CN103898361A - Zirconium alloy for nuclear reactor core - Google Patents
Zirconium alloy for nuclear reactor core Download PDFInfo
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- CN103898361A CN103898361A CN201210578413.9A CN201210578413A CN103898361A CN 103898361 A CN103898361 A CN 103898361A CN 201210578413 A CN201210578413 A CN 201210578413A CN 103898361 A CN103898361 A CN 103898361A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C16/00—Alloys based on zirconium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- C22F1/18—High-melting or refractory metals or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/186—High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
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- G21C13/00—Pressure vessels; Containment vessels; Containment in general
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21C—NUCLEAR REACTORS
- G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
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Abstract
The invention specifically relates to a zirconium alloy for a nuclear reactor core, belonging to the technical field of special alloy materials. The zirconium alloy comprises, by weight, 0.40 to 0.80% of Sn, 0.75 to 1.10% of Nb, 0.20 to 0.50% of Fe+Cr, 0.20 to 0.35% of Fe/(Nb+Fe), 0.01 to 0.1% of Cu, Bi or Ge, 0.002 to 0.02% 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, so the corrosion resistance, mechanical properties and radiation resistance of the zirconium alloy are improved; and thus, requirements of high burn-up of a nuclear reactor on a core structural material are met. An alloy material prepared from such prototype alloy has improved homogeneous corrosion resistance in pure water out of a reactor, especially in an aqueous lithium hydroxide solution. According to test results in detailed description of the invention, it is considered that the zirconium 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 nuclear power source reactor core Zirconium alloy 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 and Zircaloy-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 Other Components of VVER and RBMK Cores ", Zirconium in the Nuclear Industry:Eleventh International Symposium, ASTM STP1295, 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-Pile Properties of M5Alloy, Zirconium in the Nuclear Industry:Twelfth International Symposium, ASTM STP1354, Sabol, G, P, Moan, G.D., Eds., American Society for Testing 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 Nuclear Industry:sixteenth International Symposium; ASTM STP1529; 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 behavior and 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 process on out-of-pile and in-pile properties of M5alloy.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.
The main uniform corrosion problem of considering zirconium alloy in pressurized-water reactor, it has been generally acknowledged that in 360 DEG C of aqueous solution of out-pile and 400 DEG C of steam zircaloy corrosion experimental examination qualified can be used for pressurized-water reactor, 360 DEG C of out-piles containing qualified being more suitable in the high lithium concentration operating mode of pressurized-water reactor of experimental examination in the lithium aqueous solution.
Summary of the invention
The technical problem to be solved in the present invention is to provide the zirconium base alloy for power producer 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 nuclear power source reactor core zirconium alloy, percentage composition meter by weight, is made up of following ingredients: Sn:0.40-0.80, Nb:0.75-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, formed by following ingredients: Sn:0.4-0.8, Nb:0.75-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, O:0.06-0.15, Cu or Bi or Ge:0.01-0.1, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, formed by following ingredients: Sn:0.4-0.8, Nb:0.75-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Si or S:0.002-0.02, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.80, Nb:0.75-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Cu or Bi or Ge:0.01-0.1, Si or S:0.002-0.02, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, is made up of following ingredients: Sn:0.40-0.60, Nb:0.90-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35,, Cu or Bi or Ge:0.01-0.10, Si or S:0.002-0.020, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, is made up of following ingredients: Sn:0.40-0.60, Nb:0.90-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35,, Cu or Bi or Ge:0.01-0.1, Si or S:0.01-0.02, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, formed by following ingredients: Sn:0.60-0.80, Nb:0.75-1.00, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Cu or Bi or Ge:0.01-0.10, Si or S:0.002-0.020, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, formed by following ingredients: Sn:0.60-0.80, Nb:0.75-1.00, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Cu or Bi or Ge:0.01-0.10, Si or S:0.005-0.015, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, is made up of following ingredients: Sn:0.70, Nb:1.00, Fe:0.30, Cr:0.05, Cu or Si or Bi or Ge:0.01, O:0.10, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
The preparation method of Zirconium alloy material for a kind of nuclear power source reactor core 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 950 ° of C-1080 ° 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-650 ° of C;
(6) the base material after hot-work is carried out to cold working, and carry out process annealing at 550 ° of C-620 ° of C;
(7) in 460 ° of C-600 ° of C, carry out stress relieving or recrystallization annealing processing, obtain described Zirconium alloy material.
The present invention is associated in gold base at Zr-Sn-Nb, other are added for improving the composition of alloy property, and select suitable component concentration, especially for the addition control of Sn, Nb, Fe, Cr and Cu or Bi, 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 0.40-0.80 % 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 0.75-1.10 % 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), chromium (Cr)
Iron and chromium all can improve alloy corrosion resistance and mechanical property, but the consumption of iron and chromium is too much or very fewly all can have an adverse influence.The content sum that in the present invention, Fe and chromium add is controlled at 0.20-0.50 % by weight, and it can ensure that alloy has good corrosion resistance nature in pure water and lithium hydroxide aqueous solution.
(5) copper (Cu)
Copper can improve alloy corrosion resistance energy, but consumption too much has adverse influence.The copper 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.
(6) 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.
(7) germanium (Ge)
Germanium can improve alloy corrosion resistance energy, but consumption too much has adverse influence.The ge 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) 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 0.02 % by weight, it can ensure that alloy has good corrosion resistance nature in lithium hydroxide aqueous solution.
(9) 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 0.02 % by weight, it can ensure in alloy high-temp water vapour, to have good corrosion resistance nature.
(10) 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.
(11) 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.
(12) 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.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, is made up of following ingredients: Sn:0.40-0.80, Nb:0.75-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, formed by following ingredients: Sn:0.4-0.8, Nb:0.75-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, O:0.06-0.15, Cu or Bi or Ge:0.01-0.1, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, formed by following ingredients: Sn:0.4-0.8, Nb:0.75-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Si or S:0.002-0.02, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.80, Nb:0.75-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Cu or Bi or Ge:0.01-0.1, Si or S:0.002-0.02, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, is made up of following ingredients: Sn:0.40-0.60, Nb:0.90-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35,, Cu or Bi or Ge:0.01-0.10, Si or S:0.002-0.020, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, is made up of following ingredients: Sn:0.40-0.60, Nb:0.90-1.10, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35,, Cu or Bi or Ge:0.01-0.1, Si or S:0.01-0.02, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, formed by following ingredients: Sn:0.60-0.80, Nb:0.75-1.00, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Cu or Bi or Ge:0.01-0.10, Si or S:0.002-0.020, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, formed by following ingredients: Sn:0.60-0.80, Nb:0.75-1.00, Fe+Cr:0.20-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Cu or Bi or Ge:0.01-0.10, Si or S:0.005-0.015, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
A kind of nuclear power source reactor core zirconium alloy, percentage composition meter by weight, is made up of following ingredients: Sn:0.70, Nb:1.00, Fe:0.30, Cr:0.05, Cu or Si or Bi or Ge:0.01, O:0.10, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
Zirconium base alloy for pressurized-water reactor core structural material provided by the invention, is by optimizing Zr-Sn-Nb alloying constituent proportioning when, adds the elements such as trace Cr, Bi, Cu, to carry heavy alloyed corrosion resistance nature.
Table 1 is the composition of alloy provided by the present invention, and in table, 14* and 15* are respectively Zr-4 alloy and N36 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 Zirconium alloy material for a kind of nuclear power source reactor core 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 950 ° of C-1080 ° 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-650 ° of C;
(6) the base material after hot-work is carried out to cold working, and carry out process annealing at 550 ° of C-620 ° of C;
(7) in 460 ° of C-600 ° 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.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); Test conditions described in table 4 is: 400 ° 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).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) 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 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 corrodes the erosion rate after 300 days at 360 ° of C containing in the 70 μ g/g lithium aqueous solution
Table 4 alloy material provided by the present invention corrodes the erosion rate after 300 days in 400 ° of C steam
Application example provided by the invention shows, alloy of the present invention all shows very good corrosion resistance nature while corrosion under above-mentioned 3 kinds of water chemistry conditions, is obviously better than N36 (Zr-1.0Sn-1.0Nb-0.3Fe) alloy of Zr-4 alloy and China's research and development.The comparable N36 alloy of erosion rate that zirconium alloy of the present invention corroded after 300 days in the 360 DEG C/18.6MPa LiOH aqueous solution reduces by 21%; The comparable N36 alloy of erosion rate corroding in 360 DEG C/18.6MPa deionized water after 300 days reduces by 35%; The comparable N36 alloy of erosion rate corroding in 400 DEG C/10.3MPa superheated vapour after 300 days reduces by 23%.
Because the present invention has adopted the composition range of preferred Sn, Nb, Fe, Cr and Cu or Bi, 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 3 kinds of water chemistry conditions, all show very good corrosion resistance nature, be obviously better than optimizing N36 alloy and 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 (10)
1. a nuclear power source reactor core zirconium alloy, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.80, Nb:0.75-1.10, Fe+Cr:0.10-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
2. a nuclear power source reactor core zirconium alloy, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.80, Nb:0.75-1.10, Fe+Cr:0.10-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, O:0.06-0.15, Cu or Bi or Ge:0.01-0.10, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
3. a nuclear power source reactor core zirconium alloy, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.80, Nb:0.75-1.10, Fe+Cr:0.10-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Si or S:0.002-0.020, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
4. a nuclear power source reactor core zirconium alloy, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.40-0.80, Nb:0.75-1.10, Fe+Cr:0.10-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Cu or Bi or Ge:0.01-0.10, Si or S:0.002-0.020, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
5. a kind of nuclear power source reactor core zirconium alloy 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:0.90-1.10, Fe+Cr:0.10-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Cu or Bi or Ge:0.01-0.10, Si or S:0.002-0.020, 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 nuclear power source reactor core zirconium alloy as claimed in claim 5, it is characterized in that: percentage composition meter by weight, is made up of following ingredients: Sn:0.40-0.60, Nb:0.90-1.10, Fe+Cr:0.10-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35,, Cu or Bi or Ge:0.01-0.1, Si or S:0.01-0.02, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
7. a kind of nuclear power source reactor core zirconium alloy as claimed in claim 4, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.60-0.80, Nb:0.75-1.00, Fe+Cr:0.10-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Cu or Bi or Ge:0.01-0.10, Si or S:0.002-0.020, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
8. a kind of nuclear power source reactor core zirconium alloy as claimed in claim 7, it is characterized in that: percentage composition meter by weight, formed by following ingredients: Sn:0.60-0.80, Nb:0.75-1.00, Fe+Cr:0.10-0.50, Fe/ (Nb+Fe): 0.20 ~ 0.35, Cu or Bi or Ge:0.01-0.10, Si or S:0.005-0.015, O:0.06-0.15, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium and impurity.
9. a nuclear power source reactor core zirconium alloy, is characterized in that: percentage composition meter by weight, is made up of following ingredients: Sn:0.70, Nb:1.00, Fe:0.30, Cr:0.05, Cu or Si or Bi or Ge:0.01, O:0.10, C: be less than 0.008, N: be less than 0.006; Surplus is zirconium.
10. the preparation method of Zirconium alloy material for a kind of nuclear power source reactor core as described in any one claim in claim 1～9, is characterized in that, 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 950 ° of C-1080 ° 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-650 ° of C;
(6) the base material after hot-work is carried out to cold working, and carry out process annealing at 550 ° of C-620 ° of C;
(7) in 460 ° of C-600 ° of C, carry out stress relieving or recrystallization annealing processing, obtain described Zirconium alloy material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210578413.9A CN103898361B (en) | 2012-12-27 | 2012-12-27 | Zirconium alloy for nuclear reactor core |
| GB1512801.0A GB2523975B (en) | 2012-12-27 | 2013-12-12 | Zirconium alloy for nuclear power reactor core |
| PCT/CN2013/089201 WO2014101660A1 (en) | 2012-12-27 | 2013-12-12 | Zirconium alloy for nuclear power reactor core |
| ARP130104996A AR094256A1 (en) | 2012-12-27 | 2013-12-20 | CIRCONY ALLOY MATERIAL FOR THE NUCLEUS OF A NUCLEAR ENERGY REACTOR AND MATERIAL PREPARATION METHOD |
| ZA2015/05320A ZA201505320B (en) | 2012-12-27 | 2015-07-23 | Zirconium alloy for nuclear power reactor core |
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| CN201210578413.9A CN103898361B (en) | 2012-12-27 | 2012-12-27 | Zirconium alloy for nuclear reactor core |
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| AR (1) | AR094256A1 (en) |
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Cited By (4)
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| CN105483443A (en) * | 2015-12-09 | 2016-04-13 | 上海大学 | Zirconium-niobium-iron alloy containing copper and germanium for fuel cladding of nuclear power plant |
| CN109692880A (en) * | 2018-12-19 | 2019-04-30 | 西部超导材料科技股份有限公司 | A kind of Zr-Nb alloy bar material and its extruding method |
| CN113462998A (en) * | 2020-03-30 | 2021-10-01 | 国核宝钛锆业股份公司 | Preparation method of Zr-Nb alloy bar |
| CN117292852A (en) * | 2023-11-27 | 2023-12-26 | 西安稀有金属材料研究院有限公司 | Zirconium hydride moderating material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105483444B (en) * | 2015-12-09 | 2018-08-03 | 上海大学 | Fuel for nuclear power plant involucrum zirconium niobium iron-based alloy |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103898361B (en) | 2017-02-22 |
| GB2523975A (en) | 2015-09-09 |
| AR094256A1 (en) | 2015-07-22 |
| GB2523975B (en) | 2017-12-20 |
| GB201512801D0 (en) | 2015-09-02 |
| WO2014101660A1 (en) | 2014-07-03 |
| ZA201505320B (en) | 2016-09-28 |
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