Physical Chemistry Commons^™

The Electrochemical Separation Of Curium And Americium: Quaterly Report January - March, 2006, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium. For two and a half years, research has been actively performed on this project, and is currently on schedule for the proposed timelines.

Progress:

• The electrochemical characterization of Ce and Eu complexed with EDTA, NTA, and Citrate has been completed.

• Synthesis of the polymer substrate and the chelating ligand is underway. Approximately 50 grams of disulfide has been produced to produce the chelating thiol group required for the last set of studies.

• Gold substrates have been prepared to perform …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of nuclear waste. Iodine-129, a long-lived fission product formed by both commercial nuclear power generation and nuclear weapons production, is released when reprocessing nuclear fuel. Since iodine can be concentrated in the human thyroid, any uncontrolled release of iodine may result in an increased rate of thyroid cancer in the exposed population. For this reason, recovery of iodine is important for implementing any nuclear transmutation strategy.

The stability of the association of iodine with FCC and NOM products are studied. Product …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Oliver Hemmers, Dale L. Perry

Separations Campaign (TRP)

Argonne National Laboratory has proposed a new extraction procedure to handle TRISO-coated fuels, the Fluoride Extraction Process, or FLEX. The FLEX process is designed to separate the uranium in the fuel from the actinides and most fission products by taking advantage of the unique properties of uranium hexafluoride (UF₆). In the FLEX process, the used TRISO fuel is reacted with zirconium fluoride salt, forming UF₆ and the fluoride salts of the actinides and fission products. At process temperatures, the UF₆ volatizes into a gas, and is released from the molten salt mixture. This leaves behind the …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective of this project is to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in aqueous solution and use this data to effectively separate species with very similar chemical properties. In consultation with a national laboratory collaborators, electrochemical methods and materials will be evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing the ability to selectively target and sequester individual species from mixtures. This project is in its third year and has successfully completed Phases 1 and 2.

The following were specific goals for this year:

• To develop a fundamental …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski, Byron Bennett

Separations Campaign (TRP)

The research objectives of this project are as follows:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration (by the addition of NaNO₃), actinide ion concentration, temperature, and time.
• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and Pu are evaluated as a function of AHA concentration, metal ion concentration, …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 1st Quarterly Report, 2006, Clemens Heske

Fuels Campaign (TRP)

This project is devoted to an in-depth study of the chemical and electronic impact of metal fission products on the coating layers in TRISO nuclear fuel. In particular, there is a focus on the investigation of Pd, Cs, and Ag and their interface formation with SiC and carbon-based substrates. A variety of surface and near-surface bulk sensitive probes that investigate the occupied and unoccupied electronic states of the substrate and the metal overlayer have been utilized. By a controlled and stepwise deposition of the metal overlayer, it is possible to gain substantial insight into the formation of interfaces and their …

Interaction Between Metal Fission Products And Triso Coating Materials, Clemens Heske

Fuels Campaign (TRP)

In this project the chemical bonding and interface formation of metal fission products with the coating materials used in TRISO fuel particles is investigated. The interface formation of Pd, Cs, and Ag with SiC and pyrolytic carbon is studied in detail. Using the SiC single crystals and TRISO coating materials as substrates, interfaces are prepared under controlled conditions in an ultra-high vacuum environment and are studied with a photoelectron spectroscopy, Auger electron spectroscopy, Inverse Photoemission, X-ray emission spectroscopy, and X-ray absorption spectroscopy. Recent additions to the experimental approach include microscopic techniques (Transmission Electron Microscopy, Scanning Tunneling Microscopy, Atomic Force Microscopy) …

Dissolution, Reactor, And Environmental Behavior Of Zro2-Mgo Inert Fuel Matrix, Kenneth Czerwinski

Fuels Campaign (TRP)

This project examines inert fuels containing ZrO₂ and MgO as the inert matrix, with the relative amount of MgO varied from 30% to 70% in ZrO₂. Reactor physics calculations are used to examine suitable quantities of burnable poisons from the candidate elements Gd, Er, or Hf with reactor grade Pu providing the fissile component, with up to 10% of ²³⁹Pu. Ceramics are synthesized and characterized based on the reactor physics results. The solubility of the fuel ceramics, in reactor conditions, reprocessing conditions, and repository conditions, are investigated in a manner to provide thermodynamic data necessary for …

Solution-Based Synthesis Of Nitride Fuels, Kenneth Czerwinski, Thomas Hartmann

Fuels Campaign (TRP)

A wide variety of fuel concepts are considered for advanced reactor technology including metals, metal oxides or metal nitrides as solid solutions or composite materials. Nitride fuels have appropriate properties for advanced fuels including high thermal conductivity, thermal stability, solid-state solubility of actinides, fissile metal density, and suitable neutronic properties. A drawback of nitride fuels involves their synthesis. A key parameter for preparing oxide fuels is the precipitation step in the sol-gel process. For nitride fuels, the current synthetic route is carbothermic reduction from the oxide to the nitride. This process step is based on solid phase reactions and for …

The Electrochemical Separation Of Curium And Americium: Quaterly Report April - June, 2005, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium.

Results

• We have completed the electrochemical investigation in of the Ce³⁺/Ce⁴⁺ redox couple and have determined the optimum experimental conditions.

• Computer modeling of the cerium using the JChess speciation-modeling program has been completed for the Ce redox couple. Traditional complexing ligands such as EDTA, oxalate, NTA, phosphate, acetate, and sulfate have been purchased and will be used to initiate the complexation and electrochemical characterization.

• Electrochemical investigations have continued on the Eu²⁺/Eu³⁺ redox …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quaterly Report January-March 2005, Spencer M. Steinberg

Separations Campaign (TRP)

We have continued experiments on the reaction of iodate with sphagnum peat moss. We have established that iodate added to a suspension of peat moss undergoes reduction and to a significant extent is incorporated in to the peat moss. We have confirmed the incorporation of iodine into the peat matrix using pyrolysis GC/MS. In addition, we have performed a scaled up pyrolysis using the preparative GC system that was described in a previous report. This instrument consisted of a packed column gas chromatograph (SRI 8010) with a TCD detector and injector valve equipped with a thermal desorber. Pyrolysis experiments were …

Evaluation Of Fluorapatite As A Waste-Form Material: First Quarter Report, January 1 - March 31, 2005, Dennis W. Lindle, Oliver Hemmers

Separations Campaign (TRP)

Fluorapatite, fluorinated calcium phosphate, has been identified as a potential matrix for the entombment of the zirconium fluoride fission product waste stream from the proposed FLEX process. If the efficacy of fluorapatite-based waste-storage can be demonstrated, then new and potentially more-efficient options for handling and separating high-level wastes, based on fluoride-salt extraction, will become feasible. This proposal will develop a dual-path research project to develop a process to fabricate a synthetic fluorapatite waste form for the ZrF₄, FP waste stream, characterize the waste form, examine its performance under environmental conditions, and correlate the behavior of the waste form …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System: Quaterly Report January - March, 2005, Kenneth Czerwinski, Cynthia-May Gong, Amber Wright

Separations Campaign (TRP)

The speciation of hexavalent U and tetravalent Pu will be examined in the TBP-dodecane-nitric acid systems. This topic is chosen based on data needs for separation modeling identified by the AFCI. Emphasis will be placed on studying the influence of nitrate and acetohydroxamic acid on U and Pu speciation as well as conditions where a third phase forms in the organic phase. The organic phase will be 30% TBP in dodecane. Equal volumes of aqueous and organic phase will be used. The speciation of the actinides in the aqueous and organic phase will be determined by a number of different …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System: Quarterly Report January - March, 2006, Amber Wright, Frederic Poineau, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of hexavalent U and tetravalent Pu will be examined in the Tributylphosphate (TBP)-dodecane-nitric acid systems. This topic is chosen based on data needs for separation modeling identified by the AFCI. Emphasis will be placed on studying the influence of nitrate and acetohydroxamic acid on U and Pu speciation as well as conditions where a third phase forms in the organic phase. The organic phase will be 30% TBP in dodecane. Equal volumes of aqueous and organic phase will be used. The speciation of the actinides in the aqueous and organic phase will be determined by a number of …

Dissolution, Reactor, And Environmental Behavior Of Zro2-Mgo Inert Fuel Matrix: Quarterly Report, January 2005 To March 2005, Earl Wolfram, Thomas Hartmann, Kenneth Czerwinski

Fuels Campaign (TRP)

This project will examine inert matrix fuels containing ZrO₂ and MgO as the inert matrix, with the relative amount of MgO varied from 30% to 70% in ZrO₂. Reactor physics calculations will be used to examine suitable quantities of burnable poisons from the candidate elements Gd, Er, or Hf with reactor grade Pu providing the fissile component, with up to 10% of ²³⁹Pu. Ceramics will be synthesized and characterized based on the reactor physics results. The solubility the fuel ceramics, in reactor conditions, reprocessing conditions, and repository conditions, will be investigated in a manner to provide …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quaterly Report October-December 2004, Spencer M. Steinberg

Separations Campaign (TRP)

We have conducted a large number of experiments to determine the possible reaction of iodate with sphagnum peat moss. These experiments indicate that the natural organic material reacts with iodate resulting in the formation of organically bound iodine and/or iodide in solution.

In the last quarter, we have conducted a number of experiments at various pHs and several temperatures (70oC, 60oC and 40oC). The reaction of iodate with peat follows pseudo first-order kinetics, although the reaction rate does appear to decrease significantly with reaction time. As noted in a previous report organically bound iodine appears to go through a maximum …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of nuclear waste. Iodine-129, a long-lived fission product formed by both commercial nuclear power generation and nuclear weapons production, is released when reprocessing nuclear fuel. Since iodine can be concentrated in the human thyroid, any uncontrolled release of iodine may result in an increased rate of thyroid cancer in the exposed population. For this reason, recovery of iodine is important for implementing any nuclear transmutation strategy.

The stability of the association of iodine with FCC and NOM products are studied. Product …

Development, Fabrication And Study Of Fullerene-Containing Carbon Material (Fcc) For Immobilization Of Iodine: Progress Report #1-4, Michael Savopulo, Boris E. Burakov

Separations Campaign (TRP)

During current reporting period the experiments on synthesis of ceramic-like material by conversion of iodine-doped FCC and activated carbon to Si_xC_y have been completed. Cold pressed granules of FCC and activated carbon were rinsed in water-ethanol solution of tetraethoxysilane (TEOS), Si(OC₂H₅)₄, and then used for further synthesis. All new samples obtained have been studied using precise powder XRD analysis.

Development, Fabrication And Study Of Fullerene-Containing Carbon Material (Fcc) For Immobilization Of Iodine: Final Report 2005, Michael Savopulo, Boris E. Burakov

Separations Campaign (TRP)

Immobilization of highly radioactive and long-lived isotope of ¹²⁹I, which is a fission product in spent nuclear fuel, requires development of new durable host-materials.

Iodine is a very volatile chemical element, and even its chemically strong compounds such as AgI and CuI are not stable under ultraviolet irradiation or oxidizing conditions. Therefore, development of host materials for iodine immobilization is based on unusual approach – the search and testing of new compounds which were not studied before in respect of iodine sorption and strong fixation.

Although FCC material demonstrated high loading capacity to iodine sorption it is necessary to …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Oliver Hemmers, Dale L. Perry

Separations Campaign (TRP)

Argonne National Laboratory has proposed a new extraction procedure to handle TRISO-coated fuels, the Fluoride Extraction Process, or FLEX. The FLEX process is designed to separate the uranium in the fuel from the actinides and most fission products by taking advantage of the unique properties of uranium hexafluoride (UF₆). In the FLEX process, the used TRISO fuel is reacted with zirconium fluoride salt, forming UF₆ and the fluoride salts of the actinides and fission products. At process temperatures, the UF₆ volatizes into a gas, and is released from the molten salt mixture. This leaves behind the …

Development Of Fluorapatite As A Waste Form: Final Report #280204-1, Boris E. Burakov

Separations Campaign (TRP)

In the framework of Agreement #280204 (first year) it was necessary to review methods of apatite synthesis; identify optimal procedure of precursor preparation; obtain and study first fluorapatite samples. Although, some apatite-based ceramics were successfully synthesized using co-precipitated precursors and sintering method, there are still a lot of uncertainties related to optimal apatite doping with different radionuclides and non-radioactive elements. It is necessary to provide complete incorporation of waste elements into apatite crystalline structure avoiding formation of separate phases of radionuclides. Also, it is important to note that real waste streams might contain radionuclides with essentially different chemical features such …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective of this project is to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in aqueous solution and use this data to effectively separate species with very similar chemical properties. In consultation with our DOE collaborator, electrochemical methods and materials will be evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing our ability to selectively target and sequester individual species from mixtures.

The following were specific goals for this year:

• To develop a fundamental understanding of the thermodynamic properties of actinide and lanthanide species such as Cm, Am, Ce, Nd, …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System: Quarterly Report, Kenneth Czerwinski, Cynthia-May Gong, Amber Wright

Separations Campaign (TRP)

The speciation of hexavalent U and tetravalent Pu will be examined in the TBPdodecane- nitric acid systems. This topic is chosen based on data needs for separation modeling identified by the AFCI. Emphasis will be placed on studying the influence of nitrate and acetohydroxamic acid on U and Pu speciation as well as conditions where a third phase forms in the organic phase. The organic phase will be 30 % TBP in dodecane. Equal volumes of aqueous and organic phase will be used. The speciation of the actinides in the aqueous and organic phase will be determined by a number …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski, Byron Bennett

Separations Campaign (TRP)

The research objectives of this project are as follows:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration (by the addition of NaNO₃), actinide ion concentration, temperature, and time.
• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and Pu are evaluated as a function of AHA concentration, metal ion concentration, …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 2nd Quarter Report, 2005, Clemens Heske

Fuels Campaign (TRP)

The goal of our project is to investigate interface corrosion processes in TRISO nuclear fuel particles. For this purpose, we are undertaking a detailed study of the interface formation between potential candidates for metallic fission products (Pd, Ag, and Cs), likely to diffuse from the kernel of the TRISO particles, with the TRISO coating layers. As a starting point, we are investigating the Pd/SiC interface and will extend our studies to Ag/SiC during our current summer research campaign. The experimental approach comprises the preparation of metal/SiC interfaces in-situ in our ultra-high vacuum system by electron-beam deposition. In order to understand …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 1st Quarter Report, 2005, Clemens Heske

Fuels Campaign (TRP)

In this project we utilize a combination of state-of-the-art soft X-ray spectroscopies to understand the chemical bonding between metal fission products (Pd and Ag) with coating layers in TRISO fuel particles (SiC and pyrocarbon). We are primarily focusing on an analysis of intermediate chemical phases at the interface, the intermixing/diffusion behavior, and the electronic interface structure as a function of material choice (metal and coating materials), temperature, and external stress. In the current first project year, we are beginning these investigations with the Pd/SiC interface, as discussed in the previous two quarterly reports. Our first experiments (both using our lab …

Interaction Between Metal Fission Products And Triso Coating Materials, Clemens Heske

Fuels Campaign (TRP)

The goal of this project is to elucidate the chemical bonding and interface formation of metal fission products with the coating materials used in state-of-the-art TRISO fuel particles. Particular emphasis is placed on an analysis of intermediate chemical phases at the interface, the intermixing/diffusion behavior, and the electronic interface structure as a function of material choice (metal and coating materials), temperature, and external stress. Furthermore, the chemical state of some of the metal fission products will be assessed.

This project studies the interface formation of Pd, Ag, and Cs with SiC and pyrolytic carbon. Using the TRISO coating materials (and …

Evaluation Of Fluorapatite As A Waste-Form Material: First Quarter Report (2004-05), October 1 - December 31, 2004, Dennis W. Lindle, Oliver Hemmers

Separations Campaign (TRP)

Fluorapatite, fluorinated calcium phosphate, has been identified as a potential matrix for the entombment of the zirconium fluoride fission product waste stream from the proposed FLEX process. If the efficacy of fluorapatite-based waste-storage can be demonstrated, then new and potentially more-efficient options for handling and separating high-level wastes, based on fluoride-salt extraction, will become feasible. This proposal will develop a dual-path research project to develop a process to fabricate a synthetic fluorapatite waste form for the ZrF₄, FP waste stream, characterize the waste form, examine its performance under environmental conditions, and correlate the behavior of the waste form …

The Electrochemical Separation Of Curium And Americium: Quaterly Report August-December 2004, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium. The following pages outline the progress on our project to date. We have been actively performing research on this project for three months and are currently on schedule in terms of the proposed timelines.

The initial focus of the project involved setting up the laboratories for the studies outlined in the grant proposal. The instrumentation needed included an electrochemical work station that will perform the bulk of the electrochemical studies. This instrument will complement the electrochemical instrumentation in Dr. Hatchett’s laboratory and …

Dissolution, Reactor, And Environmental Behavior Of Zro2-Mgo Inert Fuel Matrix: Quarterly Report, October 2004 To December 2004, Earl Wolfram, Thomas Hartmann, Kenneth Czerwinski

Fuels Campaign (TRP)

This project will examine inert matrix fuels containing ZrO₂ and MgO as the inert matrix, with the relative amount of MgO varied from 30% to 70% in ZrO₂. Reactor physics calculations will be used to examine suitable quantities of burnable poisons from the candidate elements Gd, Er, or Hf with reactor grade Pu providing the fissile component, with up to 10% of ²³⁹Pu. Ceramics will be synthesized and characterized based on the reactor physics results. The solubility the fuel ceramics, in reactor conditions, reprocessing conditions, and repository conditions, will be investigated in a manner to provide …