CN103643083B - The zircalloy that fuel for nuclear power plant involucrum cupric is germanic - Google Patents
The zircalloy that fuel for nuclear power plant involucrum cupric is germanic Download PDFInfo
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- CN103643083B CN103643083B CN201310389582.2A CN201310389582A CN103643083B CN 103643083 B CN103643083 B CN 103643083B CN 201310389582 A CN201310389582 A CN 201310389582A CN 103643083 B CN103643083 B CN 103643083B
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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
Abstract
The present invention relates to the zircalloy that fuel for nuclear power plant involucrum cupric is germanic, belong to zirconium alloy technical field.The composition of this zirconium alloy is by weight percentage: 0.5% ~ 1.5%Sn, 0.01% ~ 0.4%Fe, 0.01% ~ 0.3%Cr, 0.01% ~ 0.4%Cu, 0.01% ~ 0.5%Ge; Preferable range is: 0.9% ~ 1.2%Sn, 0.1% ~ 0.3%Fe, 0.05% ~ 0.15%Cr, 0.05% ~ 0.2%Cu, 0.05% ~ 0.25%Ge, and its surplus is Zr.Zirconium alloy of the present invention all shows excellent corrosion resistance nature under 2 kinds of water chemistry conditions, is better than Zr-4 alloy, and processibility is good, can be used as the core structural material such as fuel element can and location grid band in PWR of Nuclear Power Station.
Description
Technical field
The present invention relates to the zircalloy that a kind of pressurized-water reactor nuclear power plant fuel sheath cupric is germanic, belong to Zirconium alloy material technical field.
Background technology
Zirconium alloy is little due to its thermal neutron absorption cross section, and has excellent high-temperature resistant water corrosive nature, good comprehensive mechanical property and desirable thermal conductivity, is used as the can material of Nuclear power plants water-cooled power reactor nuclear fuel element and other structured material of reactor core.In order to improve economics in nuclear power, reducing the cycle cost of nuclear fuel, deepen nuclear fuel burn up, improve nuclear plant safety reliability, need the performance improving zirconium alloy, comprise high-temperature resistant water corrosive nature, hydrogen sucking function, mechanical property and irradiation dimensional stability.Wherein, it is crucial for improving zirconium alloy water-fast side corrosive nature.
The zirconium alloy developed in the world at present mainly contains the large series of Zr-Sn, Zr-Nb and Zr-Sn-Nb tri-.Can not meet high burnup fuel assembly due to Zr-4 alloy and extend the requirement of refulling cycle, therefore, many countries have carried out the corrosion resistance nature research improving Zr-4 alloy.On Zr-Sn system basis, reduce Sn content, and after with the addition of the alloying elements such as Nb, Fe, Cr, Cu, S, develop the novel zirconium alloys such as ZIRLO, E110, E635, NDA, HANA, M5.The corrosion resistance nature of ZIRLO alloy in the out-pile 360 DEG C/18.6MPa/0.01MLiOH aqueous solution of US Westinghouse company's exploitation is obviously better than Zr-4 alloy; Then ZIRLO alloy is made fuel element to test in BR3 test reactor, after average burn-up reaches 71GWd/tU, little by 50% than Zr-4 alloy of the oxide thickness of ZIRLO alloy uniform corrosion, Flouride-resistani acid phesphatase growth and irradiation creep also good than Zr-4 alloy, show corrosion resistance nature very excellent in heap.Japan Atomic Fuel industrial group and Mitsubishi have developed jointly NDA novel zirconium alloy (Zr-1.0Sn-0.1Nb-0.28Fe-0.16Cr-0.01Ni), and adding a small amount of Nb is to make up the strength degradation reducing Sn content and cause, can also reduce suction hydrogen simultaneously.Show through Electron microscopic study, second phase particles is the ZrCr containing Fe, Nb
2and Zr
2ni intermetallic compound.When the assembly average burn-up of NorthAnna in-pile test is 27GWd/tU, the oxide thickness of NDA cladding tubes is about 15 μm, and its result and low tin Zr-4 alloy phase are seemingly.Therefore, the basis of existing zirconium alloy is added other kind alloying element and also can develop the more excellent zirconium alloy of corrosion resistance nature, to meet the needs that burnup improves constantly.
In the development and optimizing components of zirconium alloy, usually first filtered out the alloy of fine corrosion resistance by out-pile autoclave corrosion test, and then make fuel stick and be placed in test reactor and carry out Irradiation Test, understand its corrosion behavior in heap.
Summary of the invention
The object of this invention is to provide a kind of zircalloy that corrosion resistance nature is all very excellent in two kinds of water chemistry, this zirconium alloy can be used as the structured material such as fuel element can, screen work in nuclear reactor.
The object of the invention is by adding on fuel for nuclear power plant involucrum zircalloy basis simultaneously that alloy element copper (Cu) and germanium (Ge) realizes, its technical scheme is as follows:
A kind of fuel for nuclear power plant involucrum zircalloy, the chemical constitution of this zirconium alloy is by weight percentage: 0.5% ~ 1.5%Sn, 0.01% ~ 0.4%Fe, 0.01% ~ 0.3%Cr, 0.01% ~ 0.4%Cu, 0.01% ~ 0.5%Ge, and surplus is Zr.
Above-mentioned fuel for nuclear power plant involucrum zircalloy, its alloying element by weight percentage preferable range is: 0.7% ~ 1.5%Sn, 0.05% ~ 0.4%Fe, 0.03% ~ 0.2%Cr, 0.03% ~ 0.3%Cu, 0.03% ~ 0.3%Ge, and surplus is Zr.
Above-mentioned fuel for nuclear power plant involucrum zircalloy, its alloying element by weight percentage preferable range is: 0.9% ~ 1.2%Sn, 0.1% ~ 0.3%Fe, 0.05% ~ 0.15%Cr, 0.05% ~ 0.2%Cu, 0.05% ~ 0.25%Ge, and surplus is Zr.
The germanic zircalloy of cupric of the present invention is containing aerobic 900 ~ 1400ppm, and other impurity elements contained in core level zirconium sponge.
When alloy of the present invention corrodes under above-mentioned 2 kinds of water chemistry conditions, show very excellent corrosion resistance nature at the 360 DEG C/18.6MPa/0.01MLiOH aqueous solution, be obviously better than Zr-4 alloy; Work as with Zr-4 alloy phase in 360 DEG C/18.6MPa deionized water and 400 DEG C/10.3MPa superheated vapour.When corroding 300 days in the 360 DEG C/LiOH aqueous solution, the surrosion of zirconium alloy of the present invention is 146.98mg.dm
-2, and the surrosion of Zr-4 alloy reaches 260.65mg.dm
-2, the surrosion of zirconium alloy of the present invention reduces 44% than Zr-4 alloy; When corroding 390 days in 360 DEG C/18.6MPa deionized water, the surrosion of zirconium alloy of the present invention is 99.94mg.dm
-2, Zr-4 alloy is 108.4mg.dm
-2, the surrosion of zirconium alloy of the present invention is lower than Zr-4 alloy.In addition, only add the corrosion resistance nature that a small amount of Cu and Ge element just can improve zirconium alloy two kinds of water chemistry conditions in alloying constituent of the present invention, and there is good processing characteristics.
Alloying element total amount in the fuel sheath zirconium alloy (Zr-4, ZIRLO, M5 and E110 alloy) of real commercial applications is up to now little, only account for 1% ~ 3% of alloy total mass, all the other 97% ~ 99% are zirconium, so the transformable amount of each alloying element is little, the change of this alloying element seldom measured causes the change that Corrosion Resistance of Zirconium Alloys is very large just.
Accompanying drawing explanation
Fig. 1 is zirconium alloy of the present invention and the surrosion curve of Zr-4 alloy under 2 kinds of water chemistry conditions: (a) 360 DEG C/18.6MPa/0.01MLiOH aqueous solution, (b) 360 DEG C/18.6MPa/ deionized water.
Embodiment
Below in conjunction with embodiment, zirconium alloy of the present invention is described in further detail.
embodiment 1
See table 1, the one-tenth that there is shown the germanic zircalloy material of three kinds of cuprics of the present invention is grouped into.
The alloy material with composition in table 1 prepares all in accordance with the following steps:
(1) prepare burden by above-mentioned formula, the alloy pig weighed into about 65g with vacuum non-consumable arc furnace melting, fills high-purity argon gas protection, and alloy is overturn the alloy pig that uniform composition is made in melt back for 6 times during melting;
(2) above-mentioned alloy pig is carried out repeatedly hot pressing at 700 DEG C, be processed into base material, object is broken thick as-cast grain structure;
(3) base material is after scale removal and pickling, in a vacuum air cooling after the β phase Homogenization Treatments 0.5 ~ 1h of 1030 ~ 1050 DEG C; With after through 700 DEG C of hot rollings, first scale removal after hot rolling, pickling remove grease, then air cooling after the β phase of 1030 ~ 1050 DEG C is incubated 0.5 ~ 1h in a vacuum;
(4) base material carries out repeatedly cold rolling after β phase region insulation air cooling, and each cold roling reduction is not more than 40%, finally carries out 580 DEG C of final annealing 2h in a vacuum, all carries out pickling and washed with de-ionized water before each thermal treatment.
The zircalloy prepared by above-mentioned technique and the Zr-4 alloy sample prepared through same process are together put into autoclave, respectively at the 360 DEG C/18.6MPa/0.01MLiOH aqueous solution, corrosion test is carried out in 360 DEG C/18.6MPa/ deionized water, investigate their corrosion behavior, surrosion curve as shown in Figure 1.As can be seen from accompanying drawing 1 (a): when corroding 300 days (d) in the 360 DEG C/LiOH aqueous solution, the present invention adds 0.05 respectively in zircalloy simultaneously, 0.1, the surrosion of 0.2wt.%Cu and Ge alloy, be respectively 146.98mg.dm
-2, 151.84mg.dm
-2and 180.73mg.dm
-2, Zr-4 alloy sample is 260.65mg.dm
-2.The corrosion resistance nature of alloy in the 360 DEG C/18.6MPa/0.01MLiOH aqueous solution simultaneously adding Cu and Ge is obviously better than Zr-4 alloy.As can be seen from accompanying drawing 1 (b): when corroding 390 days (d) in 360 DEG C/18.6MPa deionized water, the present invention adds 0.05 respectively in zircalloy simultaneously, 0.1, the surrosion of 0.2wt.%Cu and Ge alloy is respectively 99.94mg.dm
-2, 105.78mg.dm
-2and 120.06mg.dm
-2, Zr-4 alloy sample is 108.4mg.dm
-2.In addition, only need to add a small amount of Cu and Ge element in alloying constituent of the present invention and just can improve the corrosion resistance nature of zirconium alloy in the 360 DEG C/18.6MPa/0.01MLiOH aqueous solution and in 360 DEG C/18.6MPa deionized water, and there is good processing characteristics.
Claims (3)
1. the zircalloy that fuel for nuclear power plant involucrum cupric is germanic, is characterized in that the chemical constitution of this zirconium alloy is by weight percentage: 0.5% ~ 1.5%Sn, 0.01% ~ 0.4%Fe, 0.01% ~ 0.3%Cr, 0.01% ~ 0.4%Cu, 0.01% ~ 0.5%Ge, surplus is Zr.
2., by the zircalloy that fuel for nuclear power plant involucrum cupric according to claim 1 is germanic, it is characterized in that: by weight percentage, 0.7% ~ 1.5%Sn, 0.05% ~ 0.4%Fe, 0.03% ~ 0.2%Cr, 0.03% ~ 0.3%Cu, 0.03% ~ 0.3%Ge, surplus is Zr.
3., by the zircalloy that fuel for nuclear power plant involucrum cupric according to claim 1 is germanic, it is characterized in that: by weight percentage, 0.9% ~ 1.2%Sn, 0.1% ~ 0.3%Fe, 0.05% ~ 0.15%Cr, 0.05% ~ 0.2%Cu, 0.05% ~ 0.25%Ge, surplus is Zr.
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| CN104911378A (en) * | 2015-05-25 | 2015-09-16 | 常熟锐钛金属制品有限公司 | Preparation method of zirconium pipe special for nuclear reactor |
| CN105568057B (en) * | 2016-01-06 | 2020-04-28 | 中国核动力研究设计院 | Zirconium alloy for nuclear reactor cladding material |
| CN105568056B (en) * | 2016-01-06 | 2020-08-25 | 中国核动力研究设计院 | Zirconium alloy for pressurized water reactor fuel element cladding |
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| CN102766778B (en) * | 2011-05-04 | 2015-05-06 | 上海大学 | Zircaloy for fuel cladding at nuclear power station |
| CN102925750B (en) * | 2012-10-25 | 2015-10-07 | 上海大学 | The germanic zirconium-niobium alloy of fuel for nuclear power plant involucrum |
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