CN107699739A - A kind of zircaloy of resistance to nodular corrosion and preparation method thereof - Google Patents
A kind of zircaloy of resistance to nodular corrosion and preparation method thereof Download PDFInfo
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- CN107699739A CN107699739A CN201710958708.1A CN201710958708A CN107699739A CN 107699739 A CN107699739 A CN 107699739A CN 201710958708 A CN201710958708 A CN 201710958708A CN 107699739 A CN107699739 A CN 107699739A
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- 238000005260 corrosion Methods 0.000 title claims abstract description 60
- 230000007797 corrosion Effects 0.000 title claims abstract description 60
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 26
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims description 48
- 229910045601 alloy Inorganic materials 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 16
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005482 strain hardening Methods 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 7
- 229910001128 Sn alloy Inorganic materials 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000011651 chromium Substances 0.000 description 18
- 239000011135 tin Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 238000005275 alloying Methods 0.000 description 9
- 238000005253 cladding Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000004193 disodium 5'-ribonucleotide Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 206010017553 Furuncle Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004173 sunset yellow FCF Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Abstract
The invention discloses a kind of zircaloy of resistance to nodular corrosion and preparation method thereof, solve in presurized water reactor, the problem of existing resistance to Nodular Corrosion of zircaloy is not ideal enough.Weight percentage of the present invention, including consisting of composition：Sn：0.6~1.5%, Fe：0.05~0.6%, Cr：0.1~0.45%, V：0.05~0.25% and/or Ni：0.02~0.08%, O：0.08~0.16%, surplus is Zr and other inevitable impurity.The present invention is on the basis of Zr~Sn alloys, for oxygen-containing condition of water quality, Sn contents are controlled in medium level, transition metal Fe, Cr, V, Ni content are adjusted simultaneously to proper level, and there is more excellent resistance to uniform Nodular Corrosion, higher creep resistant and fatigue properties, Flouride-resistani acid phesphatase growth performance by the rear present invention that optimizes and revises of proportioning.
Description
Technical field
The invention belongs to specialty alloy materials technical field, and in particular to a kind of zircaloy and its system of resistance to nodular corrosion
Preparation Method.
Background technology
Zircaloy has good corrosion resistance because thermal neutron absorption cross section is small in high-temperature high pressure water and steam
Can, there is fairly good anti-neutron irradiation performance in heap, thus the cladding materials of nuclear power water-cooled reactor is commonly used as,
It is the cladding materials that current nuclear power plant reactor uniquely uses.
In early days, cladding materials is generally made up of Zr-2, Zr-4 alloy.With the further development of nuclear power, ensureing that core is anti-
Answer on the basis of heap security, it is necessary to improve the economy of nuclear reactor, reduce nuclear power operating cost, thus fuel assembly is carried
Long-lived phase, high burnup, zero damaged target are gone out.This means the water side corrosion of zirconium alloy cladding aggravates, hydrogen-sucking amount increases, spoke
According to time growth, pellet and cladding interaction increase and internal pressure rise etc., so as to be proposed more to the performance of zircaloy
High requirement.
The high request proposed for Nuclear Power Technology development to fuel can, expands grinding for novel zirconium alloy in the world
Study carefully, obtain the novel zirconium alloys such as ZIRLO, E635, M5, X5A that there is more preferable decay resistance than Zr-4 alloy.Study
Show, the proportioning of composition such as might not reduce the Sn contents in ZIRLO alloys in optimized scope in existing zircaloy
Afterwards, its decay resistance further improves；The HANA-6 that micro Cu (0.05wt%) is formed afterwards is added in Zr-Nb alloys to close
Gold also has very excellent decay resistance；There is fuel rod or fuel assembly bending in heap in M5 alloys in running
And the anomaly such as Flouride-resistani acid phesphatase growth performance difference, therefore France with the addition of a small amount of Sn and Fe on the basis of M5 alloying components,
The mechanical property of alloy, especially creep and irradiation growth are greatly improved on the basis of alloy excellent corrosion resistance is kept
Energy.
In the high request proposed to fuel can, it is generally recognized that general corrosion resistance and furuncle for the zircaloy of nuclear reactor
Shape corrosion is most important corrosive nature requirement.Commercial pressurized-water reactor nuclear power plant will be dissolved by being passed through hydrogen in primary Ioops water
The content of oxygen is reduced to below 5ppb, and can water side corrosion mechanism is mainly homogeneous corrosion.But in Control for Oxygen Content
In the case of not strict or water quality deviates, local corrosion, i.e. nodular corrosion can also occur, such as the E110 of Russian VVER presurized water reactors
(Zr-1%Nb) occur with E635 (Zr-1%Nb-1.2%Sn-0.4%Fe) zircaloys in the case where oxygen concentration is less than 20ppb
Nodular corrosion, Obrigheim presurized water reactors are found that the nodular corrosion of involucrum shows after a circulation for not being hydrogenated with control oxygen terminates
As.Therefore, the nodular corrosion problem of zirconium alloy cladding material is still presurized water reactor concern.
Based on above-mentioned phenomenon, industry technical staff be known in existing zircaloy on the basis of optimized alloy composition proportion or
Person adds other alloying elements and is possible to also develop the more excellent zircaloy of decay resistance, to meet that burnup constantly carries
High needs.But in fact, how to adjust alloy composition in the prior art can effectively solve the problem that zircaloy bag with ratio
The scheme of the nodular corrosion problem of shell material.
The content of the invention
The technical problems to be solved by the invention are：In presurized water reactor, the existing resistance to Nodular Corrosion of zircaloy is inadequate
The problem of preferable, it passed through each element, and it is an object of the present invention to provide a kind of zircaloy of resistance to nodular corrosion and preparation method thereof
Selection and the optimization of proportioning, have more excellent resistance to uniform Nodular Corrosion, higher creep resistant and fatigue properties, anti-spoke
According to growth performance.
The present invention is achieved through the following technical solutions：
A kind of zircaloy of resistance to nodular corrosion, including consisting of composition：
Sn：0.6~1.5%, Fe：0.05~0.6%, Cr：0.1~0.45%, V：0.05~0.25% and Ni：0.02~
One or more in 0.08%, O：0.08~0.16%, surplus is Zr and other inevitable impurity；And Fe, Cr, V and Ni
Total amount be 0.37~1.1%.
Further, the present invention is made up of following ingredients：
Sn：0.6~0.9%, Fe：0.1~0.4%, Cr：0.1~0.4%, V：0.05~0.15% and/or Ni：0.02
~0.06%, O：0.08~0.16%, surplus is Zr and other inevitable impurity.
Further, the present invention is made up of following ingredients：
Sn：1.15~1.5%, Fe：0.18~0.24%, Cr：0.1~0.15%, V：0.05~0.15% and/or Ni：
0.02~0.06%, O：0.08~0.16%, surplus is Zr and other inevitable impurity；And Fe, Cr, V and Ni total amount are
0.37~0.62%.
Further, the present invention is made up of following ingredients：
0.9~1.15% Sn, 0.2~0.4% Fe, 0.2~0.4% Cr, 0.1~0.2% V, 0.02~
One or more in 0.08% Ni, 0.08~0.16% O, surplus are Zr and other inevitable impurity；And Fe, Cr, V
Total amount with Ni is 0.42~0.9%.
Further, the present invention is made up of following ingredients：
1.15~1.5% Sn, 0.3~0.55% Fe, 0.2~0.4% Cr, 0.1~0.2% V, 0.02~
One or more in 0.08% Ni, 0.08~0.16% O, surplus are Zr and other inevitable impurity；And Fe, Cr, V
Total amount with Ni is 0.52~1.1%.
For the zircaloy for nuclear reactor cladding materials, the decay resistance of zircaloy be overriding concern because
Element, production cost and machinability select to need to consider during alloying element on this basis.Therefore, it is necessary to which research in detail is every
The dosage of every kind of alloying element in influence and alloy system of a kind of alloying element to corrosion resistance, mechanical performance and creep behaviour
Scope.Each alloys producing and dosage concrete condition are as follows in the present invention：
(1) zirconium (Zr)
In view of the consideration to neutron economy, the zirconium of present invention selection neutron absorption cross-section smaller (0.185b) is as matrix
Element, while it is also contemplated for being added to the neutron absorption cross-section situation of other alloying elements in zirconium base body.
(2) tin (Sn)
Tin is capable of the α phases of stabilised zirconia, increases its intensity, and can offset illeffects of the nitrogen to corrosion.When tin dosage is very few
When, it is impossible to reach required effect.Sn adds content in 0.6~1.5% (weight hundred compares) in the present invention, can ensure that alloy has
There are excellent decay resistance and good mechanical property.
(3) iron (Fe)
Iron can improve alloy corrosion resistance and mechanical property, but iron dosage is excessive or very few can all produce unfavorable shadow
Ring.It is excellent corrosion-resistant can to ensure that alloy has in 0.05~0.6% (percentage by weight) for the content that Fe is added in the present invention
Performance.
(4) chromium (Cr)
Chromium can improve alloy corrosion resistance and mechanical property, but chromium dosage is excessive or very few can all produce unfavorable shadow
Ring.It is excellent corrosion-resistant can to ensure that alloy has in 0.1~0.45% (percentage by weight) for the content that Cr is added in the present invention
Performance.
(5) vanadium (V)
Alum can improve alloy corrosion resistance and mechanical property, and the corrosive nature of aluminiferous zircaloy is quicker to being heat-treated
Sense.It is excellent corrosion-resistant can to ensure that alloy has in 0.05~0.25% (percentage by weight) for the content that V is added in the present invention
Performance.
(6) nickel (Ni)
Nickel can improve alloy corrosion resistance energy, but nickel dosage can excessively have adverse effect on.Ni is added in the present invention
Content in 0.02~0.08% (percentage by weight), can ensure that alloy has excellent decay resistance.
(7) oxygen (O)
Oxygen is capable of the α phases of stabilised zirconia, and addition oxygen can improve yield strength in alloy.The content that O is added in the present invention exists
0.08~0.16% (percentage by weight), it can ensure that alloy has enough mechanical performances and creep-resistant property.Oxygen content
Increase, greatly reduces the control difficulty in material processing.
The present invention is on the basis of Zr-Sn alloys, for oxygen-containing condition of water quality, by the control of Sn contents in higher level, simultaneously
Transition metal Fe, Cr, V, Ni content is adjusted to proper level.Pass through the production prepared after present invention optimization component and proportioning
Product improve the general corrosion resistance performance in out-pile pure water and oxygenated water, improve the resistance to nodular corrosion in high-temperature steam
Energy.It is believed that these alloys are used with more excellent in reactor by the testing inspection result in embodiment
Resistance to uniform Nodular Corrosion, higher creep resistant and fatigue properties, Flouride-resistani acid phesphatase growth performance.
Thus, zircaloy of the present invention resists with more excellent resistance to uniform Nodular Corrosion, with higher
Creep and fatigue properties, Flouride-resistani acid phesphatase growth performance.
In addition, after alloying component determination, the resistance to of alloy can also further be improved using suitable heat processing technique
Corrosive nature.Such as in the higher zircaloy of Nb contents, including ZIRLO, M5 and N36 etc., after hot worked temperature is improved, by
The super saturated solid solution Nb in the roughening of the second phase and uneven distribution and alloy substrate, can cause decay resistance to be deteriorated, because
And all emphasize to use " low temperature process technique ", i.e., can using the low temperature process technique of relatively low hot processing temperature and annealing temperature
The second phase constitution of small and dispersed is obtained, so as to greatly improve the decay resistance of alloy and mechanical property.
Therefore, the present invention optimizes processing technology while optimized alloy forms and matches, and is entered by the optimization of technique
One step improves the decay resistance of alloy, and specific setting is as follows：
A kind of preparation method of the zircaloy of resistance to nodular corrosion, including：
(1) a kind of various components of the zircaloy of resistance to nodular corrosion of the present invention are subjected to dispensing according to proportioning；
(2) alloy cast ingot is made in melting；
(3) alloy cast ingot is forged into the blank material of required shape；
(4) by blank material homogeneous heating, and Quenching Treatment is carried out；
(5) blank material after quenching is subjected to hot-working；
(6) blank material after hot-working is subjected to cold working, and carries out intermediate annealing；
(7) stress relief annealing or recrystallization annealing processing are carried out, obtains the zircaloy.
Further, the melting in the step (2) is carried out in vacuum consumable electrode arc furnace.At 900 DEG C in the step (3)
~1200 DEG C of β phase regions are forged, and the β phase regions in the step (4) at 1000 DEG C~1200 DEG C are homogenized.The step
Suddenly hot worked temperature is 600 DEG C~750 DEG C in (5), and the temperature of intermediate annealing is 550 DEG C~650 DEG C in the step (6).
The temperature that stress relief annealing or recrystallization annealing processing are carried out in the step (7) is 480 DEG C~620 DEG C.
Present invention employs preferable Sn, Fe, Cr, V, Ni composition range, between alloying element within this range
Interaction, with reference to low temperature process technique, effect unexpected in advance is generated, this effect is mainly manifested in two sides
Face：1) alloy of the present invention all shows good decay resistance when corroding under the conditions of above-mentioned 3 kinds of water chemistry, hence it is evident that is better than
Zr-4 and N36 alloys；2) alloy of the present invention obtains the second phase of small and dispersed distribution after low temperature process is processed, and improves conjunction
The mechanical property (such as creep and fatigue behaviour) and Flouride-resistani acid phesphatase growth performance of gold.
The present invention compared with prior art, has the following advantages and advantages：
1st, the present invention is on the basis of Zr-Sn alloys, for oxygen-containing condition of water quality, by the control of Sn contents in higher level, together
When adjust transition metal Fe, Cr, V, Ni content to proper level；The production prepared after being optimized using composition and ratio of the present invention
Product improve the general corrosion resistance performance in out-pile pure water and oxygenated water, improve the resistance to nodular corrosion in high-temperature steam
Energy；
2nd, zircaloy of the present invention with more excellent resistance to uniform Nodular Corrosion, with higher creep resistant
With fatigue properties, Flouride-resistani acid phesphatase growth performance.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiment, the present invention is made
Further to describe in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this
The restriction of invention.
Embodiment
A kind of zircaloy of resistance to nodular corrosion, the constituent of each element and proportioning are as shown in table 1, in table 1 10* and
11* is respectively the constituent of Zr-4 alloys and N36 alloys.
Table 1
The specific preparation method of above-mentioned zircaloy is as follows：
(1) dispensing is carried out according to the proportioning in above-mentioned table 1；
(2) melting is carried out in vacuum consumable electrode arc furnace, alloy cast ingot is made；
(3) blank material of shape needed for alloy cast ingot is forged into 900 DEG C~1200 DEG C of β phase regions；
(4) by β phase region homogeneous heating of the blank material at 1000 DEG C~1200 DEG C, and Quenching Treatment is carried out；
(5) blank material after quenching is subjected to hot-working at 600 DEG C~750 DEG C；
(6) blank material after hot-working is subjected to cold working, and intermediate annealing is carried out at 550 DEG C~650 DEG C；
(7) stress relief annealing or recrystallization annealing processing are carried out in 480 DEG C~620 DEG C, obtains the zircaloy.
The zircaloy prepared by the above method is detected, due to the limitation of factors, typically entered in out-pile
Horizontal high voltage kettle corrosion test is to simulate corrosive nature of the zircaloy in heap.Although out-of-pile performances can not represent property in heap completely
Can, whether these alloys really can be applied among practice and to show satisfactory technique effect still unknown.But
By test, the alloy with preferable out-of-pile performances also shows preferable performance in heap.
Out-pile corrosion test condition mainly includes：360 DEG C of deionized waters, 360 DEG C of aqueous solution containing lithium, 400 DEG C of steam, 500
DEG C steam.Wherein, 500 DEG C of steam corrosions test the inspection for Nodular Corrosion.In 360 DEG C of aqueous solution and 400 DEG C of steam
The qualified zirconium alloy cladding material of middle experimental examination can be used for presurized water reactor, and experimental examination is qualified in 360 DEG C of aqueous solution containing lithium
The high lithium concentration operating mode of presurized water reactor is then more suitable for, and experimental examination is qualified in 500 DEG C of steam is then applicable in boiling-water reactor
In.
Out-pile corrosive nature detection mode is carried out in the present embodiment to be included：After detection is corroded 200 days in 360 DEG C of pure water
Corrosion rate, detection corrode 200 days in 360 DEG C of oxygenated waters after corrosion rate, detection corrode in 500 DEG C of steam it is 500 small
When after corrosion rate, testing result is as shown in table 2.
Table 2
From Table 2, it can be seen that alloy material provided by the present invention is in 360 DEG C of pure water, 360 DEG C of oxygenated waters and 500 DEG C
Good decay resistance is shown in steam.
In summary, application example provided by the invention shows, alloy of the present invention corrodes under the conditions of above-mentioned 3 kinds of water chemistry
When all show good decay resistance, alloy is in 360 DEG C/18.6MPa pure water, 360 DEG C/18.6MPa oxygenated waters and 500
DEG C/10.3MPa steam in synthesis decay resistance be substantially better than Zr-4 and N36 alloys.
Due to present invention employs preferable Sn, Fe, Cr, V, Ni composition range, alloying element within this range it
Between interaction, with reference to low temperature process technique, generate effect unexpected in advance, this effect is mainly manifested in two
Aspect：1) alloy of the present invention all shows good decay resistance when corroding under the conditions of above-mentioned 3 kinds of water chemistry, hence it is evident that is better than
Zr-4 and N36 alloys；2) alloy of the present invention obtains the second phase of small and dispersed distribution after low temperature process is processed, and improves conjunction
The mechanical property (such as creep and fatigue behaviour) and Flouride-resistani acid phesphatase growth performance of gold.
Above-described embodiment, the purpose of the present invention, technical scheme and beneficial effect are carried out further
Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., all should include
Within protection scope of the present invention.
Claims (10)
1. a kind of zircaloy of resistance to nodular corrosion, it is characterised in that weight percentage, including consisting of composition：
Sn：0.6~1.5%, Fe：0.05~0.6%, Cr：0.1~0.45%, V：0.05~0.25% and Ni：0.02~
One or more in 0.08%, O：0.08~0.16%, surplus is Zr and other inevitable impurity.
2. the zircaloy of a kind of resistance to nodular corrosion according to claim 1, it is characterised in that be made up of following ingredients：
Sn：0.6~0.9%, Fe：0.1~0.4%, Cr：0.1~0.4%, V：0.05~0.15% and/or Ni：0.02~
0.06%, O：0.08~0.16%, surplus is Zr and other inevitable impurity.
3. the zircaloy of a kind of resistance to nodular corrosion according to claim 1, it is characterised in that be made up of following ingredients：
Sn：1.15~1.5%, Fe：0.18~0.24%, Cr：0.1~0.15%, V：0.05~0.15% and/or Ni：0.02
~0.06%, O：0.08~0.16%, surplus is Zr and other inevitable impurity；And Fe, Cr, V and Ni total amount are 0.37
~0.62%.
4. the zircaloy of a kind of resistance to nodular corrosion according to claim 1, it is characterised in that be made up of following ingredients：
0.9~1.15% Sn, 0.2~0.4% Fe, 0.2~0.4% Cr, 0.1~0.2% V, 0.02~0.08%
Ni in one or more, 0.08~0.16% O, surplus is Zr and other inevitable impurity；And Fe, Cr, V and Ni
Total amount is 0.42~0.9%.
5. the zircaloy of a kind of resistance to nodular corrosion according to claim 1, it is characterised in that be made up of following ingredients：
1.15~1.5% Sn, 0.3~0.55% Fe, 0.2~0.4% Cr, 0.1~0.2% V, 0.02~0.08%
Ni in one or more, 0.08~0.16% O, surplus is Zr and other inevitable impurity；And Fe, Cr, V and Ni
Total amount is 0.52~1.1%.
A kind of 6. preparation method of the zircaloy of resistance to nodular corrosion, it is characterised in that including：
(1) by the various components in a kind of zircaloy of resistance to nodular corrosion described in any one of Claims 1 to 5 according to proportioning
Carry out dispensing；
(2) alloy cast ingot is made in melting；
(3) alloy cast ingot is forged into the blank material of required shape；
(4) by blank material homogeneous heating, and Quenching Treatment is carried out；
(5) blank material after quenching is subjected to hot-working；
(6) blank material after hot-working is subjected to cold working, and carries out intermediate annealing；
(7) stress relief annealing or recrystallization annealing processing are carried out, obtains the zircaloy.
A kind of 7. preparation method of the zircaloy of resistance to nodular corrosion according to claim 6, it is characterised in that the step
Suddenly the melting in (2) is carried out in vacuum consumable electrode arc furnace.
A kind of 8. preparation method of the zircaloy of resistance to nodular corrosion according to claim 6, it is characterised in that the step
Suddenly the β phase regions in (3) at 900 DEG C~1200 DEG C are forged, and the β phase regions in the step (4) at 1000 DEG C~1200 DEG C enter
Row homogenization.
A kind of 9. preparation method of the zircaloy of resistance to nodular corrosion according to claim 6, it is characterised in that the step
Suddenly hot worked temperature is 600 DEG C~750 DEG C in (5), and the temperature of intermediate annealing is 550 DEG C~650 DEG C in the step (6).
10. the preparation method of the zircaloy of a kind of resistance to nodular corrosion according to claim 6, it is characterised in that described
The temperature that stress relief annealing or recrystallization annealing processing are carried out in step (7) is 480 DEG C~620 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110284027A (en) * | 2019-08-06 | 2019-09-27 | 中国核动力研究设计院 | A kind of zirconium-base alloy of alkali resistance water quality corrosion |
| CN111254315A (en) * | 2020-03-30 | 2020-06-09 | 上海核工程研究设计院有限公司 | Furuncle-corrosion-resistant Zr-Sn-Fe-Cr-O alloy and preparation method thereof |
| CN111394617A (en) * | 2020-03-30 | 2020-07-10 | 上海核工程研究设计院有限公司 | Cladding material zirconium alloy for small water-cooled nuclear reactor and manufacturing method thereof |
| CN115747570A (en) * | 2022-10-31 | 2023-03-07 | 上海大学 | Zirconium alloy cladding material for small pressurized water reactor and preparation method thereof |
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