Patent Application
20210098138
This invention was made with government support under Contract No. DE-AC05-000R22725 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
The present invention relates generally to porous nuclear fuel elements, in particular, for use in advanced high temperature gas-cooled nuclear reactors (HTGRs) and gas-cooled fast reactors (GFRs), and to methods for fabricating same.
High temperature gas-cooled nuclear reactors (HTGRs) have been operated using pebble-bed core designs with spherical fuel elements (60 mm diameter “pebbles”) made of TRISO fuel particles embedded in a graphite matrix. Each TRISO fuel particle is a microsphere (0.9 mm diameter) comprising a kernel/core of fissile material (UO2 or UC2) coated by multiple layers of protective barrier materials (also commonly referred to as “cladding”), e.g., a porous carbon buffer layer, followed by pyrocarbon, followed by silicon carbide, followed by an external coating of pyrocarbon. A typical reactor core might contain 11,000 fuel pebbles each containing thousands of TRISO particles. TRISO filet is a key component of advanced small modular nuclear reactors due to its inherent safety at high temperatures and irradiation levels and decreased proliferation risk relative to current reactors. For HTGRs, a more efficient cooling method for TRISO fuel elements may increase thermal control and allow for an increase in fuel density.
Gas-cooled fast reactors (GFRs) are high-temperature helium-cooled fast-spectrum reactors with a closed fuel cycle. These features provide for efficient conversion of fertile uranium and management of actinides. The core of GFRs has a high fissile fuel content as well as a non-fissile, fertile, breeding component. There is no neutron moderator in (IFRs, as the chain reaction is sustained by fast neutrons. Active venting of fission product gases and the resultant decrease in cladding stress in TRISO fuel elements for GFRs would significantly increase fuel lifetime and enable operating with a deep burn fuel cycle.
Highly porous (e.g., 90% porous) metal carbide foam structures have been fabricated through chemical vapor deposition of one or more layers of a refractory metal carbide, for example, ZrC or NbC, on a porous foam skeleton made of, for example, reticulated vitreous carbon (RVC). These metal carbide foams have been used as thermal protection systems, actively cooled structures/heat exchangers, flash and blast suppressors, and lightweight mirror substrates. The interconnected open cell geometry and tortuous flow path provides excellent heat exchange properties, excellent particulate filtration, with a correspondingly low mass. However, conventional incorporation of nuclear fuel into these highly porous metal carbide foam structures has not resulted in the cooling necessary for HTGRs and the gas mobility for GFRs.
Accordingly, there remains a need for improved nuclear fuel elements exhibiting improved cooling and gas mobility.
in one embodiment, a nuclear fuel element is provided. The nuclear fuel element includes a porous support. The porous support includes a ligament and defines a pore adjacent to the ligament. The ligament has an interior surface spaced from the pore. The interior surface defines a void. The porous support includes silicon carbide. The nuclear fuel element includes a nuclear fuel material disposed in the pore. The nuclear fuel material includes a moderator and tri-structural isotropic (TRISO) particles.
In another embodiment, a nuclear fuel element is provided. The nuclear fuel element includes a porous support. The porous support includes a ligament and defines a pore adjacent to the ligament. The ligament has an interior surface spaced from the pore. The interior surface defines a void. The ligament comprises, consists essentially of, consists of, or if formed from the nuclear fuel material. The nuclear fuel element includes a facesheet overlying the porous support and defines a hole. The hole is in fluid communication with the void. The nuclear fuel material includes a nuclear fuel, in various embodiments, the nuclear fuel is further defined as a fissile nuclear fuel.
For high temperature gas-cooled reactors (HTGR), the potential exists to cast and sinter a slurry of TRISO particles and graphite into the open cells of highly porous silicon carbide foam that has hollow ligaments. The foam provides structural reinforcement for the TRISO/graphite mixture and the hollow ligaments, which can be varied in size and spacing, serving as network cooling passages thereby allowing for coolant flow in much closer proximity to the fuel particles compared to current fuel elements. In addition, by using SiC foam, the thermal conductivity of the fuel element increases. To this end, the interconnected microchannels allow helium coolant to flow close to the fuel particles for efficient heat removal. The microchannel size and spacing can be varied substantially for the TRISO particles in foam structure to establish the optimal combination of pressure drop, cooling efficiency, and fuel density.
This design capitalizes on the established technology base regarding the robustness of TRISO fuel encapsulation, and drastically reduces the thermal gradients in large compacts, yet be easy to manufacture. It also permits a substantial increase in fuel density enabling lower enrichment scenarios for the fuel. The development focuses on a thermal reactor neutron spectrum, relying on the graphite in the matrix to provide the moderation. The design also provides the significant thermal mass required for loss of pressure excursions.
For gas-cooled fast reactors (GFR) using a deep-burn fuel cycle, the potential exists to make TRISO-like hollow ligament foam in which the ligaments are composed of UCO fuel as the inner layer deposited by CVD, followed by the same cladding layers currently deposited over a UCO kernel for TRISO particles.
TRISO fuel is a key component of advanced, small modular nuclear reactors due to its inherent safety at high temperatures and irradiation levels, and decreased proliferation risk relative to current reactors. However, a more efficient cooling method for the fuel elements may increase thermal control and allow for an increase in fuel density. Also, reducing fission product gas buildup and cladding stress would significantly increase fuel lifetime for both fast and thermal reactors. For the proposed TRISO/graphite infiltrated foam for HTGR, the foam provides structural reinforcement for the TRISO/graphite mixture and the hollow s serve as a network cooling passages, thereby allowing for coolant flow in much closer proximity to the fuel particles compared to current fuel elements and potentially allow for an increase in fuel density.
For the proposed vented TRISO foam fuel for GFR using a deep-burn fuel cycle, the hollow ligaments are used to vent fission products. If not removed, the fission gases stress the fuel matrix and cladding, limiting the lifetime of the fuel and its burn-up level. Fission product gases can be removed from the fuel and transported to a reflector or blanket for more efficient transmutation, or completely removed from the core to an on-site facility where it can be processed for long-term storage. The controlled removal of fission gases from the fuel is critical to achieving deep bum-up and realization of the benefits which include significantly reducing the volume and toxicity of nuclear waste, minimizing proliferation risk, and increased power efficiency by utilizing more of the energy content in the low enriched uranium fuel.
The proposed technology development represents both near-term (HTGR) and longer term (GFR) applications for hollow ligament foam in small modular reactors, and has potential to significantly improve the performance and manufacturability of TRISO-based fuel.
These and other features and advantages of the present invention will become apparent from the following description of the invention, when viewed in accordance with the appended claims.
The accompanying drawings, which are incorporated in and form part of the specification, illustrate various examples of the present invention and, together with the detailed description, serve to explain the principles of the invention.
The porous support 12 may have a total porosity greater than about 70%. Alternatively, the total porosity may be greater than about 70% and less than about 90%. Alternatively, the total porosity may be greater than about 77% and less than about 85%. One example of an optimum total porosity is about 77%, which provides a good balance between heat transfer and pressure drop. This optimum design provides just enough fissile material to be critical, without resorting to excessively large reactor sizes or using weapons grade enrichments. The fuel matrix is adaptable to both thermal and fast reactors by inclusion or deletion of moderator material (e.g. ZrH or C). Having a thin thickness of the nuclear fuel allows for a high total porosity to maintain the heat transfer efficiency and to keep the temperature difference between the ligament (fuel) centerline and the coolant (e.g., helium or hydrogen) bulk temperature as low as possible.
The porous support 12 may be formed utilizing any method known in the art so long as the porous support 12 remains suitable for use in a nuclear fuel element 10. One exemplary process for forming the porous support 12 includes utilizing a reticulated vitreous carbon (RVC) foam skeleton. First, commercially available polyurethane foam may be purchased in the desired pore size. Then, the polyurethane foam may be infiltrated with a carbon-bearing resin and pyrolyzed to form a porous, open-celled material comprised of vitreous (glassy) carbon, which is called the RVC foam skeleton. Some shrinkage may occur at this step, but the original pore structure of the polyurethane foam may be retained during conversion to RVC. The RVC foam may have an extremely high void volume (e.g., 97%), combined with self-supporting rigidity. Pore densities from 3 to 100 pores per linear inch (ppi) are readily available, and higher ppi foams can be made by compressing 100-ppi material prior to pyrolysis in one, two, or three dimensions. Compression or stretching can also be used to create directional properties (e.g., strength, pressure drop, etc.). Additionally, the RVC foam skeleton can be machined to near final dimensions prior to vapor infiltration.
High ppi (e.g., hundreds of ppi) compressed carbon foam may be used as the skeletal structure for increasing the surface area and heat transfer of the nuclear fuel. 65 ppi foam was selected for initial development, but foams up to 130 ppi are readily produced through resin infiltration of pyrolysis of polyurethane foam, yield vitreous carbon. By compression of foam prior to the conversion to carbon, foams in excess of 1000 ppi have been fabricated. Compressed foams may be anisotropic structures with directional fluid flow, thermal, and mechanical properties, which may be tailored.
In various embodiments, the porous support 12 (e.g., the ligaments 14) includes one or more materials selected from the group consisting of carbon, graphite, SiC, Nb, Zr, Nb, Mo, Hf, Ta, W, Re, TiC, TaC, ZrC, SiC, HfC, BeC2, B4C, NbC, GdC, HfB2, ZrB2, Si3N4, TiO2, BeO, SiO2, ZrO2, Y2O3, Al2O3, Sc2O3, and Ta2O5. In one embodiment, the porous support 12 (e.g., the ligaments 14) includes silicon carbide (SiC). In another embodiment, the porous support 12 (e.g., the ligaments 14) includes niobium (Nb). Alternatively, the porous support 12 may include an open-celled foam structure/skeleton including a carbon-bearing material selected from the group of carbon bonded carbon fiber (CBCF) foam, reticulated vitreous carbon (RVC) foam, pitch derived carbon foam (PDCF), and graphite foam.
With particular reference to
With particular reference to
The nuclear fuel material 22 may further include a cladding overlying the nuclear fuel. The cladding may include a porous carbon buffer layer, followed by pyrocarbon, followed by silicon carbide, and. followed. by an external coating of pyrocarbon. The cladding may protect the underlying nuclear fuel material 22 from exposure to hot hydrogen gases, and can serve as a barrier to prevent migration of fission products, especially fission product gases. In other embodiments, the cladding may include one or more materials selected. from the group of NbC, ZrC, BeO, BeC2, ZrC2, SiC, pyrolytic carbon, diamond, and diamond-like carbon. The cladding may have any thickness suitable to function as a barrier coating (about 25 microns).
With continuing reference to
The nuclear fuel element 10 includes a facesheet 28 overlying the porous support 12. The facesheet 28 defines a hole 30. The hole 30 is in fluid communication with the void 20. In certain embodiments, the facesheet 28 defines a plurality of the holes 30 and the holes 30 are in fluid communication with the voids 20. The facesheet 28 may include, consist essentially of, consist of, or be formed from, niobium.
In some embodiments, the porous support 12 may have a first face 30A, a second face 30B opposite the first face 30A, a third face 30C transverse to the first face 30A, and a fourth face 30D opposite the third face 30C. In various embodiments, a first facesheet 28A overlies the first face 30A and a second facesheet 28B overlies the second face 30B. In this and other embodiments, the ligaments 14 adjacent the third face 30C and the fourth face 30D are substantially free of voids 20. The phrase “substantially free” as utilized herein with reference to the outer diameter face 30E means that the third and fourth faces 30C, 30D includes the voids 20 in an amount of no greater than 5, no greater than 1, no greater than 0.1, or no greater than 0.01%, based on a total surface area of the third and fourth faces 30C, 30D. By controlling flow of the first fluid 24 and the second fluid 26, the nuclear fuel element 10 exhibits a balance between (1) maximizing fuel volume to keep enrichment acceptable (50+ % vol % dense foam fuel possible), (2) maximizing open volume outside ligaments 14 for optimal helium cooling, and (3) minimizing open volume inside hollow ligament 14 purge channels for optimal fission gas removal.
Exemplary nuclear fuel elements 10 will now be described with reference to
in these and other embodiments, the porous support 12 may be infiltrated with the desired nuclear fuel to the desired overall density by using chemical vapor infiltration (CVI), or some other vapor, liquid, or physical deposition process. Typical infiltration levels, depending on the application, fall in the 10-30 vol % range (added to the 3 vol % dense RVC skeleton). At this stage, the thermal and mechanical properties of the foam may be dictated by the infiltrated material. The original RVC foam skeleton may have little influence on the final foam properties, and can often be removed through reaction with hydrogen or oxygen, depending on the particular material that was infiltrated.
Chemical vapor infiltration (CVI), a variation of the chemical vapor deposition (CVD) process, may be used primarily for depositing material inside of the porous foam, felt, mesh, or fibrous preform. The vapor deposition process is an extremely versatile and relatively inexpensive method of molecular-forming materials that are difficult to machine or otherwise produce by conventional processes. CVI relies on the decomposition of a gaseous precursor, flowed over (in the case of CVD), or through (in the case of CVI) a heated substrate, with subsequent condensation from the vapor state to form a solid deposit on the substrate. Benefits of CVD/CVI include the ability to produce deposits of controlled density, thickness, orientation, and composition. Impurity levels are typically less than 0.1%, with densities up to 99.9% being achievable. in addition, CVD/CVI coating processes exhibit the greatest throwing power, or ability to uniformly deposit on intricately shaped or textured substrates.
Perhaps the greatest benefit of CVD/CVI is that a wide variety of materials can be deposited at temperatures that are 10% to 50% of the melting point of the coating material itself, which eliminates the need to perform liquid-phase infiltration at high temperatures. In preparation for infiltration, the RVC foam substrate/skeleton can easily be machined to near final dimensions, while accounting for minor dimensional changes that occur during infiltration.
In the CVI process, reactant gases (typically metal chlorides or fluorides containing the desired coating material(s)) are flowed through a heated substrate (e.g., RVC foam). The compound(s) within the reactant gas stream react near the heated ligament surfaces to form a continuous, uniform coating. For example, NbC is deposited at 1000-1200° C. via reaction of niobium pentachloride (NbCl5) with methane (CH4) and hydrogen (H2).
Coatings of ZrC, TaC or UC can be deposited by analogous reactions. The primary process variables that may be optimized are temperature, pressure, reactant concentration and flow rate, and deposition time. Using CVI, multiple materials may be deposited simultaneously in a well-mixed state as a single deposit. Optionally, after CVI infiltration, exposure to high temperature hydrogen may be used to remove the underlying RVC foam skeleton, and any free carbon in the deposited coating. Removal of the underlying skeleton using hydrogen or oxygen has virtually no impact on the mechanical performance of the foam, since the properties are primarily determined by the stiff metal carbide coating.
In the chemical vapor infiltration (CVI) process for a single metal carbide, the appropriate metal in pellet form is first chlorinated and then flowed over a heated substrate. Hydrogen and a carbon source are added to the system. Through a combination of thermal decomposition and chemical reaction, the carbide deposits on the heated substrate surface, while HCl gas is removed from the reaction chamber by a vacuum system. Deposition of more than one metal carbide simultaneously is more complicated because the metal chlorides must be well mixed and in the desired ratio in order to form a coating of the desired composition and homogeneity. For the case of the simultaneous deposition of UC, NbC, and ZrC, one approach is to chlorinate each metal separately and then mix the gases together prior to reaching the heated substrate. This approach requires independent control of three separate chlorine sources to uniformly mix the three chlorides.
An alternate approach is to fabricate a pellet containing all of the three metals mechanically mixed together. In this case, fine powders (e.g., −325 mesh powders, 0.0017″ diameter) are mechanically mixed in an appropriate weight ratio, e.g. 10% U:45% Zr:45% Nb and then mechanically pressed under high pressure to create a pellet, e.g., a cylindrical pellet 0.5″ dia.×0.25″ long. The “mechanically alloyed” pressed pellet containing the three metals is then used in the CVI process described above.
Another approach is to manufacture a homogenous pellet that is a true metallurgical alloy of the three metals. This can be done by, for example, by liquid-phase sintering at very high temperatures. A eutectic alloy of the two or three-carbide alloys can be produced this way.
In general, fine-grained, fully dense coatings deposited by CVD have better stiffness and strength than do bulk materials having the same composition fabricated by powder processing. The elastic moduli of such CVD films have been regularly measured up to 25% higher than those of the bulk materials. RVC foam is extremely well-suited as a lightweight substrate onto which very high-stiffness coatings may be deposited/infiltrated by CVD/CVI. Since the modulus of the deposited film is so much greater than that of the vitreous carbon foam skeleton, the carbon foam has essentially no influence on the properties of the final product; it merely acts as a “locator” for the deposited films. Ceramic foams fabricated via CVI exhibit significantly greater thermal and mechanical fracture toughness than do monolithic ceramics since the ligamental structure severely inhibits crack propagation.
Optionally, a protective coating, e.g. ZrC, may be vapor deposited on top of the layer(s) of nuclear fuel as an additional moderator or encapsulation barrier. The protective coating can contribute significantly to the overall porous body's strength
Other coating techniques may be used to deposit the nuclear fuel and refractory metal carbides or carbonitrides, including chemical reaction deposition (CRD), physical vapor deposition (PVD), electrolytic deposition (ED), cathophoresis deposition (CD), electrophoresis deposition (ED), and sol-gel coating (SGC), and a liquid “painting” technique that uses vacuum infiltration to draw a suspension of fine powder in a liquid. binder into the porous body, followed by baking to drive off the liquid binder. Also, a “melt-infiltration” process may be used as a method of introducing the desired metals into the foam structure and coating the ligaments, followed by conversion to a tricarbide form. Also, the fuel material may be “cast” into a thermally/structurally stable foam material.
The above description is that of current embodiments of the invention. Various alterations and changes can be made without departing from the spirit and broader aspects of the invention as defined in the appended claims, which are to be interpreted in accordance with the principles of patent law including the doctrine of equivalents. Any reference to elements in the singular, for example, using the articles “a,” “an,” “the,” or “said,” is not o be construed as limiting the element to the singular.
This application claims the benefit of U.S. Provisional Application 62/908,779, filed Oct. 1, 2019, the disclosure of which is incorporated by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62908779 | Oct 2019 | US |
