CN110106467A - A kind of used by nuclear reactor efficiently combines clad and preparation method thereof - Google Patents
A kind of used by nuclear reactor efficiently combines clad and preparation method thereof Download PDFInfo
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- CN110106467A CN110106467A CN201910554794.9A CN201910554794A CN110106467A CN 110106467 A CN110106467 A CN 110106467A CN 201910554794 A CN201910554794 A CN 201910554794A CN 110106467 A CN110106467 A CN 110106467A
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
Abstract
The invention discloses a kind of used by nuclear reactor efficiently to combine clad, and the clad is deposited on used by nuclear reactor basis material outer surface, and clad successively includes Zr-Cr or Ti-Cr transition zone and Cr sedimentary from inside to outside.The preparation method of above-mentioned clad, using physical vaporous deposition, hot spray process, cold spraying, laser cladding, galvanoplastic or chemical vapour deposition technique, it is preferred to use the arc ion plating in physical vaporous deposition.The cladding materials that above-mentioned clad obtains is coated on zirconium alloy substrates material has good corrosion-resistant, film base cooperative transformation and oxidation-resistance property, it is a kind of promising crash-proof fuel canning material, and is performed better than by the coating cladding materials mechanical behavior under high temperature of matrix of N36 alloy.
Description
Technical field
The present invention relates to nuclear reactor material technical fields, and in particular to a kind of used by nuclear reactor efficiently combine clad and
Preparation method.
Background technique
Zircaloy shows good Flouride-resistani acid phesphatase and corrosion resistance, has become function as light water reactor cladding materials
In PWR of Nuclear Power Station decades.Zircaloy with vapor vigorous reaction, is released big at high temperature when temperature is greater than 1200 DEG C
The hydrogen and heat of amount, bring very big security risk.How light water reactor nuclear fuel element is further increased in accident conditions
Under safety and reliability at nuclear science researcher's urgent problem to be solved, therefore, reactor design to fuel
Higher safety allowance requirement can be proposed, light water reactor nuclear fuel element is exactly to research and develop novel resistance to thing in face of a breakthrough of challenge
Therefore fuel element.
Crash-proof fuel (ATF) research direction that scientists propose includes crash-proof fuel core and crash-proof involucrum material
Material.Wherein, crash-proof cladding materials be dedicated to improve cladding materials anti-accident ability, under emergency conditions as far as possible provide compared with
Big safety allowance, avoids the occurrence of the problem of reactor core seriously melts.Zr alloy surface coating is the development of crash-proof cladding materials
One Main way is dedicated to improving oxidation resistance of the zirconium alloy cladding in high-temperature vapor environment, improves it normal
Corrosion resistance under operating condition develops one kind novel high-performance crash-proof coating or cladding materials for light water reactor nuclear fuel
Element development is of great significance.
Summary of the invention
In conclusion the present invention provides a kind of used by nuclear reactor to solve the above problems efficiently to combine clad and its system
Preparation Method, the cladding materials of the above-mentioned clad of coating of acquisition have good corrosion-resistant, film base cooperative transformation and resistant to high temperatures
Oxidability meets crash-proof cladding materials requirement, is a kind of promising crash-proof fuel canning material.
The present invention is achieved through the following technical solutions:
A kind of used by nuclear reactor efficiently combines clad, and the clad is for being deposited on outside used by nuclear reactor basis material
On surface, clad successively includes Zr-Cr or Ti-Cr transition zone, Cr sedimentary from inside to outside.Signified matrix material in the present invention
Material includes cladding materials, screen work material, conduit material or the board-like fuel etc. of fuel element.
Preferably, the thickness range of the clad is 1 μm~60 μm.
Preferably, the thickness range of the clad is 5 μm~30 μm.
Preferably, the clad with a thickness of 10 μm, 15 μm, 20 μm or 25 μm.
Preferably, Zr-Cr the or Ti-Cr transition region thickness range is 1~5 μm, and from basis material to Cr sedimentary
On direction, Zr or Ti content is gradually decreased, Cr content gradually increases, forming component gradient.
A kind of used by nuclear reactor cladding materials, including basis material and coated in the clad on basis material outer surface；
Described matrix material is using zirconium or zirconium alloy at the clad uses a kind of above-mentioned used by nuclear reactor outer surface packet
Coating.
Preferably, the zircaloy includes Zr-4 alloy or N36 alloy.
Preferably, the ingredient of the N36 alloy is Zr-1Sn-1Nb-0.3Fe-0.1.
A kind of above-mentioned used by nuclear reactor efficiently combines the preparation method of clad, using physical vaporous deposition, thermal jet
Coating, cold spraying, laser cladding, galvanoplastic or chemical vapour deposition technique.
Preferably, the physical vaporous deposition uses arc ion plating, and depositing temperature is 300 DEG C~550 DEG C.
Preferably, arc ion plating concrete operations include the following steps, successively are as follows:
Step1, Zr-Cr or Ti-Cr transition zone deposition:
For Zr-Cr transition zone, the arc current for adjusting separately Zr target and Cr target is 50A~100A, bias be -100V~-
200V, duty ratio are 40%~70%, and sedimentation time is 30~120min；
For Ti-Cr transition zone, the arc current for adjusting separately Ti target and Cr target is 50A~100A, bias be -100V~-
200V, duty ratio are 40%~70%, and sedimentation time is 30~120min；
Step2, Cr sedimentary deposition:
Adjustment arc current is 80A~200A, and bias is -90V~-200V, and duty ratio is 40%~70%.
Preferably, in the concrete operations of the arc ion plating, further include before Zr-Cr or Ti-Cr transition zone deposition
Following steps:
(1) substrate material surface pre-processes:
Basis material is first cleaned by ultrasonic, then using deionized water rinse, finally in high vacuum dry room into
Row drying；
(2) substrate material surface Ion Cleaning before depositing:
Basis material after drying is packed into furnace chamber, vacuumizes, begins heat to depositing temperature, be then charged with Ar gas, apply
Increase bias, bias plasma sputter clean or electron gun etching are carried out to substrate material surface；
(3) target material surface cleans.
Preferably, in the step (1), drying temperature is 110 DEG C~125 DEG C；
In the step (2), vacuumizing vacuum degree is 1.0 × 10-3~5.0 × 10-3Pa；Furnace chamber target-substrate distance be 70mm~
220mm；The bias is pulsed bias or Dc bias；The condition of the bias plasma sputtering are as follows: Ar air pressure is 0.5Pa
~1.2Pa, high bias are -500V~-1000V, and duty ratio is 30%~80%, and scavenging period is 10~20min；The electronics
The condition of rifle etching are as follows: Ar air pressure is 1.5Pa~3.0Pa, and high bias is -100V~-300V, and pack coil current is 5A
~20A, electron gun supply voltage are 30V~50V, and electric current is 70A~100A.
Preferably, in the step (3), vacuum degree < 5.0 × 10 is kept-3Under the conditions of Pa, arc source is opened, carries out target table
Face cleaning；Wherein bias is -500V~-600V, and duty ratio is 30%~40%, and arc current is 80A~100A, and air pressure is
0.2Pa~0.5Pa.
Preferably, further comprising the steps of after CrN hardened layer deposition in the concrete operations of the arc ion plating:
(1) arc source system is closed, 30~60min is kept the temperature, is heat-treated after carrying out plated film；
(2) heating system is closed, after being cooled to 80 DEG C or less, vacuum system is closed, when filling high-purity argon gas to normal pressure
It comes out of the stove；It is used in cooling operation and cools down and fill high-purity argon gas cool-down method with furnace.
The present invention has the advantage that and the utility model has the advantages that
When selecting for the coating layer material of used by nuclear reactor material, consider that there is good high temperature oxidation resistance first
Can, also need to consider mechanical performance under the fusing point of candidate material, thermal conductivity and temperature gradient etc. and its nuclearity energy, i.e., in
Sub- absorption cross-section and anti-radiation performance etc., coating layer material of the invention set gradually metal, metal/metal mixture totally two
Layer；High pure metal Cr has many advantages, such as high temperature resistant, anti-oxidant and creep resistant, and generation oxidation rate is low at high temperature, stability is good
Cr2O3Oxidation film, and by the way that Zr-Cr or Ti-Cr transition zone is arranged between substrate material surface and Cr sedimentary, and realize
Component gradient, conducive to improving matrix and applying the film base binding performance of interlayer.The system of clad is realized using suitable preparation method
It is standby, such as physical vaporous deposition, hot spray process, cold spraying, laser cladding, galvanoplastic or chemical vapour deposition technique.Consider
Depositing temperature, coating thickness and film quality etc., physical vaporous deposition are a kind of selectable coating process, such as ion
Plating, magnetron sputtering etc..Wherein, using ion plating technique (AIP), applied to that can obtain in the present invention, film layer compactness is good, combines
The excellent coating of power is conducive to realize extensive deposition.
In existing public technology research, although disclosing some cladding materials surface covering preparations, the present invention is in matrix
Selection, coating layer thickness, binding force control, step of preparation process and parameter of material etc. are efficiently modified, and are developed full
The coating material that sufficient reactor cladding materials requires:
1, the present invention selects Zr-4 alloy or N36 alloy is basis material, using suitable arc source, with high-purity Cr target, height
Pure Zr target or high-purity Ti target are as cathode arc source, in high vacuum conditions, by be arranged suitable temperature, arc current, bias and
The parameters such as gas pressure obtain the excellent Zr-Cr/Cr or Ti-Cr/Cr coating of binding force, and surface compact is smooth, and integral thickness exists
1 μm~60 μm, wherein transition zone Zr-Cr or Ti-Cr is 1~5 μm；
2, clad of the present invention is evenly distributed in basis material outer surface, 1~60 μm of thickness section, and thickness deviation <
10%；Binding force >=100N between zircaloy and cladding bed boundary；Clad crystallinity be greater than 95%, metal Cr deposit composition of layer and
Phase structure control is good；Zirconium matrix grain is without obviously growing up, and 9 grades of grain size ﹥；Above-mentioned cladding is coated on zirconium alloy substrates material
The cladding materials that layer obtains has good film base cooperative transformation and oxidation-resistance property, meets crash-proof cladding materials and wants
It asks, is a kind of promising crash-proof fuel canning material；And the cladding materials of clad is coated using N36 as basis material
With good mechanical property, the mechanical property of N36 coating zirconium cladding is generally better than the involucrum material using Zr-4 alloy as matrix
Material, especially mechanical behavior under high temperature such as have good croop property.
Detailed description of the invention
Attached drawing described herein is used to provide to further understand the embodiment of the present invention, constitutes one of the application
Point, do not constitute the restriction to the embodiment of the present invention.In the accompanying drawings:
Fig. 1 is Zr-4 alloy tube outer surface Zr-Cr/Cr coating flattening test figure in the present invention；
Fig. 2 is N36 alloy tube outer surface Zr-Cr/Cr coating flattening test figure in the present invention.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment and attached drawing, to this
Invention is described in further detail, and exemplary embodiment of the invention and its explanation for explaining only the invention, are not made
For limitation of the invention.
Embodiment 1
The present embodiment coats Zr-Cr/Cr clad, concrete operations in Zr-4 alloy tube outer surface using following preparation method
Step are as follows:
The pretreatment of Setp1, Zr-4 alloy substrate outer surface:
Using the Zr-4 production tube for meeting reactor cladding materials technical requirement, it is super first to carry out 30min acetone soln
Sound cleaning, is then largely rinsed using deionized water, places into dedicated high vacuum dry room and dry under the conditions of 110 DEG C of temperature
30min。
Setp2, Zr-4 alloy substrate surface ion cleaning before depositing:
Zr-4 alloy substrate after drying is packed into furnace chamber, furnace chamber target-substrate distance is 100mm, is evacuated to 3.0 × 10-3Pa
Afterwards, 350 DEG C are begun heat to, being then charged with appropriate Ar gas makes air pressure reach 0.5Pa, adjusts duty ratio 50%, respectively application -500V
The total 15min of the high bias of~-900V carries out bias plasma sputter clean to Zr-4 alloy substrate.
Setp3, target material surface cleaning:
Keep vacuum degree < 3.0 × 10-3Under the conditions of Pa, arc source is opened, carries out target material surface cleaning；Wherein bias be-
500V, duty ratio 30%, arc current 80A, air pressure 0.2Pa.
Setp4, Zr-Cr transition zone deposition:
Adjust separately arc current 50A~100A, bias -100V, duty ratio 50% the deposition 50min of Zr target and Cr target.
Setp5, super thick metal Cr sedimentary deposition:
Arc current 100A, bias -150V, duty ratio 40% are adjusted, 6h is deposited.
Setp6 closes arc source system, keeps the temperature 30min, is heat-treated after carrying out plated film.
Setp7 closes heating system, after being cooled to 80 DEG C or less with furnace, closes vacuum system, fills high-purity argon gas to normal pressure
When, it can come out of the stove.
Embodiment 2
The present embodiment coats Ti-Cr/Cr clad, concrete operations in Zr-4 alloy tube outer surface using following preparation method
Step are as follows:
The pretreatment of Setp1, Zr-4 alloy substrate outer surface:
Using the Zr-4 production tube for meeting reactor cladding materials technical requirement, it is super first to carry out 30min acetone soln
Sound cleaning, is then largely rinsed using deionized water, places into dedicated high vacuum dry room and dry under the conditions of 120 DEG C of temperature
30min。
Setp2, Zr-4 alloy substrate surface ion cleaning before depositing:
Zr-4 alloy after drying is packed into furnace chamber, furnace chamber target-substrate distance is 120mm, is evacuated to 5.0 × 10-3After Pa, open
Beginning is heated to 450 DEG C, and being then charged with appropriate Ar gas makes air pressure reach 2Pa, and height is biased in -200V, pack coil current 8A, electronics
Rifle supply voltage 30V, electric current 70A carry out electron gun etching to Zr-4 alloy substrate.
Setp3, target material surface cleaning:
Keep vacuum degree < 3.0 × 10-3Under the conditions of Pa, arc source is opened, carries out target material surface cleaning；Wherein bias be-
500V, duty ratio 30%, arc current 80A, air pressure 0.2Pa.
Setp4, Ti-Cr transition zone deposition:
Adjust separately arc current 50A~100A, bias -100V, duty ratio 50% the deposition 100min of Ti target and Cr target.
Setp5, super thick metal Cr sedimentary deposition:
Arc current 100A, bias -150V, duty ratio 40% are adjusted, 5h is deposited.
Setp6 closes arc source system, keeps the temperature 40min, is heat-treated after carrying out plated film.
Setp7 closes heating system, fills after high-purity argon gas is cooled to 80 DEG C or less, closing vacuum system, then fill high-purity argon
When gas to normal pressure, it can come out of the stove.
Embodiment 3
The present embodiment coats Zr-Cr/Cr clad, concrete operations in N36 alloy tube outer surface using following preparation method
Step are as follows:
The pretreatment of Setp1, N36 alloy substrate outer surface:
Using the N36 production tube for meeting reactor cladding materials technical requirement, 30min acetone soln ultrasound is first carried out
Cleaning is then largely rinsed using deionized water, places into dedicated high vacuum dry room and dry under the conditions of 110 DEG C of temperature
3min。
Setp2, N36 alloy substrate surface ion cleaning before depositing:
N36 alloy substrate after drying is packed into furnace chamber, furnace chamber target-substrate distance is 100mm, is evacuated to 3.0 × 10-3After Pa,
Begin heat to 350 DEG C, being then charged with appropriate Ar gas makes air pressure reach 0.5Pa, adjust duty ratio 50%, respectively application -500V~-
The total 15min of 900V high bias carries out bias plasma sputter clean to N36 alloy substrate.
Setp3, target material surface cleaning:
Keep vacuum degree < 3.0 × 10-3Under the conditions of Pa, arc source is opened, carries out target material surface cleaning；Wherein bias be-
500V, duty ratio 30%, arc current 80A, air pressure 0.2Pa.
Setp4, Zr-Cr transition zone deposition:
Adjust separately arc current 50A~100A, bias -100V, duty ratio 50% the deposition 50min of Zr target and Cr target.
Setp5, super thick metal Cr sedimentary deposition:
Arc current 100A, bias -150V, duty ratio 40% are adjusted, 6h is deposited.
Setp6 closes arc source system, keeps the temperature 30min, is heat-treated after carrying out plated film.
Setp7 closes heating system, after being cooled to 80 DEG C or less with furnace, closes vacuum system, fills high-purity argon gas to normal pressure
When, it can come out of the stove.
Embodiment 4
The present embodiment coats Ti-Cr/Cr clad, concrete operations in N36 alloy tube outer surface using following preparation method
Step are as follows:
Setp1, the pretreatment of zirconium base external surface:
Using the N36 production tube for meeting reactor cladding materials technical requirement, 30min acetone soln ultrasound is first carried out
Cleaning is then largely rinsed using deionized water, places into dedicated high vacuum dry room and dry under the conditions of 120 DEG C of temperature
30min。
Setp2, N36 alloy substrate surface ion cleaning before depositing:
Zirconium base body after drying is packed into furnace chamber, furnace chamber target-substrate distance is 120mm, is evacuated to 3.0 × 10-3After Pa, start
450 DEG C are heated to, being then charged with appropriate Ar gas makes air pressure reach 2Pa, and height is biased in -200V, pack coil current 8A, electron gun
Supply voltage 30V, electric current 70A carry out electron gun etching to N36 alloy substrate.
Setp3, target material surface cleaning:
Keep vacuum degree < 3.0 × 10-3Under the conditions of Pa, arc source is opened, carries out target material surface cleaning；Wherein bias be-
500V, duty ratio 30%, arc current 80A, air pressure 0.2Pa.
Setp4, Ti-Cr transition zone deposition:
Adjust separately arc current 50A~100A, bias -100V, duty ratio 50% the deposition 100min of Ti target and Cr target.
Setp5, super thick metal Cr sedimentary deposition:
Arc current 100A, bias -150V, duty ratio 40% are adjusted, 5h is deposited.
Setp6 closes arc source system, keeps the temperature 40min, is heat-treated after carrying out plated film.
Setp7 closes heating system, fills after high-purity argon gas is cooled to 80 DEG C or less, closing vacuum system, then fill high-purity argon
When gas to normal pressure, it can come out of the stove.
Embodiment 5
Performance test: Zr-4 alloy tube outer surface Zr-Cr/Cr coating and embodiment 3 preparation prepared to embodiment 1
N36 alloy tube outer surface Zr-Cr/Cr coating detected, testing result is as follows:
One, quality characterization detects
(1) 1 product of embodiment, coating are evenly distributed, and about 16 μm of thickness, and thickness deviation ± 1.5 μm；Coating composition and phase
Structure control is good, and 9 grades of ﹥ of zirconium base body grain size；Film base interface forms transition zone, and binding force reaches between zircaloy and coating interface
150N；
(2) 3 product of embodiment, coating are evenly distributed, and about 16 μm of thickness, and thickness deviation ± 1.5 μm；Coating composition and phase
Structure control is good, and 9 grades of ﹥ of zirconium base body grain size；Film base interface forms transition zone, and binding force reaches between zircaloy and coating interface
150N。
Two, film base cooperative transformation performance test
(1) flattening examination is carried out using Zr-4 alloy tube outer surface Zr-Cr/Cr coating sample made of the embodiment of the present invention 1
Test, Fig. 1 as the result is shown 40% pressure deformation when coated pipe two sides do not observe macroscopic obvious shortcoming, the collaboration of film base
Deformation performance is good；
(2) flattening examination is carried out using N36 alloy tube outer surface Zr-Cr/Cr coating sample made of the embodiment of the present invention 1
Test, Fig. 2 as the result is shown 40% pressure deformation when coated pipe two sides do not observe macroscopic obvious shortcoming, the collaboration of film base
Deformation performance is good.
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 (15)
1. a kind of used by nuclear reactor efficiently combines clad, which is characterized in that the clad is for being deposited on used by nuclear reactor
On basis material outer surface, clad successively includes Zr-Cr or Ti-Cr transition zone, Cr sedimentary from inside to outside.
2. a kind of used by nuclear reactor according to claim 1 efficiently combines clad, which is characterized in that the clad
Thickness range is 1 μm~60 μm.
3. a kind of used by nuclear reactor according to claim 2 efficiently combines clad, which is characterized in that the clad
Thickness range is 5 μm~30 μm.
4. a kind of used by nuclear reactor according to claim 3 efficiently combines clad, which is characterized in that the clad
With a thickness of 10 μm, 15 μm, 20 μm or 25 μm.
5. a kind of used by nuclear reactor according to claim 2 efficiently combines clad, which is characterized in that the Zr-Cr or
Ti-Cr transition region thickness range is 1~5 μm, and on from basis material to Cr sedimentary direction, Zr or Ti content gradually decreases,
Cr content gradually increases, forming component gradient.
6. a kind of used by nuclear reactor cladding materials, which is characterized in that including basis material and be coated on basis material outer surface
Clad；Described matrix material is using zirconium or zirconium alloy at the clad is using described in any one of claim 1 to 5
A kind of used by nuclear reactor outer surface clad.
7. a kind of used by nuclear reactor cladding materials according to claim 6, which is characterized in that the zircaloy includes Zr-4
Alloy or N36 alloy.
8. a kind of used by nuclear reactor cladding materials according to claim 7, which is characterized in that the ingredient of the N36 alloy
For Zr-1Sn-1Nb-0.3Fe-0.1.
9. a kind of used by nuclear reactor according to any one of claims 1 to 8 efficiently combines the preparation method of clad, special
Sign is, using physical vaporous deposition, chemical vapour deposition technique, galvanoplastic, cold spraying, laser cladding or thermal spraying
Method.
10. the preparation method that a kind of used by nuclear reactor according to claim 9 efficiently combines clad, which is characterized in that
The physical vaporous deposition uses arc ion plating, and depositing temperature is 300 DEG C~550 DEG C.
11. the preparation method of clad is efficiently combined according to a kind of described in any item used by nuclear reactor of claim 9 or 10,
It is characterized in that, arc ion plating concrete operations include the following steps, successively are as follows:
Step1, Zr-Cr or Ti-Cr transition zone deposition:
For Zr-Cr transition zone, the arc current for adjusting separately Zr target and Cr target is 50A~100A, and bias is -100V~-200V,
Duty ratio is 40%~70%, and sedimentation time is 30~120min；
For Ti-Cr transition zone, the arc current for adjusting separately Ti target and Cr target is 50A~100A, bias be -100V~-200V,
Duty ratio is 40%~70%, and sedimentation time is 30~120min；
Step2, Cr sedimentary deposition:
Adjustment Cr target arc current is 80A~200A, and bias is -90V~-200V, and duty ratio is 40%~70%.
12. the preparation method that a kind of used by nuclear reactor according to claim 11 efficiently combines clad, which is characterized in that
It is further comprising the steps of before Zr-Cr or Ti-Cr transition zone deposition in the concrete operations of the arc ion plating:
(1) substrate material surface pre-processes:
Basis material is first cleaned by ultrasonic, is then rinsed using deionized water, is finally dried in high vacuum dry room
It is dry；
(2) substrate material surface Ion Cleaning before depositing:
Basis material after drying is packed into furnace chamber, vacuumizes, begins heat to depositing temperature, is then charged with Ar gas, is applied high
Bias carries out bias plasma sputter clean or electron gun etching to substrate material surface；
(3) target material surface cleans.
13. the preparation method that a kind of used by nuclear reactor according to claim 12 efficiently combines clad, which is characterized in that
In the step (1), drying temperature is 110 DEG C~125 DEG C；
In the step (2), vacuumizing vacuum degree is 1.0 × 10-3~5.0 × 10-3Pa；Furnace chamber target-substrate distance is 70mm~220mm；
The bias is pulsed bias or Dc bias；The condition of bias plasma sputtering are as follows: Ar air pressure be 0.5Pa~
1.2Pa, high bias are -500V~-1000V, and duty ratio is 30%~80%, and scavenging period is 10~20min；The electron gun
The condition of etching are as follows: Ar air pressure be 1.5Pa~3.0Pa, high bias be -100V~-300V, pack coil current be 5A~
20A, electron gun supply voltage are 30V~50V, and electric current is 70A~100A.
14. the preparation method that a kind of used by nuclear reactor according to claim 12 efficiently combines clad, which is characterized in that
In the step (3), vacuum degree < 5.0 × 10 is kept-3Under the conditions of Pa, arc source is opened, carries out target material surface cleaning；Wherein bias
For -500V~-600V, duty ratio is 30%~40%, and arc current is 80A~100A, and air pressure is 0.2Pa~0.5Pa.
15. the preparation method that a kind of used by nuclear reactor according to claim 11 efficiently combines clad, which is characterized in that
It is further comprising the steps of after CrN hardened layer deposition in the concrete operations of the arc ion plating:
(1) arc source system is closed, 30~60min is kept the temperature, is heat-treated after carrying out plated film；
(2) heating system is closed, after being cooled to 80 DEG C or less, vacuum system is closed, until can come out of the stove after normal pressure；Cooling operation
Middle use cools down with furnace and fills high-purity argon gas cool-down method.
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| CN201910554794.9A CN110106467A (en) | 2019-06-25 | 2019-06-25 | A kind of used by nuclear reactor efficiently combines clad and preparation method thereof |
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| CN201910554794.9A CN110106467A (en) | 2019-06-25 | 2019-06-25 | A kind of used by nuclear reactor efficiently combines clad and preparation method thereof |
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Cited By (3)
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| CN111636082A (en) * | 2020-06-16 | 2020-09-08 | 西安稀有金属材料研究院有限公司 | Method for electrochemically preparing accident fault-tolerant Cr coating of nuclear fuel cladding element |
| CN112164479A (en) * | 2020-08-21 | 2021-01-01 | 上海核工程研究设计院有限公司 | High-temperature steam corrosion resistant coating for zirconium alloy cladding tube |
| CN115572974A (en) * | 2022-10-17 | 2023-01-06 | 中国船舶集团有限公司第七一一研究所 | Composite coating and preparation method thereof |
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| CN115572974A (en) * | 2022-10-17 | 2023-01-06 | 中国船舶集团有限公司第七一一研究所 | Composite coating and preparation method thereof |
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