Materials Technology Support for Radioisotope Power Systems Final Report

Over the period of this sponsored research, UDRI performed a number of materials related tasks that helped to facilitate increased understanding of the properties and applications of a number of candidate program related materials including; effects of neutron irradiation on tantalum alloys using a 500kW reactor, thermodynamic based modeling of the chemical species in weld pools, and the application of candidate coatings for increased oxidation resistance of FWPF (Fine Weave Pierced Fabric) modules

Reactions of Methyl Perfluoroalkyl Ethers with Isopropyl Alcohol: Experimental and Theoretical Studies

The reaction of an isomeric mixture of the methyl perfluoroalkyl ether, C4F9OCH3 (Novec-7100), in the presence of isopropyl alcohol (IPA) and/or water has been studied by measuring the rate of product formation using an ion-selective electrode (ISE) for fluoride ion, Karl Fisher coulometric titrations for water, and 1H and 19F NMR spectroscopy for product identification and rate studies. The results showed the methyl perfluoroalkyl ether to be very stable with products forming at the rate of ∼1 ppm per year at a laboratory temperature of 20 °C. Measurements over the temperature range of 6° to 100 °C were made on samples aged for periods up to 1.8 years. Density functional theory calculations (DFT, B3LYP/6-31+G(d)) were employed to investigate different reaction pathways and formulate the probable reaction mechanism. The experimental enthalpy (ΔH⧧) and entropy (ΔS⧧) of activation were determined based on several different kinetic measurements. The ΔH⧧ values are in the range of 20–25 kcal/mol and the corresponding ΔS⧧ values range from −32 to −15 cal/(mol K). These are in good agreement with the theoretical values. While the range of ΔH⧧ values does not change appreciatively, the ΔS⧧ values are dependent on the proportion of vapor to liquid involved in the reaction of C4F9OCH3 with IPA so that the more vapor the more negative the ΔS⧧ value

Summary of Plutonium-238 Production Alternatives Analysis Final Report

The Team implemented a two-phase evaluation process. During the first phase, a wide variety of past and new candidate facilities and processing methods were assessed against the criteria established by DOE for this assessment. Any system or system element selected for consideration as an alternative within the project to reestablish domestic production of Pu-238 must meet the following minimum criteria: Any required source material must be readily available in the United States, without requiring the development of reprocessing technologies or investments in systems to separate material from identified sources. It must be cost, schedule, and risk competitive with existing baseline technology. Any identified facilities required to support the concept must be available to the program for the entire project life cycle (notionally 35 years, unless the concept is so novel as to require a shorter duration). It must present a solution that can generate at least 1.5 Kg of Pu-238 oxide per year, for at least 35 years. It must present a low-risk, near-term solution to the National Aeronautics and Space Administration’s urgent mission need. DOE has implemented this requirement by eliminating from project consideration any alternative with key technologies at less than Technology Readiness Level 5. The Team evaluated the options meeting these criteria using a more detailed assessment of the reasonable facility variations and compared them to the preferred option, which consists of target irradiation at the Advanced Test Reactor (ATR) and the High Flux Isotope Reactor (HFIR), target fabrication and chemical separations processing at the ORNL Radiochemical Engineering Development Center, and neptunium 237 storage at the Materials and Fuels Complex at INL. This preferred option is consistent with the Records of Decision from the earlier National Environmental Policy Act (NEPA) documentatio

Impedance spectroscopy characterization of neutron irradiated thermoelectric modules for space nuclear power

The European Space Agency is currently supporting the research and development of advanced radioisotope power systems utilising thermoelectric modules. The performance of thermoelectric modules following exposure to neutron radiation is of significant interest due to the likely application of radioisotope thermoelectric generators in deep space exploration or planetary landers requiring prolonged periods of operation. This study utilises impedance spectroscopy to characterise the effects of neutron irradiation on the performance of complete thermoelectric modules, as opposed to standalone material. For a 50 We americium-241 radioisotope thermoelectric generator design, it is estimated that the TE modules could be exposed to a total integrated flux of approximately 5 × 1013 neutrons cm-2 (>1 MeV). In this study, an equivalent neutron dose was simulated experimentally via an acute 2-hour exposure in a research pool reactor. Bi2Te3-based thermoelectric modules with different leg aspect ratios and microstructures were investigated. Gamma-ray spectroscopy was initially used to identify activated radionuclides and hence quantify irradiation induced transmutation doping. To evaluate the thermoelectric properties pre- and post-irradiation, impedance spectroscopy characterization was employed. Isochronal thermal annealing of defects imparted by the irradiation process, revealed that polycrystalline based modules required significantly higher temperature than those with a monolithic microstructure. Whilst this may indicate a greater susceptibility to neutron irradiation, all tested modules demonstrated sufficient radiation hardness for use within an americium-241 radioisotope thermoelectric generator. Furthermore, the work reported demonstrates that impedance spectroscopy is a highly capably diagnostic tool for characterising the in-service degradation of complete thermoelectric devices

Summary of Plutonium-238 Production Alternatives Analysis Final Report

The Team implemented a two-phase evaluation process. During the first phase, a wide variety of past and new candidate facilities and processing methods were assessed against the criteria established by DOE for this assessment. Any system or system element selected for consideration as an alternative within the project to reestablish domestic production of Pu-238 must meet the following minimum criteria: Any required source material must be readily available in the United States, without requiring the development of reprocessing technologies or investments in systems to separate material from identified sources. It must be cost, schedule, and risk competitive with existing baseline technology. Any identified facilities required to support the concept must be available to the program for the entire project life cycle (notionally 35 years, unless the concept is so novel as to require a shorter duration). It must present a solution that can generate at least 1.5 Kg of Pu-238 oxide per year, for at least 35 years. It must present a low-risk, near-term solution to the National Aeronautics and Space Administration’s urgent mission need. DOE has implemented this requirement by eliminating from project consideration any alternative with key technologies at less than Technology Readiness Level 5. The Team evaluated the options meeting these criteria using a more detailed assessment of the reasonable facility variations and compared them to the preferred option, which consists of target irradiation at the Advanced Test Reactor (ATR) and the High Flux Isotope Reactor (HFIR), target fabrication and chemical separations processing at the ORNL Radiochemical Engineering Development Center, and neptunium 237 storage at the Materials and Fuels Complex at INL. This preferred option is consistent with the Records of Decision from the earlier National Environmental Policy Act (NEPA) documentatio

Recent Joint Studies Related to the Development of Space Radioisotope Power Systems

Over the last several years there has been a mutually beneficial ongoing technical interchange between the U.K and the U.S. related to various aspects of space radioisotope power systems (RPS). While this interchange has been primarily focused on materials based activities, it has also included some aspects related to safety, environmental, and lessons learned during the application of RPSs by the U.S. during the last fifty years. Recent joint technical RPS endeavors have centered on the development of a possible “cold” ceramic surrogate for 238PuO2 and 241AmOx and the irradiation of thermoelectrics and other materials at expected RPS related neutron fluences. As the U.S. continues to deploy and Europe develops RPS capability, on-going joint RPS technical interfaces will continue to enhance each entities’ endeavors in this nuclear based power technology critical for deep space exploration

Electrochemical Evaluation of the Compatibility of Fresh and Aged NovecTM 71IPA with Beryllium, Stainless Uranium, 304L Stainless Steel, and 2024-T3 Aluminum Alloy

This study was a material compatibility assessment of four metals (beryllium, stainless uranium, 304L stainless steel, and 2024-T3 aluminum) with an environmentally benign, non-aqueous, near-azeotropic mixture of hydrofluoroether (Novec™ 7100) with 4.5 wt% isopropanol designated Novec™ 71IPA. The intent is to use the Novec™ 71IPA to clean materials in sensitive, long-term assemblies. There is concern when an aged solvent is used to clean a metal surface, it may cause corrosion due to fluoride formation as the solvent ages. Two solvent conditions, one having no detectable fluoride (fresh) and the other with ≥17 ppm fluoride (aged) were evaluated. Electrochemical evaluations using impedance spectroscopy were performed to monitor the metal surfaces for signs of reaction. Microscopic and spectroscopic techniques, including X-ray photoelectron spectroscopy, were used to characterize the metal surfaces before and after electrochemical tests. Increased impedance was observed when beryllium substrates were exposed to fresh or aged Novec™ 71IPA and was attributed to formation of organic and/or inorganic films on native beryllium oxide. Other metals exhibited insignificant changes in impedance but did show some passive film formation. Results confirmed Novec™ 71IPA, containing up to 17 ppm fluoride, had no corrosive effect on the four tested metals and may be used to safely clean them

Reactions of Methyl Perfluoroalkyl Ethers with Isopropyl Alcohol: Experimental and Theoretical Studies

The reaction of an isomeric mixture of the methyl perfluoroalkyl ether, C₄F₉OCH₃ (Novec-7100), in the presence of isopropyl alcohol (IPA) and/or water has been studied by measuring the rate of product formation using an ion-selective electrode (ISE) for fluoride ion, Karl Fisher coulometric titrations for water, and ¹H and ¹⁹F NMR spectroscopy for product identification and rate studies. The results showed the methyl perfluoroalkyl ether to be very stable with products forming at the rate of ∼1 ppm per year at a laboratory temperature of 20 °C. Measurements over the temperature range of 6° to 100 °C were made on samples aged for periods up to 1.8 years. Density functional theory calculations (DFT, <i>B3LYP/6-31+G­(d)</i>) were employed to investigate different reaction pathways and formulate the probable reaction mechanism. The experimental enthalpy (Δ<i>H</i>^⧧) and entropy (Δ<i>S</i>^⧧) of activation were determined based on several different kinetic measurements. The Δ<i>H</i>^⧧ values are in the range of 20–25 kcal/mol and the corresponding Δ<i>S</i>^⧧ values range from −32 to −15 cal/(mol K). These are in good agreement with the theoretical values. While the range of Δ<i>H</i>^⧧ values does not change appreciatively, the Δ<i>S</i>^⧧ values are dependent on the proportion of vapor to liquid involved in the reaction of C₄F₉OCH₃ with IPA so that the more vapor the more negative the Δ<i>S</i>^⧧ value