CN107142424B - A kind of nuclear reactor structure material FeCrAl base alloy material and preparation method thereof - Google Patents
A kind of nuclear reactor structure material FeCrAl base alloy material and preparation method thereof Download PDFInfo
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- CN107142424B CN107142424B CN201710390400.1A CN201710390400A CN107142424B CN 107142424 B CN107142424 B CN 107142424B CN 201710390400 A CN201710390400 A CN 201710390400A CN 107142424 B CN107142424 B CN 107142424B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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Abstract
The invention discloses a kind of nuclear reactor structure material FeCrAl base alloy materials, by weight, Cr:12.5~14.5%, Al:3.5~5.5%, Mo:1~2.5%, Nb:0.1~0.5%, Si:0~0.3%, Zr:0~0.2%, W:0~0.05%, Ga:0~0.05%, La:0.01~0.1%, surplus are iron and the impurity for meeting industrial standard.Alloy material of the invention has excellent high temperature oxidation resistance under 1000 DEG C of water vapor conditions, and alloy elevated temperature strength with higher and thermal structure stability under 800 DEG C of high temperature have very high mechanical strength and higher plasticity and toughness at room temperature.
Description
Technical field
The invention belongs to fe-based alloy structure material and specialty alloy materials technical fields, and in particular to for pressing water to react
One of heap nuclear reactor structure material FeCrAl base alloy material and preparation method thereof.
Background technique
Fuel element is the core component of power producer reactor core, and performance is directly related to the peace of nuclear reactor operation
Quan Xingyu economy.Zircaloy is that current commercial nuclear power light water reactor fuel element uniquely uses cladding materials.But in emergency case
Under (such as Fukushima, Japan nuclear accident, presurized water reactor loss of-coolant accident (LOCA)), zirconium alloy cladding and high temperature coolant water vigorous reaction are released big
Calorimetric and explosion gas hydrogen cause cladding materials mechanical property to deteriorate, generate reactor hydrogen it is quick-fried with a large amount of radioactive products outside
The nuclear catastrophes consequence such as let out.So next-generation and following advanced nuclear power presurized water reactor fuel element cladding material and current nuclear power
Zirconium alloy cladding material is compared, it is necessary to have better steam oxidation ability, elevated temperature strength and high-temperature stability resistant to high temperatures, energy
It is enough that bigger safe clearance is provided within a certain period of time and potential serious reactor core is avoided to melt accident, also referred to as crash-proof involucrum
Material.
Crash-proof cladding materials require its can in 800-1000 DEG C or so steam ambient in several hours (time it is more long more
It is good, rescue time can be increased) keep a very low oxidation rate (2 orders of magnitude at least lower than zircaloy), while the involucrum
Material has the mechanical strength for meeting short cycle reliability for (>=800 DEG C) under the high temperature conditions, just can be more than in this way design
The safety allowance of reactor core accident is improved when basic accident.Under the promotion of this tight demand background, world nuclear big country pair
Many candidate's crash-proof cladding materials have carried out a large amount of HIGH TEMPERATURE OXIDATION PERFORMANCE, most represent include Zr-2, Zr-4,
The materials such as SiC, 304SS, 310SS, FeCrAl based alloy.Result of study shows: FeCrAl based alloy is due to good anti-
Irradiation behaviour, and the oxidation-resistance property of the FeCrAl alloy containing appropriate amount Cr, Al be far superior to Zr-2, Zr-4,
304SS, 310SS alloy, high temperature oxidation resistance and the SiC material for using CVD method to prepare are substantially suitable, become elder generation
Into nuclear power crash-proof cladding materials research and development in extremely have potential cladding materials.
The high temperature oxidation resistance of commercialization FeCrAl base alloy material is more significant mostly at present, but in reactor operation work
Hardening and brittle degree are serious under condition heat aging and radiation parameter, bring major safety risks to reactor operation.Moreover,
Commercial FeCrAl based alloy room temperature mechanics plasticity is poor, leads to sheet alloy and thin-wall pipes processing difficulties, is unable to satisfy
Industrialize actual demand.
Existing FeCrAl alloy material although high temperature oxidation resistance with higher, but do not have strong plasticity and toughness
Can, it is unfavorable in nuclear reaction engineering practice.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of nuclear reactor structure material FeCrAl based alloy materials
Material, the alloy material have excellent high temperature oxidation resistance under 1000 DEG C of water vapor conditions, and alloy has under 800 DEG C of high temperature
Higher elevated temperature strength and thermal structure stability have very high mechanical strength and higher plasticity and toughness at room temperature.It is also disclosed
A kind of preparation method.
The present invention is achieved through the following technical solutions:
A kind of nuclear reactor structure material FeCrAl base alloy material, by weight, Cr:12.5~14.5%, Al:
3.5~5.5%, Mo:1~2.5%, Nb:0.1~0.5%, Si:0~0.3%, Zr:0~0.2%, W:0~0.05%, Ga:0
~0.05%, La:0.01~0.1%, surplus are iron and the impurity for meeting industrial standard.
By weight, Cr:13.0%, Al:4.0%, Mo:2.5%, Nb:0.5%, Si:0.2%, Zr:0.2%, W:
0%, Ga:0.05%, La:0.1%, surplus are iron and the impurity for meeting industrial standard.
Total weight percent content >=3.0% of Mo, Nb, Zr, W.
Total weight percent content >=16.5% of Cr, Al and Si.
C :≤0.008%, N :≤0.005%, O :≤0.003%.
The preparation method of foregoing advanced Reactor fuel element cladding FeCrAl base alloy material, specifically includes following
Step: melting ingot casting, by ingot casting annealing, forging, heat treatment, hot rolling, heat aging processing, cold rolling；Annealing temperature >=1120
DEG C, soaking time >=4h after annealing；
Forging includes begin forging and finish-forging, initial forging temperature >=1070 DEG C, final forging temperature >=820 DEG C；
Thermal treatment rate are as follows: 775 DEG C~800 DEG C/0.5-1.0h；
Hot-rolled temperature is≤850 DEG C, deflection >=55% of processed material when hot rolling；
The aging temp of heat aging processing is 700 DEG C~800 DEG C, aging time are as follows: 20h~100h；
Intermediate anneal temperature and final annealing temperature≤745 DEG C in cold-rolled process, processed material deflection when cold rolling
>=35%.
It needs to remove the oxide skin of ingot casting surface before forging and cleaning treatment is carried out to ingot casting surface.
Need to remove the table for being forged the surface scale of processing material and being forged processing material to it before heat treatment
Face carries out cleaning treatment.
Forging ratio is greater than 2 when forging.
The setting of temperature in hot rolling and cold-rolled process, effectively prevent Laves second phase particles processing and it is heat treated
Growing up in journey obtains tiny second phase particles, ensure that the high temperature oxidation resistance of alloy, while enhancing room temperature and high temperature
Strengthening effect.
Inventor has found that existing most commercialization FeCrAl base alloy material has significant oxygen resistant to high temperatures in practice process
Change performance, but hardening and brittle degree are serious under reactor operation operating condition heat aging and radiation parameter, and FeCrAl base closes
Golden room temperature mechanics plasticity is poor, and cause sheet alloy and thin-wall pipes processing difficulties, reason to be: Cr, Al content are excessively high.For
It prevents FeCrAl based alloy from hardening and the aggravation of embrittlement tendency, alloy is caused to interrupt in reactor operation and processing preparation process
It splits, the present invention carries out creative component to Cr, Al, Mo, Nb, Si, Zr, W, La, Ga etc. and matches, one side Cr, Al and Si's
Effectively cooperation, can be effectively reduced oxidation rate of the alloy material of the present invention under the conditions of 800-1000 DEG C, so that the present invention closes
The oxidation rate of golden material is maintained at a lower level, and oxidation rate speedup is slow, guarantees FeCrAl base alloy material tool
There is high temperature oxidation resistance, Laves the second phase grain of a large amount of disperses can be precipitated in effective cooperation of another aspect Mo, Nb, Zr, W
Son refines crystal grain and improves Alloy At Room Temperature mechanical property and elevated temperature strength.In general, the intensity and toughness of alloy material are one
To contradiction, usually raising intensity, toughness will be reduced or toughness improves, and intensity just reduces.Exactly the present invention using Mo, Nb,
The combination collocation of Zr, W combination and La+Ga are guaranteeing certain high temperature oxidation resistance basis on the combination foundation of Cr, Al and Si
On, it can both guarantee the intensity of alloy material, the plasticity and toughness of alloy material will not be reduced, and assign this alloy material excellent power
Learn performance and plastic toughness.
Compared with prior art, the present invention having the following advantages and benefits:
1, alloy material of the invention can have the alloy under 800 DEG C of high temperature to have on the basis of high-temperature oxidation resistant
Higher elevated temperature strength and thermal structure stability have very high mechanical strength and higher plasticity and toughness at room temperature；
2, alloy of the present invention has very excellent high temperature oxidation resistance, high-temperature steam under 1000 DEG C of water vapor conditions
Oxidation rate is well below current commercial nuclear power cladding materials Zr-4 alloy；
3, alloy of the present invention obtains small and dispersed distribution after the processing of zerolling, long-time timeliness and heat treatment process
The second phase of Laves, the heat of the mechanical property (room temperature obdurability and elevated temperature strength) and alloy structure that significantly improve alloy is steady
It is qualitative.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment, the present invention is made
Further to be described in detail, exemplary embodiment of the invention and its explanation for explaining only the invention, are not intended as to this
The restriction of invention.
Embodiment
The composition proportion of the FeCrAl based alloy embodiment of the present invention of table 1 (remainder is iron)
The preparation method for passing through identical (i.e. parameter is identical) with the alloy material proportion of embodiment 1-7#: as previously described
Advanced Reactor fuel element cladding FeCrAl base alloy material preparation method, specifically includes the following steps:
(1) high purity alloys with ingot iron and purity greater than 99.9% are formulated ingredient by table 1, use vacuum induction melting furnace
Melting prepares 20~30 kilograms of ingot castings；
(2) above-mentioned ingot casting is subjected to high temperature homogenizing annealing temperature.Annealing temperature are as follows: >=1150 DEG C, soaking time >=3h；
(3) surface scale for removing ingot casting after homogenizing annealing, carries out high temperature forging, forging of beginning after surface cleaning is handled
Temperature are as follows: >=1050 DEG C, final forging temperature are as follows: >=850 DEG C, forging ratio >=2；
(4) after removal forging plate surface scale, by surface cleaning, treated that plate is heat-treated, heat treatment
System are as follows: 780~800 DEG C/0.5~1h.It is heat-treated the hot rolling of laggard andante material, hot-rolled temperature≤850 DEG C, material deflection >=
50%；
(5) plate after hot rolling is subjected to heat aging processing, specific aging temp are as follows: 700 DEG C~800 DEG C, aging time
Are as follows: 20h~100h；
(6) heat aging treated hot rolled plate is subjected to cold rolling, intermediate anneal temperature in cold-rolled process and most retreated
Fiery temperature≤750 DEG C, cold rolling reduction >=30%；
For the advance for further illustrating formula of the invention, the present invention uses optimal case 6# for basic embodiment,
Test is compared on the basis of 6#, and the ratio other than the scope of the invention is selected to compare test, the preparation of all comparative examples
Method is all identical with 6#.
Comparative example 1*: only add Cr, Al, Si, Mo, and ingredient is identical with 6#；
Comparative example 2*: only add Cr, Al, Si, Nb, and ingredient is identical with 6#；
Comparative example 3*: only add Cr, Al, Si, Zr, and ingredient is identical with 6#；
Comparative example 4*: only add Cr, Al, Si, Mo, Ga, La, and ingredient is identical with 6#；
Comparative example 5*: only add Cr, Al, Si, Nb, Ga, La, and ingredient is identical with 6#；
Comparative example 6*: raw material is identical with 6#, and the content that the content that the content of Mo is 0.8%, Nb is 0.05%, Zr is
The content of 0.3%, La are 0.009%, Ga:0.1%, remaining ingredient is consistent with 6#；
Comparative example 7*: raw material is identical with 6#, and the content that the content that the content of Mo is 3.0%, Nb is 0.6%, Zr is
The content of 0.4%, La are 0.18%, Ga:0.2%, remaining ingredient is consistent with 6#；
Comparative example 8*:Cr content is 12%, Al content 3%, Si content are 0.4%, remaining ingredient and comparative example 7* phase
Together；
Comparative example 9*:Cr content is 15%, Al content 5.9%, Si content are 0.5%, remaining ingredient and comparative example 7*
It is identical.
The composition proportion of the FeCrAl based alloy comparative example of the present invention of table 2 (remainder is iron)
Alloy material (summary sheet is shown in Table 3) prepared by embodiment 1-7# and comparative example 1*-9* carries out all-round property testing,
Its test result is as follows table 4.
4 Contrast on effect of table
It can find out from table, the alloy material of embodiment 1-4# is under the conditions of only meeting basic components, although having
Certain high temperature oxidation resistance, but its high temperature oxidation resistance is not so good as to meet the good of the alloy material of 5-7#.(5-7# is simultaneously
Meet total weight percent content >=3.0% of Mo, Nb, Zr, W；Total weight percent content >=16.5% of Cr, Al and Si)
By embodiment 6# and comparative example 1-5* it is found that Cr, Al and Si content are constant in the case where, arbitrarily single plus Mo, Nb,
The comprehensive performance of Zr, W, La+Ga, alloy material are poor.
By embodiment 6# and comparative example 6-9* it is found that Cr, Al and Si, Mo, Nb, Zr, W, La+Ga out of the range of the present invention
Any combination, the comprehensive performance of alloy material also not no embodiment it is good.
It is worth noting that, the performance evaluation of FeCrAl base alloy material is the fastidious process of a synthesis, single number
Height do not have decisive significance to the judge of its performance quality, those skilled in the art are in evaluation FeCrAl base alloy material
Performance when, should consider high temperature oxidation resistance while also need to consider the size of its toughness and strength values, such as anti-height
But its low toughness of warm oxidation susceptibility and intensity cannot reach using level, and for another example toughness is strong, its intensity is not high, have upper
The FeCrAl base alloy material for stating performance is not needed for application, not in the scope of the excellent identification of comprehensive performance.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (6)
1. a kind of nuclear reactor structure material FeCrAl base alloy material, which is characterized in that by weight, Cr:12.5~
14.5%, Al:3.5~5.5%, Mo:1~2.5%, Nb:0.1~0.5%, Si:0.1~0.3%, Zr:0.1~0.2%, W:0.02~
0.05%, Ga:0.01~0.05%, La:0.01~0.1%, surplus is iron and the impurity for meeting industrial standard, by following methods
It obtains: melting ingot casting, by ingot casting annealing, forging, heat treatment, hot rolling, heat aging processing, cold rolling；Annealing temperature >=1120
DEG C, soaking time >=4h after annealing；Forging includes begin forging and finish-forging, initial forging temperature >=1070 DEG C, final forging temperature >=820 DEG C；
Heat treating regime are as follows: 775 DEG C~800 DEG C/0.5-1.0h；Hot-rolled temperature is≤850 DEG C, the deformation of processed material when hot rolling
Amount >=55%；The aging temp of heat aging processing is 700 DEG C~800 DEG C, aging time are as follows: 20h~100h；In cold-rolled process
Intermediate anneal temperature and final annealing temperature≤745 DEG C, processed material deflection >=35% when cold rolling；
Total weight percent content >=3.0% of Mo, Nb, Zr, W；
Total weight percent content >=16.5% of Cr, Al and Si.
2. nuclear reactor structure material FeCrAl base alloy material according to claim 1, which is characterized in that impurity
In, C :≤0.008%, N :≤0.005%, O :≤0.003%.
3. the preparation side of -2 described in any item nuclear reactor structure material FeCrAl base alloy materials according to claim 1
Method, which is characterized in that specifically includes the following steps: melting ingot casting, at ingot casting annealing, forging, heat treatment, hot rolling, heat aging
Reason, cold rolling；Annealing temperature >=1120 DEG C, soaking time >=4h after annealing；Forging includes begin forging and finish-forging, initial forging temperature
>=1070 DEG C, final forging temperature >=820 DEG C；Heat treating regime are as follows: 775 DEG C~800 DEG C/0.5-1.0h；Hot-rolled temperature is≤850
DEG C, deflection >=55% of processed material when hot rolling；The aging temp of heat aging processing is 700 DEG C~800 DEG C, aging time
Are as follows: 20h~100h；Intermediate anneal temperature and final annealing temperature≤745 DEG C in cold-rolled process, processed material when cold rolling
Deflection >=35%.
4. preparation method according to claim 3, which is characterized in that need to remove the oxide skin of ingot casting surface before forging
And cleaning treatment is carried out to ingot casting surface.
5. the preparation method according to claim 4, which is characterized in that removal is needed to be forged processing material before heat treatment
Surface scale and it is forged processing material surface carry out cleaning treatment.
6. the preparation method according to claim 4, which is characterized in that when forging, forging ratio is greater than 2.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319369A (en) * | 2016-10-12 | 2017-01-11 | 苏州热工研究院有限公司 | FeCrAl base alloy material for nuclear fuel cladding material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106319369A (en) * | 2016-10-12 | 2017-01-11 | 苏州热工研究院有限公司 | FeCrAl base alloy material for nuclear fuel cladding material |
Non-Patent Citations (2)
| Title |
|---|
| Design of alumina forming FeCrAl steels for lead or lead-bismuth;Jun Lim等;《 Journal of Nuclear Materials》;20120427;第441卷;图1 |
| Development and property evaluation of nuclear grade wrought FeCrAl fuel cladding for light water reactors;Y. Yamamoto等;《Journal of Nuclear Materials》;20151019;第467卷;第705页表2中C35MNC合金;第705页左栏第2段 |
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