CN108588532A - Multi-element alloy coat, zirconium alloy cladding and fuel assembly - Google Patents
Multi-element alloy coat, zirconium alloy cladding and fuel assembly Download PDFInfo
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- CN108588532A CN108588532A CN201810491248.0A CN201810491248A CN108588532A CN 108588532 A CN108588532 A CN 108588532A CN 201810491248 A CN201810491248 A CN 201810491248A CN 108588532 A CN108588532 A CN 108588532A
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- coat
- alloy
- zirconium alloy
- zirconium
- alloy coat
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/06—Alloys based on chromium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21C—NUCLEAR REACTORS
- G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
- G21C3/02—Fuel elements
- G21C3/04—Constructional details
- G21C3/06—Casings; Jackets
- G21C3/07—Casings; Jackets characterised by their material, e.g. alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Plasma & Fusion (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coating By Spraying Or Casting (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a kind of multi-element alloy coat, zirconium alloy cladding and fuel assembly, multi-element alloy coat includes the element of following mass percent：Cr 65% 90%, Al 3% 13%, N 0.5% 8%, Fe 5% 20%, Zr 1.5% 12%.The multi-element alloy coat of the present invention; it can be applicable on zirconium alloy cladding; it is unmatched effectively to solve the problems, such as that coating is thermally expanded with matrix; reduce thermal stress; further improve the hardness and wear-resisting property of conventional Cr coatings; by the regulation and control of multielement ingredient, antioxygenic property is enhanced, realizes anti-oxidation protection effect of the coating under 1200 DEG C of high temperature steam environments.
Description
Technical field
The present invention relates to a kind of nuclear fuel technical field more particularly to multi-element alloy coat, zirconium alloy cladding and fuel stacks
Part.
Background technology
Under the high temperature conditions, heat production, production hydrogen reaction easily occur for zircaloy, and it is hidden to bring greatly safety for nuclear reactor
Suffer from.Currently, mainly there are two approach to improve the surface property of zircaloy, and then the security performance of nuclear fuel heap is substantially improved：
(1) surface-coating technology is covered by technologies such as plating, chemical plating, thermal spraying, cold spraying, vapor depositions in Zr alloy surface
It is resistance under the conditions of high-temperature water vapor can to significantly improve zircaloy by combining closely for heterogeneous membrane and matrix for one layer of heterogeneous membrane
Corrosive nature；(2) process for modifying surface passes through the side such as Surface heat-treatent, thermo-chemical treatment, Laser Surface Treatment, ion implanting
Formula changes pattern, chemical composition, phase composition, microstructure, defect state or the stress state of Zr alloy surface, to improve
Its surface property.
Current zirconium alloy cladding principal focal point inhales hydrogen, wear-resisting etc. in burn into, wherein coating containing Cr is closed extensively
Note, but the big problem of interface coefficient of thermal expansion difference of coating and zirconium alloy substrates under normal conditions, lead to the coating under thermal shock
Thermal stress is generated with zirconium alloy substrates, reduces coating binding force.Conventional metal coating generally existing hardness and Abrasion properties compared with
Low problem, and coating is prone to eutectic reaction with zirconium alloy substrates at high temperature；Although Cr coatings have preferable high temperature resistance
Steam oxidation performance, but antioxygenic property still has the space further promoted.
Invention content
The technical problem to be solved in the present invention is, provides a kind of with excellent high temperature oxidation resistance and wear-resisting property
Multi-element alloy coat and zirconium alloy cladding, fuel assembly with the coating.
The technical solution adopted by the present invention to solve the technical problems is：A kind of multi-element alloy coat is provided, including following
The element of mass percent：Cr 65%-90%, Al 3%-13%, N 0.5%-8%, Fe 5%-20%, Zr 1.5%-
12%.
Preferably, the consistency of the multi-element alloy coat is 95%-100%, porosity≤5%.
Preferably, in the multi-element alloy coat, Cr and Zr form solid solution, and in the solid solution, Cr and Zr's
Atomic ratio is 64:36-69:31.
The present invention also provides a kind of zirconium alloy cladding, including zirconium alloy substrates, it is arranged on the zirconium alloy substrates surface
Multi-element alloy coat；The multi-element alloy coat includes the element of following mass percent：Cr65%-90%, Al 3%-
13%, N 0.5%-8%, Fe 5%-20%, Zr 1.5%-12%.
Preferably, the consistency of the multi-element alloy coat is 95-100%, porosity≤5%.
Preferably, in the multi-element alloy coat, Cr and Zr form solid solution, and in the solid solution, Cr and Zr's
Atomic ratio is 64:36-69:31.
Preferably, the thickness of the multi-element alloy coat is 1-100 microns.
Preferably, the thickness of the multi-element alloy coat is 1-20 microns.
Preferably, the multi-element alloy coat using physical vapour deposition (PVD), sputtering, pulsed laser deposition, thermal spraying, etc. from
Sub spraying, the coating of silk arc, chemical vapor deposition, plating, electrophoretic deposition, be formed in without electrocoat or Atomic layer deposition method described in
The surface of zirconium alloy substrates.
The present invention also provides a kind of fuel assembly, including fuel rod, the fuel rod includes the zirconium described in any of the above item
Alloy cladding.
The multi-element alloy coat of the present invention, can be applicable on zirconium alloy cladding, effectively solves coating and is thermally expanded not with matrix
The problem of matching, reduces thermal stress, further improves the hardness and wear-resisting property of conventional Cr coatings, pass through multielement ingredient
Regulation and control enhance antioxygenic property, realize anti-oxidation protection effect of the coating under 1200 DEG C of high temperature steam environments.
Specific implementation mode
The zirconium alloy cladding of the present invention, as cladding nuclear fuels comprising zirconium alloy substrates are arranged in zirconium alloy substrates table
The multi-element alloy coat in face.
Wherein, multi-element alloy coat has multielement comprising the element of following mass percent：Cr (chromium) 65%-
90%, Al (aluminium) 3%-13%, N (nitrogen) 0.5%-8%, Fe (iron) 5%-20%, Zr (zirconium) 1.5%-12%.
The consistency of multi-element alloy coat is 95-100%, porosity≤5%.
On zirconium alloy substrates, the thickness of multi-element alloy coat is 1-100 microns, preferably 1-20 microns.
Multi-element alloy coat can be used but be not limited to physical vapour deposition (PVD), sputtering, pulsed laser deposition, thermal spraying, etc. from
Sub- spraying, chemical vapor deposition, plating, electrophoretic deposition, without the methods of electrocoat or atomic layer deposition is formed in zirconium at the coating of silk arc
The surface of alloy substrate.According to the difference of forming method, each element can mix in multi-element alloy coat, can also be successively
Superposition.
In multi-element alloy coat (CrAlNFeZr), Cr is alloy host element, has good passivation, in high temperature
Under steam oxidation environment, oxidation film can be effectively generated, inhibits further oxidation corrosion.Cr adds as alloy host element
Enter Al elements, can quickly form fine and close oxidation film at a lower temperature, promotes corrosion resistance.On the basis of CrAl elements
On, it, can be effectively element alloyed with Al by introducing Fe elements, avoid simple substance Al due to the too low coating at high temperature of fusing point
Failure.On the basis of CrAlFe elements, by introducing Zr elements, Cr-Zr solid solution is formed, can be closed to avoid Cr elements and zirconium
Eutectic reaction occurs at high temperature for auri body；In Cr-Zr solid solution, the atomic ratio (the ratio between atomicity) of Cr and Zr are 64:36-
69:31.On the basis of CrAlFeZr elements, by introducing N element, the hardness and resistance to abrasion of alloy coat can be promoted
Can, further decrease the breakage rate of cladding nuclear fuels.In multi-element alloy coat, Cr and Zr form solid solution, and in the solid solution
In body,
The multi-element alloy coat of the present invention has excellent high temperature oxidation resistance and wear-resisting property, in zirconium alloy cladding
In, play the role of protecting zirconium alloy cladding high-temperature oxydation and the fretting for resisting screen work under accident conditions.
Multi-element alloy coat in the present invention is not limited to the zirconium alloy cladding in fuel assembly, can also be provided at other core combustions
Expect assembly surface, such as gauge pipe, guide pipe, greatly improves nuclear reactor and maintain nuclear fuel group under major accident operating mode
The anti-accident ability and secure threshold of part structure and functional completeness.
The fuel assembly of the present invention, including fuel rod, fuel rod include above-mentioned zirconium alloy cladding.In fuel assembly, also
Including gauge pipe, guide pipe etc., the surface of gauge pipe and guide pipe can also be arranged as required to above-mentioned multi-element alloy coat.
Below by way of specific embodiment, the invention will be further described.
Embodiment 1
By multi-arc ion coating, the CrAlNFeZr multicomponent alloys that 5 μ m thicks are deposited in the matrix surface of zirconium alloy cladding apply
Layer, wherein each element mass percent are as follows：Cr 73%, Al 8%, N 4%, Fe 13%, Zr 2%, the consistency of coating
＞ 99%, porosity ＜ 1%, coating and zirconium alloy substrates bond strength ＞ 100MPa.In terms of pyro-oxidation resistance, pass through
After 1200 DEG C of pyrogenic steam oxidations 1 hour, the zirconium alloy cladding oxidation weight gain with the multi-element alloy coat is only 0.25mg/
cm2。
Embodiment 2
By plasma spraying, the CrAlNFeZr multicomponent alloys of 100 μ m thicks are deposited in the matrix surface of zirconium alloy cladding
Coating, wherein each element mass percent are as follows：Cr 82%, Al 6%, N 2%, Fe 8%, Zr 2%, the consistency of coating
＞ 98%, porosity ＜ 2%, coating and zirconium alloy substrates bond strength ＞ 80MPa.In terms of pyro-oxidation resistance, pass through
After 1200 DEG C of pyrogenic steam oxidations 1 hour, the zirconium alloy cladding oxidation weight gain with the multi-element alloy coat is only 0.45mg/
cm2。
Embodiment 3
By magnetron sputtering, the CrAlNFeZr multicomponent alloys that 1 μ m thick is deposited in the matrix surface of zirconium alloy cladding apply
Layer, wherein each element mass percent are as follows：Cr 65%, Al 6%, N 8%, Fe 9%, Zr 12%, the consistency of coating
＞ 99%, porosity ＜ 1%, coating and zirconium alloy substrates bond strength ＞ 120MPa.In terms of pyro-oxidation resistance, pass through
After 1200 DEG C of pyrogenic steam oxidations 1 hour, the zirconium alloy cladding oxidation weight gain with the multi-element alloy coat is only 0.34mg/
cm2。
Embodiment 4
By magnetron sputtering, the CrAlNFeZr multicomponent alloys that 20 μ m thicks are deposited in the matrix surface of zirconium alloy cladding apply
Layer, wherein each element mass percent are as follows：Cr 52%, Al 13%, N 7%, Fe 20%, Zr 8%, the consistency of coating
＞ 99%, porosity ＜ 1%, coating and zirconium alloy substrates bond strength ＞ 90MPa.In terms of pyro-oxidation resistance, pass through
After 1200 DEG C of pyrogenic steam oxidations 1 hour, the zirconium alloy cladding oxidation weight gain with the multi-element alloy coat is only 0.3mg/
cm2。
Embodiment 5
By magnetron sputtering, the CrAlNFeZr multicomponent alloys that 10 μ m thicks are deposited in the matrix surface of zirconium alloy cladding apply
Layer, wherein each element mass percent are as follows：Cr 90%, Al 3%, N 0.5%, Fe 5%, Zr 1.5%, the densification of coating
Spend ＞ 99%, porosity ＜ 1%, coating and zirconium alloy substrates bond strength ＞ 100MPa.In terms of pyro-oxidation resistance, lead to
It crosses after 1200 DEG C of pyrogenic steam oxidations 1 hour, the zirconium alloy cladding oxidation weight gain with the multi-element alloy coat is only
0.18mg/cm2。
Comparative example
To not have cated zirconium alloy cladding in 1200 DEG C of pyrogenic steam oxidations 1 hour, oxidation weight gain 37mg/cm2。
It is compared it is found that polynary from the zirconium alloy cladding of above-described embodiment 1-5 and comparative example in pyro-oxidation resistance
Alloy coat effectively reduces zirconium alloy cladding pyrogenic steam oxidation 2 orders of magnitude of weightening.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (10)
1. a kind of multi-element alloy coat, which is characterized in that include the element of following mass percent：Cr 65%-90%、Al 3%-
13%、N 0.5%-8%、Fe 5%-20%、Zr 1.5%-12%。
2. multi-element alloy coat according to claim 1, which is characterized in that the consistency of the multi-element alloy coat is
95%-100%, porosity≤5%.
3. multi-element alloy coat according to claim 1, which is characterized in that in the multi-element alloy coat, Cr and Zr shapes
At solid solution, and in the solid solution, the atomic ratio of Cr and Zr are 64:36-69:31.
4. a kind of zirconium alloy cladding, which is characterized in that including zirconium alloy substrates, be arranged in the polynary of the zirconium alloy substrates surface
Alloy coat；The multi-element alloy coat includes the element of following mass percent：Cr 65%-90%、Al 3%-13%、N
0.5%-8%、Fe 5%-20%、Zr 1.5%-12%。
5. zirconium alloy cladding according to claim 4, which is characterized in that the consistency of the multi-element alloy coat is 95-
100%, porosity≤5%.
6. zirconium alloy cladding according to claim 4, which is characterized in that in the multi-element alloy coat, Cr and Zr are formed
Solid solution, and in the solid solution, the atomic ratio of Cr and Zr are 64:36-69:31.
7. zirconium alloy cladding according to claim 4, which is characterized in that the thickness of the multi-element alloy coat is 1-100
Micron.
8. zirconium alloy cladding according to claim 7, which is characterized in that the thickness of the multi-element alloy coat is that 1-20 is micro-
Rice.
9. zirconium alloy cladding according to claim 4, which is characterized in that the multi-element alloy coat is heavy using physical vapor
Product, sputtering, pulsed laser deposition, thermal spraying, plasma spraying, the coating of silk arc, chemical vapor deposition, plating, electrophoretic deposition, nothing
Electrocoat or Atomic layer deposition method are formed in the surface of the zirconium alloy substrates.
10. a kind of fuel assembly, which is characterized in that including fuel rod, the fuel rod includes described in claim any one of 4-9
Zirconium alloy cladding.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810491248.0A CN108588532B (en) | 2018-05-21 | 2018-05-21 | Multi-element alloy coat, zirconium alloy cladding and fuel assembly |
| PCT/CN2018/101375 WO2019223138A1 (en) | 2018-05-21 | 2018-08-20 | Multi-element alloy coating, zirconium alloy cladding, and fuel assembly |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810491248.0A CN108588532B (en) | 2018-05-21 | 2018-05-21 | Multi-element alloy coat, zirconium alloy cladding and fuel assembly |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108588532A true CN108588532A (en) | 2018-09-28 |
| CN108588532B CN108588532B (en) | 2019-08-30 |
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Country Status (2)
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| WO (1) | WO2019223138A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109811316A (en) * | 2019-04-04 | 2019-05-28 | 中国核动力研究设计院 | Long-lived phase zircaloy coating of a kind of high burnup and preparation method thereof |
| EP3680917A1 (en) * | 2019-01-14 | 2020-07-15 | Westinghouse Electric Sweden AB | A cladding tube for a fuel rod for nuclear reactors |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN108588532B (en) | 2019-08-30 |
| WO2019223138A1 (en) | 2019-11-28 |
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