefficient for a particular situation, dissolution will control and flow should have no effect. This is clearly untenable for FAC, so it is often assumed that mass transfer controls and the contribution from oxide dissolution is ignored - on occasion when data on dissolution kinetics are available and sometimes when those data show that dissolution should control. In most cases, however, dissolution rate constants for magnetite are not available. At UNB Nuclear we have a research program using a high-temperature loop to measure dissolution rates of magnetite in water under various conditions of flow, temperature and

Preliminary assessment of the controlled release of radionuclides from waste packages containing borosilicate waste glass

International Nuclear Information System (INIS)

Strachan, D.M.; McGrail, B.P.; Apted, M.J.; Engle, D.W.; Eslinger, P.W.

1990-06-01

The purpose of this report is to provide a preliminary assessment of the release-rate for an engineered barriers subsystem (EBS) containing waste packages of defense high-level waste borosilicate glass at geochemical and hydrological conditions similar to the those at Yucca Mountain. The relationship between the proposed Waste Acceptance Preliminary Specifications (WAPS) test of glass- dissolution rate and compliance with the NRC's release-rate criterion is also evaluated. Calculations are reported for three hierarchical levels: EBS analysis, waste-package analysis, and waste-glass analysis. The following conclusions identify those factors that most acutely affect the magnitude of, or uncertainty in, release-rate performance

On the estimate of the rate constant in the homogeneous dissolution model

Czech Academy of Sciences Publication Activity Database

Čupera, Jakub; Lánský, Petr

2013-01-01

Roč. 39, č. 10 (2013), s. 1555-1561 ISSN 0363-9045 Institutional support: RVO:67985823 Keywords : dissolution * estimation * rate constant Subject RIV: FR - Pharmacology ; Medidal Chemistry Impact factor: 2.006, year: 2013

Atomic size effect on critical cooling rate and glass formation

International Nuclear Information System (INIS)

Jalali, Payman; Li Mo

2005-01-01

Atomic size effect on critical cooling rate and glass formability in a model binary system is investigated using molecular dynamics simulation. To isolate atomic size effect from the rest of the factors that critically influence the glass formation, a hard sphere model is employed in conjunction with a newly developed densification method. The glass formability is defined as a set of optimal conditions that result in the slowest cooling rate of the glass-forming liquid. Critical cooling rates are identified from extensive molecular dynamics simulations. A kinetic glass-forming diagram is mapped out that marks the boundary between the glass-forming regions and competing crystalline phases in terms of the parameters of the atomic size ratio and alloy concentration. It is found that the potency of the atomic size difference on glass formation is influenced greatly by the competing metastable and equilibrium crystalline phases in the system, and the kinetic processes leading to the formation of these phases. The mechanisms of the atomic size effect on topological instability of crystal packing and glass formation are discussed

Alloying effects on dissolution rate of crevice corrosion for austenitic stainless steels in 3% NaCl solution at 80 C

International Nuclear Information System (INIS)

Chen, P.; Shinohara, Tadashi; Tsujikawa, Shigeo

1996-01-01

Chloride stress corrosion cracking (SCC) has been a problem for austenitic stainless steel in aqueous environments containing chlorides. Studies have found that SCC initiates only from a dissolving surface and under the condition that the crack growth rate is higher than the dissolution rate of the dissolving surface. Research conducted to improve the resistance to SCC for Type 304 steels (UNS S30400) have revealed that while molybdenum and phosphorus are unfavored, the combined alloying of 3% aluminum with 2% copper can almost nullify their detrimental effect. Based on the mentioned criteria, this study was dedicated to clarify the mechanism behind these alloying effects by examining the relationship between the measured enhancements on SCC resistance and the dissolution rate observed via the moire technique. It was found that the addition of both molybdenum and phosphorus reduces the dissolution rate and therefore impaired SCC resistance; the addition of copper increases the dissolution rate of steady growth stage where crevice corrosion proceeds at a constant rate. Moreover this dissolution rate could further be increased when combined with the alloying of aluminum. These observed results correspond well to that of the measured behavior of the SCC critical temperature, T c , suggesting that the SCC susceptibility is influenced by anodic dissolution

Determination of dissolution rates of spent fuel in carbonate solutions under different redox conditions with a flow-through experiment

International Nuclear Information System (INIS)

Roellin, S.; Spahiu, K.; Eklund, U.-B.

2001-01-01

Dissolution rates of spent UO 2 fuel have been investigated using flow-through experiments under oxidizing, anoxic and reducing conditions. For oxidizing conditions, approximately congruent dissolution rates were obtained in the pH range 3-9.3 for U, Np, Ba, Tc, Cs, Sr and Rb. For these elements, steady-state conditions were obtained in the flow rate range 0.02-0.3 ml min -1 . The dissolution rates were about 3 mg d -1 m -2 for pH>6. For pH 2 (g) saturated solutions dropped by up to four orders of magnitude as compared to oxidizing conditions. Because of the very low concentrations, only U, Pu, Am, Mo, Tc and Cs could be measured. For anoxic conditions, both the redox potential and dissolution rates increased approaching the same values as under oxidizing conditions

Dissolution rate measurements of sea water soluble pigments for antifouling paints

DEFF Research Database (Denmark)

Yebra, Diego Meseguer; Kiil, Søren; Erik Weinell, Claus

2006-01-01

The dissolution of soluble pigments from both tin-based and tin-free chemically active antifouling (AF) paints is a key process influencing their polishing and biocide leaching rates. In this context, a low time- and resources-consuming method capable of screening the pigment behaviour in the sea...

On the Impact of the Fuel Dissolution Rate Upon Near-Field Releases From Nuclear Waste Disposal

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A Pereira

2016-09-01

Full Text Available Calculations of the impact of the dissolution of spent nuclear fuel on the release from a damaged canister in a KBS-3 repository are presented. The dissolution of the fuel matrix is a complex process and the dissolution rate is known to be one of the most important parameters in performance assessment models of the near-field of a geological repository. A variability study has been made to estimate the uncertainties associated with the process of fuel dissolution. The model considered in this work is a 3D model of a KBS-3 copper canister. The nuclide used in the calculations is Cs-135. Our results confirm that the fuel degradation rate is an important parameter, however there are considerable uncertainties associated with the data and the conceptual models. Consequently, in the interests of safety one should reduce, as far as possible, the uncertainties coupled to fuel degradation.

In situ corrosion tests on HLW glass as part of a larger approach

International Nuclear Information System (INIS)

Van Iseghem, P.

1997-01-01

In-situ corrosion tests were performed on various candidate high-level waste glasses in the underground laboratory in clay underneath SCK x CEN. The tests exposed the glass samples directly to the Boom clay rock, for maximum durations of 7.5 years. We succeeded to interpret the corrosion data at 90 deg C in terms of dissolution mechanisms, and we concluded that the glass composition has a determining effect on the corrosion stability. The data from our in-situ tests were of high relevance for estimating the long-term behaviour of the glasses. The long-term in-situ tests provide corrosion data which show different trends than other corrosion tests, e.g. shorter duration tests in Boom clay, or tests in deionized water. The initial dissolution rate using MCC1 test at 90 deg C is about the same for the three glasses discussed, but the longest duration in Boom clay at 90 deg C shows a difference in mass loss of about 25 times. We finally present some ideas on how the corrosion tests can meet the needs, such as the modelling of the glass corrosion or providing input in the performance assessment. (author)

Dissolution of nuclear fuels

International Nuclear Information System (INIS)

Uriarte Hueda, A.; Berberana Eizmendi, M.; Rainey, R.

1968-01-01

A laboratory study was made of the instantaneous dissolution rate (IDR) for unirradiated uranium metal rods and UO 2 , PuO 2 and PuO 2 -UO 2 pellets in boiling nitric acid alone and with additives. The uranium metal and UO 2 dissolved readily in nitric acid alone; PuO 2 dissolved slowly even with the addition of fluoride; PuO 2 -UO 2 pellets containing as much as 35% PuO 2 in UO 2 gave values of the instantaneous dissolution rate to indicate can be dissolved with nitric acid alone. An equation to calculate the time for complete dissolution has been determinate in function of the instantaneous dissolution rates. The calculated values agree with the experimental. Uranium dioxide pellets from various sources but all having a same density varied in instantaneous dissolution rate. All the pellets, however, have dissolved ved in the same time. The time for complete dissolution of PuO 2 -UO 2 pellets, having the same composition, and the concentration of the used reagents are function of the used reagents are function of the fabrication method. (Author) 8 refs

Evaluation of glass leaching as nutrient source for microalgae growth

International Nuclear Information System (INIS)

Grabska, N.; Tamayo, A.; Mazo, M. A.; Pascual, L.; Rubio, J.

2015-01-01

Three glasses with an elemental composition similar to the nutrient ratio required for Spirulina platensis growth and with different SiO 2 content have been prepared. The glasses were crushed and sieved into 2 different fractions and the effect of the particle size has been studied in terms of the leaching kinetics of each element. The chemical analysis of the leaching water was used for obtaining the dissolution rate curves for each element taking part of the glass composition. From the calculation of the leaching rate constant and the exponential constant of the lixiviation reaction, it has been evaluated the Spirulina platensis growth in ambient normal conditions of light, temperature and pH of the growing media. It has been concluded that, either from the modification of the chemical composition of the glass or its particle size, it is possible to tune the delivery of the nutrients to match the growth rate of Spirulina platensis. (Author)

Etching of fission tracks in silicate glasses by means of deionized water

International Nuclear Information System (INIS)

Dran, J.C.; Petit, J.C.

1985-09-01

Fission tracks have been revealed in silicate glasses with deionized water. Their sharp conical shape implies a marked enhancement of the dissolution rate along their core and consequently a cone angle and an etching efficiency (close to 100%) much higher than previously reported for glasses. We show that etching of fission tracks in natural environments has generally very limited geochemical implications except in specific cases such as that found in the Oklo uranium ores

Effect of Na{sub 2}O on aqueous dissolution of nuclear waste glasses

Energy Technology Data Exchange (ETDEWEB)

Farooqi, Rahmat Ullah, E-mail: rufarooqi@live.com [Division of Advanced Nuclear Engineering, Pohang University of Science and Technology, 77 Cheongam-Ro, Nam-Gu, Pohang, Gyeongbuk 790-784 (Korea, Republic of); Hrma, Pavel [Division of Advanced Nuclear Engineering, Pohang University of Science and Technology, 77 Cheongam-Ro, Nam-Gu, Pohang, Gyeongbuk 790-784 (Korea, Republic of); Pacific Northwest National Laboratory, Richland, WA (United States)

2017-04-15

Sodium oxide is present in the majority of commercial and waste glasses as a viscosity-reducing component. In some nuclear waste glasses, its source is the waste itself. As such, it can limit the waste loading because of its deleterious effect on the resistance of the glass to attack by aqueous media. The maximum tolerable content of Na{sub 2}O in glass depends on the presence and concentration of components that interact with it. To assess the acceptability limits of Na{sub 2}O in the composition region of nuclear waste glasses, we formulated 11 baseline compositions by varying the content of oxides of Si, B, Al, Ca, Zr, and Li. In each of these compositions, we varied the Na{sub 2}O fraction from 8–16 mass% to 23–30 mass%. To each of 146 glasses thus formulated, we applied the seven-day Product Consistency Test (PCT) to determine normalized B and Na releases (r{sub i}, where i ≡ B or Na). Fitting approximation functions ln(r{sub i}/gm{sup −2}) = Σb{sub ij}g{sub j} to r{sub i} data (g{sub j} is the j-th component mass fraction and b{sub ij} the corresponding component coefficient), we showed that the r{sub B} (and, consequently, the initial glass alteration rate) was proportional to the glass component mass fractions in the order Al{sub 2}O{sub 3}glass structure would fall apart or beyond which a continuous nondurable phase would be separated. Specific examples are given to demonstrate restrictions imposed on the boundary of the composition region of acceptable glasses by the maximum allowable r{sub B} and by the melt viscosity required for glass melter operation. Finally, the role that PCT data may play in understanding the evolution of the glass alteration process is discussed.

Solidification of glass powder by a hydrothermal hot-pressing technique

International Nuclear Information System (INIS)

Nishioka, Mamoru; Yanagisawa, Kazumichi; Yamasaki, Nakamichi

1986-01-01

A borosilicate glass powder was solidified with a NaOH solution or distilled water by the hydrothermal hot-pressing technique. The effect of hydrothermal conditions on the compressive strength was investigated, and the densification mechanism of the glass powder during the hydrothermal hot-pressing was discussed in terms of isothermal shrinkage. The glass powder was successfully solidified by hydrothermal hot-pressing at a reaction temperature lower than that of an ordinary pressure sintering. The solidified body obtained in the presence of distilled water (10 wt%) at 280 deg C had a high compressive strength of about 2300 kg/cm 2 . The analysis of initial densification process of the glass powder in hydrothermal hot-pressing with Murray's rate equation revealed that the densification proceeds both by viscous flow and by rearrangement process. Analysis of the shrinkage rates with a rate equation of hydrothermal reaction suggested that the dissolution of particles into solution controlled the initial densification of the glass powder, and that the alkaline metal acted as a catalyst. (author)

Effect of chemical composition of man-made vitreous fibers on the rate of dissolution in vitro at different pHs.

Science.gov (United States)

Christensen, V R; Jensen, S L; Guldberg, M; Kamstrup, O

1994-10-01

Measurements of rates of dissolution of typical insulation wool fibers (glasswool and basalt based stonewool) and an experimental fiber were made using a flow-through equipment. The liquids used were a modified Gamble's solution, adjusted to pH 4.8 and 7.7 +/- 0.2, respectively. The dissolution of SiO2 and CaO was determined over periods of up to three months. The rate of dissolution of stonewool fibers was lower than that of glasswool fibers at pH 7.7, whereas the opposite was true at pH 4.8. The stonewool fibers dissolve congruently, but glasswool fibers tend to dissolve with leaching. The rates of dissolution of fibers of different compositions, including insulation wool (glasswool, basalt-based stonewool, slagwool) and experimental fibers were screened using a stationary set-up. Both the chemical composition and pH influenced the rates of dissolution. At pH 7.7 alumina was a determining component and at pH 4.8 the content of SiO2 and CaO was determinant. One experimental fiber with a high content of alumina was an exception having a fairly high rate of dissolution both at pH 4.8 and 7.7.

Leaching of glass

International Nuclear Information System (INIS)

Hench, L.L.

1977-01-01

Understanding surface compositional profiles of glasses over a range of 0-2000 A with a variety of analytical instruments shows that five general types of glass surfaces exist. The surface character of a glass article depends upon bulk composition and environmental history during which surface dealkalization, film formation, and network dissolution can occur. Environmental-surface interactions generally result in complex compositional profiles of all the constituents in a glass. Durable glasses almost always develop a stable surface film which has a higher concentration of network formers than the bulk composition. Compositional effects that are used to improve glass durability usually improve the stability of the surface films. Durability tests or service conditions that lead to film destruction are especially severe for the most silicate glasses. 43 references

Determination of alpha dose rate profile at the HLW nuclear glass/water interface

Energy Technology Data Exchange (ETDEWEB)

Mougnaud, S., E-mail: sarah.mougnaud@cea.fr [CEA Marcoule, DEN/DTCD/SECM, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Tribet, M.; Rolland, S. [CEA Marcoule, DEN/DTCD/SECM, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Renault, J.-P. [CEA Saclay, NIMBE UMR 3685 CEA/CNRS, 91191 Gif-sur-Yvette cedex (France); Jégou, C. [CEA Marcoule, DEN/DTCD/SECM, BP 17171, 30207 Bagnols-sur-Cèze cedex (France)

2015-07-15

Highlights: • The nuclear glass/water interface is studied. • The way the energy of alpha particles is deposited is modeled using MCNPX code. • A model giving dose rate profiles at the interface using intrinsic data is proposed. • Bulk dose rate is a majoring estimation in alteration layer and in surrounding water. • Dose rate is high in small cracks; in larger ones irradiated volume is negligible. - Abstract: Alpha irradiation and radiolysis can affect the alteration behavior of High Level Waste (HLW) nuclear glasses. In this study, the way the energy of alpha particles, emitted by a typical HLW glass, is deposited in water at the glass/water interface is investigated, with the aim of better characterizing the dose deposition at the glass/water interface during water-induced leaching mechanisms. A simplified chemical composition was considered for the nuclear glass under study, wherein the dose rate is about 140 Gy/h. The MCNPX calculation code was used to calculate alpha dose rate and alpha particle flux profiles at the glass/water interface in different systems: a single glass grain in water, a glass powder in water and a water-filled ideal crack in a glass package. Dose rate decreases within glass and in water as distance to the center of the grain increases. A general model has been proposed to fit a dose rate profile in water and in glass from values for dose rate in glass bulk, alpha range in water and linear energy transfer considerations. The glass powder simulation showed that there was systematic overlapping of radiation fields for neighboring glass grains, but the water dose rate always remained lower than the bulk value. Finally, for typical ideal cracks in a glass matrix, an overlapping of irradiation fields was observed while the crack aperture was lower than twice the alpha range in water. This led to significant values for the alpha dose rate within the crack volume, as long as the aperture remained lower than 60 μm.

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

International Nuclear Information System (INIS)

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

2012-01-01

Document available in extended abstract form only. In France, high-level nuclear waste (HLW) is confined in a glass matrix packaged into stainless steel canister and carbon steel overpack. The HLW should be buried in a geological clay formation like, potentially, the Callovian-Oxfordian (COx) clay-stone located in the north-eastern Parisian basin. The COx clay-stone contains minerals that can feed the near-field with soluble Mg. Such minerals are carbonates (ankerite, dolomite) as well as clay minerals (chlorite, illite, interstratified illite/smectite). Previous laboratory experiments have proved that aqueous solutions of Mg salts could significantly increase the alteration rate of nuclear glass (Jollivet et al., 2012). This motivated to go a step further by studying the alteration of nuclear glass put in contact with Mg minerals. A first set of experiments have revealed that the rate of glass dissolution was increased with hydro-magnesite (4MgCO 3 .Mg(OH) 2 .4H 2 O, a chemically simple model mineral) and dolomite. In both cases, Mg coming from carbonate dissolution reacts with Si, provided by the glass, in order to form Mg silicates (Debure et al., 2012). In that case, Si consumption sustains glass alteration. Mg silicate precipitation also consumes protons; therefore the interdiffusion of alkali within the glass alteration layer eventually becomes a driving force that sustains Mg silicate precipitation. The second set of experiments, presented here, aimed at better characterizing the role of the COx clayey fraction. The separation of the clayey phases of the COx clay-stone has been made in collaboration with the LEM lab (Nancy, France) by a sequence of sieving, acidic dissolution of carbonates, NaCl washing and sedimentation (Rivard, 2011). According to XRD and infrared analyses, the clayey fraction was mainly composed of kaolinite, illite, interstratified illite/smectite and chlorite (plus a little residual amount of quartz). This first step aimed to remove

The influence of pressure on the intrinsic dissolution rate of amorphous indomethacin

DEFF Research Database (Denmark)

Löbmann, Korbinian; Flouda, Konstantina; Qiu, Danwen

2014-01-01

of different compression pressures on the IDR was determined from powder compacts of amorphous (ball-milling) indomethacin (IND), a glass solution of IND and poly(vinylpyrrolidone) (PVP) and crystalline IND. Solid state properties were analyzed with X-ray powder diffraction (XRPD) and the final compacts were...... and to test the potential dissolution advantage of the amorphous form. However, neither the United States Pharmacopeia (USP) nor the European Pharmacopeia (Ph.Eur) state specific limitations for the compression pressure in order to obtain compacts for the IDR determination. In this study, the influence...... visually observed to study the effects of compaction pressure on their surface properties. It was found that there is no significant correlation between IDR and compression pressure for crystalline IND and IND-PVP. This was in line with the observation of similar surface properties of the compacts. However...

Differing disintegration and dissolution rates, pharmacokinetic profiles and gastrointestinal tolerability of over the counter ibuprofen formulations.

Science.gov (United States)

Bjarnason, Ingvar; Sancak, Ozgur; Crossley, Anne; Penrose, Andrew; Lanas, Angel

2018-02-01

Formulations of over the counter (OTC) NSAIDs differ substantially, but information is lacking on whether this alters their gastrointestinal profiles. To assess disintegration and dissolution rates and pharmacokinetics of four preparations of OTC ibuprofen and relate these with spontaneously reported gastrointestinal adverse events. Disintegration and dissolution rates of ibuprofen tablets as (a) acid, (b) sodium salt, (c) lysine salt, and (d) as a liquid gelatine capsule were assessed. Pharmacokinetic data gastrointestinal and spontaneously reported adverse events arising from global sales were obtained from files from Reckitt Benckiser. Disintegration at low pH was progressively shorter for the preparations from a-to-d with formation of correspondingly smaller ibuprofen crystals, while dissolution was consistently poor. Dissolution at a neutral pH was least rapid for the liquid gelatine capsule. Pharmacokinetic data showed a shorter t max and a higher C max for preparations b-d as compared with ibuprofen acid. Spontaneously reported abdominal symptoms were rare with the liquid gelatine preparation. The formulations of OTC ibuprofen differ in their disintegration and dissolution properties, pharmacokinetic profiles and apparent gastrointestinal tolerability. Spontaneously reported abdominal symptoms were five times lower with the liquid gelatine capsule as compared with ibuprofen acid despite a 30% increase in C max . © 2017 Royal Pharmaceutical Society.

Analytical Plan for Roman Glasses

Energy Technology Data Exchange (ETDEWEB)

Strachan, Denis M.; Buck, Edgar C.; Mueller, Karl T.; Schwantes, Jon M.; Olszta, Matthew J.; Thevuthasan, Suntharampillai; Heeren, Ronald M.

2011-01-01

Roman glasses that have been in the sea or underground for about 1800 years can serve as the independent “experiment” that is needed for validation of codes and models that are used in performance assessment. Two sets of Roman-era glasses have been obtained for this purpose. One set comes from the sunken vessel the Iulia Felix; the second from recently excavated glasses from a Roman villa in Aquileia, Italy. The specimens contain glass artifacts and attached sediment or soil. In the case of the Iulia Felix glasses quite a lot of analytical work has been completed at the University of Padova, but from an archaeological perspective. The glasses from Aquileia have not been so carefully analyzed, but they are similar to other Roman glasses. Both glass and sediment or soil need to be analyzed and are the subject of this analytical plan. The glasses need to be analyzed with the goal of validating the model used to describe glass dissolution. The sediment and soil need to be analyzed to determine the profile of elements released from the glass. This latter need represents a significant analytical challenge because of the trace quantities that need to be analyzed. Both pieces of information will yield important information useful in the validation of the glass dissolution model and the chemical transport code(s) used to determine the migration of elements once released from the glass. In this plan, we outline the analytical techniques that should be useful in obtaining the needed information and suggest a useful starting point for this analytical effort.

Dissolution of minerals with rough surfaces

Science.gov (United States)

de Assis, Thiago A.; Aarão Reis, Fábio D. A.

2018-05-01

We study dissolution of minerals with initial rough surfaces using kinetic Monte Carlo simulations and a scaling approach. We consider a simple cubic lattice structure, a thermally activated rate of detachment of a molecule (site), and rough surface configurations produced by fractional Brownian motion algorithm. First we revisit the problem of dissolution of initial flat surfaces, in which the dissolution rate rF reaches an approximately constant value at short times and is controlled by detachment of step edge sites. For initial rough surfaces, the dissolution rate r at short times is much larger than rF ; after dissolution of some hundreds of molecular layers, r decreases by some orders of magnitude across several time decades. Meanwhile, the surface evolves through configurations of decreasing energy, beginning with dissolution of isolated sites, then formation of terraces with disordered boundaries, their growth, and final smoothing. A crossover time to a smooth configuration is defined when r = 1.5rF ; the surface retreat at the crossover is approximately 3 times the initial roughness and is temperature-independent, while the crossover time is proportional to the initial roughness and is controlled by step-edge site detachment. The initial dissolution process is described by the so-called rough rates, which are measured for fixed ratios between the surface retreat and the initial roughness. The temperature dependence of the rough rates indicates control by kink site detachment; in general, it suggests that rough rates are controlled by the weakest microscopic bonds during the nucleation and formation of the lowest energy configurations of the crystalline surface. Our results are related to recent laboratory studies which show enhanced dissolution in polished calcite surfaces. In the application to calcite dissolution in alkaline environment, the minimal values of recently measured dissolution rate spectra give rF ∼10-9 mol/(m2 s), and the calculated rate

Long term effects of bioactive glass particulates on dental pulp stem cells in vitro

Directory of Open Access Journals (Sweden)

Gholami Sanaz

2017-12-01

Full Text Available Bioactive glasses (BG are known for their ability to induce bone formation by the action of their dissolution products. Glasses can deliver active ions at a sustained rate, determined by their composition and surface area. Nanoporous sol-gel derived BGs can biodegrade rapidly, which can lead to a detrimental burst release of ions and a pHrise. The addition of phosphate into the glass can buffer the pH during dissolution. Here, dissolution of BG with composition 60 mol% SiO2, 28 mol% CaO and 12 mol% P2O5 at 600 μg/ml were investigated. Initially, the dissolution and apatite formation of the BG particulates were examined in simulated body fluid using FTIR and XRD. BG particulates were indirectly exposed to dental pulp stem cells, and the effect of 14 days continuous ion release on human dental pulp stem cells (hDPSC viability and differentiation was evaluated. Alamar blue assay showed that cell proliferation was not inhibited by the continuous release of Ca, P and soluble silica. In fact, hDPSC in the presence of BG particulate displayed a higher density of mineralized nodules than untreated cells, as assessed by Alizarin red. The results will have a great contribution to the in vivo application of this particular BG.

Evaluation of a three compartment in vitro gastrointestinal simulator dissolution apparatus to predict in vivo dissolution.

Science.gov (United States)

Takeuchi, Susumu; Tsume, Yasuhiro; Amidon, Gregory E; Amidon, Gordon L

2014-11-01

In vitro dissolution tests are performed for new formulations to evaluate in vivo performance, which is affected by the change of gastrointestinal (GI) physiology, in the GI tract. Thus, those environmental changes should be introduced to an in vitro dissolution test. Many studies have successfully shown the improvement of in vitro-in vivo correlations (IVIVC) by introducing those physiological changes into dissolution tests. The gastrointestinal simulator (GIS), a multicompartment in vitro dissolution apparatus, was developed to evaluate in vivo drug dissolution. A gastric-emptying rate along with transit rate are key factors to evaluate in vivo drug dissolution and, hence, drug absorption. Dissolution tests with the GIS were performed with Biopharmaceutical Classification System class I drugs at five different gastric-emptying rates in the fasted state. Computational models were used to determine in vivo gastric-emptying time for propranolol and metoprolol based on the GIS dissolution results. Those were compared with published clinical data to determine the gastric half-emptying time. In conclusion, the GIS is a practical tool to assess dissolution properties and can improve IVIVC. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Alkali-free bioactive glasses for bone regeneration =

Science.gov (United States)

Kapoor, Saurabh

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

Predicting bioactive glass properties from the molecular chemical composition: glass transition temperature.

Science.gov (United States)

O'Donnell, Matthew D

2011-05-01

The glass transition temperature (T(g)) of inorganic glasses is an important parameter than can be used to correlate with other glass properties, such as dissolution rate, which governs in vitro and in vivo bioactivity. Seven bioactive glass compositional series reported in the literature (77 in total) were analysed here with T(g) values obtained by a number of different methods: differential thermal analysis, differential scanning calorimetry and dilatometry. An iterative least-squares fitting method was used to correlate T(g) from thermal analysis of these compositions with the levels of individual oxide and fluoride components in the glasses. When all seven series were fitted a reasonable correlation was found between calculated and experimental values (R(2)=0.89). When the two compositional series that were designed in weight percentages (the remaining five were designed in molar percentage) were removed from the model an improved fit was achieved (R(2)=0.97). This study shows that T(g) for a wide range in compositions (e.g. SiO(2) content of 37.3-68.4 mol.%) can be predicted to reasonable accuracy enabling processing parameters to be predicted such as annealing, fibre-drawing and sintering temperatures. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Enhancement of dissolution rate of piroxicam by electrospinning technique

International Nuclear Information System (INIS)

Begum, S K Raziya; Varma, M Mohan; Raju, D B; Prasad, R G S V; Phani, A R; Jacob, Biju; Salins, Paul C

2012-01-01

The use of electrospun nanofibers to enhance dissolution of poorly soluble drugs could be a novel strategy in future for pharmaceutical applications. In the present work electrospun nanofibers were prepared as a novel system for enhancing the delivery of piroxicam, a non-steroidal anti-inflammatory drug (NSAID). These nanofibers were prepared from polyvinyl pyrrolidone (PVP) (pharmaceutical grade), a biodegradable polymer, to obtain a solution with drug:polymer ratio of 1:4. The release rate of the piroxicam nanofibers was studied in simulated gastric fluid. Fourier transform infrared (FTIR) and scanning electron microscopy (SEM) are used to evaluate the chemical and physical nature. The results showed that the release rates were twice increased in comparison with the pure drug. However, the blend of drug and polymer could be varied to optimize the release rates depending upon the need and formulation (paper)

Enhancement of dissolution rate of piroxicam by electrospinning technique

Science.gov (United States)

Raziya Begum, S. K.; Mohan Varma, M.; Raju, D. B.; Prasad, R. G. S. V.; Phani, A. R.; Jacob, Biju; Salins, Paul C.

2012-12-01

The use of electrospun nanofibers to enhance dissolution of poorly soluble drugs could be a novel strategy in future for pharmaceutical applications. In the present work electrospun nanofibers were prepared as a novel system for enhancing the delivery of piroxicam, a non-steroidal anti-inflammatory drug (NSAID). These nanofibers were prepared from polyvinyl pyrrolidone (PVP) (pharmaceutical grade), a biodegradable polymer, to obtain a solution with drug:polymer ratio of 1:4. The release rate of the piroxicam nanofibers was studied in simulated gastric fluid. Fourier transform infrared (FTIR) and scanning electron microscopy (SEM) are used to evaluate the chemical and physical nature. The results showed that the release rates were twice increased in comparison with the pure drug. However, the blend of drug and polymer could be varied to optimize the release rates depending upon the need and formulation

Enhanced dissolution rate of dronedarone hydrochloride via preparation of solid dispersion using vinylpyrrolidone-vinyl acetate copolymer (Kollidone® VA 64)

Energy Technology Data Exchange (ETDEWEB)

Jung, Hyuck Jun; Kang, Myung Joo [College of Pharmacy, Dankook University, Cheonan (Korea, Republic of); Han, Sang Duk [Dong-A ST Rese arch Institute, Pharmaceutical Product Research Laboratories, Yongin (Korea, Republic of)

2015-09-15

Solid dispersion (SD) systems have been widely used to increase the dissolution rate and oral absorption of poorly water-soluble compounds. In order to enhance the dissolution rate of dronedarone hydrochloride (DRN), a recent antiarrhythmic agent, SDs of DRN were formulated using conventional solvent evaporation method with amorphous polymers including hydroxypropyl methyl cellulose (HPMC), poly(vinyl pyrrolidone) (PVP), and vinylpyrrolidone-vinyl acetate copolymer (VA64). The prepared SDs were characterized in terms of drug crystallinity, morphology, and in vitro dissolution profile in aqueous medium. The physical characterization using differential scanning calorimetry and X-ray powder diffraction revealed that the active compound was molecularly dispersed in all polymeric carriers tested, in a stable amorphous form in drug to polymer ratios ranging from 1:0.5 to 1:2. The dissolution rates of DRN in all SDs were much higher than those from the corresponding physical mixture and drug powder alone. In particular, the greatest dissolution enhancement was obtained from the VA64-based SD in a drug to polymer weight ratio of 1:1, achieving almost complete drug release after 120 min at pH 1.2. Thus, VA64-based SD with higher drug dissolution rate along with a simple preparation process is suggested as an alternative for the oral formulation of the benzofuran derivative.

Relationship between the shear viscosity and heating rate in metallic glasses below the glass transition

International Nuclear Information System (INIS)

Khonik, Vitaly A.; Kobelev, N. P.

2008-01-01

It has been shown that first-order irreversible structural relaxation with distributed activation energies must lead to a linear decrease of the logarithm of Newtonian shear viscosity with the logarithm of heating rate upon linear heating of glass. Such a behavior is indeed observed in the experiments on metallic glasses. Structural relaxation-induced viscous flow leads to infra-low-frequency Maxwell viscoelastic internal friction, which is predicted to increase with the heating rate

Liquigroud technique: a new concept for enhancing dissolution rate of glibenclamide by combination of liquisolid and co-grinding technologies.

Science.gov (United States)

Azharshekoufeh, Leila; Shokri, Javad; Barzegar-Jalali, Mohammad; Javadzadeh, Yousef

2017-01-01

Introduction: The potential of combining liquisolid and co-grinding technologies (liquiground technique) was investigated to improve the dissolution rate of a water-insoluble agent (glibenclamide) with formulation-dependent bioavailability. Methods: To this end, different formulations of liquisolid tablets with a wide variety of non-volatile solvents contained varied ratios of drug: solvent and dissimilar carriers were prepared, and then their release profiles were evaluated. Furthermore, the effect of size reduction by ball milling on the dissolution behavior of glibenclamide from liquisolid tablets was investigated. Any interaction between the drug and the excipient or crystallinity changes during formulation procedure was also examined using X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results: The present study revealed that classic liquisolid technique did not significantly affect the drug dissolution profile as compared to the conventional tablets. Size reduction obtained by co-grinding of liquid medication was more effective than the implementation of liquisolid technique in enhancing the dissolution rate of glibenclamide. The XRD and DSC data displayed no formation of complex or any crystallinity changes in both formulations. Conclusion: An enhanced dissolution rate of glibenclamide is achievable through the combination of liquisolid and co-grinding technologies.

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

Heterogeneities in nuclear waste glass

International Nuclear Information System (INIS)

Ladirat, Ch.

1997-01-01

The industrial vitrification of high level radioactive wastes is a 2 stage process. During the first stage, the concentrated solution is heated in a spinning resistance oven at the temperature of 400 Celsius degrees till evaporation and calcination. The second stage begins when the dry residue falls into a melting pot that is maintained at a temperature of 1100-1150 Celsius degrees. Glass fretting is added and the glass is elaborated through the fusion of the different elements present in the melting pot. Heterogeneities in the glass may be associated to: - the presence in the solution to vitrify of insoluble elements from the dissolution of the fuel (RuO 2 , Rh, Pd), - the presence of minuscule metal scraps (Zr) that have been produced during the cutting of the fuel element, - the failures to conform to the technical specifications of the vitrification process, for instance, temperatures or flow rates when introducing the different elements in the melting pot. (A.C.)

The dissolution rate of UO2 in the alkaline regime under oxidizing conditions using a simplified ground water analog

International Nuclear Information System (INIS)

Leider, H.R.; Nguyen, S.N.; Weed, H.C.; Steward, S.A.

1992-01-01

The major factor controlling the long term release of radionuclides from spent fuel in a geologic repository is the leaching/dissolution by groundwater of the UO 2 matrix, since more than 90% of the radionuclide waste is contained in the fuel matrix. The objective of this investigation is to provide experimental dissolution rates for UO 2 samples which can be used to develop a mechanistic release model (or models) for UO 2+x (x≥0) under repository conditions. Several types of data will be obtained from this study: (1) the dissolution rates of UO 2 as a function of pI-L temperature, carbonate and oxygen fugacity; (2) the comparison of the steady state dissolution rates of ''not-reduced'' versus ''reduced'' UO 2 samples and of single crystal versus polycrystalline UO 2 under identical experimental conditions; (3) the pre- and post-test surface analyses of the samples to provide information on the surface phases that may be formed under experimental conditions

Influence of Type and Neutralisation Capacity of Antacids on Dissolution Rate of Ciprofloxacin and Moxifloxacin from Tablets

Directory of Open Access Journals (Sweden)

Alija Uzunović

2009-02-01

Full Text Available Dissolution rate of two fluoroquinolone antibiotics (ciprofloxacin and moxifloxacin was analysed in presence/absence of three antacid formulations. Disintegration time and neutralisation capacity of antacid tablets were also checked. Variation in disintegration time indicated the importance of this parameter, and allowed evaluation of the influence of postponed antacid-fluoroquinolone contact. The results obtained in this study showed decreased dissolution rate of fluoroquinolone antibiotics from tablets in simultaneous presence of antacids, regardless of their type and neutralisation capacity.

Laboratory testing of glasses for Lockheed Idaho Technology Company: Final report

International Nuclear Information System (INIS)

Ellison, A.J.G.; Buck, E.C.; Dietz, N.L.; Ebert, W.L.; Luo, J.S.; Wolf, S.F.; Bates, J.K.

1997-06-01

Tests have been conducted at Argonne National Laboratory (ANL) in support of the efforts of Lockheed Idaho Technology Company (LITCO) to vitrify high-level waste calcines. Tests were conducted with three classes of LITCO glass formulations: Formula 127 (fluorine-bearing), Formula 532 (fluorine-free), and 630 series (both single- and mixed-alkali) glasses. The test matrices included, as appropriate, the Product Consistency Test Method B (PCT-B), the Materials Characterization Center Test 1 (MCC-1), and the Argonne vapor hydration test (VHT). Test durations ranged from 7 to 183 d. In 7-d PCT-Bs, normalized mass losses of major glass-forming elements for the LITCO glasses are similar to, or lower than, normalized mass losses obtained for other domestic candidate waste glasses. Formula 532 glasses form zeolite alteration phases relatively early in their reaction with water. The formation of those phases increased the dissolution rate. In contrast, the Formula 127 glass is highly durable and forms alteration phases only after prolonged exposure to water in tests with very high surface area to volume ratios; these alteration phases have a relatively small effect on the rate of glass corrosion. No alteration phases formed within the maximum test duration of 183 d in PCT-Bs with the 630 series glasses. The corrosion behavior of the mixed-alkali 630 series glasses is similar to that of 630 series glasses containing sodium alone. In VHTs, both single- and mixed-alkali glasses form zeolite phases that increase the rate of glass reaction. The original 630 series glasses and those based on a revised surrogate calcine formulation react at the same rate in PCT-Bs and form the same major alteration phases in VHTs

Effects of Quartz Particle Size and Sucrose Addition on Melting Behavior of a Melter Feed for High-Level Waste Glass

International Nuclear Information System (INIS)

Marcial, Jose; Hrma, Pavel R.; Schweiger, Michael J.; Swearingen, Kevin J.; Tegrotenhuis, Nathan E.; Henager, Samuel H.

2010-01-01

The behavior of melter feed (a mixture of nuclear waste and glass-forming additives) during waste-glass processing has a significant impact on the rate of the vitrification process. We studied the effects of silica particle size and sucrose addition on the volumetric expansion (foaming) of a high-alumina feed and the rate of dissolution of silica particles in feed samples heated at 5 C/min up to 1200 C. The initial size of quartz particles in feed ranged from 5 to 195 (micro)m. The fraction of the sucrose added ranged from 0 to 0.20 g per g glass. Extensive foaming occurred only in feeds with 5-(micro)m quartz particles; particles (ge) 150 (micro)m formed clusters. Particles of 5 (micro)m completely dissolved by 900 C whereas particles (ge) 150 (micro)m did not fully dissolve even when the temperature reached 1200 C. Sucrose addition had virtually zero impact on both foaming and the dissolution of silica particles.

DETERMINATION OF HLW GLASS MELT RATE USING X-RAY COMPUTED TOMOGRAPHY

Energy Technology Data Exchange (ETDEWEB)

Choi, A.; Miller, D.; Immel, D.

2011-10-06

The purpose of the high-level waste (HLW) glass melt rate study is two-fold: (1) to gain a better understanding of the impact of feed chemistry on melt rate through bench-scale testing, and (2) to develop a predictive tool for melt rate in support of the on-going frit development efforts for the Defense Waste Processing Facility (DWPF). In particular, the focus is on predicting relative melt rates, not the absolute melt rates, of various HLW glass formulations solely based on feed chemistry, i.e., the chemistry of both waste and glass-forming frit for DWPF. Critical to the successful melt rate modeling is the accurate determination of the melting rates of various HLW glass formulations. The baseline procedure being used at the Savannah River National Laboratory (SRNL) is to; (1) heat a 4 inch-diameter stainless steel beaker containing a mixture of dried sludge and frit in a furnace for a preset period of time, (2) section the cooled beaker along its diameter, and (3) measure the average glass height across the sectioned face using a ruler. As illustrated in Figure 1-1, the glass height is measured for each of the 16 horizontal segments up to the red lines where relatively large-sized bubbles begin to appear. The linear melt rate (LMR) is determined as the average of all 16 glass height readings divided by the time during which the sample was kept in the furnace. This 'visual' method has proved useful in identifying melting accelerants such as alkalis and sulfate and further ranking the relative melt rates of candidate frits for a given sludge batch. However, one of the inherent technical difficulties of this method is to determine the glass height in the presence of numerous gas bubbles of varying sizes, which is prevalent especially for the higher-waste-loading glasses. That is, how the red lines are drawn in Figure 1-1 can be subjective and, therefore, may influence the resulting melt rates significantly. For example, if the red lines are drawn too low

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

Science.gov (United States)

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

1989-04-01

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

Preparation and evaluation of azithromycin binary solid dispersions using various polyethylene glycols for the improvement of the drug solubility and dissolution rate

Directory of Open Access Journals (Sweden)

Ehsan Adeli

Full Text Available ABSTRACT Azithromycin is a water-insoluble drug, with a very low bioavailability. In order to increase the solubility and dissolution rate, and consequently increase the bioavailability of poorly-soluble drugs (such as azithromycin, various techniques can be applied. One of such techniques is "solid dispersion". This technique is frequently used to improve the dissolution rate of poorly water-soluble compounds. Owing to its low solubility and dissolution rate, azithromycin does not have a suitable bioavailability. Therefore, the main purpose of this investigation was to increase the solubility and dissolution rate of azithromycin by preparing its solid dispersion, using different Polyethylene glycols (PEG. Preparations of solid dispersions and physical mixtures of azithromycin were made using PEG 4000, 6000, 8000, 12000 and 20000 in various ratios, based on the solvent evaporation method. From the studied drug release profile, it was discovered that the dissolution rate of the physical mixture, as the well as the solid dispersions, were higher than those of the drug alone. There was no chemical incompatibility between the drug and polymer from the observed Infrared (IR spectra. Drug-polymer interactions were also investigated using Differential Scanning Calorimetry (DSC, Powder X-Ray Diffraction (PXRD and Scanning Election Microscopy (SEM. In conclusion, the dissolution rate and solubility of azithromycin were found to improve significantly, using hydrophilic carriers, especially PEG 6000.

Formalization of the kinetics for autocatalytic dissolutions. Focus on the dissolution of uranium dioxide in nitric medium

International Nuclear Information System (INIS)

Charlier, F.; Canion, D.; Gravinese, A.; Magnaldo, A.; Lalleman, S.; Borda, G.; Schaer, E.

2017-01-01

Uranium dioxide dissolution in nitric acid is a complex reaction. On the one hand, the dissolution produces nitrous oxides (NOX), which makes it a triphasic reaction. On the other hand, one of the products accelerates the kinetic rate; the reaction is hence called autocatalytic.The kinetics for these kinds of reactions need to be formalized in order to optimize and design innovative dissolution reactors. In this work, the kinetics rates have been measured by optical microscopy using a single particle approach. The advantages of this analytical technique are an easier management of species transport in solution and a precise following of the dissolution rate. The global rate is well described by a mechanism considering two steps: a non-catalyzed reaction, where the catalyst concentration has no influence on the dissolution rate, and a catalyzed reaction. The mass transfer rate of the catalyst was quantified in order to discriminate when the reaction was influenced by catalyst accumulated in the boundary layer or uncatalyzed. This first approximation described well the sigmoid dissolution curve profile. Moreover, experiments showed that solutions filled with catalyst proved to lose reactivity over time. Results pointed out that the higher the liquid-gas exchanges, the faster the kinetic rate decreases with time. Thus, it was demonstrated, for the first time, that there is a link between catalyst and nitrous oxides. The outcome of this study leads to new ways for improving the design of dissolvers. Gas-liquid exchanges are indeed a lever to impact dissolution rates. Temperature and catalyst concentration can be optimized to reduce residence times in dissolvers. (authors)

Agitation Rate and Time for Complete Dissolution in BCS Biowaivers Based on Investigation of a BCS Biowaiver for Dexketoprofen Tablets.

Science.gov (United States)

Garcia-Arieta, Alfredo; Gordon, John; Gwaza, Luther; Mangas-Sanjuan, V; Álvarez, Covadonga; Torrado, Juan J

2015-09-08

The objective of the present work is to investigate the validity of the existing requirements for BCS biowaivers of immediate release products containing a class I drug in relation to the agitation rate (50 or 75 rpm in the paddle apparatus) and the time limit for complete dissolution (30 min) in the current biowaivers in vitro dissolution tests. Further, the possibility of extensions will be examined since it has been proposed that the time limit for complete dissolution should be revised to 60 min, and also, if cone formation occurs with apparatus 2 at 50 rpm, then a higher agitation rate is acceptable to eliminate it. The development of four generic dexketoprofen immediate release tablets is described. Dexketoprofen is the eutomer of ketoprofen. According to the BCS, dexketoprofen is a class I drug. Three out of the four products failed to show bioequivalence for Cmax in the initial bioequivalence study conducted with the product despite similar but nonrapid dissolution profiles at 50 rpm in the paddle apparatus, or similar and very rapid dissolution profiles at 75 rpm. In conclusion, these data indicate that BCS biowaivers for class I drugs should be granted only when dissolution with the paddle apparatus is complete in 30 min at 50 rpm. The time limit for complete dissolution should not be extended to 60 min. Furthermore, the agitation rate should not be increased to 75 rpm, even in the case of a coning effect.

Enhancement of Solubility, Dissolution rate and Bioavailability of Efavirenz by Cyclodextrins and Solutol HS15 - A Factorial Study

OpenAIRE

R. Yogananda; K. P. R. Chowdary

2013-01-01

Efavirenz widely prescribed anti-retroviral drug belongs to class II BCS and exhibit low and variable oral bioavailability due to its poor aqueous solubility and it requires enhancement in solubility and dissolution rate for increasing its oral bioavailability. The objective of the present investigation is to enhance the solubility, dissolution rate and bioavailability of efavirenz by the use of cyclodextrins (%CD and HP%CD) and surfactant, Solutol HS15. The individual main effects and combin...

Accurate rates of the complex mechanisms for growth and dissolution of minerals using a combination of rare event theories

International Nuclear Information System (INIS)

Stack, Andrew G.; Raiten, Paolo; Gale, Julian D.

2012-01-01

Mineral growth and dissolution are often treated as occurring via a single, reversible process that governs the rate of reaction. We show that multiple, distinct intermediate states can occur during both growth and dissolution. Specifically, we have used metadynamics, a method to efficiently explore the free energy landscape of a system, coupled to umbrella sampling and reactive flux calculations, to examine the mechanism and rates of attachment and detachment of a barium ion onto a stepped, barite (BaSO4) surface. The activation energies calculated for the rate limiting reactions, which are different for attachment and detachment, precisely match those measured experimentally during both growth and dissolution. These results can potentially explain anomalous, non-steady state mineral reaction rates observed experimentally, and will enable the design of more efficient growth inhibitors and facilitate an understanding of the effect of impurities.

Influence of nuclear glasses composition on their liability to deterioration; Influence de la composition des verres nucleaires sur leur alterabilite

Energy Technology Data Exchange (ETDEWEB)

Tovena, I

1995-09-29

This contributes to the study of the nuclear glasses composition influence on their liability to deterioration. The methodology of the experimental research used has lead to define between the thirty oxides which form the reference glass light water, six oxides of interest. For each of these oxides, a composition variation area has been defined. A matrix of twenty glass compositions has then been defined. The preparation of materials of these compositions has sometimes lead to materials weakly heterogeneous which have been characterized before deterioration. This study has been completed by those of three glasses in a composition variation area narrower of the light water nuclear glass : the R7T7 and two glasses at limits having respectively an initial dissolution velocity at 100 degrees Celsius theoretically maximum and minimum. Some deterioration parameters in pure water have been experimentally measured on the twenty three glasses : 1) an initial dissolution velocity at 100 degrees (Vo{sub 1}00) Celsius and another one at 90 degrees Celsius (Vo{sub 9}0) 2) a dissolution velocity in conditions near the saturation at 90 degrees Celsius 3) an apparent solubility of glass based on the ortho silicic acid activity 4) the evolution of the dissolution kinetics at 90 degrees Celsius in sub-saturated medium towards saturated medium 5) the alteration films nature developed at the glasses surface during these last alteration tests. Some thermodynamic and structural models have been studied in order to predict Vo{sub 9}0 and Vo{sub 1}00. The dissolution kinetic law developed from reference glass dissolution results has been studied with the calculation code LIXIVER. It has not been able to be used for most of the glasses compositions studied. As a consequence, the glasses dissolution control by a surface reaction which are itself controlled by the only dissolved silica is an hypothesis which is not verified for the greater part of the glasses. (O.L.). refs., figs., tabs.

Dissolution and Precipitation Behaviour during Continuous Heating of Al–Mg–Si Alloys in a Wide Range of Heating Rates

Science.gov (United States)

Osten, Julia; Milkereit, Benjamin; Schick, Christoph; Kessler, Olaf

2015-01-01

In the present study, the dissolution and precipitation behaviour of four different aluminium alloys (EN AW-6005A, EN AW-6082, EN AW-6016, and EN AW-6181) in four different initial heat treatment conditions (T4, T6, overaged, and soft annealed) was investigated during heating in a wide dynamic range. Differential scanning calorimetry (DSC) was used to record heating curves between 20 and 600 °C. Heating rates were studied from 0.01 K/s to 5 K/s. We paid particular attention to control baseline stability, generating flat baselines and allowing accurate quantitative evaluation of the resulting DSC curves. As the heating rate increases, the individual dissolution and precipitation reactions shift to higher temperatures. The reactions during heating are significantly superimposed and partially run simultaneously. In addition, precipitation and dissolution reactions are increasingly suppressed as the heating rate increases, whereby exothermic precipitation reactions are suppressed earlier than endothermic dissolution reactions. Integrating the heating curves allowed the enthalpy levels of the different initial microstructural conditions to be quantified. Referring to time–temperature–austenitisation diagrams for steels, continuous heating dissolution diagrams for aluminium alloys were constructed to summarise the results in graphical form. These diagrams may support process optimisation in heat treatment shops.

Dissolution and Precipitation Behaviour during Continuous Heating of Al–Mg–Si Alloys in a Wide Range of Heating Rates

Directory of Open Access Journals (Sweden)

Julia Osten

2015-05-01

Full Text Available In the present study, the dissolution and precipitation behaviour of four different aluminium alloys (EN AW-6005A, EN AW-6082, EN AW-6016, and EN AW-6181 in four different initial heat treatment conditions (T4, T6, overaged, and soft annealed was investigated during heating in a wide dynamic range. Differential scanning calorimetry (DSC was used to record heating curves between 20 and 600 °C. Heating rates were studied from 0.01 K/s to 5 K/s. We paid particular attention to control baseline stability, generating flat baselines and allowing accurate quantitative evaluation of the resulting DSC curves. As the heating rate increases, the individual dissolution and precipitation reactions shift to higher temperatures. The reactions during heating are significantly superimposed and partially run simultaneously. In addition, precipitation and dissolution reactions are increasingly suppressed as the heating rate increases, whereby exothermic precipitation reactions are suppressed earlier than endothermic dissolution reactions. Integrating the heating curves allowed the enthalpy levels of the different initial microstructural conditions to be quantified. Referring to time–temperature–austenitisation diagrams for steels, continuous heating dissolution diagrams for aluminium alloys were constructed to summarise the results in graphical form. These diagrams may support process optimisation in heat treatment shops.

Modelling of the UO2 dissolution mechanisms in synthetic groundwater solutions. Dissolution experiments carried out under oxic conditions

International Nuclear Information System (INIS)

Cera, E.; Grive, M.; Bruno, J.; Ollila, K.

2001-02-01

The analytical data generated during the last three years within the 4th framework program of the European Community at VTT Chemical Technology concerning UO 2 dissolution under oxidising conditions have been modelled in the present work. The modelling work has been addressed to perform a kinetic study of the dissolution data generated by Ollila (1999) under oxidising conditions by using unirradiated uranium dioxide as solid sample. The average of the normalised UO 2 dissolution rates determined by using the initial dissolution data generated in all the experimental tests is (6.06 ± 3.64)* 10 -7 mol m -2 d -1 . This dissolution rate agrees with most of the dissolution rates reported in the literature under similar experimental conditions. The results obtained in this modelling exercise show that the same bicarbonate promoted oxidative dissolution processes operate for uranium dioxide, as a chemical analogue of the spent fuel matrix, independently of the composition of the aqueous solution used. (orig.)

Simulation of Self-Irradiation of High-Sodium Content Nuclear Waste Glasses

International Nuclear Information System (INIS)

Pankov, Alexey S.; Ojovan, Michael I.; Batyukhnova, Olga G.; Lee, William E.

2007-01-01

Alkali-borosilicate glasses are widely used in nuclear industry as a matrix for immobilisation of hazardous radioactive wastes. Durability or corrosion resistance of these glasses is one of key parameters in waste storage and disposal safety. It is influenced by many factors such as composition of glass and surrounding media, temperature, time and so on. As these glasses contain radioactive elements most of their properties including corrosion resistance are also impacted by self-irradiation. The effect of external gamma-irradiation on the short-term (up to 27 days) dissolution of waste borosilicate glasses at moderate temperatures (30 deg. to 60 deg. C) was studied. The glasses studied were Magnox Waste glass used for immobilisation of HLW in UK, and K-26 glass used in Russia for ILW immobilisation. Glass samples were irradiated under γ-source (Co-60) up to doses 1 and 11 MGy. Normalised rates of elemental release and activation energy of release were measured for Na, Li, Ca, Mg, B, Si and Mo before and after irradiation. Irradiation up to 1 MGy results in increase of leaching rate of almost all elements from both MW and K-26 with the exception of Na release from MW glass. Further irradiation up to a dose of 11 MGy leads to the decrease of elemental release rates to nearly initial value. Another effect of irradiation is increase of activation energies of elemental release. (authors)

Improvement of the stability of hydroxyapatite through glass ceramic reinforcement.

Science.gov (United States)

Ha, Na Ra; Yang, Zheng Xun; Hwang, Kyu Hong; Kim, Tae Suk; Lee, Jong Kook

2010-05-01

Hydroxyapatite has achieved significant application in orthopedic and dental implants due to its excellent biocompatibility. Sintered hydroxyapatites showed significant dissolution, however, after their immersion in water or simulated body fluid (SBF). This grain boundary dissolution, even in pure hydroxyapatites, resulted in grain separation at the surfaces, and finally, in fracture. In this study, hydroxyapatite ceramics containing apatite-wollastonite (AW) or calcium silicate (SG) glass ceramics as additives were prepared to prevent the dissolution. AW and SG glass ceramics were added at 0-7 wt% and powder-compacted uniaxially followed by firing at moisture conditions. The glass phase was incorporated into the hydroxyapatite to act as a sintering aid, followed by crystallization, to improve the mechanical properties without reducing the biocompatibility. As seen in the results of the dissolution test, a significant amount of damage was reduced even after more than 14 days. TEM and SEM showed no decomposition of HA to the secondary phase, and the fracture toughness increased, becoming even higher than that of the commercial hydroxyapatite.

The dissolution of chalcopyrite in chloride media

International Nuclear Information System (INIS)

Ibanez, T.; Velasquez, L.

2013-01-01

The aim of this investigation is to determinate the effects of parameters and additives on the kinetics of dissolution of chalcopyrite on moderated conditions by means of dissolutions test with chalcopyrite concentrate and pure chalcopyrite in shake flasks and instrumented stirred reactors. A study of the dissolution of chalcopyrite in chloride solutions has demonstrated that the rate of dissolution of chalcopyrite is strongly dependent on the potential of the solution within a range of 540 to 630 mV (versus SHE). Leaching at pH around 2.5 results in increased rates of copper dissolution suggesting the possibility to keep the solution potential within the range. Both pyrite and silver ions enhance the dissolution of chalcopyrite and this effect increases when both species are present. The MnO 2 has a negative effect on the dissolution increasing the solution potential to values where the rate decreases considerably. (Author)

Apatite formation on organic polymers by biomimetic process using Na2O-SiO2 glasses as nucleating agent

Energy Technology Data Exchange (ETDEWEB)

Tanahashi, M; Yao, t; Kokubo, T [Kyoto University, Kyoto (Japan). Faculty of Engineering; Minoda, M; Miyamoto, T [Kyoto University, Kyoto (Japan). Institute for Chemical Research; Nakamura, T [Kyoto University, Kyoto (Japan). Research Center for Biomedical Engineering; Yamamuro, T [Kyoto University, Kyoto (Japan). Faculty of Medicine

1994-09-01

In this investigation, CaO-SiO2-based glass, which was previously used as the nucleating agent, was replaced by Na2O-SiO2 glasses, SiO2 glass, and SiO2 gel. The induction period for the apatite nucleation on various organic polymer substrates and the adhesive strength of the apatite layer to the substrates were examined. It was considered that the short induction period for the glasses with high Na2O contents was attributed to high dissolution rates of sodium and silicate ions from them. It was also considered that highly polar carboxyl or sulfinyl groups were formed on the polymer surfaces by the hydrolysis of their ester, amide or sulfonyl group in simulated body fluid with its pH increased by the Na{sup +} dissolution from the glass, and that these polar groups formed a strong bond with the apatite. It is suggested that thus formed apatite-organic polymer composites are useful as the bone-repairing as well as soft tissue-repairing materials. 11 refs., 13 figs., 3 tabs.

Leach rate studies on glass containing actual radioactive waste

International Nuclear Information System (INIS)

Walker, D.D.; Wiley, J.R.; Dukes, M.D.; LeRoy, J.H.

1980-01-01

Borosilicate glass containing radioactive wastes from the Savannah River Plant have been leached for 900 days. The International Standards Organization's (ISO) static leach test procedure was used on glass buttons in various leachants. Leach rates based on 90 Sr and 137 Cs analyses were similar: 2 x 10 -8 to 3 x 10 -8 g/(cm 2 )(d) in distilled water, 1 x 10 -8 to 3 x 10 -7 g/(cm 2 )(d) in pH 7 buffer, 3 x 10 -7 to 7 x 10 -7 g/(cm 2 )(d) in pH 9 buffer, and 7 x 10 -6 to 8 x 10 -5 g/(cm 2 )(d) in pH 4 buffer. Rates based on Pu analyses were the same as above in distilled water and pH 9 buffer, but were lower by an order of magnitude in pH 4 and pH 7 buffers. Almost all leach rates remained constant between 200 and 900 days of leaching. Increasing the concentration of the buffering agents had no effect on the leach rates at pH 7 (phosphate) and pH 9 (carbonate), but dramatically increased the rates at pH 4 (acetate). Leach rates did not differ significantly between high aluminum and high iron waste glasses

Non-destructive prediction of enteric coating layer thickness and drug dissolution rate by near-infrared spectroscopy and X-ray computed tomography.

Science.gov (United States)

Ariyasu, Aoi; Hattori, Yusuke; Otsuka, Makoto

2017-06-15

The coating layer thickness of enteric-coated tablets is a key factor that determines the drug dissolution rate from the tablet. Near-infrared spectroscopy (NIRS) enables non-destructive and quick measurement of the coating layer thickness, and thus allows the investigation of the relation between enteric coating layer thickness and drug dissolution rate. Two marketed products of aspirin enteric-coated tablets were used in this study, and the correlation between the predicted coating layer thickness and the obtained drug dissolution rate was investigated. Our results showed correlation for one product; the drug dissolution rate decreased with the increase in enteric coating layer thickness, whereas, there was no correlation for the other product. Additional examination of the distribution of coating layer thickness by X-ray computed tomography (CT) showed homogenous distribution of coating layer thickness for the former product, whereas the latter product exhibited heterogeneous distribution within the tablet, as well as inconsistent trend in the thickness distribution between the tablets. It was suggested that this heterogeneity and inconsistent trend in layer thickness distribution contributed to the absence of correlation between the layer thickness of the face and side regions of the tablets, which resulted in the loss of correlation between the coating layer thickness and drug dissolution rate. Therefore, the predictability of drug dissolution rate from enteric-coated tablets depended on the homogeneity of the coating layer thickness. In addition, the importance of micro analysis, X-ray CT in this study, was suggested even if the macro analysis, NIRS in this study, are finally applied for the measurement. Copyright © 2017 Elsevier B.V. All rights reserved.

Improvement of dissolution rate of indomethacin by inkjet printing

DEFF Research Database (Denmark)

Wickström, Henrika; Palo, Mirja; Rijckaert, Karen

2015-01-01

The aim of this study was to prepare printable inks of the poorly water soluble drug indomethacin (IMC), fabricate printed systems with flexible doses and investigate the effect of ink excipients on the printability, dissolution rate and the solid state properties of the drug. A piezoelectric...... the spectra of the carrier substrate. Yet, the samples retained their yellow color after 6months of storage at room temperature and after drying at elevated temperature in a vacuum oven. This suggests that the samples remained either in a dissolved or an amorphous form. Based on the results from this study...... a formulation guidance for inkjet printing of poorly soluble drugs is also proposed....

Morphological evolution of dissolving feldspar particles with anisotropic surface kinetics and implications for dissolution rate normalization and grain size dependence: A kinetic modeling study

Science.gov (United States)

Zhang, Li; Lüttge, Andreas

2009-11-01

With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms ( Zhang and Lüttge, 2008, 2009), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si ( ΦSi-O-Si/ kT) and Al-(O)-Si ( ΦAl-O-Si/ kT). When the ratio of ΦSi-O-Si/ kT to ΦAl-O-Si/ kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive

Boron isotope fractionation in magma via crustal carbonate dissolution.

Science.gov (United States)

Deegan, Frances M; Troll, Valentin R; Whitehouse, Martin J; Jolis, Ester M; Freda, Carmela

2016-08-04

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

Boron isotope fractionation in magma via crustal carbonate dissolution

Science.gov (United States)

Deegan, Frances M.; Troll, Valentin R.; Whitehouse, Martin J.; Jolis, Ester M.; Freda, Carmela

2016-08-01

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to -41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

The dissolution rate constant of magnetite in water at different temperatures and neutral or ammoniated chemistry conditions

International Nuclear Information System (INIS)

Mohajery, K.; Lister, D.H.

2012-01-01

In this study, the dissolution rate constants of magnetite were measured at various water chemistry conditions and different temperatures, corresponding to several feedwater conditions of water-cooled reactors. Sintered magnetite pellets were used as the dissolving material and these were mounted in a jet-impingement apparatus in a recirculating water loop. Exposures were carried out at temperatures of 25, 55 and 140 o C and pHs of neutral and 9.2 in which many FAC (Flow Accelerated Corrosion) studies have been conducted. Average dissolution rate constants were estimated by measuring the volume of lost material with a profilometry technique. The excellent correspondent between the calculated value of dissolution rate constant of 2.20 mm/s for the synthesized magnetite and 2.05 mm/s for the single crystal of magnetite at neutral condition shows that the particle removal from the synthesized pellets is not an obstruction in this technique. Also, good agreement between the values calculated in duplicated runs at neutral condition at room temperature supports the accuracy of the method. (author)

Bioactivity of gel-glass powders in the CaO-SiO2 system: a comparison with ternary (CaO-P2O5-SiO2) and quaternary glasses (SiO2-CaO-P2O5-Na2O).

Science.gov (United States)

Saravanapavan, Priya; Jones, Julian R; Pryce, Russell S; Hench, Larry L

2003-07-01

Bioactive glasses react chemically with body fluids in a manner that is compatible with the repair processes of the tissues. This results in the formation of an interfacial bond between the glasses and living tissue. Bioactive glasses also stimulate bone-cell proliferation. This behavior is dependent on the chemical composition as well as the surface texture of the glasses. It has been recently reported that gel-derived monolith specimens in the binary SiO2 - CaO are bioactive over a similar molar range of SiO2 content as the previously studied ternary CaO-P2O5-SiO2 system. In this report, the preparation and bioactivity of the binary gel-glass powder with 70 mol % SiO2 is discussed and its bioactivity is compared with the melt-derived 45S5 (quaternary) Bioglass and sol-gel-derived 58S (ternary) bioactive gel-glass compositions. Dissolution kinetic parameters K(1) and K(2) were also computed based on the silicon release for all glass powders. It was shown that the simple two-component SiO2-CaO gel-glass powder is bioactive with comparable dissolution rates as the clinically used melt-derived 45S5 Bioglass powder and extensively studied sol-gel-derived 58S gel-glass powder. Copyright 2003 Wiley Periodicals, Inc.

Engineering Glass Passivation Layers -Model Results

Energy Technology Data Exchange (ETDEWEB)

Skorski, Daniel C.; Ryan, Joseph V.; Strachan, Denis M.; Lepry, William C.

2011-08-08

The immobilization of radioactive waste into glass waste forms is a baseline process of nuclear waste management not only in the United States, but worldwide. The rate of radionuclide release from these glasses is a critical measure of the quality of the waste form. Over long-term tests and using extrapolations of ancient analogues, it has been shown that well designed glasses exhibit a dissolution rate that quickly decreases to a slow residual rate for the lifetime of the glass. The mechanistic cause of this decreased corrosion rate is a subject of debate, with one of the major theories suggesting that the decrease is caused by the formation of corrosion products in such a manner as to present a diffusion barrier on the surface of the glass. Although there is much evidence of this type of mechanism, there has been no attempt to engineer the effect to maximize the passivating qualities of the corrosion products. This study represents the first attempt to engineer the creation of passivating phases on the surface of glasses. Our approach utilizes interactions between the dissolving glass and elements from the disposal environment to create impermeable capping layers. By drawing from other corrosion studies in areas where passivation layers have been successfully engineered to protect the bulk material, we present here a report on mineral phases that are likely have a morphological tendency to encrust the surface of the glass. Our modeling has focused on using the AFCI glass system in a carbonate, sulfate, and phosphate rich environment. We evaluate the minerals predicted to form to determine the likelihood of the formation of a protective layer on the surface of the glass. We have also modeled individual ions in solutions vs. pH and the addition of aluminum and silicon. These results allow us to understand the pH and ion concentration dependence of mineral formation. We have determined that iron minerals are likely to form a complete incrustation layer and we plan

Solid dispersions, part II: new strategies in manufacturing methods for dissolution rate enhancement of poorly water-soluble drugs.

Science.gov (United States)

Bikiaris, Dimitrios N

2011-12-01

The absorption of poorly water-soluble drugs, when presented in the crystalline state to the gastrointestinal tract, is typically dissolution rate-limited, and according to BCS these drugs belong mainly to class II. Both dissolution kinetics and solubility are particle size dependent. Nowadays, various techniques are available to the pharmaceutical industry for dissolution rate enhancement of such drugs. Among such techniques, nanosuspensions and drug formulation in solid dispersions are those with the highest interest. This review discusses strategies undertaken over the last 10 years, which have been applied for the dissolution enhancement of poorly water-soluble drugs; such processes include melt mixing, electrospinning, microwave irradiation and the use of inorganic nanoparticles. Many problems in this field still need to be solved, mainly the use of toxic solvents, and for this reason the use of innovative new procedures and materials will increase over the coming years. Melt mixing remains extremely promising for the preparation of SDs and will probably become the most used method in the future for the preparation of solid drug dispersions.

Dissolution of uranium oxide TBP-HNO3 complex

International Nuclear Information System (INIS)

Mizuno, Mineo; Kosaka, Yuji; Mori, Yukihide; Shimada, Takashi

2002-12-01

As a head end process for the pulverization of the spent fuel, the mechanical method (the shredder method) and the pyro-chemical method (oxidisation heat-treatment) have been examined. UO 2 is a main ingredient of Uranium oxide powder by the mechanical method, and U 3 O 8 is that by the pyro-chemical method. Moreover, the particle size of the pulverized powder depend on the conditions of the pulverizing process. As it was considered that the difference of dissolution rates of samples was caused by the difference of sample chemical forms and dissolution temperature, parametric surveys on chemical form and particle size of powder and dissolution temperature were carried out, and the following results were obtained. 1) The remarkable difference of dissolution rate between U 3 O 8 powder (average particle size 3.7 μm) and UO 2 powder (average particle size 2.4 μm) which have comparatively similar particle size was not observed. 2) It was confirmed that the dissolution rate became lower according to the particle size increase (average particle size 2.4 μm-1 mm). And it was considered that dissolution rate had strong dependency on particle size, according to the results that the powder with 1 mm particle size did not dissolute completely after 5 hours test. 3) The temperature dependency of the dissolution rate was confirmed by dissolution test with UO 2 powder (average particle size 2.4 μm-1 mm). The higher dissolution rate was obtained in the higher dissolution temperature, and 11 kcal/mol was obtained as activation energy of dissolution. 4) In the dissolution test of UO 2 powder, the nitric acid concentration started to change earlier than that of U 3 O 8 powder and concentration change range became larger compared with that in the dissolution test of U 3 O 8 powder. It was considered that those differences were caused by difference in mole ratio of Uranium and nitric acid which are consumed in the dissolution reaction (3:7 for U 3 O 8 , 3:8 for UO 2 ). 5) In case

Natural analogues of nuclear waste glass corrosion

International Nuclear Information System (INIS)

Abrajano, T.A. Jr.; Ebert, W.L.; Luo, J.S.

1999-01-01

This report reviews and summarizes studies performed to characterize the products and processes involved in the corrosion of natural glasses. Studies are also reviewed and evaluated on how well the corrosion of natural glasses in natural environments serves as an analogue for the corrosion of high-level radioactive waste glasses in an engineered geologic disposal system. A wide range of natural and experimental corrosion studies has been performed on three major groups of natural glasses: tektite, obsidian, and basalt. Studies of the corrosion of natural glass attempt to characterize both the nature of alteration products and the reaction kinetics. Information available on natural glass was then compared to corresponding information on the corrosion of nuclear waste glasses, specifically to resolve two key questions: (1) whether one or more natural glasses behave similarly to nuclear waste glasses in laboratory tests, and (2) how these similarities can be used to support projections of the long-term corrosion of nuclear waste glasses. The corrosion behavior of basaltic glasses was most similar to that of nuclear waste glasses, but the corrosion of tektite and obsidian glasses involves certain processes that also occur during the corrosion of nuclear waste glasses. The reactions and processes that control basalt glass dissolution are similar to those that are important in nuclear waste glass dissolution. The key reaction of the overall corrosion mechanism is network hydrolysis, which eventually breaks down the glass network structure that remains after the initial ion-exchange and diffusion processes. This review also highlights some unresolved issues related to the application of an analogue approach to predicting long-term behavior of nuclear waste glass corrosion, such as discrepancies between experimental and field-based estimates of kinetic parameters for basaltic glasses

Natural analogues of nuclear waste glass corrosion.

Energy Technology Data Exchange (ETDEWEB)

Abrajano, T.A. Jr.; Ebert, W.L.; Luo, J.S.

1999-01-06

This report reviews and summarizes studies performed to characterize the products and processes involved in the corrosion of natural glasses. Studies are also reviewed and evaluated on how well the corrosion of natural glasses in natural environments serves as an analogue for the corrosion of high-level radioactive waste glasses in an engineered geologic disposal system. A wide range of natural and experimental corrosion studies has been performed on three major groups of natural glasses: tektite, obsidian, and basalt. Studies of the corrosion of natural glass attempt to characterize both the nature of alteration products and the reaction kinetics. Information available on natural glass was then compared to corresponding information on the corrosion of nuclear waste glasses, specifically to resolve two key questions: (1) whether one or more natural glasses behave similarly to nuclear waste glasses in laboratory tests, and (2) how these similarities can be used to support projections of the long-term corrosion of nuclear waste glasses. The corrosion behavior of basaltic glasses was most similar to that of nuclear waste glasses, but the corrosion of tektite and obsidian glasses involves certain processes that also occur during the corrosion of nuclear waste glasses. The reactions and processes that control basalt glass dissolution are similar to those that are important in nuclear waste glass dissolution. The key reaction of the overall corrosion mechanism is network hydrolysis, which eventually breaks down the glass network structure that remains after the initial ion-exchange and diffusion processes. This review also highlights some unresolved issues related to the application of an analogue approach to predicting long-term behavior of nuclear waste glass corrosion, such as discrepancies between experimental and field-based estimates of kinetic parameters for basaltic glasses.

The Influence of Na and Ti on the In Vitro Degradation and Bioactivity in 58S Sol-Gel Bioactive Glass

Directory of Open Access Journals (Sweden)

Shirong Ni

2012-01-01

Full Text Available The aim of this study was to investigate the effect of Na and Ti on the in vitro degradation and bioactivity in the 58S bioactive glass. The degradation was evaluated through the activation energy of Si ion release from bioactive glasses and the weight loss of bioactive glasses in Tris-HCl buffer solution. The in vitro bioactivity of the bioactive glasses was investigated by analysis of apatite-formation ability in the simulated body fluid (SBF. The results showed that Na in the 58S glass accelerated the dissolution rate of the glass, whereas Ti in the 58S glass slowed down the rate of glass solubility. Bioactivity tests showed that Na in glass increased the apatite-forming ability in SBF. In contrast, Ti in glass retards the apatite formation at the initial stage of SBF soaking but does not affect the growth of apatite after long periods of soaking.

Dissolution of aluminium; Disolucion de aluminio

Energy Technology Data Exchange (ETDEWEB)

Uriarte Hueda, A; Berberana Eizmendi, M; Pereira Sanchez, G

1968-07-01

The dissolution of aluminum with acid solutions ( nitric acid-mercuric nitrate) and alkaline solutions (sodium hydroxide-sodium nitrate) has been studied. The instantaneous dissolution rate (IDR) has been studied in function of the concentration of the used reagents and the dissolution temperature. The complete dissolution has been included in the second part of this report, to know the total dissolution time, the consume of reagents and the stability of the resultant solutions. (Author)

Structural and thermochemical properties of sodium magnesium phosphate glasses

Energy Technology Data Exchange (ETDEWEB)

Oueslati Omrani, Refka [Université de Tunis El Manar, Faculté des Sciences de Tunis, Chemistry Department, LR01SE10 Applied Thermodynamics Laboratory, 2092 Tunis (Tunisia); Kaoutar, Abdeltif; El Jazouli, Abdelaziz [LCMS, URAC 17, Faculté des Sciences Ben M’Sik, UH2MC, Casablanca (Morocco); Krimi, Saida [LPCMI, Faculté des Sciences Aïn Chok, UH2C, Casablanca (Morocco); Khattech, Ismail, E-mail: ismail.khattech@fst.rnu.tn [Université de Tunis El Manar, Faculté des Sciences de Tunis, Chemistry Department, LR01SE10 Applied Thermodynamics Laboratory, 2092 Tunis (Tunisia); Jemal, Mohamed [Université de Tunis El Manar, Faculté des Sciences de Tunis, Chemistry Department, LR01SE10 Applied Thermodynamics Laboratory, 2092 Tunis (Tunisia); Videau, Jean-Jacques [ICMCB, Institut de Chimie de la matière condensée, Université de Bordeaux 1 (France); Couzi, Michel [Institut des Sciences Moléculaires, CNRS-Université de Bordeaux 1 (France)

2015-05-25

Highlights: • Phosphate glasses were prepared by met quenching technique. • Structural study is investigated using FTIR, Raman and {sup 31}PNMR spectroscopy. • A 4.5% weight of H{sub 3}PO{sub 4} solution has use for glass dissolution. • Dissolution is endothermic for lower MgO content and becomes exothermic when x rises. - Abstract: Ternary phosphate based glasses with the general formula (50−x/2)Na{sub 2}O–xMgO–(50−x/2)P{sub 2}O{sub 5} (0 ⩽ x ⩽ 42.8 mol%), where the O/P ratio was varied from 3 to 3.75, have been prepared using a conventional melt quenching technique. Samples were investigated by means of density measurements, Fourier-transformed infrared (FTIR), Raman and {sup 31}P solid state magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopies, differential scanning calorimetry (DSC), inductively coupled plasma atomic emission spectroscopy (ICP/AES) analysis and calorimetric dissolution. The depolymerization of metaphosphate chains are described by the decrease of Q{sup 2} tetrahedral sites allowing the formation of pyrophosphate groups (Q{sup 1}) revealed by spectroscopic investigations. As a result, the increase of density and glass transition temperature when x rises. Calorimetric study shows that the dissolution phenomenon is endothermic for a lower MgO content and becomes exothermic when magnesium oxide is gradually incorporated, suggesting the disruption of phosphate chains with increasing O/P ratio.

Energy absorption at high strain rate of glass fiber reinforced mortars

Directory of Open Access Journals (Sweden)

Fenu Luigi

2015-01-01

Full Text Available In this paper, the dynamic behaviour of cement mortars reinforced with glass fibers was studied. The influence of the addition of glass fibers on energy absorption and tensile strength at high strain-rate was investigated. Static tests in compression, in tension and in bending were first performed. Dynamic tests by means of a Modified Hopkinson Bar were then carried out in order to investigate how glass fibers affected energy absorption and tensile strength at high strain-rate of the fiber reinforced mortar. The Dynamic Increase Factor (DIF was finally evaluated.

Corrosion of K-3 glass-contact refractory in sodium-rich aluminosilicate melts

International Nuclear Information System (INIS)

Lu, X.D.; Gan, H.; Buechele, A.C.; Pegg, I.L.

1999-01-01

The corrosion of the glass-contact refractory Monofrax K-3 in two sodium-rich aluminosilicate melts has been studied at 1,208 and 1,283 C using a modified ASTM procedure with constant agitation of the melt by air bubbling. The results for the monolithic refractory indicate a fast initial stage involving phase dissolution and transformation and a later passivated stage in which the surface of the refractory has been substantially modified. The composition of the stable spinel phase in the altered layer on monolithic coupons of K-3 is almost identical to the equilibrium composition bracketed by the dissolution of powdered K-3 into under-saturated melts on the other. The temperature and melt shear viscosity were found to have significant effects on the rates of K-3 dissolution and transformation

The incorporation of technetium into a representative low-activity waste glass

International Nuclear Information System (INIS)

Ebert, W.L.; Bakel, A.J.; Bowers, D.L.; Buck, E.C.; Emery, J.W.

1997-01-01

A glass that has been tested to understand the corrosion behavior of waste glasses with high soda contents for immobilizing Hanford incidental wastes has been made by melting crushed glass with either TcO 2 or NaTcO 4 at 1,100--1,300 C. Incorporation of technetium in the glass was affected by solubility or kinetic effects. Metallic technetium inclusions formed in all the TcO 2 -doped glasses. Inclusions also formed in glasses with added NaTcO 4 that were melted at 1,100 C, but a glass melted at 1,200 C did not contain detectable inclusions. The presence of Tc-bearing inclusions complicates the interpretation of results from dissolution tests because of the simultaneous release of technetium from more than one phase, the unknown surface areas of each phase, and the possible incorporation of technetium that is released from one phase into another phase. A glass containing about 0.15 mass % Tc dissolved in the glass is being used in dissolution tests to study the release behavior of technetium

Experimental investigation of aqueous corrosion of R7T7 nuclear glass at 90 degrees C in the presence of humic acids: A kinetic approach

International Nuclear Information System (INIS)

Gin, S.; Godon, N.; Mestre, J.P.; Vernaz, E.Y.; Beaufort, D.

1994-01-01

The dissolution kinetics of the French open-quotes R7T7close quotes nonradioactive LWR reference glass in solutions containing dissolved humic acids were investigated at 9O degrees C during static tests with imposed or free pH. Experiments conducted in highly dilute media, with a glass-surface-area-to-solution-volume (SA/V) ratio of 5 m -1 , showed that the glass dissolution surface reaction is catalyzed by humic acids. With higher degrees of reaction progress (SA/V = 100 m -1 and free pH) the humic acids impose pH modifications on the system compared with inorganic media; moreover, they directly or indirectly enhance the dissolution of certain alkali metals and transition elements, forming aqueous complexes with the latter. During experiments with an imposed pH of 8.5 (SA/V = 1300 and 5300 m -1 ), the humic acids appear to cause increased silica solubility that cannot be accounted for by the formation of silica complexes. A residual corrosion rate in the humic acid media exceeding the rate measured in inorganic media suggests that, in addition to silica, one or more element complexes formed by humic acids may be a kinetically limiting factor. This hypothesis must be confirmed, however, as the quantity of humic acids per unit glass surface area was too small in this experiment to allow unambiguous characterization of the phenomenon

In vitro Dissolution Studies on Solid Dispersions of Mefenamic Acid.

Science.gov (United States)

Rao, K R S Sambasiva; Nagabhushanam, M V; Chowdary, K P R

2011-03-01

Solid dispersions of mefanamic acid with a water-soluble polymer polyvinyl pyrrolidine and a super disintegrant, primojel were prepared by common solvent and solvent evaporation methods employing methanol as the solvent. The dissolution rate and dissolution efficiency of the prepared solid dispersions were evaluated in comparison to the corresponding pure drug. Solid dispersions of mefenamic acid showed a marked enhancement in dissolution rate and dissolution efficiency. At 1:4 ratio of mefenamic acid-primojel a 2.61 fold increase in the dissolution rate of mefenamic acid was observed with solid dispersion. The solid dispersions in combined carriers gave much higher rates of dissolution than super disintegrants alone. Mefanamic acid-primojel-polyvinyl pyrrolidine (1:3.2:0.8) solid dispersion gave a 4.11 fold increase in the dissolution rate of mefenamic acid. Super disintegrants alone or in combination with polyvinyl pyrrolidine could be used to enhance the dissolution rate of mefenamic acid.

Disintegration rate and properties of active pharmaceutical ingredient particles as determined from the dissolution time profile of a pharmaceutical formulation: an inverse problem.

Science.gov (United States)

Horkovics-Kovats, Stefan

2014-02-01

Dissolution profile of a finished dosage form (FDF) contains hidden information regarding the disintegration of the form and the particle properties of the active pharmaceutical ingredient. Here, an extraction of this information from the dissolution profile without limitation to sink conditions is provided. In the article, mathematical relationships between the continuously measured dissolution profile of an FDF containing uniform or heterogeneous particles and its disintegration rate are developed. Further, the determinability of the disintegration kinetics and particle properties released from an FDF using the derived recurrent procedure was analyzed. On the basis of the theoretical data sets, it was demonstrated that the introduced analysis of dissolution profiles correctly identifies the disintegration rate of FDF containing multiple particle types. Furthermore, for known disintegration rates, the intrinsic lifetime of particles (time needed for total particle dissolution in infinite volume) released from the FDF and their relative amount can be determined. The extractable information from FDF dissolution time profiles can be utilized in designing of the formulation process, resulting in improved understanding of FDF properties, contributing thus to the implementation of quality by design in the FDF development. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Lyoluminescence of irradiated carbohydrates - the role of dissolution rate and oxygen

International Nuclear Information System (INIS)

Baugh, P.J.; Laflin, P.

1980-01-01

The lyoluminescent emission from γ-irradiated carbohydrates is shown to be strictly controlled by the rate of dissolution of the solid and the availability of oxygen for reaction during dissolution. These effects are explained in terms of oxidation of trapped radicals diffusing from the dissolving carbohydrate which react in an 'active volume' set up at the onset of dissolution at the crystal-water interface. At irradiation doses greater than 82.5 krad for mannose there is a suppression of the emission which results from an incomplete oxidation of the diffusing radicals due to insufficient O 2 in the active volume leading to a reaction involving unoxidised radicals and peroxyl radicals which are believed to be the precursors of the emission. This reaction is suppressed when the oxygen supply to the 'active volume' is increased. This can be achieved by increasing the oxygen content of the injector gas and indirectly by decreasing the solubility of the carbohydrate. Under these conditions the linear dose range of the lyoluminescence response is extended to ca. 330 krad close to the dose at which trapped radicals saturate in the irradiated solid carbohydrate. Although lyoluminescence is a liquid surface-layer effect as expected the generation of the emission is greatly influenced by oxygen present in the injection atmosphere. Quenching of lyoluminescence by adding peroxyl radical quenchers Cu(II) ions and hydroquinone, suggests that the reaction involving these quenchers also occurs in the 'active volume'. The results generally can be interpreted in terms of a diffusion model. (author)

Glasses for the solidification of high-level radioactive waste: their behavior in the presence of water

International Nuclear Information System (INIS)

Grauer, R.

1983-02-01

Because of their amorphous structure, glasses are particularly suitable for the solidification of the mixture of high-level radioactive wastes resulting from reactor fuel reprocessing: they are not sensitive to variations in the compositions of waste oxides and are resistant to the damaging effects of radiation. The borosilicate glasses used for this purpose have been investigated for about 25 years, and waste vitrification techniques have been tested on a commercial scale. In view of possible accidents in a final waste repository, the chemical resistance of this type of glasses to attack by groundwaters is of special interest. The present report deals with the corrosion behaviour of glasses and discusses the most significant controlling parameters. The dissolution rates needed for safety analysis must be determined in relatively short-term experiments. Since the results can depend strongly on the type of test procedures used, a critical assessment of these techniques is necessary. Experimental results are illustrated by means of selected examples. Particular emphasis is placed upon the effects of increased temperatures and of nuclear radiation. The models which have been proposed for the estimation of the long-term behavior of vitrified waste are not yet fully complete and require improvement. Furthermore, the actual dissolution rates which are used in such models should be revised: to be desired are values which take into account the actual environmental conditions at the storage site. It should be noted, however, that even with current conservative input data on corrosion rates, a lifetime on the order of 10 5 years can be expected for the glass blocks to be deposited. The report concludes with recommendations fo further investigations

Effects of network dissolution changes on pore-to-core upscaled reaction rates for kaolinite and anorthite reactions under acidic conditions

KAUST Repository

Kim, Daesang

2013-11-01

We have extended reactive flow simulation in pore-network models to include geometric changes in the medium from dissolution effects. These effects include changes in pore volume and reactive surface area, as well as topological changes that open new connections. The computed changes were based upon a mineral map from an X-ray computed tomography image of a sandstone core. We studied the effect of these changes on upscaled (pore-scale to core-scale) reaction rates and compared against the predictions of a continuum model. Specifically, we modeled anorthite and kaolinite reactions under acidic flow conditions during which the anorthite reactions remain far from equilibrium (dissolution only), while the kaolinite reactions can be near-equilibrium. Under dissolution changes, core-scale reaction rates continuously and nonlinearly evolved in time. At higher injection rates, agreement with predictions of the continuum model degraded significantly. For the far-from-equilibrium reaction, our results indicate that the ability to correctly capture the heterogeneity in dissolution changes in the reactive mineral surface area is critical to accurately predict upscaled reaction rates. For the near-equilibrium reaction, the ability to correctly capture the heterogeneity in the saturation state remains critical. Inclusion of a Nernst-Planck term to ensure neutral ionic currents under differential diffusion resulted in at most a 9% correction in upscaled rates.

Oxidation and dissolution of UO{sub 2} in bicarbonate media: Implications for the spent nuclear fuel oxidative dissolution mechanism

Energy Technology Data Exchange (ETDEWEB)

Gimenez, J. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain)]. E-mail: francisco.javier.gimenez@upc.edu; Clarens, F. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Casas, I. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Rovira, M. [CTM Centre Tecnologic, Avda. Bases de Manresa 1. 08240 Manresa (Spain); Pablo, J. de [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Bruno, J. [Enresa-Enviros Environmental Science and Waste Management Chair, UPC, Jordi Girona 1-3 B2, 08034 Barcelona (Spain)

2005-10-15

The objective of this work is to study the UO{sub 2} oxidation by O{sub 2} and dissolution in bicarbonate media and to extrapolate the results obtained to improve the knowledge of the oxidative dissolution of spent nuclear fuel. The results obtained show that in the studied range the oxygen consumption rate is independent on the bicarbonate concentration while the UO{sub 2} dissolution rate does depend on. Besides, at 10{sup -4} mol dm{sup -3} bicarbonate concentration, the oxygen consumption rate is almost two orders of magnitude higher than the UO{sub 2} dissolution rate. These results suggest that at low bicarbonate concentration (<10{sup -2} mol dm{sup -3}) the alteration of the spent nuclear fuel cannot be directly derived from the measured uranium concentrations in solution. On the other hand, the study at low bicarbonate concentrations of the evolution of the UO{sub 2} surface at nanometric scale by means of the SFM technique shows that the difference between oxidation and dissolution rates is not due to the precipitation of a secondary solid phase on UO{sub 2}.

Optimization of Dissolution Compartments in a Biorelevant Dissolution Apparatus Golem v2, Supported by Multivariate Analysis

Directory of Open Access Journals (Sweden)

Ivan Stupák

2017-11-01

Full Text Available Biorelevant dissolution instruments represent an important tool for pharmaceutical research and development. These instruments are designed to simulate the dissolution of drug formulations in conditions most closely mimicking the gastrointestinal tract. In this work, we focused on the optimization of dissolution compartments/vessels for an updated version of the biorelevant dissolution apparatus—Golem v2. We designed eight compartments of uniform size but different inner geometry. The dissolution performance of the compartments was tested using immediate release caffeine tablets and evaluated by standard statistical methods and principal component analysis. Based on two phases of dissolution testing (using 250 and 100 mL of dissolution medium, we selected two compartment types yielding the highest measurement reproducibility. We also confirmed a statistically ssignificant effect of agitation rate and dissolution volume on the extent of drug dissolved and measurement reproducibility.

Effect of Feed Melting, Temperature History and Minor Component Addition on Spinel Crystallization in High-Level Waste Glass

International Nuclear Information System (INIS)

Izak, Pavel; Hrma, Pavel R.; Arey, Bruce W.; Plaisted, Trevor J.

2001-01-01

This study was undertaken to help design mathematical models for high-level waste (HLW) glass melter that simulate spinel behavior in molten glass. Spinel, (Fe,Ni,Mn) (Fe,Cr)2O4, is the primary solid phase that precipitates from HLW glasses containing Fe and Ni in sufficient concentrations. Spinel crystallization affects the anticipated cost and risk of HLW vitrification. To study melting reactions, we used simulated HLW feed, prepared with co-precipitated Fe, Ni, Cr, and Mn hydroxides. Feed samples were heated up at a temperature-increase rate (4C/min) close to that which the feed experiences in the HLW glass melter. The decomposition, melting, and dissolution of feed components (such as nitrates, carbonates, and silica) and the formation of intermediate crystalline phases (spinel, sodalite (Na8(AlSiO4)6(NO2)2), and Zr-containing minerals) were characterized using evolved gas analysis, volume-expansion measurement, optical microscope, scanning electron microscope, thermogravimetric analysis, differential scanning calorimetry, and X-ray diffraction. Nitrates and quartz, the major feed components, converted to a glass-forming melt by 880C. A chromium-free spinel formed in the nitrate melt starting from 520C and Sodalite, a transient product of corundum dissolution, appeared above 600C and eventually dissolved in glass. To investigate the effects of temperature history and minor components (Ru,Ag, and Cu) on the dissolution and growth of spinel crystals, samples were heated up to temperatures above liquidus temperature (TL), then subjected to different temperature histories, and analyzed. The results show that spinel mass fraction, crystals composition, and crystal size depend on the chemical and physical makeup of the feed and temperature history

Growth of hydrated gel layers in nuclear waste glasses

International Nuclear Information System (INIS)

Sullivan, T.M.; Machiels, A.J.

1984-01-01

The hydration kinetics of waste glasses in contact with an aqueous solution has been studied by using three different approaches. Emphasis has been placed on modeling processes in the transition zone defined as the region in which the nature of the glass changes from the original dry glass to an open hydrated structure. The first model relies on concentration-dependent diffusion coefficients to obtain a transition zone in which the ions mobility is extremely low compared to that in the gel layer. In the second model, the transition zone and hydrated layer are treated as distinct phases and it is assumed that ion exchange at their common boundary is the rate-controlling process. The third model treats the transition zone as a thin film of constant thickness and low diffusivity. In the absence of appreciable network dissolution, all three models indicate that growth of the gel layer becomes eventually proportional to the square root of time; however, as long as processes in the transition zone are rate controlling, growth is linearly proportional to time

Durability of Silicate Glasses: An Historical Approach

International Nuclear Information System (INIS)

Farges, Francois; Etcheverry, Marie-Pierre; Haddi, Amine; Trocellier, Patrick; Curti, Enzo; Brown, Gordon E. Jr.

2007-01-01

We present a short review of current theories of glass weathering, including glass dissolution, and hydrolysis of nuclear waste glasses, and leaching of historical glasses from an XAFS perspective. The results of various laboratory leaching experiments at different timescales (30 days to 12 years) are compared with results for historical glasses that were weathered by atmospheric gases and soil waters over 500 to 3000 years. Good agreement is found between laboratory experiments and slowly leached historical glasses, with a strong enrichment of metals at the water/gel interface. Depending on the nature of the transition elements originally dissolved in the melt, increasing elemental distributions are expected to increase with time for a given glass durability context

Durability of Silicate Glasses: An Historical Approach

Energy Technology Data Exchange (ETDEWEB)

Farges, Francois; /Museum Natl. Hist. Natur. /Stanford U., Geo. Environ. Sci.; Etcheverry, Marie-Pierre; /Marne la Vallee U.; Haddi, Amine; /Marne la Valle U.; Trocellier,; /Saclay; Curti, Enzo; /PSI, Villigen; Brown, Gordon E., Jr.; /SLAC, SSRL

2007-01-02

We present a short review of current theories of glass weathering, including glass dissolution, and hydrolysis of nuclear waste glasses, and leaching of historical glasses from an XAFS perspective. The results of various laboratory leaching experiments at different timescales (30 days to 12 years) are compared with results for historical glasses that were weathered by atmospheric gases and soil waters over 500 to 3000 years. Good agreement is found between laboratory experiments and slowly leached historical glasses, with a strong enrichment of metals at the water/gel interface. Depending on the nature of the transition elements originally dissolved in the melt, increasing elemental distributions are expected to increase with time for a given glass durability context.

Dissolution behaviour of silicon nitride coatings for joint replacements

Energy Technology Data Exchange (ETDEWEB)

Pettersson, Maria [Materials in Medicine Group, Div. of Applied Materials Science, Dept. of Engineering Sciences, Uppsala University, Uppsala (Sweden); Bryant, Michael [Institute of Functional Surfaces (iFS), School of Mechanical Engineering, University of Leeds, Leeds (United Kingdom); Schmidt, Susann [Thin Film Physics, Department of Physics, Chemistry and Biology (IFM), Linköping University, Linköping (Sweden); Engqvist, Håkan [Materials in Medicine Group, Div. of Applied Materials Science, Dept. of Engineering Sciences, Uppsala University, Uppsala (Sweden); Hall, Richard M. [Institute of Medical and Biological Engineering (iMBE), School of Mechanical Engineering, University of Leeds, Leeds (United Kingdom); Neville, Anne [Institute of Functional Surfaces (iFS), School of Mechanical Engineering, University of Leeds, Leeds (United Kingdom); Persson, Cecilia, E-mail: cecilia.persson@angstrom.uu.se [Materials in Medicine Group, Div. of Applied Materials Science, Dept. of Engineering Sciences, Uppsala University, Uppsala (Sweden)

2016-05-01

In this study, the dissolution rate of SiN{sub x} coatings was investigated as a function of coating composition, in comparison to a cobalt chromium molybdenum alloy (CoCrMo) reference. SiN{sub x} coatings with N/Si ratios of 0.3, 0.8 and 1.1 were investigated. Electrochemical measurements were complemented with solution (inductively coupled plasma techniques) and surface analysis (vertical scanning interferometry and x-ray photoelectron spectroscopy). The dissolution rate of the SiN{sub x} coatings was evaluated to 0.2–1.4 nm/day, with a trend of lower dissolution rate with higher N/Si atomic ratio in the coating. The dissolution rates of the coatings were similar to or lower than that of CoCrMo (0.7–1.2 nm/day). The highest nitrogen containing coating showed mainly Si–N bonds in the bulk as well as at the surface and in the dissolution area. The lower nitrogen containing coatings showed Si–N and/or Si–Si bonds in the bulk and an increased formation of Si–O bonds at the surface as well as in the dissolution area. The SiN{sub x} coatings reduced the metal ion release from the substrate. The possibility to tune the dissolution rate and the ability to prevent release of metal ions encourage further studies on SiN{sub x} coatings for joint replacements. - Graphical abstract: Dissolution rates of SiN{sub 0.3}, SiN{sub 0.8}, and SiN{sub 1.1} coatings on CoCrMo compared to uncoated CoCrMo. Dissolution rates were obtained from i) electrochemical measurements of I{sub corr}, ii) the step height between covered and solution-exposed surfaces, measured using VSI, and iii) the ion concentration in the solution, measured with ICP. - Highlights: • The dissolution of SiN{sub x} coatings was investigated in comparison to (bulk) CoCrMo. • The coatings gave a lower or similar dissolution rate to CoCrMo, of 0.2–1.2 nm/day. • An increased nitrogen content in the coatings gave lower dissolution rates. • SiN{sub x} coatings on CoCrMo reduced the metal ion release

Corrosion rate of nuclear glass in saturated media

International Nuclear Information System (INIS)

Fillet, S.; Vernaz, E.; Nogues, J.L.; Jacquet-Francillon, N.

1986-01-01

Leaching experiments under a static mode have shown that, after a given time, the concentration of the solubilized elements reaches an apparent steady state which can be detected by a plateau in the curve of cumulated leach rates vs time. Since the real slope of this plateau is a key datum to modernize the source term, works related to the evaluation of this slope and based on a statistical approach have been necessary. Twelve static leaching experiments carried out for one year at 90 0 C were scrutinized. Various glasses, both active and nonactive, akin to the LWR French reference glass were involved. Previously, an abnormally high corrosion rate had been found after 12 months of testing. This feature could have been interpreted as a further leaching step occuring after the plateau period. The corrosion rates at 90 0 C with deionized water are compared to those gained from integral tests at 90 0 C

Low leach rate glasses for immobilization of nuclear wastes

International Nuclear Information System (INIS)

Chick, L.A.; Buckwalter, C.Q.

1980-10-01

Improved defense and commercial waste glass have about one order of magnitude lower leach rates at 90 0 C in static deionized water than reference glasses. This durability difference diminishes as the leaching temperature is raised, but at repository temperature less than 150 0 C, the improved compositions would have considerable advantages over reference glases. At the melting temperatures necessary for most of the high-durability glasses, volatility was found to be higher than that experienced in processing current reference glases. Higher volatilities might be compensated for by specific design of the off-gas system for improved off-gas treatment and volatile materials recovery. 6 figures, 2 tables

Relationship between reaction layer thickness and leach rate for nuclear waste glasses

International Nuclear Information System (INIS)

Chick, L.A.; Pederson, L.R.

1984-02-01

Three leaching tests, devised to distinguish among several proposed nuclear waste glass leaching mechanisms, were carried out for four different waste glasses. In the first test, the influence of a pre-formed reaction layer on elemental release was evaluated. In the second test, glass specimens were replaced with fresh samples halfway through the leaching experiment, to evaluate the influence of the concentration of glass components in leaching. Finally, regular replacement of the leachant at fixed time intervals essentially removed the variable changing solution concentration, and allowed an assessment of the influence of reaction layer thickness on the leaching rate. Results for all glasses tested indicated that the reaction layer presented little or no barrier to leaching, and that most of the retardation on leaching rates generally observed are attributable to saturation effects. 20 references, 6 figures, 1 table

Conversion of Nuclear Waste into Nuclear Waste Glass: Experimental Investigation and Mathematical Modeling

International Nuclear Information System (INIS)

Hrma, Pavel

2014-01-01

The melter feed, slurry, or calcine charged on the top of a pool of molten glass forms a floating layer of reacting material called the cold cap. Between the cold-cap top, which is covered with boiling slurry, and its bottom, where bubbles separate it from molten glass, the temperature changes by up to 1000 K. The processes that occur over this temperature interval within the cold cap include liberation of gases, conduction and consumption of heat, dissolution of quartz particles, formation and dissolution of intermediate crystalline phases, and generation of foam and gas cavities. These processes have been investigated using thermal analyses, optical and electronic microscopies, x-ray diffraction, as well as other techniques. Properties of the reacting feed, such as heat conductivity and density, were measured as functions of temperature. Investigating the structure of quenched cold caps produced in a laboratory-scale melter complemented the crucible studies. The cold cap consists of two main layers. The top layer contains solid particles dissolving in the glass-forming melt and open pores through which gases are escaping. The bottom layer contains bubbly melt or foam where bubbles coalesce into larger cavities that move sideways and release the gas to the atmosphere. The feed-to-glass conversion became sufficiently understood for representing the cold-cap processes via mathematical models. These models, which comprise heat transfer, mass transfer, and reaction kinetics models, have been developed with the final goal to relate feed parameters to the rate of glass melting

Waste form dissolution in bedded salt

International Nuclear Information System (INIS)

Kaufman, A.M.

1980-01-01

A model was devised for waste dissolution in bedded salt, a hydrologically tight medium. For a typical Spent UnReprocessed Fuel (SURF) emplacement, the dissolution rate wll be diffusion limited and will rise to a steady state value after t/sub eq/ approx. = 250 (1+(1-epsilon 0 ) K/sub D//epsilon 0 ) (years) epsilon 0 is the overpack porosity and K/sub d/ is the overpack sorption coefficient. The steady state dissolution rate itself is dominated by the solubility of UO 2 . Steady state rates between 5 x 10 -5 and .5 (g/year) are achievable by SURF emplacements in bedded salt without overpack, and rates between 5 x 10 -7 and 5 x 10 -3 (g/year) with an overpack having porosity of 10 -2

Kinetics of oxidic phase dissolution in acids

International Nuclear Information System (INIS)

Gorichev, I.G.; Kipriyanov, N.A.

1981-01-01

The critical analysis of the experimental data on dissolution kinetics of metal oxides (BeO, V 2 O 5 , UO 2 , Nb 2 O 5 , Ta 2 O 5 etc.) in acid media is carried out. Kinetic peculiarities of oxide dissolution are explained on the basis of the notions of electron- proton theory. It is established that the surface nonstoichiometric ccomposition of oxide phase and potential jump, appearing on the interface of the oxide-electrolyte phase are the important factors, determining the dissolution rate of a solid phase. The dissolution rate of metal oxides is limited by the transition of protons into the solid oxide phase. Morphological models of heterogeneous kinetics are used when explaining kinetic regularities of oxide dissolution process [ru

Chemical durability of borosilicate glasses containing simulated high-level nuclear wastes, 1

International Nuclear Information System (INIS)

Hara, Shigeo; Terai, Ryohei; Yamanaka, Hiroshi

1983-01-01

The Soxhlet-type leaching test apparatus has been developed to evaluate the chemical durability of some borosilicate glasses containing simulated High-Level nuclear Wastes, HLW. After the leaching over the temperature range of 50 0 -95 0 C, the weight loss of specimens with time was determined on both the samples of blocks and grains, and various components dissolved into water were analyzed by atomic absorption and colorimetry technique. It was found that Soxhlet-type test method was more useful than JIS test method, because the specimens in Soxhlet type apparatus were forced always to react with pure water and the mechanism of leaching could be evaluate accurately. The chemical durability of commercial glasses decreases generally with increasing of alkali contents in glasses. In the case of these borosilicate glasses containing HLW, however, the leachability was apparently independent on the alkali contents because of the complexity of these glass compositions. The variation of leaching rate with temperature suggests that dissolution mechanism changes with temperature. (author)

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).

In-vitro dissolution rate and molecular docking studies of cabergoline drug with β-cyclodextrin

Science.gov (United States)

Shanmuga priya, Arumugam; Balakrishnan, Suganya bharathi; Veerakanellore, Giri Babu; Stalin, Thambusamy

2018-05-01

The physicochemical properties and dissolution profile of cabergoline drug (CAB) with β-cyclodextrin (β-CD) inclusion complex were investigated by the UV spectroscopy. The inclusion complex has used to calculate the stability constant and gives the stoichiometry molar ratio is 1:1 between CAB and β-CD. The phase solubility diagram and the aqueous solubility of CAB (60%) was found to be enhanced by β-CD. In addition, the phase solubility profile of CAB with β-CD was classified as AL-type. Binary systems of CAB with β-CD were prepared by Physical mixture, Kneading and solvent evaporation methods. The solid-state properties of the inclusion complex were characterized by Fourier transformation-infrared spectroscopy, Differential scanning calorimetry, Powder X-ray diffractometric patterns and Scanning electron microscopic techniques. Theoretically, β-CD and CAB inclusion complex obtained by molecular docking studies, it is in good correlation with the results obtained through experimental methods using the Schrödinger software program. In-vitro dissolution profiles of the inclusion complexes were carried out and obvious increase in dissolution rate was observed when compared with pure CAB drug and the complexes.

Thermo-chemistry of nuclear waste glasses: a new approach

International Nuclear Information System (INIS)

Linard, Y.; Neuville, D.R.; Richet, P.

1997-01-01

Understanding of the stability and weathering of glasses used for storing fission products is hampered by a general lack of basic thermochemical information. Models have been setup to predict Gibbs free energies of dissolution of glasses, but ascertaining their accuracy is made difficult by the very lack of reliable experimental data with which model results should be compared. As enthalpies of formation can in principle be determined from usual solution calorimetry experiments, the lack of Gibbs-free energy data for glasses mainly stems from the fact that, as disordered substances, glasses do not obey the third principle and have indeed large configurational entropies. These entropies can be determined from thermochemical measurements only when there exist a congruently melting crystalline compound with the same composition. Using available data, we have calculated the Gibbs-free energies of formation of a series of silicate glasses for which such a calorimetric determination is possible. With these results, we assess the predictions of Paul's model (1977) for calculating Gibbs-free energies of dissolution. As the complex compositions of the borosilicate glasses used for nuclear waste storage prevent determining configurational entropies by calorimetric methods, we point out how these can be determined instead from viscosity measurements. We finally discuss the implications of this approach for modeling of water-glass interactions. (authors)

Examining porous bio-active glass as a potential osteo-odonto-keratoprosthetic skirt material.

Science.gov (United States)

Huhtinen, Reeta; Sandeman, Susan; Rose, Susanna; Fok, Elsie; Howell, Carol; Fröberg, Linda; Moritz, Niko; Hupa, Leena; Lloyd, Andrew

2013-05-01

Bio-active glass has been developed for use as a bone substitute with strong osteo-inductive capacity and the ability to form strong bonds with soft and hard tissue. The ability of this material to enhance tissue in-growth suggests its potential use as a substitute for the dental laminate of an osteo-odonto-keratoprosthesis. A preliminary in vitro investigation of porous bio-active glass as an OOKP skirt material was carried out. Porous glass structures were manufactured from bio-active glasses 1-98 and 28-04 containing varying oxide formulation (1-98, 28-04) and particle size range (250-315 μm for 1-98 and 28-04a, 315-500 μm for 28-04b). Dissolution of the porous glass structure and its effect on pH was measured. Structural 2D and 3D analysis of porous structures were performed. Cell culture experiments were carried out to study keratocyte adhesion and the inflammatory response induced by the porous glass materials. The dissolution results suggested that the porous structure made out of 1-98 dissolves faster than the structures made from glass 28-04. pH experiments showed that the dissolution of the porous glass increased the pH of the surrounding solution. The cell culture results showed that keratocytes adhered onto the surface of each of the porous glass structures, but cell adhesion and spreading was greatest for the 98a bio-glass. Cytokine production by all porous glass samples was similar to that of the negative control indicating that the glasses do not induce a cytokine driven inflammatory response. Cell culture results support the potential use of synthetic porous bio-glass as an OOKP skirt material in terms of limited inflammatory potential and capacity to induce and support tissue ingrowth.

Mathematical modeling of drug dissolution.

Science.gov (United States)

Siepmann, J; Siepmann, F

2013-08-30

The dissolution of a drug administered in the solid state is a pre-requisite for efficient subsequent transport within the human body. This is because only dissolved drug molecules/ions/atoms are able to diffuse, e.g. through living tissue. Thus, generally major barriers, including the mucosa of the gastro intestinal tract, can only be crossed after dissolution. Consequently, the process of dissolution is of fundamental importance for the bioavailability and, hence, therapeutic efficacy of various pharmaco-treatments. Poor aqueous solubility and/or very low dissolution rates potentially lead to insufficient availability at the site of action and, hence, failure of the treatment in vivo, despite a potentially ideal chemical structure of the drug to interact with its target site. Different physical phenomena are involved in the process of drug dissolution in an aqueous body fluid, namely the wetting of the particle's surface, breakdown of solid state bonds, solvation, diffusion through the liquid unstirred boundary layer surrounding the particle as well as convection in the surrounding bulk fluid. Appropriate mathematical equations can be used to quantify these mass transport steps, and more or less complex theories can be developed to describe the resulting drug dissolution kinetics. This article gives an overview on the current state of the art of modeling drug dissolution and points out the assumptions the different theories are based on. Various practical examples are given in order to illustrate the benefits of such models. This review is not restricted to mathematical theories considering drugs exhibiting poor aqueous solubility and/or low dissolution rates, but also addresses models quantifying drug release from controlled release dosage forms, in which the process of drug dissolution plays a major role. Copyright © 2013 Elsevier B.V. All rights reserved.

Importance of surface structure on dissolution of fluorite

DEFF Research Database (Denmark)

Godinho, Jose; Piazolo, Sandra; Balic Zunic, Tonci

2014-01-01

forming the initial surface and its inclination to the closest stable planes, which are specific for each surface orientation. During an initial dissolution regime dissolution rates decrease significantly, even though the total surface area increases. During a second dissolution regime, some surfaces...... by the relative stability of the planes and type of edges that constitute a surface needs to be considered. Significant differences between dissolution rates calculated based on surface area alone, and based on surface reactivity are expected for materials with the fluorite structure....

Dissolution rate enhancement of repaglinide by solid dispersion

African Journals Online (AJOL)

Keywords: Diabetes, Solid dispersion, Repaglinide, Solubility, Dissolution, Burst release. Tropical Journal of ... high lipophilicity (logP = 3.97) and relatively low oral bioavailability (56 .... II drug, i.e., low soluble and high permeable in nature. As.

Low temperature dissolution flowsheet for plutonium metal

Energy Technology Data Exchange (ETDEWEB)

Daniel, W. E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Almond, P. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Rudisill, T. S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2016-05-01

The H-Canyon flowsheet used to dissolve Pu metal for PuO₂ production utilizes boiling HNO₃. SRNL was requested to develop a complementary dissolution flowsheet at two reduced temperature ranges. The dissolution and H₂ generation rates of Pu metal were investigated using a dissolving solution at ambient temperature (20-30 °C) and for an intermediate temperature of 50-60 °C. Additionally, the testing included an investigation of the dissolution rates and characterization of the off-gas generated from the ambient temperature dissolution of carbon steel cans and the nylon bags that contain the Pu metal when charged to the dissolver.

Montmorillonite dissolution kinetics: Experimental and reactive transport modeling interpretation

Science.gov (United States)

Cappelli, Chiara; Yokoyama, Shingo; Cama, Jordi; Huertas, F. Javier

2018-04-01

The dissolution kinetics of K-montmorillonite was studied at 25 °C, acidic pH (2-4) and 0.01 M ionic strength by means of well-mixed flow-through experiments. The variations of Si, Al and Mg over time resulted in high releases of Si and Mg and Al deficit, which yielded long periods of incongruent dissolution before reaching stoichiometric steady state. This behavior was caused by simultaneous dissolution of nanoparticles and cation exchange between the interlayer K and released Ca, Mg and Al and H. Since Si was only involved in the dissolution reaction, it was used to calculate steady-state dissolution rates, RSi, over a wide solution saturation state (ΔGr ranged from -5 to -40 kcal mol-1). The effects of pH and the degree of undersaturation (ΔGr) on the K-montmorillonite dissolution rate were determined using RSi. Employing dissolution rates farthest from equilibrium, the catalytic pH effect on the K-montmorillonite dissolution rate was expressed as Rdiss = k·aH0.56±0.05 whereas using all dissolution rates, the ΔGr effect was expressed as a non-linear f(ΔGr) function Rdiss = k · [1 - exp(-3.8 × 10-4 · (|ΔGr|/RT)2.13)] The functionality of this expression is similar to the equations reported for dissolution of Na-montmorillonite at pH 3 and 50 °C (Metz, 2001) and Na-K-Ca-montmorillonite at pH 9 and 80 °C (Cama et al., 2000; Marty et al., 2011), which lends support to the use of a single f(ΔGr) term to calculate the rate over the pH range 0-14. Thus, we propose a rate law that also accounts for the effect of pOH and temperature by using the pOH-rate dependence and the apparent activation energy proposed by Rozalén et al. (2008) and Amram and Ganor (2005), respectively, and normalizing the dissolution rate constant with the edge surface area of the K-montmorillonite. 1D reactive transport simulations of the experimental data were performed using the Crunchflow code (Steefel et al., 2015) to quantitatively interpret the evolution of the released cations

Contributions of vitreous natural analogs to the investigation of long-term nuclear glass behavior

International Nuclear Information System (INIS)

Techer, I.

1999-01-01

This study assesses the extend of the analogy between the alteration behavior in water and in a moist clay environment of aluminosilicate volcanic glass and alumino-borosilicate nuclear containment glass. Basaltic glass alteration in water initially occurs by hydrolysis processes with an activation energy on the order of 73 kJ.mol -1 . As the reaction progresses, the alteration rate drops by over four orders of magnitude from the initial rate r 0 , The alteration kinetics are not governed by the alteration solution chemistry alone, the glass alteration film appears to have a major role as a diffusion barrier limiting the transfer of reaction species and products. All these aspects highlight the behavioral analogy between basaltic glass and nuclear borosilicate glass in aqueous media. Conversely, the alteration reaction of obsidian-type volcanic glass involves other mechanisms than those governing the dissolution of borosilicate glass. Basaltic glass alteration is also examined in the presence of a clay environmental material, in a study of the natural basaltic glass and argillaceous pelites system of the Salagou basin in southern France, in an approach combining mineralogical, chemical and isotopic data to assess the interactions between a basaltic glass and the argillaceous pelites. Laboratory leach test results with basaltic glass and measured data for the Salagou glass in its natural environment are modeled using a code implementing a kinetic law coupling diffusive transfer of dissolved silica with a reaction affinity law. (author)

Spent fuel dissolution mechanisms

International Nuclear Information System (INIS)

Ollila, K.

1993-11-01

This study is a literature survey on the dissolution mechanisms of spent fuel under disposal conditions. First, the effects of radiolysis products on the oxidative dissolution mechanisms and rates of UO 2 are discussed. These effects have mainly been investigated by using electrochemical methods. Then the release mechanisms of soluble radionuclides and the dissolution of the UO 2 matrix including the actinides, are treated. Experimental methods have been developed for measuring the grain-boundary inventories of radionuclides. The behaviour of cesium, strontium and technetium in leaching tests shows different trends. Comparison of spent fuel leaching data strongly suggests that the release of 90 Sr into the leachant can be used as a measure of the oxidation/dissolution of the fuel matrix. Approaches to the modelling UO 2 , dissolution are briefly discussed in the next chapter. Lastly, the use of natural material, uraninite, in the evaluation of the long-term performance of spent fuel is discussed. (orig.). (81 ref., 37 figs., 8 tabs.)

(Alpha, gamma) irradiation effect on the alteration of high-level radioactive wastes matrices (UO2, hollandite, glass SON68)

International Nuclear Information System (INIS)

Suzuki, T.

2007-06-01

The aim of this work is to determine the effect of irradiation on the alteration of high level nuclear waste forms matrices. The matrices investigated are UO 2 to simulate the spent fuel, the hollandite for the specific conditioning of Cs, and the inactive glass SON68 representing the nuclear glass R7T7) The alpha irradiation experiments on UO 2 colloids in aqueous carbonate media have enabled to distinguish between the oxidation of UO 2 matrix as initial and dissolution as subsequent step. The simultaneous presence of carbonate and H 2 O 2 (product resulting from water radiolysis) increased the dissolution rate of UO 2 to its maximum value governed by the oxidation rate. ii) The study of hollandite alteration under gamma irradiation confirmed the good retention capacity for Cs and Ba. Gamma irradiation had brought only a little influence on releasing of Cs and Ba in solution. Electronic irradiation had conducted to the amorphization of the hollandite only for a dose 1000 times higher than the auto-induced dose of Ba over millions of years. iii) The experiences of glass irradiation under alpha beam and of helium implantation in the glass SON68 were analyzed by positon annihilation spectroscopy. No effect has been observed on the solid surface for an irradiation dose equal to 1000 years of storage. (author)

Dissolution of nuclear fuels; Disolucion de combustibles Nucleares

Energy Technology Data Exchange (ETDEWEB)

Uriarte Hueda, A; Berberana Eizmendi, M; Rainey, R

1968-07-01

A laboratory study was made of the instantaneous dissolution rate (IDR) for unirradiated uranium metal rods and UO{sub 2}, PuO{sub 2} and PuO{sub 2}-UO{sub 2} pellets in boiling nitric acid alone and with additives. The uranium metal and UO{sub 2} dissolved readily in nitric acid alone; PuO{sub 2} dissolved slowly even with the addition of fluoride; PuO{sub 2}-UO{sub 2} pellets containing as much as 35% PuO{sub 2} in UO{sub 2} gave values of the instantaneous dissolution rate to indicate can be dissolved with nitric acid alone. An equation to calculate the time for complete dissolution has been determinate in function of the instantaneous dissolution rates. The calculated values agree with the experimental. Uranium dioxide pellets from various sources but all having a same density varied in instantaneous dissolution rate. All the pellets, however, have dissolved ved in the same time. The time for complete dissolution of PuO{sub 2}-UO{sub 2} pellets, having the same composition, and the concentration of the used reagents are function of the used reagents are function of the fabrication method. (Author) 8 refs.

The effect of fuel chemistry on UO{sub 2} dissolution

Energy Technology Data Exchange (ETDEWEB)

Casella, Amanda, E-mail: amanda.casella@pnnl.gov [Pacific Northwest National Laboratory, PO Box 999, MSIN P7-25, Richland, WA 99352 (United States); Hanson, Brady, E-mail: brady.hanson@pnnl.gov [Pacific Northwest National Laboratory, PO Box 999, MSIN P7-27, Richland, WA 99352 (United States); Miller, William [University of Missouri Research Reactor, 1513 Research Park Drive, Columbia, MO 65211 (United States)

2016-08-01

The dissolution rate of both unirradiated UO{sub 2} and used nuclear fuel has been studied by numerous countries as part of the performance assessment of proposed geologic repositories. In the scenario of waste package failure and groundwater contact with the fuel, the effects of variables such as temperature, dissolved oxygen, and water and fuel chemistry on the dissolution rates of the fuel are necessary to provide a quantitative estimate of the potential release over geologic time frames. The primary objective of this research was to determine the influence these parameters, with primary focus on the fuel chemistry, have on the dissolution rate of unirradiated UO{sub 2} under oxidizing repository conditions and compare them to the rates predicted by current dissolution models. Both unirradiated UO{sub 2} and UO{sub 2} doped with varying concentrations of Gd{sub 2}O{sub 3}, to simulate used fuel composition after long time periods when radiolysis has minor contributions to dissolution, were examined. In general, a rise in temperature increased the dissolution rate of UO{sub 2} and had a larger effect on pure UO{sub 2} than on those doped with Gd{sub 2}O{sub 3}. Oxygen dependence was observed in the UO{sub 2} samples with no dopant and increased as the temperature rose; in the doped fuels less dependence was observed. The addition of gadolinia into the UO{sub 2} matrix resulted in a significant decrease in the dissolution rate. The matrix stabilization effect resulting from the dopant proved even more beneficial in lowering the dissolution rate at higher temperatures and dissolved O{sub 2} concentrations in the leachate where the rates would typically be elevated. - Highlights: • UO{sub 2} dissolution rates were measured for a matrix of repository relevant conditions. • Dopants in the UO{sub 2} matrix lowered the dissolution rate. • Reduction in rates by dopants were increased at elevated temperature and O{sub 2} levels. • UO{sub 2} may be overly

8 Dissolution Kinetics

African Journals Online (AJOL)

user

Experiments measuring the dissolution rates of stilbite (NaCa [Al Si O ].14H O) in pH-buffered ... The rate law was established as R = k (a ) , where k is ... crystalline hydrated aluminosilicate minerals ..... from the crushing process, thin edges or.

Dissolution kinetics of lead telluride in alkali solutions of hydrogen peroxide

International Nuclear Information System (INIS)

Danilova, M.G.; Sveshnikova, L.L.; Stavitskaya, T.A.; Repinskij, S.M.

1991-01-01

Dissolution kinetics of lead telluride in alkali solutions of hydrogen peroxide was investigated. Dependences of change of PbTe dissolution rate on concentration of hydrogen peroxide and alkali in the solution were obtained. It is shown that dissolution rate of lead telluride is affected by dissolution rate of lead oxide, representing the product of ReTe dissolution. The obtained regularities can be explained by change of solution structure with increase of KOH concentration and by the state of hydrogen peroxide in the solution

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

Dissolution of ion exchange resin by hydrogen peroxide

International Nuclear Information System (INIS)

Lee, S.C.

1981-08-01

The resin dissolution process was conducted successfully in full-scale equipment at the SRL Semiworks. A solution containing 0.001M Fe 2+ , or Fe 3+ , and 3 vol % H 2 O 2 in 0.1M HNO 3 is sufficient to dissolve up to 40 vol % resin slurry (Dowex 50W-X8). Foaming and pressurization can be eliminated by maintaining the dissolution temperature below 99 0 C. The recommended dissolution temperature range is 85 to 90 0 C. Premixing hydrogen peroxide with all reactants will not create a safety hazard, but operating with a continual feed of hydrogen peroxide is recommended to control the dissolution rate. An air sparging rate of 1.0 to 1.5 scfm will provide sufficient mixing. Spent resin from chemical separation contains DTPA (diethylenetriaminepentaacetic acid) residue, and the resin must be washed with 0.1M NH 4 OH to remove excess DTPA before dissolution. Gamma irradiation of resin up to 4 kW-hr/L did not change the dissolution rate significantly

Dissolution of mixed oxide spent fuel from FBR

International Nuclear Information System (INIS)

Sanyoshi, H.; Nishina, H.; Toyota, O.; Yamamoto, R.; Nemoto, S.; Okamoto, F.; Togashi, A.; Kawata, T.; Hayashi, S.

1991-01-01

At the Tokai Works of the Power Reactor and Nuclear Fuel Development Corporation (PNC), the Chemical Processing Facility (CPF) has been continuing operation since 1982 for laboratory scale hot experiments on reprocessing of FBR mixed oxide fuel. As a part of these experiments, dissolution experiments have been performed to define the key parameters affecting dissolution rates such as concentration of nitric acid, temperature and burnup and also to confirm the amount of insoluble residue. The dissolution rate of the irradiated fuel was determined to be in proportion to the 1.7 power of the nitric acid concentration. The activation energy determined from the experiments varied from 6 to 11 kcal/mol depending on the method of dissolution. The dissolution rate decreased as the fuel burnup increased in low nitric acid media below 5 mol/l. However, it was found that the effect of the burnup became negligible in a high concentration of nitric acid media. The amount of insoluble residue and its constituents were evaluated by changing the dissolution condition. (author)

Elemental redistribution behavior in tellurite glass induced by high repetition rate femtosecond laser irradiation

International Nuclear Information System (INIS)

Teng, Yu; Zhou, Jiajia; Khisro, Said Nasir; Zhou, Shifeng; Qiu, Jianrong

2014-01-01

Highlights: • Abnormal elements redistribution behavior was observed in tellurite glass. • The refractive index and Raman intensity distribution changed significantly. • The relative glass composition remained unchanged while the glass density changed. • First time report on the abnormal element redistribution behavior in glass. • The glass network structure determines the elemental redistribution behavior. - Abstract: The success in the fabrication of micro-structures in glassy materials using femtosecond laser irradiation has proved its potential applications in the construction of three-dimensional micro-optical components or devices. In this paper, we report the elemental redistribution behavior in tellurite glass after the irradiation of high repetition rate femtosecond laser pulses. The relative glass composition remained unchanged while the glass density changed significantly, which is quite different from previously reported results about the high repetition rate femtosecond laser induced elemental redistribution in silicate glasses. The involved mechanism is discussed with the conclusion that the glass network structure plays the key role to determine the elemental redistribution. This observation not only helps to understand the interaction process of femtosecond laser with glassy materials, but also has potential applications in the fabrication of micro-optical devices

The kinetics of Dissolution of Biologically Formed Calcific Deposits.

Science.gov (United States)

Rokidi, Stamatia; Koutsoukos, Petros

2015-04-01

The calcification of aortic valves results in the formation of non stoichiometric apatitic deposits which may have serious health implications because of the fact that these minerals adhere tenaciously on tissues like heart valves and arteries causing permanent damage which is partly due to their low solubility. In the present work, calcium phosphate biominerals were extracted from clinically removed tissues and were characterized with respect to their mineralogical constituents and other properties including morphology, specific surface area analyses and thermogravimetric analysis. In all cases, the biominerals may be described as non stoichiometric apatitic materials, although traces of the precursor phase of octacalcium phosphate (Ca8H2(PO4)6•5H2O, OCP) were identified on the basis of their morphological examination. The kinetics of dissolution of the biomineral deposits was investigated in solutions undersaturated with respect to hydroxyapatite (Ca5(PO4)3OH, HAP) at conditions of constant undersaturation at pH 7.40, 37°C, 0.15M NaCl. Synthetic stoichiometric HAP was used as the control mineral. The experiments in the present work used solutions prepared from calcium chloride and sodium hydrogen phosphate and the relative undersaturation, σ, was in the range 0.38-0.74 with respect to HAP and 0.49-0.85 with respect to OCP (σ=1 in water). The dissolution process started immediately upon the introduction of an accurately weighted amount of powdered biomineral in the undersaturated solutions homogenized by magnetic stirring. Inert atmosphere was ensured with the bubbling of water vapor saturated nitrogen through the demineralizing solutions. A glass/Ag/AgCl combination electrode was used as a probe to monitor the process and to control the addition of diluent solutions with the stoichiometry of the dissolving mineral. The measurements of the rates of crystal dissolution, showed a parabolic dependence on the relative solution undersaturation for HAP and higher

Does the dose-solubility ratio affect the mean dissolution time of drugs?

Science.gov (United States)

Lánský, P; Weiss, M

1999-09-01

To present a new model for describing drug dissolution. On the basis of the new model to characterize the dissolution profile by the distribution function of the random dissolution time of a drug molecule, which generalizes the classical first order model. Instead of assuming a constant fractional dissolution rate, as in the classical model, it is considered that the fractional dissolution rate is a decreasing function of the dissolved amount controlled by the dose-solubility ratio. The differential equation derived from this assumption is solved and the distribution measures (half-dissolution time, mean dissolution time, relative dispersion of the dissolution time, dissolution time density, and fractional dissolution rate) are calculated. Finally, instead of monotonically decreasing the fractional dissolution rate, a generalization resulting in zero dissolution rate at time origin is introduced. The behavior of the model is divided into two regions defined by q, the ratio of the dose to the solubility level: q 1 (saturation of the solution, saturation time). The singular case q = 1 is also treated and in this situation the mean as well as the relative dispersion of the dissolution time increase to infinity. The model was successfully fitted to data (1). This empirical model is descriptive without detailed physical reasoning behind its derivation. According to the model, the mean dissolution time is affected by the dose-solubility ratio. Although this prediction appears to be in accordance with preliminary application, further validation based on more suitable experimental data is required.

Status report on dissolution model development

International Nuclear Information System (INIS)

Jackson, D.D.

1983-07-01

The computer program PROTOCOL models the dissolution reactions of chemical species in water. It is being developed particularly to study the dissolution of proposed nuclear waste forms and related phases. Experimentally derived leaching rate functions are coupled to thermochemical equilibrium calculations and water flow rates. The program has been developed over a period of years. This report describes improvements that have been done in the past year

Preparation of Vitexin Nanoparticles by Combining the Antisolvent Precipitation and High Pressure Homogenization Approaches Followed by Lyophilization for Dissolution Rate Enhancement.

Science.gov (United States)

Gu, Chengbo; Liu, Ziwei; Yuan, Xiaohan; Li, Wang; Zu, Yuangang; Fu, Yujie

2017-11-22

Vitexin, a natural flavonoid found in many medicinal plants, is well known for its rich pharmacological activities. However, the poor water solubility of vitexin has limited its therapeutic application. The aim of this study was to prepare the nanoparticles of vitexin by combining the antisolvent precipitation (ASP) and high pressure homogenization (HPH) approaches followed by lyophilization for improving the dissolution rate of this poorly water-soluble drug. The effects of main factors influencing the mean particle size (MPS) of vitexin were investigated and optimized. Under optimum conditions, vitexin nanosuspensions with an MPS of 80.5 nm were obtained and then lyophilized to form nanoparticles. The obtained vitexin nanoparticles were further characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), mass spectrometry (MS), X-ray powder diffraction (XRPD), gas chromatography (GC) and dissolution testing. The results showed that the nanoparticles of vitexin were converted into an amorphous form, with its chemical structure unchanged. Additionally, the residual dimethyl sulfoxide (DMSO) is lower than the International Conference on Harmonization (ICH) limit for class 3 solvents. The dissolution rate of processed vitexin was significantly higher (5.58-fold) than that of raw drug. Overall, the combinative process we developed is an effective way to produce vitexin nanoparticles with markedly enhanced dissolution rate.

On-line monitoring of lithium carbonate dissolution

Energy Technology Data Exchange (ETDEWEB)

Sun, Yuzhu; Song, Xingfu; Wang, Jin; Luo, Yan; Yu, Jianguo [National Engineering Research Center for Integrated Utilization Salt Lake Resources, East China University of Science and Technology, Shanghai (China)

2009-11-15

Dissolution of lithium carbonate (Li{sub 2}CO{sub 3}) in aqueous solution was investigated using three on-line apparatuses: the concentration of Li{sub 2}CO{sub 3} was measured by electrical conductivity equipment; CLD (Chord Length Distribution) was monitored by FBRM (Focused Beam Reflectance Measurement); crystal image was observed by PVM (Particle Video Microscope). Results show dissolution rate goes up with a decrease of particle size, and with an increase in temperature; stirring speed causes little impact on dissolution; ultrasound facilitates dissolution obviously. The CLD evolution and crystal images of Li{sub 2}CO{sub 3}powders in stirred fluid were observed detailedly by FBRM and PVM during dissolution. Experimental data were fitted to Avrami model, through which the activation energy was found to be 34.35 kJ/mol. PBE (Population Balance Equation) and moment transform were introduced to calculate dissolution kinetics, obtaining correlation equations of particle size decreasing rate as a function of temperature and undersaturation. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Plasma spraying of bioactive glass-ceramics containing bovine bone

Directory of Open Access Journals (Sweden)

Annamária Dobrádi

2017-06-01

Full Text Available Natural bone derived glass-ceramics are promising biomaterials for implants. However, due to their price and weak mechanical properties they are preferably applied as coatings on load bearing implants. This paper describes result obtained by plasma spraying of bioactive glass-ceramics containing natural bone onto selected implant materials, such as stainless steel, alumina, and titanium alloy. Adhesion of plasma sprayed coating was tested by computed X-ray tomography and SEM of cross sections. The results showed defect free interface between the coating and substrate, without cracks or gaps. Dissolution rate of the coating in simulated body fluid (SBF was readily controlled by the bone additives (phase composition, as well as microstructure. The SBF treatment of the plasma sprayed coating did not influence the boundary between the coating and substrate.

Dissolution rates of aluminum-based spent fuels relevant to geological disposal

International Nuclear Information System (INIS)

Mickalonis, J.I.

2000-01-01

The Department of Energy is pursuing the option of direct disposal of a wide variety of spent nuclear fuels under its jurisdiction. Characterization of the various types of spent fuel is required prior to licensing by the Nuclear Regulatory Commission and acceptance of the fuel at a repository site. One category of required data is the expected rate of radionuclide and fissile release to the environment as a result of exposure to groundwater after closure of the repository. To provide this type of data for four different aluminum-based spent fuels, tests were conducted using a flow through method that allows the dissolution rate of the spent fuel matrix to be measured without interference by secondary precipitation reactions that would muddle interpretation of the results. Similar tests had been conducted earlier with light water reactor spent fuel, thereby allowing direct comparisons

A 25-year laboratory experiment on French SON68 nuclear glass leached in a granitic environment - First investigations

Energy Technology Data Exchange (ETDEWEB)

Guittonneau, C. [CEA Marcoule DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze Cedex (France); Gin, S., E-mail: stephane.gin@cea.f [CEA Marcoule DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze Cedex (France); Godon, N.; Mestre, J.P. [CEA Marcoule DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze Cedex (France); Dugne, O.; Allegri, P. [CEA Marcoule DTEC/SGCS/LMAC, BP 17171, 30207 Bagnols-sur-Ceze Cedex (France)

2011-01-01

We have investigated a 25.75-year old leaching experiment to improve our understanding of the mechanisms controlling glass dissolution in geological disposal conditions. A SON68 glass block was leached in slowly renewed synthetic groundwater (at 90 {sup o}C, 100 bar) in contact with some pieces of granite and Ni-Cr-Mo alloy as environmental storage materials. One hundred and sixty-three samplings were carried out over the entire duration of the experiment and were used to calculate the mean thickness of the altered glass (28 ({+-}9) {mu}m) and the glass dissolution rate. After few months, the rate remained very constant at 6 x 10{sup -3} g m{sup -2} d{sup -1} which is about 20 times higher than the residual rate measured in a batch reactor at the same temperature. At the end of the experiment, mainly SEM analyses were performed on the entire glass block. Surprisingly, the glass alteration layer has neither a homogeneous thickness, nor a homogeneous morphology. The location of the sampling valve (at half height of the glass block) seems to divide the glass block into two parts. In the upper half (above the sampling valve), the general morphology of the alteration layer consists in a relatively simple and uniform gel and some secondary phases which are rare-earth phosphates. The mean measured thickness of this alteration layer is 6.7 ({+-}0.3) {mu}m. However, in the lower half of the glass block, the gel is globally larger and frequently contains rounded shapes which are rare-earth phosphates. This section is edged by secondary phases bearing Mg, Na, Zn and Ni. The mean measured thickness is 81.3 ({+-}1.1) {mu}m in the lower half. In this experiment, the flow rate which leads to the hydrodynamic transport of the soluble species must be a key factor for the local glass alteration process. We have also shown that this unexpected behavior is likely due to heterogeneities of the chemistry of the solution. This conclusion is supported by the behavior of Mg. This element

Evaluation of glass leaching as nutrient source for microalgae growth; Evaluacion del comportamiento de vidrios lixiviados como nutrientes de algas

Energy Technology Data Exchange (ETDEWEB)

Grabska, N.; Tamayo, A.; Mazo, M. A.; Pascual, L.; Rubio, J.

2015-10-01

Three glasses with an elemental composition similar to the nutrient ratio required for Spirulina platensis growth and with different SiO{sub 2} content have been prepared. The glasses were crushed and sieved into 2 different fractions and the effect of the particle size has been studied in terms of the leaching kinetics of each element. The chemical analysis of the leaching water was used for obtaining the dissolution rate curves for each element taking part of the glass composition. From the calculation of the leaching rate constant and the exponential constant of the lixiviation reaction, it has been evaluated the Spirulina platensis growth in ambient normal conditions of light, temperature and pH of the growing media. It has been concluded that, either from the modification of the chemical composition of the glass or its particle size, it is possible to tune the delivery of the nutrients to match the growth rate of Spirulina platensis. (Author)

Faster dissolution of PuO2 in nitrous media by means of electrolytic oxidation

International Nuclear Information System (INIS)

Baumgaertner, F.; Kim, J.I.; Luckner, N.; Brueckl, N.; Lieberer, E.

1984-03-01

The contribution shows that the dissolution of PuO 2 in HNO 3 can be accelerated considerably by means of electrolytic oxidation. A glass apparatus has been developed which uses platinum electrodes providing for sufficient contact between electrodes and solids. Increase of temperature, acid concentration, and electrode current density, and a good contact between electrode and metal oxide will improve the dissolution kinetics. The reaction could be made even faster by addition of Ce 4+ . (orig.) [de

Material Removal Rate for Magnetorheological Finishing (MRF) of Optical Glasses with Nanodiamond MR Fluid

Energy Technology Data Exchange (ETDEWEB)

DeGroote, J.E.; Marino, A.E.; Wilson, J.P.; Bishop, A.L.; Jacobs, S.D.

2007-07-13

We present a material removal rate model for MRF of optical glasses using nanodiamond MR fluid. The new model incorporates terms for drag force, polishing particle properties, chemical durability and glass composition into an existing model that contains only terms for the glass mechanical properties. Experimental results for six optical glasses are given that support this model.

Material Removal Rate for Magnetorheological Finishing (MRF) of Optical Glasses with Nanodiamond MR Fluid

International Nuclear Information System (INIS)

DeGroote, J.E.; Marino, A.E.; Wilson, J.P.; Bishop, A.L.; Jacobs, S.D.

2007-01-01

We present a material removal rate model for MRF of optical glasses using nanodiamond MR fluid. The new model incorporates terms for drag force, polishing particle properties, chemical durability and glass composition into an existing model that contains only terms for the glass mechanical properties. Experimental results for six optical glasses are given that support this model

Chemical dissolution of spent fuel and cladding using complexed fluoride species

International Nuclear Information System (INIS)

Rance, P.J.W.; Freeman, G.A.; Mishin, V.; Issoupov, V.

2001-01-01

The dissolution of LWR fuel cladding using two fluoride ion donors, HBF 4 and K 2 ZrF 6 , in combination with nitric acid has been investigated as a potential reprocessing head-end process suitable for chemical decladding and fuel dissolution in a single process step. Maximum zirconium concentrations in the order of 0,75 to 1 molar have been achieved and dissolution found to continue to low F:Zr ratios albeit at ever decreasing rates. Dissolution rates of un-oxidised zirconium based fuel claddings are fast, whereas oxidised materials exhibit an induction period prior to dissolution. Data is presented relating to the rates of dissolution of cladding and UO 2 fuels under various conditions. (author)

High rate operation of micro-strip gas chambers on diamond-coated glass

CERN Document Server

Bouclier, Roger; Million, Gilbert; Ropelewski, Leszek; Sauli, Fabio; Temmel, T; Cooke, R A; Donnel, S; Sastri, S A; Sonderer, N

1996-01-01

Very high rate operation of micro­strip gas chambers can be achieved using slightly conducting substrates. We describe preliminary measurements realized with detectors manufactured on boro-silicate glass coated, before the photo-lithographic processing, with a diamond layer having a surface resistivity of around 1014 ‡/o. Stable medium-term operation, and a rate capability largely exceeding the one obtained with identical plates manufactured on uncoated glass are demonstrated. If these results are confirmed by long-term measurements the diamond coating technology appears very attractive since it allows, with a moderate cost overhead, to use thin, commercially available glass with the required surface quality for the large-scale production of gas micro-strip detectors.

Alkaline glass as induced fission fragment detectors

International Nuclear Information System (INIS)

Amorim, A.M.M.

1986-01-01

The slide glass, registered trade marks INLAB, INVICT and PERFECTA were compared. For the three kinds of glasses the following studies were done: chemical composition; general dissolution rate for hydrofluoric acid solutions of concentrations between 1 and 10M, at 30 0 C and ultrasound shaking; relative efficiency for recording fission fragment tracks from 252 Cf. The INLAB glass was selected due to the better quality of its surface after chemical etching. The HF concentration 2.5M was determined for chemical etching of INLAB glass, and the optimum etching time was chosen between 8 and 10 minutes. The thermal attenuation of latent tracks in the environmental temperature was observed for intervals uo to 31 days between the detector exposure to the fission fragment source and etching of tracks. Several methods were used for determining the detector parameters, such as: critical angle, angle of the cone and efficiency of etching. The effects of gamma irradiation from 60 Co and reactor neutrons in material properties as track detector were studied. Attenuation of latent tracks and saturation of color centers were observed for doses over 100M Rad. Since this kind of material contains uranium as impurity, uniformely distributed, slide glass were calibrated to be applied as a monitor of thermal neutron flux in nuclear reactor. (Author) [pt

Modeling a novel glass immobilization waste treatment process using flow

International Nuclear Information System (INIS)

Ferrada, J.J.; Nehls, J.W. Jr.; Welch, T.D.; Giardina, J.L.

1996-01-01

One option for control and disposal of surplus fissile materials is the Glass Material Oxidation and Dissolution System (GMODS), a process developed at ORNL for directly converting Pu-bearing material into a durable high-quality glass waste form. This paper presents a preliminary assessment of the GMODS process flowsheet using FLOW, a chemical process simulator. The simulation showed that the glass chemistry postulated ion the models has acceptable levels of risks

Kinetics of Inorganic Calcite Dissolution in Seawater under Pressure

Science.gov (United States)

Dong, S.; Subhas, A.; Rollins, N.; Berelson, W.; Adkins, J. F.

2016-02-01

While understanding calcium carbonate dissolution is vital in constructing global carbon cycles and predicting the effect of seawater acidification as a result of increasing atmospheric CO2, there is still a major debate over the basic formulation of a dissolution rate law. The kinetics of calcium carbonate dissolution are typically described by the equation: Rate=k(1-Ω)n, while Ω=[Ca2+][CO32-]/Ksp. In this study, 13C-labeled calcite is dissolved in unlabeled seawater and the evolving d13C composition of the fluid is traced over time to establish dissolution rate. Instead of changing ion concentration to obtain varying Ω (as in our previous study; Subhas et al. 2015), we changed Ksp by conducting experiments under different pressures (described in theory as ∂lnKsp/∂P=-ΔV/RT, where ΔV is partial molal volume). This involved the construction of a pressure vessel that could hold our sample bag and provide aliquots while remaining pressurized. Pressure experiments were conducted between 0-2000PSI. Results support the conclusion in our previous study that near-equilibrium dissolution rates are highly nonlinear, but give a disparate relationship between undersaturation and dissolution rate if Ω is calculated assuming the specific ΔV embedded in CO2SYS. A revised ΔV from -37cm3 to -65cm3 would make the dissolution formulation equation agree, but clearly appears unreasonable. Our results are explained by a pressure effect on carbonate dissolution kinetics over and above the influence of pressure on Ω. If this is a phenomenon that occurs in nature, then we would predict that dissolution should be occurring shallower in the water column (as sometimes observed) than indicated by standard Ω calculations.

Quantifying silica reactivity in subsurface environments: Reaction affinity and solute matrix controls on quartz and SiO2 glass. 1997 annual progress report

International Nuclear Information System (INIS)

Dove, P.M.

1997-01-01

'The author reports the preliminary results of the experiments on the dissolution behavior of vitreous silica (v-SiO 2 ) into aqueous solutions of variable pH and ionic strength. The experiments are being conducted in mixed flow reactors with a high circulation rate that simulates constant-stirred conditions, the efficacy of which the authors discuss below. The preliminary results indicate that v-SiO 2 dissolves into aqueous solutions approximately two orders of magnitude more quickly than crystalline silica (e.g., quartz). With additional experiments, they will utilize the dissolution rate data as a framework for understanding the behavior of waste glass compositions in the subsurface. In other work related to the studies of glass reactivity, the author has written one book chapter that will be published as part of a proceedings for the CEA/VALRHO international nuclear waste disposal conference held in Mejannes le Clap, France. In separate work, she is presently writing a second book chapter for the volume entitled Adsorption on Silica Surfaces.'

High temperature dissolution of chromium substituted nickel ferrite in nitrilotriacetic acid medium

Energy Technology Data Exchange (ETDEWEB)

Sathyaseelan, V.S.; Chandramohan, P.; Velmurugan, S., E-mail: svelu@igcar.gov.in

2016-12-01

High temperature (HT) dissolution of chromium substituted nickel ferrite was carried out with relevance to the decontamination of nuclear reactors by way of chemical dissolution of contaminated corrosion product oxides present on stainless steel coolant circuit surfaces. Chromium substituted nickel ferrites of composition, NiFe{sub (2−x)}Cr{sub x}O{sub 4} (x ≤ 1), was synthetically prepared and characterized. HT dissolution of these oxides was carried out in nitrilotriacetic acid medium at 160 °C. Dissolution was remarkably increased at 160 °C when compared to at 85 °C in a reducing decontamination formulation. Complete dissolution could be achieved for the oxides with chromium content 0 and 0.2. Increasing the chromium content brought about a marked reduction in the dissolution rate. About 40 fold decrease in rate of dissolution was observed when chromium was increased from 0 to 1. The rate of dissolution was not very significantly reduced in the presence of N{sub 2}H{sub 4}. Dissolution of oxide was found to be stoichiometric. - Highlights: • Dissolution of NiFe{sub (2−x)}Cr{sub x}O{sub 4} was remarkably increased at 160 °C in NTA medium. • The dissolution was significantly decreasing with the increase in Cr content in the oxide. • Dissolution rate is dependent on the lability of metal-oxo bonds. • The rate of dissolution was not significantly reduced in the presence of N{sub 2}H{sub 4.} • NTA at high temperature is effective for decontamination of stainless steel surfaces.

Characterization of aqueous interactions of copper-doped phosphate-based glasses by vapour sorption.

Science.gov (United States)

Stähli, Christoph; Shah Mohammadi, Maziar; Waters, Kristian E; Nazhat, Showan N

2014-07-01

Owing to their adjustable dissolution properties, phosphate-based glasses (PGs) are promising materials for the controlled release of bioinorganics, such as copper ions. This study describes a vapour sorption method that allowed for the investigation of the kinetics and mechanisms of aqueous interactions of PGs of the formulation 50P2O5-30CaO-(20-x)Na2O-xCuO (x=0, 1, 5 and 10mol.%). Initial characterization was performed using (31)P magic angle spinning nuclear magnetic resonance and attenuated total reflectance-Fourier transform infrared spectroscopy. Increasing CuO content resulted in chemical shifts of the predominant Q(2) NMR peak and of the (POP)as and (PO(-)) Fourier transform infrared absorptions, owing to the higher strength of the POCu bond compared to PONa. Vapour sorption and desorption were gravimetrically measured in PG powders exposed to variable relative humidity (RH). Sorption was negligible below 70% RH and increased exponentially with RH from 70 to 90%, where it exhibited a negative correlation with CuO content. Vapour sorption in 0% and 1% CuO glasses resulted in phosphate chain hydration and hydrolysis, as evidenced by protonated Q(0)(1H) and Q(1)(1H) species. Dissolution rates in deionized water showed a linear correlation (R(2)>0.99) with vapour sorption. Furthermore, cation release rates could be predicted based on dissolution rates and PG composition. The release of orthophosphate and short polyphosphate species corroborates the action of hydrolysis and was correlated with pH changes. In conclusion, the agreement between vapour sorption and routine characterization techniques in water demonstrates the potential of this method for the study of PG aqueous reactions. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Influence of fining agents on glass melting: A review, Part 2

Czech Academy of Sciences Publication Activity Database

Hujová, Miroslava; Vernerová, Miroslava

2017-01-01

Roč. 61, č. 3 (2017), s. 202-208 ISSN 0862-5468 Institutional support: RVO:67985891 Keywords : glass melting * sodium sulphate * chemical reactions * gas evolution * dissolution * fining * bubble nucleation * foaming Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 0.439, year: 2016

Influence of fining agents on glass melting: A review, Part 1

Czech Academy of Sciences Publication Activity Database

Hujová, Miroslava; Vernerová, Miroslava

2017-01-01

Roč. 61, č. 2 (2017), s. 119-126 ISSN 0862-5468 Institutional support: RVO:67985891 Keywords : glass melting * sodium sulphate * chemical reactions * gas evolution * dissolution * fining * bubble nucleation * foaming Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 0.439, year: 2016

Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

Science.gov (United States)

Ngwack, Bernd; Sigg, Laura

1997-03-01

The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

Investigation of platinum alloys for melting of inclusion free laser glass: Final report

International Nuclear Information System (INIS)

Izumitani, T.; Toratani, H.; Meissner, H.E.

1986-01-01

The objective of this work is to evaluate the suitability of Pt alloys as crucible materials for melting LHG-8 phosphate laser glass. The tendency of forming metallic inclusions and ionic dissolution of alloy components in the glass is to be compared with that of pure Pt. Ionic Pt is introduced into the glass melt by direct dissolution of Pt at the crucible-melt interface and by vapor phase transport. It was felt that a Pt-alloy may behave sufficiently differently from Pt that a number of alloys should be studied. Pt inclusions may originate from Pt which reprecipitates from the glass melt on cooling or change in redox-conditions; from volatilized Pt which deposits in colder zones of the melting environment as crystallites which may drop back into the glass melt; and/or from Pt particles which are mechanically removed from the crucible and drop into the glass melt. Besides pure Pt, the following alloys have been tested: Pt/ 10 Ir, Pt/ 10 Rh, Pt/ 5 Au, Pt-ZGS, Pt/ 5 Au-ZGS, Pt/ 10 Rh-ZGS