CN115305443B - Preparation method and application of zirconium-based amorphous multicomponent oxide coating - Google Patents
Preparation method and application of zirconium-based amorphous multicomponent oxide coating Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 170
- 239000011248 coating agent Substances 0.000 title claims abstract description 165
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 113
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 229910001093 Zr alloy Inorganic materials 0.000 claims abstract description 55
- 230000003647 oxidation Effects 0.000 claims abstract description 48
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 238000004544 sputter deposition Methods 0.000 claims abstract description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000005554 pickling Methods 0.000 claims abstract description 12
- 244000137852 Petrea volubilis Species 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005498 polishing Methods 0.000 claims abstract description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 11
- 238000005477 sputtering target Methods 0.000 claims abstract 9
- 238000005520 cutting process Methods 0.000 claims abstract 4
- 229910045601 alloy Inorganic materials 0.000 claims description 72
- 239000000956 alloy Substances 0.000 claims description 72
- 239000007789 gas Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002344 surface layer Substances 0.000 claims description 29
- 239000011159 matrix material Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 10
- 238000005253 cladding Methods 0.000 claims description 9
- 239000003758 nuclear fuel Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 36
- 239000010703 silicon Substances 0.000 abstract description 36
- 239000001301 oxygen Substances 0.000 abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 18
- 239000013077 target material Substances 0.000 abstract description 11
- 230000004888 barrier function Effects 0.000 abstract description 8
- 230000000903 blocking effect Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 description 29
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 21
- 238000005260 corrosion Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 16
- 229910018125 Al-Si Inorganic materials 0.000 description 12
- 229910018520 Al—Si Inorganic materials 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 239000011253 protective coating Substances 0.000 description 7
- 238000004098 selected area electron diffraction Methods 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910002064 alloy oxide Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 229910018191 Al—Fe—Si Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 229910020489 SiO3 Inorganic materials 0.000 description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000001106 transmission high energy electron diffraction data Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910009817 Ti3SiC2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 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
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008844 regulatory mechanism Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C23C14/08—Oxides
-
- 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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive 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
- C23C14/22—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
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21C—NUCLEAR REACTORS
- G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
- G21C3/02—Fuel elements
- G21C3/04—Constructional details
- G21C3/06—Casings; Jackets
- G21C3/07—Casings; Jackets characterised by their material, e.g. alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Abstract
The invention belongs to the field of surface processing, and relates to a preparation method and application of a zirconium-based amorphous multicomponent oxide coating. Firstly, pickling a silicon wafer, ultrasonically cleaning the silicon wafer, and drying the silicon wafer with nitrogen for later use; pickling a zirconium alloy substrate, polishing silicon carbide sand paper, ultrasonically cleaning, and drying with nitrogen for later use; and then cutting and combining the zirconium-based multi-element target material into a sputtering target material A, cutting and combining the Si-based multi-element target material into a sputtering target material B, connecting the sputtering target material A with a direct current power supply, connecting the sputtering target material B with a radio frequency power supply, simultaneously introducing Ar and O 2 into a cavity, and preparing the zirconium-based amorphous multi-element oxide coating by a reactive co-sputtering method based on magnetron sputtering. The zirconium-based amorphous multicomponent oxide coating prepared by the invention is compatible with a zirconium alloy interface, has good oxygen blocking effect, and the barrier layer prepared by surface oxygen reduction treatment stably exists in a high-temperature high-pressure hydrothermal environment (used in a normal working condition state) and has good high-temperature oxidation resistance (used in a high-temperature accident state).
Description
Technical Field
The invention belongs to the technical field of surface processing, and relates to a preparation method and application of a zirconium-based amorphous multicomponent oxide coating.
Background
The price of fossil energy in the world has risen rapidly in the next half of 2021, and a world-wide energy crisis mat has been involved, which has not been completely relieved until now. Currently, global energy patterns are in deep regulation, traditional energy is gradually replaced by novel clean low-carbon energy, and nuclear power is recognized as a large-scale power supply with reliability, sustainable environment and high cost efficiency. The nuclear energy plays a very important role in coping with climate change, promoting technological progress, realizing carbon neutralization target, improving national comprehensive strength, guaranteeing energy safety and the like. According to the statistical data of the international atomic energy related mechanism, 448 nuclear power units are shared worldwide by the year 2020, the total power generation amount of the global installed nuclear power units is about 2600 TWh, the nuclear power generating capacity accounts for about 10% of the total power generation amount, and the worldwide low-carbon power supply is about 33% from nuclear power generation. The great development of nuclear power technology is now one of important energy strategy plans in countries around the world.
Cladding is an important barrier to nuclear reactor safety and is used to encapsulate and seal the outer shell of nuclear fuel and other critical materials. The zirconium alloy has the advantages of small thermal neutron absorption section, high thermal conductivity, good mechanical property, good processability, good compatibility with uranium dioxide and the like, and is an cladding material adopted by the major nuclear China at present. Currently, cladding materials for nuclear power are subjected to extremely severe operating conditions: the inside is affected by fission products, the outside is affected by coolant corrosion, high temperature and high pressure, and also by strong neutron radiation and coolant corrosion, vibration and internal stress. For nuclear fuel cladding, it is critical to slow down the oxidation kinetics, thereby reducing heat generation and hydrogen release. The oxygen or hydrogen solid solution weakens the mechanical property of the zirconium alloy and is easy to generate corrosion cracking. Under normal working conditions, zirconia formed on the surface of the Zr alloy in situ can be used as a passivation film, so that corrosion resistance is improved to a certain extent. However, significant volume expansion occurs due to oxide phase changes, and the resulting void cracks can act as short diffusion paths for the corrosive medium. The development of the oxide coating with structural stability and protective performance has application prospect. The oxide coating has higher elastic modulus and stronger binding energy, the interatomic force is mainly ionic bond and covalent bond, the oxide coating has excellent chemical stability and high-temperature corrosion resistance, the thinner oxide coating has limited influence on the performance of the zirconium alloy, and the oxide coating can replace zirconium oxide on the surface and is used as an ideal zirconium alloy coating material. The main factors determining the diffusion of elements in the coating are the compactness and stability of the tissue structure. Studies have shown that the amorphous oxide layer is a favourable barrier against oxygen ion movement due to its dense and borderless character, oxygen element diffusion at the grain boundaries being more pronounced than bulk diffusion. In addition, the amorphous oxide film can easily eliminate lattice mismatch of interface atomic bonds, relieve strain between interfaces and lead to low interface gibbs energy by using flexibility of atomic bonds, and provide protection for metal substrates. Amorphous oxide coatings have potential for application. It was found that when the volume content of doped SiO 2 in the ZrO 2 film exceeds 30at.%, the formed SiO 2-ZrO2 film is an amorphous film. Meanwhile, the addition of Si element can improve the oxygen barrier capability of the oxide layer. Therefore, the Si element has a great application prospect in the amorphous coating field in the nuclear power field.
However, the ideal coating not only needs to meet the high-temperature oxidation resistance, but also meets the related requirements under normal working conditions (high-temperature high-pressure water). Studies have reported that silica and alumina tend to dissolve rapidly to H 2SiO3 and AlO (OH) in a high temperature environment (nucleic. MAX phase coatings such as Ti 2AlC,Ti3SiC2, although stable at high temperatures, have limited barrier properties under normal operating conditions due to the tendency of the surface to form aluminum oxide or silicon oxide (Joseph W, MAX PHASE CERAMICS for nuclear applications, the University of Manchester, 2018). Therefore, how to coordinate the differential requirements of stability and oxygen barrier properties of working conditions on the material element chemistry is a key scientific problem in developing zirconium-based coatings.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method and application of a zirconium-based amorphous multicomponent oxide coating, which are applied to a zirconium alloy protective coating to relieve water side corrosion or oxidation in a high-temperature air environment.
The invention also aims to provide a preparation method of the zirconium alloy protective coating, so as to reduce the risk of damage to the zirconium alloy cladding under accident conditions.
The invention also aims to provide a preparation method of the zirconium alloy protective coating, so as to improve the corrosion resistance and the oxidation resistance of the zirconium alloy cladding, and the protective coating shows ultra-slow oxidation kinetics.
The invention also aims to provide a preparation method of the zirconium alloy protective coating with a denser coating.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
A preparation method of a zirconium-based amorphous multi-component oxide coating adopts a metal combined target material, and forms the zirconium-based amorphous multi-component oxide coating on a silicon wafer and a zirconium alloy matrix by utilizing a reactive co-sputtering method.
Step 1: cleaning the silicon wafer and the zirconium alloy by using an acid pickling solution (a mixed solution of HNO 3 with the volume concentration of 10%, HF with the volume concentration of 10% and H 2O2 with the volume concentration of 10%);
step 2: polishing the zirconium alloy matrix by using silicon carbide sand paper;
Step 3: sequentially placing a silicon wafer and a zirconium alloy matrix in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20 min respectively;
step 4: taking out the silicon wafer and the zirconium alloy after ultrasonic cleaning, and blow-drying the silicon wafer and the zirconium alloy for later use by a nitrogen gun;
Step 5: attaching the pretreated silicon chip and zirconium alloy substrate to a substrate, placing the substrate on a rotary heating table in a magnetron sputtering chamber, and adjusting the target base distance to 15cm; the zirconium-based multi-element target is arranged on a target head connected with a direct current power supply, and the Si-based multi-element target is arranged on a target head connected with a radio frequency power supply;
Step 6: pumping the vacuum degree of the chamber to be lower than 6 multiplied by 10 -4 Pa by utilizing a vacuum system (a mechanical pump and a molecular pump), opening a process gas control valve through an operation panel to introduce Ar and O 2 into the chamber after the vacuum degree in the chamber reaches the required vacuum degree (the pressure in the chamber is observed to be increased and the Ar and O 2 are ensured to be normally introduced), adjusting a gas flow meter to set the gas flow of Ar to be 20sccm, setting the gas flow of O 2 to be 0.6-1.2sccm, and adjusting the pressure in the chamber to be 3-5Pa (+ -0.02 Pa) through an insert plate valve between the adjustment chamber and the molecular pump after the gas flow is set;
Step 7: the method comprises the steps that preheating is required for 3-5min before the Radio Frequency (RF) power supply is formally started, the power of the radio frequency power supply is adjusted to start after the preheating is finished, and the power is adjusted to the power required by sputtering after the starting of the RF power supply is finished;
Step 8: opening a DC power supply to start, and after the DC power supply starts, adjusting the voltage and the current of the DC power supply to enable the power of the DC power supply to reach the required power;
Step 9: after the RF power and the DC power are regulated, regulating a molecular pump gate valve again, emphasizing the cavity pressure to be 1.5Pa of working air pressure during normal sputtering, sputtering two targets for 15min, and removing the oxide on the surfaces of the targets;
Step 10: after the sputtering is finished, the rotating function of the rotating heating table is turned on to enable the rotating heating table to rotate at a certain rotating speed, the substrate baffle is turned on manually, and the zirconium-based amorphous multicomponent oxide coating is prepared by reactive co-sputtering.
Further, in step 5, during target design and installation, the zirconium-based multi-element target comprises at least two of Zr, nb, cr, mo, and the Si-based multi-element target comprises at least one element of Al, si, fe, ta;
further, in step7, after the RF power supply is started, the power is adjusted to 80-120W.
Further, in step 8, after the DC power supply is started, the power is adjusted to 3 to 60W.
Further, in step 10, when a fully oxidized multi-component oxide coating is deposited by magnetron sputtering, the flow rate of O 2 is set to 1.2sccm by adjusting the flow rate of gas; when the magnetron sputtering is used for depositing the multicomponent oxide coating in the oxidation state from the surface to the inner, the gas flow rate of O 2 is set to be 0.6-0.8sccm by adjusting a gas flow meter.
Further, in step 2, the zirconium alloy substrate is a Zr-4 alloy plate substrate.
Furthermore, the surface layer of the prepared zirconium-based amorphous multicomponent oxide coating is in a complete oxidation state or in a gradient oxidation state from the surface to the inside.
Further, the oxygen content in the surface layer of the surface-to-inside gradient oxidation state coating is reduced in a gradient manner, and the oxygen content of the outer layer is lower than that of the inner layer.
Furthermore, in the zirconium-based amorphous multicomponent oxide coating, various elements are uniformly distributed, no crystalline phase appears, the coating structure is stable, and the thickness of the film is 0.2-3 mu m.
Further, when the surface layer is a zirconium-based amorphous multicomponent oxide coating in a complete oxidation state or in a gradient oxidation state from the outside to the inside, both coatings have high-temperature oxidation resistance; when the surface layer is a completely oxidized zirconium-based amorphous multicomponent oxide coating, the coating has stability under high-temperature and high-pressure water environment (320 ℃ and 16 MPa); when the surface layer is a zirconium-based amorphous multi-component oxide coating with the oxidation state of gradient from the outside to the inside, the stability of the zirconium-based amorphous multi-component oxide coating is higher than that of the zirconium-based amorphous multi-component oxide coating with the complete oxidation state of the surface layer under the high-temperature and high-pressure water environment.
Furthermore, the prepared zirconium-based amorphous multicomponent oxide coating can be applied to the field of antioxidation, and particularly can be applied to the surface protection of zirconium alloy of nuclear fuel cladding materials.
The invention has the following beneficial effects:
1. The invention adopts a reactive co-sputtering method through the design of a target material, utilizes a high vacuum single-chamber three-target magnetron sputtering film deposition system to carry out multi-component modification based on zirconium silicon oxide, regulates and controls an atomic structure, and forms a zirconium-based amorphous multi-component oxide coating. The zirconium-based amorphous multi-component oxide coating can be used for surface protection of nuclear fuel cladding materials or other antioxidation fields, and the zirconium-based amorphous multi-component coating structure is designed, so that the disadvantages of a single element coating are avoided, the compatibility with Zr-4 alloy is good when the zirconium-based amorphous multi-component oxide coating is oxidized at high temperature, and the shedding phenomenon of the coating does not occur.
2. The multi-component strategy can effectively block the formation of a continuous Si-O network, and avoid H 2SiO3 formed by the reaction of a Si-O bonding system and water; the intermolecular channels are reduced by a bond energy regulation mechanism, so that corrosive media can be further blocked. The high mixing entropy in the zirconium-based amorphous multi-component oxide coating enhances the intersolubility among elements, inhibits the formation of compounds and can play a role in stabilizing an amorphous system. At the same time, amorphous oxides exist stably due to high interfacial energy and kinetic barrier (slow kinetics) of atomic diffusion during crystallization.
3. When the performance evaluation of the high-temperature high-pressure water environment stability of the zirconium-based amorphous multi-component oxide coating is carried out, the interface between the zirconium-based amorphous multi-component oxide coating and the Zr-4 alloy is stable, and no severe element diffusion phenomenon occurs at the interface in the process of high temperature. After hydrothermal corrosion in LiOH solution (320 ℃,16MPa,0.01 mol/L) with high temperature and high pressure for a certain time, the stable existence of the coating structure and components can be maintained. When the surface layer is a completely oxidized zirconium-based amorphous multicomponent oxide coating, the coating has stability under high-temperature and high-pressure water environment; when the surface layer is a zirconium-based amorphous multicomponent oxide coating with the oxidation state gradient from the outside to the inside, the stability of the zirconium-based amorphous multicomponent oxide coating is further improved under the high-temperature and high-pressure water environment.
4. The zirconium-based amorphous multicomponent oxide coating constructed by the invention can obtain a coating material which accords with the endowment characteristics of zirconium alloy, has compatible interface and good oxygen inhibition effect according to the regulation and control of components and bonding states, and is beneficial to promoting the safe, long-life and sustainable development of nuclear power materials.
5. The zirconium-based amorphous multicomponent oxide coating prepared by the method can be used as a zirconium alloy protective coating, and can be used as a diffusion barrier layer of a metal coating to inhibit the phenomenon of violent element diffusion at the interface position when the metal coating is directly used as the zirconium alloy protective coating due to the strong high-temperature interface stability.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the morphology of a TEM section of a ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 1 of the present invention in the as-is state and after annealing at 700℃for 4 hours in an air environment; (a), (b) and (c) are respectively prepared cross-sectional morphology, a high-resolution image and a selected-area electron diffraction image; (d) And (e) and (f) are respectively the shape of the annealed section, the selected area electron diffraction pattern and the high resolution pattern.
FIG. 2 shows the TEM cross-sectional morphology (a) and the selected area electron diffraction pattern (b) of the ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 1 of the present invention after annealing at 900℃for 4 hours in an air environment.
FIG. 3 is a TEM sectional morphology and a high resolution diagram of ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 1 of the present invention after annealing at 800 ℃, 900 ℃, 1000 ℃ for 2 hours, respectively; (a), (b) and (c) correspond to the sectional morphology of the TEM after annealing at 800 ℃, 900 ℃ and 1000 ℃ for 2 hours, respectively, and (a 1）、（b1）、（c1) corresponds to the high resolution graph after annealing at 800 ℃, 900 ℃ and 1000 ℃ for 2 hours, respectively.
FIG. 4 shows the cross-sectional EDS-scanning element distribution of ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 1 of the present invention after annealing at 1000℃for 2 hours.
FIG. 5 is a SAED pattern of ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 1 of the present invention after annealing for 2 hours at 800℃ (a), 900℃ (b), 1000℃ (c), respectively.
FIG. 6 is a view showing the surface and cross-sectional morphology of a light microscope of the as-prepared state of the ZrNbCrAlSiO Zr-4 alloy protected by the zirconium-based amorphous multicomponent oxide coating prepared in example 3 of the present invention and after 2 hours of oxidation at 1000 ℃.
FIG. 7 is a SEM cross-sectional morphology of ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating-protected Zr-4 alloy prepared in example 3 of the present invention, etched for 5h in LiOH solution (320 ℃,16MPa,0.01 mol/L) at high temperature and high pressure: and (a) and (b) preparing sectional morphology, and (c) and (d) corroding the sectional morphology after 5 h.
FIG. 8 is a view showing the surface and cross-sectional morphology of a ZrNbCrAlSiO surface layer zirconium-base amorphous multicomponent oxide coating-protected Zr-4 alloy and bare Zr-4 alloy prepared in example 4 of the present invention after hydrothermal corrosion in 0.01mol/L LiOH solution (320 ℃,16 MPa,0.01 mol/L) for 20 h: (a) and (b) surface and cross-sectional morphology patterns of Zr-4 alloy after 20h of hydrothermal corrosion without coating protection, and (c) and (d) surface and cross-sectional morphology patterns of Zr-4 alloy after 20h of hydrothermal corrosion with coating protection.
FIG. 9 is an SEM cross-sectional morphology and element distribution diagram of ZrNbCrAlSiO surface layer zirconium-based amorphous multicomponent oxide coating prepared in example 4 of the present invention before and after 20h of corrosion in LiOH solution (320 ℃,16MPa,0.01 mol/L) at high temperature and high pressure: (a) as-prepared morphology; (b) etching for 20h to obtain the appearance.
FIG. 10 is a morphology diagram of a ZrNbCrAlSiO surface layer zirconium-based amorphous multicomponent oxide coating protective Zr-4 alloy and a bare Zr-4 alloy prepared in example 4 of the present invention oxidized for 2 hours in a 1200 ℃ water vapor environment: (a) a cross-sectional profile of Zr-4 alloy without coating protection for 2h oxidation in 1200 ℃ water vapor environment, (b) a cross-sectional profile of Zr-4 alloy with coating protection for 2h oxidation in 1200 ℃ water vapor environment, and (c) a plan profile of interface position.
FIG. 11 is a graph showing the variation of the thickness of oxide films of ZrNbCrAlSiO surface layer zirconium-base amorphous multicomponent oxide coating layer under the condition of 1200 ℃ water vapor, wherein the zirconium-4 alloy and the bare zirconium-4 alloy are prepared in example 4 according to the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment is a preparation method of ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating, comprising the following steps:
Firstly, preparing monocrystalline silicon pieces and Zr-4 alloy plates, wherein the size of a monocrystalline silicon piece matrix is 40mm multiplied by 0.5mm, and the size of the Zr-4 alloy plate matrix is 30mm multiplied by 2mm. Cleaning the monocrystalline silicon wafer and the Zr-4 alloy plate substrate by using pickling solution (mixed solution of HNO 3 with volume concentration of 10%, HF with volume concentration of 10% and H 2O2 with volume concentration of 10%), polishing the zirconium alloy substrate by using 600-mesh silicon carbide sand paper, sequentially placing the silicon wafer and the polished Zr-4 alloy substrate in acetone, absolute ethyl alcohol and deionized water for respectively carrying out ultrasonic cleaning for 20min, taking out the silicon wafer and the zirconium alloy after ultrasonic cleaning, drying by using a nitrogen gun for standby, attaching the pretreated silicon wafer and the zirconium alloy substrate on a substrate, placing the substrate on a rotary heating table in a magnetron sputtering chamber, and adjusting the target base distance to 15cm. A zirconium-based multi-element (Zr-Mo-Cr) target mounted on a target head connected to a direct current power supply (DC), a Si-based multi-element (Al-Si) target mounted on a target head connected to a radio frequency power supply (RF); and (3) pumping the vacuum degree of the chamber to be less than 6 multiplied by 10 -4 Pa by using a vacuum system (a mechanical pump and a molecular pump), introducing Ar and O 2 into the chamber after the vacuum degree in the chamber reaches the requirement, adjusting a gas flow meter to set the gas flow of Ar to 20sccm, setting the gas flow of O 2 to 1.2sccm, and adjusting the pressure in the chamber to 3Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump after the gas flow is set. And (3) opening an RF power supply to preheat, opening a target head shielding plate of the Al-Si combined target through a control panel after the RF power supply is preheated, opening the RF power supply, adjusting power to start, setting the power of the RF power supply to be 100W after the RF power supply is started, and adjusting the working air pressure in the cavity to be 1.5Pa through adjusting a molecular pump gate valve. Opening a target head shielding plate of the Zr-Mo-Cr combined target material through a control panel, opening a DC power supply, adjusting the voltage and the current of the DC power supply to start, and adjusting the current to 0.2A after the start of the DC power supply is completed, wherein the voltage at the moment is 120V, and the power of the DC power supply is 24W; and pre-sputtering the two targets for 15min under the power to remove the oxide on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, the sputtering is carried out for 10 hours, and the deposition thickness of the ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating is about 300nm.
Example 2
The embodiment is a preparation method of ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating, comprising the following steps:
Firstly, preparing monocrystalline silicon pieces and Zr-4 alloy plates, wherein the size of a monocrystalline silicon piece matrix is 40mm multiplied by 0.5mm, and the size of the Zr-4 alloy plate matrix is 30mm multiplied by 2mm. Cleaning the monocrystalline silicon wafer and the Zr-4 alloy plate substrate by using pickling solution (mixed solution of HNO 3 with volume concentration of 10%, HF with volume concentration of 10% and H 2O2 with volume concentration of 10%), polishing the zirconium alloy substrate by using 600-mesh silicon carbide sand paper, sequentially placing the silicon wafer and the polished Zr-4 alloy substrate in acetone, absolute ethyl alcohol and deionized water for respectively carrying out ultrasonic cleaning for 20min, taking out the silicon wafer and the zirconium alloy after ultrasonic cleaning, drying by using a nitrogen gun for standby, attaching the pretreated silicon wafer and the zirconium alloy substrate on a substrate, placing the substrate on a rotary heating table in a magnetron sputtering chamber, and adjusting the target base distance to 15cm. A zirconium-based multi-element (Zr-Nb-Cr) target mounted on a target head connected to a direct current power supply (DC), a Si-based multi-element (Al-Si) target mounted on a target head connected to a radio frequency power supply (RF); and (3) pumping the vacuum degree of the chamber to be less than 6 multiplied by 10 -4 Pa by using a vacuum system (a mechanical pump and a molecular pump), introducing Ar and O 2 into the chamber after the vacuum degree in the chamber reaches the requirement, adjusting a gas flow meter to set the gas flow of Ar to 20sccm, setting the gas flow of O 2 to 1.2sccm, and adjusting the pressure in the chamber to 5Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump after the gas flow is set. And (3) opening an RF power supply to preheat, opening a target head shielding plate of the Al-Si combined target through a control panel after the RF power supply is preheated, opening the RF power supply, adjusting power to start, setting the power of the RF power supply to 80W after the RF power supply is started, and adjusting the working air pressure in the cavity to 1.5Pa through adjusting a molecular pump gate valve. Opening a target head shielding plate of the Zr-Nb-Cr combined target through a control panel, opening a DC power supply, adjusting the voltage and the current of the DC power supply to start, and adjusting the current to 0.3A after the DC power supply starts, wherein the voltage at the moment is 140V, and the power of the DC power supply is 42W; and pre-sputtering the two targets for 15min under the power to remove the oxide on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, the ZrNbCrAlSiOzirconium-based amorphous multicomponent oxide coating is sputtered for 10 hours, and the deposition thickness of the ZrNbCrAlSiOzirconium-based amorphous multicomponent oxide coating is about 200nm.
Example 3
The embodiment is a preparation method of ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating, comprising the following steps:
Firstly, preparing monocrystalline silicon pieces and Zr-4 alloy plates, wherein the size of a monocrystalline silicon piece matrix is 40mm multiplied by 0.5mm, and the size of the Zr-4 alloy plate matrix is 30mm multiplied by 2mm. Cleaning the monocrystalline silicon wafer and the Zr-4 alloy plate substrate by using pickling solution (mixed solution of HNO 3 with volume concentration of 10%, HF with volume concentration of 10% and H 2O2 with volume concentration of 10%), polishing the zirconium alloy substrate by using 600-mesh silicon carbide sand paper, sequentially placing the silicon wafer and the polished Zr-4 alloy substrate in acetone, absolute ethyl alcohol and deionized water for respectively carrying out ultrasonic cleaning for 20min, taking out the silicon wafer and the zirconium alloy after ultrasonic cleaning, drying by using a nitrogen gun for standby, attaching the pretreated silicon wafer and the zirconium alloy substrate on a substrate, placing the substrate on a rotary heating table in a magnetron sputtering chamber, and adjusting the target base distance to 15cm. A zirconium-based multi-element (Zr-Nb-Cr) target mounted on a target head connected to a direct current power supply (DC), a Si-based multi-element (Al-Si) target mounted on a target head connected to a radio frequency power supply (RF); and (3) pumping the vacuum degree of the chamber to be less than 6 multiplied by 10 -4 Pa by using a vacuum system (a mechanical pump and a molecular pump), introducing Ar and O 2 into the chamber after the vacuum degree in the chamber reaches the requirement, adjusting a gas flow meter to set the gas flow of Ar to 20sccm, setting the gas flow of O 2 to 1.2sccm, and adjusting the pressure in the chamber to 5Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump after the gas flow is set. And (3) opening an RF power supply to preheat, opening a target head shielding plate of the Al-Si combined target through a control panel after the RF power supply is preheated, opening the RF power supply, adjusting power to start, setting the power of the RF power supply to 120W after the RF power supply starts, and adjusting the working air pressure in the cavity to 1.5Pa through adjusting a molecular pump gate valve. Opening a target head shielding plate of the Zr-Nb-Cr combined target through a control panel, opening a DC power supply, adjusting the voltage and the current of the DC power supply to start, and adjusting the current to 0.2A after the start of the DC power supply is completed, wherein the voltage at the moment is 120V, and the power of the DC power supply is 24W; and pre-sputtering the two targets for 15min under the power to remove the oxide on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, the co-sputtering is carried out for 12 hours, and the deposition thickness of the ZrNbCrAlSiOzirconium-based amorphous multicomponent oxide coating is about 3 mu m.
Example 4
The embodiment is a preparation method of ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating with surface layer in a gradient oxidation state from the outside to the inside, comprising the following steps:
Firstly, preparing monocrystalline silicon pieces and Zr-4 alloy plates, wherein the size of a monocrystalline silicon piece matrix is 40mm multiplied by 0.5mm, and the size of the Zr-4 alloy plate matrix is 30mm multiplied by 2mm. Cleaning the monocrystalline silicon wafer and the Zr-4 alloy plate substrate by using pickling solution (mixed solution of HNO 3 with volume concentration of 10%, HF with volume concentration of 10% and H 2O2 with volume concentration of 10%), polishing the zirconium alloy substrate by using 600-mesh silicon carbide sand paper, sequentially placing the silicon wafer and the polished Zr-4 alloy substrate in acetone, absolute ethyl alcohol and deionized water for respectively carrying out ultrasonic cleaning for 20min, taking out the silicon wafer and the zirconium alloy after ultrasonic cleaning, drying by using a nitrogen gun for standby, attaching the pretreated silicon wafer and the zirconium alloy substrate on a substrate, placing the substrate on a rotary heating table in a magnetron sputtering chamber, and adjusting the target base distance to 15cm. A zirconium-based multi-element (Zr-Nb-Cr) target mounted on a target head connected to a direct current power supply (DC), a Si-based multi-element (Al-Si) target mounted on a target head connected to a radio frequency power supply (RF); and (3) pumping the vacuum degree of the chamber to be less than 6 multiplied by 10 -4 Pa by using a vacuum system (a mechanical pump and a molecular pump), introducing Ar and O 2 into the chamber after the vacuum degree in the chamber reaches the requirement, adjusting a gas flow meter to set the gas flow of Ar to 20sccm, setting the gas flow of O 2 to 1.2sccm, and adjusting the pressure in the chamber to 4Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump after the gas flow is set. And (3) opening an RF power supply to preheat, opening a target head shielding plate of the Al-Si combined target through a control panel after the RF power supply is preheated, opening the RF power supply, adjusting power to start, setting the power of the RF power supply to 120W after the RF power supply starts, and adjusting the working air pressure in the cavity to 1.5Pa through adjusting a molecular pump gate valve. ; opening a target head shielding plate of the Zr-Nb-Cr combined target through a control panel, opening a DC power supply, adjusting the voltage and the current of the DC power supply to start, and adjusting the current to 0.2A after the start of the DC power supply is completed, wherein the voltage at the moment is 120V, and the power of the DC power supply is 24W; and pre-sputtering the two targets for 15min under the power to remove the oxide on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, and the coating layers with two different thicknesses are prepared by co-sputtering for different times.
In the sputtering process of the first stage, under the power of the power supply and the process conditions, preparing a ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating in a complete oxidation state, co-sputtering for 10 hours, and depositing the coating with the thickness of about 2.5 mu m; in the sputtering process of the second stage, the gas flow of O 2 is regulated to be 0.8sccm, the power supply power and other process conditions are kept consistent with those of the first stage, the ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating with the surface layer in an incomplete oxidation state is prepared, and the total sputtering is carried out for 30min, wherein the sputtering thickness of the stage is 1 mu m.
Example 5
The embodiment is a preparation method of ZrFeCrAlSiO zirconium-based amorphous multicomponent oxide coating, comprising the following steps:
Firstly, preparing monocrystalline silicon pieces and Zr-4 alloy plates, wherein the size of a monocrystalline silicon piece matrix is 40mm multiplied by 0.5mm, and the size of the Zr-4 alloy plate matrix is 30mm multiplied by 2mm. Cleaning the monocrystalline silicon wafer and the Zr-4 alloy plate substrate by using pickling solution (mixed solution of HNO 3 with volume concentration of 10%, HF with volume concentration of 10% and H 2O2 with volume concentration of 10%), polishing the zirconium alloy substrate by using 600-mesh silicon carbide sand paper, sequentially placing the silicon wafer and the polished Zr-4 alloy substrate in acetone, absolute ethyl alcohol and deionized water for respectively carrying out ultrasonic cleaning for 20min, taking out the silicon wafer and the zirconium alloy after ultrasonic cleaning, drying by using a nitrogen gun for standby, attaching the pretreated silicon wafer and the zirconium alloy substrate on a substrate, placing the substrate on a rotary heating table in a magnetron sputtering chamber, and adjusting the target base distance to 15cm. A zirconium-based multielement (Zr-Cr) target mounted on a target connected to a direct current power supply (DC), a Si-based multielement (Al-Fe-Si) target mounted on a target connected to a radio frequency power supply (RF); and (3) pumping the vacuum degree of the chamber to be less than 6 multiplied by 10 -4 Pa by using a vacuum system (a mechanical pump and a molecular pump), introducing Ar and O 2 into the chamber after the vacuum degree in the chamber reaches the requirement, adjusting a gas flow meter to set the gas flow of Ar to 20sccm, setting the gas flow of O 2 to 1.2sccm, and adjusting the pressure in the chamber to 5Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump after the gas flow is set. And (3) opening an RF power supply to preheat, opening a target head shielding plate of the Al-Fe-Si combined target through a control panel after the RF power supply is preheated, opening the RF power supply, adjusting power to start, setting the power of the RF power supply to be 100W after the RF power supply starts, and adjusting the working air pressure in the cavity to be 1.5Pa through adjusting a molecular pump gate valve. Opening a target head shielding plate of the Zr-Cr combined target through a control panel, opening a DC power supply, adjusting the voltage and the current of the DC power supply to start, and adjusting the current to 0.24A after the DC power supply starts, wherein the voltage at the moment is 130V, and the power of the DC power supply is 31.2W; and pre-sputtering the two targets for 15min under the power to remove the oxide on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, the ZrFeCrAlSiO zirconium-based amorphous multicomponent oxide coating is co-sputtered for 10 hours, and the deposition thickness of the ZrFeCrAlSiO zirconium-based amorphous multicomponent oxide coating is about 2.5 mu m.
Example 6
The preparation method of ZrTaCrAlSiO multi-component amorphous oxide coating comprises the following steps:
Firstly, preparing monocrystalline silicon pieces and Zr-4 alloy plates, wherein the size of a monocrystalline silicon piece matrix is 40mm multiplied by 0.5mm, and the size of the Zr-4 alloy plate matrix is 30mm multiplied by 2mm. Cleaning the monocrystalline silicon wafer and the Zr-4 alloy plate substrate by using pickling solution (mixed solution of HNO 3 with volume concentration of 10%, HF with volume concentration of 10% and H 2O2 with volume concentration of 10%), polishing the zirconium alloy substrate by using 600-mesh silicon carbide sand paper, sequentially placing the silicon wafer and the polished Zr-4 alloy substrate in acetone, absolute ethyl alcohol and deionized water for respectively carrying out ultrasonic cleaning for 20min, taking out the silicon wafer and the zirconium alloy after ultrasonic cleaning, drying by using a nitrogen gun for standby, attaching the pretreated silicon wafer and the zirconium alloy substrate on a substrate, placing the substrate on a rotary heating table in a magnetron sputtering chamber, and adjusting the target base distance to 15cm. A zirconium-based multi-element (Zr-Cr) target is mounted on a target head connected with a direct current power supply (DC), and a Si-based multi-element (Al-Ta-Si) target is mounted on a target head connected with a radio frequency power supply (RF); and (3) pumping the vacuum degree of the chamber to be less than 6 multiplied by 10 -4 Pa by using a vacuum system (a mechanical pump and a molecular pump), introducing Ar and O 2 into the chamber after the vacuum degree in the chamber reaches the requirement, adjusting a gas flow meter to set the gas flow of Ar to 20sccm, setting the gas flow of O 2 to 1.2sccm, and adjusting the pressure in the chamber to 5Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump after the gas flow is set. And (3) opening an RF power supply to preheat, opening a target head shielding plate of the Al-Ta-Si combined target through a control panel after the RF power supply is preheated, opening the RF power supply, adjusting power to start, setting the power of the RF power supply to 90W after the RF power supply starts, and adjusting the working air pressure in the cavity to 1.5Pa through adjusting a molecular pump gate valve. Opening a target head shielding plate of the Zr-Cr combined target through a control panel, opening a DC power supply, adjusting the voltage and the current of the DC power supply to start, and adjusting the current to 0.18A after the DC power supply starts, wherein the voltage at the moment is 110V, and the power of the DC power supply is 19.8W; and pre-sputtering the two targets for 15min under the power to remove the oxide on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, the ZrTaCrAlSiOzirconium-based amorphous multicomponent oxide coating is co-sputtered for 10 hours, and the deposition thickness of the ZrTaCrAlSiOzirconium-based amorphous multicomponent oxide coating is about 2 mu m.
Example 7
The embodiment is a preparation method of ZrNbMoAlSiO zirconium-based amorphous multicomponent oxide coating with surface layer in a gradient oxidation state from the outside to the inside, comprising the following steps:
Firstly, preparing monocrystalline silicon pieces and Zr-4 alloy plates, wherein the size of a monocrystalline silicon piece matrix is 40mm multiplied by 0.5mm, and the size of the Zr-4 alloy plate matrix is 30mm multiplied by 2mm. Cleaning the monocrystalline silicon wafer and the Zr-4 alloy plate substrate by using pickling solution (mixed solution of HNO 3 with volume concentration of 10%, HF with volume concentration of 10% and H 2O2 with volume concentration of 10%), polishing the zirconium alloy substrate by using 600-mesh silicon carbide sand paper, sequentially placing the silicon wafer and the polished Zr-4 alloy substrate in acetone, absolute ethyl alcohol and deionized water for respectively carrying out ultrasonic cleaning for 20min, taking out the silicon wafer and the zirconium alloy after ultrasonic cleaning, drying by using a nitrogen gun for standby, attaching the pretreated silicon wafer and the zirconium alloy substrate on a substrate, placing the substrate on a rotary heating table in a magnetron sputtering chamber, and adjusting the target base distance to 15cm. A zirconium-based multi-element (Zr-Nb-Mo) target mounted on a target head connected to a direct current power supply (DC), a Si-based multi-element (Al-Si) target mounted on a target head connected to a radio frequency power supply (RF); and (3) pumping the vacuum degree of the chamber to be less than 6 multiplied by 10 -4 Pa by using a vacuum system (a mechanical pump and a molecular pump), introducing Ar and O 2 into the chamber after the vacuum degree in the chamber reaches the requirement, adjusting a gas flow meter to set the gas flow of Ar to 20sccm, setting the gas flow of O 2 to 1.2sccm, and adjusting the pressure in the chamber to 4Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump after the gas flow is set. And (3) opening an RF power supply to preheat, opening a target head shielding plate of the Al-Si combined target through a control panel after the RF power supply is preheated, opening the RF power supply, adjusting power to start, setting the power of the RF power supply to be 110W after the RF power supply is started, and adjusting the working air pressure in the cavity to be 1.5Pa through adjusting a molecular pump gate valve. Opening a target head shielding plate of the Zr-Nb-Mo combined target material through a control panel, opening a DC power supply, adjusting the voltage and the current of the DC power supply to start, and adjusting the current to 0.2A after the start of the DC power supply is completed, wherein the voltage at the moment is 120V, and the power of the DC power supply is 60W; and pre-sputtering the two targets for 15min under the power to remove the oxide on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, and the coating layers with two different thicknesses are prepared by co-sputtering for different times.
In the sputtering process of the first stage, under the power of the power supply and the process conditions, preparing a ZrNbMoAlSiO zirconium-based amorphous multicomponent oxide coating in a complete oxidation state, co-sputtering for 10 hours, and depositing the coating with the thickness of about 2.5 mu m; in the sputtering process of the second stage, the gas flow of O 2 is regulated to be 0.6sccm, the power supply power and other process conditions are kept consistent with those of the first stage, the ZrNbMoAlSiO zirconium-based amorphous multicomponent oxide coating with the surface layer in an incomplete oxidation state is prepared, and the total sputtering is carried out for 30min, wherein the sputtering thickness of the stage is 1 mu m.
Example 8
The embodiment is a preparation method of ZrNbCrMoAlSiO zirconium-based amorphous multicomponent oxide coating, comprising the following steps:
Firstly, preparing monocrystalline silicon pieces and Zr-4 alloy plates, wherein the size of a monocrystalline silicon piece matrix is 40mm multiplied by 0.5mm, and the size of the Zr-4 alloy plate matrix is 30mm multiplied by 2mm. Cleaning the monocrystalline silicon wafer and the Zr-4 alloy plate substrate by using pickling solution (mixed solution of HNO 3 with volume concentration of 10%, HF with volume concentration of 10% and H 2O2 with volume concentration of 10%), polishing the zirconium alloy substrate by using 600-mesh silicon carbide sand paper, sequentially placing the silicon wafer and the polished Zr-4 alloy substrate in acetone, absolute ethyl alcohol and deionized water for respectively carrying out ultrasonic cleaning for 20min, taking out the silicon wafer and the zirconium alloy after ultrasonic cleaning, drying by using a nitrogen gun for standby, attaching the pretreated silicon wafer and the zirconium alloy substrate on a substrate, placing the substrate on a rotary heating table in a magnetron sputtering chamber, and adjusting the target base distance to 15cm. A zirconium-based multi-element (Zr-Nb-Cr-Mo) target mounted on a target head connected to a direct current power supply (DC), a Si-based multi-element (Al-Si) target mounted on a target head connected to a radio frequency power supply (RF); and (3) pumping the vacuum degree of the chamber to be less than 6 multiplied by 10 -4 Pa by using a vacuum system (a mechanical pump and a molecular pump), introducing Ar and O 2 into the chamber after the vacuum degree in the chamber reaches the requirement, adjusting a gas flow meter to set the gas flow of Ar to 20sccm, setting the gas flow of O 2 to 1.2sccm, and adjusting the pressure in the chamber to 5Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump after the gas flow is set. And (3) opening an RF power supply to preheat, opening a target head shielding plate of the Al-Si combined target through a control panel after the RF power supply is preheated, opening the RF power supply, adjusting power to start, setting the power of the RF power supply to 90W after the RF power supply is started, and adjusting the working air pressure in the cavity to 1.5Pa through adjusting a molecular pump gate valve. Opening a target head shielding plate of the Zr-Nb-Cr-Mo combined target material through a control panel, opening a DC power supply, adjusting the voltage and the current of the DC power supply to start, and adjusting the current to 0.18A after the start of the DC power supply is completed, wherein the voltage at the moment is 110V, and the power of the DC power supply is 3W; and pre-sputtering the two targets for 15min under the power to remove the oxide on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, the ZrNbCrMoAlSiO zirconium-based amorphous multicomponent oxide coating is sputtered for 10 hours, and the deposition thickness of the ZrNbCrMoAlSiO zirconium-based amorphous multicomponent oxide coating is about 2 mu m.
Effect example: characterization and performance evaluation
1. Coating characterization
After the preparation of the zirconium-based amorphous multi-component oxide coating is finished, measuring the thickness of the zirconium-based amorphous multi-component oxide coating by using a step instrument, analyzing the component distribution and the crystal structure of a cross-section sample of the zirconium-based amorphous multi-component oxide coating by using a transmission electron microscope (TEM, FEI TecnaiG 2 F20), and characterizing the plane and the cross-section morphology of the coating before and after oxidation by using a JEOL field emission scanning electron microscope (FE-SEM), wherein the combination condition of the coating before and after oxidation and a Zr-4 alloy substrate material is realized. And through a scanning electron microscope, the difference of oxidation depths of the protective positions of the coating can be clearly seen after oxidation under different conditions.
2. Structural phase transition of zirconium-based amorphous multicomponent oxide coatings at high temperatures
The high-temperature annealing experiment of the zirconium-based amorphous multi-component oxide coating is carried out in a rapid annealing furnace, wherein the temperature is set to be 700 ℃, 800 ℃, 900 ℃ and 1000 ℃ and the time range is 2-20 h. And preparing a TEM section sample from the sample subjected to high-temperature annealing by using an ion thinning instrument, and observing and analyzing microstructure and component change of the zirconium-based amorphous multicomponent oxide coating.
First, a high temperature annealing experiment was performed on ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared on a monocrystalline silicon piece according to the preparation conditions of example 1. FIG. 1 is a TEM sectional morphology diagram of a ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating in a preparation state and annealed in an air environment at 700 ℃ for 4 hours, wherein (1 a), (1 b) and (1 c) are respectively a preparation state sectional morphology diagram, a high resolution diagram and a selected area electron diffraction diagram; (1d) (1 e) and (1 f) are respectively an annealed section morphology, a selected area electron diffraction pattern and a high resolution pattern; the prepared cross section shape (1 a) of the coating can show that the coating is firmly combined with the substrate material, and the coating has no defects such as cracks, holes and the like. The high resolution (1 b) and selected area electron diffraction (1 c) patterns can be seen that ZrMoCrAlSiO coating in the as-prepared state is a dense amorphous structure. The cross section morphology graph (1 d) of the ZrMoCrAlSiO coating after annealing for 4 hours in the 700 ℃ air environment can be seen that the originally compact amorphous structure of the ZrMoCrAlSiO coating disappears after annealing for 4 hours at 700 ℃ and the coating is crystallized. EDS point measurement is carried out on the coating before and after 700 ℃ annealing, compared with the prepared coating, the Mo element is greatly reduced after the annealing at 700 ℃ for 4 hours (the atomic percent of the Mo element in the prepared coating is 5.48 percent, and the atomic percent of the Mo element is reduced to 0.97 percent after the annealing at 700 ℃ for 4 hours), and serious Mo element loss phenomenon occurs. After Mo element loss, the originally dense amorphous coating crystallizes, and a large number of nano-scale holes are observed on the partial enlarged view (1 d) of the coating cross section.
FIG. 2 is a TEM cross-sectional morphology of ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 1 after annealing at 900℃for 4 hours in an air environment. (2a) EDS point measurement after annealing at 900 ℃ for 4 hours shows that the atomic percent of Mo element in the coating is only 0.13%, which shows that the sublimation speed of the Mo element is very high during annealing at 900 ℃. After the original compact amorphous structure is destroyed, the nano-scale holes are left to be further increased and enlarged. (2b) The EDS element distribution diagram can obviously see the existence of nanoscale holes after the loss of Mo element.
A ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared on a monocrystalline silicon piece according to the preparation conditions of example 3 was subjected to a high-temperature annealing experiment. FIG. 3 is a TEM image of ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 3 annealed at different temperatures in an air environment: (3a) (3 b) and (3 c) are respectively the cross-sectional morphology of annealing at 800 ℃, 900 ℃ and 1000 ℃ for 2 hours; (3 a 1）、（3b1）、（3c1) are respectively corresponding high-resolution maps. The high resolution chart (3 a 1) and the selected area electron diffraction (3 a) show that the ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating has stable amorphous structure after being annealed for 2 hours at 800 ℃, and the defects such as cracks or holes and the like are not observed in the cross section morphology. The results of annealing for 2 hours in the air environment of 900 ℃ (3 b 1) and 1000 ℃ (3 c 1) show that the zirconium-based amorphous multicomponent oxide coating does not have large-area crystallization phenomenon after high-temperature annealing, but has amorphous coating nanocrystalline structure.
FIG. 4 is a cross-sectional EDS-scan elemental distribution of a ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 3 after annealing at 1000℃for 2 hours. EDS surface scanning results of the amorphous nanocrystalline structure region after annealing for 2 hours in an air environment at 1000 ℃ show that the elements in the region are uniformly distributed, and the segregation and aggregation phenomena of the elements do not occur.
FIG. 5 is a SAED pattern of ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 3 after annealing at 800, 900, 1000℃ for 2 hours, respectively. The electron diffraction ring in the selected area is calibrated, and the result shows that the phase structure of the nano-crystal particles formed after the annealing for 2 hours at 900 ℃ (5 b) and 1000 ℃ (5 c) is the same, and the nano-crystal particles are composed of tetragonal phase and hexagonal phase. The amorphous phase of the amorphous nanocrystalline structure mainly consists of amorphous SiO 2, and the nanocrystalline structure mainly consists of tetragonal phase and hexagonal phase high-entropy oxide particle phase. Further, the statistical calculation is carried out on the sizes of a large number of nanocrystalline grains, the average grain size of the nanocrystalline after annealing at 900 ℃ for 2 hours is 3.86nm, and the average grain size of the nanocrystalline after annealing at 1000 ℃ for 2 hours is 4.32nm. The amorphous SiO 2 wraps the nanocrystalline structure, not only can effectively inhibit the growth of nanocrystalline grains, but also can fill up crystal defects among nanocrystalline grains, prevent oxygen from diffusing along a grain boundary path, and has a good oxygen blocking effect.
3. High temperature oxidation protection performance of zirconium-based amorphous multicomponent oxide coating
A ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared on Zr-4 alloy according to the preparation conditions of example 3 was subjected to a high temperature oxidation experiment. In order to examine the protective effect of ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating in practical application on Zr-4 alloy, the coating with the thickness of 3 μm is prepared on Zr-4 alloy, oxidation experiments are respectively carried out for different time in an air environment at 1000 ℃, and then the thickness of the oxide film with or without the protective position of the coating is characterized.
FIG. 6 is an optical microscope surface and cross-sectional morphology diagram of the ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 3 in the as-prepared state and after 2 hours of oxidation at 1000 ℃, wherein no obvious oxide layer is found on the Zr-4 alloy for coating protection, and the oxidation resistance of the Zr-4 alloy is obviously improved.
4. High-temperature high-pressure water environment stability of zirconium-based amorphous multicomponent oxide coating
A ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared on Zr-4 alloy according to the preparation conditions of example 3 was subjected to a high-temperature high-pressure hydrothermal corrosion experiment. FIG. 7 is a SEM cross-sectional morphology of a ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating as prepared on a Zr-4 alloy, and (7 a) it can be seen that the coating as prepared is structurally dense and strongly bonded to the Zr-4 alloy. (7c) As can be seen from the SEM sectional morphology graph after 5h of hydrothermal corrosion in 0.01mol/L LiOH solution (320 ℃, 16mpa,0.01 mol/L), the coating structure becomes loose after the hydrothermal corrosion, and the coating is separated from the Zr-4 alloy substrate to some extent. The EDS point measurement results of (7 b, 7 d) show that the atomic percentage of silicon element in the coating is reduced from 22.5% of the prepared state to 14.5% after 5h of hydrothermal corrosion, the atomic percentage of aluminum element in the coating is reduced from 1.8% of the prepared state to 1.0%, the relative atomic percentages of other elements in the coating are not greatly changed, and the reduction of the silicon and aluminum element contents occurs.
A ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating in a surface layer incomplete oxidation state was prepared on a Zr-4 alloy according to the preparation conditions of example 4, and subjected to a high-pressure hydrothermal corrosion experiment. FIG. 8 is a view showing the surface and cross-sectional morphology of a mirror after hydrothermal corrosion of a surface layer low-oxygen zirconium-based amorphous multicomponent oxide coating layer prepared in example 4 of the present invention in a 0.01mol/L LiOH solution (320 ℃, 16MPa,0.01 mol/L), and (8 b, 8 d) comparison shows that the coating layer protected Zr-4 alloy has no obvious oxide layer.
Fig. 9 shows SEM cross-sectional morphology and element distribution diagrams of the surface layer low-oxygen zirconium-based amorphous multicomponent oxide coating prepared in example 4 of the present invention before and after corrosion for 20h in LiOH solution (320 ℃,16mpa,0.01 mol/L), and fig. 9a shows that EDS point measurement results show that the atomic percentage of surface layer oxygen is only 26% (the atomic percentage of oxygen in the fully oxidized state is 65% or more), and the surface layer low-oxygen zirconium-based amorphous multicomponent oxide coating is in an oxygen-deficient state. The EDS facial-sweep element distribution also demonstrates a lower oxygen content of the top coat. FIG. 9b shows the SEM cross-sectional morphology and element distribution of a surface hypoxia-modified ZrNbCrAlSiO coating after 20h of corrosion with a LiOH solution (320 ℃,16MPa,0.01 mol/L) at high temperature and high pressure. EDS spot scans showed 71 atomic percent oxygen in the top layer coating, the top layer converted to a fully oxidized state, while no decrease in the relative amounts of silicon and aluminum elements was detected in the coating, which were present in a stable state in this structure. At this time, EDS surface scanning shows that all elements are uniformly distributed, and the surface scanning diagram of oxygen element can show that Zr-4 alloy is not oxidized. The non-complete zirconia-based amorphous multi-component oxide coating has better effect than the complete zirconia-based amorphous multi-component oxide coating, and can further improve the stability of Zr-4 alloy in high-temperature and high-pressure water environment.
5. Stability of surface layer low oxygen zirconium based amorphous multicomponent oxide coating in high temperature vapor environment
ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating in the surface layer incomplete oxidation state was prepared on Zr-4 alloy according to the preparation conditions of example 4 and subjected to high temperature vapor corrosion experiments. FIG. 10 is a view showing the morphology of a ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating-protected Zr-4 alloy and a bare Zr-4 alloy with low oxygen on the surface layer oxidized for 2 hours in a 1200 ℃ water vapor environment, FIG. 10a is a view showing the cross-sectional morphology of an uncoated Zr-4 alloy oxidized for 2 hours in a 1200 ℃ water vapor environment, it can be seen that the Zr-4 alloy oxide film on the side without coating protection grows to about 420 μm at this time, FIG. 10b is a view showing the cross-sectional morphology of a coated Zr-4 alloy oxidized for 2 hours in a 1200 ℃ water vapor environment, and FIG. 10c is a plan morphology of the interface position, and it can be seen that the oxide film grows only about 35 μm at this time at the coated protection position. FIG. 11 is a plot of the oxidation film thickness versus time for bare Zr-4 alloy and ZrNbCrAlSiO coating protected Zr-4 alloy with subsurface hypoxia in a 1200 ℃ water vapor environment. The oxidation film thickening curves of the bare Zr-4 alloy and the ZrNbCrAlSiO coating protective Zr-4 alloy with the surface layer being low-oxygen all follow the approximate parabolic rule in the high-temperature vapor environment within 1200 ℃/2 hours. The thickening speed of the Zr-4 alloy oxide film of the coating protection is far lower than that of the Zr-4 alloy oxide film of the bare stage, and the coating protection can slow down the oxidation kinetic rate of the Zr-4 alloy in a 1200 ℃ water vapor environment. The surface layer low-oxygen zirconium-based amorphous multi-component oxide coating has good stability in a high-temperature vapor environment.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (5)
1. A preparation method of a zirconium-based amorphous multicomponent oxide coating is characterized by comprising the following steps: the method for preparing the zirconium-based amorphous multi-component oxide coating on the zirconium alloy matrix by using the reaction co-sputtering method of magnetron sputtering comprises the following steps:
(1) Washing a zirconium alloy substrate with acid, polishing silicon carbide sand paper, ultrasonically cleaning, and drying with nitrogen for later use;
(2) Attaching the zirconium alloy matrix obtained in the step (1) onto a substrate, placing the substrate in a rotary heating table of a magnetron sputtering chamber, and adjusting the target base distance to 15cm;
(3) Cutting and combining a zirconium-based multi-element target into a sputtering target A, cutting a Si-based multi-element target into a sputtering target B, connecting the sputtering target A with a direct current power supply, connecting the sputtering target B with a radio frequency power supply, preparing the sputtering target B, and preparing a zirconium-based amorphous multi-component oxide coating in a gradient oxidation state from the surface to the inner on a substrate obtained in the step (2) by a reaction co-sputtering method based on magnetron sputtering after the preparation;
The zirconium-based multi-element target in the step (3) comprises at least one element of Nb, cr or Mo and Zr, the Si-based multi-element target comprises Si, al or the Si-based multi-element target comprises at least one element of Fe and Ta and Si and Al;
The preparation work in the step (3) is as follows: pumping the vacuum degree of the chamber to be less than 6 multiplied by 10 -4 Pa, introducing Ar and O 2 after the vacuum degree in the chamber reaches the required vacuum degree, setting the gas flow of Ar to be 20sccm, setting the gas flow of O 2 to be 0.6-1.2sccm, adjusting the pressure in the chamber to be 3-5Pa after the gas flow is set, starting a radio frequency power supply to preheat for 3-5min, and adjusting the power of the radio frequency power supply to be 80-120W after the radio frequency power supply starts; after starting a direct current power supply, adjusting the power of the direct current power supply to 3-30W, then adjusting the air pressure in a cavity to 1.5Pa, and pre-sputtering two targets for 15min;
The reactive co-sputtering method based on the magnetron sputtering comprises the following steps: opening a substrate shielding plate, and performing reactive co-sputtering for 10 hours by adjusting a gas flow meter to set the gas flow of O 2 to be 1.2sccm when the fully oxidized zirconium-based amorphous multi-component oxide coating is deposited by utilizing magnetron sputtering, so as to prepare the zirconium-based amorphous multi-component oxide coating; and then, setting the gas flow of O 2 to be 0.6-0.8sccm by adjusting a gas flow meter, performing reactive co-sputtering for 30min, and preparing the zirconium-based amorphous multi-component oxide coating with the surface layer in an incomplete oxidation state, thereby obtaining the zirconium-based amorphous multi-component oxide coating with the gradient oxidation state from the surface to the inner.
2. The method for preparing a zirconium-based amorphous multicomponent oxide coating according to claim 1, characterized in that: the pickling solvent in the step (1) is a mixed solution of HNO 3 with volume concentration of 10%, HF with volume concentration of 10% and H 2O2 with volume concentration of 10%, and the ultrasonic cleaning method comprises the following steps: sequentially placing the zirconium alloy matrix in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min respectively; the zirconium alloy matrix is a Zr-4 alloy plate.
3. The zirconium-based amorphous multicomponent oxide coating in the oxidation state from the outside to the inside, which is produced by the production method according to claim 1 or 2, characterized in that: the stability of the surface layer of the zirconium-based amorphous multi-component oxide coating in the surface-to-inner gradient oxidation state under the high-temperature and high-pressure water environment at 320 ℃ and 16MPa is greater than that of the zirconium-based amorphous multi-component oxide coating in the surface layer in the complete oxidation state.
4. Use of a zirconium-based amorphous multicomponent oxide coating in the oxidation-resistant field in the oxidation-resistant state of claim 3 in a surface-to-interior gradient oxidation state.
5. The use according to claim 4, characterized in that: the application of the zirconium-based amorphous multi-component oxide coating in the surface protection of the zirconium alloy of the nuclear fuel cladding material from the surface to the inside is provided.
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