CN103074521A - Palladium-containing zirconium alloy for fuel cladding in nuclear power station - Google Patents
Palladium-containing zirconium alloy for fuel cladding in nuclear power station Download PDFInfo
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- CN103074521A CN103074521A CN2013100148767A CN201310014876A CN103074521A CN 103074521 A CN103074521 A CN 103074521A CN 2013100148767 A CN2013100148767 A CN 2013100148767A CN 201310014876 A CN201310014876 A CN 201310014876A CN 103074521 A CN103074521 A CN 103074521A
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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
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Abstract
The invention relates to palladium-containing zirconium alloy for a fuel cladding in a nuclear power station and belongs to the technical field of zirconium alloy materials. The zirconium alloy comprises the following chemical compositions in percentage by weight: 0.5-1.5 percent Sn, 0.05-0.4 percent of Fe, 0.05-0.3 percent of Cr, 0.01-0.5 percent of Pd and the balance of Zr; the preferable range of the zirconium alloy is: 0.7-1.5 percent of Sn, 0.2-0.4 percent of Fe, 0.05-0.15 percent of Cr, 0.03-0.3 percent of Pd and the balance of Zr. The palladium-containing zirconium alloy shows excellent corrosion resistance in 360 DEG C/18.6 MPa/0.01MLiOH aqueous solution, is obviously superior to Zr-4 alloy, is good in processability and can be used as materials for the fuel element cladding, a grillwork and other reactor core structure bodies in a pressurized water reactor in the nuclear power station.
Description
Technical field
The present invention relates to a kind of pressurized-water reactor nuclear power plant fuel sheath with the zirconium alloy that contains palladium, belong to the Zirconium alloy material technical field.
Background technology
Zirconium alloy is because its thermal neutron absorption cross section is little, 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.Along with the power producer technology prolongs refulling cycle and the future development that reduces fuel cycle cost, raising reactor thermo-efficiency, raising safe reliability towards the raising fuel burnup, performance to key core parts fuel element can material zirconium alloy is had higher requirement, comprise corrosion resistance nature, hydrogen sucking function, mechanical property and irradiation dimensional stability etc., wherein, it is crucial improving zirconium alloy water side corrosion resistance nature.
At present on the engineering novel zirconium alloy of application and development to mainly contain Zr-Sn system, Zr-Sn-Nb system and Zr-Nb be that three large zirconium alloys are serial.Because the requirement that the Zr-4 alloy can not satisfy the high burnup fuel assembly and prolong the refulling cycle, therefore, many countries have carried out improving the corrosion resistance nature research of Zr-4 alloy.To Zr-Nb system, the novel zirconium alloys such as M5, HANA-6, E110 have been developed after in the Zr-1%Nb alloy, adding the elements such as O, Cu, S.By the research and development of French Fa Matong company the M5 alloy be the cladding tubes of the AFM-3G fuel assembly of (55-60) GWd/MTU as design burn-up, erosion rate is little under high burnup, inhale hydrogen and lack than improving Zr-4, irradiation growth is lower than improving Zr-4, and the anti-uniform corrosion performance of this alloy is better than improving the Zr-4 alloy.
Taken into account the advantage of Zr-Sn and two kinds of alloys of Zr-Nb by the ZIRLO alloy (Zr-1.0Sn-1.0Nb-0.1Fe) of US Westinghouse company's exploitation.Make the fuel assembly of involucrum with the ZIRLO alloy, operation in No. 1 heap of Bei'an Na (North Anna), measured burnup and be the oxidated layer thickness on 37.8 GWd/tU and two assembly fuel sticks of 45.8 GWd/tU, the result shows, no matter hanging down burnup, or than high burnup, the oxidated layer thickness of the ZIRLO alloy cladding all zone of oxidation than the Zr-4 alloy is much thin.The mechanical property of ZIRLO alloy and Zr-4 alloy are basic identical, but in heap under the operational conditions, fuel sheath irradiation growth and creep ratio Zr-4 alloy are little, and irradiation growth is less by 40%～60% than Zr-4 alloy, and irradiation creep is than Zr-4 alloy low 20%.
In the research and development of new zirconium alloy, usually filter out the alloy of fine corrosion resistance by out-pile autoclave corrosion test first, and then make fuel stick and be placed on and carry out Irradiation Test in the test reactor, understand its corrosion behavior in heap.Owing in a Loop Water, having added H during the pressurized-water reactor nuclear power plant operation
3BO
3, use
10B controls and regulates superfluous nuclear reactivity as burnable poison, for the release that reduces various steel corrosion of component products in the loop and the migration of radioactive substance, reduce staff's raying dosage level, needs to adopt alkalescent water (pH 7.1～7.2).For this reason, adding H in the Loop Water
3BO
3The time, regulate the pH value with adding LiOH again.Abroad when the corrosion behavior of research new zirconium alloy, also find: because the variation of alloying constituent, can not judge the corrosion resistance nature of new zirconium alloy in pressurized-water reactor (PWR) with the experiment in 400 ℃ of superheated vapours of out-pile autoclave, and the test-results in the high-temperature high pressure water that adds LiOH more can represent the corrosion behavior in PWR.
Summary of the invention
The purpose of this invention is to provide the fuel for nuclear power plant involucrum zirconium alloy that contains palladium of a kind of fine corrosion resistance and good processability, this zirconium alloy can be used as the structured materials such as fuel element can, screen work in PWR of Nuclear Power Station.
The objective of the invention is that alloying element Pd realizes by adding, its technical scheme is as follows:
A kind of fuel for nuclear power plant involucrum zirconium alloy that contains palladium, the chemical constitution of this zirconium alloy is by weight percentage: 0.5%～1.5%Sn, 0.05%～0.4%Fe, 0.05%～0.3%Cr, 0.01%～0.5%Pd, surplus is Zr.
The above-mentioned fuel for nuclear power plant involucrum zirconium alloy that contains palladium, by weight percentage, 0.7%～1.5%Sn, 0.2%～0.4%Fe, 0.05%～0.15%Cr, 0.03%～0.3%Pd, surplus is Zr.
The above-mentioned fuel for nuclear power plant involucrum zirconium alloy that contains palladium, its Pd content by weight percentage preferable range is: 0.05%～0.2% Pd.
Effect of the present invention: application example provided by the invention shows, when alloy corrodes in 360 ℃/18.6 MPa/0.01 M LiOH aqueous solution, show very good corrosion resistance nature, obviously be better than the Zr-4 alloy, corrosion is in the time of 130 days in the 360 ℃/LiOH aqueous solution, and the surrosion of zirconium alloy of the present invention is 61mg.dm
-2, and the surrosion of Zr-4 alloy is just up to 203 mg.dm
-2When zirconium alloy of the present invention continued to erode to 310 days, surrosion also only had 156mg.dm
-2In addition, only add a small amount of Pd element in the alloying constituent of the present invention and just can obviously improve the corrosion resistance nature of zirconium alloy in the 360 ℃/LiOH aqueous solution, and have good processing characteristics.
Description of drawings
Fig. 1 is zirconium alloy and the surrosion curve of Zr-4 alloy in 360 ℃/18.6MPa/0.01 M LiOH aqueous solution that the present invention contains palladium.
Embodiment
Below in conjunction with embodiment the zirconium alloy that contains palladium of fine corrosion resistance of the present invention is described in further detail.
Embodiment 1
Table 1 has provided the one-tenth that three kinds of typical cases according to the present invention contain the Zirconium alloy material of palladium and has been grouped into.
Having the alloy material that forms in the table 1 all prepares in accordance with the following steps:
(1) by above-mentioned prescription batching, into about the heavy alloy pig of 65g, fills the high-purity argon gas protection with the vacuum non-consumable arc furnace melting during melting, and the alloy melt back of overturning is made alloy pig 6 times;
(2) above-mentioned alloy pig is carried out repeatedly hot pressing under 700 ℃, be processed into the base material, purpose is broken thick as-cast grain structure;
(3) the base material is through after scale removal and the pickling, in a vacuum air cooling after 1030～1050 ℃ β phase homogenizing is processed 0.5～1 h; With by 700 ℃ of hot rollings, first pickling scale removal and grease after the hot rolling, again air cooling after 1030～1050 ℃ β phase homogenizing is processed 0.5～1 h in a vacuum;
(4) carry out repeatedly behind the base material air cooling cold rolling, and repeatedly process annealing.Each cold roling reduction is not more than 40%, carries out in a vacuum 580 ℃ ~ 600 ℃ process annealing 1h between cold rolling per twice.Carry out in a vacuum at last 580 ℃ of recrystallization annealing 50 h, all carry out pickling and washed with de-ionized water before each process annealing or the recrystallization annealing.
To together put into autoclave with the Zr-4 alloy sample for preparing through same process by the zirconium alloy of above-mentioned technique preparation, in 360 ℃/18.6 MPa/0.01 M LiOH aqueous solution, carry out corrosion test, investigate their corrosion behavior, the surrosion curve as shown in Figure 1, can find out from accompanying drawing 1: when the 360 ℃/LiOH aqueous solution, corroding, the present invention adds respectively 0.05,0.1 in the Zr alloy, the surrosion of 0.2wt.% Pd alloy, is respectively 63 mg.dm in 130 days
-2, 61 mg.dm
-2With 65 mg.dm
-2, be respectively 158 mg.dm in 310 days
-2, 156 mg.dm
-2With 176 mg.dm
-2And 130 days weightening finish of Zr-4 alloy corrosion is just up to 203 mg.dm
-2Document (Sabol, G. P., Comstock, R. J., Weiner, R. A., et al, In-reactor corrosion performance of ZIRLO and Zircaloy-4. Zirconium in the Nuclear Industry:Tenth International Symposium, ASTM STP 1245,1994, pp. 724-744) the ZIRLO alloy that provides corrosion data in the 360 ℃/LiOH aqueous solution shows: 130 days and surrosion in 310 days are respectively 93 mg.dm
-2With 187 mg.dm
-2Therefore, the corrosion resistance nature of alloy of the present invention in the 360 ℃/M LiOH aqueous solution obviously is better than Zr-4 and ZIRLO alloy.In addition, only need to add a small amount of Pd element in the alloying constituent of the present invention and just can obviously improve the corrosion resistance nature of zirconium alloy in the 360 ℃/LiOH aqueous solution, as seen, when optimizing the zirconium alloy composition, after adding alloying element Pd, can reduce alloying element addition total when making zirconium alloy reach excellent corrosion resistance, thereby the process industrial art performance of zirconium alloy is improved.
Claims (3)
1. a fuel for nuclear power plant involucrum is characterized in that the chemical constitution of this zirconium alloy is by weight percentage with the zirconium alloy that contains palladium: 0.5%～1.5%Sn, and 0.05%～0.4%Fe, 0.05%～0.3%Cr, 0.01%～0.5%Pd, surplus is Zr.
2. by the fuel for nuclear power plant involucrum claimed in claim 1 zirconium alloy that contains palladium, it is characterized in that: by weight percentage, 0.7%～1.5%Sn, 0.2%～0.4%Fe, 0.05%～0.15%Cr, 0.03%～0.3%Pd, surplus is Zr.
3. by the fuel for nuclear power plant involucrum claimed in claim 2 zirconium alloy that contains palladium, it is characterized in that Pd content is 0.05%～0.2% by weight percentage.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01215943A (en) * | 1988-02-24 | 1989-08-29 | Sumitomo Metal Ind Ltd | High corrosion-resistant zirconium alloy |
| CN1045480A (en) * | 1989-01-23 | 1990-09-19 | 法玛通公司 | Anticorrosive and wear and tear fuel assembly for nuclear reactor rod |
| US20120201341A1 (en) * | 2011-02-04 | 2012-08-09 | Battelle Energy Alliance, Llc | Zirconium-based alloys, nuclear fuel rods and nuclear reactors including such alloys, and related methods |
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- 2013-01-16 CN CN2013100148767A patent/CN103074521A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01215943A (en) * | 1988-02-24 | 1989-08-29 | Sumitomo Metal Ind Ltd | High corrosion-resistant zirconium alloy |
| CN1045480A (en) * | 1989-01-23 | 1990-09-19 | 法玛通公司 | Anticorrosive and wear and tear fuel assembly for nuclear reactor rod |
| US20120201341A1 (en) * | 2011-02-04 | 2012-08-09 | Battelle Energy Alliance, Llc | Zirconium-based alloys, nuclear fuel rods and nuclear reactors including such alloys, and related methods |
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