CN109666911A - The high entropy alloy coating and preparation method thereof of nuclear-used zirconium alloy involucrum surface refractory corrosion - Google Patents
The high entropy alloy coating and preparation method thereof of nuclear-used zirconium alloy involucrum surface refractory corrosion Download PDFInfo
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- CN109666911A CN109666911A CN201910084692.5A CN201910084692A CN109666911A CN 109666911 A CN109666911 A CN 109666911A CN 201910084692 A CN201910084692 A CN 201910084692A CN 109666911 A CN109666911 A CN 109666911A
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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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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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
- C23C14/06—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
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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Abstract
The invention discloses a kind of high entropy alloy coatings and preparation method thereof of nuclear-used zirconium alloy involucrum surface refractory corrosion, the high entropy alloy coating for being deposited on Zr alloy surface is CrCuFeMoNi high-entropy alloy, wherein Cr, Cu, Fe, Mo, Ni shared atomic percent in high-entropy alloy are as follows: Cr 25~35%, Cu 20~30%, Fe 10~14%, Mo 15~20%, Ni 15~20%.The high entropy alloy coating is deposited on Zr alloy surface by multi-target magnetic control sputtering technology.The CrCuFeMoNi high entropy alloy coating, the hardness for not only increasing Zr alloy surface improves corrosion resistance and radioresistance, and shows good high temperature resistant, corrosion resistance, it can satisfy practical engineering application, be the potential candidate material of accident fault tolerant fuel involucrum coating.The multi-target magnetic control sputtering technology maturation that the present invention uses, it is easy to operate, it can be achieved that the high entropy alloy coating of nuclear-used zirconium alloy involucrum surface refractory corrosion has good development prospect in the industrialized production of engineering field.
Description
Technical field
The invention belongs to technical field of metal surface modification, are related to nuclear-used zirconium alloy process for modifying surface, and in particular to
Zr alloy surface prepares high temperature corrosion CrCuFeMoNi high entropy alloy coating and preparation method thereof.
Background technique
In past decades, zirconium alloy cladding has shown good Flouride-resistani acid phesphatase and corrosion resistance successfully
Applied to light water reactor (LWR), but cooling water loss of-coolant accident (LOCA) (LOCA) and beyond design basis accident are occurring for cladding materials
(BDBA) under the conditions of, zirconium alloy cladding high-temperature oxydation will discharge a large amount of hydrogen and heat, cause serious nuclear accident, cause largely to put
Penetrating property substance leaked, to environment for human survival bringing on a disaster property consequence, such as 2011 " Fukushima nuclear power plant accident ".How further
Improving cladding materials accident fault-tolerant ability becomes a urgent problem to be solved, and the research of crash-proof cladding materials is mainly concentrated
In meeting reactor just to substitute traditional zircaloy, the fault-tolerant material requirements of accident to developing the novel fault-tolerant material of accident (ATF)
Zircaloy performance is used or can improved under normal working condition, and more most important required when reactor core loss of-coolant accident (LOCA) occurs, can be
The stability of reactor core is maintained in certain time, to take accident measure to provide enough time.The fault-tolerant material of accident is wherein most important
A concept be exactly to Zr alloy surface coating protect, improve zirconium alloy cladding material high-temperature oxidation resistance and intensity,
Further increase the safety and economy of nuclear reactor.
Zr alloy surface coating is kept under environment in heap for a long time with raising zircaloy under fuel can size is not changed
Stability, while surface-coating technology main advantage is its economy, it is easy to accomplish the commercialization of zircaloy coating involucrum is answered
With.It is directed to the coating modified research of Zr alloy surface at present, coating candidates mainly include ceramic coating (Ti2AlC MAX
Phase, SiC carbide), metal coating (Cr, FeCrAl) etc., B.R.Maier etc. is prepared for Ti using cold spraying2AlC MAX phase is made pottery
Porcelain coating, while there is also other a small amount of Ti3AlC2、TiAl2With TiC phase, shown under 1005 DEG C of water vapor atmospheres good
Antioxygenic property, but then research shows that Al and C changes between will form metal with Zr respectively in MAX phase during the preparation process
Object is closed, needing to pay close attention to MAX phase coating and zirconium alloy substrates interface stability and its influences performance.SiC coating is in low temperature corruption
Losing has preferable protective effect in water environment, but the Si (OH) easy to form under high-temperature water corrosive environment4, reduce the guarantor of matrix
Shield property, while there is the phenomenon that cracking and flaking off during steam oxidation.There is preparation process, interface are steady for ceramic coating
Many problems such as the oxidation of qualitative and high-temperature vapor and high temperature corrosion mechanism have to be solved.W.C.Zhong etc. is splashed using magnetic control
The FeCrAl coating for being prepared for high Al content is penetrated, research finds that coating steam resistance oxidation characteristics can increase with Al content and be enhanced,
But coating is deteriorated in corrosion resistance.Y.D.Wang etc. is successfully made on Zr-4 matrix respectively using atmospheric plasma spraying technology
Standby metal Cr and FeCrAl coating, after 1200 DEG C of progress high-temperature oxydation 1h, FeCrAl coating is caused due to phase counterdiffusion to base
Body protectiveness reduces, and Cr coating has excellent inoxidizability, and Cr coating surface forms fine and close Cr2O3, effectively become
Oxygen diffusion barrier layer.Above-mentioned coating is respectively provided with good mechanical property, high-temperature oxidation resistance in the case where simulating nuclear reactor environment
Energy and corrosion resistance, provide valuable reference for zirconium alloy cladding material surface coating.However, holding as novel accident
The arguement of wrong candidate material, the long-term effectiveness of coating material in normal conditions of use is still continuing.
High-entropy alloy (HEA) is concerned in the latest 20 years because of its unique structure and excellent performance.With Conventional alloys
It compares, high-entropy alloy is made of host element of at least five atom content between 5-35at.%, these elements are formed simply
Fcc or bcc crystal structure solid solution, rather than complicated intermetallic compound.Under the influence of high entropy effect, so that high-entropy alloy
Excellent properties are shown compared with conventional alloys, it is excellent such as high thermal stability, intensity, hardness, high-wearing feature and high fatigability
Corrosion resistance and brilliant radioresistance.However, since high-entropy alloy has lower neutron economy and machinability, with Zr
Alloy is compared, it is difficult to be directly used as fuel covering material.The exploitation of high entropy alloy coating shows the excellent of similar high-entropy alloy
Gesture.Therefore, exploring has important science meaning in the protectiveness high entropy alloy coating that Zr alloy surface preparation meets engineer application
Justice and engineering application value.
Summary of the invention
For high temperature resistant, poor corrosion resistance and coating and zircaloy existing for the current fault-tolerant material of nuclear-used zirconium alloy coating
Between the technical problems such as binding force is bad, the purpose of the present invention is intended to provide a kind of high-temperature corrosion resistance high entropy alloy coating and its system
Preparation Method prepares the high entropy alloy coating that dense uniform, binding force are strong and high temperature corrosion is good in Zr alloy surface.
In order to achieve the above object, the present invention is realized using following technical scheme.
The present invention provides a kind of high entropy alloy coatings of nuclear-used zirconium alloy involucrum surface refractory corrosion, are deposited on Zr conjunction
The high entropy alloy coating of gold surface is CrCuFeMoNi high-entropy alloy, wherein Cr, Cu, Fe, Mo, Ni shared original in high-entropy alloy
Sub- percentage are as follows: Cr 25~35%, Cu 20~30%, Fe 10~14%, Mo 15~20%, Ni 15~20%.It should
It is tightly combined between CrCuFeMoNi high entropy alloy coating and zirconium alloy substrates (present invention is using Zr-4 alloy substrate), and
CrCuFeMoNi high entropy alloy coating improves the hardness of Zr alloy surface.It has been investigated that the CrCuFeMoNi high-entropy alloy applies
Layer has good adhesive force and durability in high-temperature high pressure water corrosive environment, this is because the CrCuFeMoNi high-entropy alloy
The corrosion product that coating generates in corrosion process by Spinel FeCr2O4、NiMoO4And Cr2O3Composition, FeCr2O4Have
Excellent corrosion resistance and insoluble, Cr2O3It is capable of forming a kind of fine and close and continuous passive oxidation film, to be beneficial to prevent
Oxygen is diffused into coating, while this layer of passivating film is preventing ease of solubility erosion (such as NiMoO4) dissolve play important work in water
With.And CrCuFeMoNi high entropy alloy coating thickness after corrosion obviously increases, and can further improve CrCuFeMoNi high
The high temperature corrosion of entropy alloy coat.In addition, the CrCuFeMoNi high entropy alloy coating is after corrosion, oxygen element content is very
It is few, it is only collected into faint oxygen signal in Zr alloy substrates, also shows it with excellent corrosion resistance.The high-entropy alloy
Coating with a thickness of 3~5 μm.
Invention further provides the systems of the high entropy alloy coating of above-mentioned nuclear-used zirconium alloy involucrum surface refractory corrosion
Preparation Method proposes that high-temperature corrosion resistance CrCrCuFeMoNi high-entropy alloy applies using magnetron sputtering technique physical gas phase deposition technology
Layer mentality of designing is realized that is, by changing the sputtering power and deposition pressure of five Cr, Cu, Fe, Mo and Ni targets in zircaloy table
The standby CrCrCuFeMoNi high entropy alloy coating for meeting engineer application of wheat flour, specifically includes the following steps:
(1) basis material pre-processes: Zr alloy base material is successively polished and cleaned；
(2) basis material reverse sputtering cleans: pretreated basis material is placed in the vacuum furnace chamber of magnetron sputtering apparatus
On interior sample stage, and in vacuum less than 2 × 10-4Under the conditions of Pa, cleaned using bias reverse sputtering；
(3) target pre-sputtering: under Ar gas atmosphere, pre-sputtering is carried out to Cr, Cu, Fe, Mo, Ni target, to remove target
The oxide or adsorbing contaminant on surface；
(4) it sputters CrCuFeMoNi high entropy alloy coating: under Ar gas atmosphere, being arranged within the scope of 50~120W respectively
Then the sputtering power of Cr, Cu, Fe, Mo, Ni target carries out cosputtering to five targets, until being deposited on zirconium alloy substrates material
On CrCuFeMoNi high-entropy alloy reach setting thickness, obtain CrCuFeMoNi high entropy alloy coating.
The preparation method of the high entropy alloy coating of above-mentioned nuclear-used zirconium alloy involucrum surface refractory corrosion, step (1) purpose
It is first to handle basis material, in order to which high entropy alloy coating can be preferably attached to it.The present invention uses water first
Dry sanding paper polishes to zircaloy, then is processed by shot blasting, after polishing smooth, most successively cleans through acetone and dehydrated alcohol afterwards
It is clean stand-by.The specific implementation of polishing treatment are as follows: antiscuffing paste is used to zircaloy, is carried out at polishing on metallic phase polisher milling
Reason.Zircaloy after polishing successively uses acetone and dehydrated alcohol to be cleaned by ultrasonic 15~20min, with remove Zr alloy surface grease with
And the impurity such as adsorbate.
The preparation method of the high entropy alloy coating of above-mentioned nuclear-used zirconium alloy involucrum surface refractory corrosion in step (2), is
Further removal Zr alloy substrate surface impurity is prepared for deposition CrCuFeMoNi high entropy alloy coating, is pacified in Zr alloy
It is attached to the intracavitary sample stage of vacuum drying oven of superhigh vacuum magnetron sputtering equipment and then reverse sputtering cleaning is carried out to it.Reverse sputtering is clear
Wash condition are as follows: reverse sputtering gas is Ar, and reverse sputtering air pressure is 2~3Pa, and reverse sputtering bias is -700~-800V, reverse sputtering time
For 10~15min.
The preparation method of the high entropy alloy coating of above-mentioned nuclear-used zirconium alloy involucrum surface refractory corrosion, in step (3), to
It after the completion of the cleaning of Zr alloy substrate surface reverse sputtering, then uses radio-frequency power supply by after the rapid build-up of luminance of Cr, Cu, Fe, Mo, Ni target, closes
Baffle is closed, pre-sputtering is carried out to each target material surface, with oxide or the adsorbing contaminant etc. for removing target material surface.Pre-sputtering condition
Are as follows: under Ar gas atmosphere, the sputtering power of Cr, Cu, Fe, Mo, Ni target is set within the scope of 50~120W respectively, closes gear
Plate carries out pre-sputter cleaning to each target, and scavenging period is 10~15min, and pre-sputtering air pressure is 0.3~0.6Pa.
The preparation method of the high entropy alloy coating of above-mentioned nuclear-used zirconium alloy involucrum surface refractory corrosion in step (4), is
Simplified technique, this step do not use biasing, also do not heat to Zr alloy substrate.In order to more accurately control target as sputter power
And coating layer thickness, this step sputtering pressure are 0.4~0.7Pa, the control of Ar throughput is in 30~60sccm, target and Zr alloy-based
The distance between body is 6~7cm.Sputtering time can be set according to required coating layer thickness.In a preferred embodiment, respectively
It is 90~110W that the sputtering power of target, which is respectively as follows: Cr sputtering power, and Cu sputtering power is 55~60W, and Fe sputtering power is 60
~80W, Mo sputtering power are 50~70W, and Ni sputtering power is 70~80W.In above-mentioned Cr, Cu, Fe, Mo, Ni sputtering power model
It can be good in enclosing regulating and controlling Cr, Cu, Fe, Mo, Ni atomic percent, obtain high temperature resistant, excellent anti-corrosion performance
CrCuFeMoNi high entropy alloy coating.
The high entropy alloy coating of above-mentioned nuclear-used zirconium alloy involucrum surface refractory corrosion, Cr, Cu, Fe, Mo, Ni of use are each
Target purity-homogeneous 99.99%, Zr alloy base material are Zr-4 alloy.
Compared with prior art, the high entropy alloy coating of nuclear-used zirconium alloy involucrum surface refractory corrosion provided by the invention
And preparation method thereof have the advantages that
(1) present invention deposits CrCuFeMoNi high entropy alloy coating in Zr alloy surface, not only increases Zr alloy surface
Hardness, improve corrosion resistance and radioresistance, be tightly combined between zircaloy substrate；And due to the CrCuFeMoNi
FeCr of the high entropy alloy coating in the corrosion product generated in high-temperature high pressure water corrosive environment2O4With excellent corrosion-resistant
Property and insoluble, Cr2O3It is capable of forming a kind of fine and close and continuous passive oxidation film, oxygen is beneficial to prevent and is diffused into coating, together
When prevent ease of solubility erosion from dissolving in water, thus the CrCuFeMoNi high entropy alloy coating show good high temperature resistant,
Corrosion resistance can satisfy practical engineering application, be the potential candidate material of accident fault tolerant fuel involucrum coating.
(2) present invention is by multi-target magnetic control sputtering technology, the CrCuFeMoNi high entropy prepared on zirconium alloy substrates material
Alloy coat, dense uniform, excellent bonding performance have excellent high-temperature corrosion resistance performance, and can satisfy practical engineering application needs
It asks.
(3) present invention passes through the parameters such as regulation sputtering power, sputtering pressure, realization pair by multi-target magnetic control sputtering technology
The accurate control of CrCuFeMoNi high entropy alloy coating ingredient and thickness, and then prepare high temperature resistant, excellent anti-corrosion performance
CrCuFeMoNi high entropy alloy coating.
(4) present invention can obtain cause of the thickness in 3-5 μ m in Zr alloy surface by multi-target magnetic control sputtering technology
Close CrCuFeMoNi high entropy alloy coating, Zr alloy surface coating technology are the important sides of crash-proof fuel canning material research
To the failure of the cladding materials as caused by the factors such as burn into hydrogen embrittlement, stress cracking and irradiation starts from surface mostly, passes through surface
Coating modified is the effective means for promoting existing zirconium alloy cladding performance, and this technology path can high degree keep existing
There is the equipment capacity of zirconium alloy cladding, is easier to realize the engineering application of crash-proof involucrum in short term, there is manufacture well
Economy.
(5) the multi-target magnetic control sputtering technology maturation that the present invention uses, it is easy to operate, it can be achieved that nuclear-used zirconium alloy involucrum surface
The high entropy alloy coating of high-temperature corrosion resistance has good development prospect in the industrialized production of engineering field.
Detailed description of the invention
Fig. 1 is Cr prepared by the embodiment of the present invention 22.6Cu3FeMo1.5Ni1.9High entropy alloy coating shape appearance figure, wherein (a) is
Coating surface figure (b) is schemed for coating cross sections SEM.
Fig. 2 is Cr prepared by the embodiment of the present invention 22.6Cu3FeMo1.5Ni1.9High entropy alloy coating AFM figure.
Fig. 3 is Cr prepared by the embodiment of the present invention 22.6Cu3FeMo1.5Ni1.9High entropy alloy coating scratch metallographic microscope
Figure.
Fig. 4 is Cr prepared by the embodiment of the present invention 22.6Cu3FeMo1.5Ni1.9High entropy alloy coating be corroded after surface
SEM figure.
Fig. 5 is Cr prepared by the embodiment of the present invention 22.6Cu3FeMo1.5Ni1.9High entropy alloy coating be corroded after GIXRD
Figure.
Fig. 6 is Cr prepared by the embodiment of the present invention 22.6Cu3FeMo1.5Ni1.9Pattern after high entropy alloy coating is corroded shows
It is intended to, wherein (a) is section SEM figure, it (b) is EDS line scanning figure.
Specific embodiment
The embodiment of the present invention is provided below with reference to attached drawing, and technical solution of the present invention is carried out into one by embodiment
Clear, the complete explanation of step.Obviously, the embodiment is only a part of the embodiments of the present invention, rather than whole implementation
Example.Based on the content of present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiments belong to the range that the present invention is protected
Embodiment 1
The present embodiment is in Zr-4 alloy base material surface deposition CrCuFeMoNi high entropy alloy coating using superelevation
Vacuum More target sputtering together technology, used splash-proofing sputtering metal target Cr, Cu, Fe, Mo, Ni purity-homogeneous 99.99%, working gas Ar
Purity is 99.999%, specific preparation process the following steps are included:
(1) basis material pre-processes
By Zr-4 alloy be processed into side length be 1cm, with a thickness of the square piece of 3mm, successively with 240 mesh, 600 mesh, 1000 mesh,
1500 mesh, 3000 mesh silicon carbide papers are polished from coarse to fine Zr-4 alloy substrate, reuse antiscuffing paste on metallic phase polisher milling
It is processed by shot blasting, after polishing smooth, is successively cleaned by ultrasonic 15min with acetone and dehydrated alcohol, drying is stand-by.
(2) basis material reverse sputtering cleans
It is on the intracavitary sample stage of the vacuum drying oven that pretreated basis material is placed in magnetron sputtering apparatus, vacuum furnace chamber is true
Empty pump is to 2 × 10-4Pa then passes to Ar gas, and holding sputtering pressure is 2Pa, and control bias is -700V, to Zr-4 alloy substrate
Carry out reverse sputtering cleaning, scavenging period 10min.
(3) target pre-sputtering
Continue sputtering pressure to be adjusted to 0.3Pa, respectively to Cr, Cu, Fe, Mo and Ni target using Ar gas as working gas
Rapid build-up of luminance closes baffle, and adjusting each target power is respectively Cr 100W, Cu 60W, Fe 60W, Mo 70W, Ni 80W, so
Pre-sputtering is carried out to each target afterwards, the pre-sputtering time is 10min；
(4) CrCuFeMoNi high entropy alloy coating is sputtered
Continue using Ar gas as working gas, Ar flow is 30sccm, target-substrate distance 6cm, not biasing, Zr-4 alloy-based
Body does not heat, and sputtering pressure is adjusted to 0.4Pa, and adjusting each target power is respectively Cr 100W, Cu 60W, Fe 60W, Mo
70W, Ni 80W, then open baffle, carry out cosputterings to five targets, and sputtering time is 3h to get to being deposited with
Cr3Cu2.3FeMo1.7Ni2The zircaloy of high entropy alloy coating.
Embodiment 2
The present embodiment is in Zr-4 alloy base material surface deposition CrCuFeMoNi high entropy alloy coating using superelevation
Vacuum More target sputtering together technology, used splash-proofing sputtering metal target Cr, Cu, Fe, Mo, Ni purity-homogeneous 99.99%, working gas Ar
Purity is 99.999%, specific preparation process the following steps are included:
(1) basis material pre-processes
By Zr-4 alloy be processed into side length be 1cm, with a thickness of the square piece of 3mm, successively with 240 mesh, 600 mesh, 1000 mesh,
1500 mesh, 3000 mesh silicon carbide papers are polished from coarse to fine Zr-4 alloy substrate, reuse antiscuffing paste on metallic phase polisher milling
It is processed by shot blasting, after polishing smooth, is successively cleaned by ultrasonic 15min with acetone and dehydrated alcohol, drying is stand-by.
(2) basis material reverse sputtering cleans
It is on the intracavitary sample stage of the vacuum drying oven that pretreated basis material is placed in magnetron sputtering apparatus, vacuum furnace chamber is true
Empty pump is to 1 × 10-4Pa then passes to Ar gas, and holding sputtering pressure is 2Pa, and control bias is -700V, to Zr-4 alloy substrate
Carry out reverse sputtering cleaning, scavenging period 15min.
(3) target pre-sputtering
Continue sputtering pressure to be adjusted to 0.4Pa, respectively to Cr, Cu, Fe, Mo and Ni target using Ar gas as working gas
Rapid build-up of luminance closes baffle, and adjusting each target power is respectively Cr 90W, Cu 60W, Fe 70W, Mo 50W, Ni80W, then
Pre-sputtering is carried out to each target, the pre-sputtering time is 15min；
(4) CrCuFeMoNi high entropy alloy coating is sputtered
Continue using Ar gas as working gas, Ar flow is 40sccm, target-substrate distance 6.5cm, not biasing, Zr-4 alloy
Matrix does not heat, and sputtering pressure is adjusted to 0.5Pa, and adjusting each target power is respectively Cr 90W, Cu 60W, Fe 70W, Mo
50W, Ni 80W, then open baffle, carry out cosputterings to five targets, and sputtering time is 3h to get to being deposited with
Cr2.6Cu3FeMo1.5Ni1.9The zircaloy of high entropy alloy coating.
Embodiment 3
The present embodiment is in Zr-4 alloy base material surface deposition CrCuFeMoNi high entropy alloy coating using superelevation
Vacuum More target sputtering together technology, used splash-proofing sputtering metal target Cr, Cu, Fe, Mo, Ni purity-homogeneous 99.99%, working gas Ar
Purity is 99.999%, specific preparation process the following steps are included:
(1) basis material pre-processes
By Zr-4 alloy be processed into side length be 1cm, with a thickness of the square piece of 3mm, successively with 240 mesh, 600 mesh, 1000 mesh,
1500 mesh, 3000 mesh silicon carbide papers are polished from coarse to fine Zr-4 alloy substrate, reuse antiscuffing paste on metallic phase polisher milling
It is processed by shot blasting, after polishing smooth, is successively cleaned by ultrasonic 20min with acetone and dehydrated alcohol, drying is stand-by.
(2) basis material reverse sputtering cleans
It is on the intracavitary sample stage of the vacuum drying oven that pretreated basis material is placed in magnetron sputtering apparatus, vacuum furnace chamber is true
Empty pump is to 1 × 10-4Pa then passes to Ar gas, and holding sputtering pressure is 3Pa, and control bias is -800V, to Zr-4 alloy substrate
Carry out reverse sputtering cleaning, scavenging period 10min.
(3) target pre-sputtering
Continue sputtering pressure to be adjusted to 0.6Pa, respectively to Cr, Cu, Fe, Mo and Ni target using Ar gas as working gas
Rapid build-up of luminance closes baffle, and adjusting each target power is respectively Cr 110W, Cu 55W, Fe 80W, Mo 60W, Ni 70W, so
Pre-sputtering is carried out to each target afterwards, the pre-sputtering time is 10min；
(4) CrCuFeMoNi high entropy alloy coating is sputtered
Continue using Ar gas as working gas, Ar flow is 60sccm, target-substrate distance 7cm, not biasing, Zr-4 alloy-based
Body does not heat, and sputtering pressure is adjusted to 0.7Pa, and adjusting each target power is respectively Cr 110W, Cu 55W, Fe 80W, Mo
60W, Ni 70W, then open baffle, carry out cosputterings to five targets, and sputtering time is 3h to get to being deposited with
Cr3.5Cu1.9Fe1.4Mo1.5Ni1.7The zircaloy of high entropy alloy coating.
CrCuFeMoNi high entropy alloy coating structure, mechanical property and the high-temperature corrosion resistance performance deposited on Zr alloy substrate
Characterization:
(1) structure, morphology characterization
The Cr that embodiment 2 is prepared using scanning electron microscope2.6Cu3FeMo1.5Ni1.9High entropy alloy coating carries out SEM points
Analysis analyzes result as shown in Figure 1, as can be seen from the figure coating surface densification continuously, is not observed obvious in a big way
Defect, and uniform coating thickness, about 2.29 μm, without the trend of column crystal growth.
The Cr that embodiment 2 is prepared using atomic force microscope2.6Cu3FeMo1.5Ni1.9High entropy alloy coating carries out
AFM analysis, analysis result are only 0.59nm as shown in Fig. 2, as can be seen from the figure coating surface mean roughness is very low, this
Advantageously reduce the frictional resistance on fuel canning material surface.
(2) mechanical property
The Cr that embodiment 2 is prepared using nano-hardness tester2.6Cu3FeMo1.5Ni1.9High entropy alloy coating carries out hard
Degree analysis, obtaining coating hardness is about 12.5GPa, about three times of Zr-4 alloy (about 4.1GPa), shows the coating energy
The hardness of Zr alloy surface is enough greatly improved.
Using coating binding test instrument using the bond strength of automatic scarification tester estimation coating, increase in linear dynamic
Scratch test is carried out under load, while scratch pattern is observed using metallographic microscope, and test results are shown in figure 3, applies
Acoustic emission signal is not observed in layer at 0~100N, and coating scratch metallographic microscope figure is displayed without apparent layering or stripping
It falls, shows that coating is tightly combined with matrix, coating and matrix surface binding force have been more than 100N, illustrate coating and substrate associativity
Can be excellent, it is vital that this, which meets practical engineering application to coating,.
(3) high-temperature corrosion resistance performance
High temperature corrosion test: Cr is deposited with by prepared by embodiment 22.6Cu3FeMo1.5Ni1.9The zirconium of high entropy alloy coating closes
Gold was under 360 DEG C, the saturation pressure of 18.7MPa, by 40 days autoclave corrosion tests.
Then to the Cr after corrosion2.6Cu3FeMo1.5Ni1.9High entropy alloy coating carries out SEM and EDS analysis, analyzes result
As shown in Figure 4 and Figure 6.Fig. 4 shows that coating surface forms some particulate materials, but coating surface does not form crackle, divides
Layer peels off, and shows the Cr2.6Cu3FeMo1.5Ni1.9High entropy alloy coating has good adhesive force in supercritical water corrosion
And durability.Fig. 6 coating cross sections SEM figure and EDS line scanning result are shown simultaneously, after high temperature and pressure aqueous corrosion, the thickness of coating
The reason of increase, increment rate 19.2%, coating thickens, can be attributed to the generation of oxidation product after corrosion.In addition, after corrosion
Cr2.6Cu3FeMo1.5Ni1.9The EDS line scanning result of coating shows that from coating surface to inside, oxygen element content shows
The trend being substantially reduced only is collected into faint oxygen signal in Zr-4 substrate, shows that coating can effectively prevent oxygen element internally
Diffusion, coating show excellent high-temperature corrosion resistance performance.
In order to study corrosion behavior of the coating in high temperature and pressure water environment, to the Cr after corrosion2.6Cu3FeMo1.5Ni1.9
High entropy alloy coating carries out GIXRD analysis, as a result as shown in figure 5, showing Cr2.6Cu3FeMo1.5Ni1.9Coating corrosion product passes through
Analysis is confirmed as the FeCr by Spinel2O4、NiMoO4And Cr2O3Composition.Cr2O3Formation be attributable to
Cr2.6Cu3FeMo1.5Ni1.9High Cr and Fe atomic ratio (Cr/Fe ≈ 2.6) in deposited coating.Due to the FeCr of generation2O4Oxygen
The ratio of Cr and Fe is 2:1, therefore Cr in compound2.6Cu3FeMo1.5Ni1.9FeCr is generated after coating corrosion2O4Afterwards, rich in coating
Remaining Cr element is easy to oxidize at Cr2O3Form exist.Although FeCr2O4With excellent corrosion resistance and insoluble, but point
The FeCr of spar phase2O4Particle growth pattern determines that it cannot form continuous fine and close protectiveness film in coating surface, this can promote
Make oxygen atom internally diffusive migration between particle gap.However, Cr2O3What is formed is a kind of fine and close and continuous passive oxidation
Film is beneficial to prevent oxygen and is diffused into coating, while this layer of passivating film is preventing ease of solubility corrosion product (such as NiMoO4) in water
It plays an important role in middle dissolution.Therefore, Cr2.6Cu3FeMo1.5Ni1.9The excellent high-temperature corrosion resistance performance of high entropy alloy coating is returned
Because in FeCr2O4And Cr2O3The compact oxidation layer of formation.
In conclusion being deposited under the technique using magnetron sputtering in the CrCuFeMoNi high entropy of zircaloy (Zr-4) preparation
Alloy coat carries out coating modified raising zircaloy accident fault-tolerance to Zr alloy surface and provides new research direction and candidate
Material.
Claims (8)
1. a kind of high entropy alloy coating of nuclear-used zirconium alloy involucrum surface refractory corrosion, it is characterised in that be deposited on Zr alloy table
The high entropy alloy coating in face is CrCuFeMoNi high-entropy alloy, wherein Cr, Cu, Fe, Mo, Ni shared atom hundred in high-entropy alloy
Divide ratio are as follows: Cr 25~35%, Cu 20~30%, Fe 10~14%, Mo 15~20%, Ni 15~20%.
2. the high entropy alloy coating of nuclear-used zirconium alloy involucrum surface refractory corrosion according to claim 1, it is characterised in that
The high entropy alloy coating with a thickness of 3-5 μm.
3. the preparation method of the high entropy alloy coating of the corrosion of nuclear-used zirconium alloy involucrum surface refractory described in claim 1, special
Sign be the following steps are included:
(1) basis material pre-processes: Zr alloy base material is successively polished and cleaned；
(2) basis material reverse sputtering cleans: the intracavitary sample of the vacuum drying oven that pretreated basis material is placed in magnetron sputtering apparatus
In sample platform, and in vacuum less than 2 × 10-4Under the conditions of Pa, cleaned using bias reverse sputtering；
(3) target pre-sputtering: under Ar gas atmosphere, pre-sputtering is carried out to Cr, Cu, Fe, Mo, Ni target, to remove target material surface
Oxide or adsorbing contaminant；
(4) sputter CrCuFeMoNi high entropy alloy coating: under Ar gas atmosphere, respectively within the scope of 50~120W be arranged Cr, Cu,
Then the sputtering power of Fe, Mo, Ni target carries out cosputtering to five targets, until being deposited on zirconium alloy substrates material
CrCuFeMoNi high-entropy alloy reaches setting thickness, obtains CrCuFeMoNi high entropy alloy coating.
4. the preparation method of the high entropy alloy coating of nuclear-used zirconium alloy involucrum surface refractory corrosion according to claim 3,
It is characterized in that in step (2), reverse sputtering cleaning condition are as follows: reverse sputtering gas is Ar, and reverse sputtering air pressure is 2~3Pa, reverse sputtering
Bias is -700~-800V, and the reverse sputtering time is 10~15min.
5. the preparation method of the high entropy alloy coating of nuclear-used zirconium alloy involucrum surface refractory corrosion according to claim 3,
It is characterized in that in step (3), pre-sputtering condition are as follows: under Ar gas atmosphere, be arranged within the scope of 50~120W respectively Cr, Cu,
The sputtering power of Fe, Mo, Ni target closes baffle, carries out pre-sputter cleaning to each target, scavenging period is 10~15min, in advance
Sputtering pressure is 0.3~0.6Pa.
6. the preparation method of the high entropy alloy coating of nuclear-used zirconium alloy involucrum surface refractory corrosion according to claim 3,
It is characterized in that sputtering pressure is 0.4~0.7Pa in step (4), target-substrate distance is 6~7cm.
7. the preparation method of the high entropy alloy coating of nuclear-used zirconium alloy involucrum surface refractory corrosion according to claim 3,
It is characterized in that it is 90~110W that the sputtering power of each target, which is respectively as follows: Cr sputtering power, in step (4), Cu sputtering power is
55~60W, Fe sputtering power are 60~80W, and Mo sputtering power is 50~70W, and Ni sputtering power is 70~80W.
8. the high-entropy alloy corroded according to nuclear-used zirconium alloy involucrum surface refractory described in claim 3 to 7 any claim
Coating, it is characterised in that the Zr alloy base material is Zr-4 alloy.
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