Physical Sciences and Mathematics Commons^™

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 …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic 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 radioactive iodine. During the first two years of this program we have examined the potential of Fullerene Containing Carbon compounds (FCC) developed by KRI, and natural organic matter (NOM) as sorbents for iodine released during the reprocessing of nuclear fuel. This work involved the development of bench-scale testing of the FCC and NOM material in a simulated process off-gas environment.

Research Objectives and Goals

• Develop bench-scale experimental set-up and procedures for simulating PUREX head-end vapor phase; Develop experimental procedures …

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

Separations Campaign (TRP)

During first year of the project we were able to demonstrate iodine sorption by a sphagnum peat and Ca(OH)2 mixture. We decided to explore varying the ratio of Ca(OH)2 to sphagnum on the retention of iodine in both the iodine generator experiments and the fuel rod simulator experiments.

We also constructed a device for simulating the dissolution of fuel rods. Early experiments were impacted by sorption of iodine onto various components of the sorption train. We have eliminated or minimized iodine sorption by the system components. We retested both FCC and the sphagnum using this device. In these experiments a …

Evaluation Of Fluorapatite As A Waste-Form Material: Fourth Quarter Report, June 1 - September 30, 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 …

Dissolution, Reactor, And Environmental Behavior Of Zro2-Mgo Inert Fuel Matrix: Quarterly Report, July 2004 To September 2004, Kenneth Czerwinski, Earl Wolfram

Fuels Campaign (TRP)

This project will examine 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 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 …

Nondipole Effects In The Photoionization Of Xe 4d5/2 And 4d3/2: Evidence For Quadrupole Satellites, Oliver Hemmers, Renaud Guillemin, D. Rolles, A. Wolska, Dennis W. Lindle, K. T. Cheng, W. R. Johnson, H. L. Zhou, S. T. Manson

Environmental Studies Faculty Publications

Measurements of nondipole parameters in spin-orbit-resolved Xe 4d photoionization demonstrate dynamical differences arising from relativistic effects. The experimental data do not agree with relativistic random-phase approximation calculations of single ionization dipole and quadrupole channels. It is suggested that the discrepancy is due to the omission of multiple-excitation quadrupole channels, i.e., quadrupole satellite transitions.

Probing Cation Antisite Disorder In Gd2ti2o7 Pyrochlore By Site-Specific Nexafs And Xps, Ponnusamy Nachimuthu, S. Thevuthasan, Mark H. Engelhard, W. J. Weber, D. K. Shuh, N. M. Hamdan, B. S. Mun, E. M. Adams, D. E. Mccready, V. Shutthanandan, Dennis W. Lindle, G. Balakrishnan, R. C. Ewing

Chemistry and Biochemistry Faculty Research

Disorder in Gd₂Ti₂O₇ is investigated by near-edge x-ray-absorption fine structure (NEXAFS) and x-ray photoelectron spectroscopy (XPS). NEXAFS shows Ti⁴⁺ ions occupy octahedral sites with a tetragonal distortion induced by vacant oxygen sites. O 1s XPS spectra obtained with a charge neutralization system from Gd₂Ti₂O₇(100) and the Gd₂Ti₂O₇ pyrochlore used by Chen et al. [Phys. Rev. Lett. 88, 105901 (2002)], both yielded a single peak, unlike the previous result on the latter that found two peaks. The current results give no evidence for …

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

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. This proposal will develop and examine the use of Fullerene Containing Carbon (FCC) compounds as potential sorbents for iodine release from the reprocessing of nuclear fuel. This work will also include the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC material in a simulated process off-gas environment. This experimental capability will also be used to test other potential sorption materials and processes, such as natural organic matter (NOM) and other promising alternatives. …

Nearest-Neighbor-Atom Core-Hole Transfer In Isolated Molecules, Renaud Guillemin, Oliver Hemmers, D. Rolles, S. W. Yu, A. Wolska, I. Tran, A. C. Hudson, J. Baker, Dennis W. Lindle

Environmental Studies Faculty Publications

A new phenomenon sensitive only to next-door-neighbor atoms in isolated molecules is demonstrated using angle-resolved photoemission of site-selective core electrons. Evidence for this interatomic core-to-core electron interaction is observable only by measuring nondipolar angular distributions of photoelectrons. In essence, the phenomenon acts as a very fine atomic-scale sensor of nearest-neighbor elemental identity.

Evaluation Of Fluorapatite As A Waste-Form Material: Third Quarter Report, March 1- May 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 …

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

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 …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. During the first two years of this program the use of Fullerene Containing Carbon (FCC) compounds and Natural Organic Matter (NOM) as potential sorbents for iodine release from the reprocessing of nuclear fuel was examined. This work also included the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC and NOM materials in a simulated process off-gas environment. In the final year of the project we will complete studies of FCC and NOM …

The Electrochemical Separation Of Curium And Americium: Quaterly Report January - March 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.

Data collection and analysis of the Ce³⁺/Ce⁴⁺ redox couple in various supporting electrolytes has continued. All electrolyte systems were investigated at Pt, Au, and Glassy Carbon working electrodes. Analysis of these data was accomplished by performing appropriate background subtractions to reveal net peaks due to Ce redox behavior. Successful identification of the Ce redox couple was achieved with all electrolyte/electrode systems, although a decline in peak resolution was observed with increasing acid concentration. Optimal conditions in this experiment were …

Development, Fabrication And Study Of Fullerene-Containing Carbon Material (Fcc) For Immobilization Of Iodine: Progress Reports 1-1 And 1-2, 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. Such materials should be characterized with the following principal features:

• High loading capacity to iodine incorporation
• Chemical durability and radiation resistance in order to prevent iodine release over long time (higher than 105 years) storage under conditions of underground repository of radioactive wastes
• Possibility to use iodine-doped material as a target for iodine transmutation.

Iodine is a very volatile chemical element, and even its chemically strong compounds such as AgI and CuI are not stable …

Development, Fabrication And Study Of Fullerene-Containing Carbon Material (Fcc) For Immobilization Of Iodine: Final Report #1, 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.

Laboratory of Applied Mineralogy and Radiogeochemistry of the V.G. Khlopin Radium Institute carries out …

Development, Fabrication And Study Of Fullerene-Containing Carbon Material (Fcc) For Immobilization Of Iodine: Progress Report 1-3, Michael Savopulo, Boris E. Burakov

Separations Campaign (TRP)

During previous reporting periods we studied properties of iodine doped FCC in comparison with activated carbon. An additional goal was to investigate the possibility to convert iodine doped FCC and activated carbon into ceramic-like material avoiding iodine loss. In order to obtain ceramic based on C_xN_y with fullerene structure we decided to carry out gamma irradiation of iodine doped samples in nitrogen atmosphere (0.7 atm. N₂). It was found that iodine doping and irradiation caused principal changes in composition of FCC such as substituting of fullerene C₆₀ and graphite (both formed by benzene-like carbon …

Evaluation Of Fluorapatite As A Waste-Form Material, 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 is for renewal of the UNLV portion of 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 …

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

Separations Campaign (TRP)

This research attempts to develop a waste form for disposing of the zirconium fluoride fission product waste stream. Fluorapatite, a naturally-occurring fluorinated calcium phosphate, has been identified as a potential matrix for the entombment of this waste stream. If the efficacy of fluorapatite-based wastestorage 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.

The research effort has been divided along two parallel paths: the Fabrication Path, led by collaborators at the Khlopin Radium Institute (KRI) in St. Petersburg, Russia; and the Characterization Path, led by researchers …

Development Of Fluorapatite As A Waste Form: Progress Report 1-2, Boris E. Burakov

Separations Campaign (TRP)

In the framework of this stage of research the samples of Sr-fluorapatite synthesized earlier had to be studied using different methods.

These are samples of the following desired compositions:

1) Sr₁₀(PO₄)₆F₂ from precipitated precursor;

2) Sr₁₀(PO₄)₆F₂ from precipitated precursor and adding Sr(NO₃)₂;

3) Sr₈CsNd(PO₄)₆F_2.3;

4) Initial precursor for the synthesis of un-doped Sr-fluorapatite.

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

Separations Campaign (TRP)

Research on the apatite family of minerals to determine their suitability in the Flouride Extraction (FLEX) Process, which is part of the radioactive waste management stream.

1) KRI has fabricated and tested special high temperature furnace for fluorapatite synthesis. This equipment might be installed into glove box in order to carry out experiments with real actinides and technetium. The same equipment might be fabricated and installed in Actinide laboratory at HRC by KRI technical staff;

2) Samples of undoped polycrystalline apatite, Ca₅(PO₄)₃F, of low porosity were successfully obtained by sintering in air at 1300°C. …

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

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 …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion, 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, we intend to assess the chemical state of some of the metal fission products. The findings are expected to give valuable information about failure mechanisms of TRISO particles and fission product transport. Secondly, through simulating …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 3rd Quarter Report, 2004, Clemens Heske

Fuels Campaign (TRP)

The goal of this project, which started in May 2004, 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.

In detail, this project is devoted to studying the interface formation of Pd, Ag, and Cs with SiC and pyrolytic carbon. Using the TRISO coating materials and single crystal references as …

Interaction Between Metal Fission Products And Triso Coating Materials: A Study Of Chemical Bonding And Interdiffusion: 4th Quarter Report, 2004, Clemens Heske

Fuels Campaign (TRP)

The goal of this project, which started in May 2004, 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. In detail, this project is devoted to studying the interface formation of Pd, Ag, and Cs with SiC and pyrolytic carbon. In order to study the properties of the relevant interfaces, …

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

Fuels Campaign (TRP)

This project will examine 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 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 …

Performance Characteristics Of Beamline 6.3.1 From 200 Ev To 2000 Ev At The Advanced Light Source, Ponnusamy Nachimuthu, J. H. Underwood, C. D. Kemp, Eric M. Gullikson, Dennis W. Lindle, David K. Shuh, Rupert C. Perera

Chemistry and Biochemistry Faculty Research

Bend magnet beamline 6.3.1 at the Advanced Light Source operates from 200 eV to 2000 eV, primarily used for x-ray absorption fine structure investigations. The beamline optics consist of a compact, entrance-slitless, Hettrick-Underwood type variable-line-spacing plane-grating monochromator and refocusing mirrors to provide a 25 μm × 500 μm spot at the focal point in the reflectometer end station. Wavelength is scanned by the simple rotation of the grating and illuminates a fixed exit slit. The LabView based beamline control and data acquisition computer code has been implemented to provide a convenient interface to the user. The dedicated end station is …