Plated metal substrate and method for manufacturing the same

Abstract

A plated metal substrate and method of manufacture are provided. The method includes depositing a first layer on at least a portion of the metal substrate using physical vapor deposition to create a coated substrate. The method includes electroplating a second layer comprising chromium, a chromium alloy, or a combination thereof on at least a portion of the first layer to create the plated substrate.

Description

Background Art

[0001] Cross - reference to Related Applications This application claims the benefit of U.S. Provisional Application No. 63 / 016,174, filed Apr. 27, 2020, the contents of which are hereby incorporated by reference in their entirety.

[0002] Government Support This invention was made with government support under Contract No. DE - NE0008824 awarded by the U.S. Department of Energy. The government has certain rights in this invention.

[0003] For example, a light water reactor (LWR) such as a pressurized water reactor (PWR) may include nuclear fuel rods suitable for holding nuclear fuel. The nuclear fuel may include uranium, uranium alloy, plutonium, plutonium alloy, thorium, thorium alloy, or combinations thereof. Some of the nuclear fuel rods include zirconium or zirconium alloy, such as ZIRLO (registered trademark) provided by Westinghouse Electric Company, Cranberry Township, Pennsylvania. The nuclear fuel rods may be subjected to various corrosion processes during operation in a PWR, such as water - side corrosion and hydrogen pickup. There are challenges in enhancing the manufacturability and corrosion performance of nuclear fuel rods containing zirconium or zirconium alloy.

Summary of the Invention

[0004] The present disclosure provides a method for processing a metal substrate. The method includes depositing a first layer on at least a portion of the metal substrate using physical vapor deposition to create a coated substrate, the first layer being configured to be electroplated. The method includes electroplating a second layer including chromium, chromium alloy, or combinations thereof on at least a portion of the first layer to create a plated substrate.

[0005] The disclosure also provides a plated nuclear fuel rod comprising a substrate, a first layer, and a second layer. The substrate comprises zirconium or a zirconium alloy. The first layer is deposited on the substrate by physical vapor deposition. The thickness of the first layer is in the range of 0.1 microns to 5 microns. The second layer is deposited by electroplating. The second layer comprises chromium, a chromium alloy, or a combination thereof. The thickness of the second layer is in the range of 0.1 microns to 50 microns.

[0006] It should be understood that the present invention as described herein is not limited to the embodiments summarized in this summary. Various other embodiments are described and illustrated herein. [Brief explanation of the drawing]

[0007] The features and advantages of the embodiments, as well as the methods for achieving them, will become clearer, and the embodiments will be better understood by referring to the following description of the embodiments used in conjunction with the accompanying drawings.

[0008] [Figure 1] This is a schematic diagram illustrating an example of a method for processing nuclear fuel rods made of zirconium or a zirconium alloy according to the present disclosure. [Figure 2] This is a schematic diagram illustrating an example of a plated portion of a nuclear fuel rod as described in this disclosure.

[0009] Corresponding reference letters indicate the corresponding parts throughout several figures. The examples described herein illustrate specific embodiments in one form, and such examples should not be construed as limiting the scope of the embodiments in any way. [Modes for carrying out the invention]

[0010] Herein, specific exemplary embodiments of the present disclosure are described to provide an overall understanding of the composition, function, manufacture, and use principles of the compositions, articles, and methods disclosed herein. Examples of these embodiments are illustrated in the accompanying drawings. Those skilled in the art will understand that the compositions, articles, and methods specifically described herein and illustrated in the accompanying drawings are non-limiting exemplary embodiments, and that the scope of the various embodiments of the invention is defined solely by the claims. Features described or described in relation to one exemplary embodiment may be combined with features of other embodiments. Such modifications and variations are intended to fall within the scope of the invention.

[0011] Throughout this specification, references to “various embodiments,” “several embodiments,” “one embodiment,” and “one embodiment” mean that a particular feature, structure, or characteristic described in relation to that embodiment is included in that embodiment. Therefore, expressions such as “various embodiments,” “several embodiments,” “one embodiment,” and “one embodiment” appearing throughout this specification do not necessarily all refer to the same embodiment. Furthermore, certain features, structures, or characteristics may be combined in any preferred manner in an embodiment. Thus, certain features, structures, or characteristics described or mentioned in relation to one embodiment may be combined, in whole or in part, with features, structures, or characteristics of another embodiment or other embodiment, without limitation. Such modifications and variations are intended to be included within the scope of this embodiment.

[0012] As used herein, particularly in relation to coating layers or films, the terms “on,” “onto,” “over,” and variations thereof (e.g., “applied on,” “formed on,” “deposited on,” “provided on,” “located on,” “electroplated on,” etc.) mean applied on, formed on, deposited on, provided on, or otherwise located on the surface of a substrate, but not necessarily in contact with the surface of the substrate. For example, a coating layer “applied on” a substrate does not exclude the presence of another coating layer or other coating layer of the same or different composition located between the applied coating layer and the substrate. Similarly, a second coating layer “applied on” a first coating layer does not exclude the presence of another coating layer or other coating layer of the same or different composition located between the applied second coating layer and the applied first coating layer.

[0013] As used herein, “intermediate” means that the referenced element is located between two elements, but does not necessarily have to be in contact with them. Therefore, unless otherwise stated herein, an element “intermediate” between the first and second elements may or may not be adjacent to or in contact with the first and / or second elements, and other elements may be located between the intermediate element and the first and / or second elements.

[0014] For example, LWRs such as PWRs are equipped with fuel rods to support the nuclear fuel in the reactor. Typically, fuel rods have a tubular shape and, in various embodiments, have a length of 4 meters, an outer diameter of 1 centimeter (cm), and a wall thickness of 0.6 millimeters (mm). Fuel rods may contain zirconium or a zirconium alloy. Fuel rods can act as a barrier to the release of fission products from the nuclear fuel into the primary circuit of a PWR. Therefore, it may be desirable to enhance the corrosion resistance of the fuel rods in order to maintain a desirable barrier to the release of fission products from the nuclear fuel and to enhance the high-temperature performance of the fuel rods.

[0015] The inventors of this disclosure have found that thin layers (e.g., 5 microns or less) of chromium or chromium alloys applied by cold spraying may present a challenge. Furthermore, the inventors have found that physical vapor deposition has an undesirable deposition rate (e.g., 1 micron per hour), which can prevent the formation of thicker layers by physical vapor deposition. Furthermore, the inventors of this disclosure have determined that faster deposition rates (e.g., 12-15 microns per hour) can be achieved by electroplating chromium or chromium alloys. However, the inventors have also determined that zirconium or zirconium alloy fuel rods cannot be directly electroplated with chromium, typically due to the presence of zirconium oxide present on the surface of the zirconium or zirconium alloy fuel rod. For example, chemical baths used to electroplat chromium typically cannot adequately remove zirconium oxide (if present) so that chromium or chromium alloys can be properly electroplated onto the surface of the zirconium or zirconium alloy fuel rod.

[0016] Accordingly, the present disclosure provides a method for processing a zirconium or zirconium alloy nuclear fuel rod, to which chromium or a chromium alloy of a desired layer thickness can be applied to prevent corrosion at a desired deposition rate. Furthermore, the present disclosure provides a plated nuclear fuel rod that may be suitable for rapid manufacturing while enhancing corrosion resistance. The plated nuclear fuel rod according to the present disclosure may be accident-resistant and suitable for LWRs such as PWRs.

[0017] Furthermore, this disclosure may also be applicable to other metal substrates that cannot be directly electroplated with chromium. For example, this disclosure may be applicable to nuclear fuel rods, aerospace components, chemically processed components, or combinations thereof. Metal substrates may include zirconium, zirconium alloys, titanium, titanium alloys, hafnium, hafnium alloys, or combinations thereof. For clarity, the metal substrate will be described in relation to nuclear fuel rods containing zirconium or zirconium alloys, but it will be understood that nuclear fuel rods containing zirconium or zirconium alloys may include, be replaced by, or further include other types of metal substrates, such as aerospace components, chemically processed components, or other components.

[0018] Referring to Figure 1, a method for processing a nuclear fuel rod made of zirconium or a zirconium alloy is provided. As described, an optional intermediate layer may be deposited on the nuclear fuel rod prior to the first layer (102). The intermediate layer may be deposited by physical vapor deposition, which may include pre-deposit ion etching of the surface of the nuclear fuel rod. In various embodiments, at least a portion of the zirconium oxide on the surface of the nuclear fuel rod is removed by depositing the intermediate layer.

[0019] Subsequently, the first layer may be deposited on at least a portion of the nuclear fuel rod using physical vapor deposition to create a coated nuclear fuel rod (104). In embodiments where the first layer is applied directly to the nuclear fuel rod, it may be desirable that the physical vapor deposition of the first layer include pre-deposited ion etching of the surface or intermediate layer of the nuclear fuel rod. In various embodiments, depositing the first layer removes at least a portion of the zirconium oxide on the surface of the nuclear fuel rod. The first layer may be conductive and suitable for electroplating. For example, the first layer may enable subsequent electroplating processes that may not have been possible without the first layer.

[0020] Physical deposition can be carried out under at least an incomplete vacuum and may include sputtering or evaporation. For example, physical deposition may include vaporizing a solid raw material using high temperature or plasma, transporting the vaporized solid raw material to the surface of a nuclear fuel rod, and condensing the vaporized solid raw material into a desired layer (e.g., an intermediate layer, a first layer) on the nuclear fuel rod. In various embodiments, the solid raw material may include a desired composition to be deposited on the nuclear fuel rod. In embodiments where a first layer is deposited, the solid raw material may include chromium, chromium alloys, iron, iron alloys, tantalum, tantalum alloys, tungsten, tungsten alloys, molybdenum, molybdenum alloys, niobium, niobium alloys, or combinations thereof. In embodiments where a first layer is deposited, the solid raw material may include chromium, chromium alloys, iron, iron alloys, or combinations thereof. In embodiments where an intermediate layer is deposited, the solid raw material may include tantalum, tantalum alloys, tungsten, tungsten alloys, molybdenum, molybdenum alloys, niobium, niobium alloys, or combinations thereof. In various embodiments, physical deposition may include magnetron sputtering or pulsed magnetron sputtering.

[0021] A second layer can be electroplated on at least a portion of the first layer to form a plated nuclear fuel rod 106. For example, the second layer may be in direct contact with the first layer. The first layer may be suitable for receiving the electroplated second layer because any oxides (if any) formed by the physical deposition of the first layer can be removed at least partially through the electroplating process to achieve the desired bond between the first and second layers. The second layer may be a corrosion-resistant (e.g., oxidation-resistant) and / or wear-resistant layer suitable for use in PWRs. The second layer can be electroplated at a faster rate than the first layer, thereby enhancing the fabrication of the plated nuclear fuel rod and enabling the formation of a thicker layer of chromium or chromium alloy. For example, the second layer can be electroplated at a rate at least 10 times faster than the rate at which the first layer is deposited.

[0022] Electroplating may include optional initial cleaning of the nuclear fuel rod, optional pretreatment of the nuclear fuel rod such as etching, to remove dirt or other surface impurities, immersion of at least a portion of the nuclear fuel rod in a chemical bath, and formation of a potential between the nuclear fuel rod and the chemical bath. The chemical bath may include components of a chromium or chromium alloy system (e.g., chromium trioxide, chromium sulfate, chromium chloride) and an electrolyte (e.g., sulfuric acid). The temperature of the chemical bath may be controlled to achieve the desired properties of the second layer formed by electroplating.

[0023] The plated nuclear fuel rod may include a first layer, a second layer, and optionally an intermediate layer and / or other layers. In various embodiments, the first layer is deposited directly on the nuclear fuel rod and the second layer is electroplated directly on the first layer. In other embodiments, the intermediate layer is deposited directly on the nuclear fuel rod, the first layer is deposited directly on the intermediate layer, and the second layer is deposited directly on the first layer. In some embodiments, another layer is deposited between the nuclear fuel rod and the intermediate layer and / or between the intermediate layer and the first layer.

[0024] A portion of the plated nuclear fuel rod 200 according to the present disclosure is described in FIG. 2. As described, the plated nuclear fuel rod 200 includes a substrate 202, a first layer 204, a second layer 206, and an optional intermediate layer 208.

[0025] The substrate 202 may include zirconium or a zirconium alloy. For example, the substrate may include pure zirconium, Zircaloy - two (trademark), Zircaloy - four (trademark), ZIRLO (registered trademark), Optimized ZIRLO (trademark), or a combination thereof. For example, the substrate 202 may include a zirconium alloy composition, which includes 0.5% to 2.0% niobium, 0.7% to 1.5% tin, 0.07% to 0.14% iron, up to 0.03% carbon, up to 0.2% oxygen, and the balance zirconium and unavoidable impurities, based on the total weight of all zirconium alloys.

[0026] The base material 202 may have a tubular shape and may have a wall thickness t0 in the range of 0.4 mm to 0.7 mm, such as 0.5 mm to 0.6 mm. In various embodiments, the thickness t0 may be 0.57 mm. The outer diameter of the base material 202 may be in the range of 7 mm to 12 mm, such as 8 mm to 11 mm or 9 mm to 10 mm. In various embodiments, the outer diameter of the base material 202 may be 9.5 mm.

[0027] The first layer 204 may be deposited on the base material 202 by physical vapor deposition. In embodiments including the intermediate layer 208, the first layer 204 may be deposited on the intermediate layer 208. The first layer 204 may provide a surface suitable for electroplating. For example, the first layer 204 may be suitably bonded to the layer immediately below the first layer 204. In certain embodiments without the intermediate layer 208, the first layer 204 may be directly bonded to the zirconium or zirconium alloy portion of the base material 202 by physical vapor deposition such that, if present, zirconium oxide is minimized between the first layer 204 and the base material 202.

[0028] The first layer 204 may include a composition suitable for electroplating. For example, the first layer 204 may include chromium, a chromium alloy, iron, an iron alloy, or a combination thereof. In various embodiments, the first layer 204 may include chromium or a chromium alloy.

[0029] The first layer 204 may include a thickness t1 of at least 0.1 micron, such as at least 1 micron, at least 2 microns, at least 3 microns, or at least 4 microns. In various embodiments, the thickness t1 may be 5 microns or less, such as 4 microns or less, 3 microns or less, or 2 microns or less. For example, the thickness t1 may be within the range of 0.1 micron to 5 microns, such as 1 micron to 5 microns, 1 micron to 4 microns, 2 microns to 4 microns, 3 microns to 5 microns, or 3 microns to 4 microns. The thickness of the first layer 204 may be selected to achieve a surface suitable for electroplating.

[0030] The second layer 206 can be deposited by electroplating on the first layer 204. For example, the second layer 206 may be in direct contact with the first layer 204. The second layer 206 may be suitable for operation in a PWR. For example, the second layer 206 can enhance the corrosion resistance of the plated nuclear fuel rod 200. The second layer includes chromium, a chromium alloy, or a combination thereof. By utilizing physical vapor deposition to create the first layer 204 and subsequent electroplating of the second layer 206, the plated nuclear fuel rod 200 can have enhanced interlayer adhesion, enhanced properties of the layer composition, and increased thickness of the second layer 206. In various embodiments, the second layer 206 is the outermost layer of the plated nuclear fuel rod 200.

[0031] In some embodiments, when the first layer 204 contains chromium or a chromium alloy, physical vapor deposition can be used for the first layer 204 to enhance the mixing of the zirconium or zirconium alloy of the substrate 202 and the chromium or chromium alloy of the first layer 204 by ionic bombardment when the object to be physically deposited and the substrate 202 are biased in the opposite direction. In certain embodiments, the microstructure of the first layer 204 and the second layer 206 may differ due to different growth mechanisms. For example, the second layer 206 may have a higher density than the first layer 204. However, in some embodiments, the film energy during the deposition of the first layer 204 can be maintained at a high level by heating the substrate or by using higher energy processing that bombards the surface with ions during deposition. This can be difficult for zirconium or zirconium alloy substrates, as zirconium or zirconium alloy substrates typically have a heat-treated microstructure. In various embodiments, increasing the thickness of the first layer 204 can be difficult. This is because the stress accumulated within the first layer 204 by the physical vapor deposition method may cause the first layer 204 to crack or delaminate. In various embodiments, the second layer 206 has an improved granular structure compared to the first layer 204. This is because the physical vapor deposition method can result in a columnar granular structure that may not be useful for corrosion protection.

[0032] The second layer 206 may have a thickness t2 of at least 0.1 microns, such as at least 5 microns, at least 10 microns, at least 15 microns, at least 20 microns, at least 25 microns, or at least 30 microns. In various embodiments, the thickness t2 may be 50 microns or less, such as 40 microns or less, 30 microns or less, 25 microns or less, 20 microns or less, 15 microns or less, or 10 microns or less. For example, the thickness t2 may be in the range of 0.1 microns to 50 microns, such as 5 microns to 50 microns, 5 microns to 40 microns, 10 microns to 50 microns, or 15 microns to 50 microns.

[0033] The intermediate layer 208 can be deposited on the substrate 202 by physical vapor deposition. For example, the intermediate layer 208 may be in direct contact with the substrate 202. The intermediate layer 208 may include tantalum, tantalum alloys, tungsten, tungsten alloys, molybdenum, molybdenum alloys, niobium, niobium alloys, or combinations thereof. In certain embodiments, the intermediate layer 208 may include tantalum, tantalum alloys, tungsten, tungsten alloys, niobium, niobium alloys, or combinations thereof. For example, the intermediate layer 208 may include niobium or a niobium alloy. The intermediate layer 208 can minimize or prevent the formation of eutectic alloys from the substrate 202 and the first layer 204. For example, the intermediate layer 208 may be configured to minimize or prevent the formation of eutectic alloys containing zirconium and chromium. The intermediate layer 208 can suppress oxidation of the substrate 202 and enable higher operating temperatures for the plated nuclear fuel rod 200. For example, a plated nuclear fuel rod 200 can operate at temperatures exceeding 900 degrees Celsius inside a PWR.

[0034] The intermediate layer 208 may include a thickness t3 of at least 0.01 microns, such as at least 1 micron, at least 2 microns, at least 3 microns, at least 4 microns, or at least 5 microns. The thickness t3 may be 10 microns or less, such as 9 microns or less, 7 microns or less, 6 microns or less, 5 microns or less, 4 microns or less, or 3 microns or less. For example, the thickness t3 may be in the range of 0.01 microns to 10 microns, such as 1 micron to 10 microns, 3 microns to 7 microns, or 4 microns to 6 microns. The thickness t3 may be selected to achieve desired resistance to eutectic alloy formation between the substrate 202 and the first layer 204.

[0035] The plated nuclear fuel rod 200 may comprise a substrate 202, a first layer 204, a second layer 206, and optionally, an intermediate layer 208 and / or other layers. In various embodiments, the first layer 204 is deposited directly on the substrate 202, and the second layer 206 is electroplated directly onto the first layer 204. In other embodiments, as shown in Figure 2, the intermediate layer 208 is deposited directly on the substrate 202, the first layer 204 is deposited directly on the intermediate layer 208, and the second layer 206 is deposited directly on the first layer 204. In some embodiments, another layer (not shown) is deposited between the substrate 202 and the intermediate layer 208, and / or between the intermediate layer 208 and the first layer 204.

[0036] Various aspects of the present invention as described herein include, but are not limited to, those listed in the following numbered clauses.

[0037] 1. A method for processing a metal substrate, A method of depositing a first layer onto at least a portion of a metal substrate using physical vapor deposition to create a coated substrate, wherein the first layer is configured to be electroplated. A method comprising electroplating a second layer containing chromium, a chromium alloy, or a combination thereof onto at least a portion of a first layer to create a plated substrate.

[0038] 2. The method according to Clause 1, wherein the physical deposition includes ion etching.

[0039] 3. The method according to Clause 1 or 2, wherein the first layer includes chromium, chromium alloys, iron, iron alloys, tantalum, tantalum alloys, tungsten, tungsten alloys, molybdenum, molybdenum alloys, niobium, niobium alloys, or a combination thereof.

[0040] 4. The method according to any one of the clauses 1 to 3, wherein the first layer has a thickness in the range of 0.1 microns to 5 microns.

[0041] 5. Further comprising depositing an intermediate layer on a metal substrate prior to the first layer, The method according to any one of the clauses 1 to 4, wherein the intermediate layer includes tantalum, tantalum alloy, tungsten, tungsten alloy, molybdenum, molybdenum alloy, niobium, niobium alloy, or a combination thereof.

[0042] 6. The method according to Clause 5, wherein the intermediate layer has a thickness in the range of 0.01 microns to 10 microns.

[0043] 7. The metal substrate includes a nuclear fuel rod made of zirconium or a zirconium alloy. The method according to clause 5 or 6, wherein depositing an intermediate layer removes at least a portion of the zirconium oxide on the surface of the nuclear fuel rod.

[0044] 8. The metal substrate includes a nuclear fuel rod made of zirconium or a zirconium alloy. The method according to any one of claims 1 to 4, wherein depositing a first layer removes at least a portion of the zirconium oxide on the surface of the nuclear fuel rod.

[0045] 9. The method according to any one of the clauses 1 to 8, wherein the second layer includes a thickness in the range of 0.1 microns to 50 microns.

[0046] 10. The first layer has a thickness in the range of 3 microns to 5 microns. The method according to any one of the clauses 1 to 9, wherein the second layer has a thickness of more than 15 microns.

[0047] 11. The metal substrate includes an atomic fuel rod. The nuclear fuel rod contains a zirconium alloy composition, The zirconium alloy composition is based entirely on the total weight of the zirconium alloy. 0.5% to 2.0% niobium, 0.7% to 1.5% tin, 0.07% to 0.14% iron, With a maximum of 0.03% carbon, With a maximum of 0.2% oxygen, The method according to any one of the clauses 1 to 10, comprising the remainder being zirconium and unavoidable impurities.

[0048] 12. The method according to any one of the clauses 1 to 11, wherein the plated substrate is suitable for use in a pressurized water reactor.

[0049] 13. The method according to any one of the clauses 1 to 12, wherein the second layer is electroplated at a rate at least 10 times faster than the rate at which the first layer is deposited.

[0050] 14. A plated nuclear fuel rod, A substrate containing zirconium or a zirconium alloy, A first layer deposited on a substrate by physical vapor deposition, wherein the thickness of the first layer is in the range of 0.1 microns to 5 microns, A plated nuclear fuel rod comprising a second layer deposited by electroplating, wherein the second layer contains chromium, a chromium alloy, or a combination thereof, and the thickness of the second layer is in the range of 0.1 microns to 50 microns.

[0051] 15. A plated nuclear fuel rod as described in Clause 14, wherein the first layer comprises chromium, a chromium alloy, iron, an iron alloy, or a combination thereof.

[0052] 16. Further comprising an intermediate layer located between the substrate and the first layer, A plated nuclear fuel rod as described in Clause 14 or 15, wherein the intermediate layer comprises tantalum, tantalum alloy, tungsten, tungsten alloy, molybdenum, molybdenum alloy, niobium, niobium alloy, or a combination thereof.

[0053] 17. A plated nuclear fuel rod as described in Clause 16, wherein the intermediate layer has a thickness in the range of 0.01 microns to 10 microns.

[0054] 18. The first layer has a thickness in the range of 3 microns to 5 microns. A plated nuclear fuel rod according to any one of clauses 14 to 17, wherein the second layer has a thickness of more than 15 microns.

[0055] 19. The base material contains a zirconium alloy composition, The zirconium alloy composition is based entirely on the total weight of the zirconium alloy. 0.5% to 2.0% niobium, 0.7% to 1.5% tin, 0.07% to 0.14% iron, With a maximum of 0.3% carbon, With a maximum of 0.2% oxygen, A plated nuclear fuel rod according to any one of clauses 14 to 18, comprising the remainder zirconium and unavoidable impurities.

[0056] 20. Plated nuclear fuel rods as described in any one of Clauses 14 to 19, which are suitable for use in a pressurized water reactor.

[0057] Those skilled in the art will recognize that the compositions, articles, methods, and accompanying considerations described herein are intended as illustrative examples to clarify concepts, and that various configuration modifications are contemplated. Therefore, when used herein, the specific examples and accompanying considerations described are intended to represent a more general class of such examples. In general, the use of any particular example is intended to represent a class, and the absence of specific components (e.g., operations), devices, and objects should not be considered limiting.

[0058] To provide an understanding of the compositions, structures, manufactures, functions, and / or operations of the present invention, including the disclosed compositions, coatings, and methods, various features and properties are described herein. It is understood that the various features and properties of the present invention described herein may be combined in any preferred manner, whether such features and properties are expressly described herein in combination. The inventors and applicants expressly intend that such combinations of features and properties fall within the scope of the present invention as described herein. Thus, the claims may be amended to enumerate any combination of any features and properties that are expressly or inherently described herein, or otherwise expressly or inherently supported. Furthermore, the applicants reserve the right to amend the claims to positively waive any features and properties that may exist in the prior art, even if such features and properties are not expressly described herein. Accordingly, any such amendment shall not add any new matter to this specification or the claims and shall be subject to the requirements of description, sufficiency of description, and additions.

[0059] With respect to the attached claims, those skilled in the art will understand that the operations listed therein can generally be performed in any order. Furthermore, although various operation flowcharts are presented in sequence, it should be understood that various operations can be performed in other orders than those illustrated, or simultaneously. Examples of such alternative orderings include, unless otherwise indicated by the context, overlap, alternating, interruption, reordering, incremental, substituting, supplementing, simultaneous, reverse, or various other orderings. Moreover, unless otherwise indicated by the context, terms such as “responding to,” “related to,” or other past tense adjectives are generally not intended to exclude such variations.

[0060] The present invention as described herein may include, consist of, or essentially consist of, various features and properties described herein. The terms “comprise” (and any form of “comprise,” such as “comprises” and “comprising”), “have” (and any form of “have,” such as “has” and “having”), “include” (and any form of “include,” such as “includes” and “including”), and “contain” (and any form of “contains” and “containing”) are open-ended linking verbs. Thus, a composition, nuclear fuel rod, or method that “comprises,” “have,” “include,” or “contains” features and / or properties may have, but is not limited to having only, these features and / or properties. Similarly, elements, coatings, or processes of a composition that “comprise,” “have,” “include,” or “contain” features and / or properties will have, but will not be limited to having only, these features and / or properties, and may have additional features and / or properties.

[0061] Where used herein, including in the claims, grammatical articles such as “a,” “an,” and “the” are intended to include “at least one” or “one or more,” unless otherwise stated. Thus, articles are used herein to refer to one or more of the grammatical objects of the article (i.e., “at least one”). For example, “a component” means one or more components, and therefore, in some cases, two or more components may be conceived and used in the implementation examples of compositions, coatings, and processes described. Nevertheless, if the terms “at least one” or “one or more” are used in some cases and not in others, it is understood that the absence of these terms does not imply that the objects of the grammatical articles “a,” “an,” and “the” are limited to only one. Furthermore, unless otherwise required in the context in which they are used, the use of singular nouns includes the plural form, and the use of plural nouns includes the singular form.

[0062] In this specification, unless otherwise stated, all numerical parameters should be understood in all cases to be prefaced and modified by the term “approximately,” which implies that the numerical parameter has inherent variability characteristics of the underlying measurement technique used to determine the numerical value of the parameter. At least, not as an attempt to limit the application of the doctrine of equivalents to the claims, each numerical parameter described herein should be interpreted at least in light of the reported number of significant figures and by applying ordinary rounding techniques.

[0063] Any numerical range enumerated herein includes all subranges contained within the enumerated range. For example, the range "1 to 10" includes all subranges (including boundary values) between the enumerated minimum value of 1 and the enumerated maximum value of 10, i.e., all subranges where the minimum value is 1 or greater and the maximum value is 10 or less. Furthermore, all ranges enumerated herein include the endpoints of the enumerated range. For example, the range "1 to 10" includes endpoints 1 and 10. Any maximum numerical limit enumerated herein is intended to include all lower numerical limits contained within the range, and any minimum numerical limit enumerated herein is intended to include all higher numerical limits contained within the range. Accordingly, the applicant reserves the right to amend this specification, including the claims, to explicitly enumerate any subranges contained within the explicitly enumerated range. All such ranges are originally described herein.

[0064] Any patent, publication, or other document identified herein is incorporated herein by reference in its entirety unless otherwise stated, but only to the extent that the incorporated material does not contradict existing descriptions, definitions, statements, examples, or other disclosures expressly provided herein. Therefore, to the extent necessary, disclosures expressly provided herein take precedence over any contradictory material incorporated by reference. Any material or portion thereof incorporated herein by reference that contradicts existing definitions, statements, or other disclosures provided herein is incorporated only to the extent that the incorporated material does not contradict existing disclosures. The applicant reserves the right to amend this specification to expressly enumerate any subject matter or portion thereof incorporated by reference. Any amendment to this specification to add such incorporated subject matter shall be subject to the requirements of description, sufficiency of description, and additions.

[0065] While specific embodiments of the present invention have been described above for illustrative purposes, it will be apparent to those skilled in the art that numerous modifications of the details of the present invention can be made without departing from the present invention as defined in the appended claims.

Claims

1. A method for processing a metal substrate containing zirconium or a zirconium alloy, A layer containing tantalum, tantalum alloy, tungsten, tungsten alloy, molybdenum, molybdenum alloy, niobium, niobium alloy, or a combination thereof is deposited on the metal substrate so as to be in contact with the entire first surface of the metal substrate. A first layer comprising chromium, chromium alloy, iron, iron alloy, tantalum, tantalum alloy, tungsten, tungsten alloy, molybdenum, molybdenum alloy, niobium, niobium alloy, or a combination thereof is deposited on at least a portion of the intermediate layer using physical vapor deposition to create a coated substrate, The method includes electroplating a second layer containing chromium or a chromium alloy onto at least a portion of the first layer to create a plated substrate, A method in which different materials are used for the intermediate layer and the first layer.

2. The method according to claim 1, wherein the physical deposition includes ion etching.

3. The method according to claim 1, wherein the first layer has a thickness in the range of 0.1 microns to 5 microns.

4. The method according to claim 1, wherein the intermediate layer has a thickness in the range of 0.01 microns to 10 microns.

5. The aforementioned metal substrate includes a nuclear fuel rod made of zirconium or a zirconium alloy. The method according to claim 1, wherein depositing the intermediate layer removes at least a portion of the zirconium oxide on the surface of the nuclear fuel rod.

6. The aforementioned metal substrate includes a nuclear fuel rod made of zirconium or a zirconium alloy. The method according to claim 1, wherein depositing the first layer removes at least a portion of the zirconium oxide on the surface of the nuclear fuel rod.

7. The method according to claim 1, wherein the second layer has a thickness in the range of 0.1 microns to 50 microns.

8. The first layer has a thickness in the range of 3 microns to 5 microns, The method according to claim 1, wherein the second layer has a thickness of more than 15 microns.

9. The metal substrate includes an atomic fuel rod, The nuclear fuel rod comprises a zirconium alloy composition, The zirconium alloy composition is determined based on the total weight of the zirconium alloy. 0.5% to 2.0% niobium, 0.7% to 1.5% tin, 0.07% to 0.14% iron, Up to 0.03% carbon, With a maximum of 0.2% oxygen, The method according to claim 1, comprising the remainder zirconium and unavoidable impurities.

10. The method according to claim 1, wherein the plated substrate is suitable for use in a pressurized water reactor.

11. The method according to claim 1, wherein the second layer is electroplated at a rate at least 10 times faster than the rate at which the first layer is deposited.

12. A plated nuclear fuel rod, A substrate containing zirconium or a zirconium alloy, A first layer deposited on the substrate by physical vapor deposition, wherein the first layer contains chromium, chromium alloy, iron, iron alloy, tantalum, tantalum alloy, tungsten, tungsten alloy, molybdenum, molybdenum alloy, niobium, niobium alloy, or a combination thereof, and the thickness of the first layer is in the range of 0.1 microns to 5 microns. A second layer deposited on the first layer by electroplating, wherein the second layer contains chromium or a chromium alloy, and the thickness of the second layer is in the range of 0.1 microns to 50 microns. An intermediate layer located between the substrate and the first layer, wherein the intermediate layer includes tantalum, tantalum alloy, tungsten, tungsten alloy, molybdenum, molybdenum alloy, niobium, niobium alloy, or a combination thereof. Different materials are used for the intermediate layer and the first layer. A plated nuclear fuel rod in which the intermediate layer is in contact with the entire first surface of the substrate.

13. The plated nuclear fuel rod according to claim 12, wherein the intermediate layer has a thickness in the range of 0.01 microns to 10 microns.

14. The first layer has a thickness in the range of 3 microns to 5 microns, The plated nuclear fuel rod according to claim 12, wherein the second layer has a thickness of more than 15 microns.

15. The substrate comprises a zirconium alloy composition, The zirconium alloy composition is determined based on the total weight of the zirconium alloy. 0.5% to 2.0% niobium, 0.7% to 1.5% tin, 0.07% to 0.14% iron, Up to 0.3% carbon, With a maximum of 0.2% oxygen, A plated nuclear fuel rod according to claim 12, comprising the remainder zirconium and unavoidable impurities.

16. The plated nuclear fuel rod according to claim 12, wherein the nuclear fuel rod is suitable for use in a pressurized water reactor.

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