CN115961175A - Low-tin high-niobium zirconium alloy for fuel assembly, preparation method of low-tin high-niobium zirconium alloy and cladding tube of fuel assembly - Google Patents
Low-tin high-niobium zirconium alloy for fuel assembly, preparation method of low-tin high-niobium zirconium alloy and cladding tube of fuel assembly Download PDFInfo
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- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 83
- 239000000446 fuel Substances 0.000 title claims abstract description 46
- 238000005253 cladding Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052718 tin Inorganic materials 0.000 claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 239000000956 alloy Substances 0.000 claims abstract description 34
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 238000005242 forging Methods 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 238000003723 Smelting Methods 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 39
- 239000010955 niobium Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 12
- 230000000712 assembly Effects 0.000 claims description 11
- 238000000429 assembly Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- 238000005097 cold rolling Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- GFUGMBIZUXZOAF-UHFFFAOYSA-N niobium zirconium Chemical compound [Zr].[Nb] GFUGMBIZUXZOAF-UHFFFAOYSA-N 0.000 claims 3
- 230000007797 corrosion Effects 0.000 abstract description 36
- 238000005260 corrosion Methods 0.000 abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003758 nuclear fuel Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910008933 Sn—Nb Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- 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
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- Monitoring And Testing Of Nuclear Reactors (AREA)
Abstract
The invention discloses a low-tin high-niobium zirconium alloy for a fuel assembly, a preparation method thereof and a cladding tube of the fuel assembly, wherein the low-tin high-niobium zirconium alloy comprises metal Zr, nb, sn, fe, V and a non-metal element O, and the mass percentages of the metal Zr, nb, sn, fe and V in the alloy are respectively as follows: nb is more than or equal to 1.4 percent and less than or equal to 1.6 percent, sn is more than or equal to 0.15 percent and less than or equal to 0.35 percent, fe is more than or equal to 0.02 percent and less than or equal to 0.2 percent, V is more than or equal to 0.03 percent and less than or equal to 0.2 percent, O is more than or equal to 0.1 percent and less than or equal to 0.2 percent, and the mass of Fe and V meets the following requirements: the mass percentage content of Fe + V is less than or equal to 0.25 percent; the balance being Zr; the preparation method comprises the following steps: weighing, smelting, forging, processing and final annealing; a cladding tube: is made of the zirconium alloy. The low-tin high-niobium zirconium alloy prepared by the invention has excellent high-Li corrosion resistance, high-temperature pure water corrosion resistance and creep resistance, and can be used as a material of a fuel assembly cladding tube.
Description
Technical Field
The invention relates to the technical field of nuclear fuel, in particular to a low-tin high-niobium zirconium alloy for a fuel assembly, a preparation method thereof and a cladding tube of the fuel assembly.
Background
The development of zirconium alloys for nuclear fuel assemblies has now been followed, and three generations of commercial zirconium alloys have been iterated. The first generation was traditional Zr-4 and Zr-2, both of which were widely used in nuclear reactors since the 50 s of the last century. The second generation is low-tin Zr-4 and optimized Zr-4, and compared with the low-tin Zr-4 alloy, the optimized Zr-4 has higher Fe and Cr contents and better corrosion resistance. The third generation is M5 alloy, the corrosion resistance of the M5 alloy is obviously improved compared with that of the optimized Zr-4 alloy, but the corrosion resistance of the M5 alloy is poorer in the environment with high Li concentration, and the creep resistance of the M5 alloy is general.
Along with the increase of irradiation burnup, dirt on the surface of a fuel cladding is increased, boron is enriched in the dirt due to supercooling boiling, and further the axial power deviation phenomenon of a reactor core is increasingly obvious, so that the safety of the reactor core is influenced. One of the methods for alleviating the axial power deviation of the reactor core is to increase and stabilize the pH of a primary circuit by increasing the Li concentration and reduce the migration of dirt in the primary circuit. In addition, when the surface of the fuel rod is fouled, the heat transfer efficiency of the fuel rod is reduced, and local boiling may occur at the cladding surface, resulting in the existence of two phases of coolant at the cladding surface, and in turn, in the enrichment of Li concentration. Therefore, the improvement of the high Li corrosion resistance of the fuel cladding can provide higher safety guarantee for the operation of the reactor. The performance of the existing zirconium alloy is not optimal at present, and the component proportion has a further optimization space, so that the corrosion resistance of the zirconium alloy needs to be improved on the premise of not obviously influencing other performances, including under the water chemistry condition of high Li.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art and provides a low-tin high-niobium zirconium alloy for a fuel assembly, a preparation method thereof and a cladding tube of the fuel assembly.
The technical scheme adopted by the invention for solving the technical problem is as follows: a low-tin high-niobium zirconium alloy for fuel assemblies comprises metals Zr, nb, sn, fe, V and a non-metal element O, wherein the mass percentages of the metals Zr, nb, sn, fe and V in the alloy are respectively as follows: nb is more than or equal to 1.4 percent and less than or equal to 1.6 percent, sn is more than or equal to 0.15 percent and less than or equal to 0.35 percent, fe is more than or equal to 0.02 percent and less than or equal to 0.2 percent, V is more than or equal to 0.03 percent and less than or equal to 0.2 percent, O is more than or equal to 0.1 percent and less than or equal to 0.2 percent, and the mass of Fe and V meets the following requirements: the mass percentage content of Fe + V is less than or equal to 0.25 percent; the balance being Zr.
Preferably, in the alloy, the following elements are in percentage by mass: fe is more than or equal to 0.03% and less than or equal to 0.1%, V is more than or equal to 0.03% and less than or equal to 0.1%, O is more than or equal to 0.1% and less than or equal to 0.16%, and the mass of Fe and V satisfies the following conditions: the mass percentage content of Fe + V is less than or equal to 0.15 percent; the balance being Zr.
Preferably, the total content of all impurity elements of the alloy in parts per million by mass is not higher than 265ppm, and the impurity elements comprise: the mass ppm of C is not more than 100ppm, the mass ppm of N is not more than 45ppm, the mass ppm of Hf is not more than 100ppm, and the mass ppm of H is not more than 20ppm.
A preparation method of a low-tin high-niobium zirconium alloy for a fuel assembly comprises the following steps:
s1, weighing: pure niobium, pure tin, pure iron, pure vanadium, zirconium oxide and pure zirconium are used as raw materials, and the proportion of the raw materials satisfies the following element mass percentage: nb is more than or equal to 1.4 percent and less than or equal to 1.6 percent, sn is more than or equal to 0.15 percent and less than or equal to 0.35 percent, fe is more than or equal to 0.02 percent and less than or equal to 0.2 percent, V is more than or equal to 0.03 percent and less than or equal to 0.2 percent, O is more than or equal to 0.1 percent and less than or equal to 0.2 percent, and the mass of Fe and V meets the following requirements: the mass percentage content of Fe + V is less than or equal to 0.25 percent; the balance being Zr;
s2, smelting: mixing the raw materials obtained in the step S1 and smelting to obtain an alloy ingot;
s3, forging: forging the alloy ingot obtained in the step S2 at 800-1100 ℃ to obtain a blank 1;
s4, processing: carrying out beta quenching and hot working on the blank 1 obtained in the step S3 at 950-1100 ℃, and then carrying out cold rolling and intermediate annealing for multiple times to obtain a blank 2;
s5, final annealing: and (3) performing final annealing on the blank 2 obtained in the step (S4) at the temperature of 450-600 ℃ to obtain the low-tin high-niobium zirconium alloy.
Preferably, in the step S3, the forging temperature is 900 to 1100 ℃.
Preferably, in the step S4, the β quenching temperature is 1000 to 1100 ℃.
Preferably, in the step S4, the number of cold rolling is 3 to 6.
Preferably, in the step S5, the final annealing temperature is 470-580 ℃; the final annealing mode is recrystallization annealing or stress relief annealing.
The cladding tube of the fuel assembly is made of low-tin high-niobium zirconium alloy.
Preferably, the outer diameter of the cladding tube is 8-11 mm, the wall thickness is 0.5-1.1 mm, and the height is 3500-4500 mm.
The invention has the beneficial effects that:
the invention provides a low-tin high-niobium zirconium alloy for a fuel assembly, which improves the corrosion resistance and the creep resistance of the zirconium alloy by controlling the content of transition metal elements Fe and V and meeting the requirements on low content of tin element and high content of niobium element.
The invention provides a preparation method of a low-tin high-niobium zirconium alloy for a fuel assembly, which is simple, convenient and feasible, adopts pure raw materials, and prepares a zirconium alloy with excellent high-Li corrosion resistance, high-temperature pure water corrosion resistance and creep resistance by controlling the components and the content of the zirconium alloy and the preparation process parameters of the alloy.
The invention provides a cladding tube of a fuel assembly, which is made of the low-tin high-niobium zirconium alloy, so that the fuel assembly runs to higher fuel consumption, and the service performance and safety of the fuel assembly are improved.
Detailed Description
In order to make the technical features, objects and effects of the present invention more clearly understood, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
A low-tin high-niobium zirconium alloy for fuel assemblies, comprising metals Zr (zirconium), nb (niobium), sn (tin), fe (iron), V (vanadium) and a non-metallic element O (oxygen), wherein the mass percentages in the alloy are respectively as follows: nb is more than or equal to 1.4 percent and less than or equal to 1.6 percent, sn is more than or equal to 0.15 percent and less than or equal to 0.35 percent, fe is more than or equal to 0.02 percent and less than or equal to 0.2 percent, V is more than or equal to 0.03 percent and less than or equal to 0.2 percent, O is more than or equal to 0.1 percent and less than or equal to 0.2 percent, and the mass of the Fe and the V meets the following requirements: the mass percentage of Fe + V is less than or equal to 0.25 percent, namely the total mass percentage of Fe + V is less than or equal to 0.25 percent, and the same applies below; the balance being Zr. The balance of elements refers to elements except Nb, sn, fe, V and O in the alloy raw materials, namely a matrix element Zr of the zirconium alloy.
Preferably, in the above alloy, the following elements are in mass percent: fe is more than or equal to 0.03% and less than or equal to 0.1%, V is more than or equal to 0.03% and less than or equal to 0.1%, O is more than or equal to 0.1% and less than or equal to 0.16%, and the mass of Fe and V satisfies the following conditions: the mass percentage of Fe + V is less than or equal to 0.15 percent.
The total million parts by mass content of all impurity elements of the alloy is not higher than 265ppm (ppm is parts per million), namely the million parts by mass ratio of all impurity elements is not higher than 265ppm. Among the impurity elements: c (carbon) of not more than 100ppm by mass, N (nitrogen) of not more than 45ppm by mass, hf (hafnium) of not more than 100ppm by mass, and H (hydrogen) of not more than 20ppm by mass. The content of all impurity elements may be controlled within a corresponding range, and is not particularly limited herein.
The low-tin high-niobium zirconium alloy for the fuel assembly has the following functions of elements:
zr: alloy matrix elements.
Nb: after Nb is dissolved in the zirconium alloy, the zirconium alloy is beneficial to the corrosion resistance, creep resistance and hydrogen absorption resistance of the zirconium alloy, and the hydrogen content in the alloy is reduced to bring higher safety margin, so that the mass percentage of Nb in the invention is limited to 1.4-1.6%, thereby ensuring that the alloy has excellent corrosion resistance (under the condition of containing a small amount of Sn) and creep resistance.
Sn: the solid solubility of Sn in zirconium is high, and the strength and the creep resistance of the zirconium alloy can be improved by adding a certain amount of Sn, but the corrosion resistance of the zirconium alloy is obviously influenced by the addition of Sn. When the mass percentage of the added Sn is less than 0.45 percent for the Zr-Sn-Nb alloy, the influence on the corrosion resistance is small. Therefore, the method comprehensively considers the damage of Sn to the corrosion resistance and the benefit of the creep resistance when determining the Sn content, and limits the mass percentage of Sn to 0.15-0.35%, thereby not only improving the creep resistance of the zirconium alloy, but also reducing the influence of Sn on the corrosion resistance.
Fe. V: the corrosion resistance of the alloy can be improved by adding a certain amount of transition group metal elements such as Fe and V elements, and the hydrogen absorption resistance of the zirconium alloy can be improved by adding the V elements. However, if the amount of the transition metal element such as Fe or V is too large, the embrittlement resistance after high-temperature oxidation quenching is remarkably lowered. Therefore, the mass percentage of the Fe element in the invention is limited to 0.02-0.2%, preferably 0.03-0.1%, the mass percentage of the V element is limited to 0.03-0.2%, preferably 0.03-0.1%, and the mass of Fe and V satisfies the following conditions: the mass percentage of Fe + V is less than or equal to 0.25 percent, and preferably, the mass percentage of Fe + V is less than or equal to 0.15 percent.
O: the addition of O element in zirconium alloy can improve the strength and creep resistance of the alloy, but as the content of O is increased, the processability of the zirconium alloy is reduced, especially the punching resistance. Therefore, the present invention limits the content of the element O to 0.1 to 0.2% by mass, preferably 0.1 to 0.16% by mass.
C. N, hf, H: the mechanical property and the corrosion resistance of the alloy can be influenced by C and N, the mechanical property of the zirconium alloy can be influenced by over-high H content, and the neutron benefit of the cladding in the reactor can be reduced by the Hf with a high thermal neutron absorption cross section. Therefore, C, N, hf and H should be strictly controlled without significantly increasing the difficulty of smelting.
The preparation method of the low-tin high-niobium zirconium alloy for the fuel assembly comprises the following steps of:
s1, weighing: pure niobium, pure tin, pure iron, pure vanadium, zirconium oxide and pure zirconium are used as raw materials, and the mixture ratio of the raw materials satisfies the following element mass percentage: nb is more than or equal to 1.4 percent and less than or equal to 1.6 percent, sn is more than or equal to 0.15 percent and less than or equal to 0.35 percent, fe is more than or equal to 0.02 percent and less than or equal to 0.2 percent, V is more than or equal to 0.03 percent and less than or equal to 0.2 percent, O is more than or equal to 0.1 percent and less than or equal to 0.2 percent, and the mass of the Fe and the V meets the following requirements: the mass percentage content of Fe + V is less than or equal to 0.25 percent; the balance being Zr;
s2, smelting: mixing the raw materials obtained in the step S1 and smelting to obtain an alloy ingot;
s3, forging: forging the alloy ingot obtained in the step S2 at 800-1100 ℃ to obtain a blank 1; wherein the forging temperature is preferably 900 to 1100 ℃.
S4, processing: carrying out beta quenching and hot working on the blank 1 obtained in the step S3 at 950-1100 ℃, and then carrying out cold rolling and intermediate annealing to obtain a blank 2; wherein the beta quenching temperature is preferably 1000-1100 ℃, and the cold rolling times are 3-6.
S5, final annealing: carrying out final annealing on the blank 2 obtained in the step S4 at the temperature of 450-600 ℃ to obtain a low-tin high-niobium zirconium alloy; wherein the final annealing mode is recrystallization annealing or stress relief annealing, and the final annealing temperature is preferably 470-580 ℃.
The cladding tube of the fuel assembly is made of the low-tin high-niobium zirconium alloy, the outer diameter of the cladding tube is 8-11 mm, the wall thickness is 0.5-1.1 mm, and the height is 3500-4500 mm.
The invention provides a low-tin high-niobium zirconium alloy for a fuel assembly, which improves the corrosion resistance and the creep resistance of the zirconium alloy by controlling the content of transition metal elements Fe and V and meeting the requirements on low content of tin element and high content of niobium element.
The invention provides a preparation method of a low-tin high-niobium zirconium alloy for a fuel assembly, which is simple, convenient and feasible, adopts pure raw materials, and prepares a zirconium alloy with excellent high-Li corrosion resistance, high-temperature pure water corrosion resistance and creep resistance by controlling the components and content of the zirconium alloy and the preparation process parameters of the alloy.
The invention provides a cladding tube of a fuel assembly, which is made of the low-tin high-niobium zirconium alloy, so that the fuel assembly runs to higher fuel consumption, and the service performance and safety of the fuel assembly are improved.
The following is illustrated by specific examples:
the zirconium alloys of examples 1 to 7 and comparative examples 1 to 2 were prepared by the preparation method of the present invention, and the chemical compositions of the zirconium alloys of examples 1 to 7 and comparative examples 1 to 2 are shown in table 1. Wherein, the comparative example 1 is different from the present invention in that the mass percentage content of Nb is as low as 0.85%; comparative example 2 is different from the present invention in that Sn and Fe are not added and the content of Nb is low. Further, the impurity elements of the zirconium alloys of examples 1 to 7 and comparative examples 1 to 2 were examined, and the results showed that the contents of the impurity elements C, N, hf, H in each of the zirconium alloys were controlled within the respective ranges as described above.
TABLE 1 chemical composition of examples 1-7 and comparative examples 1-2
The process parameters of forging, beta quenching, cold rolling and final annealing during the preparation of the zirconium alloys of examples 1 to 7 and comparative examples 1 to 2 are shown in table 2.
TABLE 2 preparation Process parameters of examples 1 to 7 and comparative examples 1 to 2
The zirconium alloys of examples 1 to 7 and comparative examples 1 to 2 were processed into cladding tubes for fuel assemblies, the specific dimensions of which are shown in table 3.
Table 3 dimensions of the cladding tubes of examples 1-7 and comparative examples 1-2
| Cladding tube | Outer diameter (mm) | Wall thickness (mm) | Height (mm) |
| Example 1 | 9.5 | 0.57 | 3500 |
| Example 2 | 9.5 | 0.57 | 4500 |
| Example 3 | 9.5 | 0.57 | 3800 |
| Example 4 | 9.5 | 0.57 | 4000 |
| Example 5 | 10 | 0.6 | 4000 |
| Example 6 | 8 | 0.5 | 4200 |
| Example 7 | 11 | 1.1 | 4500 |
| Comparative example 1 | 9.5 | 0.57 | 3500 |
| Comparative example 2 | 9.5 | 0.57 | 4500 |
And (3) comparison test:
comparative tests were carried out on the zirconium alloys obtained in examples 1 to 4 and comparative examples 1 to 2 and on zirconium alloys for nuclear fuel assemblies, zr-4 and Zr-1Sn-1Nb, which are international commercial zirconium alloys having chemical compositions shown in Table 4. The Zr-4 is different from the method in that Nb and V elements are not added, the Sn content is high, and Cr is additionally added; zr-1Sn-1Nb is different from the present application in that no V element is added, and the content of Sn is high and the content of Nb is low.
TABLE 4 chemical compositions of Zr-4 and Zr-1Sn-1Nb
1. Corrosion test
The zirconium alloys obtained in examples 1 to 4 and comparative examples 1 to 2 and the zirconium alloys Zr-4 and Zr-1Sn-1Nb were subjected to corrosion tests conducted in an autoclave under corrosion conditions of 360 ℃/18.6MPa/70ppm Li in water and 360 ℃/18.6 MPa/deionized water, a test time under a chemical condition of 70ppm Li in water of 310 days and a test time of deionized water of 430 days, and the test results are shown in Table 5.
2. Internal pressure creep test
The zirconium alloys obtained in examples 2 to 4 and the zirconium alloy Zr-4 were subjected to an internal pressure creep test conducted on a creep machine at a test temperature of 400 ℃ and a hoop stress of 130MPa for a test time of 240 hours, and the test results are shown in Table 6.
TABLE 5 Corrosion test results
TABLE 6 internal pressure creep test results
| Zirconium alloy | Dependent variable (mm/mm) |
| Example 2 | 0.69 |
| Example 3 | 0.78 |
| Example 4 | 0.93 |
| Zr-4 | 1.79 |
As can be seen from Table 5, in the case of Zr-4 alloy under high Li water chemistry, the corrosion rate sharply increased in 42-70 days, and the corrosion rate sharply increased in the zirconium alloy prepared by the present invention did not occur, but when the Nb content of the zirconium alloy prepared by the present invention was reduced to 0.85% (comparative example 1) or the zirconium alloy had a higher Nb content without adding a small amount of Sn (comparative example 2), the corrosion rate sharply increased in 70-100 days. In addition, the zirconium alloy of the present invention also shows better high Li water corrosion resistance (less weight gain) compared to high Li water corrosion resistance Zr-1Sn-1 Nb. Therefore, the low-tin high-niobium zirconium alloy prepared by the method has excellent chemical corrosion resistance to high Li water. In addition, under the corrosion of pure water, the zirconium alloy has lower corrosion amount which is far lower than that of the Zr-4 alloy; the invention also shows a higher resistance to pure water corrosion (less weight gain) compared to the zirconium alloy Zr-1Sn-1 Nb. Therefore, the low-tin high-niobium zirconium alloy prepared by the method has excellent pure water corrosion resistance.
As can be seen from table 6, in the internal pressure creep test, the strain amount of the low-tin high-niobium zirconium alloy prepared by the present invention is less than 1%, while the strain amount of the conventional zirconium alloy Zr-4 is 1.79%, and it can be seen that the low-tin high-niobium zirconium alloy prepared by the present invention has excellent creep resistance (less creep deformation).
From the test results, the low-tin high-niobium zirconium alloy has better chemical corrosion resistance to high Li water, pure water and creep resistance than international commercial zirconium alloy.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The low-tin high-niobium zirconium alloy for the fuel assembly is characterized by comprising metals Zr, nb, sn, fe and V and a non-metal element O, wherein the metal Zr, the Nb, the Sn, the Fe and the V are respectively as follows by mass percent in the alloy: nb is more than or equal to 1.4 percent and less than or equal to 1.6 percent, sn is more than or equal to 0.15 percent and less than or equal to 0.35 percent, fe is more than or equal to 0.02 percent and less than or equal to 0.2 percent, V is more than or equal to 0.03 percent and less than or equal to 0.2 percent, O is more than or equal to 0.1 percent and less than or equal to 0.2 percent, and the mass of the Fe and the V meets the following requirements: the mass percentage content of Fe + V is less than or equal to 0.25 percent; the balance being Zr.
2. The low tin high niobium zirconium alloy for fuel assemblies as claimed in claim 1, wherein the following elements are present in the alloy in the following percentages by mass: fe is more than or equal to 0.03% and less than or equal to 0.1%, V is more than or equal to 0.03% and less than or equal to 0.1%, O is more than or equal to 0.1% and less than or equal to 0.16%, and the mass of Fe and V satisfies the following conditions: the mass percentage content of Fe + V is less than or equal to 0.15 percent; the balance being Zr.
3. The low tin high niobium zirconium alloy for fuel assemblies according to claim 1, wherein said alloy has a total content of impurity elements of not more than 265ppm in parts per million by mass, among which: the mass parts per million of C is not more than 100ppm, the mass parts per million of N is not more than 45ppm, the mass parts per million of Hf is not more than 100ppm, and the mass parts per million of H is not more than 20ppm.
4. A preparation method of a low-tin high-niobium zirconium alloy for a fuel assembly is characterized by comprising the following steps:
s1, weighing: pure niobium, pure tin, pure iron, pure vanadium, zirconium oxide and pure zirconium are used as raw materials, and the proportion of the raw materials satisfies the following element mass percentage: nb is more than or equal to 1.4 percent and less than or equal to 1.6 percent, sn is more than or equal to 0.15 percent and less than or equal to 0.35 percent, fe is more than or equal to 0.02 percent and less than or equal to 0.2 percent, V is more than or equal to 0.03 percent and less than or equal to 0.2 percent, O is more than or equal to 0.1 percent and less than or equal to 0.2 percent, and the mass of Fe and V meets the following requirements: the mass percentage content of Fe + V is less than or equal to 0.25 percent; the balance being Zr;
s2, smelting: mixing the raw materials obtained in the step S1 and smelting to obtain an alloy ingot;
s3, forging: forging the alloy ingot obtained in the step S2 at 800-1100 ℃ to obtain a blank 1;
s4, processing: carrying out beta quenching and hot working on the blank 1 obtained in the step S3 at 950-1100 ℃, and then carrying out multiple times of cold rolling and intermediate annealing to obtain a blank 2;
s5, final annealing: and (3) performing final annealing on the blank 2 obtained in the step (S4) at the temperature of 450-600 ℃ to obtain the low-tin high-niobium zirconium alloy.
5. The method for preparing a low-tin high-niobium zirconium alloy for fuel assemblies according to claim 4, wherein the forging temperature in the step S3 is 900 to 1100 ℃.
6. The method for preparing a low-tin high-niobium zirconium alloy for fuel assemblies according to claim 4, wherein the β -quenching temperature in the step S4 is 1000 to 1100 ℃.
7. The method for preparing a low-tin high-niobium zirconium alloy for fuel assemblies according to claim 4, wherein the number of cold rolling in the step S4 is 3 to 6.
8. The method for preparing a low-tin high-niobium zirconium alloy for fuel assemblies according to claim 4, wherein in the step S5, the final annealing temperature is 470 to 580 ℃; the final annealing mode is recrystallization annealing or stress relief annealing.
9. A cladding for a fuel assembly made from a low tin high niobium zirconium alloy for use in a fuel assembly as claimed in any one of claims 1 to 3.
10. The cladding tube for a fuel assembly of claim 9, wherein the cladding tube has an outer diameter of 8 to 11mm, a wall thickness of 0.5 to 1.1mm, and a height of 3500 to 4500mm.
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|---|---|---|---|---|
| US20020136347A1 (en) * | 2001-01-19 | 2002-09-26 | Jeong Yong Hwan | Method for manufacturing a tube and a sheet of niobium-containing zirconium alloy for a high burn-up nuclear fuel |
| CN104745875A (en) * | 2013-12-30 | 2015-07-01 | 上海核工程研究设计院 | Zirconium alloy material for light water reactor under higher burnup |
| CN113201666A (en) * | 2021-04-08 | 2021-08-03 | 中广核研究院有限公司 | Zirconium alloy for fuel assembly, manufacturing method thereof and cladding tube of fuel assembly |
| CN113249616A (en) * | 2021-04-08 | 2021-08-13 | 岭澳核电有限公司 | Zirconium alloy for fuel assembly, preparation method thereof and cladding tube of fuel assembly |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020136347A1 (en) * | 2001-01-19 | 2002-09-26 | Jeong Yong Hwan | Method for manufacturing a tube and a sheet of niobium-containing zirconium alloy for a high burn-up nuclear fuel |
| CN104745875A (en) * | 2013-12-30 | 2015-07-01 | 上海核工程研究设计院 | Zirconium alloy material for light water reactor under higher burnup |
| CN113201666A (en) * | 2021-04-08 | 2021-08-03 | 中广核研究院有限公司 | Zirconium alloy for fuel assembly, manufacturing method thereof and cladding tube of fuel assembly |
| CN113249616A (en) * | 2021-04-08 | 2021-08-13 | 岭澳核电有限公司 | Zirconium alloy for fuel assembly, preparation method thereof and cladding tube of fuel assembly |
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