CN118086848A - High-temperature oxidation resistant composite coating for surface of zirconium alloy for core and preparation method thereof - Google Patents
High-temperature oxidation resistant composite coating for surface of zirconium alloy for core and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 137
- 239000011248 coating agent Substances 0.000 title claims abstract description 130
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 85
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 52
- 230000003647 oxidation Effects 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910019590 Cr-N Inorganic materials 0.000 claims abstract description 64
- 229910019588 Cr—N Inorganic materials 0.000 claims abstract description 64
- 230000007704 transition Effects 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 20
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims description 48
- 230000008021 deposition Effects 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 29
- 238000005498 polishing Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000005477 sputtering target Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910003460 diamond Inorganic materials 0.000 claims description 7
- 239000010432 diamond Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 12
- 230000004888 barrier function Effects 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- 230000004584 weight gain Effects 0.000 abstract description 8
- 235000019786 weight gain Nutrition 0.000 abstract description 8
- 229910017076 Fe Zr Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000005496 eutectics Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 239000010941 cobalt Substances 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- 229910018509 Al—N Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910007744 Zr—N Inorganic materials 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
-
- 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
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
A preparation method of a high-temperature oxidation resistant composite coating on the surface of a zirconium alloy for a core comprises the steps of firstly preparing a Cr-N transition layer on the surface of a zirconium alloy matrix through magnetron sputtering, and then preparing a FeCrAl coating on the surface of the transition layer to form a C-N/FeCrAl composite coating. In the invention, when the FeCrAl oxidation resistant coating is prepared on the surface of the zirconium alloy matrix, cr-N is firstly prepared as a transition layer, and then a FeCrAl coating is prepared, and in order to improve the wear resistance and structural stability of the surface of the coating, a double-layer composite coating is prepared by adopting materials such as a high-purity cobalt target, an iron target, an alloy target and the like. A continuous AlN diffusion barrier layer is formed at the Cr-N/FeCrAl interface in situ under a high-temperature environment, fe element is prevented from diffusing to the inside, and a Zr 2 N twin crystal layer is formed at the Zr/Cr-N interface in situ, so that the out-diffusion of Zr element can be greatly slowed down, the Fe-Zr eutectic reaction is effectively prevented, the columnar crystal structure of the FeCrAl coating is reduced, the oxidation resistance of the coating is improved, and the oxidation weight gain of the zirconium alloy of the Cr-N/FeCrAl composite coating is reduced by 56.9% compared with that of the zirconium alloy at 1200 ℃.
Description
Technical Field
The invention relates to the technical field of nuclear power metal coatings, in particular to a zirconium alloy surface high-temperature oxidation resistant composite coating for a nuclear and a preparation method thereof.
Background
Because zirconium alloys have good nuclear properties, they are the preferred material for nuclear fuel cladding, but in the event of a loss of coolant accident (LOCA, lost of Coolant Accident), zirconium alloy cladding materials rapidly rise in temperature to above 1000 ℃ and react with high temperature steam to produce large amounts of hydrogen and heat. If the temperature is higher than 1200 ℃, the reactor core is molten, the risk of hydrogen explosion is increased, and nuclear leakage is caused.
The high-temperature oxidation-resistant coating deposited on the surface of the zirconium alloy has the advantages of short research and development period, good adaptability to the production process of the zirconium alloy cladding tube and the like, and becomes an important means for improving the fault tolerance of the zirconium alloy in a short period. Currently, research into zirconium alloy surface coatings has focused mainly on pure metal coatings, ceramic coatings, alloy coatings, and composite coatings. The metal FeCrAl coating has excellent performances in the aspects of high-temperature and high-pressure water corrosion resistance, thermal shock resistance, hydrogen release reduction and the like, is a potential candidate material, and can not obviously reduce the neutron economy of the fuel cladding while improving the accident fault tolerance of the cladding, so that the existing thermal environment in the reactor is maintained to the maximum extent; and compatibility of the zirconium alloy and the fuel fission product is considered.
Magnetron sputtering is the most widely used chromium coating preparation technology at present, and a direct current magnetron sputtering technology is currently commonly adopted. Although the FeCrAl coating prepared by magnetron sputtering has the characteristics of good uniformity, stable process and the like, the FeCrAl coating prepared on the surface of the Zr alloy can generate serious Fe-Zr eutectic reaction when reaching 928 ℃, so that the coating performance is seriously attenuated, and the oxidation resistance of the coating is influenced. And the columnar crystal and the porosity of the coating are required to be improved so as to meet the use requirements.
Disclosure of Invention
Based on the technical problems, the invention aims to provide a preparation method of a high-temperature oxidation resistant composite coating on the surface of a zirconium alloy for a core, which improves the oxidation resistance of a FeCrAl coating, reduces the columnar crystal structure of the FeCrAl coating and improves the accident fault tolerance of the coating by introducing a Cr-N transition layer between a zirconium alloy substrate and the FeCrAl coating.
The invention further aims at providing the high-temperature oxidation resistant composite coating on the surface of the zirconium alloy for the core.
The invention aims at realizing the following technical scheme:
A preparation method of a high-temperature oxidation resistant composite coating on the surface of a zirconium alloy for a core is characterized by comprising the following steps: the method comprises the steps of firstly preparing a Cr-N transition layer on the surface of a zirconium alloy matrix by magnetron sputtering, and then preparing a FeCrAl coating on the surface of the transition layer to form a C-N/FeCrAl composite coating.
Further, the deposition temperature of the Cr-N transition layer is 250-350 ℃, the power of a Cr target is 240-260W, the deposition pressure is 0.3-0.5 Pa, the flow rate of N 2 is 2-10 sccm, the bias voltage is 8-12V, the rotating speed of a rotating frame is 6-10 rpm, the time is 6-8 hours, and the content of N in the Cr-N transition layer is controlled to be 15-18 at.%.
Further, the deposition temperature of the FeCrAl coating is 450-550 ℃, the power of the CrAl alloy target is 120-180W, the power of the Fe target is 280-320W, the deposition pressure is 0.3-0.5 Pa, the bias voltage is 60-80V, the rotating speed of the rotating frame is 6-10 rpm, and the time is 2-3 hours.
Further, the zirconium alloy matrix is subjected to pretreatment before the coating is prepared, specifically, 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper are sequentially used for polishing the surface of the zirconium alloy, the polished zirconium alloy matrix is sequentially polished by diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, and then acetone and absolute ethyl alcohol are sequentially used for ultrasonic cleaning for 10min and then are dried for standby.
Further, the pretreated zirconium alloy substrate is required to be subjected to ion cleaning, specifically, the zirconium alloy substrate is put into a magnetron sputtering coating furnace, ar is introduced when the vacuum degree reaches 8×10 -4 Pa, the bias voltage is adjusted to 420-480V, the power is 280-320W, and the treatment time is 8-15 min.
In the invention, N element is introduced, and an AlN diffusion barrier layer is formed in situ at a Cr-N/FeCrAl interface in a high-temperature environment, so that Fe element can be prevented from diffusing inwards; the Zr 2 N twin crystal layer formed in situ at the Zr/Cr-N interface can greatly slow down the out-diffusion of Zr element. By the single-baffle cooperation of the two interfaces, the eutectic reaction of Fe-Zr is effectively prevented. In addition, by preparing the Cr-N coating with an amorphous state on the surface of the matrix, the template effect can be inhibited, the growth effect of columnar crystals of the FeCrAl layer can be reduced, and the rapid passage of O 2 into the zirconium alloy matrix can be blocked. The FeCrAl coating with specific element ratio can rapidly form a continuous compact Al 2O3 oxide layer in a high-temperature environment, so as to prevent continuous invasion of O 2 and further improve the high-temperature oxidation resistance of the FeCrAl coating.
The preparation method of the high-temperature oxidation resistant coating on the surface of the zirconium alloy for the core is characterized by comprising the following steps of:
(1) Pretreatment of a matrix: the method comprises the steps of sequentially polishing the surface of a zirconium alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, sequentially polishing the polished zirconium alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the zirconium alloy substrate by using acetone and absolute ethyl alcohol for 10min, and drying the zirconium alloy substrate for later use;
(2) Sample loading and cleaning: filling a zirconium alloy substrate into a magnetron sputtering coating furnace chamber, when the vacuum degree in the furnace reaches 8 multiplied by 10 - 4 Pa, introducing Ar, adjusting the bias voltage to be 420-480V, the power to be 280-320W, and the treatment time to be 8-15 min;
(3) Depositing a Cr-N transition layer: taking a Cr target as a sputtering target, wherein the deposition temperature is 250-350 ℃, the power of the Cr target is 240-260W, the deposition pressure is 0.3-0.5 Pa, the flow rate of N 2 is 2-10 sccm, the bias voltage is 8-12V, the rotating speed of a rotating frame is 6-10 rpm, the time is 6-8 hours, and the content of N in a Cr-N transition layer is controlled to be 15-18 at%;
(4) Depositing a FeCrAl coating: the high-purity Fe target and the CrAl alloy target are used as sputtering targets, the deposition temperature is 450-550 ℃, the power of the CrAl alloy target is 120-180W, the power of the Fe target is 280-320W, the deposition pressure is 0.3-0.5 Pa, the bias voltage is 60-80V, the rotating speed of a rotating frame is 6-10 rpm, and the time is 2-3 hours.
A high-temperature oxidation resistant composite coating on the surface of a zirconium alloy for a core is characterized in that: the composite coating comprises a Cr-N transition layer and a FeCrAl coating, wherein the content of N in the Cr-N transition layer is 15-18 at%, and the content of Al in the FeCrAl coating is 15-22 at%.
Further, the Cr-N transition layer is prepared by magnetron sputtering, the deposition temperature is 250-350 ℃, the Cr target power is 240-260W, the deposition pressure is 0.3-0.5 Pa, the flow rate of N 2 is 2-10 sccm, the bias voltage is 8-12V, the rotating speed of the rotating frame is 6-10 rpm, and the time is 6-8 hours.
Further, the FeCrAl coating is prepared by taking an Fe target and a CrAl alloy target as sputtering targets through magnetron sputtering, wherein the specific deposition temperature is 450-550 ℃, the power of the CrAl alloy target is 120-180W, the power of the Fe target is 280-320W, the deposition pressure is 0.3-0.5 Pa, the bias voltage is 60-80V, the rotating speed of a rotating frame is 6-10 rpm, and the time is 2-3 h.
The invention has the following technical effects:
When the FeCrAl oxidation resistant coating is prepared on the surface of the zirconium alloy matrix, cr-N is firstly prepared as a transition layer, a continuous AlN diffusion barrier layer is formed in situ at a Cr-N/FeCrAl interface under a high temperature environment to block Fe element from diffusing to the inside, and a Zr 2 N twin crystal layer is formed in situ at the Zr/Cr-N interface to greatly slow down Zr element out-diffusion, effectively prevent Fe-Zr eutectic reaction, reduce columnar crystal structure of the FeCrAl coating, improve oxidation resistance of the coating, and reduce oxidation weight gain of the zirconium alloy of the Cr-N/FeCrAl composite coating by 56.9% under 1200 ℃ steam compared with that of the zirconium alloy.
Drawings
Fig. 1: the invention relates to a surface cross-section morphology graph of a magnetron sputtering deposition Cr-N/FeCrAl composite coating.
Fig. 2: surface cross-section morphology and EDS energy spectrum of the Cr-N/FeCrAl composite coating after being oxidized for 30min in a high-temperature steam environment at 1200 ℃.
Fig. 3: TEM microscopic characterization of Cr-N/FeCrAl coatings after oxidation in a high temperature steam environment at 1200 ℃ for 30 min.
Fig. 4: oxidized weight gain and XRD pattern of Cr-N/FeCrAl composite coating in high temperature steam environment.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing disclosure.
Example 1
A preparation method of a high-temperature oxidation resistant coating on the surface of a zirconium alloy for a core comprises the following steps:
(1) Pretreatment of a matrix: the method comprises the steps of sequentially polishing the surface of a zirconium alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, sequentially polishing the polished zirconium alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the zirconium alloy substrate by using acetone and absolute ethyl alcohol for 10min, and drying the zirconium alloy substrate for later use;
(2) Sample loading and cleaning: filling a zirconium alloy matrix into a magnetron sputtering coating furnace chamber, when the vacuum degree in the furnace reaches 8× - 4 Pa, introducing Ar, adjusting the bias voltage to 450V, and the power to 300W, wherein the treatment time is 10min;
(3) Depositing a Cr-N transition layer: taking a Cr target as a sputtering target, wherein the deposition temperature is 300 ℃, the power of the Cr target is 250W, the deposition pressure is 0.4Pa, the flow rate of N 2 is 2sccm, the bias voltage is 10V, the rotating speed of a rotating frame is 8rpm, the time is 7 hours, the N content in the prepared Cr-N transition layer is 15.48 at%, and the thickness of the Cr-N transition layer is 5.42 mu m;
(4) Depositing a FeCrAl coating: the high-purity Fe target and the CrAl alloy target are used as sputtering targets, the deposition temperature is 500 ℃, the power of the CrAl target is 150W, fe, the power of the target is 300W, the deposition pressure is 0.4Pa, the bias voltage is 70V, the rotating speed of a rotating frame is 8rpm, the time is 2.5 hours, the Al content in the prepared FeCrAl coating is 16.31%, and the thickness of the FeCrAl coating is 7.12 mu m.
FIG. 1 is a diagram showing the cross-sectional morphology of a Cr-N/FeCrAl composite coating in the magnetron sputtering deposition state in the embodiment. The figure shows the surface cross-section morphology and EDS energy spectrum of the deposited state of the Cr-N/FeCrAl composite coating on the surface of the zirconium alloy. In the surface topography diagram of the composite coating in fig. 1 (a), as shown in the figure, the surface grains of the FeCrAl layer are in a typical triangular prism shape, but the inter-grain distance of columnar crystals is obviously reduced, the structure is uniform and compact, and the Fe-Cr-Al element component is Fe-13.48Cr-16.31Al (at%). As shown in (b) and (c) of FIG. 1, the cross-sectional morphology of the Cr-N/FeCrAl coating is that the Cr-N/FeCrAl and Zr/Cr-N interfaces are smooth and well-combined, wherein the element component of the Cr-N layer is Cr-15.48Al (at%). The average thickness of the Cr-N/FeCrAl composite coating is about 12.5+ -0.2 μm, the thickness of the Cr-N layer is about 5.4+ -0.2 μm, and the thickness of the FeCrAl layer is about 7.1+ -0.2 μm. The surface cross section morphology shows that the Cr-N layer is in an amorphous state, the surface density of the FeCrAl layer is higher under the influence of the template effect, the inter-crystal gaps of columnar crystals of the FeCrAl are reduced, and the negative influence of the columnar crystals of the FeCrAl is relieved.
The substrate with the Cr-N/FeCrAl composite coating prepared in example 1 is subjected to an antioxidation test in a high-temperature steam environment at 1200 ℃, and the surface cross-sectional morphology and EDS energy spectrum after 30min of oxidation are shown in FIG. 2. FIG. 2 shows that after the Cr-N/FeCrAl composite coating on the surface of the zirconium alloy is subjected to steam oxidation at 1200 ℃, a continuous and compact Al 2O3 oxide layer is formed on the surface, and the thickness of the Al 2O3 oxide layer is about 549+/-50: 50 nm. The cross-sectional morphology shows that a thinner Zr-Cr-N diffusion layer exists at the Zr/Cr-N interface, which is about 670+/-20 nm, but the point scanning at the P2-5 position shows that the oxygen content in the composite coating is lower. The coating structure is very complete after oxidation, no sign of inward diffusion of Fe element occurs, and the outward diffusion rate of Zr element is slower, so that the Cr-N barrier layer can effectively prevent the eutectic reaction of Fe-Zr, and the high-temperature oxidation resistance of the zirconium alloy can be better improved.
The TEM spectrum of the oxidized Cr-N/FeCrAl composite coating is shown in figure 3. After oxidation of 30min in a 1200 ℃ steam environment, a continuous Al-N rich coating with a thickness of about 70+/-20 nm is formed in situ at the Cr-N/FeCrAl interface of the composite coating, and the phase of the Al-rich coating is AlN in combination with the SAED result. In the oxidation process, a Zr-N diffusion layer Luan Jing is formed in situ at the Zr/Cr-N interface to a thickness of about 264+ -25: 25 nm. As proved by SAED, the Zr-N diffusion layer Luan Jing is composed of Zr 2 N phase, zr still exists in the Zr-4 matrix, and oxidation reaction does not occur, which indicates that the Cr-N/FeCrAl composite coating is prepared on the surface of the zirconium alloy, and the zirconium matrix can be greatly protected in a high-temperature steam environment.
When the coating is prepared, the high-temperature oxidation resistance of the composite coating is gradually enhanced along with the increase of the thickness of the composite coating.
Comparative example 1
A Cr/FeCrAl composite coating was prepared on the surface of a zirconium alloy substrate according to the preparation process of example 1, except that N 2 was not introduced during the preparation of the Cr coating.
The Fe and Cr are mutually dissolved, and Cr can not block Zr from diffusing outwards, so that Fe in the FeCrAl coating and the substrate can not be effectively prevented from undergoing Fe-Zr eutectic reaction, and the oxidation resistance of the coating is not ideal.
The composite coatings prepared in example 1, comparative example 1 and comparative example 2 were subjected to oxidation weight gain test in a high temperature steam environment, and the test results are shown in fig. 4 (a), wherein after the Cr-N/FeCrAl coating, the Cr/FeCrAl coating and Zry-4 alloy on the surface of the zirconium alloy are subjected to steam oxidation at different temperatures (1000, 1100 and 1200 ℃) for 30 min, the weight gain (delta W/A) of the unit area of the test sample is 1.96 mg/cm 2,3.02 mg/cm2 and 11.34 mg/cm 2 (Cr-N/FeCrAl coating), respectively; 3.79 mg/cm 2,8.81 mg/cm2 and 19.93 mg/cm 2 (Cr/FeCrAl coating), whereas the oxidized weight gain of the Zry-4 alloy samples was divided into 5.88 mg/cm 2,14.67 mg/cm2 and 26.31 mg/cm 2. The weight gain curve shows that the Cr-N/FeCrAl coating prepared on the surface of the zirconium alloy has the strongest protective capability on the Zr-4 matrix in the high-temperature steam environment. The composite coating prepared in example 1 was subjected to high temperature steam oxidation tests at different temperatures, and the XRD pattern after the test was as shown in fig. 4 (b), and at 1000 ℃, the coating showed diffraction peaks of Cr 2O3、Fe2O3、Al2O3 phase, wherein the intensity of Al 2O3 peak was higher, and as the oxidation temperature was increased, the diffraction peaks of Al 2O3 phase increased, but phases of Cr 2O3 of 36.3 ° and 76.8 ° disappeared. At 1200 ℃, the XRD result of the surface of the coating shows that the intensity of the diffraction peak of the Al 2O3 phase is obviously increased, and the intensity of the diffraction peak of other oxidation is very weak, which shows that the surface is basically an Al 2O3 oxide film.
Comparative example 2
According to the preparation process of example 1, a FeCrAl coating is now prepared on the surface of the zirconium alloy substrate, and then the same Cr-N coating is prepared on the surface of the coating, i.e. the difference from example 1 is that the coating sequence is exchanged.
The FeCrAl coating is in direct contact with the Zr alloy matrix, no blocking effect is generated, obvious Fe-Zr eutectic reaction occurs, cr-N only plays a weak antioxidation role in the composite coating, but the overall high-temperature oxidation resistance is not ideal due to the performance attenuation of the FeCrAl coating, and the oxidation weight gain reaches 19.26 mg/cm 2 in a 1200 ℃ steam environment.
Based on the example 1, the sputtering power of the Cr target, the flow of N 2 and the preparation time are adjusted to adjust the content of N in the prepared Cr-N transition layer, the Cr-N transition layer with the same thickness is prepared, the sputtering power of the high-purity Fe target and the sputtering power of the CrAl alloy target are adjusted, the content proportion of Al in the FeCrAl coating is adjusted, the FeCrAl coating with the same thickness is prepared, the coating is subjected to oxidation treatment for 30min in a steam environment at 1200 ℃, and the influence of the content of N and Al in the composite coating on the high-temperature oxidation resistance of the composite coating is counted, so that the results are shown in the table 1.
Table 1: influence of N and Al contents on high-temperature oxidation resistance of composite coating
As can be seen from the table, when the N content in the Cr-N transition layer and the Al content in the FeCrAl coating are within a certain range in a high-temperature steam environment of 1200 ℃, the continuity of the Al-N diffusion barrier layer generated at the interface of the Cr-N transition layer and the FeCrAl coating is better, and the barrier effect on element diffusion is obviously improved, but when the coating is in a high-temperature steam environment for a long time after the N content is gradually increased to a certain range, N 2 is generated, so that the oxidation resistance of the coating is attenuated, and the attenuation is increased with the increase of the doping amount of N. In addition, too low or too high Al content may also reduce the continuity of the AlN barrier layer, resulting in some attenuation of the barrier effect.
Example 2
A preparation method of a high-temperature oxidation resistant coating on the surface of a zirconium alloy for a core comprises the following steps:
(1) Pretreatment of a matrix: the method comprises the steps of sequentially polishing the surface of a zirconium alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, sequentially polishing the polished zirconium alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the zirconium alloy substrate by using acetone and absolute ethyl alcohol for 10min, and drying the zirconium alloy substrate for later use;
(2) Sample loading and cleaning: filling a zirconium alloy matrix into a magnetron sputtering coating furnace chamber, when the vacuum degree in the furnace reaches 8×10 - 4 Pa, introducing Ar, adjusting the bias voltage to 420V, the power to 280W, and the treatment time to 15min;
(3) Depositing a Cr-N transition layer: taking a Cr target as a sputtering target, wherein the deposition temperature is 250 ℃, the power of the Cr target is 260W, the deposition pressure is 0.3Pa, the flow rate of N 2 is 10sccm, the bias voltage is 12V, the rotating speed of a rotating frame is 6rpm, the time is 8 hours, and the content of N in a Cr-N transition layer is controlled to be 17.8 at%;
(4) Depositing a FeCrAl coating: the high-purity Fe target and the CrAl alloy target are used as sputtering targets, the deposition temperature is 450 ℃, the power of the CrAl alloy target is 180W, fe, the power of the target is 280W, the deposition pressure is 0.3Pa, the bias voltage is 60V, the rotating speed of a rotating frame is 10rpm, the time is 2h, and the Al content in the FeCrAl coating is 21.94at.%.
Example 3
A preparation method of a high-temperature oxidation resistant coating on the surface of a zirconium alloy for a core comprises the following steps:
(1) Pretreatment of a matrix: the method comprises the steps of sequentially polishing the surface of a zirconium alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, sequentially polishing the polished zirconium alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the zirconium alloy substrate by using acetone and absolute ethyl alcohol for 10min, and drying the zirconium alloy substrate for later use;
(2) Sample loading and cleaning: filling a zirconium alloy matrix into a magnetron sputtering coating furnace chamber, when the vacuum degree in the furnace reaches 8×10 - 4 Pa, introducing Ar, adjusting the bias voltage to 480V, the power to 320W, and the treatment time period to 8min;
(3) Depositing a Cr-N transition layer: taking a Cr target as a sputtering target, wherein the deposition temperature is 350 ℃, the power of the Cr target is 240W, the deposition pressure is 0.5Pa, the flow rate of N 2 is 5sccm, the bias voltage is 8V, the rotating speed of a rotating frame is 10rpm, the time is 6 hours, and the content of N in a Cr-N transition layer is controlled to be 16.2 at%;
(4) Depositing a FeCrAl coating: the high-purity Fe target and the CrAl alloy target are used as sputtering targets, the deposition temperature is 550 ℃, the power of the CrAl alloy target is 120W, fe, the power of the target is 320W, the deposition pressure is 0.5Pa, the bias voltage is 80V, the rotating speed of a rotating frame is 6rpm, the time is 3h, and the Al content in the FeCrAl coating is 15.16at.%.
Claims (9)
1. A preparation method of a high-temperature oxidation resistant composite coating on the surface of a zirconium alloy for a core is characterized by comprising the following steps: the method comprises the steps of firstly preparing a Cr-N transition layer on the surface of a zirconium alloy matrix by magnetron sputtering, and then preparing a FeCrAl coating on the surface of the transition layer to form a C-N/FeCrAl composite coating.
2. The method for preparing the high-temperature oxidation resistant composite coating on the surface of the zirconium alloy for the nuclear use according to claim 1, which is characterized in that: the deposition temperature of the Cr-N transition layer is 250-350 ℃, the power of a Cr target is 240-260W, the deposition pressure is 0.3-0.5 Pa, the flow rate of N 2 is 2-10 sccm, the bias voltage is 8-12V, the rotating speed of a rotating frame is 6-10 rpm, the time is 6-8 hours, and the content of N in the Cr-N transition layer is controlled to be 15-18 at.%.
3. The method for preparing the high-temperature oxidation resistant composite coating on the surface of the zirconium alloy for the nuclear use according to claim 1 or 2, which is characterized in that: the deposition temperature of the FeCrAl coating is 450-550 ℃, the power of a CrAl alloy target is 120-180W, the power of a Fe target is 280-320W, the deposition pressure is 0.3-0.5 Pa, the bias voltage is 60-80V, the rotating speed of a rotating frame is 6-10 rpm, and the time is 2-3 hours.
4. A method for preparing a composite coating for nuclear zirconium alloy surface with high temperature oxidation resistance as claimed in any one of claims 1 to 3, wherein: the zirconium alloy substrate is subjected to pretreatment before the preparation of a coating, specifically, 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper are sequentially used for polishing the surface of the zirconium alloy, the polished zirconium alloy substrate is sequentially polished by diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, and then the zirconium alloy substrate is sequentially ultrasonically cleaned by acetone and absolute ethyl alcohol for 10min and then dried for standby.
5. The method for preparing the high-temperature oxidation resistant composite coating on the surface of the zirconium alloy for the nuclear use according to claim 4, which is characterized in that: the pretreated zirconium alloy substrate is required to be subjected to ion cleaning, specifically, the zirconium alloy substrate is put into a magnetron sputtering coating furnace, ar is introduced when the vacuum degree reaches 8 multiplied by 10 -4 Pa, the bias voltage is adjusted to be 420-480V, the power is 280-320W, and the treatment time is 8-15 min.
6. The preparation method of the high-temperature oxidation resistant coating on the surface of the zirconium alloy for the core is characterized by comprising the following steps of:
(1) Pretreatment of a matrix: the method comprises the steps of sequentially polishing the surface of a zirconium alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, sequentially polishing the polished zirconium alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the zirconium alloy substrate by using acetone and absolute ethyl alcohol for 10min, and drying the zirconium alloy substrate for later use;
(2) Sample loading and cleaning: filling a zirconium alloy substrate into a magnetron sputtering coating furnace chamber, when the vacuum degree in the furnace reaches 8 multiplied by 10 -4 Pa, introducing Ar, adjusting the bias voltage to be 420-480V, the power to be 280-320W, and the treatment time to be 8-15 min;
(3) Depositing a Cr-N transition layer: taking a Cr target as a sputtering target, wherein the deposition temperature is 250-350 ℃, the power of the Cr target is 240-260W, the deposition pressure is 0.3-0.5 Pa, the flow rate of N 2 is 2-10 sccm, the bias voltage is 8-12V, the rotating speed of a rotating frame is 6-10 rpm, the time is 6-8 hours, and the content of N in a Cr-N transition layer is controlled to be 15-18 at%;
(4) Depositing a FeCrAl coating: the high-purity Fe target and the CrAl alloy target are used as sputtering targets, the deposition temperature is 450-550 ℃, the power of the CrAl alloy target is 120-180W, the power of the Fe target is 280-320W, the deposition pressure is 0.3-0.5 Pa, the bias voltage is 60-80V, the rotating speed of a rotating frame is 6-10 rpm, and the time is 2-3 hours.
7. A high-temperature oxidation resistant composite coating on the surface of a zirconium alloy for a core is characterized in that: the composite coating comprises a Cr-N transition layer and a FeCrAl coating, wherein the content of N in the Cr-N transition layer is 15-18 at%, and the content of Al in the FeCrAl coating is 15-22 at%.
8. The composite coating for nuclear zirconium alloy surface high temperature oxidation resistance of claim 7, wherein: the Cr-N transition layer is prepared by magnetron sputtering, the deposition temperature is 250-350 ℃, the Cr target power is 240-260W, the deposition pressure is 0.3-0.5 Pa, the flow rate of N 2 is 2-10 sccm, the bias voltage is 8-12V, the rotating speed of the rotating frame is 6-10 rpm, and the time is 6-8 hours.
9. A composite coating for nuclear zirconium alloy surface resistant to high temperature oxidation as claimed in claim 7 or 8, wherein: the FeCrAl coating is prepared by taking an Fe target and a CrAl alloy target as sputtering targets through magnetron sputtering, wherein the specific deposition temperature is 450-550 ℃, the power of the CrAl alloy target is 120-180W, the power of the Fe target is 280-320W, the deposition pressure is 0.3-0.5 Pa, the bias voltage is 60-80V, the rotating speed of a rotating frame is 6-10 rpm, and the time is 2-3 h.
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