CN102212718B - Low tin-zirconium alloy material for nuclear reactor fuel assembly - Google Patents
Low tin-zirconium alloy material for nuclear reactor fuel assembly Download PDFInfo
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- CN102212718B CN102212718B CN2011101584815A CN201110158481A CN102212718B CN 102212718 B CN102212718 B CN 102212718B CN 2011101584815 A CN2011101584815 A CN 2011101584815A CN 201110158481 A CN201110158481 A CN 201110158481A CN 102212718 B CN102212718 B CN 102212718B
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Abstract
The invention discloses a low tin-zirconium alloy material for a nuclear reactor fuel assembly. Based on the total weight of the low tin-zirconium alloy material, the low tin-zirconium alloy material consists of 0.8 to 1.0 percent of Nb, 0.2 to 0.5 percent of Sn, 0.2 to 0.5 percent of Fe, 0.06 to 0.14 percent of O, 0.05 to 0.1 percent of Cu, 0.09 to 0.2 percent of Cr or V and the balance of Zr, wherein the weight percentage sum of Sn and Fe is 0.6 to 1.0 percent. Discovered by a large amount of experimental research, when the weight percentage sum of the Sn and the Fe in the zirconium alloy is controlled in a certain range, the specific amount of added Cr or V can greatly reduce the corrosion at the alloy seams, so that safety, cost and efficiency of the high nuclear fuel assembly can be improved, wherein the V can improve the mechanical property of the alloy; and the specific amount of added Cu is favorable for further improving the corrosion resistance of the alloy.
Description
Technical field
the present invention relates to the Zirconium alloy material field, especially relate to the corrosion-resistant zircaloy of a kind of energy as the fuel rod clad material in light-water nuclear power plant nuclear reactor.
Background technology
the thermal neutron absorption cross section of zirconium is very little, and has good high-temperature resistant water corrosive nature and mechanical property, and therefore in water cooled nuclear reactor, zircaloy is widely used as the cladding materials of fuel rod and the structural detail of nuclear reactor core.Along with the power producer technology, towards the future development that improves fuel burn-up and reduction fuel cycle cost, the raising reactor thermal efficiency, raising safe reliability, the performances such as corrosion resistance, hydrogen sucking function, mechanical property and irradiation dimensional stability of key core parts can material zirconium alloy are had higher requirement.Creep and fatigue under condition (irradiation, high temperature, high pressure and complicated stress), occur in fuel element under arms.Croop property is one of the major issue that will consider while working in the water-cooled power reactor of zircaloy, the creep of zircaloy has been carried out to a large amount of research both at home and abroad.The sixties in last century zircaloy that early development goes out as the Zr-4 alloy, it has excellent physical strength, creep resistance, heat conductivity and low neutron-absorption cross-section under the reactor working temperature, and uses so far widely.Because the burnup design load of the satisfied fuel for nuclear power plant of the Zr-4 alloy institute energy of conventional Zr-Sn system is generally 33GWd/tU, therefore, in order to meet the requirement of high burnup and long-life reactor core, on the one hand, all carried out from many countries since 20 century 70s the corrosion research that improves the Zr-4 alloy, research can better novel zirconium alloy on the other hand, the exploitation of novel zirconium alloy tends to reduce or eliminate the content of tin (Sn), wherein the most outstanding achievement is to have developed low tin Zr-4 alloy, or being referred to as to optimize the Zr-4 alloy, design burn-up can reach 45GWd/tU.
the open CN1404532 of Chinese invention patent discloses a kind of corrosion resistance zirconium-base alloy be used in the nuclear fuel coating, the tin that it contains lower content, specifically, in this zircaloy, Nb content is 0.6-2.0%, and the Sn contained and the relation with contents of Fe are: when Sn is 0.25, Fe is 0.5; When Sn is 0.4, Fe is 0.35-0.50; When Sn is 0.50, Fe is 0.25-0.50; When Sn is 0.70, Fe is 0.05-0.50; When Sn is 1.0, Fe is 0.05-0.50, the content sum of Fe and Sn is greater than 0.75, other other component is no more than 0.5%, surplus is Zr, such alloy composition has improved the decay resistance of Zr-Nb-Sn-Fe alloy, has improved it in water and steam, particularly the even corrosion resistant in the lithium hydroxide aqueous solution environment.
Summary of the invention
technical matters to be solved by this invention is to provide low tin Zirconium alloy material for a kind of fuel assembly for nuclear reactor, and it has the particularly decay resistance of commissure of more excellent decay resistance.
for solving above technical matters, a kind of technical scheme that the present invention adopts is:
a kind of low tin Zirconium alloy material, the general assembly (TW) of described low tin Zirconium alloy material of take is benchmark, described low tin Zirconium alloy material is by 0.8%～1.0% Nb; 0.2% ~ 0.5% Sn; 0.2%～0.5% Fe; 0.06%～0.14% O; 0.05%～0.1%Cu; 0.09%～0.2% Cr or V; And surplus is that Zr forms, wherein: the percentage by weight sum of Sn and Fe is 0.6%～1.0%.
according to a preferred aspect of the present invention, by weight, described low tin Zirconium alloy material is by 0.9%～1.0% Nb; 0.3% ~ 0.5% Sn; 0.3%～0.4% Fe; 0.06%～0.14% O; 0.05%～0.1% Cu; 0.1%～0.2% Cr, and surplus is that Zr forms.
according to a further preferred aspect of the invention, by weight, described low tin Zirconium alloy material is by 0.9%～1.0% Nb; 0.2% ~ 0.5% Sn; 0.3%～0.4% Fe; 0.06%～0.14% O; 0.05%～0.1% Cu; 0.09%～0.2% V, and surplus is that Zr forms.
the another technical scheme that the present invention takes is: low tin Zirconium alloy material for a kind of fuel assembly for nuclear reactor, and the general assembly (TW) of described low tin Zirconium alloy material of take is benchmark, described low tin Zirconium alloy material is by 0.8%～1.0% Nb; 0.2% ~ 0.5% Sn; 0.2%～0.5% Fe; 0.06%～0.14% O; 0.05%～0.1%Cu; 0.09%～0.2% Cr; 0.09%～0.2% V; And surplus is that Zr forms, wherein: the percentage by weight sum of Sn and Fe is 0.6%～1.0%.
in above-mentioned alloy formula, C and the N inevitable impurity for bringing from raw material, one of ordinary skill in the art should be understood, other inevitable impurity component that some that may also comprise in above-mentioned alloy formula are brought from raw material, can not cause adverse effect to zircaloy of the present invention when these impurity components exist inevitably to measure.
the present invention compared with prior art has the following advantages: the present invention finds by lot of experiments, in controlling zircaloy, the percentage by weight sum of Sn and Fe is within the specific limits the time, the Cr of the specified quantitative added or V can greatly reduce the corrosion of alloy commissure, can improve thus security, cost and the efficiency of nuclear fuel assembly, wherein, V can also improve the mechanical property of alloy, and the Cu of the specified quantitative added can contribute to further to improve the decay resistance of alloy.
Embodiment
below in conjunction with specific embodiment, the present invention will be further described, but the invention is not restricted to following examples:
referring to table 1, wherein provided according to the one-tenth of seven kinds of typical Zirconium alloy materials of the present invention and be grouped into.
the zircaloy of table 1 embodiment 1 to 7 forms
having the Zirconium alloy material formed in table 1 all prepares in accordance with the following steps: the elements such as Nb, Sn, Fe, Cu, Cr, V are prepared burden by mass percentage and mixed and be pressed into electrode with core level sponge zirconium with the form of intermediate alloy, adopt vacuum consumable electrode arc furnace to carry out three meltings and make alloy pig.Ingot casting forges processing through 900 ℃ ~ 1020 ℃; Again through the solid solution of 990 ℃ ~ 1020 ℃ of β phases quenching; Again through hot rolling, repeatedly cold rolling, intermediate annealing and make the zircaloy sheet material of corresponding composition through 580 ℃ of operations such as final annealing.
the zircaloy sheet material of 7 kinds of typical compositions of the present invention and Zr-1Nb sheet alloy are carried out to the corrosive nature test.Corrosion test is carried out in autoclave, and etching condition is 400 ℃, 10.3MPa deionized water steam and 360 ℃, 18.6MPa deionized water, and the corrosion test time is 100 days, and table 1 has provided the chemical composition of these 5 kinds of zircaloys.Table 2 has been listed the surrosion of the embodiment of the present invention under above-mentioned two kinds of etching conditions.As a comparison, the test figure of the same test conditions of Zr-1Nb alloy is listed too in table 2.
150 days corrosion tests of table 2 embodiment 1-7 zircaloy sheet material and Zr-1Nb alloy relatively
from the data of table 2, can find out, zircaloy of the present invention and existing Zr-1Nb alloy phase ratio have excellent corrosion resistance in high-temperature steam.In addition, the corrosion rate of alloy of the present invention in 360 ℃, 18.6MPa deionized water is significantly lower than the corrosion rate of CN 1404532 embodiment.Thereby zircaloy of the present invention can be as clad, grid and other structural member material of nuclear reactor core fuel rod.
above-described embodiment is only explanation technical conceive of the present invention and characteristics, and its purpose is to allow the person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that Spirit Essence is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (5)
1. low tin Zirconium alloy material for a fuel assembly for nuclear reactor is characterized in that: the general assembly (TW) of described low tin Zirconium alloy material of take is benchmark, and described low tin Zirconium alloy material is by 0.8%～1.0% Nb; 0.2% ~ 0.5% Sn; 0.2%～0.5% Fe; 0.06%～0.14% O; 0.05%～0.1%Cu; 0.09%～0.2% Cr or V; And surplus is that Zr forms, wherein: the percentage by weight sum of Sn and Fe is 0.6%～1.0%.
2. fuel assembly for nuclear reactor according to claim 1 is with hanging down the tin Zirconium alloy material, and it is characterized in that: by weight, described low tin Zirconium alloy material is by 0.9%～1.0% Nb; 0.3% ~ 0.5% Sn; 0.3%～0.4% Fe; 0.06%～0.14% O; 0.05%～0.1% Cu; 0.1%～0.2% Cr, and surplus is that Zr forms.
3. fuel assembly for nuclear reactor according to claim 1 is with hanging down the tin Zirconium alloy material, and it is characterized in that: by weight, described low tin Zirconium alloy material is by 0.9%～1.0% Nb; 0.2% ~ 0.5% Sn; 0.3%～0.4% Fe; 0.06%～0.14% O; 0.05%～0.1% Cu; 0.09%～0.2% V, and surplus is that Zr forms.
4. low tin Zirconium alloy material for a fuel assembly for nuclear reactor is characterized in that: the general assembly (TW) of described low tin Zirconium alloy material of take is benchmark, and described low tin Zirconium alloy material is by 0.8%～1.0% Nb; 0.2% ~ 0.5% Sn; 0.2%～0.5% Fe; 0.06%～0.14% O; 0.05%～0.1%Cu; 0.09%～0.2% Cr; 0.09%～0.2% V; And surplus is that Zr forms, wherein: the percentage by weight sum of Sn and Fe is 0.6%～1.0%.
5. fuel assembly for nuclear reactor according to claim 4 is with hanging down the tin Zirconium alloy material, and it is characterized in that: by weight, described low tin Zirconium alloy material is by 0.9%～1.0% Nb; 0.2% ~ 0.5% Sn; 0.3%～0.4% Fe; 0.06%～0.14% O; 0.05%～0.1% Cu; 0.09%～0.2% Cr; 0.09%～0.2% V, and surplus is that Zr forms.
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| KR101800265B1 (en) * | 2011-10-21 | 2017-11-22 | 꽁빠뉘 뿌르 레뛰드 에 라 레알리자씨옹 드 꽁뷔스띠블 아토미크 | Method for producing nuclear fuel products with a high loading of low enriched uranium and corresponding nuclear kernbrennstoff |
| 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 |
| CN103898368B (en) * | 2012-12-27 | 2017-05-17 | 中国核动力研究设计院 | Zirconium-based alloy for nuclear fuel assembly |
| 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 |
| CN105441717B (en) * | 2016-01-06 | 2017-09-26 | 中国核动力研究设计院 | A kind of nuclear power core structural material zirconium-base alloy |
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| CN101270426A (en) * | 2008-03-24 | 2008-09-24 | 中国核动力研究设计院 | Zirconium based alloy for nuclear reactor |
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| KR20080074568A (en) * | 2007-02-09 | 2008-08-13 | 한국원자력연구원 | High fe contained zirconium alloy compositions having excellent corrosion resistance and preparation method thereof |
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Address after: 215004 West Ring Road, Jiangsu, Suzhou, No. 1788 Patentee after: Suzhou Nuclear Power Research Institute Co., Ltd. Patentee after: China Nuclear Power Engineering Co., Ltd. Patentee after: China General Nuclear Power Corporation Address before: 215004 West Ring Road, Jiangsu, Suzhou, No. 1788 Patentee before: Suzhou Nuclear Power Research Institute Co., Ltd. Patentee before: China Nuclear Power Engineering Co., Ltd. Patentee before: China Guangdong Nuclear Power Group Co., Ltd. |