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WO2017062332A1 - Revêtement céramique pour la résistance à la corrosion de gaine de combustible nucléaire - Google Patents

Revêtement céramique pour la résistance à la corrosion de gaine de combustible nucléaire Download PDF

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Publication number
WO2017062332A1
WO2017062332A1 PCT/US2016/055263 US2016055263W WO2017062332A1 WO 2017062332 A1 WO2017062332 A1 WO 2017062332A1 US 2016055263 W US2016055263 W US 2016055263W WO 2017062332 A1 WO2017062332 A1 WO 2017062332A1
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Prior art keywords
coating
tin
layers
coating system
substrate
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PCT/US2016/055263
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English (en)
Inventor
Douglas E. Wolfe
Arthur M. T. MOTTA
Timothy J. EDEN
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The Penn State Research Foundation
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Priority to US15/764,103 priority Critical patent/US20180294062A1/en
Publication of WO2017062332A1 publication Critical patent/WO2017062332A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C21/00—Apparatus or processes specially adapted to the manufacture of reactors or parts thereof
    • G21C21/02—Manufacture of fuel elements or breeder elements contained in non-active casings
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
    • G21C3/02—Fuel elements
    • G21C3/04—Constructional details
    • G21C3/06—Casings; Jackets
    • G21C3/07—Casings; Jackets characterised by their material, e.g. alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors

Definitions

  • the present disclosure relates to coatings used for radioactive fuel, such as nuclear fuel cladding, and/or structural components in radioactive fuel reactors.
  • Cladding is typically an outer layer of a radioactive fuel material, e.g., nuclear fuel rods, and is typically used to prevent radioactive fission fragments from escaping the fuel and entering coolant typically circulated around the fuel material and contaminating it.
  • Cladding is typically made of a corrosion-resistant material with low absorption cross section for thermal neutrons.
  • Zirconium-based alloys are currently used as structural components and as nuclear fuel cladding in nuclear power reactors because of their low neutron absorption cross section, resistance to high temperature steam corrosion, good thermal conductivity, good mechanical properties and resistance to void swelling.
  • zirconium-based nuclear fuel cladding alloys undergo waterside corrosion by the primary coolant water. A fraction of the hydrogen generated in the corrosion reaction, as shown in Eq. (1), may be picked up in the cladding and precipitate as hydrides which can lead to cladding embrittlement.
  • Zr +2H 2 0 Zr0 2 +2H 2 (Eq. 1)
  • U.S. patent application publications 2015/0050521 and 2015/0063523 relate to coatings for nuclear fuel.
  • US 2015/0050521 discloses multilayer coatings including metallic layers and US 2015/0063523 discloses coating nuclear fuel cladding with a total thickness coating up to 1,000 nm (1 ⁇ ).
  • Ceramic TiN and TiAIN coatings have been widely used for years on high speed tool steels, cemented carbides, and cermet substrates for various cutting and finishing operations in the tooling industry.
  • TiN provides good chemical inertness up to 600°C depending on the metal to nitrogen ratio (stoichiometry).
  • An advantage of the present disclosure is a coating useful for radioactive fuel or a structural component in a radioactive fuel reactor, e.g., nuclear fuel cladding alloys. Such coatings are corrosion resistance in the environment of a radioactive fuel reactor.
  • a coating system on a substrate used for radioactive fuel or a structural component in a radioactive fuel reactor comprises a multilayer coating on the substrate including (i) one or more layers including a ternary metal compound, e.g., a ternary metal nitride, ternary metal carbide, ternary metal oxide or combinations thereof such as ternary metal carbonides, oxynitrides, oxycarbides, etc., and (ii) a top coat layer that does not include aluminum.
  • a ternary metal compound e.g., a ternary metal nitride, ternary metal carbide, ternary metal oxide or combinations thereof such as ternary metal carbonides, oxynitrides, oxycarbides, etc.
  • the one or more layers can comprise a nitride, oxide, or carbide or mixed combination (i.e., carbonides, oxynitrides, oxycarbides, etc.) from Ti, Al, Zr, Cr, Si, Nb, Hf, or mixed combination (i.e., TiAlCi_ y N y , wherein the value of y completes the valancy for the compound).
  • Ternary or binary metal compounds of such can include TiAlN TiZrN, TiCrN, TiNbN, TiHfN, TaHfN, TaNbN, or mixed combinations and/or CrN, ZrN, NbN, TiN, TaN, Si3N4, and/or HfN, for example.
  • the multilayer coating includes one or more layers of TiAlN TiZrN, TiCrN, or TiNbN as the ternary metal compound and/or one or more layers of CrN, ZrN, NbN, or TiN as binary compounds.
  • the TiAlN layer can have the formula of Tij-xALN, where x can be between about 0.1 and about 0.9, for example.
  • the number of layers can range from 2-1000 layers, such as from about 4, 6, 8, 16, 32, etc. layers or from about 4 to 32 or 4 to 20 layers.
  • the coating can have a total coating thickness within a thickness range of 0.2 micron to 35 microns or higher e.g., from about 1 micron to about 20 microns, in which the coating is directly or indirectly on a structural component in radioactive fuel reactor.
  • the coating is doped with a dopant, e.g., at least one of the layers of the multilayer coating is doped with one or more dopants, e.g., a rare earth metal (e.g., Y, Yb, etc.) or a metal from group IVB and group VB.
  • the dopant is in an amount of from about 0.1 atomic % to about 25 atomic % of one or more layers of the coating.
  • the multilayer coating can be directly or indirectly deposited on radioactive fuel or on a structural component in radioactive fuel reactor.
  • Another aspect of the present disclosure includes a process for preparing a coating system provided above.
  • the process comprises applying the multilayer coating of any one of the embodiments described above by either a physical vapor deposition (PVD) coating process or chemical vapor deposition (CVD) and its derivatives, or a mixed PVD/CVD system on to radioactive fuel or a structural component used in a radioactive fuel reactor.
  • the process includes process applying the coating system by cathodic arc PVD. Applying a coating by cathodic arc PVD is accomplished by vaporizing the target material under vacuum via an electric arc and allowing the ionized target atoms (and reactant gas species) to deposit on the substrate.
  • Figure 1 is a schematic illustrating a coating system on a ZIRLO® substrate in accordance with an embodiment of the present disclosure.
  • Figure 2 is another schematic illustrating a coating system on a ZIRLO® substrate in accordance with another embodiment of the present disclosure.
  • Figure 3 is a chart showing sample weight gain data with respect to Ti bond coat thickness with TiAlN (-13 ⁇ thickness) top coating after autoclave test exposure at 360°C for 3 days.
  • a coating of about 0.6 ⁇ Ti bond coat thickness was an optimal minimum value for coating durability and to prevent spallation during the corrosion tests for the deposition conditions studied.
  • Figures 4(a)-4(b) are optical microscope images showing the polished cross section of TiAlN (-8 ⁇ ) deposited onto a ZIRLO® substrate with Ti BC of 0.6 ⁇ in the as deposited condition have a substrate surface roughness of (a) 0.25 ⁇ R a (E10) and (b) 0.875 ⁇ R a (E12), respectively.
  • Figure 5 is a chart showing weight gain data as a function of ZIRLO® substrate surface roughness values and TiAlN coating thickness values after autoclave testing at 360°C for 3 days.
  • Figures 6(a)-6(b) are secondary electron SEM image and (b) Backscattered electron SEM image. These images were obtained from a polished cross section of a GEN-2 TiAlN/Ti/ZIRLO® sample, following autoclave testing for 3 days at 360°C. Aluminum migration from the TiAlN coating is observed to have occurred in the top 4 microns of the 10 ⁇ thick TiAlN. The phase, boehmite (AIOOH), appears to have grown on the outer surface, above the TiAlN coating. The layers are 'wavy' because the ZIRLO® substrate was roughened before coating deposition.
  • AIOOH boehmite
  • Figure 7(a)-(d) are SEM image of the surface morphology of TiN coated
  • Figure 8 is a chart of weight gain data obtained after an autoclave test at 360°C and 18.7 MPa (saturation pressure) for 90 days of uncoated ZIRLO® and a number of samples with various coatings.
  • Figures 9 is a chart of oxide thickness as a function of dopant concentration over time. DETAILED DESCRIPTION OF THE DISCLOSURE
  • the present disclosure relates to coatings used for radioactive fuel, such as nuclear fuel cladding, and/or structural components in radioactive fuel reactors.
  • radioactive fuel such as nuclear fuel cladding
  • an approach to addressing the problem of improving nuclear fuel cladding was to change the materials used for the nuclear fuel cladding.
  • the present disclosure advantageously provides a protective, multilayer coating system that can improve the corrosion characteristics of currently used zirconium-based claddings without requiring a major change in cladding material. This approach can also advantageously have the benefit of reducing corrosion and hydrogen pickup during normal operation, further improving design safety. While the coating system of the present disclosure can be used with conventional cladding, it is versatile enough that it can be used with new cladding materials as well.
  • a substrate can advantageously be protected by a coating system.
  • Substrates contemplated by the present disclosure include those used for radioactive fuel or a structural component in a radioactive fuel reactor.
  • Substrates that can benefit from the present disclosure include those comprising zirconium- based alloys, steel, FeCrAl and SiC, for example.
  • Nuclear fuel cladding can also benefit from the coating system f the present invention.
  • Such cladding materials can be composed of a zirconium-based alloy, steel, FeCrAl, SiC, etc.
  • the fuel cladding can be ZIRLO®, or another zirconium-based alloy, or steel cladding in which the coating system of the present disclosure advantageously provides improvements in oxidation resistance.
  • the coating system on a substrate used for radioactive fuel or a structural component in a radioactive fuel reactor includes a multilayer coating on the substrate.
  • the multilayer coating includes: (i) one or more layers including a ternary metal compound, e.g., a ternary metal nitride, ternary metal carbide, ternary metal oxide or combinations thereof such as ternary metal carbonides, oxynitrides, oxycarbides, etc., and (ii) a top coat layer that does not include aluminum, e.g., the top coat does not include aluminum either as the metal or alloy thereof.
  • a ternary metal compound e.g., a ternary metal nitride, ternary metal carbide, ternary metal oxide or combinations thereof such as ternary metal carbonides, oxynitrides, oxycarbides, etc.
  • a top coat layer that does not include aluminum, e.g., the top coat does not include aluminum either as the metal or alloy thereof.
  • one or more layers of the multilayer can comprise a nitride, oxide, or carbide or mixed combination (i.e., carbonides, oxynitrides, oxycarbides, etc.) from Ti, Al, Zr, Cr, Si, Nb, Hf, or mixed combination (i.e., TiAlCi_ y N y , wherein the value of y completes the valancy for the compound).
  • Ternary metal compounds can include TiAIN TiZrN, TiCrN, TiNbN, TiHfN, TaHf , TaNbN, or mixed combinations and binary metal compounds can include CrN, ZrN, NbN, TiN, TaN, Si3N4, and/or HfN, for example.
  • the TiAlN layer can have the formula of Ti 1-X A1 X N, where x can be between about 0.1 and about 0.9, for example.
  • the number of layers can range from 2-1000 layers, such as from about 4, 6, 8, 16, 32, etc. layers or from about 4 to 32 or 4 to 20 layers.
  • the coating can have a total coating thickness within a thickness range of 0.2 micron to 35 microns or higher, e.g., from about 1 micron to about 20 microns, in which the coating is directly or indirectly on a structural component in radioactive fuel reactor.
  • the multilayer coating includes one or more layers of
  • the top layer comprises TiN or some other metal nitride, carbide, oxide, or combinations thereof that do not include aluminum.
  • the individual layers of the multilayer coating can have a thickness greater than 0.1 ⁇ , such as greater than 0.5 ⁇ and even greater than about 0.75 ⁇ . In an aspect of the present disclosure, the individual layers have a thickness in a range of between 0.1 ⁇ -2 ⁇ .
  • the coating system can further include a bond coat on the substrate and the multilayer coating on the bond coat.
  • the bond coat can have a thickness of no less than 0.2 ⁇ , preferably no less than 0.6 ⁇ , such as a thickness of greater than about 1 ⁇ . In one aspect of the present disclosure, the bond coat has a thickness between 0.2 ⁇ to 1.5 ⁇ .
  • the bond coat can comprise Ti, Cr, Zr, Nb and/or another transition metal or alloys thereof.
  • At least one of the one or more of layers is doped with one or more dopants.
  • Figures 1 and 2 illustrate certain embodiments of the present disclosure.
  • FIG. 1 shows ZIRLO® substrate 10 having a titanium bond coat 12 thereon and a multilayer coating of alternating TiAlN and TiN with a TiN top coat 14 over the bond coat. As shown in the figure, the multilayer coating has a total thickness of about 10 microns.
  • Figure 2 shows ZIRLO® substrate 20 having a coating system on both major surfaces thereof which include titanium bond coat 22 having a thickness of about 0.6 microns thereon and a multilayer coating of TiAIN and TiN with a TiN top coat 24 over the bond coat 22. As shown in the figure, the TiN top coat has a thickness of about 1 micron.
  • the coating system can comprise one or more layers of
  • TiAIN and TiN with a TiN top coat In terms of corrosion resistance, TiN provides good chemical inertness up to 600°C depending on the metal to nitrogen ratio (stoichiometry). Titanium aluminum nitride (TiAIN), formed by incorporation of Al into TiN, is a good coating candidate for high temperature oxidation resistance and improved wear/abrasion resistance and toughness under extreme environments. The ternary nitrides composed of a combination of two binary nitrides can produce coatings with properties which exceed that of the individual binary coatings (i.e., solid solution hardening). Titanium nitride and aluminum nitride nano domains co-exist in Ti !
  • an interlayer improves the adhesion between the coating and the substrate.
  • the bond coat can be made of Ti, Cr, Zr, Nb, Ta or other transition metal and/or alloys thereof and/or nitrides/carbides/oxides thereof.
  • the main reason for improved adhesion and coating system performance is the dissolution of substrate oxides (gettering effect) to promote adhesion, provide increased compliance and by accommodating high compressive coating residual stress across the coating substrate interface from the deposition technique. If the bond coat is too thin, it cannot absorb extrinsic (thermal) stresses associated with coating degradation exposed to extreme environmental conditions such as oxidation, moisture, or elevated temperatures.
  • Thickness of bond coat is no less than 0.2 ⁇ , preferably no less than 0.6 ⁇ , such as a thickness of greater than about 1 ⁇ . In one aspect of the present disclosure, the bond coat has a thickness between 0.2 ⁇ to 1.5 ⁇ .
  • the bond coat can comprise Ti, Cr, Zr, Nb and/or another transition metal or alloys thereof.
  • CTE of ZIRLO® can be assumed to be -6.3 x 10 "6 K "1 at 360°C. Therefore, application of a titanium bond coating would be expected to improve adhesion since its CTE of 8.5 x 10 "6 K "1 (at room temperature), lies in between that of the substrate and the coating.
  • coating process parameters such as substrate temperature, bias voltage, arc current and nitrogen pressure allow the coating properties to be tailored for application-specific use in extreme environments.
  • the properties of a multilayer coating including TiN and TiAIN was improved through a systematic investigation of the effect of bias voltage, N2 partial pressure and cathode composition on arc deposited coating properties.
  • the substrate bias affects film micros gagture, coating composition (Al content in TiAIN coating), impinging ion energy on the growing film (i.e., residual stress, density) which leads to a denser coating, backscattering of target atoms, and surface texture.
  • bias voltage is related to the reaction kinetics; a high bias voltage results in increased substrate surface temperature, thus increasing the kinetic energy of ions which facilitates the chemical reaction (Ti + V2N2 TiN) by overcoming the activation barrier at much lower temperatures as compared to standard equilibrium conditions. Additionally, nitrogen content (i.e., partial pressure) affects the coating composition, crystallography, hardness, toughness, wear/abrasion performance and degree of adhesion. [0042] As stated above, the bond coating can have a significant effect on the top coating adhesion and coating system performance as it can dissolve substrate oxides promoting adhesion as well as accommodate high compressive residual stress from the deposition technique due to its compliancy.
  • the effect of titanium bond coating thickness on total coating system corrosion resistance was investigated by depositing various Ti BC thicknesses. Thicknesses of 0.2 (El), 0.4 (E2), 0.6 (E3) and 0.8 (E4) ⁇ were achieved with a deposition times of 6, 8, 10, 15 min respectively, as previously shown in Table 2, which indicates a proportionality between the deposition time and the coating thickness. However, depending on the sample geometry and coating deposition parameters, these can be varied and controlled. After Ti BC deposition, a TiAIN coating with a thickness of -13 ⁇ was deposited and these samples were then subjected to the corrosion testing.
  • the weight gain data collected after the corrosion testing for these samples is presented in Figure 3.
  • the samples with 0.2 and 0.4 ⁇ bond coat thickness suffered weight loss, indicating an unstable coating layer in which coating delamination occurred during corrosion.
  • the thicker bond coating samples showed better behavior: the average weight gain of both thicker (0.6 and 0.8 ⁇ ) bond coat samples was minimal compared to that of the uncoated ZIRLO® sample.
  • the 0.8 ⁇ bond coating thickness showed a positive weight gain of only 3 mg/dm and no indication of coating spallation under visual inspection while the 0.6 ⁇ samples showed a similarly low average weight gain without spallation.
  • the absence of delamination and the minimal weight gain indicate that these bond layer/coating thickness value combinations provided good protection for increased durability against cladding corrosion under the autoclave conditions selected.
  • SEM analysis was conducted to further investigate the coating performance and durability after corrosion test exposure.
  • the SEM surface micrographs from a sample with a bond coating thickness of 0.6 ⁇ show areas of coating failure and areas where the coating was intact.
  • the overall weight gain data was negative for this particular sample, which was confirmed by the presence of coating spallation.
  • SEM provides good insight into the surface morphology of the TiAlN-based coatings after 3 days of exposure when the bond coating is applied to the desired requirements and what occurs when the bond coat is not optimized for subsequent coating deposition.
  • SEM examination confirms that there were delaminated regions, indicating poor coating adhesion; cracks were observed around delaminated regions which are attributed to stresses caused by oxide formation of the underlying ZIRLO® substrate.
  • EDS Energy Dispersive Spectroscopy
  • the main results of the first generation were: (i) A 0.6 ⁇ thick Ti bond coating between the ZIRLO® substrate and the TiAlN top coating is enough to achieve good layer adhesion to the substrate and corrosion resistant coating performance; (ii) Boehmite phase with nonuniform distribution forms on top of TiAlN coatings as a result of outward migration of aluminum after 3 days of autoclave test at 360°C and 18.7 MPa; (iii) Although boehmite phase formation was observed, TiAlN coating was determined to provide good protection against corrosion of Zr alloys according to an order of magnitude decrease in the weight gain data compared to the uncoated ZIRLO® for the short term study investigated.
  • boehmite is detrimental due to its high growth rate and poor adhesion which results in spallation and subsequent oxidation and therefore recession of the coating. Boehmite formation was prevented when utilizing TiN layers which do not produce the boehmite phase. Thus, it was discovered that producing multilayer coatings with an exterior top coat that does not include aluminum, such as TiN, can act as a barrier for boehmite phase formation and such a multicoating system can benefit from advanced properties of the underlying layers and top layer to form significantly improved coatings with high temperature corrosion resistance.
  • PVD coatings containing high levels of compressive stress often result in poor coating durability if the deposited coating thickness exceeds 12 microns, as the internal intrinsic coating stresses can often exceed the interfacial adhesion strength. This results in a lower critical load for coating spallation. The occurrence of this phenomenon depends on multiple factors, including environment, temperature, material systems, microstructure and design architecture. In general, a rougher substrate results in better coating adhesion, as there is a larger number of atomic bonds for a rougher substrate as compared to a smooth substrate. Improved coating adhesion results from the mechanical interlocking of the layer on the rougher substrate.
  • Second generation coatings investigated the influence of ZIRLO® substrate surface roughness (R a ) and TiAIN coating layer thickness on corrosion resistance.
  • R a substrate surface roughness
  • TiAIN coating layer thickness ZIRLO® substrate surface roughness values of 0.1, 0.25, 0.5 and 0.875 ⁇ R a were prepared prior to coating deposition.
  • TiAIN top coat thickness 4 ⁇ thickness were deposited on ZIRLO® substrate coupons (with fixed 0.6 ⁇ Ti BC thickness layer).
  • optical microscopy images of the polished cross sections for samples (E10 and E12) with 0.25 ⁇ R a and 0.875 ⁇ R a in the as deposited state (before autoclave testing) are presented in Figures 4a and 4b, respectively, where the difference in substrate surface roughness is evident.
  • EDS data shows that the majority of both the white and dark regions on the TiAlN coated surface were rich in aluminum as evident by the higher aluminum to titanium ratio (greater than 2).
  • the white regions appeared to show a greater concentration of aluminum, but this is attributed to a greater volume of the boehmite phase changing (masking) the EDS interaction volume, thus changing the depth within the coating from which EDS data is obtained.
  • the main results of the second generation were: (i) The thickness of the boehmite phase formed is not uniform but appears to nucleate at grain boundaries; (ii) Despite the formation of boehmite phase during corrosion, the combination of a 0.25 ⁇ R a substrate surface roughness and a 12 ⁇ top coat layer thickness provide the optimum coating characteristics to obtain best adhesion for CA-PVD TiAlN coatings on ZIRLO® substrates with Ti BC.
  • Table 1 Cathodic Arc Physical Vapor Deposition Parameters with the weight gain value after the autoclave test for TiAIN coating fabrication.
  • Table 1 shows select weight gain averages for GEN-3 coatings deposited as a function of nitrogen partial pressure and substrate bias.
  • a higher substrate bias results in a denser coating which was expected to minimize the formation of the boehmite phase by retarding aluminum migration.
  • the increase in nitrogen partial pressure was expected to assist in modifying the metal/nitrogen ratio as it was believed that unreacted or lightly bound aluminum was diffusing to the coating surface and reacting with the water forming the boehmite phase.
  • changing the bias and the partial pressure of nitrogen showed mixed results with regards to weight gain and the effects on corrosion are indeterminable.
  • TiAIN is still not completely understood, but is believed to be initiated at the N grain boundaries which are rich in aluminum due to aluminum diffusion. This is supported by the appearance of non-uniform growth on the surface of the Ti ! _ x Al x N in which there appears to be a pattern to the boehmite phase formation. The authors suspect that the larger boehmite regions are the sites where aluminum migration first occurred and reacted with the water to form boehmite which then grew with increased exposure. With increasing test duration, aluminum migration continued due to the chemical potential gradient within the Al depleted region of the TiAIN coating. However, this mechanism needs to be verified by performing a systematic study of autoclave testing and transmission electron microscopy analysis. SEM images support this reasoning in which there appears to be localized nucleation and growth on the TiAIN coating surface. This hypothesis is further supported from the literature in that boehmite has been shown to nucleate at grain boundaries for pure aluminum metal at elevated temperature.
  • Figure 7(a)-(d) are SEM image of the surface morphology of TiN coated ZIRLO®; (a) before autoclave testing, (b) after autoclave testing, and the polished cross section of TiN coated ZIRLO® (c) before and (d) after autoclave testing. As shown by the polished cross sections, no boehmite phase is detected on the surface of the autoclave sample.
  • a coating used for radioactive fuel or a structural component in a radioactive fuel reactor that includes a coating comprising a ternary monolithic coating or multiple layers of one or more layers of TiAIN TiZrN, TiCrN, TiNbN and/or CrN, ZrN, NbN, TiN, TiHfN, TaHfN, TaNbN, or mixed combinations and/or CrN, ZrN, NbN, TiN, TaN, Si3N4, and/or HfN.
  • one or more layers can be comprised of a nitride, oxide, or carbide or mixed combination (i.e., carbonides, oxynitrides, oxycarbides, etc.) from Ti, Al, Zr, Cr, Si, Nb Hf, or mixed combination (i.e., TiAlCi_ x N x ).
  • a nitride, oxide, or carbide or mixed combination i.e., carbonides, oxynitrides, oxycarbides, etc.
  • Ti Al, Zr, Cr, Si, Nb Hf
  • mixed combination i.e., TiAlCi_ x N x
  • coatings used for radioactive fuel or a structural component in a radioactive fuel reactor can include a coating comprising a ternary monolithic coating or multiple layers of one or more layers of TiAIN TiZrN, TiCrN, TiNbN and/or CrN, ZrN, NbN, TiN in which at least one of the layers is doped with one or more dopants.
  • the coatings can be prepared by applying the coating on radioactive fuel or a structural component used in a radioactive fuel reactor by either a physical vapor deposition (PVD) coating process (such as cathodic arc, sputtering (magnetron, HIPIMS, ion plating, pulsed laser deposition, evaporation, EB-PVD, etc.) or chemical vapor deposition (CVD) and its derivatives, or a mixed PVD/CVD system.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • cathodic arc PVD cathodic arc PVD
  • steered cathodic arc PVD filtered cathodic arc PVD
  • plasma-assisted PVD laser-assisted PVD
  • DC magnetron sputtering DC magnetron reactive sputtering
  • RF magnetron sputtering unbalanced magnetron sputtering
  • high power impulse magneton sputtering high power impulse magneton sputtering
  • CVD chemical vapor deposition
  • plasma-assisted CVD laser-assisted CVD
  • plasma enhanced CVD photo-enhanced VCD, meal-organic VCD
  • atmospheric pressure CVD ion plating
  • pulsed laser deposition atomic laser deposition, cold spray, thermal spray, solution plasma spray, solution precursor plasma spray, plating, reactive evaporation, and reactive ion beam assisted deposition, and/or mixed combination, derivative or hybrid process.
  • Dopant that are useful for the present disclosure include, for example, one or more of a rare earth metal or a metal from group IVB, such as zirconium and hafnium, and group VB.
  • a layer e.g., the top coat, ternary monolithic layer or a layer of the multilayer coating (e.g., one or more layers of TiAIN TiZrN, TiCrN, TiNbN and/or CrN, ZrN, NbN, TiN) is or are doped with one or more of one or more of Yb, Y, Hf, Zr, or other Rare Earth element.
  • the amount of dopant in the various layers can vary.
  • the amount of dopant is in an amount of from about 0.1 atomic % to about 25 atomic % of one or more layers of the coating. In another embodiment of the present disclosure, the amount of dopant can be range from about 0.5 atomic % to about 10 atomic percent, e.g., from about 0.5 at% to about 4.0 at% of one or more layers of the coating.
  • the dopant can be included in multilayer coating by evaporating the dopant along with other components when preparing the multilayer coating either as a separate component or as part of a target containing the other components to prepare the multiple layer coating. Manufacturing techniques can include chemical vapor deposition, physical vapor deposition and hybrid PVD/CVD.
  • Figure 9 shows oxide thickness as a function of time for Yb-doped titanium aluminum nitride coatings Bl, B2, and B3 (0.0, 0.5, 1.52 at. % Yb respectively). Low concentrations of dopants can be seen to reduce the oxide thickness relative to the coating with dopants at all times.
  • the multilayer coating of the present disclosure can be used for radioactive fuel or a structural component in radioactive fuel reactors comprising a multilayer coating of one or more layers of TiAIN or TiN.
  • the Examples below show that TiAIN and TiN monolayer ceramic coatings applied to ZIRLO® coupons improved corrosion resistance in high temperature water. Both types of coatings adhered well to ZIRLO® with proper surface preparation and with an application of a Ti bond coating layer of the proper thickness. Coating parameters were optimized to achieve a coating that would withstand 3 days at 360°C with minimal weight gain, and no penetration of oxygen, no cracking, and no debonding.
  • a Ti bond layer with 0.6 ⁇ thickness and a substrate surface roughness of 0.25 ⁇ R a provided the smallest weight gain.
  • TiAIN CA-PVD layer with an outer TiN layer can be effective in increasing corrosion resistance of ZIRLO®, as long as the optimal surface bond coat, layer thickness, surface roughness, N2 pressure and bias are applied.
  • Optimum TiN thickness value can be determined for the guidance provided herein to form the barrier for the boehmite and evaluate the effect of multilayer coatings.
  • ZIRLO® was provided by Westinghouse in the form of cold-worked stress-relieved sheet material of the typical clad thickness (-600 microns) with the usual fabrication texture in which the basal poles are preferentially oriented in the normal or radial direction.
  • the chemical composition of ZIRLO® is nominally l Nb, l Sn, 300-600 wt ppm Fe and balance Zr.
  • the ZIRLO® sheets were cut into coupons (2.54cm x 5.08cm x 0.043cm) for subsequent coating surface preparation, deposition and corrosion testing. Each coupon had a small hole (1.6 mm) drilled near one end, and which was used for hanging the coupons in an autoclave tree during corrosion testing.
  • the coupons were prepared by hand grinding the edges and corners with 240 grit SiC paper and the surfaces with 240, 600, and 800 grit SiC paper in that sequence to obtain the desired surface roughness of 0.1-0.875 ⁇ (4-35 microinch).
  • the samples were then cleaned in an ultrasonic cleaner with acetone for 10 minutes, deionized water rinse, followed by ultrasonic cleaning for 10 minutes in methanol, deionized water rinse and nitrogen gas blow dry. Roughness measurements were done using a SJ-201P Surface Roughness Tester.
  • CA-PVD which can be scaled to production-sized components.
  • the term PVD denotes those vacuum deposition processes where the coating material is evaporated or removed by various mechanisms (resistant heating, ablation, high-energy ionized gas bombardment, or electron gun), and the vapor phase is transported to the substrate forming a coating.
  • a continuous or pulsed high current-density, low voltage electric current is passed between two separate electrodes (cathode and anode) under low pressure vacuum, vaporizing the cathode material while simultaneously ionizing the vapor, forming a plasma.
  • the high current density (usually 10 4 -10 6 A/cm 2 ) causes arc erosion by vaporization and melting while ejecting molten solid particles from the cathode surface, with a high percentage of the vaporized species being ionized with elevated energy (50-150 eV) and causing some species to be multiply charged.
  • applying a coating by cathodic arc PVD is accomplished by vaporizing the target material under vacuum via an electric arc and allowing the ionized target atoms (and reactant gas species) to deposit on the substrate.
  • the high ionization and energy of the vapor species result in an intermixing of the coating/substrate interface which results in increased coating adhesion compared to other PVD processes.
  • the higher energy of the plasma i.e., vapor
  • the cathodic species is evaporated in a nitrogen-rich, carbon-rich, or other reactant gas species results in nitrides, carbides, carbonitrides, etc. which provides increased versatility of the process.
  • cathode target passes through the arc it becomes ionized, forming a plasma.
  • the plasma is directed towards the substrate's surface, and in the presence of nitrogen, forms a TiAIN coating.
  • the kinetic energies of the depositing species in cathodic arc are much greater than those of other PVD processes. Therefore, the plasma becomes highly reactive as a greater percentage of the vapor is ionized.
  • the cathodic arc process allows tailoring of the interfacial products, especially in multilayer coatings, and does not produce a distinct coating/substrate interface.
  • CA-PVD coating residual stresses are generally compressive, which can be controlled by deposition parameters.
  • CA-PVD The main disadvantage of CA-PVD is the metal macro particle production due to either droplet formation because of low melting point materials (Al in case of TiAIN) during arc evaporation or intense, localized heating by the arc, which become entrapped within the depositing coating and serve as stress concentrations and crack initiation sites or incompletely ionized excess atoms that coalesce to macro particles during flight towards the substrate [10,16,34].
  • Several methods that were previously applied to decrease these macro particles include application of a straight duct particle filter and plasma refining by electromagnetic field, which avoid deposition of larger macro particles on the substrate [20].
  • the CA-PVD process was performed in a chamber with dimensions of 50.8 cm x 50.8 cm x 50.8 cm.
  • two cathodes of different composition were used: dished high purity (99.999%) elemental titanium (for the bond coating) and titanium aluminum (33at.%Ti-67at.%Al) for the top coating to enhance corrosion protection at elevated temperature), which were individually evaporated by Miller XMT 304 CC/CV DC welder power supplies.
  • These cathodes were cylindrical with a diameter of 6.3 cm and a thickness of 3.2 cm and were oriented 180° from each other with the ZIRLO® coupons located between the cathodes with a spacing of 22.9 cm.
  • the plasma density and location were controlled by placing magnets behind the cathode targets.
  • the samples were mounted in sample holders which were in turn mounted on an 8-post planetary rotation setup with shadow bars along the edge of each sample to avoid increased coating buildup along the sample edges.
  • the substrate coupon temperature was 325°C during coating deposition, as measured by thermocouples placed inside the deposition chamber.
  • the deposition parameters were systematically varied and grouped according to generations.
  • the thickness of the bond coating was optimized by depositing and corrosion testing samples with titanium bond coating (BC) thicknesses values of 0.2, 0.4, 0.6 and 0.8 ⁇ .
  • the second generation GEN- 2
  • both the ZIRLO® coupon surface roughness before deposition 0.1 to 0.875 ⁇
  • total coating thickness 4 to 12 ⁇
  • the primary variable investigated in generation 3 GEN-3) samples was composition, i.e., removing the aluminum content from TiAlN to form TiN to determine its resistance to forming the boehmite phase.
  • the deposition parameters for the three generations of coatings are summarized in Table 2.
  • Table 2 Cathodic Arc Physical Vapor Deposition Parameters for TiAlN and TiN coating fabrication.
  • Corrosion testing was performed at Westinghouse in a static autoclave in pure water for 3 days at 360°C and saturation pressure, corresponding to 18.7 MPa at this temperature. Weight gain measurements were performed following the autoclave test to assess the coating durability and corrosion resistance. Post-autoclave coatings were analyzed by X-ray diffraction (XRD), optical microscopy (OM), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Both surface and cross-section analyses were performed. Surface analyses were conducted directly after the autoclave test without any surface treatment to preserve the surface integrity. Analyses of coating cross section samples were conducted after cutting samples into half, mounting in cold mount epoxy, grinding and polishing.
  • XRD X-ray diffraction
  • OM optical microscopy
  • SEM scanning electron microscopy
  • EDS energy dispersive X-ray spectroscopy
  • MPD PANalytical XPert Pro Multi- Purpose Diffractometer
  • Multilayer coatings were deposited onto ZIRLO® 1 coupon substrates by cathodic arc physical vapor deposition (CA-PVD). Coatings were composed of alternating TiN (top) and Til-xAlxN (2-layer, 4-layer, 8-layer and 16-layer) to investigate the minimum TiN top coating thickness necessary and optimum coating architecture for good corrosion and oxidation resistance. Corrosion tests were performed in static pure water at 360° C and 18.7 MPa for up to 90 days. Coatings having no spallation/delamination survived the autoclave test exposure with a maximum 6 mg/dm 2 weight gain, which is 6 times smaller than that of the uncoated ZIRLOTM sample having a weight gain of 40.2 mg/dm 2 . A top layer of about ⁇ of TiN prevented boehmite formation and TiN/TiAIN 8-layer architecture provided best corrosion performance due to no boehmite phase formation, no delamination/spallation and oxygen ingress prevention.
  • CA-PVD cathodic
  • the coatings were deposited using cathodic arc physical vapor deposition (CA-PVD).
  • CA-PVD cathodic arc physical vapor deposition
  • the CA-PVD process was performed in a chamber with dimensions of 50.8 cm x 50.8 cm x 50.8 cm.
  • two cathodes of different composition were used: dished high purity (99.999%) elemental titanium (for the bond coating) and titanium aluminum (33at.%Ti- 67at.%Al) for the top coating to enhance corrosion protection at elevated temperature), which were individually evaporated by Miller XMT 304 CC/CV DC welder power supplies.
  • cathodes were cylindrical with a diameter of 6.3 cm and a thickness of 3.2 cm and were oriented 180° from each other with the ZIRLOTM coupons located between the cathodes with a spacing of 22.9 cm.
  • the plasma density and location were controlled by placing magnets behind the cathode targets.
  • the samples were mounted in sample holders which were in turn mounted on an 8-post planetary rotation setup with shadow bars along the edge of each sample to avoid increased coating buildup along the sample edges.
  • the substrate coupon temperature was 325°C during coating deposition, as measured by thermocouples placed inside the deposition chamber.
  • the thickness of the Ti bond layer applied was 0.6 ⁇ and the substrate surface roughness was prepared to be 0.25 ⁇ Ra. Coating properties specific for each sample are provided in Table 1. The thickness of each layer ranged from 0.7 ⁇ to 6 ⁇ . The total layer thickness was around 10 ⁇ which for the elements used provided a negligible neutronic penalty.
  • Table 3 Cathodic Arc Physical Vapor Deposition Parameters for monolithic TiN and multilayer TiN/TiAIN coating fabrication.
  • Corrosion testing was performed at Westinghouse in a static autoclave in pure water for 7-90 days at 360°C and saturation pressure, corresponding to 18.7 MPa at this temperature. Weight gain measurements were performed following the autoclave test to assess the coating durability and corrosion resistance. Initial analyses using optical microscopy (OM) were conducted on 7 days autoclave tested samples to evaluate the deposited coating thickness and corrosion performance. Samples tested for 33 and 90 days were characterized in the same manner. The structural and morphological properties of the longer duration (33 and 90 days) tested post-autoclave samples were further characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS).
  • XRD X-ray diffraction
  • SEM scanning electron microscopy
  • EDS energy dispersive X-ray spectroscopy
  • XRD analysis with Grazing Incidence (GI) and Bragg-Brentano (BB) scans were performed with a step size of 0.026° two-theta to reveal the phases formed during corrosion.
  • GI scans were conducted at incidence angles of 0.5°, 1°, 5°, 10° or 15° to achieve the appropriate depth of penetration for the incident beam and to be able to distinguish phases at different layers of the coating. The penetration depth was estimated using PANalytical High Score software.
  • Backscatter and secondary electron scanning electron microscopy (SEM) measurements were conducted using a FEI Quanta 200 Environmental SEM at 80 Pa pressure and 20 kV high voltage.
  • Multilayer coatings provide advanced functionality compared to the single layer coating by combining the beneficial properties of constituent coating layers.
  • Multilayer architecture improves the corrosion tolerance of the coating, in other words when oxygen and hydrogen diffuses through one layer and forms boehmite phase resulting in the degradation and spallation of the exterior coating layer, the alternating layers act as new barriers for oxygen and hydrogen ingress.
  • Weight gain data was previously presented in Figure 8. Overall, samples that were autoclave tested for 90 days demonstrated a weight gain in the range of 1.6-6.0 mg/dm 2 . These weight gain values are much lower than that of uncoated ZIRLOTM sample which had a weight gain of 40 mg/dm 2 after 90 days autoclave test. Weight gain data showed that, in addition to TiN(thin)/TiAlN(thick) sample, the 2- and 4-layered coatings also showed some weight loss after 50 days, indicating spallation/delamination of the coating. This was followed by a weight increase trend due to oxidation.
  • TiN/TiAIN 8-layer coating was determined to be the optimum architecture that makes it possible to stop boehmite phase formation with ⁇ 1 ⁇ thickness TiN layer, to show good adhesion, and to have the lowest weight gain without spallation or delamination.
  • TiN/TiAIN multilayer coatings showed approximately an order of magnitude lower weight gain compared to uncoated ZIRLOTM substrate and no delamination or spallation indicating lower oxidation. Only a thin layer of ( ⁇ 1 ⁇ ) TiN is needed under the system tested as a barrier to terminate Al migration and prevent boehmite phase formation. All coatings were able to withstand the autoclave test without any spallation/delamination up to 7 days and most of them were maintained on the surface up to 33 days.
  • TiN/TiAIN 8 -layer architecture coatings showed the best corrosion performance at 360°C and 18.7 MPa (saturation pressure) compared to other tested multilayer architectures due to no boehmite phase formation, approximately linear weight gain data without any delamination/spallation and oxygen ingress prevention.

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Abstract

L'invention concerne un revêtement utilisé pour du combustible radioactif ou un élément de structure dans des réacteurs à combustible radioactif, par exemple des alliages de gaine de combustible nucléaire, pouvant comprendre un revêtement monolithique ternaire ou de multiples couches d'une ou plusieurs couches de TiAlN TiZrN, CrN, TiNbN et/ou TiCrN, ZrN, NbN, TiN, TaN, HfN,TiHfN, TaHfN, TaNbN, ou des associations mixtes et/ou CrN, ZrN, NbN, TiN, TaN, HfN, Si3N4 et/ou HfN. De plus, une ou plusieurs couches peuvent être constituées d'un nitrure, d'un oxyde ou d'un carbure ou d'une association mixte (c'est-à-dire des carbonides, des oxynitrures, des oxycarbures, etc.) parmi Ti, Al, Zr, Cr, Si, Nb, Hf, ou une association mixte (c'est-à-dire TiAlC1-xNx). Ce revêtement multicouche peut être dopé avec un dopant.
PCT/US2016/055263 2015-10-06 2016-10-04 Revêtement céramique pour la résistance à la corrosion de gaine de combustible nucléaire WO2017062332A1 (fr)

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