CN104745875A - Zirconium alloy material for light water reactor under higher burnup - Google Patents
Zirconium alloy material for light water reactor under higher burnup Download PDFInfo
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Abstract
The invention discloses a zirconium alloy material for a light water reactor under higher burnup. The zirconium alloy material comprises 0.10-0.40 weight% of tin, 0.50-1.50 weight% of niobium, 0.01-0.20 weight% of iron and 0.06-0.20 weight% of oxygen, and further comprises 0.01-0.09 weight% of vanadium and/or 0.01-0.09 weight% of copper and the balance of zirconium. The zirconium alloy has excellent corrosion resistance; and compared with the zirconium alloy in the prior art, the zirconium alloy has more excellent corrosion resistance in high-temperature pure water, and is suitable for fuel rod cladding materials and corrosion resistant zirconium alloy materials of grillwork strips and structural parts under higher burnout of nuclear reactors.
Description
Technical field
The present invention relates to a kind of alloy material, particularly relate to a kind of for light water reactor compared with the Zirconium alloy material under high burnup.
Background technology
The zirconium alloy comparatively early used in pressurized-water reactor is Zr-4 alloy.The average discharge burn-up of Foreign Pressurized Water fuel assembly last century late nineteen seventies be in 30 ~ 35GWd/tU.The Sn content of Zr-4 alloy is higher, is 1.2 ~ 1.7%.Service experience shows, the Sn content of alloy is high unfavorable to corrosion resistance nature.Therefore, US Westinghouse company last century the seventies start the research carrying out ZIRLO alloy, its Sn content is only 0.90 ~ 1.10%.As Zr-Sn-Nb alloy, its Nb content is 0.80 ~ 1.20%, Fe content be 0.08 ~ 0.12%, O content is 0.105 ~ 0.145%.When in pressurized-water reactor, burnup is 60GWd/tU, the corrosion resistance nature of ZIRLO alloy is better than optimizing Zr-4 alloy greatly, and oxide thickness only has optimizes 30% of Zr-4 alloy.The Sn content of the optimization ZIRLO alloy of Westinghouse Electric declines further, is 0.6 ~ 0.8%, and its corrosion resistance nature is better than the ZIRLO alloy of standard, and when burnup is more than 70GWd/tU, its oxide thickness is about 40 μm.Except Westinghouse Electric, also have many countries to carry out the improvement of zirconium alloy to carry heavy alloyed corrosion resistance nature, the M5 alloy of wherein French Framatome exploitation is good.The composition of M5 alloy is: Zr-1.0%Nb-0.12%O, and it is not containing Sn.When in pressurized-water reactor, burnup reaches 60GWd/tU, its peak oxidation film thickness is 1/6 of Zr-4 alloy, and this also shows that the corrosion resistance nature of M5 alloy in heap is better than ZIRLO alloy.
ZIRLO alloy and M5 alloy low due to erosion rate, make their hydrogen－sucking amount all low than Zr-4 alloy.M5 alloy is as 17 × 17 fuel rod clad pipes when burnup reaches 77GWd/tU, and hydrogen－sucking amount is 100ppm, and the hydrogen－sucking amount of Zr-4 alloy wants much higher times.The hydrogen－sucking amount of ZIRLO alloy cladding pipe is higher than M5 alloy, but lower than Zr-4 alloy.Hydrogen－sucking amount is high, will produce zircoium hydride, because the volume conference of zircoium hydride impels involucrum irradiation growth and breakage.Therefore, reach high burnup, the hydrogen－sucking amount of zirconium alloy should be low.Zr-4 alloy, because of containing Cr, generates Zr (Fe, Cr)
2second-phase, can absorb more hydrogen.
Zr-4 alloy is because of high hydrogen－sucking amount, and irradiation growth is very remarkable, is 21.0 × 10 at neutron fluence
25n/cm
2time, irradiation growth reaches 1.9%.The irradiation growth of M5 alloy is starkly lower than Zr-4 alloy, is 17 × 10 at neutron fluence
25n/cm
2time, irradiation growth only has 0.3%.Irradiation growth, except relevant with hydrogen－sucking amount, also comprises the growth of corrosion oxidation generation and the free growth of irradiation generation.The growth that corrosion oxidation produces causes because zirconic volume is greater than zirconium, and therefore corrosion resistance and good just has lower irradiation growth.The stability of irradiation free growth and Second Phase Particle is closely related, particle stabilized Non-amorphized, alloying element in particle is separated out just few, and the density of <C> type dislocation loop is just low, and therefore the free growth that causes of irradiation is just little.When irradiation growth is comparatively large, will impel fuel stick and fuel assembly flexural deformation, and hinder the control rod being used for reactive control to move, thus disadvantageous effect will be caused to the power regulation of reactor, power distributed controll and scram.Therefore in order to low irradiation growth, the corrosion resistance nature of zirconium alloy should be got well, hydrogen－sucking amount should should be stablized low, Second Phase Particle.
Irradiation creep is relevant with the alloying element be dissolved in alloy substrate, and Sn, Nb, O irradiation creep impact on zirconium alloy is comparatively large, and M5 alloy is not containing Sn, and its irradiation creep is larger than ZIRLO alloy.Nb, O content is higher, and creep strain is just little.Creep is also relevant with the thermal treatment process of zirconium alloy, and perfect recrystallization can make the crystal grain of zirconium alloy increase, and therefore creep speed is just slow.The impact of creep on fuel assembly performance is larger.When the external coolant pressure of fuel stick is higher than interior pressure, the inside creep of zirconium alloy cladding, if creep speed is large, just there will be cladding tubes and contacts with fuel pellet, produces the interaction of pellet and involucrum, causes involucrum to damage.While Radial creep, also can with the axial growth of involucrum.When pressure in fuel stick is greater than the pressure of external coolant, involucrum there will be outside creep, and radius clearance in rod is increased, and between rod, coolant flow channel narrows, and clad temperature raises, and causes departure from nucleate boiling (DNB) wide spread.Therefore, to high burnup fuel assembly, zirconium alloy must have low creep speed.
Under in reactor, high neutron fluence irradiates, the yield strength of zirconium alloy and tensile strength can significantly improve, and therefore the volume averaging effective stress of zirconium alloy cladding still can meet criterion of strength.But under the load-following operation condition that power plant is long-term, cladding tubes should be able to bear tired test.The fatigue property of alloy is relevant with neutron fluence, and neutron fluence is high, and plasticity declines, and impels fatigue cracking to produce.When fuel assembly continues to run, neutron fluence must increase, and therefore during zirconium alloy irradiation, plasticity is well very important.In reactor, the plasticity of zirconium alloy is relevant with its hydrogen－sucking amount.Test shows, Zr-4 alloy is when hydrogen－sucking amount is 850ppm, and its fatigue life cycle is the low several magnitude of the Zr-4 alloy of 10ppm than hydrogen－sucking amount, and this shows that hydrogen－sucking amount is comparatively large to Influence of Fatigue Properties, and hydrogen richness is high, and the plasticity of material is just poor.
From explanation above, the erosion rate that zirconium alloy is low, hydrogen－sucking amount, irradiation growth, irradiation creep and the good fuel assembly of fatigue property to high burnup are very important, and these good performances are indispensable.
The publication number that US Westinghouse company proposes is the zirconium alloy patent of invention of CN 101175864A, and the alloy manufacture with following composition has the article of the such as pipeline or lath of excellent corrosion resistance to the steam under water or high temperature: 0.2 ~ 1.5%Nb; 0.01 ~ 0.45%Fe; Be selected from the alloying element that at least one in 0.02 ~ 0.8%Sn, 0.05 ~ 0.5%Cr, 0.02 ~ 0.3%Cu, 0.1 ~ 0.3%V, 0.01 ~ 0.1% is other; Surplus is at least 97%Zr comprising impurity.This alloy is manufactured: alloy forging is become material by following steps method; β quenching is carried out to material; Material forming is made by extruded material or hot-finished material; With one or many cold working step, cold working is carried out to material, cold working step comprise cold thinning material and under the intermediate anneal temperature of 516 DEG C ~ 596 DEG C to anneal of material; Material is finally processed and anneals.With the addition of Cr in composition, easily form Zr (Fe, Cr)
2, be unfavorable for the absorption and the irradiation growth that reduce hydrogen.In addition, the manufacturing process described in the patent in western room is conventional, and annealing temperature is higher, and in the matrix of zirconium alloy, Nb content is lower, is unfavorable for improving corrosion resistance nature.
Framatome of France develops not containing the M5 alloy (Zr-1Nb-0.125O) of Sn, and the approved fuel-assembly burn-up of M5 alloy is 52-62GWd/tU, and the M5 alloy fuel assembly burnup of Germany's approval reaches 70GWd/tU.Because Sn content mainly exists with solution in zirconium alloy, thus larger to the contribution of mechanical property.M5 alloy does not contain Sn, so Flouride-resistani acid phesphatase creep property is poor.France improves M5 alloy again, adds the Sn of the 0.3% and Fe of 0.1%, to improve the Flouride-resistani acid phesphatase creep property of M5 alloy.Framatome's publication number is the zirconium alloy patent of CN 1833038A, and its chemical composition is: 0.2 ~ 0.5%Sn, 0.2 ~ 0.8%Nb, 0.05 ~ 0.40%Fe, 0 ~ 0.20%V, 0.12 ~ 0.20%O, 80 ~ 120ppm Si ,≤120ppmC.From the compositional data of Fa Matong, the content of its Nb is lower than Nb content disclosed in US Westinghouse company patent CN101175864A.
As can be seen here, people are constantly being devoted to improve in Nuclear power plants the erosion resistance of zirconium alloy of the material being used as nuclear fuel assembly, Flouride-resistani acid phesphatase creep property and mechanical property.But, consider lithium concentration higher in the burnup that the demand for development of light-water reactor is higher, longer refulling cycle, higher coolant temperature, refrigerant, the residence time that heap in-core is longer, still constantly need that there is the zirconium alloy improving erosion resistance further, for guaranteeing that nuclear fuel is in high burnup/the prolong integrity in macrocyclic operation.
In addition, another potential mode of the erosion resistance of raising zirconium alloy is the method itself by forming alloy.Existing zirconium alloy complete processing comprises successively: hammer cogging operation, β phase quenching process, α phase hot rolling/hot extrusion operation, process annealing and cold working operation, and the final recrystallization annealing operation of finished product sheet material/tubing.Wherein, hammer cogging operation is in the environment of 900 DEG C ~ 1150 DEG C, and the zirconium alloy of the as cast condition obtained the vacuum arc melting through more than three times or three times carries out hammer cogging process; β phase quenching process the product obtained after above-mentioned operation is carried out in the environment of 1030 DEG C 10min ~ 50min insulation, then carries out shrend; α phase hot rolling/hot extrusion operation refers to first be incubated by the said products, carries out hot rolling/hot extrusion afterwards to obtain hot rolling slab/pipe; Process annealing and cold working operation refer to carries out repeatedly process annealing to above-mentioned hot rolling slab/pipe and after each process annealing, carries out cold working, finally to obtain cold rolling slab/pipe; Finished product sheet material/tubing final annealing operation carries out final annealing after referring to and above-mentioned cold rolling slab/pipe being processed as finished product sheet material/tubing, finally obtains zirconium alloy product.
But, large size ingot casting ingot casting heart portion rate of cooling after β phase quenching process is not enough, inevitably produce precipitated phase at α phase boundary place, precipitated phase in existing zirconium alloy complete processing is zonal arrangement, and unevenly in the insulating process of α phase hot-rolled process to grow up, to cause in zirconium alloy second phase particles cannot Dispersed precipitate, cause the plastic deformation ability of zirconium alloy poor, the plastic working ability of zirconium alloy.In addition, precipitated phase is zonal arrangement, and unevenly in the insulating process of α phase hot rolling/hot extrusion operation to grow up, cause second phase particles size in zirconium alloy comparatively large and cannot Dispersed precipitate, the corrosion resistance nature of the core structural material causing zirconium alloy to make in nuclear reactor declines.
Therefore, those skilled in the art is constantly devoted on the basis of existing technology, the Zirconium alloy material that exploitation performance is more excellent.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is to provide a kind of not containing chromium and the higher Zirconium alloy material of niobium content, this material erosion resistance is better, and hydrogen－sucking amount, irradiation growth, irradiation creep and fatigue property etc. are comparatively balanced.
For achieving the above object, the invention provides a kind of Zirconium alloy material, the component of this Zirconium alloy material is: the tin of 0.10 ~ 0.40 % by weight, the niobium of 0.50 ~ 1.50 % by weight, the iron of 0.01 ~ 0.20 % by weight, the oxygen of 0.06 ~ 0.20 % by weight; The vanadium of 0.01 ~ 0.09 % by weight and/or the copper of 0.01 ~ 0.09 % by weight, surplus is zirconium.Zirconium alloy material also may comprise the impurity of denier.This be a kind of light water reactor that can be used in compared with the Zirconium alloy material under high burnup, comparatively high burnup refers to that burnup is more than 60GWd/tU herein.
The present invention adds the tin of 0.10 ~ 0.40 % by weight, is taken into full account the balance between corrosion resistance nature and Flouride-resistani acid phesphatase creep property, has excellent corrosion resistance nature and Flouride-resistani acid phesphatase creep property concurrently to make zirconium alloy of the present invention.
The present invention adds the niobium of 0.50 ~ 1.50 % by weight, is conducive to generating more β-Nb second-phases, can improve its corrosion resistance nature in high temperature pure water, impel the corrosion resistance nature and low irradiation growth that have had in heap.
The present invention adds the iron of 0.01 ~ 0.20 % by weight, can make up alloy and reduce due to Sn content the shortcoming causing mechanical properties decrease, carry heavy alloyed hydrogen sucking function, corrosion resistance nature and Flouride-resistani acid phesphatase growth performance simultaneously.
In addition, the present invention also by adding vanadium and copper, improves the corrosion resistance nature of zirconium alloy, can also put forward heavy alloyed mechanical property, Flouride-resistani acid phesphatase growth and Flouride-resistani acid phesphatase creep property simultaneously.
Containing Second Phase Particle in Zirconium alloy material provided by the invention.
Preferably, the median size of Second Phase Particle is not more than 100nm.Median size refers to the mean value of the Second Phase Particle particle diameter participating in statistics in a plane, adopts and measures from two different directions simultaneously, then get the treatment process of its mean value for Second Phase Particle in irregular shape.
Preferably, the area fraction of Second Phase Particle is 3.5 ~ 15%.Area fraction refers to that the area of the Second Phase Particle participating in statistics in a plane accounts for the percentage of this face total area.
Preferably, the component of zirconium alloy is: the tin of 0.10 ~ 0.40 % by weight, the niobium of 0.85 ~ 1.50 % by weight, 0.01 ~ 0.20 % by weight iron, the oxygen of 0.06 ~ 0.20 % by weight, the vanadium of 0.01 ~ 0.09 % by weight; Surplus is zirconium.
More preferably, the component of zirconium alloy is: the tin of 0.15 ~ 0.35 % by weight, the niobium of 0.85 ~ 1.20 % by weight, 0.08 ~ 0.12 % by weight iron, the oxygen of 0.10 ~ 0.20 % by weight, the vanadium of 0.04 ~ 0.06 % by weight; Surplus is zirconium.
Especially preferably, the component of zirconium alloy is: the tin of 0.25 % by weight, the niobium of 1.00 % by weight, 0.10 % by weight iron, the oxygen of 0.13 % by weight, the vanadium of 0.05 % by weight; Surplus is zirconium.
Preferably, the component of zirconium alloy is: the tin of 0.10 ~ 0.40 % by weight, the niobium of 0.85 ~ 1.50 % by weight, 0.01 ~ 0.20 % by weight iron, the oxygen of 0.06 ~ 0.20 % by weight, the copper of 0.01 ~ 0.09 % by weight; Surplus is zirconium.
More preferably, the component of zirconium alloy is: the tin of 0.15 ~ 0.35 % by weight, the niobium of 0.85 ~ 1.20 % by weight, 0.08 ~ 0.12 % by weight iron, the oxygen of 0.10 ~ 0.20 % by weight, the copper of 0.04 ~ 0.06 % by weight; Surplus is zirconium.
Especially preferably, the component of zirconium alloy is: the tin of 0.25 % by weight, the niobium of 1.00 % by weight, 0.10 % by weight iron, the oxygen of 0.13 % by weight, the copper of 0.05 % by weight; Surplus is zirconium.
Preferably, the component of zirconium alloy is: the tin of 0.10 ~ 0.40 % by weight, the niobium of 0.85 ~ 1.50 % by weight, the iron of 0.01 ~ 0.20 % by weight, oxygen, the vanadium of 0.01 ~ 0.09 % by weight, the copper of 0.01 ~ 0.09 % by weight of 0.06 ~ 0.20 % by weight; Surplus is zirconium.
More preferably, the component of zirconium alloy is: the tin of 0.15 ~ 0.35 % by weight, the niobium of 0.85 ~ 1.20 % by weight, the iron of 0.08 ~ 0.12 % by weight, oxygen, the vanadium of 0.04 ~ 0.06 % by weight, the copper of 0.04 ~ 0.06 % by weight of 0.10 ~ 0.20 % by weight; Surplus is zirconium.
Especially preferably, the component of zirconium alloy is: the tin of 0.25 % by weight, the niobium of 1.00 % by weight, the iron of 0.10 % by weight, oxygen, the vanadium of 0.05 % by weight, the copper of 0.05 % by weight of 0.13 % by weight; Surplus is zirconium.
Above-mentioned zirconium alloy, prepares according to following steps:
A) zirconium sponge and pure metal or master alloy prepare burden according to the component of described zirconium alloy, mix after obtain zirconium alloy ingot casting 2 times through melting;
B) the zirconium alloy ingot casting of step a) gained is forged for the first time;
C) step b) gained ingot casting is obtained finished product ingot casting through vacuum melting again;
D) by step c) gained finished product ingot casting through second time forging after again through β shrend, obtain zirconium alloy base material;
E) the zirconium alloy base material of step d) gained is carried out more than 5 times hot rollings, then through vacuum annealing;
F) the zirconium alloy base material of step e) gained is carried out cold rolling and vacuum annealing, be cycled to repeat at least 4 times, obtained described zirconium alloy.
580 DEG C are with the temperature of vacuum annealing in step f) in above-mentioned steps step e).
The concrete steps preparing zirconium alloy are as follows:
A) be specially: with core level zirconium sponge and core level pure metal or master alloy for raw material, carry out preparing burden according to the component of described zirconium alloy, mix, melting 2 times, make zirconium alloy ingot casting;
B) be specially: the zirconium alloy ingot casting of step a) gained is forged for the first time;
C) be specially: step b) is obtained ingot casting and carry out melting through vacuum non-consumable arc furnace, make zirconium alloy finished product ingot casting;
D) be specially: by the forging of step c) gained finished product ingot casting to 10mm thickness, scale removal, pickling remove grease; Shrend after the β phase Homogenization Treatments 30min of 1050 DEG C, quenching velocity is greater than 50 DEG C/s;
E) be specially: the zirconium alloy base material of step d) gained is carried out more than 5 times hot rollings, then through vacuum annealing, annealing temperature is set to 580 DEG C, the time is set to 1 hour;
F) be specially: the zirconium alloy of step e) gained is carried out cold rolling and vacuum annealing, repeats at least 4 times, obtained described zirconium alloy; Each annealing temperature is set to 580 DEG C, and each process annealing time is set to 1 hour, and final annealing is 5 hours.
The present invention adopts the process annealing of 580 DEG C and the final annealing of 580 DEG C respectively afterwards by cold rolling, reduces the alloying element content in matrix and increases the quantity of Second Phase Particle, thus improve the corrosion resistance nature of zirconium alloy further.
The technique effect of the zirconium alloy for light-water reactor of the present invention is as follows:
Because the corrosion resistance nature impact of Sn content on zirconium alloy is very large, reduces Sn content to scope above, the corrosion resistance and good of these alloys can be made.In order to put forward heavy alloyed creep property, the content of Sn do not cancelled by the zirconium alloy for light-water reactor of the present invention, namely adds the irradiation creep performance that Sn contributes to zirconium alloy.This low Sn zirconium alloy is except corrosion-resistant, the creep property had, and hydrogen－sucking amount is also low, and therefore irradiation growth performance might as well.
Because Nb can stop the Li in pressurized-water reactor inner cooling water to enter in the oxide film of Zr alloy surface, this element can make the creep speed of zirconium alloy low simultaneously, therefore the higher Nb content of the zirconium alloy for light-water reactor of the present invention will improve corrosion resistance nature and the creep property of zirconium alloy well, make alloy have higher intensity simultaneously.In superincumbent technical scheme, Nb content is the highest, and therefore β-Nb is maximum in Second Phase Particle, and is the most stable in heap, and it is low that this makes the in-pile irradiation of alloy grow.
Because the solubleness of Fe in zirconium matrix is very low, therefore Second Phase Particle can be formed with other alloying elements.Fe content is more, then the particle formed is just many.In zirconium alloy, Second Phase Particle is tiny, amount is many, be uniformly distributed, and the corrosion resistance nature of alloy is all right, therefore of the present inventionly also impels the corrosion resistance nature of zirconium alloy to improve for measuring many Fe in the zirconium alloy of light-water reactor.This element also will put forward heavy alloyed intensity, but amount is unfavorable for the processing of product more.
Energy due to V higher and and O have high avidity, impel Zr alloy surface oxide film stablize.Therefore, the corrosion resistance that V can improve zirconium alloy is added.Higher based on the Nb content in design, according to related tests, the V content added by the zirconium alloy for light-water reactor of the present invention is not high had both been conducive to the advantageous effect playing Nb, can also keep the advantageous effect of V.Added V can also reduce the absorption of hydrogen, and this will inevitably reduce the irradiation growth of zirconium alloy and improve fatigue property.
Because the membership that adds of less Cu makes Second Phase Particle tiny, be conducive to the improvement of corrosion resistance nature, therefore of the present invention for adding less Cu in the zirconium alloy of light-water reactor.Test shows, in zirconium alloy, existing Cu has V again, then the corrosion resistance nature of alloy is better.
Because in zirconium alloy, O is larger to the effect reducing irradiation creep, therefore of the present invention for the zirconium alloy of light-water reactor in add more O to raising creep property be better.Meanwhile, O also can improve the intensity of zirconium alloy, but O too high levels is unfavorable for the processing of zirconium alloy.
Reducing the annealing temperature of zirconium alloy makes zirconium matrix interalloy constituent content few, makes that the Second Phase Particle of alloy is tiny, amount is many, and particularly β-Nb, therefore improves the corrosion resistance nature of the zirconium alloy for light-water reactor of the present invention.
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.
Accompanying drawing explanation
Fig. 1 is the microstructure SEM picture of zirconium alloy prepared by first preferred embodiment of the present invention;
Fig. 2 is the microstructure SEM picture of zirconium alloy prepared by second preferred embodiment of the present invention;
Fig. 3 is the microstructure SEM picture of the 3rd zirconium alloy prepared by preferred embodiment of the present invention;
Fig. 4 is the surrosion graphic representation of three zirconium alloy samples shown in Fig. 1, Fig. 2 and Fig. 3;
Fig. 5 is the corrosion resistance nature figure making the fuel stick of involucrum with Zr-Sn-Nb-(Fe, Cr, V).
Embodiment
Zirconium alloy disclosed by the present invention, its component is: the tin of 0.10 ~ 0.40 % by weight, the niobium of 0.50 ~ 1.50 % by weight, the iron of 0.01 ~ 0.20 % by weight, the oxygen of 0.06 ~ 0.20 % by weight; The vanadium of 0.01 ~ 0.09 % by weight and/or the copper of 0.01 ~ 0.09 % by weight, surplus is zirconium.
Preferably, the component of zirconium alloy is: the tin of 0.15 ~ 0.35 % by weight, the niobium of 0.85 ~ 1.20 % by weight, 0.08 ~ 0.12 % by weight iron, the oxygen of 0.10 ~ 0.20 % by weight, the vanadium of 0.04 ~ 0.06 % by weight; Surplus is zirconium.
Preferably, the component of zirconium alloy is: the tin of 0.15 ~ 0.35 % by weight, the niobium of 0.85 ~ 1.20 % by weight, 0.08 ~ 0.12 % by weight iron, the oxygen of 0.10 ~ 0.20 % by weight, the copper of 0.04 ~ 0.06 % by weight; Surplus is zirconium.
Preferably, the component of zirconium alloy is: the tin of 0.15 ~ 0.35 % by weight, the niobium of 0.85 ~ 1.20 % by weight, the iron of 0.08 ~ 0.12 % by weight, oxygen, the vanadium of 0.04 ~ 0.06 % by weight, the copper of 0.04 ~ 0.06 % by weight of 0.10 ~ 0.20 % by weight; Surplus is zirconium.
Below, the embodiment in reference table 1 describes the present invention.
Table 1
Elaborate for embodiment in table 11.The component of zirconium alloy is: the tin of 0.25 % by weight, the niobium of 1.00 % by weight, 0.10 % by weight iron, the oxygen of 0.13 % by weight, the vanadium of 0.05 % by weight; Surplus is zirconium.
The concrete steps preparing zirconium alloy are as follows:
The first step, prepares zirconium alloy ingot
Adopt core level zirconium sponge and core level pure metal raw material (Nb, Sn, Fe, V, Cu) or master alloy to prepare burden by the alloy compositions of embodiment 1 respectively, melting 2 times, form ingot casting; Ingot casting is forged, then adopts vacuum non-consumable arc furnace melting 1 time, make alloy pig;
Second step, forging and β shrend
Forged at 950 ~ 1050 DEG C by alloy pig, be processed into alloy preform material, after scale removal, pickling remove grease, shrend after the β phase Homogenization Treatments 30min of 1050 DEG C, quenching velocity is greater than 50 DEG C/s.
3rd step, hot rolling process
Alloy preform material is carried out 5 ~ 6 hot rollings after 600 DEG C of preheating 40min, and after hot rolling, first scale removal, pickling are removed grease, then are carried out 580 DEG C of process annealings 1 hour in a vacuum.
4th step, cold-rolling treatment
Alloy preform material is carried out 4 times cold rolling, each cold roling reduction 20% ~ 50%, until alloy preform material thickness is down to 0.65mm, i.e. this alloy material obtained.Twice cold rolling between carry out 580 DEG C of process annealings 1 hour in a vacuum.Wherein, alloy preform material all carries out scale removal before each process annealing or final annealing, grease process is removed in pickling.
Embodiment 2 is identical with the preparation method of embodiment 3, and difference is only that component is different, enumerates in table 1.In embodiment 2, the component of zirconium alloy is: the tin of 0.25 % by weight, the niobium of 1.00 % by weight, 0.10 % by weight iron, the oxygen of 0.13 % by weight, the copper of 0.05 % by weight; Surplus is zirconium.
In embodiment 3, the component of zirconium alloy is: the tin of 0.25 % by weight, the niobium of 1.00 % by weight, the iron of 0.10 % by weight, oxygen, the vanadium of 0.05 % by weight, the copper of 0.05 % by weight of 0.13 % by weight; Surplus is zirconium.
Through processing above, the better performances of zirconium alloy.Find after deliberation, the Second Phase Particle median size of zirconium alloy is at 50 ~ 70nm, and area fraction about 10%, this shows that Second Phase Particle is tiny, and quantity is many, makes the corrosion resistance nature of zirconium alloy better.Median size refers to the mean value of the Second Phase Particle size participating in statistics in a plane, adopts and measures from two different directions simultaneously, then get the treatment process of its mean value for Second Phase Particle in irregular shape.Area fraction refers to that the area of the Second Phase Particle participating in statistics in a plane accounts for the percentage of this face total area.The Second Phase Particle situation of these 3 alloys is shown in Fig. 1, Fig. 2 and Fig. 3 respectively.
Fig. 1 is the microstructure SEM picture of zirconium alloy prepared by embodiment 1.The Second Phase Particle of zirconium alloy alloy prepared by embodiment 1 is a lot, and main particle is β-Nb, and tiny amount is many.
Fig. 2 is the microstructure SEM picture of zirconium alloy prepared by embodiment 2, and zirconium alloy prepared by embodiment 2 not containing V, but adds the Cu of 0.05%.The Second Phase Particle that this figure shows is more tiny than figure above, and this is that Cu makes Second Phase Particle diminish, and corrosion resistance nature is better, also proposes this effect of Cu in external research.
Fig. 3 is the microstructure SEM picture of zirconium alloy prepared by embodiment 3.The zirconium alloy that this figure also shows embodiment 3 preparation has a lot of Second Phase Particles.Very tiny particle is not more than Fig. 2, and this is the effect of Cu.The Second Phase Particle amount of zirconium alloy is a lot, and mainly Nb content is many, forms much tiny β-Nb, also has Zr (Fe, Nb) in addition
2particle, Zr (Fe, V)
2particle, these particles are slightly larger than β-Nb, and the inside also has a small amount of Cu.Here Zr (Fe, V)
2particle is also more stable in heap, and the Fe content of its amorphized portion is Zr (Fe, Cr)
22 times of particle corresponding section, this shows Zr (Fe, V)
2the decrystallized speed of particle wants slow a lot.These Second Phase Particles are stablized, and the corrosion resistance nature, the low irradiation growth that impel this alloy to have in heap, can improve the burnup of fuel assembly.
From 3 figure above, the Second Phase Particle amount of these 3 zirconium alloys is many, and tiny is β-Nb particle, larger mainly Zr (Nb, Fe)
2particle, has in a small amount of V or Cu or V+Cu, β-Nb particle these elements also having seldom amount in this particle.The composition of zirconium alloy Second Phase Particle prepared by these 3 embodiments sees the following form 2.
Table 2
Corrosion resistance nature is preferably embodiment 3 relatively, and it contains V, Cu, and this proves that these two kinds of element collocation are good.Pure water corrosion in 360 DEG C/18.6MPa autoclave, the surrosion of the zirconium alloy that 3 embodiments are prepared respectively is in table 3 and Fig. 4.From available data, the surrosion of zirconium alloy prepared by embodiment 3 is lower by 28% than the corrosion of ZIRLO alloy out-pile.This proves that the design of alloying element of the present invention and the complete processing of alloy are effective.The publication number of the composition of embodiment 1 and France be Zr-0.30Sn-0.75Nb-0.13Fe-0.07V-0.14O-0.011Si zirconium alloy D that in the zirconium alloy patent of CN 1833038A, performance is best relatively, the corrosion resistance nature of embodiment 1 is close with it, and embodiment 3 is better.
Table 3
In addition, prepare zirconium alloy according to the component in table 4, preparation method is consistent with aforesaid.
Table 4
That the zirconium alloy prepared of embodiment 4-9 is in the data of corroding through 360 DEG C/18.6MPa pure water shown in table 5.
Table 5
Fig. 5 shows to pile interior corrosion resistance nature it is preferred that low Sn height Nb adds the zirconium alloy (Zr0.25Sn0.75Nb0.25TM) of Fe, V again, and its surrosion when burnup reaches 98MWd/kgU is minimum and very stable.In zirconium alloy prepared by embodiment 1, Nb content wants height a bit, be conducive to corrosion resistance nature, but its Fe+V content is slightly lower, in the corrosion resistance nature of zirconium alloy prepared by contemplated embodiments 1 and Fig. 5, nethermost Zr0.25Sn0.75Nb0.25TM is close, is good.The zirconium alloy prepare than embodiment 1 of corrosion resistance nature in the pure water of zirconium alloy prepared by embodiment 3 is good, and the in-pile corrosion of the zirconium alloy of therefore embodiment 3 preparation also can be fine, and best close in figure.Zr1.0Sn1.0Nb0.1TM above in figure is exactly ZIRLO alloy, and the corrosion resistance nature of Zr0.25Sn0.75Nb0.25TM alloy is well more a lot of than Zr1.0Sn1.0Nb0.1TM.
More than describe preferred embodiment of the present invention in detail.The design innovation that invention technician proposes these new zirconium alloys according to the requirement of high burnup fuel assembly is useful; therefore; all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (12)
1. a Zirconium alloy material, is characterized in that, the component of described Zirconium alloy material is:
The tin of 0.10 ~ 0.40 % by weight;
The niobium of 0.50 ~ 1.50 % by weight;
The iron of 0.01 ~ 0.20 % by weight;
The oxygen of 0.06 ~ 0.20 % by weight;
The vanadium of 0.01 ~ 0.09 % by weight and/or the copper of 0.01 ~ 0.09 % by weight; With
Surplus zirconium.
2. Zirconium alloy material as claimed in claim 1, it is characterized in that, also comprise Second Phase Particle in described Zirconium alloy material, the area fraction of described Second Phase Particle is 3.5 ~ 15%.
3. Zirconium alloy material as claimed in claim 2, it is characterized in that, the median size of wherein said Second Phase Particle is not more than 100nm.
4. the Zirconium alloy material as described in claim 1,2 or 3, is characterized in that, the component of described Zirconium alloy material is:
The tin of 0.10 ~ 0.40 % by weight;
The niobium of 0.85 ~ 1.50 % by weight;
The iron of 0.01 ~ 0.20 % by weight;
The oxygen of 0.06 ~ 0.20 % by weight;
The vanadium of 0.01 ~ 0.09 % by weight; With
Surplus zirconium.
5. Zirconium alloy material as claimed in claim 4, it is characterized in that, the component of described Zirconium alloy material is:
The tin of 0.15 ~ 0.35 % by weight;
The niobium of 0.85 ~ 1.20 % by weight;
The iron of 0.08 ~ 0.12 % by weight;
The oxygen of 0.10 ~ 0.20 % by weight;
The vanadium of 0.04 ~ 0.06 % by weight; With
Surplus zirconium.
6. Zirconium alloy material as claimed in claim 5, it is characterized in that, the component of described Zirconium alloy material is:
The tin of 0.25 % by weight;
The niobium of 1.00 % by weight;
The iron of 0.10 % by weight;
The oxygen of 0.13 % by weight;
The vanadium of 0.05 % by weight; With
Surplus zirconium.
7. the Zirconium alloy material as described in claim 1,2 or 3, is characterized in that, the component of described Zirconium alloy material is:
The tin of 0.10 ~ 0.40 % by weight;
The niobium of 0.85 ~ 1.50 % by weight;
The iron of 0.01 ~ 0.20 % by weight;
The oxygen of 0.06 ~ 0.20 % by weight;
The copper of 0.01 ~ 0.09 % by weight; With
Surplus zirconium.
8. Zirconium alloy material as claimed in claim 7, it is characterized in that, the component of described Zirconium alloy material is:
The tin of 0.15 ~ 0.35 % by weight;
The niobium of 0.85 ~ 1.20 % by weight;
The iron of 0.08 ~ 0.12 % by weight;
The oxygen of 0.10 ~ 0.20 % by weight;
The copper of 0.04 ~ 0.06 % by weight; With
Surplus zirconium.
9. Zirconium alloy material as claimed in claim 8, it is characterized in that, the component of described Zirconium alloy material is:
The tin of 0.25 % by weight;
The niobium of 1.00 % by weight;
The iron of 0.10 % by weight;
The oxygen of 0.13 % by weight;
The copper of 0.05 % by weight; With
Surplus zirconium.
10. the Zirconium alloy material as described in claim 1,2 or 3, is characterized in that, the component of described Zirconium alloy material is:
The tin of 0.10 ~ 0.40 % by weight;
The niobium of 0.85 ~ 1.50 % by weight;
The iron of 0.01 ~ 0.20 % by weight;
The oxygen of 0.06 ~ 0.20 % by weight;
The vanadium of 0.01 ~ 0.09 % by weight;
The copper of 0.01 ~ 0.09 % by weight; With
Surplus zirconium.
11. Zirconium alloy materials as claimed in claim 10, it is characterized in that, the component of described Zirconium alloy material is:
The tin of 0.15 ~ 0.35 % by weight;
The niobium of 0.85 ~ 1.20 % by weight;
The iron of 0.08 ~ 0.12 % by weight;
The oxygen of 0.10 ~ 0.20 % by weight;
The vanadium of 0.04 ~ 0.06 % by weight;
The copper of 0.04 ~ 0.06 % by weight; With
Surplus zirconium.
12. Zirconium alloy materials as claimed in claim 11, it is characterized in that, the component of described Zirconium alloy material is:
The tin of 0.25 % by weight;
The niobium of 1.00 % by weight;
The iron of 0.10 % by weight;
The oxygen of 0.13 % by weight;
The vanadium of 0.05 % by weight;
The copper of 0.05 % by weight; With
Surplus zirconium.
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| CN105441716A (en) * | 2016-01-06 | 2016-03-30 | 中国核动力研究设计院 | Zirconium alloy for pressurized water reactor core structure |
| CN111218632A (en) * | 2020-01-13 | 2020-06-02 | 中国科学院金属研究所 | Preparation method of zirconium and zirconium alloy coarse crystals |
| CN113201665A (en) * | 2021-04-08 | 2021-08-03 | 中广核研究院有限公司 | Zirconium alloy for fuel assembly cladding, manufacturing method thereof and fuel assembly cladding tube |
| CN113249616A (en) * | 2021-04-08 | 2021-08-13 | 岭澳核电有限公司 | Zirconium alloy for fuel assembly, preparation method thereof and cladding tube of fuel assembly |
| CN115961175A (en) * | 2022-11-25 | 2023-04-14 | 岭澳核电有限公司 | Low-tin high-niobium zirconium alloy for fuel assembly, preparation method of low-tin high-niobium zirconium alloy and cladding tube of fuel assembly |
| WO2023087898A1 (en) * | 2021-11-18 | 2023-05-25 | 中国核动力研究设计院 | Fuel assembly grid, fuel assembly, and pressurized water reactor core |
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