US20160307651A1 - Zirconium alloy having excellent corrosion resistance for nuclear fuel cladding tube and method of manufacturing the same - Google Patents
Zirconium alloy having excellent corrosion resistance for nuclear fuel cladding tube and method of manufacturing the same Download PDFInfo
- Publication number
- US20160307651A1 US20160307651A1 US15/097,341 US201615097341A US2016307651A1 US 20160307651 A1 US20160307651 A1 US 20160307651A1 US 201615097341 A US201615097341 A US 201615097341A US 2016307651 A1 US2016307651 A1 US 2016307651A1
- Authority
- US
- United States
- Prior art keywords
- rolled
- cold
- nuclear fuel
- reduction ratio
- zirconium alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/005—Castings of light metals with high melting point, e.g. Be 1280 degrees C, Ti 1725 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/186—High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon
-
- 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
- G21C21/10—Manufacture of fuel elements or breeder elements contained in non-active casings by extrusion, drawing, or stretching by rolling, e.g. "picture frame" technique
-
- G21Y2002/103—
-
- G21Y2004/10—
-
- 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 invention relates to a zirconium alloy for a nuclear fuel cladding tube and a method of manufacturing the same and, more particularly, to a zirconium alloy having excellent corrosion resistance, suitable for use in nuclear fuel cladding tubes and spacer grids for light and heavy water reactor nuclear power plants, and to a method of manufacturing the same.
- zirconium having a low neutron absorption cross-section and superior corrosion resistance and mechanical properties, is provided in the form of an alloy containing small amounts of other elements, and is thus widely utilized as a material for nuclear fuel cladding tubes, supporting grids and structures in reactors.
- U.S. Pat. No. 5,024,809 discloses a zirconium alloy having improved corrosion resistance, composed essentially of 0.5 to 2.0 wt % of Sn and 0.5 to 2.5 wt % of Bi, and including Mo, Nb, and Te, the sum of which is set to the range of 0.5 to 1.0 wt %, with the balance of Zr.
- This alloy is designed as an inner zircaloy protection layer while being metallurgically bonded to an inner barrier layer of pure zirconium clad on a zirconium tube, and has a thickness corresponding to about 1 to 30% of that of the inner tube.
- U.S. Pat. No. 5,017,336 discloses a zirconium alloy having improved corrosion resistance and mechanical properties, composed essentially of 0.2 to 0.9 wt % of Sn, 0.18 to 0.6 wt % of Fe, and 0.07 to 0.4 wt % of Cr, and including 0.05 to 1.0 wt % of Nb or 0.01 to 0.2 wt % of Ta, and 0.05 to 1.0 wt % of either or both of V and Mo, with the balance of Zr, wherein the amount of Sn is decreased, the amounts of Fe and Cr are increased, and the other alloy elements are added in small amounts.
- U.S. Pat. No. 6,261,516 discloses a method of manufacturing a zirconium alloy from a mixture of Nb and Sn or from a mixture of Nb, Sn and Fe, wherein 0.8 to 1.2 wt % of Nb, 0.2 to 0.5 wt % of Sn, and 0.1 to 0.3 wt % of Fe are essentially contained, any one or more of Cr, Mo, Cu, and Mn is used in an amount of 0.1 to 0.3 wt %, and 80 to 120 ppm of Si, 600 to 1400 ppm of 0, and the balance of Zr are used, whereby the solute elements, other than the essential elements, are contained in an amount of 0.3 wt % or less, while the amount of Sn is reduced, thus improving corrosion resistance.
- This alloy was subjected to cold rolling two times at a reduction ratio of 45 to 50% at an interval of 0.5 mm for each pass, and final annealing was performed for 3 hr at 470° C., which is the stress relief annealing temperature.
- U.S. Pat. No. 5,972,288 discloses an alloy having superior corrosion resistance, composed essentially of 0.05 to 0.3 wt % of Nb, 0.8 to 1.6 wt % of Sn, and 0.2 to 0.4 wt % of Fe, and including 0.05 to 0.2 wt % of at least one of V, Te, Sb, Mo, Ta, and Cu, 600 to 1400 ppm of O, and the balance of Zr.
- This alloy was subjected to a series of processes, including annealing at 700° C., hot rolling at a reduction ratio of 70%, primary intermediate annealing at 700° C., primarily cold-rolled at a reduction ratio of 30%, secondary and tertiary annealing processes at 610° C., and two rolling processes.
- U.S. Pat. No. 6,325,966 discloses an alloy having superior corrosion resistance and mechanical properties, composed essentially of 0.15 to 0.25 wt % of Nb, 1.10 to 1.40 wt % of Sn, 0.35 to 0.45 wt % of Fe, and 0.15 to 0.25 wt % of Cr, and including 0.08 to 0.12 wt % of any one of Mo, Cu, and Mn, 1000 to 1400 ppm of O, and the balance of zirconium.
- This alloy was subjected to a series of processes, including annealing at 700° C., hot rolling at a reduction ratio of 60%, primarily cold-rolled at a reduction ratio of 30%, secondarily cold-rolled at a reduction ratio of 50%, primary intermediate annealing at 680° C., and secondary intermediate annealing at 580° C.
- Final annealing was performed at 505° C., which is the stress relief annealing temperature.
- zirconium alloys including Zircaloy-4, etc., suitable for use as a material for in-core instruments including nuclear fuel cladding tubes for nuclear power plants, have been devised.
- Patent Document 1 U.S. Pat. No. 5,024,809 (Registration Date: Jun. 18, 1991)
- Patent Document 2 U.S. Pat. No. 5,017,336 (Registration Date: May 21, 1991)
- Patent Document 3 U.S. Pat. No. 6,261,516 (Registration Date: Jul. 17, 2001)
- Patent Document 4 U.S. Pat. No. 5,972,288 (Registration Date: Oct. 26, 1999)
- Patent Document 5 U.S. Pat. No. 6,325,966 (Registration Date: Dec. 4, 2001)
- an object of the present invention is to provide a zirconium alloy having improved corrosion resistance for use in nuclear fuel cladding tubes and structural materials, and a method of manufacturing the same, wherein optimal annealing conditions are set by completely eliminating Sn, which negatively affects corrosion resistance, increasing the amount of Mo so that it is equal to or greater than a solubility limit.
- the present invention provides a zirconium alloy for a nuclear fuel cladding tube, comprising: 0.5 to 1.2 wt % of Nb, 0.4 to 0.8 wt % of Mo, 0.1 to 0.15 wt % of Cu, 0.15 to 0.2 wt % of Fe, and the balance of zirconium.
- the present invention provides a method of manufacturing a zirconium alloy for a nuclear fuel cladding tube, comprising the steps of:
- step (1) melting a mixture of zirconium alloy elements, thus preparing an ingot; (2) subjecting the ingot prepared in step (1) to solution heat treatment at 1,000 to 1,050° C. ( ⁇ ) for 30 to 40 min and then to ⁇ -quenching using water; (3) preheating the ingot treated in step (2) at 630 to 650° C. for 20 to 30 min and subjecting the ingot to hot rolling at a reduction ratio of 60 to 65%; (4) subjecting the material hot-rolled in step (3), to primary intermediate vacuum annealing at 570 to 590° C.
- step (6) subjecting the material primarily cold-rolled in step (4), to secondary intermediate vacuum annealing at 560 to 580° C. for 2 to 3 hr and then to secondarily cold-rolled at a reduction ratio of 50 to 60%; (6) subjecting the material secondarily cold-rolled in step (5), to tertiary intermediate vacuum annealing at 560 to 580° C. for 2 to 3 hr and then to tertiarily cold-rolled at a reduction ratio of 30 to 40%; and (7) subjecting the material tertiarily cold-rolled in step (6), to final vacuum annealing.
- a zirconium alloy for use in nuclear fuel cladding tubes and a method of manufacturing the same according to the present invention the kinds and amounts of alloy elements and the annealing temperatures are appropriately adjusted, whereby corrosion resistance superior to that of Zircaloy-4 can be exhibited, and furthermore, corrosion resistance even in a high-concentration Li atmosphere (70 ppm) is high.
- this zirconium alloy can be efficiently applied to cladding tubes and spacer grids for nuclear power plants.
- FIG. 1 illustrates the process of manufacturing a zirconium alloy for a nuclear fuel cladding tube according to the present invention
- FIGS. 2A and 2B are graphs illustrating the weight gain over time in corrosion testing of the zirconium alloy according to the present invention.
- the present invention addresses a zirconium alloy for a nuclear fuel cladding tube, comprising: 0.5 to 1.2 wt % of Nb, 0.4 to 0.8 wt % of Mo, 0.1 to 0.15 wt % of Cu, 0.15 to 0.2 wt % of Fe, and the balance of zirconium.
- the present invention addresses a zirconium alloy for a nuclear fuel cladding tube, comprising: 0.5 to 0.6 wt % of Nb, 0.4 to 0.5 wt % of Mo, 0.1 to 0.15 wt % of Cu, 0.15 to 0.2 wt % of Fe, and the balance of zirconium.
- the present invention addresses a zirconium alloy for a nuclear fuel cladding tube, comprising: 1.1 to 1.2 wt % of Nb, 0.4 to 0.5 wt % of Mo, 0.1 to 0.15 wt % of Cu, 0.15 to 0.2 wt % of Fe, and the balance of zirconium.
- the present invention addresses a zirconium alloy for a nuclear fuel cladding tube, comprising: 0.5 to 0.6 wt % of Nb, 0.7 to 0.8 wt % of Mo, 0.1 to 0.15 wt % of Cu, 0.15 to 0.2 wt % of Fe, and the balance of zirconium.
- the present invention addresses a method of manufacturing a zirconium alloy for a nuclear fuel cladding tube, comprising the steps of:
- step (1) melting a mixture of zirconium alloy elements, thus preparing an ingot; (2) subjecting the ingot prepared in step (1) to solution heat treatment at 1,000 to 1,050° C. ( ⁇ ) for 30 to 40 min and then to ⁇ -quenching using water; (3) preheating the ingot, annealed in step (2), at 630 to 650° C. for 20 to 30 min and subjecting the ingot to hot rolling at a reduction ratio of 60 to 65%; (4) subjecting the material hot-rolled in step (3), to primary intermediate vacuum annealing at 570 to 590° C.
- step (6) subjecting the material primarily cold-rolled in step (4), to secondary intermediate vacuum annealing at 560 to 580° C. for 2 to 3 hr and then to secondarily cold-rolled at a reduction ratio of 50 to 60%; (6) subjecting the material secondarily cold-rolled in step (5), to tertiary intermediate vacuum annealing at 560 to 580° C. for 2 to 3 hr and then to tertiarily cold-rolled at a reduction ratio of 30 to 40%; and (7) subjecting the material tertiarily cold-rolled in step (6), to final vacuum annealing.
- Zirconium alloys were prepared using components in the amounts and through the annealing shown in Table 1 below, and the alloys were manufactured into alloy sheets through the following method.
- step (1) zirconium alloy elements are formed into an ingot using VAR (Vacuum Arc Remelting).
- this process is repeated about three times, and the alloy is melted under the condition that the chamber for VAR is maintained at a vacuum level of 10 ⁇ 5 torr or less, thus forming an ingot.
- cooling is performed in the presence of an inert gas such as argon.
- the Zr that was used is zirconium sponge (Reactor Grade ASTM B349), and the added elements, such as Nb, Mo, Fe, Cu and the like, have a high purity of 99.99% or more.
- step (2) the ingot is annealed in the ⁇ -range and then quenched using water so that the alloy composition in the prepared ingot is made homogenous and fine precipitates are obtained.
- the ingot is clad with a stainless steel plate having a thickness of 1 mm and then spot welded.
- the annealing is performed at 1,000 to 1,050° C. for about 30 to 40 min.
- ⁇ -quenching is performed so as to uniformly distribute the size of SPP (Secondary Phase Particles) in the matrix and to control the size thereof, and is carried out through water cooling at a cooling rate of about 300 ° C./sec or more.
- step (3) the ⁇ -quenched sample is subjected to hot rolling.
- the sample is preheated at 630 to 650° C. for about 20 to 30 min, and then rolled at a reduction ratio of about 60 to 65%.
- the reduction ratio of hot rolling is less than 60%, the tissue of the zirconium material becomes non-uniform, undesirably deteriorating hydrogen brittleness resistance. On the other hand, if the reduction ratio is higher than 80%, subsequent processability may become problematic.
- the material hot-rolled, is treated as follows: the clad stainless steel plate is removed, an oxide film and impurities are removed using a pickling solution comprising water, nitric acid and hydrofluoric acid at a volume ratio of 50:40:10, and the remaining oxide film is completely mechanically removed using a wire brush in order to facilitate subsequent processing.
- primary vacuum annealing is performed at about 570 to 590° C. for about 3 to 4 hr.
- the sample is covered with a piece of stainless steel foil and the vacuum level is maintained at 10 ⁇ 5 torr or less.
- the intermediate vacuum annealing is preferably carried out at a temperature elevated to a recrystallization annealing temperature. If the temperature falls out of the above range, corrosion resistance may deteriorate.
- the rolled material After completion of the primary intermediate vacuum annealing, the rolled material is subjected to primarily cold-rolled at a reduction ratio of about 40 to 50% at an interval of about 0.3 mm for each pass.
- the rolled material After completion of the primarily cold-rolled, the rolled material is subjected to secondary intermediate vacuum annealing at 560 to 580° C. for about 2 to 3 hr.
- the rolled material After completion of the secondary intermediate vacuum annealing, the rolled material is subjected to secondarily cold-rolled at a reduction ratio of about 50 to 60% at an interval of about 0.3 mm for each pass.
- the rolled material After completion of the secondarily cold-rolled, the rolled material is subjected to tertiary intermediate vacuum annealing at 560 to 580° C. for 2 to 3 hr.
- the rolled material After completion of the tertiary intermediate vacuum annealing, the rolled material is subjected to tertiarily cold-rolled at a reduction ratio of about 30 to 40% at an interval of about 0.3 mm for each pass.
- the rolled material is finally annealed in a high vacuum of 10 ⁇ 5 torr or less.
- Final annealing is performed for about 8 hr in three temperature ranges, including SRA (Stress Relief Annealing) at 460 to 470° C., PRXA (Partial Recrystallization Annealing) at 510 to 520° C., and RXA (Recrystallization Annealing) at 580 to 590° C.
- SRA Stress Relief Annealing
- PRXA Partial Recrystallization Annealing
- RXA Recrystallization Annealing
- Zircaloy-4 As a commercially available zirconium alloy for use in nuclear power plants, Zircaloy-4 was used.
- Each of the zirconium alloys of Examples 1 to 9 was manufactured into a sheet sample through the above manufacturing process, which was then formed into a corrosion test sample having a size of 20 mm ⁇ 20 mm ⁇ 1.0 mm, followed by stepwise mechanical polishing using #400 to #1200 SiC abrasive paper.
- the sample was pickled using a solution comprising water, nitric acid and hydrofluoric acid at a volume ratio of 50:40:10, sonicated with acetone, and then completely dried in an oven for 24 hr or longer.
- the surface area and the initial weight of the alloy were measured before the alloy was loaded in an autoclave.
- the loaded sample was subjected to corrosion testing for 100 days using a static autoclave at 360° C. in an 18.6 MPa pure water atmosphere and a 70 ppm Li atmosphere.
- the samples were taken out a total of three times, i.e. 50 days, 75 days, and 100 days after the corrosion testing, and the weights thereof were measured, and the weight gains were calculated so as to quantitatively evaluate the extent of corrosion.
- the results are shown in Table 2 below.
- the zirconium alloys of Examples 1 to 9 according to the present invention were low in weight gain in both the water atmosphere and the 70 ppm Li atmosphere, compared to Zircaloy-4 of Comparative Example 1.
- Examples 1 to 9 manifested the weight gain ranging from 17 to 21 mg/dm 2 , and Comparative Example 1 exhibited a significant weight gain, as large as 46 mg/dm 2 . Hence, corrosion resistance was greatly improved when using the compositions of Examples 1 to 9 under the annealing conditions of Examples 1 to 9.
- Comparative Example 1 For corrosion properties in a Li atmosphere, the weight gain was greatly increased after 75 days in Comparative Example 1. After 100 days, the weight gain of Comparative Example 1 approximated 72 mg/dm 2 , which is regarded as significantly different from 26 to 51 mg/dm 2 , which was the weight gain of Examples 1 to 9 after 100 days.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- High Energy & Nuclear Physics (AREA)
- General Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Monitoring And Testing Of Nuclear Reactors (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
Description
- 1. Field of the Invention
- The present invention relates to a zirconium alloy for a nuclear fuel cladding tube and a method of manufacturing the same and, more particularly, to a zirconium alloy having excellent corrosion resistance, suitable for use in nuclear fuel cladding tubes and spacer grids for light and heavy water reactor nuclear power plants, and to a method of manufacturing the same.
- 2. Description of the Related Art
- Typically, zirconium, having a low neutron absorption cross-section and superior corrosion resistance and mechanical properties, is provided in the form of an alloy containing small amounts of other elements, and is thus widely utilized as a material for nuclear fuel cladding tubes, supporting grids and structures in reactors.
- With the goal of reducing nuclear fuel turnover in order to improve the economic efficiency of reactors, high-burnup nuclear fuel is receiving increased consideration these days. In the case where conventional Zircaloy-2 and Zircaloy-4 are used for nuclear fuel cladding tubes, corrosion may be accelerated, undesirably causing hydrogen brittleness and deteriorating mechanical properties.
- Hence, there is an urgent need to develop a zirconium alloy having high corrosion resistance, and thorough research thereon is ongoing.
- Since corrosion resistance and the mechanical properties of the zirconium alloy are highly variable depending on the kinds and amounts of alloy elements that are added and the type of manufacturing process, it is critical to optimize the elements for the alloy and the manufacturing process.
- With regard to conventional techniques, U.S. Pat. No. 5,024,809 discloses a zirconium alloy having improved corrosion resistance, composed essentially of 0.5 to 2.0 wt % of Sn and 0.5 to 2.5 wt % of Bi, and including Mo, Nb, and Te, the sum of which is set to the range of 0.5 to 1.0 wt %, with the balance of Zr.
- This alloy is designed as an inner zircaloy protection layer while being metallurgically bonded to an inner barrier layer of pure zirconium clad on a zirconium tube, and has a thickness corresponding to about 1 to 30% of that of the inner tube.
- U.S. Pat. No. 5,017,336 discloses a zirconium alloy having improved corrosion resistance and mechanical properties, composed essentially of 0.2 to 0.9 wt % of Sn, 0.18 to 0.6 wt % of Fe, and 0.07 to 0.4 wt % of Cr, and including 0.05 to 1.0 wt % of Nb or 0.01 to 0.2 wt % of Ta, and 0.05 to 1.0 wt % of either or both of V and Mo, with the balance of Zr, wherein the amount of Sn is decreased, the amounts of Fe and Cr are increased, and the other alloy elements are added in small amounts.
- U.S. Pat. No. 6,261,516 discloses a method of manufacturing a zirconium alloy from a mixture of Nb and Sn or from a mixture of Nb, Sn and Fe, wherein 0.8 to 1.2 wt % of Nb, 0.2 to 0.5 wt % of Sn, and 0.1 to 0.3 wt % of Fe are essentially contained, any one or more of Cr, Mo, Cu, and Mn is used in an amount of 0.1 to 0.3 wt %, and 80 to 120 ppm of Si, 600 to 1400 ppm of 0, and the balance of Zr are used, whereby the solute elements, other than the essential elements, are contained in an amount of 0.3 wt % or less, while the amount of Sn is reduced, thus improving corrosion resistance.
- This alloy was subjected to cold rolling two times at a reduction ratio of 45 to 50% at an interval of 0.5 mm for each pass, and final annealing was performed for 3 hr at 470° C., which is the stress relief annealing temperature.
- U.S. Pat. No. 5,972,288 discloses an alloy having superior corrosion resistance, composed essentially of 0.05 to 0.3 wt % of Nb, 0.8 to 1.6 wt % of Sn, and 0.2 to 0.4 wt % of Fe, and including 0.05 to 0.2 wt % of at least one of V, Te, Sb, Mo, Ta, and Cu, 600 to 1400 ppm of O, and the balance of Zr.
- This alloy was subjected to a series of processes, including annealing at 700° C., hot rolling at a reduction ratio of 70%, primary intermediate annealing at 700° C., primarily cold-rolled at a reduction ratio of 30%, secondary and tertiary annealing processes at 610° C., and two rolling processes.
- Final annealing was performed for 3 hr at 480° C., which is the stress relief annealing temperature.
- U.S. Pat. No. 6,325,966 discloses an alloy having superior corrosion resistance and mechanical properties, composed essentially of 0.15 to 0.25 wt % of Nb, 1.10 to 1.40 wt % of Sn, 0.35 to 0.45 wt % of Fe, and 0.15 to 0.25 wt % of Cr, and including 0.08 to 0.12 wt % of any one of Mo, Cu, and Mn, 1000 to 1400 ppm of O, and the balance of zirconium.
- This alloy was subjected to a series of processes, including annealing at 700° C., hot rolling at a reduction ratio of 60%, primarily cold-rolled at a reduction ratio of 30%, secondarily cold-rolled at a reduction ratio of 50%, primary intermediate annealing at 680° C., and secondary intermediate annealing at 580° C.
- Final annealing was performed at 505° C., which is the stress relief annealing temperature.
- As is apparent from these techniques, various zirconium alloys, including Zircaloy-4, etc., suitable for use as a material for in-core instruments including nuclear fuel cladding tubes for nuclear power plants, have been devised.
- However, nuclear power plants are currently used under severe operating conditions to improve the economic efficiency thereof, and thus limitations are imposed on the use of nuclear fuel cladding tubes made of Zircaloy-4, etc. Hence, research into zirconium alloys having improved corrosion resistance, which may ensure performance of nuclear fuel under operating conditions of high burn up/extended fuel cycles, is still ongoing.
- (Patent Document 1) U.S. Pat. No. 5,024,809 (Registration Date: Jun. 18, 1991)
- (Patent Document 2) U.S. Pat. No. 5,017,336 (Registration Date: May 21, 1991)
- (Patent Document 3) U.S. Pat. No. 6,261,516 (Registration Date: Jul. 17, 2001)
- (Patent Document 4) U.S. Pat. No. 5,972,288 (Registration Date: Oct. 26, 1999)
- (Patent Document 5) U.S. Pat. No. 6,325,966 (Registration Date: Dec. 4, 2001)
- Therefore, the present invention has been made keeping in mind the problems encountered in the related art, and an object of the present invention is to provide a zirconium alloy having improved corrosion resistance for use in nuclear fuel cladding tubes and structural materials, and a method of manufacturing the same, wherein optimal annealing conditions are set by completely eliminating Sn, which negatively affects corrosion resistance, increasing the amount of Mo so that it is equal to or greater than a solubility limit.
- In order to accomplish the above object, the present invention provides a zirconium alloy for a nuclear fuel cladding tube, comprising: 0.5 to 1.2 wt % of Nb, 0.4 to 0.8 wt % of Mo, 0.1 to 0.15 wt % of Cu, 0.15 to 0.2 wt % of Fe, and the balance of zirconium.
- In addition, the present invention provides a method of manufacturing a zirconium alloy for a nuclear fuel cladding tube, comprising the steps of:
- (1) melting a mixture of zirconium alloy elements, thus preparing an ingot; (2) subjecting the ingot prepared in step (1) to solution heat treatment at 1,000 to 1,050° C. (β) for 30 to 40 min and then to β-quenching using water; (3) preheating the ingot treated in step (2) at 630 to 650° C. for 20 to 30 min and subjecting the ingot to hot rolling at a reduction ratio of 60 to 65%; (4) subjecting the material hot-rolled in step (3), to primary intermediate vacuum annealing at 570 to 590° C. for 3 to 4 hr and then to primarily cold-rolled at a reduction ratio of 30 to 40%; (5) subjecting the material primarily cold-rolled in step (4), to secondary intermediate vacuum annealing at 560 to 580° C. for 2 to 3 hr and then to secondarily cold-rolled at a reduction ratio of 50 to 60%; (6) subjecting the material secondarily cold-rolled in step (5), to tertiary intermediate vacuum annealing at 560 to 580° C. for 2 to 3 hr and then to tertiarily cold-rolled at a reduction ratio of 30 to 40%; and (7) subjecting the material tertiarily cold-rolled in step (6), to final vacuum annealing.
- As described above, in a zirconium alloy for use in nuclear fuel cladding tubes and a method of manufacturing the same according to the present invention, the kinds and amounts of alloy elements and the annealing temperatures are appropriately adjusted, whereby corrosion resistance superior to that of Zircaloy-4 can be exhibited, and furthermore, corrosion resistance even in a high-concentration Li atmosphere (70 ppm) is high. Hence, this zirconium alloy can be efficiently applied to cladding tubes and spacer grids for nuclear power plants.
- The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
-
FIG. 1 illustrates the process of manufacturing a zirconium alloy for a nuclear fuel cladding tube according to the present invention; and -
FIGS. 2A and 2B are graphs illustrating the weight gain over time in corrosion testing of the zirconium alloy according to the present invention. - Hereinafter, a detailed description will be given of the present invention.
- The present invention addresses a zirconium alloy for a nuclear fuel cladding tube, comprising: 0.5 to 1.2 wt % of Nb, 0.4 to 0.8 wt % of Mo, 0.1 to 0.15 wt % of Cu, 0.15 to 0.2 wt % of Fe, and the balance of zirconium.
- Alternatively, the present invention addresses a zirconium alloy for a nuclear fuel cladding tube, comprising: 0.5 to 0.6 wt % of Nb, 0.4 to 0.5 wt % of Mo, 0.1 to 0.15 wt % of Cu, 0.15 to 0.2 wt % of Fe, and the balance of zirconium.
- Alternatively, the present invention addresses a zirconium alloy for a nuclear fuel cladding tube, comprising: 1.1 to 1.2 wt % of Nb, 0.4 to 0.5 wt % of Mo, 0.1 to 0.15 wt % of Cu, 0.15 to 0.2 wt % of Fe, and the balance of zirconium.
- Alternatively, the present invention addresses a zirconium alloy for a nuclear fuel cladding tube, comprising: 0.5 to 0.6 wt % of Nb, 0.7 to 0.8 wt % of Mo, 0.1 to 0.15 wt % of Cu, 0.15 to 0.2 wt % of Fe, and the balance of zirconium.
- The preparation of the zirconium alloy having the above composition according to the present invention is described below.
- The present invention addresses a method of manufacturing a zirconium alloy for a nuclear fuel cladding tube, comprising the steps of:
- (1) melting a mixture of zirconium alloy elements, thus preparing an ingot; (2) subjecting the ingot prepared in step (1) to solution heat treatment at 1,000 to 1,050° C. (β) for 30 to 40 min and then to β-quenching using water; (3) preheating the ingot, annealed in step (2), at 630 to 650° C. for 20 to 30 min and subjecting the ingot to hot rolling at a reduction ratio of 60 to 65%; (4) subjecting the material hot-rolled in step (3), to primary intermediate vacuum annealing at 570 to 590° C. for 3 to 4 hr and then to primarily cold-rolled at a reduction ratio of 30 to 40%; (5) subjecting the material primarily cold-rolled in step (4), to secondary intermediate vacuum annealing at 560 to 580° C. for 2 to 3 hr and then to secondarily cold-rolled at a reduction ratio of 50 to 60%; (6) subjecting the material secondarily cold-rolled in step (5), to tertiary intermediate vacuum annealing at 560 to 580° C. for 2 to 3 hr and then to tertiarily cold-rolled at a reduction ratio of 30 to 40%; and (7) subjecting the material tertiarily cold-rolled in step (6), to final vacuum annealing.
- A better understanding of the present invention may be obtained through the following examples.
- Zirconium alloys were prepared using components in the amounts and through the annealing shown in Table 1 below, and the alloys were manufactured into alloy sheets through the following method.
- The chemical compositions for the zirconium alloys and the final annealing temperatures are summarized in Table 1 below.
-
TABLE 1 Chemical Composition (wt %) Final Annealing Temp. Nb Sn Mo Fe Cu Cr Zr (° C.) Ex. 1 0.5 — 0.4 0.2 0.1 — Balance 460 Ex. 2 0.5 — 0.4 0.2 0.1 — Balance 520 Ex. 3 0.5 — 0.8 0.2 0.1 — Balance 580 Ex. 4 0.5 — 0.8 0.2 0.1 — Balance 460 Ex. 5 0.5 — 0.8 0.2 0.1 — Balance 520 Ex. 6 0.5 — 0.8 0.2 0.1 — Balance 580 Ex. 7 1.2 — 0.4 0.2 0.1 — Balance 460 Ex. 8 1.2 — 0.4 0.2 0.1 — Balance 520 Ex. 9 1.2 — 0.4 0.2 0.1 — Balance 580 C. Ex. 1 — 1.5 — 0.2 — 0.1 Balance Commercially available - (1) Formation of Ingot
- In step (1), zirconium alloy elements are formed into an ingot using VAR (Vacuum Arc Remelting).
- In order to prevent the segregation of impurities and the non-uniform distribution of the alloy composition, this process is repeated about three times, and the alloy is melted under the condition that the chamber for VAR is maintained at a vacuum level of 10−5 torr or less, thus forming an ingot.
- To prevent the surface of the sample from being oxidized during the cooling, cooling is performed in the presence of an inert gas such as argon.
- The Zr that was used is zirconium sponge (Reactor Grade ASTM B349), and the added elements, such as Nb, Mo, Fe, Cu and the like, have a high purity of 99.99% or more.
- (2) β-Solution Heat Treatment and β-Quenching
- In step (2), the ingot is annealed in the β-range and then quenched using water so that the alloy composition in the prepared ingot is made homogenous and fine precipitates are obtained.
- In order to prevent the oxidation of the ingot, the ingot is clad with a stainless steel plate having a thickness of 1 mm and then spot welded. The annealing is performed at 1,000 to 1,050° C. for about 30 to 40 min.
- Also, β-quenching is performed so as to uniformly distribute the size of SPP (Secondary Phase Particles) in the matrix and to control the size thereof, and is carried out through water cooling at a cooling rate of about 300 ° C./sec or more.
- (3) Annealing and Hot Rolling
- In step (3), the β-quenched sample is subjected to hot rolling.
- To this end, the sample is preheated at 630 to 650° C. for about 20 to 30 min, and then rolled at a reduction ratio of about 60 to 65%.
- If the processing temperature falls out of the above range, it is difficult to obtain the rolled material suitable for use in subsequent step (4).
- If the reduction ratio of hot rolling is less than 60%, the tissue of the zirconium material becomes non-uniform, undesirably deteriorating hydrogen brittleness resistance. On the other hand, if the reduction ratio is higher than 80%, subsequent processability may become problematic.
- The material hot-rolled, is treated as follows: the clad stainless steel plate is removed, an oxide film and impurities are removed using a pickling solution comprising water, nitric acid and hydrofluoric acid at a volume ratio of 50:40:10, and the remaining oxide film is completely mechanically removed using a wire brush in order to facilitate subsequent processing.
- (4) Primary Intermediate Annealing and Primary Cold Rolling
- In order to remove residual stress after hot rolling and prevent damage to the sample upon primary cold processing, primary vacuum annealing is performed at about 570 to 590° C. for about 3 to 4 hr.
- To prevent oxidation during the annealing, the sample is covered with a piece of stainless steel foil and the vacuum level is maintained at 10−5 torr or less.
- The intermediate vacuum annealing is preferably carried out at a temperature elevated to a recrystallization annealing temperature. If the temperature falls out of the above range, corrosion resistance may deteriorate.
- After completion of the primary intermediate vacuum annealing, the rolled material is subjected to primarily cold-rolled at a reduction ratio of about 40 to 50% at an interval of about 0.3 mm for each pass.
- (5) Secondary Intermediate Vacuum Annealing and Secondary Cold Rolling
- After completion of the primarily cold-rolled, the rolled material is subjected to secondary intermediate vacuum annealing at 560 to 580° C. for about 2 to 3 hr.
- If the intermediate annealing temperature falls out of the above range, corrosion resistance may deteriorate.
- After completion of the secondary intermediate vacuum annealing, the rolled material is subjected to secondarily cold-rolled at a reduction ratio of about 50 to 60% at an interval of about 0.3 mm for each pass.
- (6) Tertiary Intermediate Vacuum Annealing and Tertiary Cold Rolling
- After completion of the secondarily cold-rolled, the rolled material is subjected to tertiary intermediate vacuum annealing at 560 to 580° C. for 2 to 3 hr.
- If the intermediate annealing temperature falls out of the above range, corrosion resistance may deteriorate.
- After completion of the tertiary intermediate vacuum annealing, the rolled material is subjected to tertiarily cold-rolled at a reduction ratio of about 30 to 40% at an interval of about 0.3 mm for each pass.
- (7) Final Vacuum Annealing
- After completion of the tertiarily cold-rolled, the rolled material is finally annealed in a high vacuum of 10−5 torr or less.
- Final annealing is performed for about 8 hr in three temperature ranges, including SRA (Stress Relief Annealing) at 460 to 470° C., PRXA (Partial Recrystallization Annealing) at 510 to 520° C., and RXA (Recrystallization Annealing) at 580 to 590° C.
- As a commercially available zirconium alloy for use in nuclear power plants, Zircaloy-4 was used.
- In order to evaluate the corrosion resistance of the zirconium alloy composition according to the present invention, corrosion testing was performed as follows.
- Each of the zirconium alloys of Examples 1 to 9 was manufactured into a sheet sample through the above manufacturing process, which was then formed into a corrosion test sample having a size of 20 mm×20 mm×1.0 mm, followed by stepwise mechanical polishing using #400 to #1200 SiC abrasive paper.
- After completion of the surface polishing, the sample was pickled using a solution comprising water, nitric acid and hydrofluoric acid at a volume ratio of 50:40:10, sonicated with acetone, and then completely dried in an oven for 24 hr or longer.
- In order to determine the extent of corrosion of the alloy, the surface area and the initial weight of the alloy were measured before the alloy was loaded in an autoclave.
- The loaded sample was subjected to corrosion testing for 100 days using a static autoclave at 360° C. in an 18.6 MPa pure water atmosphere and a 70 ppm Li atmosphere.
- In the corrosion testing, the samples of Examples 1 to 9 and the Zircaloy-4 sample of Comparative Example 1 were placed in the autoclave together.
- The samples were taken out a total of three times, i.e. 50 days, 75 days, and 100 days after the corrosion testing, and the weights thereof were measured, and the weight gains were calculated so as to quantitatively evaluate the extent of corrosion. The results are shown in Table 2 below.
-
TABLE 2 Weight Gain (mg/dm2) 360° C., 2700 psi, Water 360° C., 2700 psi, 70 ppm Li 50 days 75 days 100 days 50 days 75 days 100 days Ex. 1 17.0171 17.3227 18.5474 25.3438 31.7743 41.9875 Ex. 2 15.0506 16.0417 17.5433 20.5044 22.7827 26.2001 Ex. 3 14.2910 14.8125 18.5156 20.4824 23.1375 31.8615 Ex. 4 14.7509 16.8371 18.1544 25.5202 39.0309 51.7910 Ex. 5 14.1838 15.9509 18.3740 24.6221 31.1623 31.5470 Ex. 6 12.7171 15.7901 16.9807 22.5986 26.1053 33.1187 Ex. 7 14.1545 18.1708 21.2821 23.0809 23.8376 27.2430 Ex. 8 15.5565 18.1167 20.1212 17.1323 22.0816 29.6960 Ex. 9 14.0958 18.4966 20.3069 25.3782 28.4544 31.1460 C. Ex. 1 26.3268 33.1276 46.0908 27.7393 54.3227 71.6597 - As is apparent from Table 2, the zirconium alloys of Examples 1 to 9 according to the present invention were low in weight gain in both the water atmosphere and the 70 ppm Li atmosphere, compared to Zircaloy-4 of Comparative Example 1.
- For corrosion properties in a pure water atmosphere after 100 days, Examples 1 to 9 manifested the weight gain ranging from 17 to 21 mg/dm2, and Comparative Example 1 exhibited a significant weight gain, as large as 46 mg/dm2. Hence, corrosion resistance was greatly improved when using the compositions of Examples 1 to 9 under the annealing conditions of Examples 1 to 9.
- For corrosion properties in a Li atmosphere, the weight gain was greatly increased after 75 days in Comparative Example 1. After 100 days, the weight gain of Comparative Example 1 approximated 72 mg/dm2, which is regarded as significantly different from 26 to 51 mg/dm2, which was the weight gain of Examples 1 to 9 after 100 days.
- Particularly in the Sn-free alloy containing Mo and Cu, corrosion resistance was high in both a pure water atmosphere and a high-concentration Li atmosphere under annealing conditions of 520° C. and 580° C.
- Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/677,904 US11195628B2 (en) | 2015-04-14 | 2019-11-08 | Method of manufacturing a corrosion-resistant zirconium alloy for a nuclear fuel cladding tube |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020150052710A KR101604103B1 (en) | 2015-04-14 | 2015-04-14 | The composition and fabrication method of corrosion resistance zirconium alloys for nuclear fuel rod and components |
KR10-2015-0052710 | 2015-04-14 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/677,904 Division US11195628B2 (en) | 2015-04-14 | 2019-11-08 | Method of manufacturing a corrosion-resistant zirconium alloy for a nuclear fuel cladding tube |
Publications (1)
Publication Number | Publication Date |
---|---|
US20160307651A1 true US20160307651A1 (en) | 2016-10-20 |
Family
ID=55645690
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/097,341 Abandoned US20160307651A1 (en) | 2015-04-14 | 2016-04-13 | Zirconium alloy having excellent corrosion resistance for nuclear fuel cladding tube and method of manufacturing the same |
US16/677,904 Active 2036-07-09 US11195628B2 (en) | 2015-04-14 | 2019-11-08 | Method of manufacturing a corrosion-resistant zirconium alloy for a nuclear fuel cladding tube |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/677,904 Active 2036-07-09 US11195628B2 (en) | 2015-04-14 | 2019-11-08 | Method of manufacturing a corrosion-resistant zirconium alloy for a nuclear fuel cladding tube |
Country Status (6)
Country | Link |
---|---|
US (2) | US20160307651A1 (en) |
EP (1) | EP3284837B1 (en) |
JP (1) | JP6734867B2 (en) |
KR (1) | KR101604103B1 (en) |
CN (1) | CN107429331B (en) |
WO (1) | WO2016167404A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021133194A1 (en) | 2019-12-26 | 2021-07-01 | Акционерное Общество "Твэл" | Method of manufacturing tubular products from a zirconium alloy |
WO2021133195A1 (en) | 2019-12-26 | 2021-07-01 | Акционерное Общество "Твэл" | Method of producing tubular products from a zirconium-based alloy |
WO2021133196A1 (en) | 2019-12-26 | 2021-07-01 | Акционерное Общество "Твэл" | Method of manufacturing tubular products from a zirconium alloy |
CN115261772A (en) * | 2022-07-09 | 2022-11-01 | 北京市春立正达医疗器械股份有限公司 | Method for rapidly preparing ceramic modified layer on surface of zirconium alloy |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7526204B2 (en) | 2019-12-26 | 2024-07-31 | 株式会社クラレ | Vinyl chloride resin composition and molded article |
CN113732102A (en) * | 2020-05-27 | 2021-12-03 | 国核宝钛锆业股份公司 | Method for manufacturing small-caliber thin-wall cladding pipe and cladding pipe |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0762225B2 (en) * | 1986-08-29 | 1995-07-05 | 株式会社日立製作所 | Manufacturing method of highly corrosion resistant zirconium alloy products |
US4814136A (en) | 1987-10-28 | 1989-03-21 | Westinghouse Electric Corp. | Process for the control of liner impurities and light water reactor cladding |
JPH01116057A (en) * | 1987-10-30 | 1989-05-09 | Hitachi Ltd | Manufacture of nuclear reactor spacer |
FR2626291B1 (en) | 1988-01-22 | 1991-05-03 | Mitsubishi Metal Corp | ZIRCONIUM-BASED ALLOY FOR USE AS A FUEL ASSEMBLY IN A NUCLEAR REACTOR |
US5024809A (en) | 1989-05-25 | 1991-06-18 | General Electric Company | Corrosion resistant composite claddings for nuclear fuel rods |
JPH08253828A (en) | 1995-03-14 | 1996-10-01 | Sumitomo Metal Ind Ltd | Highly corrosion resistant zirconium alloy |
KR100261665B1 (en) | 1998-02-04 | 2000-07-15 | 장인순 | Composition of zirconium alloy having high corrosion resistance and high strength |
KR100286871B1 (en) * | 1998-10-21 | 2001-04-16 | 장인순 | Zirconium alloy composition with excellent corrosion resistance and mechanical properties |
KR100334252B1 (en) * | 1999-11-22 | 2002-05-02 | 장인순 | Niobium-containing zirconium alloys for nuclear fuel cladding |
KR100382997B1 (en) * | 2001-01-19 | 2003-05-09 | 한국전력공사 | Method of Manufacturing A Tube and A Sheet of Niobium-containing Zirconium Alloys for High Burn-up Nuclear Fuel |
US20060243358A1 (en) | 2004-03-23 | 2006-11-02 | David Colburn | Zirconium alloys with improved corrosion resistance and method for fabricating zirconium alloys with improved corrosion |
CN101175864A (en) * | 2004-03-23 | 2008-05-07 | 西屋电气有限责任公司 | Zirconium alloys with improved corrosion resistance and method for fabricating zirconium alloys with improved corrosion resistance |
US9284629B2 (en) * | 2004-03-23 | 2016-03-15 | Westinghouse Electric Company Llc | Zirconium alloys with improved corrosion/creep resistance due to final heat treatments |
US20100040189A1 (en) * | 2006-10-16 | 2010-02-18 | Commissariat A L'energie Atomique | Erbium-containing zirconium alloy, methods for preparing and shaping the same, and structural component containing said alloy. |
KR100831578B1 (en) * | 2006-12-05 | 2008-05-21 | 한국원자력연구원 | Zirconium alloy compositions having excellent corrosion resistance for nuclear applications and preparation method thereof |
CN100510134C (en) * | 2007-09-13 | 2009-07-08 | 上海大学 | Nodular corrosion resistant modified Zr-4 alloy and method for making same |
KR100960894B1 (en) * | 2008-02-27 | 2010-06-04 | 한국원자력연구원 | Zirconium alloys compositions having excellent resistance against hydrogen embrittlement and preparation method thereof |
KR101058872B1 (en) * | 2009-01-07 | 2011-08-23 | 한국원자력연구원 | High concentration molybdenum-containing zirconium alloy composition having excellent corrosion resistance and creep resistance, preparation method thereof and use thereof |
CN101935778B (en) * | 2010-08-17 | 2011-12-28 | 苏州热工研究院有限公司 | Zirconium-based alloy for nuclear reactors and preparation method thereof |
KR20130098618A (en) | 2012-02-28 | 2013-09-05 | 한국원자력연구원 | Zirconium alloys for nuclear fuel claddings having a superior oxidation resistance in the reactor accident conditions, zirconium alloy nuclear fuel claddings prepared by using thereof and method of preparing the same |
KR101378066B1 (en) * | 2012-02-28 | 2014-03-28 | 한국수력원자력 주식회사 | Zirconium alloys for nuclear fuel cladding, having a superior corrosion resistance by reducing the amount of alloying elements, and the preparation method of zirconium alloys nuclear fuel claddings using thereof |
CN103194650B (en) * | 2013-04-10 | 2015-08-19 | 苏州热工研究院有限公司 | A kind of preparation method of Zr-1Nb alloy |
FR3025929B1 (en) | 2014-09-17 | 2016-10-21 | Commissariat Energie Atomique | NUCLEAR FUEL TANKS, METHODS OF MANUFACTURE AND USE AGAINST OXIDATION. |
-
2015
- 2015-04-14 KR KR1020150052710A patent/KR101604103B1/en active IP Right Grant
- 2015-05-27 JP JP2017553417A patent/JP6734867B2/en active Active
- 2015-05-27 EP EP15889284.4A patent/EP3284837B1/en active Active
- 2015-05-27 WO PCT/KR2015/005319 patent/WO2016167404A1/en unknown
- 2015-05-27 CN CN201580078743.3A patent/CN107429331B/en active Active
-
2016
- 2016-04-13 US US15/097,341 patent/US20160307651A1/en not_active Abandoned
-
2019
- 2019-11-08 US US16/677,904 patent/US11195628B2/en active Active
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021133194A1 (en) | 2019-12-26 | 2021-07-01 | Акционерное Общество "Твэл" | Method of manufacturing tubular products from a zirconium alloy |
WO2021133195A1 (en) | 2019-12-26 | 2021-07-01 | Акционерное Общество "Твэл" | Method of producing tubular products from a zirconium-based alloy |
WO2021133196A1 (en) | 2019-12-26 | 2021-07-01 | Акционерное Общество "Твэл" | Method of manufacturing tubular products from a zirconium alloy |
CN113316490A (en) * | 2019-12-26 | 2021-08-27 | Tvel股份公司 | Method for manufacturing zirconium-based alloy pipe |
CN113316489A (en) * | 2019-12-26 | 2021-08-27 | Tvel股份公司 | Method for manufacturing zirconium alloy tubular product |
KR20220023762A (en) * | 2019-12-26 | 2022-03-02 | 조인트-스탁 컴퍼니 “티브이이엘” | Manufacturing method of zirconium alloy pipe |
US20220316041A1 (en) * | 2019-12-26 | 2022-10-06 | Joint-Stock Company "Tvel" | Manufacturing Method for Tubular Products made of Zirconium-Based Alloy |
US20220314289A1 (en) * | 2019-12-26 | 2022-10-06 | Joint-Stock Company "Tvel" | Manufacturing Method for Zirconium Alloy Tubular Products |
EP4091731A4 (en) * | 2019-12-26 | 2023-11-01 | Joint-Stock Company "TVEL" | Method of manufacturing tubular products from a zirconium alloy |
EP4082686A4 (en) * | 2019-12-26 | 2024-01-24 | Joint-Stock Company "TVEL" | Method of producing tubular products from a zirconium-based alloy |
KR102680922B1 (en) * | 2019-12-26 | 2024-07-02 | 조인트-스탁 컴퍼니 “티브이이엘” | Manufacturing method of zirconium alloy pipe |
CN115261772A (en) * | 2022-07-09 | 2022-11-01 | 北京市春立正达医疗器械股份有限公司 | Method for rapidly preparing ceramic modified layer on surface of zirconium alloy |
Also Published As
Publication number | Publication date |
---|---|
KR101604103B1 (en) | 2016-03-25 |
US11195628B2 (en) | 2021-12-07 |
JP2018514649A (en) | 2018-06-07 |
CN107429331A (en) | 2017-12-01 |
EP3284837A4 (en) | 2018-12-26 |
WO2016167404A1 (en) | 2016-10-20 |
JP6734867B2 (en) | 2020-08-05 |
EP3284837B1 (en) | 2019-10-23 |
CN107429331B (en) | 2020-06-23 |
US20200075181A1 (en) | 2020-03-05 |
EP3284837A1 (en) | 2018-02-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11195628B2 (en) | Method of manufacturing a corrosion-resistant zirconium alloy for a nuclear fuel cladding tube | |
US20160304991A1 (en) | Zirconium alloy having excellent corrosion resistance and creep resistance and method of manufacturing the same | |
US20080131306A1 (en) | Zirconium alloy composition having excellent corrosion resistance for nuclear applications and method of preparing the same | |
US6261516B1 (en) | Niobium-containing zirconium alloy for nuclear fuel claddings | |
US9481921B2 (en) | Zirconium alloy composition having low hydrogen pick-up rate and high hydrogen embrittlement resistance and method of preparing the same | |
US20100108204A1 (en) | Zirconium alloy composition for nuclear fuel cladding tube forming protective oxide film, zirconium alloy nuclear fuel cladding tube manufactured using the composition, and method of manufacturing the zirconium alloy nuclear fuel cladding tube | |
KR100707502B1 (en) | Method for making thin zirconium alloy elements and wafers obtained | |
EP3241920B1 (en) | Method for manufacturing nuclear fuel zirconium part by using multi-stage hot-rolling | |
KR101833404B1 (en) | High strength Fe―Cr―Ni―Al multiplex stainless steels and method of making | |
KR101779128B1 (en) | Alumina-forming duplex stainless steels as accident resistant fuel cladding materials for light water reactors | |
KR101265261B1 (en) | Zirconium alloy manufacturing method having excellent corrosion resistance and high strength | |
JP6228231B2 (en) | Zirconium alloy processing method, zirconium alloy obtained by the method, and nuclear reactor component comprising the alloy | |
JPH024937A (en) | Zr alloy for reactor fuel assembled body | |
KR100296952B1 (en) | New zirconium alloys for fuel rod cladding and process for manufacturing thereof | |
KR20090079866A (en) | Zirconium alloys having excellent resistance property in both water and steam reaction | |
KR20080097380A (en) | Zirconium alloys having excellent resistance property in both water and steam reaction | |
JP2001220632A (en) | Zirconium alloy small in hydrogen absorption and excellent in corrosion resistance and its producing method | |
JPH05163545A (en) | Zr base alloy excellent in corrosion resistance |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: KEPCO NUCLEAR FUEL CO., LTD., KOREA, REPUBLIC OF Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHOI, MIN YOUNG;MOK, YONG KYOON;KIM, YOON HO;AND OTHERS;REEL/FRAME:038262/0865 Effective date: 20160407 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |