Publications

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The Sandia S-CO₂ Recompression Closed Brayton Cycle (RCBC) utilizes a series of gas foil bearings in its turbine-alternator-compressors. At high shaft rotational speed these bearings allow the shaft to ride on a cushion of air. Conversely, during startup and shutdown, the shaft rides along the foil bearing surface. Low-friction coatings are used on bearing surfaces in order to facilitate rotation during these periods. An experimental program was initiated to elucidate the behavior of coated bearing foils in the harsh environments of this system. A test configuration was developed enabling long duration exposure tests, followed by a range of analyses relevant to their performance in a bearing. This report provides a detailed overview of this work. The results contained herein provide valuable information in selecting appropriate coatings for more advanced future bearing-rig tests at the newly established test facility in Sandia-NM.

The supercritical carbon dioxide (S-CO2) Brayton Cycle has gained significant attention in the last decade as an advanced power cycle capable of achieving high efficiency power conversion. Sandia National Laboratories, with support from the U.S. Department of Energy Office of Nuclear Energy (US DOE-NE), has been conducting research and development in order to deliver a technology that is ready for commercialization. Root cause analysis has been performed on the Recompression Loop at Sandia National Laboratories. It was found that particles throughout the loop are stainless steel, likely alloy 316 based upon the elemental composition. Deployment of a filter scheme is underway to both protect the turbomachinery and also for purposes of determining the specific cause for the particulate. Shake down tests of electric resistance (ER) as a potential in-situ monitoring scheme shows promise in high temperature systems. A modified instrument was purchased and held at 650°C for more than 1.5 months to date without issue. Quantitative measurements of this instrument will be benchmarked against witness samples in the future, but all qualitative trends to date are as to be expected. ER is a robust method for corrosion monitoring, but very slow at responding and can take several weeks under conditions to see obvious changes in behavior. Electrochemical noise was identified as an advanced technique that should be pursued for the ability to identify transients that would lead to poor material performance.

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The performance of Y2O3-stabilized ZrO2 (YSZ), Y2O3, and Al2O3 plasma sprayed coatings are investigated for their ability to prevent attack of Haynes 230 by a near-eutectic Cu-Mg-Si metallic phase change material (PCM) in a closed environment at 820 °C. Areas where coatings failed were identified with optical and scanning electron microscopy, while chemical interactions were clarified through elemental mapping using electron microprobe analysis. Despite its susceptibility to reduction by Mg, the Al2O3 coating performed well while the YSZ and Y2O3 coating showed clear signs of failure. Due to a lack of reliable melting in the PCM, these results are attributed to the evolution of gaseous Mg leading to the formation of MgO and MgAl2O4.

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The supercritical carbon dioxide (S - CO2) Brayton Cycle has gained significant attention in the last decade as an advanced power cycle capab le of achieving high efficiency power conversion. Sandia National Laboratories, with support from the U.S. Department of Energy Office of Nuclear Energy (US DOE - NE), has been conducting research and development in order to deliver a technology that is rea dy for commercialization. There are a wide range of materials related challenges that must be overcome for the success of this technology. At Sandia, recent work has focused on the following main areas: (1) Investigating the potential for system cost re duction through the introduction of low cost alloys in low temperature loop sections, (2) Identifying material options for 10MW RCBC systems, (3) Understanding and resolving turbine degradation, (4) Identifying gas foil bearing behavior in CO 2 , and (5) Ide ntifying the influence of gas chemistry on alloy corrosion. Progress in each of these areas is provided in this report.

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The systematic development of microstructure, solidification characteristics, and heat of solidification with composition in copper-silicon-magnesium alloys for thermal energy storage is presented. Differential scanning calorimetry was used to relate the thermal characteristics to microstructural development in the investigated alloys and clarifies the location of one of the terminal three-phase eutectics. Repeated thermal cycling highlights the thermal storage stability of the transformation through multiple melting events. In conclusion, two near-terminal eutectic alloys display high enthalpies of solidification, relatively narrow melting ranges, and stable transformation hysteresis behaviors suited to thermal energy storage.

Dish-Stirling systems are a strong candidate to meet cost production goals for solar thermal power production. Thermal energy storage improves the capacity factor of thermal power systems; copper-silicon-magnesium eutectic alloys have been investigated as potential latent heat storage materials. This work examines the ability of commercially available plasma spray coatings to serve as protective barriers with these alloys, while highlighting mechanistic insights into materials for latent heat storage systems. Computed tomography was leveraged as a rapid screening tool to assess the presence of localized attack in tested coatings.

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This report outlines the thermodynamics of a supercritical carbon dioxide (sCO₂) recompression closed Brayton cycle (RCBC) coupled to a Helium-cooled nuclear reactor. The baseline reactor design for the study is the AREVA High Temperature Gas-Cooled Reactor (HTGR). Using the AREVA HTGR nominal operating parameters, an initial thermodynamic study was performed using Sandia's deterministic RCBC analysis program. Utilizing the output of the RCBC thermodynamic analysis, preliminary values of reactor power and of Helium flow rate through the reactor were calculated in Sandia's HelCO₂ code. Some research regarding materials requirements was then conducted to determine aspects of corrosion related to both Helium and to sCO₂ , as well as some mechanical considerations for pressures and temperatures that will be seen by the piping and other components. This analysis resulted in a list of materials-related research items that need to be conducted in the future. A short assessment of dry heat rejection advantages of sCO₂> Brayton cycles was also included. This assessment lists some items that should be investigated in the future to better understand how sCO₂ Brayton cycles and nuclear can maximally contribute to optimizing the water efficiency of carbon free power generation

Polymeric materials have played a significant role in the adoption of a multi-materials approach towards the development of a safe and cost-effective solution for hydrogen fuel storage in Fuel Cell Vehicles (FCVs). Numerous studies exist with regards to the exposure of polymeric materials to gaseous hydrogen as applicable to the hydrogen infrastructure and related compression, storage, delivery, and dispensing operations of hydrogen at fueling stations. However, the behavior of these soft materials under high pressure hydrogen environments has not been well understood. This study involves exposure of select thermoplastic and elastomeric polymers to high pressure hydrogen (70-100 MPa) under static, isothermal, and isobaric conditions followed by characterization of physical properties and mechanical performance. Special attempt has been made to explain hydrogen effects on polymer properties in terms of polymer structure-property relationships, and also understand the influential role played by additives such as fillers, plasticizers, and processing AIDS in polymers exposed to hydrogen. Efforts have also been focused on deriving suitable conditions of static testing in high pressure hydrogen environments as a valuable part of developing a suitable test methodology for such systems. Understanding the relationships between polymer composition and microstructure, time of exposure, rate of depressurization, purge and exposure conditions, etc. in this simple study will help better define the test parameters for upcoming high pressure cycling experiments in hydrogen.

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Supercritical Carbon Dioxide (S-CO2) is an efficient and flexible working fluid for power production. Research to interface S-CO2 systems with nuclear, thermal solar, and fossil energy sources is currently underway. To proceed, we must address concerns regarding compatibility of materials, at high temperature, and compatibility between significantly different heat transfer fluids. Dry, pure S-CO2 is thought to be relatively inert [1], while the addition of ppm levels of water and oxygen result in formation of a protective chromia layer and iron oxide [2]. Thin oxides are favorable as diffusion barriers, and for their minimal impact on heat transfer. While S-CO2 is typically understood to be the secondary fluid, many varieties of primary fluids exist for nuclear applications. Molten salts, for use in the Molten Salt Reactor concept, are given as an example to contrast the materials requirements of primary and secondary fluids. Thin chromia layers are soluble in molten salt systems (nitrate, chloride, and fluoride based salts) [3-8], making materials selection for heat exchangers a precarious balancing act between high temperature oxidation (S-CO2) and metal dissolution (salt side of heat exchanger). Because concerns have been raised regarding component lifetimes, S-CO2 work has begun to characterize starting materials and to establish a baseline by analysis of 1) as-received stainless steel piping, and 2) piping exposed to S-CO2 under typical operating conditions with Sandia National Laboratories Brayton systems. A second issue discovered by SNL involves substantial erosion in the turbine blade and inlet nozzle. It is believed that this is caused by small particulates that originate from different materials around the loop that are entrained by the S-CO2 to the nozzle, where they impact the inlet nozzle vanes, causing erosion. We believe that, in some way, this is linked to the purity of the S-CO2, the corrosion contaminants, and the metal particulates that are present in the loop and its components.

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Supercritical Carbon Dioxide (S-CO2) is an efficient and flexible working fluid for power production. Research to interface S-CO2 systems with nuclear, thermal solar, and fossil energy sources are currently underway. To proceed, we must address concerns regarding high temperature compatibility of materials and compatibility between significantly different heat transfer fluids. Dry, pure S-CO2 is thought to be relatively inert [1], while ppm levels of water and oxygen result in formation of a protective chromia layer and iron oxide [2] Thin oxides are favorable as diffusion barriers, and for their minimal impact on heat transfer. Chromia, however, is soluble in molten salt systems (nitrate, chloride, and fluoride based salts) [3-8]. Fluoride anion based systems required the development of the alloy INOR-8 (Hastelloy N, base nickel, 17%Mo) [9] to ensure that chromium diffusion is minimized, thereby maximizing the life of containment vessels. This paper reviews the thermodynamic and kinetic considerations for promising, industrially available materials for both salt and S-CO2 systems.

Two classes of materials, poly(methylene diphenyl diisocyanate) or PMDI foam, and cross-linked epoxy resins, were characterized using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), to help understand the effects of aging and %E2%80%9Cbake-out%E2%80%9D. The materials were evaluated for mass loss and the onset of decomposition. In some experiments, volatile materials released during heating were analyzed via mass spectroscopy. In all, over twenty materials were evaluated to compare the mass loss and onset temperature for decomposition. Model free kinetic (MFK) measurements, acquired using variable heating rate TGA experiments, were used to calculate the apparent activation energy of thermal decomposition. From these compiled data the effects of aging, bake-out, and sample history on the thermal stability of materials were compared. No significant differences between aged and unaged materials were detected. Bake-out did slightly affect the onset temperature of decomposition but only at the highest bake-out temperatures. Finally, some recommendations for future handling are made.

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High temperature flow sensors must be developed for use with molten salts systems at temperatures in excess of 600ÀC. A novel magneto-hydrodynamic sensing approach was investigated. A prototype sensor was developed and tested in an aqueous sodium chloride solution as a surrogate for molten salt. Despite that the electrical conductivity was a factor of three less than molten salts, it was found that the electrical conductivity of an electrolyte was too low to adequately resolve the signal amidst surrounding noise. This sensor concept is expected to work well with any liquid metal application, as the generated magnetic field scales proportionately with electrical conductivity.

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A secondary containment vessel, made of stainless 316, failed due to severe nitrate salt corrosion. Corrosion was in the form of pitting was observed during high temperature, chemical stability experiments. Optical microscopy, scanning electron microscopy and energy dispersive spectroscopy were all used to diagnose the cause of the failure. Failure was caused by potassium oxide that crept into the gap between the primary vessel (alumina) and the stainless steel vessel. Molten nitrate solar salt (89% KNO{sub 3}, 11% NaNO{sub 3} by weight) was used during chemical stability experiments, with an oxygen cover gas, at a salt temperature of 350-700 C. Nitrate salt was primarily contained in an alumina vessel; however salt crept into the gap between the alumina and 316 stainless steel. Corrosion occurred over a period of approximately 2000 hours, with the end result of full wall penetration through the stainless steel vessel; see Figures 1 and 2 for images of the corrosion damage to the vessel. Wall thickness was 0.0625 inches, which, based on previous data, should have been adequate to avoid corrosion-induced failure while in direct contact with salt temperature at 677 C (0.081-inch/year). Salt temperatures exceeding 650 C lasted for approximately 14 days. However, previous corrosion data was performed with air as the cover gas. High temperature combined with an oxygen cover gas obviously drove corrosion rates to a much higher value. Corrosion resulted in the form of uniform pitting. Based on SEM and EDS data, pits contained primarily potassium oxide and potassium chromate, reinforcing the link between oxides and severe corrosion. In addition to the pitting corrosion, a large blister formed on the side wall, which was mainly composed of potassium, chromium and oxygen. All data indicated that corrosion initiated internally and moved outward. There was no evidence of intergranular corrosion nor were there any indication of fast pathways along grain boundaries. Much of the pitting occurred near welds; however this was the hottest region in the chamber. Pitting was observed up to two inches above the weld, indicating independence from weld effects.

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