Classifications

• • 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
  • C23C14/14—Metallic material, boron or silicon
  • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
  • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
• • 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
  • C23C14/34—Sputtering
• • 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
  • C23C14/34—Sputtering
  • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
• • 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
  • C23C16/06—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 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
  • C23C28/02—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 only including layers of 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
  • C23C28/02—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 only including layers of metallic material
  • C23C28/021—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 only including layers of metallic material including at least one metal alloy layer
• • 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
  • C23C28/02—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 only including layers of metallic material
  • C23C28/023—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 only including layers of metallic material only coatings of metal elements only
• • 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
• • 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
  • G21C3/16—Details of the construction within the casing
  • G21C3/20—Details of the construction within the casing with coating on fuel or on inside of casing; with non-active interlayer between casing and active material with multiple casings or multiple active layers
• • 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
• • 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
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T50/00—Aeronautics or air transport
  • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12771—Transition metal-base component
  • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12771—Transition metal-base component
  • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
  • Y10T428/12819—Group VB metal-base component
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12771—Transition metal-base component
  • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
  • Y10T428/12826—Group VIB metal-base component
  • Y10T428/12847—Cr-base component

Definitions

• the present invention belongs to the field of materials used in the nuclear field, in particular the materials intended to best withstand the physicochemical conditions encountered during a nuclear reactor accident.
• the invention more particularly relates to such a material, its coating, a part comprising the material or the coating, their uses, as well as the method of manufacturing the material.
• the coolant of a Pressurized Water Nuclear Reactor is a water that is pressurized to 190 bar and reaches a maximum temperature of 360 ° C.
• the zirconium alloy constituting the nuclear fuel cladding oxidizes in contact with the coolant.
• the industrial fuel suppliers have developed new alloys that are more resistant to corrosion under nominal conditions, such as the M5 TM alloy from the Areva-NP company.
• the high temperatures are generally above 700 ° C, in particular between 800 ° C and 1200 ° C. They are for example reached in the case of accidental hypothetical scenarios such as "Reactivity Insertion Accident” or "APRP", or even in dewatering conditions of the spent fuel storage pool. . At such temperatures, the coolant is in the form of water vapor.
• the high temperature oxidation is much more critical than at low temperature, because the deterioration of cladding, the first fuel containment barrier, is faster and associated risks greater. These risks include:
• FR 1493040 A proposes to coat a zirconium alloy with a layer of chromium. This monolayer coating is presented to protect the zirconium alloy from oxidation at a temperature of 600 ° C at atmospheric pressure and in carbon dioxide. However, as demonstrated experimentally below, the proposed coating fails to significantly limit the oxidation at high temperature.
• One of the aims of the invention is therefore to avoid, mitigate and / or delay the disadvantages described above, by proposing a material which can in particular provide a significantly improved resistance against accidental oxidation of a nuclear fuel cladding based on zirconium, while preserving or even improving the resistance to oxidation of this cladding under service conditions.
• Another object of the invention is to improve the mechanical properties of the material, in particular its ductility and its mechanical strength, following oxidation under accident conditions.
• Another object of the invention is to reduce the production of hydrogen gas (hydrogen hazard) or hydrogen diffusing into the cladding (embrittlement by hydriding).
• the present invention thus relates to a multilayer material comprising a zirconium substrate coated with a multilayer coating, the multilayer coating comprising metal layers composed of identical or different materials chosen from chromium, a chromium alloy or a ternary alloy of the system. Nb-Cr-Ti.
• the percentages of composition are expressed as atomic percentage.
• the metallic materials mentioned below in particular zirconium, chromium or their alloys, and / or the ternary alloy of the Nb-Cr-Ti system
• the nature and the contents of these impurities are generally the natures and contents typical of the impurities of the industrial metallic materials used in particular in the nuclear field and thus compatible in particular with the requirements of the specifications of this industry.
• the levels of inevitable impurities are less than 200 ppm, preferably less than 100 ppm, even more preferably less than 50 ppm.
• a verb such as “to understand”, “to include”, “to incorporate”, “to include” and its conjugated forms are open terms and thus do not exclude the presence of element (s) and / or stage (s) additions to the initial element (s) and / or step (s) listed after those terms.
• these open terms also include a particular embodiment in which only the element (s) and / or initial stage (s), to the exclusion of all others, are targeted; in which case the term “open” also refers to the closed term “consisting of", “constituting” and its associated forms.
• the multilayer material of the invention may comprise a zirconium substrate coated with a multilayer coating, the multilayer coating consisting of metal layers composed of identical or different materials selected from chromium, a chromium alloy or an alloy. ternary Nb-Cr-Ti system.
• the multilayer material of the invention undergoes only limited oxidation during the accident of a reactor nuclear, whose conditions are characterized in particular by temperatures above 700 ° C, typically between 700 ° C and 1200 ° C, or possibly between 800 ° C and 1200 ° C or between 1000 ° C and 1200 ° C .
• This oxidation resistance makes it possible in particular to limit the release or setting of hydrogen and to reduce the brittleness of a part composed in whole or part of this material, such as for example a nuclear fuel cladding.
• the hydrogen thus released diffuse into the zirconium alloy of the sheath and can form a hydride with the zirconium not yet oxidized of the sheath according to the reaction
• index "x" indicates that hydrides of variable stoichiometry can be formed, this index being in particular equal to 2.
• Hydrogen in solid solution, but especially in the form of zirconium hydride precipitate, has the drawback of reducing the ductility of zirconium alloys, and thus of weakening the sheath, especially at low temperature.
• This embrittlement is all the more to be feared when one seeks to achieve high burnup rates because, at these rates, there is an increase in the proportion of zirconium oxidized according to the reaction (1) and therefore the amount of hydrides formed according to reaction (2).
• She usually leads to corrosion of conventional industrial alloys to prohibitive levels vis-à-vis the safety criteria and integrity of the sheath, and poses problems for transport and post ⁇ Service warehousing. Observed under nominal conditions, hydriding is generally observed under accident conditions only in the vicinity of 1000 ° C.
• Zr- ⁇ structure the a phase of a zirconium alloy (denoted “Zr-a”, of compact hexagonal crystallographic structure) at low temperature is transformed into a ⁇ phase (denoted "Zr- ⁇ ", of crystallographic structure centered cubic) in a temperature range typically from 700 ° C to 1000 ° C and varying according to the alloy, the heating rate, the hydrogen content 3 ⁇ 4 ...
• the alloy undergoes local dimensional variations.
• the oxidation then continues under the outer layer of ZrO 2 until the oxygen reaches its solubility limit which is relatively low in Zr- ⁇ , typically less than 1% by mass at 1100 ° C.
• Zr- ⁇ then becomes a solid solution Zr- (O) which can contain between 2% and 7% by mass of oxygen in solid solution, whereas only ZrO 2 is formed at low temperature.
• the following layers then follow one another from the outer surface to the surface internal sheath: ZrC> 2 , Zr- (0), Zr- (0) + Zr-ex- ⁇ , Zr-ex- ⁇ .
• this material has been able to develop a multilayer material that has improved resistance to oxidation under such conditions.
• this material also has the advantages that its multilayer coating has good adhesion to the zirconium-based substrate, despite local dimensional variations due to the Zr- ⁇ structure, the acceleration of the diffusion mechanisms and the instability phenomena in the oxide layer Zr0 2 - It also has good resistance to hydriding.
• these properties of the multilayer material of the invention are due to the combination of a particular structure and composition.
• the structure of the multilayer material is such that the coating results from the superposition of at least two metal layers in order to form a multilayer coating which makes it possible to improve the resistance to oxidation, or even to hydridation, with respect to a coating. monolayer of the same composition.
• a multilayer material is distinguished from a monolayer material of equivalent overall chemical composition, in particular by the presence of interface between the layers.
• This interface is such that it generally corresponds to a perturbation of the microstructure at the atomic scale. It is for example identified using a fine characterization technique such as high resolution Transmission Electron Microscopy (TEM), EXAFS spectroscopy ("Extended X-Ray Absorption Fine Structure”), ....
• TEM Transmission Electron Microscopy
• EXAFS spectroscopy Extended X-Ray Absorption Fine Structure
• a multilayer material is generally obtained by a method for sequentially depositing different monolayers.
• the structure of the multilayer material may be such that:
• the multilayer coating comprises from 2 to 2000 metal layers, preferentially from 2 to 1000, even more preferably from 2 to 50 metal layers, and / or;
• each of the metal layers has a thickness of at least 3 nm, preferably 3 nm to 1 ⁇ m, and / or;
• the cumulative thickness of the metal layers is from 6 nm to 10 ⁇ m.
• the small cumulative thickness of metal layers makes it possible to limit the impact on the neutron behavior of the core of a nuclear reactor.
• a cumulative thickness not exceeding 10 ⁇ m does not preclude making a multilayer material according to the invention in which the total thickness of the coating is greater than 10 ⁇ m, typically 1 ym to 20 ym.
• the multilayer coating may comprise one or more additional layers positioned between two layers of the coating or on the surface of the coating to provide at least one additional property.
• the cumulative thickness of the metal layers of 3 nm each is 10 ⁇ m, this implies that the number of layers is 3334.
• the multilayer coating comprises at least ten metal layers, each of which has a thickness of at least 100 nm, the cumulative thickness of the metal layers being from 1 ⁇ m to 6 ym.
• the multilayer material of the invention is such that the metal layers constituting all or part of the multilayer coating are composed of identical or different materials selected from chromium, a chromium alloy or a ternary alloy of the Nb-Cr-Ti system. Since the multilayer coating can be composed of layers of identical or different compositions, several embodiments are possible.
• the multilayer coating is composite: the metal layers are of different compositions.
• This is for example a multilayer coating noted “Cr / Nb-Cr-Ti”
• the metal layers are composed of a material based on chromium (chromium and / or chromium alloy), and a ternary alloy of the Nb-Cr-Ti system.
• the metal layers are i) one or more layers composed of chromium and / or a chromium alloy and ii) one or more layers composed of the ternary alloy of the Nb-Cr-Ti system.
• the layers of different compositions may be present in the composite multilayer coating in a variable proportion, and arranged alternately or in a random order.
• a metal layer composed of chromium or chromium alloy, said intermediate bonding layer is generally that in contact with the zirconium-based substrate with which it has good adhesion and compatibility.
• the multilayer coating is predominant in chromium: the metal layers are all composed of chromium and / or a chromium alloy, and form a multilayer coating denoted "Cr / Cr".
• a multilayer material provided with such a coating has proved particularly resistant to oxidation under accident conditions.
• the multilayer coating is a minority in chromium: the metal layers are all composed of a ternary alloy of the Nb-Cr-Ti system and form a multilayer coating denoted "Nb-Cr-Ti / Nb-Cr- Ti ".
• the chromium alloy is composed of 80% to 99% chromium atom, and / or;
• the metal layers composed of chromium or of a chromium alloy contain at least one chemical element chosen from silicon or yttrium, such an element present for example at a content of 0.1% to 20% by atom capable of conferring further improvement in corrosion resistance, and / or;
• the metal layer or layers composed of a ternary alloy of the Nb-Cr-Ti system provide additional ductility. They then generally have a small thickness, which is preferably 5 nm to 500 nm, in order to limit neutron capture or flux activation problems.
• the ternary alloy of the Nb-Cr-Ti system is the name given by the person skilled in the art to designate this type of alloy, but this does not correspond to a nomenclature or to a defined stoichiometry.
• This ternary alloy of the Nb-Cr-Ti system is described, for example, in the publication "DL DAVIDSON, KS CHAN, and DL ANTON, The Effects on Fracture Toughness of Ductile-Phase Composition and Morphology in Nb-Cr-Ti and Nb-Si. In Situ Composites, METALLURGICAL AND MATERIALS TRANSACTIONS A, 27A (1996) 3007-3018.
• niobium may for example comprise at least 50% to 75% of niobium, 5% to 15% of chromium and 20% to 35% of titanium, which is equivalent to a ternary alloy comprising by weight of 65% ci. 85% niobium, 3% to 11% chromium and 12% to 24% titanium.
• the substrate is based on zirconium, namely that it contains between 50% and 100% of zirconium atom.
• the substrate is therefore zirconium or a zirconium alloy.
• the zirconium alloy may be selected from Zircaloy-2, Zircaloy-4, Zirlo TM or M5 TM. These zirconium alloys are well known to those skilled in the nuclear field.
• the compositions of these alloys are such that they comprise, for example, by weight:
• Zircaloy-2 alloy 1.20% to 1.70% Sn; 0.07% to 0.20% Fe; 0.05% to 1.15% Cr; 0.03% to 0.08% Ni; 900 ppm to 1500 ppm O; the rest of zirconium
• Zircaloy-4 alloy 1.20% to 1.70% Sn; 0.18% to 0.24% Fe; 0.07% to 1.13% Cr; 900 ppm to 1500 ppm O; less than 0.007% Ni; the rest of zirconium
• Zirlo alloy 0.5% to 2.0% Nb; 0.7% to 1.5% Sn; 0.07% to 0.28% of at least one element selected from Fe, Ni, Cr; up to 200 ppm C; the rest of zirconium
• M5 alloy 0.8% to 1.2% niobium; 0, 090% to
• the substrate is usually a massive element.
• This massive element may be blank of any coating, and is for example a constituent part of a nuclear reactor, such as a nuclear fuel cladding, a guide tube, a spacer grid or a plate fuel.
• the invention also relates to a multilayer coating as such comprising metal layers all or part of which is composed of a ternary alloy of the Nb-Cr-Ti system.
• the composite multilayer coating is for example such that the metal layers are i) one or more layers composed of chromium and / or chromium alloy and ii) one or more layers composed of the ternary alloy of the Nb-Cr-Ti system (multilayer coating denoted "Cr / Nb-Cr-Ti").
• the multilayer coating 1 of the invention comprises at least two layers, and optionally further an outer layer of attachment.
• This bonding layer is positioned on one side of the multilayer coating, in order to facilitate subsequent bonding with a substrate. It is preferably composed of chromium or a chromium alloy, especially when the substrate is composed of zirconium or zirconium alloy.
• This outer bonding layer will constitute the intermediate bonding layer when the substrate will be provided with the multilayer coating.
• the multilayer coating 1 of the invention may be in one or more of the variants described above for the multilayer material, including variants relating to its structure and / or its composition.
• the multilayer coating of the invention may be deposited on a substrate using a method such as diffusion bonding, realized by for example by heating the multilayer coating at a temperature of 500 ° C to 600 ° C.
• the invention also relates to a part composed in whole or in part of the multilayer material or the multilayer coating of the invention as defined above, the part constituting a nuclear reactor, for example of the pressurized water reactor type ("PWR "), With Boiling Water (“ REB ”) or fourth generation reactors.
• PWR pressurized water reactor type
• REB With Boiling Water
• the piece is for example a tubular piece such as a nuclear fuel sheath or a guide tube, a spacer grid or a plate fuel (for example a Fast Neutron Reactor Type RNR-G).
• a tubular piece such as a nuclear fuel sheath or a guide tube, a spacer grid or a plate fuel (for example a Fast Neutron Reactor Type RNR-G).
• the multilayer material or the coating covers the outer surface of the part.
• the invention also relates to the use of a multilayer material, a multilayer coating or a part according to any one of the preceding claims, in order to improve the resistance to oxidation under accident conditions in a nuclear environment.
• a substrate based on zirconium a substrate based on zirconium.
• the invention also relates to a method of manufacturing a multilayer material as defined above, especially in one or more of the variants of this material, comprising a step in which a zirconium-based substrate is covered with a multilayer coating comprising layers metallic materials composed of identical or different materials selected from chromium, a chromium alloy or a ternary alloy of the Nb-Cr-Ti system.
• the substrate is covered with a multilayer coating by sequentially depositing the metal layers, that is to say a deposit in which the metal layers are deposited one after the other.
• the sequenced deposition comprises at least one pause time separating the deposition of each of the metal layers and during which the deposit ceases.
• a sequential deposition technique may be chosen so that the multilayer coating produced is sufficiently dense to cover, without major sealing defects, the substrate or the lower metal layer on which the deposition, structure and materials are deposited. usual properties of the latter not being significantly affected.
• the substrate may be covered by sequential deposition by means of a physical vapor deposition (“PVD”) operation, chemical vapor deposition (“Chemical Vapor Deposition”) said CVD) or electrodeposition (for example by pulsed electrolysis).
• PVD physical vapor deposition
• CVD chemical vapor deposition
• electrodeposition for example by pulsed electrolysis
• the zirconium-based substrate should preferably not be subjected to a temperature higher than the temperature of the last heat treatment that it has undergone during its manufacture, for example a sequenced deposition is carried out at a maximum temperature of 580 ° C as recommended for a recrystallized state of Zr-Nb alloy. This makes it possible to avoid a metallurgical modification such as a partial transformation in the Zr- ⁇ phase that may adversely affect the properties, for example mechanical properties, of the substrate.
• the physical vapor deposition is carried out at a temperature of 200 ° C to 600 ° C, preferably 200 ° C to 450 ° C.
• the physical vapor deposition is a cathodic sputtering (or "sputtering").
• Sputtering consists of making thin layers by ejection of atoms from a target material during a bombardment by rare gas ions accelerated under high voltage. The ejected atoms then form a metal vapor that condenses on the surface of a substrate to form a coating.
• the cathodic sputtering may be carried out using a planar cathode and a planar target, or a cylindrical cathode and a hollow target containing the substrate.
• the cathode sputtering is of the magnetron type.
• a magnetron is a set of permanent magnets located under the target to increase the ion density in the vicinity of the target. The magnetron effect makes it possible to maintain the discharge with a lower pressure, thereby improving the quality of the spray.
• Magnetron cathode sputtering is therefore a fast, reproducible process for producing a dense coating. It is known to those skilled in the art, and described for example in the document "Engineering Techniques, Magnetron Sputtering, Reference Ml 654".
• the invention also relates to a multilayer material obtained or obtainable by the manufacturing method of the invention.
• FIGS. 1 to 4 represent Scanning Electron Microscopy (SEM) photographs of materials consisting of a Zircaloy-4 substrate provided with a Cr monolayer coating (FIG. 1), a Cr / Cr multilayer coating (FIG. 2), a Nb monolayer -Cr-Ti ( Figure 3) and multilayer
• Figure 5 is a graph indicating the mass gain in nominal conditions, as a function of time, of materials consisting of a Zircaloy-4 substrate with or without a monolayer or multilayer coating.
• FIGS. 7 to 12 illustrate this weight gain, for materials consisting of a Zircaloy-4 substrate:
• FIGS. 13 to 18 are micrographs obtained by polished section optical microscopy of materials consisting of a Zircaloy-4 substrate: - without coating, after undergoing oxidation under nominal conditions ( Figure 13) and then oxidation under accident conditions (Figure 14),
• Figure 18 is a micrograph of the material of Figure 17 of an area not shown in this figure and wherein the coating has a crack.
• Figure 19 shows the flexural deformation at room temperature as a function of stress applied to uncoated Zircaloy-4 specimens and Cr / Nb-Cr-Ti and Cr / Cr multilayer coatings.
• FIGS. 20 and 21 are SEM images illustrating oxidation after 15000 seconds under water vapor at 1000 ° C., for materials consisting of an uncoated Zircaloy-4 substrate (FIG. 20) and provided with a Cr / Cr multilayer coating ( Figure 21).
• the effects of this oxidation are illustrated by the graph of Figure 22 which shows the evolution of the weight gain over time for materials consisting of a substrate of Zircaloy-4 without coating (right 1) and provided with a Cr / Cr multilayer coating (straight 2).
• chromium or ternary alloy monolayer control coatings of the Nb-Cr-Ti system and ii) multilayer coatings according to the invention alternating layers of chromium (Cr / Cr), or layers of chromium and layers of the ternary alloy of the Nb-Cr-Ti system (Cr / Nb-Cr-Ti).
• L x ternary alloy selected from Nb-Cr-Ti system alloy Cry Nb67% 0% 3% TI 2, the formula is expressed in atomic percent.
• the resistance to oxidation and hydriding, the structural characteristics and the mechanical properties of the materials are tested under nominal conditions (360 ° C., water at 190 bars) and in conditions representative of an APRP type accident (1100 ° C.). C, steam) with or without prior oxidation under nominal conditions, according to the conditions representative of those encountered for a PWR type nuclear reactor.
• the structural analyzes are in particular carried out by optical microscopy on polished section.
• the platelets of the analyzed materials are prepared by covering them with a platinum coating (flash) and a gold coating (electrolytic) before coating in a resin for polishing.
• platinum and protective gold coatings prevent tearing during the polishing of the monolayer or multilayer PVD coating which is weakened by oxidation. They also make it possible to improve the image quality under a microscope by electronic conduction.
• These protective coatings are indicated on the micrographs when they appear sufficiently clearly.
• Platelets of Zircaloy-4 measuring 45 mm x 14 mm ⁇ 1.2 mm are defatted in an alkaline lye, rinsed with water, cleaned with ultrasound for 30 minutes in an acetone bath, then rinsed with water. ethanol and parboiled.
• the partial pressure of argon is 0.5 Pa, it is generally between 0.05 Pa and 2 Pa.
• the bias voltage is -100 V. It is typically between -10 V and -400 V.
• the monolayer coating Nb-Cr-Ti is made on a 500 nm chrome bonding layer covering the Zircaloy-4.
• the thickness of the bonding layer may be decreased to limit its impact on the overall composition of the coating, particularly when the coating has few layers.
• the Cr / Cr multilayer coatings are made by interrupting the magnetron discharge several times during the deposition, each discharge being separated by a pause time.
• the Cr / Nb-Cr-Ti multilayer coatings are produced by alternating passage of the samples facing each target of Cr and then of Nb-Cr-Ti, with a discharge time with respect to each target set as a function of the " ⁇ " period. desired.
• the kinematics of the metal precursors in the enclosure makes it possible to precisely control the thickness of each elementary layer forming the multilayer coating. This control is possible from a layer thickness of 3 nm.
• the operating conditions of the magnetron sputtering and the characteristics of the coatings obtained are given in Table 1.
• One period corresponds to the production of a chromium layer for the Cr / Cr multilayer coatings, or to the pattern resulting from the addition of a Cr layer and a layer of Nb-Cr-Ti deposited successively for Cr / Nb-Cr-Ti multilayer coatings.
• Table 1 The microstructure of the coatings is observed by SEM on polished section. It is represented in FIGS. 1 to 4, in which the Zircaloy-4 substrate, the chromium and Nb-Cr-Ti layers appear.
• the interfaces between the 14 layers of the Cr / Cr multilayer coating do not appear on the plate of Figure 4. They can nonetheless be visualized using a high resolution technique such as Transmission Electron Microscopy (TEM).
• TEM Transmission Electron Microscopy
• the light gray and dark gray layers correspond respectively to the layers of the Nb-Cr-Ti alloy and to the chromium layers.
• the coated zirconium-based platelets made in Example 1 remain 60 days in an autoclave whose medium is representative of the nominal operating conditions of a PWR type nuclear reactor.
• the autoclave medium is a water containing 650 ppm of boron and 10 ppm of lithium, raised to 360 ° C. and pressurized to 190 bars.
• the oxidation resistance under nominal conditions is similar for the Cr / Cr multilayer coating, or even higher for two Cr / Nb-Cr-Ti multilayer coatings (references N10-200 ° C and N100-200 ° C) when exposure to oxidation is less than 60 days.
• polished section optical micrographs are made on the edge of a Zircaloy-4 wafer with Cr / Nb-Cr-Ti multilayer coating (reference M600 of Table 1). They confirm that this coating prevents the formation of ZrO2 found for an uncoated control wafer. This property is achieved through the formation on the surface of the coating of a protective layer of chromium oxide (Cr 2 03) 100 nm thick, which is an oxygen diffusion barrier limiting or even preventing the formation of Zr0 2 under the multilayer coating. Compared to a monolayer material with coating
• Tests are carried out in order to evaluate the oxidation resistance under accident conditions of the zirconium-based platelets made in Example 1.
• the conditions are those of an accident of the APRP type during which the temperature of the nuclear fuel cladding rapidly increases to more than 800 ° C or even more than 1050 ° C until it can reach 1200 ° C., then decreases suddenly more soaking in the water of safety showers to drown the heart again.
• the conditions of the tests correspond to the enveloped conditions of an APRP accident taken into account in the safety calculations.
• the wafers are held at the end of an alumina cane, then placed for 850 seconds in an enclosure in which circulates water vapor heated to 1100 ° C using a furnace for the oxidation of steam. 'water.
• the platelets are then dropped in a quench bath filled with water at room temperature.
• the bottom of the bath is provided with a cushion cushioning the falling of the platelets and a white cloth in order to recover the particles separating the platelets in the event of a desquamation of the weakened phases following the thermal shock of quenching.
• the oxidized platelets and any desquamated pieces are weighed to determine the weight gain due to the amount of oxygen diffused into the platelets.
• the measurement is repeated once for the uncoated Zircaloy-4 wafer, and twice for the Cr / Nb-Cr-Ti multilayer wafers (M600 reference) and with Cr / Cr multilayer coating.
• the difference obtained in the values for the same plate is due to the experimental dispersion.
• the measured mass catches are grouped in the
• This resistance is particularly improved for multilayer coatings containing at least 10 layers (and therefore with a minimum layer thickness of 100 nm, preferably between 100 nm and 500 nm), more particularly for multilayer coatings Cr / Nb-Cr -Ti reference M600 (10 periods) and multilayer Cr / Cr.
• the thickness of the ZrO 2 and Zr- (O) phases in coated platelets is evaluated by microstructural examinations by polished section optical microscopy.
• micrographs obtained show the microstructures after oxidation under accident conditions uncoated platelets (FIG. 7), and platelets with Nb-Cr-Ti monolayer coating (FIG. 8), Cr / Nb-Cr-Ti multilayers (reference M600: FIG. 9, reference M1000: FIG. Figure 11) and Cr / Cr multilayer (Figure 12) leading to the lowest mass taps at 1100 ° C.
• Figure 7 ZrO 2 outer layer, Zr- (O) layer, Zircaloy-4 substrate;
• FIG. 11 Partially oxidized chromium coating, Zr- (O) layer extending in places in the Zircaloy-4 substrate in the form of Zr- (O) needles of less than 100 ⁇ m in projected length, substrate Zircaloy-4;
• the equivalent thickness of Zr- (O) corresponds to the thickness of the layer of Zr- (O) to which is added the thickness of a layer whose surface is equivalent to the surface of the Zr- ⁇ (0).
• the equivalent thickness of oxidized Zircaloy-4 (i.e., Zircaloy-4 embrittled by oxygen penetration) is calculated from the following formula:
• Equivalent Thickness of Zircaloy-4 Oxidized Equivalent Thickness of Zr- (O) + Thickness of Zr0 2 / 1.56
• Pilling-Bedworth coefficient which has a value of 1.56, reflects the density variation during the oxidation of Zirconium to ZrO 2 .
• Table 3 shows that the Cr / Cr multilayer coating has a good seal because, even if some oxygen penetration in Zircaloy-4 is product, this penetration is not significant enough that Zr- (O) appears.
• the materials with Cr / Nb-Cr-Ti and particularly Cr / Cr multilayer coatings therefore make it possible to ensure ductility in the core of a sheath. nuclear fuel based on zirconium. Such a property is decisive with respect to the quenching behavior and after quenching of the sheath in order to meet the safety criteria related to the LOCA.
• a wafer consisting of a Zircaloy-4 substrate provided with a TiN / AlTiN multilayer coating based on titanium nitride and mixed nitride is produced. aluminum and titanium.
• the TiN / AlTiN multilayer coating with a total thickness of 3.4 ⁇ m consists of a TiN sublayer of 200 nm thick, over which are superposed more than 400 alternating layers of AlTiN or TiN of approximately 7 ⁇ m. nm of thickness whose cumulative thickness is 3 ⁇ m, then a final layer of AlTiN 200 nm thick.
• This multilayer coating is tested under nominal and accident conditions according to the protocols of examples 2 and 3. Even if the oxidation resistance of the zirconium alloy substrate is improved by the TiN / AlTiN coating under nominal conditions, no improvement is possible. however, found in accident conditions.
• the weight gain of approximately 10 mg / cm after 800 seconds and 18 mg / cm 2 after 3000 seconds, as well as the thickness of the oxides formed, are indeed comparable to the uncoated Zircaloy-4 wafer.
• Example 3 shows that it is the combination of the structure and the composition of the multilayer material of the invention which makes it possible to improve the resistance to oxidation under accident conditions.
• a hypothetical accidental APRP type scenario can occur at any stage of the life of the nuclear fuel cladding in service, so after some low temperature oxidation.
• the following measurements are intended to evaluate the impact of prior oxidation under nominal conditions on the effectiveness of Cr / Nb-Cr-Ti, Cr monolayer and Cr / Cr multilayer coatings with respect to protection against oxidation under accident conditions.
• the following platelets are subjected to the oxidation and measurement protocol, successively, according to Example 2 (nominal conditions) and then according to Example 3 (accident conditions):
• a Zircaloy-4 wafer with a Cr / Cr multilayer coating - a Zircaloy-4 plate with Cr / Nb-Cr-Ti multilayer coating (Reference M600).
• FIGS. 13 to 18 The micrographs obtained by polished section optical microscopy are reproduced in FIGS. 13 to 18. They show that the presence of a pre-oxide layer (Z rO 2 or (3 ⁇ 4O 3 ) formed in nominal conditions on the surface of the platelets has little influence on subsequent oxidation under accident conditions.
• a ZrO 2 layer is formed under nominal conditions on the uncoated Zircaloy-4 wafer surface ( Figure 13). This oxide layer then thickens significantly under accident conditions and is accompanied by the formation of an underlying layer of Zr- (O) with a thickness of 62 ⁇ m ( Figure 14). This behavior is similar to that of accidental oxidation alone.
• a Cr 2 O 3 layer is formed at the surface in nominal conditions (not shown). Under accident conditions (FIG. 15), the Cr 2 0 3 layer thickens (dark gray layer of 1.5 ⁇ m), the unoxidized Cr layer remains (white layer of 2 ⁇ m) but is no longer protective. which leads to the oxidation of the substrate in the form of a layer of Z r0 2 of about twenty microns and Zr- (o) of about sixty microns.
• a layer of Cr2O 3 forms at the surface under nominal conditions ( Figure 16). At the right of a crack in the coating (rare defect), islets of Zr0 2 can be formed, of comparable thickness to the uncoated material. Under accidental conditions, the layer of (3 ⁇ 40> 3 then thickens while continuing advantageously to play a protective sacrificial role, since the underlying multilayer Cr / Cr coating preserves a significant thickness (FIG.
• Table 5 indicates for the various platelets the equivalent thicknesses of oxidized Zircaloy-4 under accident conditions without (example 3) or with prior oxidation under nominal conditions (example 4).
• the residual ductility of a nuclear fuel cladding subjected to accidental conditions, even during and after quenching following the accident, is essentially ensured by the thickness of the residual layer of Zr-ex- ⁇ , provided that the oxygen content this layer remains below the limiting content of 0.4% by weight at 20 ° C.
• specimens of dimension 25 mm to 45 mm X 3 mm x 1 mm in uncoated Zircaloy-4 and with multilayer coatings Cr / Nb-Cr-Ti (reference M600) and Cr / Cr are removed. in platelets having undergone oxidation under accident conditions according to Example 3. Their mechanical strength is then tested in three-point bending at room temperature.
• Zircaloy-4 test specimens with multilayer coatings have a non-breaking deformation at least as important, while avoiding brittle phase flaking phenomena on the surface.
• the Zircaloy-4 test specimen with a Cr / Cr multilayer coating has, in particular, a significantly improved mechanical strength, since it has an arrow from 5 mm to 6 mm for a stress of up to 42 MPa at 47 MPa.
• the platelets with Zircaloy-4 substrate without coating and with Cr / Cr multilayer coating were oxidized at 1000 ° C. for 15000 seconds.
• the temperature of 1000 ° C is in a range which leads to instability of the ZrO 2 layer which can be surface formed.
• FIGS. 20 and 21 The evolution over time of the weighting of the wafers is illustrated by FIGS. 20 and 21, as well as by Table 6 to which the graph of FIG. 22 corresponds.
• Figure 20 ZrO 2 outer layer, Zr- (O) layer, Zircaloy-4 substrate;
• platelet surface plates show that only the surface of the uncoated wafer exhibits strong desquamation due to the low mechanical strength of ZrO 2. Cr / Cr multilayer does not exhibit any detachment.
• the platelets are brought to 600 ° C in order to dissolve all the hydrides formed therein.
• the hydrogen content is then measured by integration of the hydrothermal precipitation exothermic peak after cooling.
• the measured hydrogen content shows the gain provided by the material with Cr / Cr multilayer coating for resistance to hydriding during oxidation under accident conditions.
• -Cr-Ti has the following advantages:
• the multilayer material of the invention also has the advantages that it has a low impact on:

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