CN110055496A - A kind of preparation process preparing Cr coating in nuclear-used zirconium alloy substrate surface - Google Patents
A kind of preparation process preparing Cr coating in nuclear-used zirconium alloy substrate surface Download PDFInfo
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- CN110055496A CN110055496A CN201910517214.9A CN201910517214A CN110055496A CN 110055496 A CN110055496 A CN 110055496A CN 201910517214 A CN201910517214 A CN 201910517214A CN 110055496 A CN110055496 A CN 110055496A
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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
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
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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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- 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
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Abstract
The invention discloses a kind of preparation processes that Cr coating is prepared in nuclear-used zirconium alloy substrate surface, grind to zircaloy substrate, are finally processed by shot blasting on metallic phase polisher milling using antiscuffing paste, after polishing smooth, clean to zircaloy piece surface and oil contaminant；The vacuum drying oven for being placed in superhigh vacuum magnetron sputtering equipment is intracavitary, reaches base vacuum 2 × 10 to vacuum degree‑4After Pa, it is passed through gas and is cleaned 10 minutes with bias backwash；After the completion of the cleaning of substrate surface backwash, using radio-frequency power supply by after the rapid build-up of luminance of Cr target, baffle is closed, target material surface is carried out pre-sputtering 10 minutes, removes oxide on surface or adsorbing contaminant；It opens Cr target baffle and carries out deposition Cr coating；Under the conditions of not closing vacuum system, zircaloy cools to 100 DEG C with the furnace hereinafter, carrying out destressing and correction deformation process.The magnetron sputtering technique that the present invention uses deposits strong binding force, Gao Houdu Cr coating in nuclear-used zirconium alloy substrate.
Description
Technical field
The present invention relates to metal surface modification fields, and in particular to a kind of to prepare Cr coating in nuclear-used zirconium alloy substrate surface
Preparation process.
Background technique
Zirconium alloy cladding shows good Flouride-resistani acid phesphatase and corrosion resistance has been applied successfully to light water reactor
(LWR), but cladding materials is under the conditions of occurring cooling water loss of-coolant accident (LOCA) (LOCA) and beyond design basis accident (BDBA), zirconium
Alloy cladding high-temperature oxydation will discharge a large amount of hydrogen and heat, cause serious nuclear accident, and a large amount of radioactive substances is caused to leak, right
Environment for human survival bringing on a disaster property consequence, such as 2011 " Fukushima nuclear power plant accident ".The research of crash-proof cladding materials is main
It concentrates on to the novel fault-tolerant material of accident (ATF) is developed to substitute traditional zircaloy, the fault-tolerant material requirements of accident, which meets, reacts
Zircaloy performance is used or can improved under the conditions of heap nominal situation, more most important required when reactor core loss of-coolant accident (LOCA) occurs,
The stability of reactor core can be maintained, within a certain period of time to take accident measure to provide enough time.The fault-tolerant material needs pair of accident
Zr alloy surface coating is protected, and is improved the high-temperature oxidation resistance and intensity of zirconium alloy cladding material, is further increased core
The safety and economy of reactor.
The dense oxidation film that metal coating layer material is capable of forming in high-temperature vapor and aqueous corrosion environment, being capable of effective ground resistance
Gear oxygen diffuses into substrate, while metal coating and basal body interface bond strength are high, so that metal coating changes Zr alloy surface
Property become one of most promising accident tolerance candidate material.
However Cr coating is that most promising accident tolerance involucrum applies to Zr alloy surface modification in metal coating
Layer material prepares Cr coating at present and mainly uses arc ion plating, air plasma spraying, cold spraying and 3D laser coatings skill
Art, but existing Cr coating is in the preparation process of Zr alloy surface, as deposition thickness is more than coating and base after 20 microns
Binding force between bottom can reduce, and be unfavorable for being used in core in field, and its obtained material at high temperature corrosion-resistant
It can also be significantly reduced with oxidation resistance, not only reduce service life and efficiency, be also easy to that safety accident occurs.
Summary of the invention
The technical problem to be solved by the present invention is to existing Cr coatings in the preparation process of Zr alloy surface, obtain
Coating cannot keep preferable binding force, high-temperature oxidation resistance and corrosion resistance under thicker thickness, service efficiency compared with
It is low, and it is an object of the present invention to provide a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface, solve Cr coating and closed in zirconium
The problem of preparation of gold surface.
The present invention is achieved through the following technical solutions:
A kind of preparation process preparing Cr coating in nuclear-used zirconium alloy substrate surface, comprising the following steps:
(1) successively zircaloy substrate is ground from thick to thin with silicon carbide paper, is finally thrown using antiscuffing paste in metallographic
It is processed by shot blasting on ray machine, after polishing smooth, zircaloy piece surface and oil contaminant is cleaned；
(2) vacuum drying oven for treated zircaloy piece being placed in superhigh vacuum magnetron sputtering equipment is intracavitary, to vacuum
After degree reaches 2 × 10-4Pa of base vacuum, it is passed through gas and is cleaned 10 minutes with bias backwash；
(3) after the completion of the cleaning of substrate surface backwash, baffle after the rapid build-up of luminance of Cr target, will be closed using radio-frequency power supply, it is right
Target material surface carries out pre-sputtering 10 minutes, removes oxide on surface or adsorbing contaminant；
(4) it opens Cr target baffle and carries out deposition Cr coating；
(5) under the conditions of not closing vacuum system, zircaloy cools to 100 DEG C with the furnace hereinafter, carrying out destressing and correction
Deformation process.
Wherein, a kind of preparation process preparing Cr coating in nuclear-used zirconium alloy substrate surface, the middle use 240# of step (1),
600#, 1000#, 1500#, 3000# silicon carbide paper from thick to thin successively grind zircaloy substrate.In step (1), polishing
After smooth, successively ultrasonic cleaning 10-20 minutes in acetone and alcohol.In step (2) substrate bias backwash cleaning be -
700V bias, Ar atmosphere clean 10min under 2Pa vacuum degree condition.It is 0.4Pa, sputtering that pre-sputtering, which is in air pressure, in step (3)
Power is 100W, sputters 10min under the conditions of work atmosphere Ar, target-substrate distance 6cm.In the step (4) in deposition parameter, sputtering
Air pressure is 0.3-0.6Pa, work atmosphere Ar, and flow is 30~60sccm, target-substrate distance 6-7cm, bias operation voltage 0V~-
150V, deposition substrate heating temperature are 200-400 DEG C, sputter Cr coating in Zr-4 substrate surface, sputtering time is according to painting thickness
Degree determines；The target sputtering power is 120-160W.Cr target purity is 99.99% in the step (4).In the step (5)
After zircaloy cools to 90~120 DEG C or less with the furnace, vacuum system is closed, and sample is saved in the vacuum chamber 9~11 hours
More than, to go to avoid coating to cause stress to be removed because of ambient pressure mutation.Zircaloy cools to 100 with the furnace in the step (5)
DEG C or less after, close vacuum system, and sample saved in the vacuum chamber 10 hours or more, to go to avoid coating because of ambient pressure
Mutation causes stress to be removed.Obtain Cr coating with a thickness of 5~50 μm.
Further, the present invention uses magnetron sputtering technique physical gas phase deposition technology, by the sputtering function for changing Cr target
Rate, substrate bias, base reservoir temperature and deposition pressure obtain the Cr coating with strong binding force, Gao Houdu, realize in zircaloy table
Wheat flour is standby to be met in the core Cr coating of field high temperature high pressure；And it by destressing and is corrected at deformation in this preparation method
Reason, all samples under the conditions of not closing vacuum system, straight 100 DEG C of sample furnace cooling hereinafter, be then turned off vacuum system, and
Sample is saved in the vacuum chamber 10 hours or more, to go to avoid coating to cause stress to be removed because of ambient pressure mutation.
Existing research prepares Cr coating in Zr alloy surface using ion plating technique, and there may be drops, big for surface covering
Particle phenomenon is controlled more preferably using the metal Cr coating surface film quality of magnetron sputtering technique preparation, is had preferably anticorrosive
Performance.Sample, target material surface cleaning are carried out before coating preparation, film-substrate cohesion is good after coating deposition.It is deposited on certain temperature
Lower progress, it is determined that fast deposition may be implemented in deposition power, and film-substrate cohesion is good, super thick of surface compact to obtain
Cr coating shows preferable antioxygenic property under the high temperature conditions.
Compared with prior art, the present invention having the following advantages and benefits:
1, a kind of preparation process that Cr coating is prepared in nuclear-used zirconium alloy substrate surface of the present invention, the magnetic control that the present invention uses
Sputtering technology deposits strong binding force, Gao Houdu Cr coating in nuclear-used zirconium alloy substrate, not only than tradition plating hard chrome coating
Performance is more excellent, and also overcomes tradition plating hard chrome technology because the metal chromium ions of contained strong oxidizing property are tight caused by environment
Heavily contaminated；
2, a kind of preparation process that Cr coating is prepared in nuclear-used zirconium alloy substrate surface of the present invention, the present invention are splashed using magnetic control
It penetrates and prepares the technique of Cr coating in zircaloy substrate surface, this technological operation is simple, and it is accurate to control target as sputter power, apply thickness
Cr coating surface dense uniform that is controllable, and preparing is spent, binding force is excellent；
3, a kind of preparation process that Cr coating is prepared in nuclear-used zirconium alloy substrate surface of the present invention, the material that the present invention obtains
It is effective to carry out destressing and correction deformation process, so that not only performance is more excellent for material prepared by the present invention, and it is more suitable for
In the environment of core has corrosivity with high temperature and pressure, use is safer, more efficient.
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 be the present invention with SEM to the Cr coating being prepared bias be 0V (a figure) and bias for -50V (b figure) into
Capable surface microscopic topographic characterization；
Fig. 2 be the present invention with SEM to the Cr coating being prepared bias be 0V (a figure) and bias for -50V (b figure) into
Capable cross-section morphology characterization；
Fig. 3 is that the present invention is 0V (a figure) in bias and bias is the binding force test chart of -50V (b figure)；
Fig. 4 is that coating scratch of the present invention is 0V (a figure) in bias and bias is the pattern SEM figure of -50V (b figure), and c figure is a
Scheme the enlarged drawing of medium and small figure.
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
As shown in figures 1-4, a kind of preparation process that Cr coating is prepared in nuclear-used zirconium alloy substrate surface of the present invention, including
Following steps:
(1) zircaloy square piece is had with 240#, 600#, 1000#, 1500#, 3000# silicon carbide paper it is thick to carefully successively polishing,
It is finally processed by shot blasting on metallic phase polisher milling using antiscuffing paste, after polishing smooth, is cleaned by ultrasonic 15- using acetone and alcohol
It is stand-by after 20min；
(2) vacuum drying oven for treated zircaloy piece being placed in superhigh vacuum magnetron sputtering equipment is intracavitary, to vacuum
Degree reaches base vacuum 2 × 10-4After Pa, be passed through gas and cleaned 10 minutes with bias backwash, backwash bias operation voltage be-
700V, work atmosphere Ar, working vacuum degree 2Pa；
(3) after the completion of the cleaning of substrate surface backwash, baffle after the rapid build-up of luminance of Cr target, will be closed using radio-frequency power supply, it is right
Target material surface carries out pre-sputtering 10 minutes, and to remove oxide on surface or adsorbing contaminant, pre-sputtering is 0.4Pa, sputtering in air pressure
Power is 100W, sputters 10min under the conditions of work atmosphere Ar, target-substrate distance 6cm.
(4) it after adjusting sputtering parameter to set parameter, opens Cr target baffle and carries out deposition Cr coating, sputtering pressure is
0.5Pa, work atmosphere Ar, flow 50sccm, target-substrate distance 7cm, bias operation voltage 120V, deposition substrate heating temperature are
350 DEG C, Cr coating, sputtering time 6h are sputtered in Zr-4 substrate surface；The target sputtering power is 140W；The Cr target purity
It is 99.99%.
(5) by Zirconium alloy material under the conditions of not closing vacuum system, straight 100 DEG C of sample furnace cooling is hereinafter, then close
Vacuum system is closed, and sample is saved in the vacuum chamber 10 hours or more, to go to avoid coating to cause to answer because of ambient pressure mutation
Power removing.
Embodiment 2
(1) matrix surface polishing and cleaning: successively with the waterproof abrasive paper of 800~5000 mesh and polishing flannelet to substrate coupons into
Row surface grinding polishing, looking-glass finish roughness Ra are less than 10nm；Then, being sequentially placed into concentration is that 40% cleanser is water-soluble
Liquid, saturation Na2CO3 aqueous solution, dehydrated alcohol, are respectively cleaned by ultrasonic 15min in deionized water at acetone, will with N2 gas after completion
Substrate coupons drying；
(2) substrate coupons after cleaning are placed in vacuum chamber and carry out the cleaning of bias plasma backwash, technological parameter are as follows:
Base vacuum 5 × 10-4Pa, backwash bias are 200V, backwash air pressure is 1.0Pa, the backwash time is 20min；
(3) nanometer gradient coating, the plated film are deposited in matrix surface using ultrahigh vacuum multi-target magnetic control sputtering coating machine
Machine background vacuum is 5 × 10-4200 DEG C of Pa, depositing temperature specifically include following 3 continuous time periods: in first sputtering
Between in section, after vacuum chamber pumping reaches background vacuum, Ar gas is passed through into vacuum chamber, throughput 32sccm works
Air pressure is 0.3Pa, and later on Cr, Al, Si target is sputtered, and Al target is gradually linearly increasing to 100W by 20W for power, is realized
Cr target, Al target, three target co-sputtering of Si target, to obtain the Cr that Al content gradually increases in gradientxAlySi1-x-yCoating.
Embodiment 3
(1) matrix surface polishing and cleaning: successively with the waterproof abrasive paper of 800~5000 mesh and polishing flannelet to substrate coupons into
Row surface grinding polishing, looking-glass finish roughness Ra are less than 10nm；Then, being sequentially placed into concentration is that 40% cleanser is water-soluble
Liquid, saturation Na2CO3 aqueous solution, dehydrated alcohol, are respectively cleaned by ultrasonic 15min in deionized water at acetone, will with N2 gas after completion
Substrate coupons drying；
(2) substrate coupons after cleaning are placed in vacuum chamber and carry out the cleaning of bias plasma backwash, technological parameter are as follows:
Base vacuum 5 × 10-4Pa, backwash bias are 200V, backwash air pressure is 1.0Pa, the backwash time is 20min；
(3) nanometer gradient coating, the plated film are deposited in matrix surface using ultrahigh vacuum multi-target magnetic control sputtering coating machine
Machine background vacuum is 5 × 10-4200 DEG C of Pa, depositing temperature, after vacuum chamber pumping reaches background vacuum, into vacuum chamber
It is passed through Ar gas, throughput 32sccm, operating air pressure 0.3Pa, later on Cr target is sputtered, and Cr target power output is
100W。
Embodiment 4
(1) matrix surface polishing and cleaning: successively with the waterproof abrasive paper of 800~5000 mesh and polishing flannelet to substrate coupons into
Row surface grinding polishing, looking-glass finish roughness Ra are less than 10nm；Then, being sequentially placed into concentration is that 40% cleanser is water-soluble
Liquid, saturation Na2CO3 aqueous solution, dehydrated alcohol, are respectively cleaned by ultrasonic 15min in deionized water at acetone, will with N2 gas after completion
Substrate coupons drying；
(2) substrate coupons after cleaning are placed in vacuum chamber and carry out the cleaning of bias plasma backwash, technological parameter are as follows:
Base vacuum 5 × 10-4Pa, backwash bias are 200V, backwash air pressure is 1.0Pa, the backwash time is 20min；
(3) nanometer gradient coating, the plated film are deposited in matrix surface using ultrahigh vacuum multi-target magnetic control sputtering coating machine
Machine background vacuum is 5 × 10-4200 DEG C of Pa, depositing temperature, after vacuum chamber pumping reaches background vacuum, into vacuum chamber
It is passed through Ar gas, throughput 32sccm, operating air pressure 0.3Pa, later on Cr target is sputtered, and Cr target power output is
100W。
(4) by Zirconium alloy material under the conditions of not closing vacuum system, straight 100 DEG C of sample furnace cooling is hereinafter, then close
Vacuum system is closed, and sample is saved in the vacuum chamber 10 hours or more, to go to avoid coating to cause to answer because of ambient pressure mutation
Power removing.
Embodiment 5
(1) zircaloy square piece is had with 240#, 600#, 1000#, 1500#, 3000# silicon carbide paper it is thick to carefully successively polishing,
It is finally processed by shot blasting on metallic phase polisher milling using antiscuffing paste, after polishing smooth, is cleaned by ultrasonic 15- using acetone and alcohol
It is stand-by after 20min；
(2) vacuum drying oven for treated zircaloy piece being placed in superhigh vacuum magnetron sputtering equipment is intracavitary, to vacuum
Degree reaches base vacuum 2 × 10-4After Pa, be passed through gas and cleaned 10 minutes with bias backwash, backwash bias operation voltage be-
700V, work atmosphere Ar, working vacuum degree 2Pa；
(3) after the completion of the cleaning of substrate surface backwash, baffle after the rapid build-up of luminance of Cr target, will be closed using radio-frequency power supply, it is right
Target material surface carries out pre-sputtering 10 minutes, and to remove oxide on surface or adsorbing contaminant, pre-sputtering is 0.4Pa, sputtering in air pressure
Power is 100W, sputters 10min under the conditions of work atmosphere Ar, target-substrate distance 6cm.
(4) nanometer gradient coating, the plated film are deposited in matrix surface using ultrahigh vacuum multi-target magnetic control sputtering coating machine
Machine background vacuum is 5 × 10-4200 DEG C of Pa, depositing temperature specifically include following 3 continuous time periods: in first sputtering
Between in section, after vacuum chamber pumping reaches background vacuum, Ar gas is passed through into vacuum chamber, throughput 32sccm works
Air pressure is 0.3Pa, and later on Cr, Al, Si target is sputtered, and Al target is gradually linearly increasing to 100W by 20W for power, is realized
Cr target, Al target, three target co-sputtering of Si target, to obtain the Cr that Al content gradually increases in gradientxAlySi1-x-yCoating.
(5) by Zirconium alloy material under the conditions of not closing vacuum system, straight 100 DEG C of sample furnace cooling is hereinafter, then close
Vacuum system is closed, and sample is saved in the vacuum chamber 10 hours or more, to go to avoid coating to cause to answer because of ambient pressure mutation
Power removing.
It opens superhigh vacuum magnetron sputtering equipment Cr target baffle and carries out deposition Cr coating, following parameter is set separately, obtains
Table 1:
Table 1
Under the process step of the invention, style is prepared according to the sputtering parameter of table 1, is prepared according to the method for Examples 1 to 5
Zirconium closes
Gold substrate Cr coating, obtains following data:
Parameter area in table 1 is outside parameter area of the invention, and style 1~4 is according to 1 the step of system of embodiment
It is standby, since its parameter is outside parameter of the invention, by above-mentioned data it is found that its binding force and anti-height at high temperature
Warm oxidation susceptibility is poor.
Embodiment 2 is existing preparation process, and embodiment 3 is also existing preparation process, and Cr, Al, Si target are changed
There was only Cr target；Embodiment 4 is also existing technique, and embodiment 5 is under technique of the invention, and target is changed to the prior art
The sputtering of three targets；
It is special as above data analysis it is found that the performance of embodiment 2~5 is worse than coating obtained by the embodiment of the present invention 1
It is not oxidation resistance at high temperature.The coated film base junction prepared under present invention process parameter closes high-quality, film surface cause
Close, deposition efficiency is very high, has good antioxygenic property under the high temperature conditions.Therefore, present invention process is that one kind has development
Material surface antioxidant coating technology of preparing in the reactor of prospect.
Surface is carried out to the Cr coating being prepared with SEM and cross-section morphology characterizes, it is as shown in Figs. 1-2, prepared
Cr coating surface it is fine and close, continuous, do not observe that apparent defect exists in a big way, section SEM figure, which show paintings
Layer has uniform thickness.
Using the bond strength of automatic scarification tester estimation coating, scratch examination is carried out in the case where linear dynamic increases load
It tests, while scratch pattern is observed using scanning electron microscope.Test results are shown in figure 3 for binding force, and Fig. 4 is coating
Scratch pattern SEM figure, the Cr coating binding force that bias is 0V are more than 30N, and bias is that the Cr coating of -50V is more than 100N, in 0-
Acoustic emission signal is not observed at 100N, and scrapes relatively fewer, no significantly layering or peeling, it can be found that all
Coating is tightly combined with matrix, and coating and matrix interface are fuzzy, show coating and matrix surface to adhere to each other ability strong, apply
Layer is excellent with substrate binding performance.Coating layer thickness prepared by the present invention is 20 microns to 30 microns, and is had preferable
Oxidation-resistance property, corrosion resistance, binding force and intensity, be better than the obtained coating of existing preparation process, and
And it obtains material and is more suitable for core field.
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 (10)
1. a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface, which comprises the following steps:
(1) successively zircaloy substrate is ground from thick to thin with silicon carbide paper, finally using antiscuffing paste in metallic phase polisher milling
On be processed by shot blasting, after polishing smooth, zircaloy piece surface and oil contaminant is cleaned；
(2) vacuum drying oven for treated zircaloy piece being placed in superhigh vacuum magnetron sputtering equipment is intracavitary, reaches to vacuum degree
To base vacuum 2 × 10-4After Pa, it is passed through gas and is cleaned 10 minutes with bias backwash；
(3) after the completion of the cleaning of substrate surface backwash, using radio-frequency power supply by after the rapid build-up of luminance of Cr target, baffle is closed, to target
Surface carries out pre-sputtering 10 minutes, removes oxide on surface or adsorbing contaminant；
(4) it opens Cr target baffle and carries out deposition Cr coating；
(5) under the conditions of not closing vacuum system, zircaloy cools to 100 DEG C with the furnace hereinafter, carrying out destressing and correction deformation
Processing.
2. a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface according to claim 1, feature
Be, in step (1) with 240#, 600#, 1000#, 1500#, 3000# silicon carbide paper from thick to thin successively to zircaloy substrate into
Row grinding.
3. a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface according to claim 1, feature
It is, in step (1), after polishing smooth, successively ultrasonic cleaning 10-20 minutes in acetone and alcohol.
4. a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface according to claim 1, feature
It is, the cleaning of substrate bias backwash is to clean 10min under -700V bias, Ar atmosphere, 2Pa vacuum degree condition in step (2).
5. a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface according to claim 1, feature
It is, it is 0.4Pa, sputtering power 100W, work atmosphere Ar, target-substrate distance 6cm condition that pre-sputtering, which is in air pressure, in step (3)
Lower sputtering 10min.
6. a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface according to claim 1, feature
Be, in the step (4) in deposition parameter, sputtering pressure 0.3-0.6Pa, work atmosphere Ar, flow be 30~
60sccm, target-substrate distance 6-7cm, bias operation voltage 0V~-150V, deposition substrate heating temperature is 200-400 DEG C, in Zr-4 base
Bottom surface sputters Cr coating；The target sputtering power is 120-160W.
7. a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface according to claim 1, feature
It is, Cr target purity is 99.99% in the step (4).
8. a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface according to claim 1, feature
It is, after zircaloy cools to 90~120 DEG C or less with the furnace in the step (5), closes vacuum system, and by sample in vacuum
It is saved 9~11 hours or more in chamber, to go to avoid coating to cause stress to be removed because of ambient pressure mutation.
9. a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface according to claim 8, feature
It is, after zircaloy cools to 100 DEG C or less with the furnace in the step (5), closes vacuum system, and in the vacuum chamber by sample
Save 10 hours or more, to go to avoid coating to cause stress to be removed because of ambient pressure mutation.
10. a kind of preparation process for preparing Cr coating in nuclear-used zirconium alloy substrate surface according to claim 1, feature
Be, obtained Cr coating with a thickness of 5~50 μm.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110499495A (en) * | 2019-09-05 | 2019-11-26 | 西安交通大学 | It is a kind of using Zr as Cr-Me multilayer film of substrate and preparation method thereof |
| CN110499494A (en) * | 2019-09-05 | 2019-11-26 | 西安交通大学 | It is a kind of using Zr as Cr/Al monofilm of substrate and preparation method thereof |
| CN110629176A (en) * | 2019-09-05 | 2019-12-31 | 西安交通大学 | Cr-Al alloy film with Zr as substrate and preparation method thereof |
| CN111041412A (en) * | 2019-12-07 | 2020-04-21 | 西北有色金属研究院 | Preparation method of interface integrated zirconium or zirconium alloy cladding surface functional coating |
| CN112899682A (en) * | 2021-01-20 | 2021-06-04 | 哈尔滨工业大学 | Preparation method of zirconium cladding protective coating |
| CN113061859A (en) * | 2021-03-19 | 2021-07-02 | 成都齐兴真空镀膜技术有限公司 | Metal coating for X-ray tube anode target and preparation method thereof |
| CN113088884A (en) * | 2021-03-09 | 2021-07-09 | 哈尔滨工业大学 | Method for preparing chromium coating with high-temperature oxidation resistance on zirconium cladding |
| CN113293354A (en) * | 2021-05-27 | 2021-08-24 | 重庆文理学院 | High-temperature oxidation resistant coating for cladding substrate and preparation process |
| CN114134456A (en) * | 2021-11-04 | 2022-03-04 | 苏州热工研究院有限公司 | Magnetron sputtering preparation method of Cr coating of zirconium alloy cladding |
| CN116377404A (en) * | 2022-12-06 | 2023-07-04 | 哈尔滨工业大学 | Composite coating based on high-entropy alloy diffusion resistance on surface of cladding and preparation method thereof |
| CN116516309A (en) * | 2023-05-10 | 2023-08-01 | 重庆文理学院 | Single-layer Cr-enriched N-doped coating on surface of zirconium alloy for nuclear and preparation method thereof |
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| CN110499495A (en) * | 2019-09-05 | 2019-11-26 | 西安交通大学 | It is a kind of using Zr as Cr-Me multilayer film of substrate and preparation method thereof |
| CN110499494A (en) * | 2019-09-05 | 2019-11-26 | 西安交通大学 | It is a kind of using Zr as Cr/Al monofilm of substrate and preparation method thereof |
| CN110629176A (en) * | 2019-09-05 | 2019-12-31 | 西安交通大学 | Cr-Al alloy film with Zr as substrate and preparation method thereof |
| CN111041412A (en) * | 2019-12-07 | 2020-04-21 | 西北有色金属研究院 | Preparation method of interface integrated zirconium or zirconium alloy cladding surface functional coating |
| CN112899682A (en) * | 2021-01-20 | 2021-06-04 | 哈尔滨工业大学 | Preparation method of zirconium cladding protective coating |
| CN113088884A (en) * | 2021-03-09 | 2021-07-09 | 哈尔滨工业大学 | Method for preparing chromium coating with high-temperature oxidation resistance on zirconium cladding |
| CN113061859A (en) * | 2021-03-19 | 2021-07-02 | 成都齐兴真空镀膜技术有限公司 | Metal coating for X-ray tube anode target and preparation method thereof |
| CN113293354A (en) * | 2021-05-27 | 2021-08-24 | 重庆文理学院 | High-temperature oxidation resistant coating for cladding substrate and preparation process |
| CN114134456A (en) * | 2021-11-04 | 2022-03-04 | 苏州热工研究院有限公司 | Magnetron sputtering preparation method of Cr coating of zirconium alloy cladding |
| CN114134456B (en) * | 2021-11-04 | 2023-12-22 | 苏州热工研究院有限公司 | Magnetron sputtering preparation method of Cr coating of zirconium alloy cladding |
| CN116377404A (en) * | 2022-12-06 | 2023-07-04 | 哈尔滨工业大学 | Composite coating based on high-entropy alloy diffusion resistance on surface of cladding and preparation method thereof |
| CN116377404B (en) * | 2022-12-06 | 2023-09-22 | 哈尔滨工业大学 | Composite coating based on high-entropy alloy diffusion resistance on surface of cladding and preparation method thereof |
| CN116516309A (en) * | 2023-05-10 | 2023-08-01 | 重庆文理学院 | Single-layer Cr-enriched N-doped coating on surface of zirconium alloy for nuclear and preparation method thereof |
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