CN103898367A - Zirconium-based alloy for nuclear reactor core - Google Patents
Zirconium-based alloy for nuclear reactor core Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 126
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 111
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 41
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 22
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 18
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 32
- 239000004615 ingredient Substances 0.000 claims description 18
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- 238000000034 method Methods 0.000 claims description 13
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- 238000012545 processing Methods 0.000 claims description 7
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- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000005482 strain hardening Methods 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 54
- 230000007797 corrosion Effects 0.000 abstract description 54
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 238000012360 testing method Methods 0.000 abstract description 9
- 229910008933 Sn—Nb Inorganic materials 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000010955 niobium Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 16
- 239000011651 chromium Substances 0.000 description 16
- 238000005275 alloying Methods 0.000 description 9
- 230000003628 erosive effect Effects 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 230000002411 adverse Effects 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910052758 niobium Inorganic materials 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
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- 238000005253 cladding Methods 0.000 description 4
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
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- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
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- RETIMRUQNCDCQB-UHFFFAOYSA-N mepivacaine hydrochloride Chemical compound Cl.CN1CCCCC1C(=O)NC1=C(C)C=CC=C1C RETIMRUQNCDCQB-UHFFFAOYSA-N 0.000 description 1
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- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention specifically relates to a zirconium-based alloy for a nuclear reactor core structural material, belonging to the technical field of special alloy materials. The zirconium-based alloy comprises, by weight, 0.20 to 0.60% of Sn, 0.10 to 0.25% of Nb, 0.30 to 0.50% of Fe, 0.20 to 0.30% of Cr, 0 to 0.1% of As, Sb or Bi, 0 to 0.03% of Si or S, 0.06 to 0.15% of O, less than 0.008% of C, less than 0.006% of N, with the balance being zirconium. According to the invention, on the basis of a Zr-Sn-Nb alloy, other components used for improving alloy performance are added and proper component contents are selected, so the corrosion resistance, mechanical properties and radiation resistance of the zirconium-based alloy are improved; the performance of the zirconium-based alloy meets requirements of high burn-up of a nuclear reactor on a core structural material. The zirconium-based alloy has improved homogeneous corrosion resistance in pure water out of a reactor, especially in an aqueous lithium hydroxide solution. According to test results, it is considered that the zirconium-based alloy has more excellent homogeneous corrosion resistance, high creep resistance and fatigue resistance and anti-irradiation growth performance when used in a reactor.
Description
Technical field
The invention belongs to special alloy material technology field, be specifically related to a kind of zirconium base alloy for power producer core structural material.
Background technology
Zirconium alloy is widely used as power producer fuel element can and other in-pile components owing to having low, the good advantage such as corrosion resistance and mechanical property in neutron-absorption cross-section.In the evolution of pressurized water reactor, fuel design, to reactor core structure parts, as fuel element can, screen work, guide pipe etc., has proposed very high requirement, and early stage, these parts are made up of Zr-4 alloy conventionally.The design of high fuel burnup, require to extend the residence time and the raising coolant temperature of these parts in heap, thereby make zirconium alloy parts be faced with more harsh corrosive environment, these high requests have promoted the research of the corrosion resistance nature that improves Zr-4 alloy, have promoted the exploitation of the novel zirconium alloy to having better corrosion resistance nature.
The high request that development proposes fuel sheath for Nuclear Power Technology, has launched the research of novel zirconium alloy in the world.As in the tenth zirconium alloy international symposium, GEORGE P.SABOL has reported " the in-pile corrosion behavior of ZIRLO and Zr-4 alloy " (" In-Reactor Corrosion Performance of ZIRLO andZircaloy-4 ", Zirconium in the Nuclear Industry:Tenth International Symposium, ASTM STP1245, A.M.Garde and E.R.Bradley, Eds., American Society for Testingand Materials, Philadelphia, 1994, pp.724-744), show that ZIRLO has corrosion resistance nature in better heap than Zircaloy-4.Muscovite Nikulina in the 11 zirconium alloy international symposium, A.V. reported " as the E635 zirconium alloy of VVER and RBMK reactor fuel rod involucrum and component materials " (" Zirconium Alloy E635 as a Material for Fuel Rod Cladding and OtherComponents of VVER and RBMK Cores ", Zirconium in the Nuclear Industry:Eleventh International Symposium, ASTM STP 1295, E.R.Bradley and G.P.Sabol, Eds., American Society for Testing and Materials, Philadelphia, 1996, pp.785-804), the composition of having announced E635 is Zr-1.0～1.4wt%Nb-0.9～1.1wt%Sn-0.3～0.5wt%Fe.The out-of-pile performances of this alloy is better than Zircaloy-4 and E110 alloy.In the 12 zirconium alloy international symposium, the Jean-Paul Mardon of France has reported " impact on M5 alloy Cladding materials of composition and manufacturing process " (" Influence of Composition and Fabrication Process on Out-of-Pile and In-PileProperties of M5 Alloy, Zirconium in the Nuclear Industry:Twelfth InternationalSymposium, ASTM STP 1354, Sabol, G, P, Moan, G.D., Eds., American Society forTesting and Materials, West Conshohocken, 2000, pp.505 ~ 524), announce the M5 alloy (Zr-1Nb-O) that under high burnup (> 65GWd) corrosion resistance nature is better than Zircaloy-4.In the 16 zirconium alloy international symposium, the A.M.Garde of the U.S. has reported " pressurized-water reactor Advanced Zirconium Alloys " (" Advanced Zirconium Alloy for PWR Application; Zirconium in the NuclearIndustry:sixteenth International Symposium; ASTM STP 1529; 2010; pp.784 ~ 826), has announced the X5A alloy (Zr-0.5Sn-0.3Nb-0.35Fe-0.25Cr) that Cladding materials is better than ZIRLO alloy.
There are some researches show, in existing zirconium alloy, the proportioning of composition might not be in optimized scope, after the Sn content in ZIRLO alloy is reduced, its corrosion resistance nature further improves (Yueh, H.K., Kesterson, R.L., Comstock, R.J., et al., Improved ZIRLOTM cladding performancethrough chemistry and process modifications.Zirconium in the Nuclear Industry:Fourteenth International Symposium, ASTM STP1467,2004, pp.330-346.); In Zr-Nb alloy, add micro-Cu(0.05wt%) after form HANA-6 alloy also there is very good corrosion resistance nature (Park J.Y., Choi, B.K., Yoo, S.J.Jeong Y.H., Corrosion behaviorand oxide properties of Zr-1.1wt%Nb-0.05wt%Cu alloy, J.Nucl.Mater., 359 (2006) 59 – 68.); In heap, in operational process, there is the unusual phenomenon such as fuel stick or fuel assembly bending and anti-irradiation growth poor performance in M5 alloy, therefore France has added a small amount of Sn and Fe on M5 alloying constituent basis, in mechanical property, the especially creep and the irradiation growth performance that keep significantly having improved on alloy excellent corrosion resistance basis alloy.Therefore, optimized alloy composition proportion or add other alloying element and also can develop the better zirconium alloy of corrosion resistance nature, the needs that improve constantly to meet burnup on the basis of existing zirconium alloy.
In addition, after alloying constituent is determined, adopt suitable heat processing technique can also further improve the corrosion resistance nature of alloy.In the higher zirconium alloy of Nb content, comprise ZIRLO, M5 and N36 etc., when improving after hot worked temperature, due to super saturated solid solution Nb in the alligatoring of second-phase and uneven distribution and alloy substrate, can cause corrosion resistance nature variation, thereby all emphasize to adopt " machining at low temperature technique " (Mardon, J.P., Charquet, D., and Senevat, J., Influence of composition and fabrication processon out-of-pile and in-pile properties of M5 alloy.Zirconium in the Nuclear Industry:Twelfth International Symposium, ASTM STP1354, 2000, pp.505-524.).Adopt the machining at low temperature technique of lower extrusion temperature and annealing temperature can obtain the second-phase tissue of small and dispersed, significantly improved corrosion and mechanical property, the especially corrosion resistance nature of alloy.
It has been generally acknowledged that for resistance to all even nodular corrosions of the zirconium alloy of nuclear reactor structured material be most important corrosive nature requirement.Corrosive nature at out-pile inspection zirconium alloy comprises: 360 ° of C deionized waters; 360 ° of C are containing the lithium aqueous solution; The corrosion test of 400 ° of C, 500 ° of C steam.Although people can accept following viewpoint: the material that test is up to the standards in 360 ° of C aqueous solution and 400 ° of C steam can be used for pressurized-water reactor, 360 ° of C are containing qualified being more suitable in the high lithium concentration operating mode of pressurized-water reactor of experimental examination in the lithium aqueous solution, experimental examination in 500 ° of above steam of C qualified applicable in boiling-water reactor; And, in above-mentioned published document, all prove by test example, relevant zirconium alloy zirconium-2 and zirconium-4 alloy more in the past has more excellent performance, but whether these alloys can really be applied in the middle of practice, and it is still unknown to show satisfactory technique effect.And above-mentioned document does not all provide about the anti-nodular corrosion behavior of alloy in 500 ° of C steam yet.
Summary of the invention
The technical problem to be solved in the present invention is to provide the zirconium base alloy for power producer core structural material a kind of novelty, that have good corrosion resistance.
In order to realize this purpose, the technical scheme that the present invention takes is:
A kind of zirconium base alloy for power producer core structural material, percentage composition meter by weight, formed by following ingredients: Sn:0.20-0.60, Nb:0.10-0.25, Fe:0.30-0.50, Cr:0.20-0.30, As or Sb or Bi:0-0.1, Si or S:0-0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of zirconium base alloy for power producer core structural material, percentage composition meter by weight, formed by following ingredients: Sn:0.20-0.40, Nb:0.10-0.25, Fe:0.35-0.50, Cr:0.20-0.30, As or Sb or Bi:0-0.1, Si or S:0-0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
A kind of zirconium base alloy for power producer core structural material, percentage composition meter by weight, formed by following ingredients: Sn:0.20-0.40, Nb:0.10-0.25, Fe:0.35-0.50, Cr:0.20-0.30, As or Sb or Bi:0-0.1, Si or S:0.01-0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
A kind of zirconium base alloy for power producer core structural material, percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.60, Nb:0.10-0.25, Fe:0.30-0.50, Cr:0.20-0.30, As or Sb or Bi: be less than 0.1, Si or S: be less than 0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
A kind of zirconium base alloy for power producer core structural material, percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.60, Nb:0.10-0.25, Fe:0.30-0.50, Cr:0.20-0.30, As or Sb or Bi: be less than 0.1, Si or S:0.005-0.02, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
For a zirconium base alloy for power producer core structural material, percentage composition meter by weight, is made up of following ingredients: Sn:0.40, Nb:0.20, Fe:0.40, Cr:0.25, Si or S:0.01, O:0.10, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
The preparation method of a kind of used by nuclear reactor Zirconium alloy material as above, comprises the following steps:
(1) the various components in zirconium alloy are prepared burden according to the formula ratio of alloy compositions;
(2) in vacuum consumable electrode arc furnace, carry out melting, make alloy cast ingot;
(3) alloy cast ingot is forged into the base material of desired shape at the β of 900 ° of C-1050 ° of C phase region;
(4) by base material in the β of 1000 ° of C-1100 ° of C phase region homogeneous heating, and carry out quench treatment;
(5) the base material after quenching is carried out to hot-work in the alpha phase zone of 600 ° of C-700 ° of C;
(6) the base material after hot-work is carried out to cold working, and carry out process annealing at 560 ° of C-650 ° of C;
(7) in 480 ° of C-620 ° of C, carry out stress relieving or recrystallization annealing processing, obtain described Zirconium alloy material.
The present invention is on Zr-Sn-Nb alloy basis, other are added for improving the composition of alloy property, and select suitable component concentration, especially for the addition control of Sn, Nb, Fe, As, Bi, Si, Sb, S, both improved the corrosion resistance nature of alloy, improved again mechanical property and the anti-radiation performance of alloy, alloy property provided by the invention, meets the requirement of power producer high burnup to core structural material.The alloy material of being prepared by this prototype alloy has improved in the particularly resistance to uniform corrosion performance in lithium hydroxide aqueous solution of out-pile pure water.By the test detected result in embodiment, can think these alloys in reactor, use there is better resistance to uniform corrosion performance, higher creep resistance and fatigue characteristic, anti-irradiation growth performance.
Embodiment
Below by embodiment, the present invention is described in more detail.
To the Zirconium alloy material for nuclear reactor, the corrosion resistance nature of alloy is the factor of overriding concern, when production cost and workability are selected alloying element on this basis, to consider, therefore, need to study the impact of each alloying element on erosion resistance, mechanical property and creep behaviour and the amount ranges of alloy system and every kind of alloying element in great detail.Zirconium base alloy of the present invention, has better resistance to all even Nodular Corrosions, has higher creep resistance and fatigue characteristic, has anti-irradiation growth performance, and particular case is as follows:
(1) zirconium (Zr)
By the consideration to neutron absorption factor, the present invention selects zirconium as fundamental element, also considers the neutron-absorbing situation of adding other alloying elements in basic zirconium to simultaneously.
(2) tin (Sn)
Tin can stabilised zirconia α-phase, can increase its intensity, and can offset the deleterious effect of nitrogen to corrosion.In the time that tin consumption is few, can not reach required effect.In the present invention, Sn adds content in 0.20-0.60 % by weight, and it can ensure that alloy has good corrosion resistance nature and good mechanical property.
(3) niobium (Nb)
Niobium can stabilised zirconia β-phase, niobium has higher strengthening effect to zirconium.Niobium consumption is crossed multipair thermal treatment sensitivity.In the present invention, Nb adds content in 0.10-0.25 % by weight, and it can ensure that alloy has good corrosion resistance nature and good mechanical property in pure water and lithium hydroxide aqueous solution.
(4) iron (Fe)
Iron can improve alloy corrosion resistance and mechanical property, but the consumption of iron is too much or very fewly all can have an adverse influence.The content that in the present invention, Fe adds is in 0.30-0.50 % by weight, and it can ensure that alloy has good corrosion resistance nature in pure water and lithium hydroxide aqueous solution.
(5) chromium (Cr)
Chromium can improve alloy corrosion resistance and mechanical property, but the consumption of iron is too much or very fewly all can have an adverse influence.The content that in the present invention, chromium adds is in 0.20-0.30 % by weight, and it can ensure that alloy has good corrosion resistance nature in pure water and lithium hydroxide aqueous solution.
(6) arsenic (As)
Arsenic can improve alloy corrosion resistance energy, but consumption too much has adverse influence.The arsenic content adding in the present invention is less than 0.1 % by weight, and it can ensure that alloy has good corrosion resistance nature in pure water and lithium hydroxide aqueous solution.
(7) bismuth (Bi)
Bismuth can improve alloy corrosion resistance energy, but consumption too much has adverse influence.The bi content adding in the present invention is less than 0.1 % by weight, and it can ensure that alloy has good corrosion resistance nature in pure water and lithium hydroxide aqueous solution.
(8) antimony (Sb)
Antimony can improve alloy corrosion resistance energy, but consumption too much has adverse influence.The antimony content adding in the present invention is less than 0.1 % by weight, and it can ensure that alloy has good corrosion resistance nature in pure water and lithium hydroxide aqueous solution.
(9) silicon (Si)
Silicon can affect being uniformly distributed of alloy precipitated phase, thereby the consumption of silicon too much has adverse influence.In the present invention, the silicone content of interpolation is less than to 0.03 % by weight, it can ensure that alloy has good corrosion resistance nature in lithium hydroxide aqueous solution.
(10) sulphur (S)
In alloy, add appropriate S and can improve alloy creep intensity, improve the corrosion resistance of alloy simultaneously.But the consumption of sulphur too much has adverse influence.In the present invention, the sulphur content of interpolation is less than to 0.03 % by weight, it can ensure in alloy high-temp water vapour, to have good corrosion resistance nature.
(11) oxygen (O)
Oxygen can stabilised zirconia α-phase, in alloy, add oxygen and can improve yield strength.The content that in the present invention, oxygen adds is in 0.06-0.15 % by weight, and it can ensure that alloy has enough mechanical propertys and creep-resistant property.The increase of oxygen level, greatly reduces the control difficulty in material processing.
(12) carbon (C)
When carbon in alloy exists as inevitable impurity element and content is higher, low-alloyed corrosion resistance can fall.In the present invention, the weight percent of C is less than 0.008%, and it can ensure that alloy has good corrosion resistance nature in high temperature water and steam.
(13) nitrogen (N)
When nitrogen in alloy exists as inevitable impurity element and content is higher, low-alloyed corrosion resistance can fall.In the present invention, the weight percent of N is less than 0.006%, and it can ensure that alloy has good corrosion resistance nature in high temperature water and steam.
Concrete, technical scheme of the present invention is:
A kind of zirconium base alloy for power producer core structural material, percentage composition meter by weight, formed by following ingredients: Sn:0.20-0.60, Nb:0.10-0.25, Fe:0.30-0.50, Cr:0.20-0.30, As or Sb or Bi:0-0.1, Si or S:0-0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of zirconium base alloy for power producer core structural material, percentage composition meter by weight, formed by following ingredients: Sn:0.20-0.40, Nb:0.10-0.25, Fe:0.35-0.50, Cr:0.20-0.30, As or Sb or Bi:0-0.1, Si or S:0-0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
A kind of zirconium base alloy for power producer core structural material, percentage composition meter by weight, formed by following ingredients: Sn:0.20-0.40, Nb:0.10-0.25, Fe:0.35-0.50, Cr:0.20-0.30, As or Sb or Bi:0-0.1, Si or S:0.01-0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
A kind of zirconium base alloy for power producer core structural material, percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.60, Nb:0.10-0.25, Fe:0.30-0.50, Cr:0.20-0.30, As or Sb or Bi: be less than 0.1, Si or S: be less than 0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
A kind of zirconium base alloy for power producer core structural material, percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.60, Nb:0.10-0.25, Fe:0.30-0.50, Cr:0.20-0.30, As or Sb or Bi: be less than 0.1, Si or S:0.005-0.02, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
For a zirconium base alloy for power producer core structural material, percentage composition meter by weight, is made up of following ingredients: Sn:0.40, Nb:0.20, Fe:0.40, Cr:0.25, Si or S:0.01, O:0.10, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
Zirconium base alloy for power producer core structural material provided by the invention, is by optimizing Zr-Sn-Nb alloying constituent proportioning when, adds the elements such as micro-As, Bi, Si, Sb, S, to carry heavy alloyed corrosion resistance nature.
Table 1 is the composition of alloy provided by the present invention, and in table, 17* is Zr-4 alloy composition and corresponding experimental examination result, and in table 1, each content is the weight percent of respective components in alloy.
Table 1 alloy composition provided by the present invention
The preparation method of a kind of used by nuclear reactor Zirconium alloy material as above, comprises the following steps:
(1) the various components in zirconium alloy are prepared burden according to the formula ratio of alloy compositions;
(2) in vacuum consumable electrode arc furnace, carry out melting, make alloy cast ingot;
(3) alloy cast ingot is forged into the base material of desired shape at the β of 900 ° of C-1050 ° of C phase region;
(4) by base material in the β of 1000 ° of C-1100 ° of C phase region homogeneous heating, and carry out quench treatment;
(5) the base material after quenching is carried out to hot-work in the alpha phase zone of 600 ° of C-700 ° of C;
(6) the base material after hot-work is carried out to cold working, and carry out process annealing at 560 ° of C-650 ° of C;
(7) in 480 ° of C-620 ° of C, carry out stress relieving or recrystallization annealing processing, obtain described Zirconium alloy material.
The material of preparing by above-mentioned complete processing, by waiting α-Zr crystal grain of axle and the microtexture that equally distributed tiny second phase particles forms, can ensure in the environment of reactor core harshness, to have good use properties.The alloy material of preparing by aforesaid method, its performance test results is as shown in table 2, table 3, table 4 and table 5.Test conditions described in table 2 is specially: etching condition is 360 ° of C, 18.6MPa deionized water; Test conditions described in table 3 is: 360 ° of C, 18.6MPa are containing the 70 μ g/g lithium aqueous solution (joining in deionized water with lithium hydroxide form); Table 4 and table 5 respectively described test conditions are 400 ° of C, 10.3MPa deionized water steam and 500 ° of C, 10.3MPa deionized water steam.Etching time in 360 ° of C water and 400 ° of C steam ambient is respectively 300 days (d), and the etching time in 500 ° of C steam ambient is 500 hours (h) (reference alloy is 24 hours).In table, provide the erosion rate (mg/dm of every kind of alloy
2/ d), for the ease of comparing the relative performance of alloy, and in table, provide relative erosion rate.Can find out in (2,3,4,5) from table, all alloys are at 360 ° of C pure water, lithium hydroxide aqueous solution, and have all shown good corrosion resistance nature in 400 ° of C and 500 ° of C steam.
Table 2 alloy material provided by the present invention corrodes the erosion rate after 300 days in 360 ° of C deionized waters
Table 3 alloy material provided by the present invention contains in the 70 μ g/g lithium aqueous solution at 360 ° of C
Corrode the erosion rate after 300 days
Table 4 alloy material provided by the present invention corrodes the erosion rate after 300 days in 400 ° of C steam
Table 5 alloy material provided by the present invention corrodes the erosion rate after 500h in 500 DEG C of steam
From table 2, table 3, table 4, can find out, alloy material provided by the present invention, in 360 DEG C of pure water, lithium hydroxide aqueous solution, and has shown good corrosion resistance nature in 400 DEG C and 500 DEG C of steam.
In sum, application example provided by the invention shows, alloy of the present invention all shows very good corrosion resistance nature while corrosion under above-mentioned 4 kinds of water chemistry conditions, the erosion rate in 360 DEG C/18.6MPa deionized water, the 360 DEG C/18.6MPa LiOH aqueous solution, 400 DEG C/10.3MPa and 500 DEG C/10.3MPa superheated vapour is obviously better than Zr-4 alloy.
Because the present invention has adopted the composition range of preferred Sn, Nb, Fe and As, Bi, Si, Sb, S, interaction between alloying element within the scope of this, in conjunction with machining at low temperature technique, produce prior beyond thought effect, this effect is mainly manifested in two aspects: when 1) alloy of the present invention corrodes under above-mentioned 4 kinds of water chemistry conditions, all show very good corrosion resistance nature, be obviously better than Zr-4 alloy.2) alloy of the present invention has obtained the second-phase that small and dispersed distributes after low temperature process processing, has improved mechanical property (as creep and fatigue property) and the anti-irradiation growth performance of alloy.
Claims (7)
1. the zirconium base alloy for power producer reactor core, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.20-0.60, Nb:0.10-0.25, Fe:0.30-0.50, Cr:0.20-0.30, As or Sb or Bi:0-0.1, Si or S:0-0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
2. a kind of zirconium base alloy for power producer reactor core as claimed in claim 1, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.20-0.40, Nb:0.10-0.25, Fe:0.35-0.50, Cr:0.20-0.30, As or Sb or Bi:0-0.1, Si or S:0-0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
3. a kind of zirconium base alloy for power producer reactor core as claimed in claim 1, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.20-0.40, Nb:0.10-0.25, Fe:0.35-0.50, Cr:0.20-0.30, As or Sb or Bi:0-0.1, Si or S:0.01-0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
4. a kind of zirconium base alloy for power producer reactor core as claimed in claim 1, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.60, Nb:0.10-0.25, Fe:0.30-0.50, Cr:0.20-0.30, As or Sb or Bi: be less than 0.1, Si or S: be less than 0.03, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
5. a kind of zirconium base alloy for power producer reactor core as claimed in claim 4, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.60, Nb:0.10-0.25, Fe:0.30-0.50, Cr:0.20-0.30, As or Sb or Bi: be less than 0.1, Si or S:0.005-0.02, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
6. a kind of zirconium base alloy for power producer reactor core as claimed in claim 5, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.40, Nb:0.20, Fe:0.40, Cr:0.25, Si or S:0.01, O:0.10, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
7. the preparation method of a kind of zirconium base alloy for power producer reactor core as described in any one claim in claim 1～6, is characterized in that: comprise the following steps:
(1) the various components in zirconium alloy are prepared burden according to the formula ratio of alloy compositions;
(2) in vacuum consumable electrode arc furnace, carry out melting, make alloy cast ingot;
(3) alloy cast ingot is forged into the base material of desired shape at the β of 900 ° of C-1050 ° of C phase region;
(4) by base material in the β of 1000 ° of C-1100 ° of C phase region homogeneous heating, and carry out quench treatment;
(5) the base material after quenching is carried out to hot-work in the alpha phase zone of 600 ° of C-700 ° of C;
(6) the base material after hot-work is carried out to cold working, and carry out process annealing at 560 ° of C-650 ° of C;
(7) in 480 ° of C-620 ° of C, carry out stress relieving or recrystallization annealing processing, obtain described Zirconium alloy material.
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| CN105568057A (en) * | 2016-01-06 | 2016-05-11 | 中国核动力研究设计院 | Zirconium alloy for nuclear reactor cladding material |
| CN107304465A (en) * | 2016-04-19 | 2017-10-31 | 中国核动力研究设计院 | A kind of PWR fuel assembly zircaloy |
| CN109548765A (en) * | 2019-01-04 | 2019-04-02 | 鄱阳县黑金刚钓具有限责任公司 | A kind of fish hook and its manufacturing method |
| CN111676389A (en) * | 2020-06-30 | 2020-09-18 | 上海大学 | Zirconium alloy cladding material for small water-cooled nuclear reactor and preparation method thereof |
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