Chemistry Commons^™

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report January-March 2003, 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. …

Environment-Induced Degradation And Crack-Growth Studies Of Candidate Target Materials, Ajit K. Roy, Brendan O'Toole

Transmutation Sciences Materials (TRP)

During the past two years (2001-2002) of this project, the primary effort was focused on evaluating the effect of hydrogen on the cracking behavior of candidate target materials namely, Alloys EP-823, HT-9 and 422 in aqueous environments of different pH values at ambient and elevated temperatures. More recently, emphasis is being placed to evaluate the cracking behavior of these materials in molten lead-bismuth eutectic (LBE) environment at much higher testing temperatures so as to compare the cracking susceptibility in environments containing molten metals and aqueous solutions, respectively. The most recent tests to evaluate the cracking susceptibility were primarily based on …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics: Quarterly Progress Report 12/1/02- 2/28/03, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the AAA proposed application.

Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with very limited density. The transport of oxygen and corrosion products, their interaction and variation of corrosion/precipitation along the flow are not well understood.

The first subtask of this project involves using a …

Experimental Investigation Of Steel Corrosion In Lead Bismuth Eutectic (Lbe): Characterization, Species Identification, And Chemical Reactions, John Farley, Dale L. Perry, Allen L. Johnson

Transmutation Sciences Materials (TRP)

The goal of the present research is to achieve a basic understanding of corrosion of steels by Lead Bismuth Eutectic (LBE). Liquid LBE is under consideration in the transmuter as both a spallation target and as a blanket coolant. There have been previous studies of LBE, especially by the Russians, who have over 80 reactor-years experience with LBE coolant in their Alpha-class submarine reactors. The Russians found that the presence of small amounts (ppm) of oxygen in the LBE significantly reduced corrosion. However, a fundamental understanding and verification of its role in the corrosion of steels is still very incomplete. …

Development Of A Systems Engineering Model Of The Chemical Separations Process: Quarterly Progress Report 11/16/02- 2/15/03, Yitung Chen, Randy Clarksean, Darrell Pepper

Separations Campaign (TRP)

Two activities are proposed in this Phase I task: the development of a systems engineering model and the refinement of the Argonne code AMUSE (Argonne Model for Universal Solvent Extraction). The detailed systems engineering model is the start of an integrated approach to the analysis of the materials separations associated with the TRP Program. A second portion of the project is to streamline and improve an integral part of the overall systems model, which is the software package AMUSE. AMUSE analyzes the UREX process and other related solvent extraction processes and defines many of the process streams that are integral …

Corrosion Of Steel By Lead Bismuth Eutectic: Quarterly Report November- December 2002 January 2003, John Farley

Transmutation Sciences Materials (TRP)

We continue to get valuable data from sputter depth profiling of steel samples. We meet weekly to discuss progress. We took depth-profiling data on D9 steel that had been exposed to LBE. This the first time we have examined this type of steel. This is important because it will enable us to separate out two effects and determine their effect on corrosion: composition of the steel vs surface preparation.

We started to plan a small experiments using a crucible of heated LBE, with the research program to be conducted at UNLV, on basic aspects of corrosion in this system. The …

Calibration Of Ysz Sensors For The Measurement Of Oxygen Concentration In Liquid Pb-Bi Eutectic, Xiaolong Wu, Ramkumar Sivaraman, Ning Li, Wei Hang, T. W. Darling, Yingtao Jiang, Woosoon Yim, Bingmei Fu

Transmutation Sciences Materials (TRP)

Although liquid lead-bismuth eutectic (LBE) is a good candidate for coolant in the subcritical transmutation blanket, it is known to be corrosive to stainless steel, the material of the carrying tubes and containers. Such longterm corrosion problem can be prevented by producing and maintaining a protective oxide layer on the exposed surface of stainless steel. For this purpose, it is required to accurately control the concentration of oxygen dissolved in LBE. Currently, YSZ (Yttria Stabilized Zirconia) oxygen sensors, based on an existing automotive oxygen sensor, with molten bismuth saturated with oxygen as the reference, have been selected for oxygen-concentration measurement. …

Development Of A Systems Engineering Model Of The Chemical Separations Process, Lijian Sun, Haritha Royyuru, Yitung Chen, Randy Clarksean, Darrell Pepper, George Vandegrift, James Laidler

Separations Campaign (TRP)

Project Overview:

• Two Components

– Refine AMUSE Code

– Develop Systems Engineering Model

• Research Objectives

– Develop a framework and environment for a systems engineering analysis of the chemical separations system for the AAA program.

– Establish a baseline systems engineering model from which modifications and improvements can be made.

– Refine the existing AMUSE program that gives a detailed examination of the UREX process, a critical component of the overall separation scheme.

Corrosion Of Steel By Lead Bismuth Eutectic, John Farley, Allen L. Johnson, Dale L. Perry

Transmutation Sciences Materials (TRP)

Materials for transmuter systems must be able to tolerate high neutron fluxes, great temperatures, and chemical corrosion. For lead bismuth eutectic (LBE) systems, there is an additional challenge in that the corrosive behaviors of materials in LBE are not well understood. Most of the available information on LBE systems has come from the Russians, who have over 80 reactor-years experience with LBE coolant in their Alpha-class submarine reactors. The Russians found that the presence of small amounts of oxygen (on the order of parts per million) in the LBE significantly reduced corrosion. However, a fundamental understanding and verification of its …

Surface Studies Of Corrosion Of Stainless Steel By Lead Bismuth Eutectic, Daniel Koury, Brian D. Hosterman, John Farley, Dale L. Perry, D. Parsons, J. Manzerova, Allen L. Johnson

Transmutation Sciences Materials (TRP)

Why is Lead Bismuth Eutectic Important?

• Changing national security stances have led to reexamination of nuclear waste reprocessing

• Dangerous actinides can be separated and

• Transmuted into safer products, creating a waste form dangerous for only hundreds of years, in addition to the production (up to 1/3 of the original fission energy) of useful energy

• Non-moderating coolants or spallation targets for production of fast neutrons is required for transmutation

• Russian experience with LBE coolants in their nuclear submarine fleet makes LBE an attractive possible transmutation coolant technology

• Corrosion of steel by LBE is an important …

Environment-Induced Degradation And Crack-Growth Studies Of Candidate Target Materials, Ajit K. Roy, Brendan O'Toole, Zhiyong Wang, David W. Hatchett

Transmutation Sciences Materials (TRP)

The primary objective of this task is to evaluate the potential for the environmentally-assisted cracking of candidate target materials for applications in spallation-neutron-target systems, such as accelerator-driven system for the transmutation of waste. The materials selected for evaluation and characterization are martensitic stainless steels (SS) including Alloys HT- 9, EP 823 and Type 422 stainless steel.

More recently, this experimental program has been expanded to evaluate the effect of molten lead-bismuth eutectic (LBE) on the corrosion behavior of target materials in the presence of oxygen. Since the materials performance laboratory (MPL) at UNLV currently cannot accommodate this type of testing, …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The corrosion of structural materials is a major concern for the use of lead-bismuth eutectic (LBE) systems for nuclear applications such as in transmuter targets or fast reactors. Corrosion in liquid metal systems can occur through various processes, including, for example, dissolution, formation of inter-metallic compounds at the interface, and penetration of liquid metal along grain boundaries. Predicting the rate of these processes depends on numerous system operational factors: temperature, system geometry, thermal gradients, solid and liquid compositions, and velocity of the liquid metal, to name a few. Corrosion, along with mechanical and/or hydraulic factors, often contributes to component failure. …

Modeling Of Corrosion In Oxygen Controlled Lead Bismuth Eutectic Systems With The Coupling Of Chemical Kinetics And Hydrodynamics, Samir Moujaes, Yitung Chen, Kanthi Kiran Dasika, Chao Wu

Transmutation Sciences Materials (TRP)

Objectives:

• To simulate a 2-D model of the Materials Test Loop by approximating it to be a toroid with a pie cross section for the purpose of comparing the simulated results with the analytical results.
• The temperature and concentration profiles on the wall boundaries imposed are similar to the actual test model.
• Geometry effects have great influence on local corrosion rate.
• A 2-D benchmark problem and a sudden expansion case are studied which show good consistency to analytical solution.
• Results from 2-D sudden expansion problem are similar to experimental data obtained by other researchers.

Nuclear Criticality, Shielding, And Thermal Analyses Of Separations Processes For The Transmutation Fuel Cycle, William Culbreth, Denis Beller

Separations Campaign (TRP)

The first step in any transmutation strategy is the separation of radionuclides in used nuclear fuel. The current separation strategy supporting the Advanced Fuel Cycle Initiative (AFCI) program is based on the use of a solvent extraction separation process to separate the actinides, fission products, and uranium from used commercial nuclear fuel, and on the use of pyrochemical separation technologies to process used transmuter fuels. To separate the fission products and transuranic elements from the uranium in used fuel, the national program is developing a new solvent extraction process, the Uranium Extraction Plus, or UREX+, process, based on the traditional …

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

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, 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 actinides …

Investigation Of The Corrosion Of Steel By Lead-Bismuth Eutectic (Lbe) Using Scanning Electron Microscopy And X-Ray Photoelectron Spectroscopy, Daniel Koury

UNLV Theses, Dissertations, Professional Papers, and Capstones

Lead Bismuth Eutectic (LBE) has been proposed for use in programs for accelerator transmutation of waste. LBE is the leading candidate material as a spallation target and an option for the sub-critical blanket coolant. The corrosion of 316 and 316L stainless steels by LBE has been studied using UNLV's facilities for Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). We have compared exposed and unexposed samples and studied the differences. Some amount of surface contamination is present on the samples and has been removed by ionbeam etching. The unexposed samples reveal typical stainless steel characteristics: a chromium oxide passivation …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report September-December 2002, 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 sorbtion materials and processes, such as natural organic matter (NOM) and other promising alternatives. …

Development Of A Systems Engineering Model Of The Chemical Separations Process: Quarterly Progress Report 8/16/02- 11/15/02, Yitung Chen, Randy Clarksean, Darrell Pepper

Separations Campaign (TRP)

Two activities are proposed in this Phase I task: the development of a systems engineering model and the refinement of the Argonne code AMUSE (Argonne Model for Universal Solvent Extraction). The detailed systems engineering model is the start of an integrated approach to the analysis of the materials separations associated with the AAA Program. A second portion of the project is to streamline and improve an integral part of the overall systems model, which is the software package AMUSE. AMUSE analyzes the UREX process and other related solvent extraction processes and defines many of the process streams that are integral …

Fragmentation Processes Following Core Excitation In Acetylene And Ethylene By Partial Ion Yield Spectroscopy, Maria Novella Piancastelli, Wayne C. Stolte, Gunnar Ohrwall, S-W Yu, D. Bull, K. Lantz, Alfred S. Schlachter, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Partial ion yield spectroscopy provides a very detailed picture of fragmentation processes following core excitation in isolated molecules. We exploit this potential in the analysis of decay processes following C1s→π and C1s→Rydberg excitations in ethylene and acetylene. We show that the relative intensity of spectral features related to the excitation to empty molecular orbitals or to Rydberg states is a function of the time variation of the fragmentation process. Namely, we see an intensity increase in the Rydberg states compared to the molecular orbitals as the fragmentation process becomes more extensive, a result attributable to the diffuse nature of the …

Corrosion Of Steel By Lead Bismuth Eutectic: Quarterly Report August September October 2002, John Farley

Transmutation Sciences Materials (TRP)

We continued with sputter depth profiling of 316 and 316L steel samples that have been exposed to LBE. We also calibrated the sputter depth profiling using a sample of SiO₂ on Si, and the SEM. This is a valuable independent determination of the thickness of oxide layers.

In the laboratory, progress continues using the XPS machine. Experiments have been performed on steel samples using Argon ions to mill away the surface of the sample, thereby making measurements as a function of depth. This "ion beam milling" proceeds slowly through the oxide layer that covers the steel sample. We are …

University Of Nevada, Las Vegas Advanced Accelerator Applications University Participation Program: Quarterly Report, Third Quarter Year 2 (Sept. 2002 To Nov. 2002), Anthony Hechanova

Transmutation Research Program Reports (TRP)

This Quarterly Report is a primary deliverable from the University of Nevada, Las Vegas (UNLV) Advanced Accelerator Applications (AAA) University Participation Program (UPP) Director to the U.S. Department of Energy (DOE) as described in the UNLV AAA proposal and Statement of Work for the Fourth Quarter.

The UNLV AAA UPP Director implements the program’s administration using staff from the Harry Reid Center for Environmental Studies (HRC) to ensure that work conducted under the UNLV AAA UPP meets program objectives. The UNLV AAA program consists of three components: Program Support, Research Infrastructure Augmentation, and Student Research.

Development Of A Systems Engineering Model Of The Chemical Separations Process, Yitung Chen, Randy Clarksean, Darrell Pepper

Separations Campaign (TRP)

The AAA program is developing technology for the transmutation of nuclear waste to address many of the long-term disposal issues. An integral part of this program is the proposed chemical separations scheme. This process, as envisioned by Argonne National Laboratory (ANL) researchers, will be outlined later in this report.

Nearly all issues related to risks to future generations arising from long-term disposal of such spent nuclear fuel is attributable to ~1% of its content. This 1% is made up primarily of plutonium, neptunium, americium, and curium (the transuranic elements) and long-lived isotopes of iodine and technetium created as products from …

Preliminary Geochemical Evaluation Of Groundwaters From Wells Of The Nye County Early Warning Drilling Program, Irene Farnham, Klaus J. Stetzenbach, Amy J. Smiecinski

Publications (YM)

As part of the Yucca Mountain Oversight program, the Nye County Nuclear Waste Repository Project Office (NWRPO) has established a groundwater monitoring program to protect groundwater resources for the residents of Nye County in Amargosa and Pahrump Valleys. This groundwater monitoring program, referred to as the Nye County Early Warning Drilling Program (NCEWDP), involves drilling a series of wells down-gradient from Yucca Mountain for long term groundwater monitoring and also to provide much needed geologic and hydrologic information in this area. A comprehensive database of aquifer parameters in the alluvial, volcanic, and carbonate aquifers down-gradient hydrogeologically of Yucca Mountain is …

Holographic Analysis Of Diffraction Structure Factors, S. Marchesini, N. Mannella, C. S. Fadley, M. A. Van Hove, J. J. Bucher, D. K. Shuh, L. Fabris, M. J. Press, M. W. West, Wayne C. Stolte, Z. Hussain

Chemistry and Biochemistry Faculty Research

We combine the theory of inside-source/inside-detector x-ray fluorescence holography and Kossel lines/x ray standing waves in kinematic approximation to directly obtain the phases of the diffraction structure factors. The influence of Kossel lines and standing waves on holography is also discussed. We obtain partial phase determination from experimental data obtaining the sign of the real part of the structure factor for several reciprocal lattice vectors of a vanadium crystal.

Hydrogen-Induced Embrittlement Of Candidate Target Materials For Applications In Spallation-Neutron-Target Systems: Quarterly Progress Report (June 01 – August 31, 2002), Ajit K. Roy, Brendan O'Toole

Transmutation Sciences Materials (TRP)

The primary objective of this task is to evaluate the effect of hydrogen on environment-assisted cracking of candidate target materials for applications in spallation-neutron-target (SNT) systems such as accelerator production of tritium (APT) and accelerator transmutation of waste (ATW). The materials selected for evaluation and characterization are martensitic stainless steels including Alloy HT-9, Alloy EP 823 and Type 422 stainless steel. The susceptibility to stress corrosion cracking (SCC) and hydrogen embrittlement (HE) of these materials are being evaluated in environments of interest using tensile specimens under constant load and slow-strain-rate (SSR) conditions. Further, the localized corrosion behavior of these alloys …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Task V: Final Report -Phase I 09/01/2001-08/30/2002, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the AAA proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with only very sparse experimental data. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high …

Development Of A Systems Engineering Model Of The Chemical Separations Process: Quarterly Progress Report 5/16/02- 8/15/02, Yitung Chen, Randy Clarksean, Darrell Pepper

Separations Campaign (TRP)

Two activities are proposed in this Phase I task: the development of systems engineering model and the refinement of the Argonne code AMUSE (Argonne Model for Universal Solvent Extraction). The detailed systems engineering model is the start of an integrated approach to the analysis of the materials separations associated with the AAA Program. A second portion of the project is to streamline and improve an integral part of the overall systems model, which is the software package AMUSE. AMUSE analyzes the UREX process and other related solvent extraction processes and defines many of the process streams that are integral to …

Corrosion Of Steel By Lead Bismuth Eutectic: Quarterly Report For May-June-July 2002, John Farley

Transmutation Sciences Materials (TRP)

The goal of this project is to understand the basic science of corrosion in the steel/LBE system.

We are taking more data, typically using the newly installed X-ray Photoelectron Spectrometry (XPS) apparatus, and analyzing our existing data. Undergraduate students Denise Parsons and Julia Manzerova have helped a great deal in the analysis of the data. We can obtain the elemental composition as a function of position within the sample. This gives clues to the migration of materials, the composition of the protective oxide layer, and the basic science of the corrosion process. We found dramatic differences between the exposed and …

In-Situ X-Ray-Absorption Spectroscopy Study Of Hydrogen Absorption By Nickel-Magnesium Thin Films, B. Farangis, Ponnusamy Nachimuthu, T. J. Richardson, J. L. Slack, Rupert C. Perera, Eric M. Gullikson, Dennis W. Lindle, M. Rubin

Chemistry and Biochemistry Faculty Research

Structural and electronic properties of co-sputtered Ni-Mg thin films with varying Ni to Mg ratio were studied by in-situ x-ray absorption spectroscopy in the Ni L-edge and Mg K-edge regions. Co-deposition of the metals led to increased disorder and decreased coordination around Ni and Mg compared to pure metal films. Exposure of the metallic films to hydrogen resulted in formation of hydrides and increased disorder. The presence of hydrogen as a near neighbor around Mg caused a drastic reduction in the intensities of multiple scattering resonances at higher energies. The optical switching behavior and changes in the x-ray spectra varied …