Modelling Oxidative Dissolution of Spent Fuel

1996 ◽  
Vol 465 ◽  
Author(s):  
Ivars Neretnieks
Keyword(s):  
Redox Reaction ◽  
Uranium Oxide ◽  
Reaction Rate ◽  
Spent Nuclear Fuel ◽  
Large Fraction ◽  
Reaction Rates ◽  
Spent Fuel ◽  
First Case ◽  
Rate Of Movement

ABSTRACTSpent nuclear fuel will, by the radiation, split nearby water into oxidizing and reducing compounds. The reducing compounds are mostly hydrogen that will diffuse away. The remaining oxidizing compounds can oxidize the uranium oxide of the fuel and make it more soluble. The oxidised uranium will dissolve and diffuse away. The nuclides previously incorporated in the spent fuel matrix can then be released and also migrate away from the fuel.A model is proposed where the produced oxidizing species compete for reaction with the fuel and for escaping out of the system. The chemical reaction rate of oxygen and fuel is taken from literature values based on experiments. The escape rate of oxidants to a receding redox front in the backfill is modelled assuming a redox reaction of oxidizing component and reducing component in the surrounding. The rate of movement of the redox front is determined from the rate of production of oxidants. This is estimated using a previously devised model that has been calibrated to in situ observed radiolysis.Three cases are modelled. In the first case it is assumed that the reducing compound is insoluble and that the reaction between oxygen and reducing mineral is very fast. In the second case it is assumed that the reducing component has a known solubility and that it can migrate to meet the oxygen and quickly react. In a third case a finite reaction rate is modelled between the oxygen and the reducing species.The sample calculations show that if the reducing mineral has to be supplied from the backfill a large fraction of the spent fuel could be oxidised. If the corrosion products of a degraded steel canister can supply the reducing species and the redox reaction is fast, very small amounts of the fuel could be oxidised. Literature data indicate that the redox reaction rate may not be so fast that it can be considered instantaneous and then a considerable fraction of the fuel could be oxidised. The model gives a means of exploring which mechanisms and data may be of most importance for radiolytic fuel dissolution, but the realism of the data and the model must be tested further. There is a lack of understanding and data on reaction rates, heterogeneous as well as homogeneous. This is crucial to the results.

scholarly journals Monitoring the Interfacial Polymerization of Piperazine and Trimesoyl Chloride with Hydrophilic Interlayer or Macromolecular Additive by in-situ FT-IR Spectroscopy

2019 ◽  
Author(s):  
Xi Yang
Keyword(s):  
Ir Spectroscopy ◽  
Reaction Rate ◽  
Interfacial Polymerization ◽  
Reaction System ◽  
Reaction Rates ◽  
Water Permeation ◽  
Ft Ir ◽  
Trimesoyl Chloride ◽  
Ft Ir Spectroscopy

The interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC) has been extensively utilized to synthesize the nanofiltration (NF) membrane. However, it is still a huge challenge to monitor the IP reaction, because of the fast reaction rate and the formed ultra-thin film. Herein, two effective strategies are applied to reduce the IP reaction rate: (1) the introduction of hydrophilic interlayers between the porous substrate and the formed polyamide layer; (2) the addition of macromolecular additives in the aqueous solution of PIP. As a result, in-situ FT-IR spectroscopy was firstly used to monitor the IP reaction of PIP/TMC reaction system, with hydrophilic interlayers or macromolecular additives. Moreover, we study the formed polyamide layer growth on the substrate, in a real-time manner. The in-situ FT-IR experimental results confirm that the IP reaction rates are effectively suppressed and the formed polyamide thickness reduces from 138±24 nm to 46±2 nm. Furthermore, the optimized NF membrane with excellent performance are consequently obtained, which include the boosted water permeation flux about 141~238 (L·m2·h/MPa) and superior salt rejection of Na2SO4 > 98.4%.

REPRO: Through Diffusion Experiment (TDE) - Diffusion and Porosity Properties of Rock Matrix in Stress Field of Repository Level

2020 ◽  
Author(s):  
Kalle Rahkola ◽  
Antti Poteri ◽  
Lasse Koskinen ◽  
Peter Andersson ◽  
Kersti Nilsson ◽  
...  
Keyword(s):  
Stress Field ◽  
Performance Assessment ◽  
Spent Nuclear Fuel ◽  
Diffusion Experiment ◽  
Spent Fuel ◽  
Tracer Transport ◽  
Rock Matrix ◽  
Safety Case ◽  
Through Diffusion

<p>Radionuclides usually migrate slower than the flowing water due to sorption and matrix diffusion. The performance assessment assumes that retention takes place mostly in the vicinity of the deposition holes. REPRO (<em>REtention Properties of ROck matrix</em>) experiments analyzed the matrix retention properties of the rock matrix under realistic conditions deep in the bedrock in ONKALO underground characterization facility at Olkiluoto, Finland. The objective was to investigate tracer transport in the rock matrix, which was representative to the near-field of the final disposal repository of the spent nuclear fuel, and to demonstrate that the assumptions made in the safety case of the deep geological spent fuel repository were in line with site evidence.</p><p>REPRO is composed of several supporting laboratory and <em>in-situ</em> experiments which investigate the retention properties under different experimental configurations. The first <em>in-situ</em> experiments were water phase diffusion experiments performed 2012-2013. Through Diffusion Experiment (TDE) studies diffusion and porosity properties of rock matrix in stress field of repository level and sorption properties of nuclides in intact rock circumstances.</p><p>The TDE experiment has been performed in three parallel drillholes drilled near to each other. Breakthrough of the radioactive tracer is monitored with on-line measurements and samplings along and perpendicular to the foliation. The non-sorbing radioactive isotope traces of HTO and <sup>36</sup>Cl, as well as slightly sorbing <sup>22</sup>Na and strongly sorbing <sup>133</sup>Ba and <sup>134</sup>Cs were used. TDE was designed to control advective flow, as it had caused problems in previous <em>in-situ</em> tests.</p><p>Supporting laboratory studies were performed for drillcore samples sampled from the experimental drillholes. In these laboratory experiments, i.e. porosity, permeability and diffusion coefficients of the drillcores were determined using different methods.</p><p>The TDE experiment was carried out from 2016 to 2019. A breakthrough was seen in the timeframe predicted by scoping calculations carried out. REPRO has produced data and knowledge to the safety case and the performance assessment. According to the preliminary results, values measured in the laboratory are applicable also in larger scale and <em>in-situ</em> conditions.</p>

The Influence of Ligands and Precipitates on the Release of Nuclides from the Near Field under Natural Repository Conditions

2000 ◽  
Vol 663 ◽  
Author(s):  
L. Liu ◽  
I. Neretnieks
Keyword(s):  
Uranium Oxide ◽  
Spent Nuclear Fuel ◽  
Transport Model ◽  
Radiation Power ◽  
Near Field ◽  
Reference Scenario ◽  
Spent Fuel ◽  
Secondary Phases ◽  
Fuel Surface ◽  
Fuel Pellets

ABSTRACTOnce groundwater intrudes into a damaged canister and wets the spent fuel pellets, radiation emitted from the spent nuclear fuel splits nearby water into oxidizing and reducing species. This may lead to an oxidizing condition near the fuel pellets. As a result, uranium oxide that makes up the fuel matrix will become more soluble, and the incorporated radionuclides will be released more rapidly. The dissolution process is, however, a dynamic one that can be influenced by many factors. Of great importance are the radiation power of the fuel matrix, the concentration of ligands near the fuel surface, and the transport resistance of the near field. Consequently, the escape of nuclides from the damaged canister is dominated mainly by the intrusion of ligands, and the precipitation/dissolution of secondary phases within the fuel rods. To investigate the possible effects of ligands and precipitates, a coupled dissolution and transport model, which includes the barrier effect of the Zircaloy claddings, is developed. The application of the model to a SKB-specified reference scenario indicates that by far the largest fraction of the oxidized uranium will reprecipitate within the canister. This may significantly decrease the fuel surface available for oxidation and the water available for radiolysis. Subsequently, much less fuel matrix will be dissolved and much less of the other nuclides will be released. Simulations further identify that carbonate and silicate have the greatest influences on the formation of secondary phases, and on the release of nuclides, under natural repository conditions.

Retrograde Solubilities of Source Term Phases

1996 ◽  
Vol 465 ◽  
Author(s):  
William M. Murphy
Keyword(s):  
Heat Dissipation ◽  
Source Term ◽  
Spent Nuclear Fuel ◽  
Radioactive Decay ◽  
Source Area ◽  
Reaction Rates ◽  
Mineral Dissolution ◽  
Spent Fuel ◽  
Natural Analog ◽  
Using Data

ABSTRACTNatural analog, experimental, and thermodynamic studies indicate that the properties of secondary uranyl minerals are likely to control the source term for U and other radioéléments incorporated in these phases in the proposed Yucca Mountain repository. Thermodynamic calculations using data from the 1992 NEA data base indicate an increase in the equilibrium constant for schoepite dissolution from 103.1 to 104.8 with decreasing temperature from 100° to 25°C, i.e., retrograde solubility. Enthalpies for mineral transformation reactions that consume protons and release cations are typically negative, suggesting that solubilities of other uranyl phases such as uranophane increase more than that of schoepite with decreasing temperature. Solubilities of mineral phases associated with spent nuclear fuel will be initially relatively low under the elevated repository temperature regime. As the temperature of the repository decreases due to radioactive decay and heat dissipation, source term mineral solubilities increase. The rate of release of U and other species is controlled by a series of processes: transport of oxidants and flux of water; oxidative dissolution of spent fuel; uranyl mineral precipitation; uranyl mineral dissolution or transformation; and radionuclide transport. Decreasing diffusion and reaction rates and increasing uranyl mineral solubilities with decreasing temperature may lead to a change with time from solubility to transport or reaction rate as a source term controlling mechanism. Preservation of large quantities of uranyl minerals formed by oxidation of uraninite and radiometrie ages of secondary uranophane at the natural analog site at Peña Blanca indicate that oxidative alteration of uraninite was fast relative to transport of U away from the deposit. The successive formation of schoepite and uranophane in natural settings where uraninite has been oxidized may represent a paragenesis reflecting increasing temperature or increasing incorporation of environmental components. In contrast, diminishing temperature conditions in a repository source area could lead to the reverse sequence of mineral formation.

scholarly journals Monitoring the Interfacial Polymerization of Piperazine and Trimesoyl Chloride with Hydrophilic Interlayer or Macromolecular Additive by In Situ FT-IR Spectroscopy

Membranes ◽  
2020 ◽  
Vol 10 (1) ◽  
pp. 12 ◽  
Author(s):  
Xi Yang
Keyword(s):  
Aqueous Solution ◽  
Ir Spectroscopy ◽  
Reaction Rate ◽  
Interfacial Polymerization ◽  
Reaction Rates ◽  
Water Permeation ◽  
Ft Ir ◽  
Trimesoyl Chloride ◽  
Ft Ir Spectroscopy

The interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC) has been extensively utilized to synthesize nanofiltration (NF) membranes. However, it is still a huge challenge to monitor the IP reaction, because of the fast reaction rate and the formed ultra-thin film. Herein, two effective strategies were applied to reduce the IP reaction rate: (1) the introduction of hydrophilic interlayers between the porous substrate and the formed polyamide layer, and (2) the addition of macromolecular additives in the aqueous solution of PIP. As a result, in situ Fourier transform infrared (FT-IR) spectroscopy was firstly used to monitor the IP reaction of PIP/TMC with hydrophilic interlayers or macromolecular additives in the aqueous solution of PIP. Moreover, the formed polyamide layer growth on the substrate was studied in a real-time manner. The in situ FT-IR experimental results confirmed that the IP reaction rates were effectively suppressed and that the formed polyamide thickness was reduced from 138 ± 24 nm to 46 ± 2 nm according to TEM observation. Furthermore, an optimized NF membrane with excellent performance was consequently obtained, which included boosted water permeation of about 141–238 (L/m2·h·MPa) and superior salt rejection of Na2SO4 > 98.4%.

Development of a methodology for characterizing reaction kinetics, rheology, and in situ compaction of polyimide prepregs during cure

2019 ◽  
Vol 54 (6) ◽  
pp. 835-843
Author(s):  
James Magato ◽  
Donald Klosterman
Keyword(s):  
Reaction Rate ◽  
Reaction Rates ◽  
Void Content ◽  
Heating Rates ◽  
Pressure Application ◽  
Composite Fabrication ◽  
Novel Approach ◽  
Panel Thickness ◽  
Volatile Generation

PMR-type polyimide prepregs are challenging to fabricate into high quality composites due to volatiles that are generated and must be removed in situ during processing. The current work was conducted to develop accurate, reliable, and practical characterization techniques of the prepreg rheology, volatile generation, and subsequent volatile removal from the prepreg during composite fabrication. Thermal analysis was used to characterize volatile generation, reaction rates, and rheology. A novel approach was used to measure the thickness of the prepreg in situ during vacuum bag/oven processing using a high-temperature LVDT. Experimental results are presented for the commercially available RM-1100 polyimide/carbon prepreg system, including the reaction rate, rheology, and panel thickness results for a series of heating rates and ply counts. The results show the key interrelationships in these coupled phenomena and how that information can be used to select the optimum temperature of pressure application to minimize the final void content.

scholarly journals Monitoring the Interfacial Polymerization of Piperazine and Trimesoyl Chloride with Hydrophilic Interlayer or Macromolecular Additive by in-situ FT-IR Spectroscopy

2020 ◽  
Author(s):  
Xi Yang
Keyword(s):  
Aqueous Solution ◽  
Ir Spectroscopy ◽  
Reaction Rate ◽  
Interfacial Polymerization ◽  
Reaction Rates ◽  
Water Permeation ◽  
Ft Ir ◽  
Trimesoyl Chloride ◽  
Ft Ir Spectroscopy

The interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC) has been extensively utilized to synthesize nanofiltration (NF) membranes. However, it is still a huge challenge to monitor the IP reaction, because of the fast reaction rate and the formed ultra-thin film. Herein, two effective strategies were applied to reduce the IP reaction rate: (1) the introduction of hydrophilic interlayers between the porous substrate and the formed polyamide layer, and (2) the addition of macromolecular additives in the aqueous solution of PIP. As a result, in situ Fourier transform infrared (FT-IR) spectroscopy was firstly used to monitor the IP reaction of PIP/TMC with hydrophilic interlayers or macromolecular additives in the aqueous solution of PIP. Moreover, the formed polyamide layer growth on the substrate was studied in a real-time manner. The in situ FTIR experimental results confirmed that the IP reaction rates were effectively suppressed and that the formed polyamide thickness was reduced from 138 ± 24 nm to 46 ± 2 nm according to TEM observation. Furthermore, an optimized NF membrane with excellent performance was consequently obtained, which included boosted water permeation of about 141–238 (L/m2·h·MPa) and superior salt rejection of Na2SO4 > 98.4%.

scholarly journals Monitoring the Interfacial Polymerization of Piperazine and Trimesoyl Chloride with Hydrophilic Interlayer or Macromolecular Additive by in-situ FT-IR Spectroscopy

2019 ◽  
Author(s):  
Xi Yang
Keyword(s):  
Ir Spectroscopy ◽  
Reaction Rate ◽  
Interfacial Polymerization ◽  
Reaction System ◽  
Reaction Rates ◽  
Water Permeation ◽  
Ft Ir ◽  
Trimesoyl Chloride ◽  
Ft Ir Spectroscopy

The interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC) has been extensively utilized to synthesize the nanofiltration (NF) membrane. However, it is still a huge challenge to monitor the IP reaction, because of the fast reaction rate and the formed ultra-thin film. Herein, two effective strategies are applied to reduce the IP reaction rate: (1) the introduction of hydrophilic interlayers between the porous substrate and the formed polyamide layer; (2) the addition of macromolecular additives in the aqueous solution of PIP. As a result, in-situ FT-IR spectroscopy was firstly used to monitor the IP reaction of PIP/TMC reaction system, with hydrophilic interlayers or macromolecular additives. Moreover, we study the formed polyamide layer growth on the substrate, in a real-time manner. The in-situ FT-IR experimental results confirm that the IP reaction rates are effectively suppressed and the formed polyamide thickness reduces from 138±24 nm to 46±2 nm. Furthermore, the optimized NF membrane with excellent performance are consequently obtained, which include the boosted water permeation flux about 141~238 (L·m2·h/MPa) and superior salt rejection of Na2SO4 > 98.4%.

The Impact of Alpha-Radiolysis on the Release of Radionuclides from Spent Fuel in a Geologic Repository

1983 ◽  
Vol 26 ◽  
Author(s):  
Ivars Neretnieks
Keyword(s):  
Nuclear Fuel ◽  
Uranium Oxide ◽  
Spent Nuclear Fuel ◽  
Crystalline Rock ◽  
Reducing Agents ◽  
Spent Fuel ◽  
Geologic Repository ◽  
Oxidizing Agents ◽  
Dissolved Iron ◽  
The Impact

ABSTRACTSpent nuclear fuel buried in deep geologic repositories may eventually be wetted by water. The alfa-radiation will radiolyse the water and produce hydrogen and oxidizing agents, mainly hydrogen peroxide and oxygen. The hydrogen will escape by diffusion and the oxidizing agents may attack the canister materials, oxidize the uranium oxide matrix or diffuse out and oxidize reducing agents in the surrounding rock.The rate of radiolysis has been computed recently within the Swedish nuclear fuel safety projects KBS. It is strongly influenced by the amount of available water and by the presence of dissolved iron. The movement of the oxidizing agents out from the canister and their reaction with the reducing agents (mainly ferrous iron) in the Swedish crystalline rock has been modelled as well as the movement of the radionuclides within and past the redox front. Some substances such as uranium, neptunium and technetium will precipitate at the redox front and will be withdrawn from the water to a considerable extent.

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