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At least 739 records · Page 41

Alternate Methods for Cleaning Zirconium Plate

The United States High Performance Research Reactor Conversion Program identified the need to transition from highly enriched uranium fuel to lowly enriched uranium fuel for high power research and civil reactors. One of the fuel configurations selected for these reactors was a uranium (U) foil alloyed with 10% molybdenum (Mo). The U-10Mo fuel foil was then covered with a zirconium (Zr) interlayer and pressed into an aluminum cladding. Idaho National Laboratory prescribed a need to remove surface oxidation on the Zr prior to bonding it with U-10Mo fuel foil. To determine the best method of oxidation removal, a variety of polishing methods, including hand polishing with a diamond paste or Scotch-Brite™ pads, mechanically wet-polishing with abrasive belts, and chemical etching with hydrofluoric/nitric acid mixtures, were investigated on pre-polished Zircaloy 702 sheets purchased directly from the manufacturer. No change in surface roughness was detected using any of these methods relative to the as-received material. In fact, scanning electron microscopy detected grit from hand polishing with Amplex Grade 30 waste soluble diamond paste and Scotch-Brite™ pads. Visible staining was found, and fluorine detected via X-ray photoelectron spectroscopy on the flash etching samples. These contaminants were not seen on the as-received material. In addition to the need to remove the oxide layer on the Zr prior to co-rolling, there are concerns that the Neolube debonding agent on the co-rolling can may contaminate the Zr surface after co-rolling. The experimental results found that zirconium in contact with Neolube coated steel plates was easily cleaning with ethanol wiping after heat treated and no carbide inclusions remained on the surface. Overall, all cleaning methods tested did not significantly change the surface roughness of the plates or reduce the oxide layer present on the zirconium. Carbon was found on all the samples, before and after cleaning, except for the flash etch samples which detected fluorine instead. The insignificant changes seen in the cleaned plates relative to the as received plates question the need for cleaning prior to rolling. Further investigation in the requirements for cleaning at this step is recommended. Current methods for cleaning the surface after hot rolling with alcohol appear sufficient. After hot rolling, if Neolube does peel off the can and onto the zirconium coated foil surface, a dry abrasive or diamond paste polish is not recommended due to the chance of abrasive being embedded into the surface. However, the ability of an etchant to lift the lubricant off the zirconium surface indicates that a spot etch method could work to clean specific spots where Neolube is present, if the need arises.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Critical Literature Review of Low Global Warming Potential (GWP) Refrigerants and their Environmental Impact

Refrigeration and air conditioning currently account for ~20% of the total electricity consumption in buildings around the world. Over the next three decades as global temperatures are projected to increase, urbanization and economic growth will lead to an increased demand for refrigeration and cooling. Most commonly used refrigerants belong to the five following classes: (i) chlorofluorocarbons, (ii) hydrochlorofluorocarbons, (iii) hydrofluorocarbons (HFCs), (iv) hydrofluoroolefins (HFOs), and (v) natural refrigerants. Over the past century, there have been shifts in which compounds were used for refrigeration to improve safety and durability, allow for ozone protection, and, most recently, to reduce global warming potential (GWP). Although technological advances have led to increased cooling capacity and safer refrigerants, emissions from refrigeration systems can affect the environment by contributing to greenhouse gas emissions or by depleting the ozone layer, depending on the gas emitted. The focus is increasingly on adopting compounds that are both efficient at cooling and effective for reducing emissions and other adverse environmental impacts. Because of policy and regulatory changes to avert ozone depletion and global climate change, much discussion has centered on the environmental impacts of next-generation refrigerants. Of particular interest are the fluorinated refrigerants, HFCs and HFOs, most of which are defined as per- and polyfluoroalkyl substances (PFAS) and their breakdown products (especially trifluoroacetic acid). The US Environmental Protection Agency in 2021 drafted a Strategic Roadmap for PFAS, which has already resulted in an increase in investment in research on these compounds and has restricted the release of PFAS into the environment through the implementation of monitoring and reporting requirements. A critical evaluation of fluorinated refrigerants and their breakdown products with respect to persistence, biodegradation and toxicity, and global warming potential is needed to guide environmental regulations. This document aims to perform a critical review of the relevant scientific data on the most common refrigerants currently used, their degradation products, and their alternatives. Where available, estimates of precursor production quantities and existing environmental regulatory information are reviewed. Key data of interest for the evaluation include physicochemical properties, environmental fate parameters, ecological or human health toxicity/risk information, and GWP for compounds of interest.

54 ENVIRONMENTAL SCIENCES↗

Critical Literature Review of Low Global Warming Potential (GWP) Refrigerants and their Environmental Impact

Refrigeration and air conditioning currently account for ~20% of the total electricity consumption in buildings around the world. Over the next three decades as global temperatures are projected to increase, urbanization and economic growth will lead to an increased demand for refrigeration and cooling. Most commonly used refrigerants belong to the five following classes: (i) chlorofluorocarbons, (ii) hydrochlorofluorocarbons, (iii) hydrofluorocarbons (HFCs), (iv) hydrofluoroolefins (HFOs), and (v) natural refrigerants. Over the past century, there have been shifts in which compounds were used for refrigeration to improve safety and durability, allow for ozone protection, and, most recently, to reduce global warming potential (GWP). Although technological advances have led to increased cooling capacity and safer refrigerants, emissions from refrigeration systems can affect the environment by contributing to greenhouse gas emissions or by depleting the ozone layer, depending on the gas emitted. The focus is increasingly on adopting compounds that are both efficient at cooling and effective for reducing emissions and other adverse environmental impacts. Because of policy and regulatory changes to avert ozone depletion and global climate change, much discussion has centered on the environmental impacts of next-generation refrigerants. Of particular interest are the fluorinated refrigerants, HFCs and HFOs, most of which are defined as per- and polyfluoroalkyl substances (PFAS) and their breakdown products (especially trifluoroacetic acid). The US Environmental Protection Agency in 2021 drafted a Strategic Roadmap for PFAS, which has already resulted in an increase in investment in research on these compounds and has restricted the release of PFAS into the environment through the implementation of monitoring and reporting requirements. A critical evaluation of fluorinated refrigerants and their breakdown products with respect to persistence, biodegradation and toxicity, and global warming potential is needed to guide environmental regulations. This document aims to perform a critical review of the relevant scientific data on the most common refrigerants currently used, their degradation products, and their alternatives. Where available, estimates of precursor production quantities and existing environmental regulatory information are reviewed. Key data of interest for the evaluation include physicochemical properties, environmental fate parameters, ecological or human health toxicity/risk information, and GWP for compounds of interest.

54 ENVIRONMENTAL SCIENCES↗

Investigation of the Effect of Framework Flexibility on Adsorption in SIFSIX-3-Cu using a Machine-Learned Force Field

Metal-organic frameworks (MOFs) are a promising class of adsorbents. The performance of MOF sorbents relies on high selectivity and low regeneration energy. This work focuses on the use of machine learned force fields (MLFFs) to model adsorption in a flexible MOF, SIFSIX-3-Cu. A DeePMD-based MLFF was trained to reproduce DFT (PBE+D3) energies, forces, and stresses, using an iterative sampling scheme combining sampling based on molecular dynamics, Monte Carlo, and geometry optimization to capture both attractive and repulsive regions of the potential energy surface. Flexibility of the MOF was explicitly included in this model. Hybrid Monte Carlo/molecular dynamics (MC/MD) simulations using the MLFF predicted adsorption isotherms in good agreement with experimental data for a range of pressures (40 Pa – 104 Pa) in contrast to rigid models, which overpredict CO2 adsorption at low pressures. The improvement was the result of a description of the variability of fluorine-fluorine diagonal distances at adsorption sites. This detailed description of flexibility afforded by the MLFF resulted in more accurate predictions adsorption isotherms when compared to the experimentally measured values. These results underscore the importance of including framework flexibility when modeling adsorption phenomena in MOFs, particularly for low pressure applications and provide a robust procedure for training MLFF models for MOFs.

Atomistic Simulation↗

Development requirements for a high-energy hybrid propulsion system Final report

This document presents the development requirements, costs, and schedule for a high-energy upper-stage hybrid propulsion system. High energy is achieved through the use of a lithium fuel formulation (solid) and fluorinated oxidizer (liquid). The propulsion system contains 3 2OO lb of propellant and may be used as a terminal stage for Atlas/Centaur or DSV-3M Delta launch vehicle. A program to develop a fluorinated hybrid propulsion system could be initiated with little risk. An extensive investigation revealed that the technology required to develop most of the components has either been demonstrated or is in progress. Further, it was found that there were no areas of critical technology. The cost to develop a hybrid propulsion system to a status where it could be integrated into a flight-test stage is about $17 million. This cost does not include the development of the stage astrionics. Length of the total development program is 34 months. A total recurring cost of $381 600 was estimated for the first unit (less astrionics and fee). This includes purchased hard\rare, manufacturing, material, assembly, and test costs.

M.B. Adams↗

Process for synthesizing a new series of fluorocarbon polymers

Two-step process for preparing fluorocarbon materials includes - /1/ adding gaseous fluorine to a polyperfluoropolyene to create fluorocarbon radicals, with reactive sites at unsaturated carbon atoms, and /2/ introducing a monomer, after evacuation of fluorine gas, and allowing copolymerization with the free radicals.

Toy, M. S.↗

Preparation of perfluoropolyether prepolymers

Fluorinated prepolymers are used to generate highly fluorinated polymers which possess most of the desirable properties of polytetrafluoroethylene, such as nonflammability and high corrosion resistance, while retaining good low temperature flexibility.

Rochow, S. E.↗

Some neutron and gamma radiation characteristics of plutonium cermet fuel for isotopic power sources

Gamma and neutron measurements on various types of plutonium sources are presented in order to show the effects of O-17, O-18 F-19, Pu-236, age of the fuel, and size of the source on the gamma and neutron spectra. Analysis of the radiation measurements shows that fluorine is the main contributor to the neutron yields from present plutonium-molybdenum cermet fuel, while both fluorine and Pu-236 daughters contribute significantly to the gamma ray intensities.

Neff, R. A.↗

Adhesion and transfer of PTFE to metals studied by auger emission spectroscopy

The adhesion and transfer of polytetrafluoroethylene (PTFE) to metals in ultrahigh vacuum has been studied using Auger emission spectroscopy. The transfer was effected both by compressive static contact and by sliding contact. The transfer observed after static contact was independent of the chemical constitution of the substrate. Electron induced desorption of the fluorine in the transferred PTFE showed that the fluorine had no chemical interaction with the metal substrate. The coefficient of friction on metals was independent of the chemical constitution of the substrate. However, sliding PTFE on soft metals such as aluminum, generated wear fragments that lodged in the PTFE and machined the substrate.

Pepper, S. V.↗

Adhesion and transfer of polytetrafluorethylene to metals studied by Auger emission spectroscopy

The adhesion and transfer of polytetrafluoroethylene (PTFE) to metals in ultrahigh vacuum were studied. The transfer was effected both by compressive static contact and by sliding contact. The transfer observed after static contact was independent of the chemical constitution of the substrate. Electron-induced desorption of the fluorine in the transferred PTFE showed that the fluorine had no chemical interaction with the metal substrate. The coefficient of friction on metals was independent of the chemical constitution of the substrate. However, sliding PTFE on soft metals, such as aluminum, generated wear fragments that lodged in the PTFE and machined the substrate.

Pepper, S. V.↗

Internal motion and its pressure dependence in FeSiF6+6/H2O/.

Both wideline and pulsed NMR techniques were used to examine the internal motion in FeSiF6+6(H2O). Corrections of second moments for bulk paramagnetic effects were essential. At room temperature and pressure, the fluorine-fluorine contribution to the 19F second moment is 0.38 (plus or minus 0.06) G2, and indicates rapid orientation of the SiF6(--) group. Analysis of the second moment within the transition region allows calculation of an activation volume which is 2.4 (plus or minus 0.4) % of the molar volume. The application of pressure slows the internal motion such that the rigid lattice values of the 19F second moment are obtained above 50 kbar.

Vaughan, R. W.↗

Preparation of thin film silver fluoride electrodes from constituent elements

The feasibility of preparing thin-film metal fluoride electrodes from the elemental constituents has been demonstrated. Silver fluoride cathodes were prepared by deposition of silver on a conducting graphite substrate followed by fluorination under controlled conditions using elemental fluorine. The resulting electrodes were of high purity, and the variables such as size, shape, and thickness were easily controlled.

Odonnell, P. M.↗

Stress Corrosion Cracking and Fatigue Crack Growth Studies Pertinent to Spacecraft and Booster Pressure Vessels

This experimental program was divided into two parts. The first part evaluated stress corrosion cracking in 2219-T87 aluminum and 5Al-2.5Sn (ELI) titanium alloy plate and weld metal. Both uniform height double cantilever beam and surface flawed specimens were tested in environments normally encountered during the fabrication and operation of pressure vessels in spacecraft and booster systems. The second part studied compatibility of material-environment combinations suitable for high energy upper stage propulsion systems. Surface flawed specimens having thicknesses representative of minimum gage fuel and oxidizer tanks were tested. Titanium alloys 5Al-2.5Sn (ELI), 6Al-4V annealed, and 6Al-4V STA were tested in both liquid and gaseous methane. Aluminum alloy 2219 in the T87 and T6E46 condition was tested in fluorine, a fluorine-oxygen mixture, and methane. Results were evaluated using modified linear elastic fracture mechanics parameters.

Hall, L. R.↗

Analysis of volatile combustion products and a study of their toxicological effects.

An experimental program was conducted to study the thermochemical, flammability and toxicological characteristics of uncoated and coated polyisocyanurate foams. The coatings used were fluorinated copolymer and an intumescent material. Combustion and pyrolysis gases were analyzed by gas chromatography and mass spectrometry. The LD-50 and LD-100 tests were performed on Sprague-Dawley rats housed in an environmental chamber. The isocyanurate foam, fluorinated-copolymer-coated foam, and the intumescent-coated foam were found to have excellent flammability and insulation characteristics, although smoke development was substantial.

Seader, J. D.↗

Method for obtaining oxygen from lunar or similar soil

Recovery of oxygen from soil containing metal oxides such as alumina, silica, calcia, magnesia, and ilmenite wherein the material containing the oxides is placed in a vessel and reacted with fluorine to provide oxygen and metal fluorides. The oxygen produced from the reaction is recovered and stored, after further purifying processes, and the metal fluorides are further reacted with potassium vapor to provide potassium fluoride and free metals. The potassium fluoride is than subjected to electrolysis whereby the potassium and fluorine are separated and are recycled for further use in the system. Valuable free metals are recovered for other uses.

Downs, W. R.↗

Rotating and positive-displacement pumps for low-thrust rocket engines. Volume 1: Pump Evaluation and design

Rotating and positive displacement pumps of various types were studied for pumping liquid fluorine for low-thrust, high-performance rocket engines. Included in the analysis were: centrifugal, pitot, Barske, Tesla, drag, gear, vane, axial piston, radial piston, diaphragm, and helirotor pump concepts. The centrifugal pump and the gear pump were selected and these were carried through detailed design and fabrication. Mechanical difficulties were encountered with the gear pump during the preliminary tests in Freon-12. Further testing and development was therefore limited to the centrifugal pump. Tests on the centrifugal pump were conducted in Freon-12 to determine the hydrodynamic performance and in liquid fluorine to demonstrate chemical compatibility.

Macgregor, C.↗

Rotating and positive-displacement pumps for low-thrust rocket engines. Volume 2: Fabrication and testing

Rotating and positive displacement pumps of various types were studied for pumping liquid fluorine for low thrust high performance rocket engines. Included in the analysis were: centrifugal, pitot, Barske, Tesla, drag, gear, vane, axial piston, radial piston, diaphragm and helirotor pump concepts. The centrifugal and gear pumps were carried through detail design and fabrication. After preliminary testing in Freon 12, the centrifugal pump was selected for further testing and development. It was tested in Freon 12 to obtain the hydrodynamic performance. Tests were also conducted in liquid fluorine to demonstrate chemical compatibility.

Csomor, A.↗

Register of specialized sources for information on selected fuels and oxidizers

Thirty-eight (38) organizations are listed and described that catalog and file information in their data systems on fuel and oxidizers. The fuels include hydrogen, methane and hydrazine-type fuels; the oxidizers include oxygen, fluorine, flox, nitrogen tetroxide and ozone. The type of available information covers thermophysical properties, propellant systems, propellant fires-control-extinguishment, propellant explosions, propellant combustion, propellant safety, and fluorine chemistry. These organizations have assembled and collated their information so that it will be useful in the solution of engineering problems.

Ludtke, P. R.↗