Coatings and Surface Modifications to Mitigate SiC Cladding During Operation in Light Water Reactors

Abstract

The invention relates to SiC ceramic matrix composite (CMC) claddings with metallic, ceramic and/or multilayer coatings applied on the outer surface for improved corrosion resistance and hermeticity protection. The coating includes one or more materials selected from FeCrAl, Y, Zr and AlCr alloys, Cr.sub.2O.sub.3, ZrO.sub.2 and other oxides, chromium carbides, CrN, Zr- and Y-silicates and silicides. The coatings are applied employing a variety of known surface treatment technologies including cold spray, thermal spray process, physical vapor deposition process (PVD), and slurry coating.

Claims

1. A composite silicon carbide cladding in a light water nuclear reactor, comprising: a silicon carbide substrate having an outer surface; and a coating applied to the outer surface of the silicon carbide substrate, wherein the coating comprises one or more materials selected from the group consisting of FeCrAl, Y, Zr and AlCr alloys, Cr.sub.2O.sub.3, ZrO.sub.2, chromium carbides, CrN, Zr- and Y-silicates and silicides.

2. The cladding of claim 1, wherein the coating comprises: a FeCrAl alloy coating applied to the outer surface of the silicon carbide substrate; or an aluminum coating applied to the outer surface of the silicon carbide substrate, and a FeCrAl alloy coating applied to the aluminum coating; or an intermixed coating comprising Al.sub.4C.sub.3+Si and FeAl alloy applied to the outer surface of the silicon carbide substrate, a FeCrAl alloy coating applied to the intermixed coating, and a Cr.sub.2O.sub.3 coating applied to the FeCrAl alloy coating; or a CrN layer applied to the outer surface of the silicon carbide substrate and a chromium layer applied to the CrN layer, and one or more additional layers of alternating CrN and chromium layers; or a yttrium silicon layer applied to the outer surface of the silicon carbide; or a yttrium or zirconium silicide layer applied to the outer surface of the silicon carbide layer; or a yttrium or zirconium silicate layer applied to the outer surface of the silicon carbide layer.

3. A method of preparing a composite silicon carbide cladding for use in a light water nuclear reactor, comprising: providing a silicon carbide substrate having an outer surface; and depositing a coating on the outer surface of the silicon carbide substrate, wherein the coating comprises one or more materials selected from the group consisting of FeCrAl, Y, Zr and AlCr alloys, Cr.sub.2O.sub.3, ZrO.sub.2, chromium carbides, CrN, Zr- and Y-silicates and silicides.

4. The method of claim 3, wherein the depositing step, comprises: (a.) depositing a FeCrAl alloy coating on the outer surface of the silicon carbide substrate, or (b.) depositing an aluminum coating on the outer surface of the silicon carbide substrate, and depositing a FeCrAl alloy coating on the aluminum coating; or (c.) depositing a CrN layer on the outer surface of the silicon carbide substrate and depositing a chromium layer on the CrN layer, and depositing one or more additional layers of alternating CrN and chromium layers thereon; or (d.) depositing a yttrium silicon layer on the outer surface of the silicon carbide; or (e.) depositing a yttrium or zirconium silicide layer on the outer surface of the silicon carbide layer; or (f.) depositing a yttrium or zirconium silicate layer on the outer surface of the silicon carbide layer.

5. The method of claim 4, wherein one or more of steps (b.), (d.), (e.) and (f.) further comprise heat treating the coating.

6. The method of claim 5, further comprising heat treating the (b.) coating forming an intermixed coating comprising Al.sub.4C.sub.3+Si and FeAl alloy applied to the outer surface of the silicon carbide substrate, a FeCrAl alloy coating applied to the intermixed coating, and a Cr.sub.2O.sub.3 coating applied to the FeCrAl alloy coating.

7. The method of claim 5, further comprising heat treating the (d.) coating forming a yttrium silicate layer applied to the outer surface of the silicon carbide substrate.

8. The method of claim 5, further comprising heat treating the (e.) coating forming a yttrium or zirconium silicate layer applied to the outer surface of the silicon carbide substrate.

9. The method of claim 5, further comprising heat treating the (f.) coating forming a yttrium or zirconium silicate layer applied to the outer surface of the silicon carbide substrate.

10. The method of claim 3, wherein the step of depositing the coating comprises a process selected from the group consisting of cold spray, thermal spray, physical vapor deposition, DC reactive sputtering, and slurry coating.

11. The method of claim 5, wherein the heat treating is conducted at a temperature from 500 to 600 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] A further understanding of the invention can be gained from the following description of the preferred embodiments when read in conjunction with the accompanying drawings in which:

[0019] FIG. 1 is a simplified schematic of a prior art nuclear reactor fuel rod design to which this invention can be applied;

[0020] FIG. 2 is a plot that illustrates weight loss of CVD-SiC in water autoclave tests for various water chemistries;

[0021] FIG. 3A is a simplified schematic of a multilayer coating architecture of a cold sprayed FeCrAl alloy coating with an aluminum bond layer as-deposited on a SiC substrate, in accordance with certain embodiments of the invention; and 3B is a simplified schematic of the multilayer coating architecture of FIG. 3A following heat treatment, in accordance with certain embodiments of the invention;

[0022] FIG. 4 is a simplified schematic of a multilayer coating architecture having alternating coating layers of Cr and CrN on a SiC substrate, in accordance with certain embodiments of the invention;

[0023] FIG. 5 is a plot illustrating free energy of formation for Zr and Y oxide; and

[0024] FIG. 6A is a simplified schematic of a multilayer coating architecture of a YSi layer as-deposited by physical vapor deposition on a SiC substrate, in accordance with certain embodiments of the invention; and FIG. 6B is a simplified schematic of the multilayer coating architecture of FIG. 6A following het treatment, including a Y.sub.2Si.sub.2O.sub.7 layer, in accordance with certain embodiments of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

[0025] The invention provides novel SiC ceramic matrix composite (CMC) claddings with metallic, ceramic and/or multilayer coatings applied on the outer surface for improved corrosion resistance and hermeticity protection. The coating materials include one or more materials selected from FeCrAl, Y, Zr and AlCr alloys, Cr.sub.2O.sub.3, ZrO.sub.2 and other oxides, chromium carbides, CrN, Zr- and Y-silicates and silicides. The coatings are applied employing a variety of known surface treatment technologies including cold spray, thermal spray process, physical vapor deposition process (PVD), and slurry coating.

[0026] SiCSiC has outstanding high temperature strength and oxidation resistance, and well documented radiation damage response. Therefore, it is an excellent choice for LWR fuel cladding and core components from an accident tolerance standpoint. However, SiCSiC also exhibits notable aqueous water corrosion under normal LWR operating conditions due to the thermodynamic instability of silicon-dioxide in this environment. Furthermore, the pure SiC CMC tube is also susceptible to microcracking due to its brittle nature.

[0027] The novel features of the invention address the aforementioned issues and concerns, as well as providing an improved SiC cladding.

[0028] The SiC cladding according to the invention consists of novel metallic or ceramic or multi-layer coatings on the outside of the cladding, e.g., outer surface. In certain embodiments, a FeCrAl alloy coating is deposited on a SiC cladding. The FeCrAl alloy coating can be directly deposited on an outer surface of the SiC cladding or, alternatively, the FeCrAl alloy coating can be connected to, e.g., indirectly deposited on the SiC cladding, by being deposited on a bond layer that is directly applied to the SiC cladding.

[0029] FIG. 3A illustrates a multilayer coating architecture 20 having a SiC substrate 21 with an outer surface 25 and a FeCrAl alloy coating 28 deposited on the SiC substrate 21. Additionally, the architecture 20 has deposited between the SiC substrate 21 and the FeCrAl alloy coating 28 an aluminum (Al) layer 23, e.g., a thin film or layer. The Al layer 23 is directly deposited on the outer surface 25 of the SiC substrate 21 and the FeCrAl alloy coating 28 is directly deposited on an outer surface 26 of the Al layer 23, wherein the Al layer 23 serves as a bond layer. The outer surface 29 of the FeCrAl alloy coating 28 serves as the exterior surface of the SiC CMC, which can be in contact with a coolant, such as water, pumped through a nuclear reactor core.

[0030] The novel metallic or ceramic or multi-layer coatings of the invention can be applied using conventional cold spray coating techniques. For example, the FeCrAl alloy coating 28 can be formed by a cold spray coating technique, and the Al (bond) layer 23 provides superior adhesion of the cold sprayed FeCrAl (metallic) alloy coating 28 to the SiC (ceramic) substrate 21.

[0031] Further adhesion improvement can be achieved by subjecting the architecture 20 as-deposited in FIG. 3A to a post-deposition heat treatment, e.g., from about 500 C. to about 600 C., which promotes intermixing of the Al layer 23 with the FeCrAl alloy coating 28 and the SiC substrate 21 to increase the bond strength, and produce a dual-layered cold spray coating. FIG. 3B further illustrates the multilayer coating architecture 20 with heat treatment. FIG. 3B includes the SiC substrate 21 and the FeCrAl alloy coating 28 as shown in FIG. 3A. In addition, FIG. 3B shows an intermixed middle layer 30 positioned between the SiC substrate 21 and the FeCrAl alloy coating 28, which as a result of the heat treatment, is composed of Al.sub.4C.sub.3+Si and FeAl alloy. The intermixed middle layer 30 is directly deposited on the outer surface 25 of the SiC substrate 21. A Cr.sub.2O.sub.3 layer 32 is formed on the outer surface 29 of the FeCrAl alloy coating layer 28, such that the outer surface 33 of the Cr.sub.2O.sub.3 layer 32 forms the exterior surface of the SiC CMC, which can be in contact with a coolant, such as water, pumped through a nuclear reactor core.

[0032] As an alternative to cold spray deposition, a thermal spray process may be used in the invention. The thermal spray process generally includes melting the powder feed by a concentrated heat source to form molten particles, and spraying the molten particles on the surface of a substrate to form a dense coating. The process is widely used in industry for the deposition of ceramic coatings on ceramic and hard metal substrates. Likewise, thermal spray can be used to deposit ceramic and metalloid coating materials such as Cr, Y, Zr, Cr.sub.2O.sub.3, ZrO.sub.2, Cr.sub.3C.sub.2, CrSi.sub.2, Y.sub.2Si.sub.2O.sub.7, Y.sub.2Si.sub.3O.sub.9 and YSi.sub.2 onto SiC cladding in accordance with certain embodiments of the invention.

[0033] For example, Y.sub.2Si.sub.2O.sub.7 is highly stable in LWR coolants since silicon (Si) is highly immobile in the silicate phases of high temperature water systems. The thermal expansion coefficients of Y.sub.2Si.sub.2O.sub.7 and SiC are similar, i.e., between 4 and 510.sup.6/ C. for Y.sub.2Si.sub.2O.sub.7 and 4.3 to 5.410.sup.6/ C. for SiC, which indicates there will be minimal thermal stresses in the coating. The silicate coating will result in minimal neutron penalty because the neutron cross-section of yttrium is less than half of zirconium.

[0034] In accordance with the invention, Physical Vapor Deposition (PVD) with or without thermal conversion can be used for coating application. In general, the PVD process can deposit a wide range of coating materials with a high degree of compositional and microstructural control, uniformity and purity. Energetic ions generated (generally argon) bombard a target material, and the sputtered target atoms condense on a substrate and form a thin coating, for example, of the following materials: ZrSi.sub.2, and YSi.sub.2. The two silicide coatings are converted at high temperatures to highly corrosion-resistant ZrSiO.sub.4 and Y.sub.2Si.sub.2O.sub.7.

[0035] Furthermore, the corrosion resistance of thin PVD-applied CrN coatings has been shown to be superior to films of other nitrides such as TiAlN, TiN, and AlCrN in water autoclave tests for zirconium substrates. In accordance with the invention, a PVD process can be used to deposit the aforementioned chromium nitride (CrN) coating to SiC. Alternatively, the CrN coating can also be produced by Direct Current (DC) Reactive Sputtering, wherein a commercial Cr target is sputtered by Ar gas (for Cr) and a mixture of nitrogen and argon (for CrN) under voltage bias to increase deposition rate of the coating.

[0036] In certain embodiments, a CrCrN multilayer coating may be deposited on a SiC cladding surface. FIG. 4 illustrates a multilayer coating architecture 40 having a SiC substrate 21 (base layer as shown in FIGS. 3A and 3B) with an outer surface 25 and a first CrN coating 41 deposited on the outer surface 25 of the SiC substrate 21. A first Cr layer 44 is applied to an outer surface 42 of the first CrN coating 41. A second CrN layer 46 is applied to an outer surface 45 of the first Cr layer 44, and a second Cr layer 48 is applied to an outer surface 47 of the second CrN layer 46. An outer surface 49 of the second Cr layer 48 serves as the exterior surface of the SiC CMC, which can be in contact with a coolant, such as water, pumped through a nuclear reactor core.

[0037] Without intending to be bound by any particular theory, it is believed that in the multilayered coating architectures, crack propagation is arrested by the interfaces which would enhance the durability of coatings against corrosion.

[0038] In accordance with the invention, subjecting a deposited multilayer coating architecture to a post-coating heat treatment can result in improved corrosion-resistance of a SiC cladding. Treatment at high temperatures thermally converts the coating structure and composition as-deposited to a more corrosion-resistant configuration. For example, a PVD deposited zirconium silicide (Zr-silicide) and yttrium silicide (Y-silicide) can be thermally converted to Zr-silicate coatings and Y-silicate coatings, respectively. FIG. 5 illustrates that free energy of formation for Zr- and Y-oxide as shown by 36 and 37, respectively, is more negative than SiO.sub.2, as shown by 35. Therefore, unlike many transition metal silicides, the oxidation of Zr- or Y-silicides results in mixed metal/silicon oxide instead of a SiO.sub.2 layer. As a result, the formation of metal silicates (ZrSiO.sub.4 or Y.sub.2Si.sub.2O.sub.7) is thermodynamically favored. It has been demonstrated that a dense ZrSiO.sub.4 layer can be formed on a chemical vapor deposition (CVD) SiC surface by oxidation of a thin PVD ZrSi.sub.2 coating at a temperature of 1400 C. for 5 hours in ambient air. The ZrSiO.sub.4 top layer completely immobilizes Si in a pressurized steam environment, rendering it largely immune to corrosion.

[0039] Similarly, formation of a yttrium-silicate layer is facilitated by post-heat treatments of yttrium-silicide coatings. FIG. 6A illustrates a multilayer coating architecture 50 having a SiC substrate 21 with an outer surface 25 and a YSi coating 51 deposited on the outer surface 25 of the SiC substrate 21. The outer surface 52 of the YSi coating 51 serves as the exterior surface of the SiC CMC. As aforementioned, the YSi coating 51 can be formed by a conventional PVD technique. FIG. 6B illustrates the multilayer coating architecture 50 of FIG. 6A following heat treatment. The heat treated architecture 50 in FIG. 6B includes the SiC substrate 21 as shown in the as-deposited architecture in FIG. 6A. Further, the heat treated architecture 50 in FIG. 6B shows Y.sub.2Si.sub.2O.sub.7 layer 54 deposited on the SiC substrate 21 as a result of the heat treatment, such that the outer surface 56 of the Y.sub.2Si.sub.2O.sub.7 layer 54 forms the exterior surface of the SiC CMC, which can be in contact with a coolant, such as water, pumped through a nuclear reactor core.

[0040] Another alternative coating method is application of a slurry coating to a substrate. This processing technique is commonly referred to as Polymer Derived Ceramics (PDCs). It is an attractive alternative due to its relatively low cost, ability to perform near net-shape molding, and fabrication for complex structures, high-purity starting materials and relatively low processing temperatures (<1200 C.). PDC coatings, in the amorphous and crystalline phases, are generally of growing interest for corrosion, oxidation, and wear protection for porous non-oxidic ceramics and refractory metals.

[0041] In accordance with certain embodiments of the invention, PDC, such as silicon organometallic polymer, ethylene bis stearamide (EBS), an organic compound with the formula (CH.sub.2NHC(O)C.sub.7H.sub.35).sub.2 can be used as polymer precursors. The corrosion resistance and fracture toughness can be further improved by using filler materials, such as TiO.sub.2, Cr.sub.2O.sub.3, ZrO.sub.2, Cr, Ti, CrAl alloy, Zr alloy, ZrO.sub.2, and the like.

[0042] While specific embodiments of the invention have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular embodiments disclosed are meant to be illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the appended claims and any and all equivalents thereof