CN115305443A - Preparation method and application of zirconium-based amorphous multi-component oxide coating - Google Patents
Preparation method and application of zirconium-based amorphous multi-component oxide coating Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 182
- 239000011248 coating agent Substances 0.000 title claims abstract description 174
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 125
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 229910001093 Zr alloy Inorganic materials 0.000 claims abstract description 55
- 230000003647 oxidation Effects 0.000 claims abstract description 51
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- 238000004544 sputter deposition Methods 0.000 claims abstract description 35
- 239000013077 target material Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 22
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000005498 polishing Methods 0.000 claims abstract description 3
- 238000005477 sputtering target Methods 0.000 claims abstract 8
- 238000005520 cutting process Methods 0.000 claims abstract 4
- 229910045601 alloy Inorganic materials 0.000 claims description 73
- 239000000956 alloy Substances 0.000 claims description 73
- 239000007789 gas Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000011159 matrix material Substances 0.000 claims description 31
- 239000002344 surface layer Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 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
- 238000005253 cladding Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003758 nuclear fuel Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 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 35
- 229910052710 silicon Inorganic materials 0.000 abstract description 35
- 239000010703 silicon Substances 0.000 abstract description 35
- 239000001301 oxygen Substances 0.000 abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 230000004888 barrier function Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005554 pickling Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 abstract 1
- 238000000137 annealing Methods 0.000 description 30
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 16
- 239000010408 film Substances 0.000 description 14
- 229910018125 Al-Si Inorganic materials 0.000 description 12
- 229910018520 Al—Si Inorganic materials 0.000 description 12
- 238000010586 diagram Methods 0.000 description 12
- 238000004070 electrodeposition Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 9
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- 238000000151 deposition Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
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- 230000001681 protective effect Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000004098 selected area electron diffraction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 230000003287 optical effect Effects 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002003 electron diffraction Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 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
- 229910018191 Al—Fe—Si Inorganic materials 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910002064 alloy oxide Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
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- 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
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- 230000008719 thickening Effects 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- FUBPFRSUVOIISV-UHFFFAOYSA-N [O].[Si].[Zr] Chemical compound [O].[Si].[Zr] FUBPFRSUVOIISV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- -1 oxygen ions 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
- 230000036961 partial effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
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- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film 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
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
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- 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
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Abstract
The invention belongs to the field of surface processing, and relates to a preparation method and application of a zirconium-based amorphous multi-component oxide coating. Firstly, pickling and ultrasonically cleaning a silicon wafer, and then drying the silicon wafer by nitrogen for later use; carrying out acid cleaning, silicon carbide abrasive paper polishing and ultrasonic cleaning on the zirconium alloy substrate, and then blowing nitrogen for later use; cutting the zirconium-based multi-element target material to form a sputtering target material A, cutting the Si-based multi-element target material to form 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, and simultaneously introducing Ar and O into the chamber 2 The zirconium-based amorphous multi-component oxide coating is prepared by a magnetron sputtering-based reactive co-sputtering method. The zirconium-based amorphous multicomponent oxide prepared by the inventionThe coating is compatible with a zirconium alloy interface, has good oxygen resistance 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 multi-component oxide coating.
Background
Over the next half of 2021, the worldwide fossil energy prices have risen dramatically, and a global energy crisis has rolled up and has not yet been fully alleviated. Currently, the global energy pattern is in depth adjustment, traditional energy is gradually replaced by new clean low-carbon energy, and nuclear power is widely recognized as a large power supply which is reliable, environmentally sustainable and cost-effective. The nuclear energy plays a very important role in the aspects of coping with climate change, promoting scientific and technological progress, realizing the carbon neutralization target, improving the national comprehensive strength, guaranteeing the energy safety and the like. According to the statistical data of international mechanisms related to atomic energy, 448 nuclear power generating units are installed all over the world as far as 2020, the total power generation amount of a global installed nuclear power generating unit is about 2600 TWh, the nuclear power generating amount accounts for about 10% of the total power generation amount, and about 33% of the world low-carbon power supply comes from nuclear power generation. The vigorous development of nuclear power technology has become one of the important energy strategic plans of countries in the world today.
The cladding serves as an important barrier to nuclear reactor safety, serving to encase and seal 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 a cladding material adopted by the current major nuclear countries. At present, cladding materials for nuclear power are subjected to extremely severe working conditions: the inside is affected by fission products, the outside is affected by coolant corrosion, high temperature and high pressure, and is also affected by strong neutron radiation and coolant erosion, vibration and internal stress. For nuclear fuel cladding, it is critical to slow the kinetics of oxidation, thereby reducing heat generation and hydrogen evolution. The mechanical property of the zirconium alloy is weakened due to solid solution of oxygen or hydrogen, and corrosion cracking is easy to occur. Under normal working conditions, the zirconium oxide formed in situ on the surface of the Zr alloy can be used asThe corrosion resistance is improved to a certain extent for the passivation film. However, significant volume expansion occurs due to oxide phase transition, 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 acting 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 the zirconia on the surface and be used as an ideal zirconium alloy coating material. The main factors determining the diffusion of elements in the coating are the structural compactness and stability. Studies have shown that the amorphous oxide layer is a favorable barrier against the movement of oxygen ions due to its dense and borderless character, the diffusion of oxygen elements at the grain boundaries being more pronounced compared to bulk diffusion. In addition, the amorphous oxide film can easily eliminate lattice mismatch of interface atomic bonds, eliminate strain between interfaces and result in low interface Gibbs energy using flexibility of atomic bonds, and provide protection for a metal substrate. Amorphous oxide coatings have potential applications. Research finds that ZrO 2 Doping SiO in thin film 2 When the content exceeds 30at.% by volume, siO is formed 2 -ZrO 2 The film is an amorphous film. Meanwhile, the addition of the Si element can improve the oxygen resistance of the oxide layer. Therefore, the Si element has great application prospect in the field of amorphous coatings in the field of nuclear power.
However, the ideal coating not only needs to satisfy the high-temperature oxidation resistance, but also needs to satisfy the relevant requirements under normal working conditions (high-temperature and high-pressure water). Research reports that silica and alumina tend to rapidly dissolve to H in high temperature aqueous environments 2 SiO 3 And AlO (OH) (nuclear. Power syst. React, springer, 2018, 269-280). Such as Ti 2 AlC，Ti 3 SiC 2 Such MAX phase coatings, while stable at high temperatures, have limited protective performance under normal operating conditions due to The tendency of The surface to form alumina or silica (Joseph W, MAX phase ceramics for nuclear applications, the University of Manchester, 2018.). Thus, for exampleThe key scientific problem for researching and developing zirconium-based coatings is the differentiation requirement of the stability and oxygen resistance of the working condition conditions on the element chemistry of the materials.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method and application of a zirconium-based amorphous multi-component 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 to improve the corrosion resistance and oxidation resistance of the zirconium alloy cladding, and the protective coating shows an ultra-slow oxidation kinetic behavior.
The invention also aims to provide a preparation method of the zirconium alloy protective coating with a denser coating.
In order to achieve the 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 utilizes a reaction co-sputtering method to form the zirconium-based amorphous multi-component oxide coating on a silicon chip and a zirconium alloy matrix.
Step 1: with pickling solution (HNO with a volume concentration of 10% 3 10% HF, 10% H 2 O 2 Mixed solution of) cleaning the silicon wafer and the zirconium alloy;
step 2: polishing the zirconium alloy matrix by using silicon carbide abrasive paper;
and step 3: sequentially placing the silicon chip and the zirconium alloy matrix in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min respectively;
and 4, step 4: taking out the silicon chip and the zirconium alloy which are subjected to ultrasonic cleaning, and drying the silicon chip and the zirconium alloy for later use by using a nitrogen gun;
and 5: attaching the pretreated silicon wafer and the zirconium alloy matrix to a substrate base plate, putting the substrate base plate on a rotary heating table inside a magnetron sputtering chamber, and adjusting the target base distance to 15cm; the zirconium-based multi-element target material is arranged on a target head connected with a direct current power supply, and the Si-based multi-element target material is arranged on the target head connected with a radio frequency power supply;
step 6: the vacuum degree of the chamber is pumped to 6 x 10 by using a vacuum system (a mechanical pump and a molecular pump) -4 Below Pa, opening the process gas control valve through the operation panel to introduce Ar and O into the chamber after the vacuum degree in the chamber reaches the required vacuum degree 2 (pressure increase in the chamber was observed to ensure Ar and O 2 Normal inlet), adjusting the gas flow meter to set the gas flow of Ar to be 20sccm, and setting O 2 The gas flow of the pressure regulating valve is set to be 0.6-1.2sccm, and after the gas flow is set, the pressure in the cavity is regulated to be 3-5Pa (plus or minus 0.02 Pa) by regulating a gate valve between the cavity and the molecular pump;
and 7: preheating a Radio Frequency (RF) power supply for 3-5min before formal starting, adjusting the power of the RF power supply to start after preheating is finished, and adjusting the power to the power required by sputtering after the RF power supply finishes starting;
and 8: turning on a DC power supply to start, and after the DC power supply finishes starting, 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;
and step 9: after the RF and DC power are adjusted, adjusting the gate valve of the molecular pump again, emphasizing the chamber pressure as the working air pressure of 1.5Pa in normal sputtering, sputtering the two targets for 15min, and removing the oxide on the surfaces of the targets;
step 10: and after the sputtering is finished, opening the rotating heating table to rotate at a certain rotating speed, manually opening the substrate baffle, and preparing the zirconium-based amorphous multi-component oxide coating by reactive co-sputtering.
Further, in step 5, when designing and mounting the target, the zirconium-based multi-element target comprises at least two of Zr, nb, cr and Mo, and the Si-based multi-element target comprises at least one of Al, si, fe and Ta;
further, in step 7, after the start of the RF power is completed, the power is adjusted to 80-120W.
Further, in step 8, after the DC power is turned on, the power is adjusted to 3-60W.
Further, in step 10, when depositing the multicomponent oxide coating in a fully oxidized state by magnetron sputtering, O is added by adjusting a gas flow meter 2 The gas flow rate was set to 1.2sccm; when the multi-component oxide coating with the gradient oxidation state from the outside to the inside is deposited by magnetron sputtering, O is added by adjusting a gas flow meter 2 The gas flow rate was set to 0.6-0.8sccm.
Further, in step 2, the zirconium alloy substrate is a Zr-4 alloy sheet substrate.
Further, 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.
Furthermore, the oxygen content in the surface layer of the coating in the oxidation state from the surface to the inside 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 multi-component 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 multi-component oxide coating in a complete oxidation state or a gradient oxidation state from the surface to the inside, both coatings have high-temperature oxidation resistance; when the surface layer is a zirconium-based amorphous multi-component oxide coating in a complete oxidation state, the coating has stability under the high-temperature and high-pressure water environment (320 ℃,16 MPa); when the surface layer is the zirconium-based amorphous multi-component oxide coating with the gradient oxidation state from the surface to the inside, the stability under the high-temperature and high-pressure water environment is higher than that of the zirconium-based amorphous multi-component oxide coating with the completely oxidation state on the surface layer.
Furthermore, the prepared zirconium-based amorphous multi-component oxide coating can be applied to the oxidation resistance field, in particular to the surface protection of the zirconium alloy of the nuclear fuel cladding material.
The invention has the following beneficial effects:
1. the invention adopts a reactive co-sputtering method through the design of a target material, and utilizes a high-vacuum single-chamber three-target magnetron sputtering film deposition system to perform multi-component modification based on zirconium silicon oxygen, and regulates and controls an atomic structure to form 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 anti-oxidation fields, and the zirconium-based amorphous multi-component coating structure is designed, so that the disadvantages of a single element coating are avoided, the zirconium-based amorphous multi-component oxide coating has good compatibility with Zr-4 alloy during oxidation at high temperature, and the coating does not fall off.
2. The multi-component strategy can effectively block the formation of a continuous Si-O network and avoid the reaction of a Si-O bonding system and water to form H 2 SiO 3 (ii) a Through a bond energy regulation mechanism, intermolecular channels are reduced, and a corrosive medium can be further blocked. The high mixing entropy in the zirconium-based amorphous multi-component oxide coating enhances the intersolubility of elements, inhibits the formation of compounds and can play a role in stabilizing an amorphous system. At the same time, the amorphous oxide will exist stably due to high interfacial energy and kinetic barrier of atomic diffusion during crystallization (slow kinetics).
3. When the performance evaluation of the high-temperature and high-pressure water environment stability of the zirconium-based amorphous multi-component oxide coating is carried out, the interface of the zirconium-based amorphous multi-component oxide coating and the Zr-4 alloy is stable, and the severe element diffusion phenomenon does not occur at the interface in the high-temperature process. After hydrothermal corrosion is carried out in LiOH solution (320 ℃, 169mp, 0.01mol/L) at high temperature and high pressure for a certain time, the stable existence of the structure and components of the coating can be kept. When the surface layer is a zirconium-based amorphous multi-component oxide coating in a complete oxidation state, the coating has stability in a high-temperature and high-pressure water environment; when the surface layer is a zirconium-based amorphous multi-component oxide coating with a gradient oxidation state from the surface to the inside, the stability of the coating is further improved in a high-temperature and high-pressure water environment.
4. The zirconium-based amorphous multi-component oxide coating constructed by the invention can obtain a coating material which accords with the intrinsic characteristics of zirconium alloy, is compatible with an interface and has a good oxygen resistance 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 multi-component oxide coating prepared by the invention not only can be used as a zirconium alloy protective coating, but also can be used as a diffusion barrier layer of a metal coating due to the strong high-temperature interface stability, so that the phenomenon of severe element diffusion at the interface position when the metal coating is directly used as the zirconium alloy protective coating is inhibited.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows the original state of the ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 1 of the present invention and the TEM cross-sectional morphology after annealing at 700 ℃ for 4 hours in an air environment; (a), (b) and (c) are respectively a preparation-state section morphology, a high resolution chart and a selected area electron diffraction chart; (d) The section appearance, the selected area electron diffraction pattern and the high resolution pattern after annealing are respectively shown in (e) and (f).
FIG. 2 shows TEM cross-sectional morphology (a) and 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 4h in air environment.
FIG. 3 is a TEM cross-sectional morphology and a high resolution chart of the ZrMoCrAlSiO zirconium-based amorphous multi-component oxide coating prepared in example 1 of the present invention after annealing at 800 deg.C, 900 deg.C, 1000 deg.C for 2 hours, respectively; (a), (b) and (c) respectively correspond to TEM section appearances after annealing at 800 ℃,900 ℃ and 1000 ℃ for 2h, and (a) 1 ）、（b 1 ）、（c 1 ) Respectively corresponding to high resolution pictures after annealing for 2 hours at 800 ℃,900 ℃ and 1000 ℃.
FIG. 4 shows the cross-sectional EDS surface scan element distribution of the ZrMoCrAlSiO zirconium based amorphous multicomponent oxide coating prepared in example 1 of the invention after annealing at 1000 ℃ for 2 h.
FIG. 5 is a SAED graph of a ZrMoCrAlSiO zirconium based amorphous multi-component oxide coating prepared in example 1 of the present invention after annealing for 2h at 800 deg.C (a), 900 deg.C (b), and 1000 deg.C (c), respectively.
FIG. 6 is a diagram of the surface and cross-sectional morphology of an optical microscope in the preparation state of Zr-4 alloy protected by a ZrNbCrAlSiO zirconium based amorphous multicomponent oxide coating prepared in example 3 of the present invention and after oxidation for 2h at 1000 ℃.
FIG. 7 shows the SEM cross-sectional morphology of the Zr-4 alloy prepared by the method of the invention and protected by the ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 3, and corroded for 5h in LiOH solution (320 ℃, 169MPa, 0.01mol/L) at high temperature and high pressure: the section shapes of the prepared state (a) and the prepared state (b), and the section shapes of the etched state (c) and the etched state (d) after 5 hours.
FIG. 8 is a diagram showing the surface and cross-sectional shapes of the optical lens after hot water corrosion of the ZrNbCrAlSiO low-oxygen zirconium-based amorphous multicomponent oxide coating on the surface layer and the bare Zr-4 alloy in 0.01mol/L LiOH solution (320 ℃,16Mpa, 0.01mol/L) for 20 hours, which are prepared in example 4 of the present invention: (a) surface and cross-sectional topography maps of the Zr-4 alloy without coating protection after 20h of hydrothermal corrosion, and (c) surface and cross-sectional topography maps of the Zr-4 alloy with coating protection after 20h of hydrothermal corrosion.
FIG. 9 is an SEM cross-sectional morphology and an element distribution diagram of the ZrNbCrAlSiO low-oxygen zirconium-based amorphous multi-component oxide coating prepared in example 4 of the invention before and after 20h corrosion in a high-temperature high-pressure LiOH solution (320 ℃, 169mp, 0.01mol/L): (a) as-prepared morphology; and (b) etching the morphology after 20h.
FIG. 10 is a morphology of the Zr-4 alloy protected by the ZrNbCrAlSiO superficial layer low-oxygen zirconium-based amorphous multicomponent oxide coating and the bare Zr-4 alloy prepared in example 4 of the present invention oxidized for 2h in a water vapor environment at 1200 deg.C: the cross-sectional topography of (a) Zr-4 alloy without coating protection oxidized for 2h in a water vapor environment at 1200 ℃, (b) Zr-4 alloy with coating protection oxidized for 2h in a water vapor environment at 1200 ℃, and (c) the plane topography of the interface position.
FIG. 11 is a graph showing the change of the thickness of the oxide film of the ZrNbCrAlSiO low-oxygen Zr-based amorphous multicomponent oxide coating-protected Zr-4 alloy and the bare Zr-4 alloy prepared in example 4 of the present invention with the increase of the oxidation time in a water vapor environment at 1200 ℃.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
This example is a method for preparing a ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating, comprising the steps of:
first, a single crystal silicon wafer and a Zr-4 alloy plate were prepared, wherein the size of the single crystal silicon wafer substrate was 40mm × 40mm × 0.5mm, and the size of the Zr-4 alloy plate substrate was 30mm × 30mm × 2mm. An acid wash (HNO having a volume concentration of 10%) was applied to the above-mentioned single-crystal silicon wafer and Zr-4 alloy sheet substrate 3 10% HF, 10% H 2 O 2 The mixed solution) is cleaned, a zirconium alloy matrix is polished by 600-mesh silicon carbide abrasive paper, then the silicon wafer and the polished Zr-4 alloy matrix are sequentially placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min respectively, the silicon wafer and the zirconium alloy after ultrasonic cleaning are taken out and dried by a nitrogen gun for standby, the silicon wafer and the zirconium alloy matrix after pretreatment are attached to a substrate base plate, the substrate base plate is placed on a rotary heating table inside a magnetron sputtering chamber, and the target base distance is adjusted to 15cm. A zirconium-based multi-element (Zr-Mo-Cr) target material is arranged on a target head connected with a direct current power supply (DC), and a Si-based multi-element (Al-Si) target material is arranged on a target head connected with a radio frequency power supply (RF); the vacuum degree of the chamber is pumped to 6 x 10 by a vacuum system (mechanical pump and molecular pump) -4 Below Pa, introducing Ar and O into the chamber after the vacuum degree in the chamber meets the requirement 2 Adjusting the gas flow meter to set the gas flow of Ar to be 20sccm and O 2 The gas flow rate of (2) is set to 1.2sccm, and after the gas flow rate setting is completed, the pressure in the chamber is adjusted to 3Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump. Turning on an RF power supply for preheating, and after the RF power supply is preheated, turning on a target head shielding plate of the Al-Si combined target through a control panel, and turning onStarting the RF power supply, adjusting the power to start, setting the power of the RF power supply to 100W after the start of the RF power supply is finished, and adjusting the working air pressure in the chamber to 1.5Pa by adjusting the gate valve of the molecular pump. The target head baffle plate of the Zr-Mo-Cr combined target is opened through the control panel, the DC power supply is turned on, the voltage and the current of the DC power supply are adjusted to be started, after the DC power supply is started, the current is adjusted to be 0.2A, 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 oxides on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, and the co-sputtering is carried out for 10h, and the deposition thickness of the ZrMoCrAlSiO zirconium-based amorphous multi-component oxide coating is about 300nm.
Example 2
The embodiment is a preparation method of a ZrNbCrAlSiO zirconium-based amorphous multi-component oxide coating, which comprises the following steps:
first, a single crystal silicon wafer and a Zr-4 alloy plate were prepared, wherein the size of the single crystal silicon wafer substrate was 40mm × 40mm × 0.5mm, and the size of the Zr-4 alloy plate substrate was 30mm × 30mm × 2mm. An acid wash (HNO having a volume concentration of 10%) was applied to the above-mentioned single-crystal silicon wafer and Zr-4 alloy sheet substrate 3 10% HF, 10% H 2 O 2 The mixed solution) is cleaned, a zirconium alloy matrix is polished by 600-mesh silicon carbide abrasive paper, then the silicon wafer and the polished Zr-4 alloy matrix are sequentially placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min respectively, the silicon wafer and the zirconium alloy after ultrasonic cleaning are taken out and dried by a nitrogen gun for standby, the silicon wafer and the zirconium alloy matrix after pretreatment are attached to a substrate base plate, the substrate base plate is placed on a rotary heating table inside a magnetron sputtering chamber, and the target base distance is adjusted to 15cm. The method comprises the following steps that a zirconium-based multi-element (Zr-Nb-Cr) target is arranged on a target head connected with a direct current power supply (DC), and a Si-based multi-element (Al-Si) target is arranged on a target head connected with a radio frequency power supply (RF); the vacuum degree of the chamber is pumped to 6 x 10 by using a vacuum system (a mechanical pump and a molecular pump) -4 Below Pa, introducing Ar and O into the chamber after the vacuum degree in the chamber meets the requirement 2 Adjusting the gas flow meter to set the gas flow of Ar to be 20sccm and O 2 Gas flow setting ofAt 1.2sccm, after the gas flow setting was completed, the pressure in the chamber was adjusted to 5Pa (+ -0.02 Pa) by adjusting the gate valve between the chamber and the molecular pump. And turning on an RF power supply for preheating, after the RF power supply is preheated, turning on a target head shielding plate of the Al-Si combined target through a control panel, turning on the RF power supply, adjusting the power for starting, 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 chamber to 1.5Pa through adjusting a molecular pump gate valve. The target head baffle plate of the Zr-Nb-Cr combined target is opened through the control panel, the DC power supply is opened, the voltage and the current of the DC power supply are adjusted to be started, after the DC power supply is started, the current is adjusted to be 0.3A, 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 oxides on the surfaces of the targets. After the preparation, the substrate shielding plate was opened, and the thickness of the amorphous multicomponent oxide coating was about 200nm after co-sputtering for 10h and ZrNbCrAlSiO zirconium.
Example 3
The embodiment is a preparation method of a ZrNbCrAlSiO zirconium-based amorphous multi-component oxide coating, which comprises the following steps:
first, a single crystal silicon wafer and a Zr-4 alloy plate were prepared, wherein the size of the single crystal silicon wafer substrate was 40mm × 40mm × 0.5mm, and the size of the Zr-4 alloy plate substrate was 30mm × 30mm × 2mm. An acid wash (HNO having a volume concentration of 10%) was applied to the above-mentioned single-crystal silicon wafer and Zr-4 alloy sheet substrate 3 10% HF, 10% H 2 O 2 The mixed solution) is cleaned, a zirconium alloy matrix is polished by 600-mesh silicon carbide abrasive paper, then the silicon wafer and the polished Zr-4 alloy matrix are sequentially placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min respectively, the silicon wafer and the zirconium alloy after ultrasonic cleaning are taken out and dried by a nitrogen gun for standby, the silicon wafer and the zirconium alloy matrix after pretreatment are attached to a substrate base plate, the substrate base plate is placed on a rotary heating table inside a magnetron sputtering chamber, and the target base distance is adjusted to 15cm. The method comprises the following steps that a zirconium-based multi-element (Zr-Nb-Cr) target is arranged on a target head connected with a direct current power supply (DC), and a Si-based multi-element (Al-Si) target is arranged on a target head connected with a radio frequency power supply (RF); by means of vacuumThe system (mechanical pump and molecular pump) pumps the vacuum degree of the chamber to 6 x 10 -4 Below Pa, introducing Ar and O into the chamber after the vacuum degree in the chamber meets the requirement 2 Adjusting the gas flow meter to set the gas flow of Ar to be 20sccm and O 2 The gas flow rate of (2) is set to 1.2sccm, and after the gas flow rate is set, the pressure in the chamber is adjusted to 5Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump. And turning on an RF power supply for preheating, after the RF power supply is preheated, turning on a target head shielding plate of the Al-Si combined target through a control panel, turning on the RF power supply, adjusting the power for starting, setting the power of the RF power supply to be 120W after the RF power supply is started, and adjusting the working air pressure in the chamber to be 1.5Pa by adjusting a molecular pump gate valve. The target head baffle plate of the Zr-Nb-Cr combined target is opened through the control panel, the DC power supply is opened, the voltage and the current of the DC power supply are adjusted to be started, after the DC power supply is started, the current is adjusted to be 0.2A, 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 oxides on the surfaces of the targets. After the preparation is finished, the substrate baffle plate is opened, 12h is co-sputtered, and the deposition thickness of the ZrNbCrAlSiO zirconium-based amorphous multi-component oxide coating is about 3 mu m.
Example 4
This example is a method for preparing ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating with gradient oxidation state from surface to inside, comprising the following steps:
first, a single crystal silicon wafer and a Zr-4 alloy plate were prepared, wherein the size of the single crystal silicon wafer substrate was 40mm × 40mm × 0.5mm, and the size of the Zr-4 alloy plate substrate was 30mm × 30mm × 2mm. An acid wash (HNO having a volume concentration of 10%) was applied to the above-mentioned single-crystal silicon wafer and Zr-4 alloy sheet substrate 3 10% HF, 10% H 2 O 2 The mixed solution) is cleaned, a zirconium alloy matrix is polished by 600-mesh silicon carbide abrasive paper, then the silicon wafer and the polished Zr-4 alloy matrix are sequentially placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min respectively, the silicon wafer and the zirconium alloy after ultrasonic cleaning are taken out and dried by a nitrogen gun for standby, and the silicon wafer and the zirconium alloy matrix after pretreatment are dried for standbyThe substrate is attached to a substrate base plate, the substrate base plate is placed on a rotary heating table in a magnetron sputtering cavity, and the target base distance is adjusted to be 15cm. A zirconium-based multi-element (Zr-Nb-Cr) target material is arranged on a target head connected with a direct current power supply (DC), and a Si-based multi-element (Al-Si) target material is arranged on a target head connected with a radio frequency power supply (RF); the vacuum degree of the chamber is pumped to 6 x 10 by a vacuum system (mechanical pump and molecular pump) -4 Below Pa, introducing Ar and O into the chamber after the vacuum degree in the chamber meets the requirement 2 Adjusting the gas flow meter to set the gas flow of Ar to be 20sccm and O 2 The gas flow rate of (2) is set to 1.2sccm, and after the gas flow rate is set, the pressure in the chamber is adjusted to 4Pa (± 0.02 Pa) by adjusting the gate valve between the chamber and the molecular pump. And turning on an RF power supply for preheating, after the RF power supply is preheated, turning on a target head shielding plate of the Al-Si combined target through a control panel, turning on the RF power supply, adjusting the power for starting, setting the power of the RF power supply to be 120W after the RF power supply is started, and adjusting the working air pressure in the chamber to be 1.5Pa by adjusting a molecular pump gate valve. (ii) a The target head baffle plate of the Zr-Nb-Cr combined target is opened through the control panel, the DC power supply is opened, the voltage and the current of the DC power supply are adjusted to be started, after the DC power supply is started, the current is adjusted to be 0.2A, 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 oxides on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, and two coatings with different thicknesses are prepared in different time by co-sputtering.
In the sputtering process of the first stage, under the power supply and the process conditions, a ZrNbCrAlSiO zirconium-based amorphous multi-component oxide coating in a complete oxidation state is prepared, co-sputtering is carried out for 10 hours, and the deposition thickness is about 2.5 mu m; in the second stage of sputtering, O is added 2 The gas flow of the gas source is adjusted to be 0.8sccm, the power supply power and other process conditions are kept consistent with the first stage, the ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating with a surface layer in a non-complete oxidation state is prepared, co-sputtering is carried out for 30min, and the sputtering thickness of the first stage is 1 mu m.
Example 5
This example is a method for preparing ZrFeCrAlSiO zirconium based amorphous multicomponent oxide coating, comprising the following steps:
first, a single crystal silicon wafer and a Zr-4 alloy plate were prepared, wherein the size of the single crystal silicon wafer substrate was 40mm × 40mm × 0.5mm, and the size of the Zr-4 alloy plate substrate was 30mm × 30mm × 2mm. An acid cleaning solution (HNO having a volume concentration of 10%) was applied to the single-crystal silicon wafer and the Zr-4 alloy sheet substrate 3 10% HF, 10% H 2 O 2 The mixed solution) is cleaned, a zirconium alloy matrix is polished by 600-mesh silicon carbide abrasive paper, then the silicon wafer and the polished Zr-4 alloy matrix are sequentially placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min respectively, the silicon wafer and the zirconium alloy after ultrasonic cleaning are taken out and dried by a nitrogen gun for standby, the silicon wafer and the zirconium alloy matrix after pretreatment are attached to a substrate base plate, the substrate base plate is placed on a rotary heating table inside a magnetron sputtering chamber, and the target base distance is adjusted to 15cm. The method comprises the following steps that a zirconium-based multi-element (Zr-Cr) target material is arranged on a target head connected with a direct current power supply (DC), and a Si-based multi-element (Al-Fe-Si) target material is arranged on the target head connected with a radio frequency power supply (RF); the vacuum degree of the chamber is pumped to 6 x 10 by using a vacuum system (a mechanical pump and a molecular pump) -4 Below Pa, introducing Ar and O into the chamber after the vacuum degree in the chamber meets the requirement 2 Adjusting the gas flow meter to set the gas flow of Ar to be 20sccm and O 2 The gas flow rate of (2) is set to 1.2sccm, and after the gas flow rate is set, the pressure in the chamber is adjusted to 5Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump. And turning on an RF power supply for preheating, after the RF power supply is preheated, turning on a target head shielding plate of the Al-Fe-Si combined target through a control panel, turning on the RF power supply, adjusting the power for starting, after the RF power supply is started, setting the power of the RF power supply to be 100W, and adjusting the working air pressure in the chamber to be 1.5Pa by adjusting a molecular pump gate valve. The target head baffle plate of the Zr-Cr combined target is opened through the control panel, the DC power supply is opened, the voltage and the current of the DC power supply are adjusted to be started, after the DC power supply is started, the current is adjusted to be 0.24A, the voltage at the moment is 130V, and the power of the DC power supply is 31.2W; pre-sputtering two targets for 15min under the power, removingAnd removing the oxide on the surface of the target. After the preparation was completed, the substrate shutter was opened, and the film was co-sputtered for 10h to deposit a ZrFeCrAlSiO zirconium-based amorphous multicomponent oxide coating having a thickness of about 2.5. Mu.m.
Example 6
This example is a method for preparing a ZrTaCrAlSiO multicomponent amorphous oxide coating, comprising the steps of:
first, a single crystal silicon wafer and a Zr-4 alloy plate were prepared, wherein the size of the single crystal silicon wafer substrate was 40mm × 40mm × 0.5mm, and the size of the Zr-4 alloy plate substrate was 30mm × 30mm × 2mm. An acid wash (HNO having a volume concentration of 10%) was applied to the above-mentioned single-crystal silicon wafer and Zr-4 alloy sheet substrate 3 10% HF, 10% H 2 O 2 The mixed solution) is cleaned, a zirconium alloy matrix is polished by 600-mesh silicon carbide abrasive paper, then the silicon wafer and the polished Zr-4 alloy matrix are sequentially placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min respectively, the silicon wafer and the zirconium alloy after ultrasonic cleaning are taken out and dried by a nitrogen gun for standby, the silicon wafer and the zirconium alloy matrix after pretreatment are attached to a substrate base plate, the substrate base plate is placed on a rotary heating table inside a magnetron sputtering chamber, and the target base distance is adjusted to 15cm. A zirconium-based multi-element (Zr-Cr) target material is arranged on a target head connected with a direct current power supply (DC), and a Si-based multi-element (Al-Ta-Si) target material is arranged on a target head connected with a radio frequency power supply (RF); the vacuum degree of the chamber is pumped to 6 x 10 by a vacuum system (mechanical pump and molecular pump) -4 Below Pa, introducing Ar and O into the chamber after the vacuum degree in the chamber meets the requirement 2 Adjusting the gas flow meter to set the gas flow of Ar to be 20sccm and O 2 The gas flow rate of (2) is set to 1.2sccm, and after the gas flow rate is set, the pressure in the chamber is adjusted to 5Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump. And (3) turning on an RF power supply for preheating, after the preheating of the RF power supply is finished, turning on a target head baffle plate of the Al-Ta-Si combined target material through a control panel, turning on the RF power supply, adjusting the power for starting, after the starting of the RF power supply is finished, setting the power of the RF power supply to be 90W, and adjusting the working air pressure in the chamber to be 1.5Pa by adjusting a molecular pump gate valve. By controllingThe panel opens a target head baffle plate of the Zr-Cr combined target, opens a DC power supply, adjusts the voltage and the current of the DC power supply for starting, adjusts the current to 0.18A after the DC power supply finishes starting, 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 oxides on the surfaces of the targets. After the preparation, the substrate shielding plate was opened, and the ZrTaCrAlSiO zirconium based amorphous multicomponent oxide coating was co-sputtered for 10h to a deposition thickness of about 2 μm.
Example 7
This example is a method for preparing ZrNbMoAlSiO zirconium-based amorphous multicomponent oxide coating with gradient oxidation state from surface to inside, comprising the following steps:
first, a single crystal silicon wafer and a Zr-4 alloy plate were prepared, wherein the size of the single crystal silicon wafer substrate was 40mm × 40mm × 0.5mm, and the size of the Zr-4 alloy plate substrate was 30mm × 30mm × 2mm. An acid wash (HNO having a volume concentration of 10%) was applied to the above-mentioned single-crystal silicon wafer and Zr-4 alloy sheet substrate 3 10% HF, 10% H 2 O 2 The mixed solution) is cleaned, a zirconium alloy matrix is polished by 600-mesh silicon carbide abrasive paper, then the silicon wafer and the polished Zr-4 alloy matrix are sequentially placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min respectively, the silicon wafer and the zirconium alloy after ultrasonic cleaning are taken out and dried by a nitrogen gun for standby, the silicon wafer and the zirconium alloy matrix after pretreatment are attached to a substrate base plate, the substrate base plate is placed on a rotary heating table inside a magnetron sputtering chamber, and the target base distance is adjusted to 15cm. The method comprises the following steps that a zirconium-based multi-element (Zr-Nb-Mo) target is arranged on a target head connected with a direct current power supply (DC), and a Si-based multi-element (Al-Si) target is arranged on a target head connected with a radio frequency power supply (RF); the vacuum degree of the chamber is pumped to 6 x 10 by using a vacuum system (a mechanical pump and a molecular pump) -4 Below Pa, introducing Ar and O into the chamber after the vacuum degree in the chamber meets the requirement 2 Adjusting the gas flow meter to set the gas flow of Ar to be 20sccm and O 2 The gas flow rate of (2) is set to 1.2sccm, and after the gas flow rate is set, the pressure in the chamber is adjusted to 4Pa (± 0.02 Pa) by adjusting the gate valve between the chamber and the molecular pump. OpenAnd preheating the RF power supply, opening a target head shielding plate of the Al-Si combined target through a control panel after the RF power supply is preheated, starting the RF power supply, adjusting the 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 chamber to be 1.5Pa by adjusting a molecular pump gate valve. The target head baffle plate of the Zr-Nb-Mo combined target is opened through the control panel, the DC power supply is opened, the voltage and the current of the DC power supply are adjusted to be started, after the DC power supply is started, the current is adjusted to be 0.2A, 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 oxides on the surfaces of the targets. After the preparation is completed, the substrate shielding plate is opened, and two coatings with different thicknesses are prepared in different time by co-sputtering.
In the sputtering process of the first stage, under the power supply and the technological conditions, a ZrNbMoAlSiO zirconium-based amorphous multi-component oxide coating in a complete oxidation state is prepared, co-sputtering is carried out for 10 hours, and the deposition thickness is about 2.5 mu m; in the second stage of sputtering, O is added 2 The gas flow of the gas source is adjusted to be 0.6sccm, the power supply power and other process conditions are kept consistent with the first stage, the ZrNbMoAlSiO zirconium-based amorphous multi-component oxide coating with a surface layer in a non-complete oxidation state is prepared, co-sputtering is carried out for 30min, and the sputtering thickness of the first stage is 1 mu m.
Example 8
The embodiment is a preparation method of a ZrNbCrMoAlSiO zirconium-based amorphous multi-component oxide coating, which comprises the following steps:
first, a single crystal silicon wafer and a Zr-4 alloy plate were prepared, wherein the size of the single crystal silicon wafer substrate was 40mm × 40mm × 0.5mm, and the size of the Zr-4 alloy plate substrate was 30mm × 30mm × 2mm. An acid wash (HNO having a volume concentration of 10%) was applied to the above-mentioned single-crystal silicon wafer and Zr-4 alloy sheet substrate 3 10% HF, 10% H 2 O 2 The mixed solution) is cleaned, a zirconium alloy matrix is polished by 600-mesh silicon carbide abrasive paper, then a silicon wafer and the polished Zr-4 alloy matrix are sequentially placed in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20min respectively, the silicon wafer and the zirconium alloy after ultrasonic cleaning are taken out and dried by a nitrogen gun for standby, and the pretreatment is finishedThe silicon chip and the zirconium alloy matrix are pasted on a substrate base plate, the substrate base plate is placed on a rotary heating table inside a magnetron sputtering cavity, and the target base distance is adjusted to be 15cm. The method comprises the following steps that a zirconium-based multi-element (Zr-Nb-Cr-Mo) target is arranged on a target head connected with a direct current power supply (DC), and a Si-based multi-element (Al-Si) target is arranged on a target head connected with a radio frequency power supply (RF); the vacuum degree of the chamber is pumped to 6 x 10 by a vacuum system (mechanical pump and molecular pump) -4 Below Pa, introducing Ar and O into the chamber after the vacuum degree in the chamber meets the requirement 2 Adjusting the gas flow meter to set the gas flow of Ar to be 20sccm and O 2 The gas flow rate of (2) is set to 1.2sccm, and after the gas flow rate is set, the pressure in the chamber is adjusted to 5Pa (+ -0.02 Pa) by adjusting a gate valve between the chamber and the molecular pump. And turning on an RF power supply for preheating, after the RF power supply is preheated, turning on a target head shielding plate of the Al-Si combined target through a control panel, turning on the RF power supply, adjusting the power for starting, after the RF power supply is started, setting the power of the RF power supply to 90W, and adjusting the working air pressure in the chamber to 1.5Pa by adjusting a molecular pump gate valve. The target head baffle plate of the Zr-Nb-Cr-Mo combined target is opened through the control panel, the DC power supply is opened, the voltage and the current of the DC power supply are adjusted to be started, after the DC power supply is started, the current is adjusted to be 0.18A, 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 oxides on the surfaces of the targets. After the preparation, the substrate shutter was opened and the ZrNbCrMoAlSiO zirconium-based amorphous multicomponent oxide coating was co-sputtered for 10h to a deposition thickness of about 2 μm.
Example of effects: characterization and Performance evaluation
1. Coating characterization
After the preparation of the zirconium-based amorphous multi-component oxide coating is finished, the thickness of the zirconium-based amorphous multi-component oxide coating is measured by a step profiler, and a transmission electron microscope (TEM, FEI TecnaiG) is utilized 2 F20 Analyzing the component distribution and the crystal structure of a zirconium-based amorphous multicomponent oxide coating cross-section sample, and representing the plane and cross-sectional morphology of the coating before and after oxidation by a JEOL (JEOL-Electron microscope) field emission scanning electron microscope (FE-SEM), and the coating before and after oxidationBonding to a Zr-4 alloy substrate material. And through a scanning electron microscope, the difference of the oxidation depth of the protective position of the coating can be clearly seen after oxidation under different conditions.
2. Structural phase change of zirconium-based amorphous multi-component oxide coating at high temperature
The high-temperature annealing experiment of the zirconium-based amorphous multicomponent oxide coating is carried out in a rapid annealing furnace, the temperature is set to 700 ℃, 800 ℃,900 ℃ and 1000 ℃, and the time range is 2 to 20h. And preparing a TEM section sample of the sample after high-temperature annealing by using an ion thinning instrument, and observing and analyzing the microstructure and component change of the zirconium-based amorphous multi-component oxide coating.
First, a high-temperature annealing experiment was performed on a ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared on a single-crystal silicon wafer under the preparation conditions of example 1. FIG. 1 is a TEM cross-sectional morphology of a ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating in a preparation state and annealed in an air environment at 700 ℃ for 4h, wherein (1 a), (1 b) and (1 c) are respectively a preparation state cross-sectional morphology, a high resolution map and a selected area electron diffraction map; (1d) The (1 e) and (1 f) are respectively the cross-sectional morphology after annealing, a selected area electron diffraction pattern and a high resolution pattern; the section morphology (1 a) of the coating in the preparation state shows that the coating is firmly combined with the substrate material, and the coating has no defects such as cracks, holes and the like. The ZrMoCrAlSiO coating in the preparation state is a compact amorphous structure as can be seen from a high resolution chart (1 b) and a selective electron diffraction chart (1 c). The cross-sectional morphology (1 d) of the ZrMoCrAlSiO coating after annealing for 4h at 700 ℃ in the air environment shows that the original compact amorphous structure disappears and the coating crystallizes after the ZrMoCrAlSiO coating is annealed for 4h at 700 ℃. EDS point measurement of the coatings before and after 700 ℃ annealing shows that compared with the prepared coating, mo element is greatly reduced after 700 ℃ annealing for 4 hours (the atomic percentage of Mo element of the prepared coating is 5.48%, and the atomic percentage of Mo element is reduced to 0.97% after 700 ℃ annealing for 4 hours), and a serious Mo element loss phenomenon occurs. After the Mo element is lost, the dense amorphous coating is crystallized, and a large number of nano-scale holes are observed on a partial enlarged view of the cross section of the coating (1 d).
FIG. 2 is the TEM cross-sectional morphology of the ZrMoCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 1 after annealing at 900 ℃ for 4h in an air environment. (2a) EDS point measurement after annealing at 900 ℃ for 4h shows that the atomic percentage of Mo in the coating is only 0.13% left, which indicates that the sublimation speed of Mo is very fast when annealing at 900 ℃. After the original compact amorphous structure is damaged, the nanometer-level holes are further increased and enlarged. (2b) The EDS element distribution diagram can obviously see the existence of nano-scale holes after Mo element is lost.
The ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared on the monocrystalline silicon wafer according to the preparation conditions of the embodiment 3 is subjected to a high-temperature annealing experiment. FIG. 3 is a TEM image of the ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared in example 3 annealed at different temperatures in air environment: (3a) The sections of the (3 b) and (3 c) are respectively annealed at 800 ℃,900 ℃ and 1000 ℃ for 2 h; (3 a) 1 ）、（3b 1 ）、（3c 1 ) Respectively, corresponding high resolution maps. High resolution picture (3 a) 1 ) And selective electron diffraction (3 a) shows that the amorphous structure of the ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating stably exists after annealing for 2 hours at 800 ℃, and no defects such as cracks or holes are observed in the cross-sectional morphology. 900 ℃ (3 b) 1 ) And 1000 deg.C (3 c) 1 ) The result of annealing in the air environment for 2h shows that the zirconium-based amorphous multicomponent oxide coating does not have large-area crystallization phenomenon after high-temperature annealing, but has an amorphous-coated nanocrystalline structure.
FIG. 4 is the cross-sectional EDS area scan element distribution of the ZrNbCrAlSiO zirconium based amorphous multicomponent oxide coating prepared in example 3 after annealing at 1000 ℃ for 2 h. EDS (electro-deposition) surface scanning results of the amorphous nanocrystalline structure region after annealing for 2 hours in the air environment at the temperature of 1000 ℃ show that all elements in the region are uniformly distributed, and the segregation and aggregation phenomena of the elements do not occur.
FIG. 5 is a SAED diagram of the ZrNbCrAlSiO zirconium based amorphous multicomponent oxide coating prepared in example 3 after annealing at 800 deg.C, 900 deg.C, 1000 deg.C for 2 h. The selected zone electron diffraction ring is calibrated, and the results show that the phase structures of the nanocrystalline particles formed after annealing for 2 hours at 900 ℃ (5 b) and 1000 ℃ (5 c) are the same and both consist of a tetragonal phase and a hexagonal phase. The amorphous nanocrystalline structureThe amorphous phase consists essentially of amorphous SiO 2 The nanocrystalline structure is mainly composed of a tetragonal phase and a hexagonal phase of high-entropy oxide granular phases. Further statistical calculations were performed on the size of the bulk nanocrystalline grains, the average nanocrystalline grain size was 3.86nm after annealing at 900 ℃ for 2 hours and 4.32nm after annealing at 1000 ℃ for 2 hours. Such amorphous SiO 2 The structure wrapping the nanocrystalline can not only effectively inhibit the growth of nanocrystalline grains, but also fill up crystal defects among the nanocrystalline grains, block the path of oxygen diffusion along the grain boundary, and show better oxygen blocking effect.
3. High-temperature oxidation protective property of zirconium-based amorphous multi-component oxide coating
The ZrNbCrAlSiO zirconium-based amorphous multi-component oxide coating prepared on the Zr-4 alloy according to the preparation conditions of the embodiment 3 is subjected to a high-temperature oxidation experiment. In order to investigate the protective effect of the ZrNbCrAlSiO zirconium-based amorphous multi-component oxide coating in the practical application of the Zr-4 alloy, the coating with the thickness of 3 mu m is prepared on the Zr-4 alloy, oxidation experiments are respectively carried out for different times in an air environment at 1000 ℃, and then the thickness of an oxide film at the protective position with or without the coating is characterized.
FIG. 6 is a diagram showing the morphology of the surface and cross-section of an optical microscope at 1000 ℃ for 2 hours after preparation of the Zr-4 alloy protected by the ZrNbCrAlSiO zirconium based amorphous multicomponent oxide coating prepared in example 3, wherein no obvious oxide layer is found in the Zr-4 alloy protected by the coating, and the oxidation resistance of the Zr-4 alloy is obviously improved.
4. High-temperature high-pressure water environment stability of zirconium-based amorphous multi-component oxide coating
The ZrNbCrAlSiO zirconium-based amorphous multicomponent oxide coating prepared on the Zr-4 alloy according to the preparation conditions of the embodiment 3 is subjected to a high-temperature high-pressure hydrothermal corrosion experiment. FIG. 7 is SEM cross-sectional view of as-prepared ZrNbCrAlSiO zirconium based amorphous multicomponent oxide coating on Zr-4 alloy, (7 a) it can be seen that the as-prepared coating is dense in structure and strongly bonded with Zr-4 alloy. (7c) The SEM sectional morphology picture can be seen after hydrothermal corrosion is carried out in 0.01mol/L LiOH solution (320 ℃,16Mpa and 0.01mol/L) for 5h, the structure of the coating becomes loose after the hydrothermal corrosion, and the coating is separated from the Zr-4 alloy substrate to a certain extent. The EDS point measurement results of (7 b, 7 d) show that the atomic percent of silicon in the coating is reduced to 14.5% from 22.5% in a preparation state after 5 hours of hydrothermal corrosion, the atomic percent of aluminum in the coating is reduced to 1.0% from 1.8% in the preparation state, the relative atomic percent of other elements in the coating does not change greatly, and the reduction of the content of the silicon and the aluminum elements is realized.
ZrNbCrAlSiO zirconium-based amorphous multi-component oxide coating with incomplete oxidation state on the surface layer is prepared on Zr-4 alloy according to the preparation conditions of example 4 and is subjected to high-temperature high-pressure hydrothermal corrosion experiment. FIG. 8 is a surface and cross-sectional shape diagram of an optical lens after hydrothermal corrosion of the surface layer low-oxygen zirconium-based amorphous multicomponent oxide coating prepared in example 4 of the present invention for 20 hours in 0.01mol/L LiOH solution (320 ℃,16Mpa, 0.01mol/L), and a comparison of (8 b, 8 d) shows that no obvious oxide layer is found in the Zr-4 alloy protected by the coating.
Fig. 9 is an SEM cross-sectional morphology and an element distribution diagram of the surface layer low-oxygen zirconium-based amorphous multicomponent oxide coating prepared in example 4 of the present invention before and after 20h of corrosion in a LiOH solution (320 ℃, 169pa, 0.01mol/L) at high temperature and high pressure, and fig. 9a shows that an EDS spot measurement result shows that the atomic percentage of the surface layer oxygen is only 26% (the atomic percentage of the oxygen in a completely oxidized state is 65% or more), which is an oxygen-deficient state. The EDS surface sweep elemental profile also demonstrates a lower oxygen content of the top coat. FIG. 9b shows SEM cross-sectional morphology and element distribution of the surface layer low-oxygen modified ZrNbCrAlSiO coating after being corroded in LiOH solution (320 ℃, 169MPa, 0.01mol/L) at high temperature and high pressure for 20h. The EDS spot scan shows that the top coating oxygen is 71 atomic percent and the top layer is converted to a fully oxidized state with no detectable decrease in the relative amounts of silicon and aluminum elements present in a stable state in the coating. At this time, EDS surface scanning shows that each element is uniformly distributed, and the surface scanning of the oxygen element shows that the Zr-4 alloy is not oxidized. The incomplete oxidation state zirconium-based amorphous multi-component oxide coating has better effect than the complete oxidation state zirconium-based amorphous multi-component oxide coating, and can further improve the stability of the Zr-4 alloy in the high-temperature and high-pressure water environment.
5. Stability of surface layer low-oxygen zirconium-based amorphous multi-component oxide coating in high-temperature water vapor environment
ZrNbCrAlSiO zirconium-based amorphous multi-component oxide coating with incomplete oxidation state on the surface layer is prepared on Zr-4 alloy according to the preparation conditions of example 4 and high temperature water vapor corrosion experiment is carried out. FIG. 10 is a morphology diagram of a Zr-4 alloy and a bare Zr-4 alloy protected by a low-oxygen ZrNbCrAlSiO zirconium-based amorphous multi-component oxide coating on the surface layer, which are oxidized for 2h in a water vapor environment at 1200 ℃, FIG. 10a is a cross-sectional morphology diagram of a Zr-4 alloy not protected by a coating, which is oxidized for 2h in a water vapor environment at 1200 ℃, it can be seen that the Zr-4 alloy oxide film on the side not protected by a coating grows to about 420 μm, FIG. 10b is a cross-sectional morphology diagram of a Zr-4 alloy protected by a coating, which is oxidized for 2h in a water vapor environment at 1200 ℃, and FIG. 10c is a plane morphology diagram of an interface position, which can be seen that the oxide film at the protection position with a coating only grows to about 35 μm. FIG. 11 is a graph showing the oxide film thickness of a bare Zr-4 alloy and a Zr-4 alloy protected by a low-oxygen ZrNbCrAlSiO coating on the surface layer along with the oxidation time in a water vapor environment at 1200 ℃. The oxide film thickening curves of the naked Zr-4 alloy and the Zr-4 alloy protected by the low-oxygen ZrNbCrAlSiO coating on the surface layer in a high-temperature water vapor environment within 1200 ℃/2h follow an approximate parabolic rule. The thickening speed of the Zr-4 alloy oxide film of the coating protection is far lower than that of the bare Zr-4 alloy at the stage, and the coating protection can slow down the oxidation kinetic rate of the Zr-4 alloy in a water vapor environment at 1200 ℃. The surface layer low-oxygen zirconium-based amorphous multi-component oxide coating has good stability in a high-temperature water vapor environment.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for preparing a zirconium-based amorphous multi-component oxide coating is characterized by comprising the following steps: the zirconium-based amorphous multi-component oxide coating is prepared on a zirconium alloy matrix by a magnetron sputtering reaction co-sputtering method.
2. The method for preparing a zirconium-based amorphous multicomponent oxide coating according to claim 1, characterized by the steps of:
(1) After acid cleaning, silicon carbide abrasive paper polishing and ultrasonic cleaning are carried out on the zirconium alloy substrate, nitrogen is dried for standby;
(2) Attaching the zirconium alloy matrix obtained in the step (1) on a substrate base plate, and placing the substrate base plate in a rotary heating table of a magnetron sputtering chamber, wherein the target base distance is adjusted to 15cm;
(3) And (3) cutting and combining the zirconium-based multi-element target material into a sputtering target material A, cutting 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, carrying out preparation work, and preparing the zirconium-based amorphous multi-element oxide coating on the substrate obtained in the step (2) based on a magnetron sputtering reaction co-sputtering method after the preparation work is finished.
3. The method for preparing a zirconium based amorphous multicomponent oxide coating according to claim 2, characterized in that: the acid washing solvent in the step (1) is HNO with the volume concentration of 10 percent 3 10% HF, 10% H 2 O 2 The ultrasonic cleaning method comprises the following steps: sequentially placing the zirconium alloy matrix in acetone, absolute ethyl alcohol and deionized water, and respectively carrying out ultrasonic cleaning for 20min; the zirconium alloy substrate is a Zr-4 alloy plate.
4. The method for preparing a zirconium-based amorphous multicomponent oxide coating according to claim 3, characterized in that: the zirconium-based multi-element target material in the step (3) comprises at least two of Zr, nb, cr or Mo, and the Si-based multi-element target material comprises at least one element of Al, si, fe or Ta.
5. The method for preparing a zirconium-based amorphous multicomponent oxide coating according to claim 4, wherein the preparatory work in the step (3) is: the vacuum degree of the chamber is pumped to 6 x 10 -4 Pa or less, in a chamberAfter the vacuum degree reaches the required vacuum degree, ar and O are introduced 2 And the gas flow rate of Ar is set to 20sccm, and O is added 2 After the gas flow is set to be 0.6-1.2sccm, adjusting the pressure in the cavity to 3-5Pa (+ -0.02 Pa), then starting a radio frequency power supply to preheat for 3-5min, and adjusting the power of the radio frequency power supply to 80-120W after the radio frequency power supply is started; after the direct current power supply is started to glow, adjusting the power of the direct current power supply to 3-30W, then adjusting the air pressure in the chamber to 1.5Pa, and pre-sputtering the two targets for 15min; the reaction co-sputtering method based on magnetron sputtering comprises the following steps: and opening the substrate baffle plate, and performing reactive co-sputtering for 10h to prepare the zirconium-based amorphous multi-component oxide coating.
6. The method for preparing a zirconium-based amorphous multicomponent oxide coating according to claim 5, wherein in step (3), O is 2 The specific operating conditions for setting the gas flow of (2) to 0.6-1.2sccm are: when the zirconium-based amorphous multi-component oxide coating in a complete oxidation state is deposited by utilizing magnetron sputtering, O is added by adjusting a gas flowmeter 2 The gas flow rate was set to 1.2sccm; when the zirconium-based amorphous multi-component oxide coating with the gradient oxidation state from the outside to the inside is deposited by magnetron sputtering, O is added by adjusting a gas flow meter 2 The gas flow rate was set to 0.6-0.8sccm.
7. A zirconium based amorphous multicomponent oxide coating prepared by the method according to any one of claims 1-6, characterized in that: the surface layer of the zirconium-based amorphous multi-component oxide coating is in a complete oxidation state or a gradient oxidation state from the surface to the inside, various elements in the zirconium-based amorphous multi-component oxide coating are uniformly distributed, no crystalline phase appears, the coating structure is stable, and the thickness of the film is 0.2-3 mu m.
8. The zirconium-based amorphous multicomponent oxide coating according to claim 7, characterized in that: the surface layer of the zirconium-based amorphous multicomponent oxide coating is in a complete oxidation state or a gradient oxidation state from the surface to the inside, and has high-temperature oxidation resistance; when the surface layer of the zirconium-based amorphous multi-component oxide coating is in a complete oxidation state, the zirconium-based amorphous multi-component oxide coating has stability at 320 ℃ in a 16MPa high-temperature and high-pressure water environment; when the surface layer of the zirconium-based amorphous multi-component oxide coating is in a gradient oxidation state from the outside to the inside, the stability of the zirconium-based amorphous multi-component oxide coating at 320 ℃ and under 16MPa high-temperature and high-pressure water environment is higher than that of the zirconium-based amorphous multi-component oxide coating with the completely oxidized surface layer.
9. Use of a zirconium based amorphous multicomponent oxide coating according to claim 7 in the field of oxidation resistance.
10. Use of a zirconium based amorphous multicomponent oxide coating according to claim 8 for surface protection of a zirconium alloy as a nuclear fuel cladding material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784308A (en) * | 2022-11-13 | 2023-03-14 | 重庆交通大学 | Method for preparing amorphous multicomponent refractory transition metal oxide nanoparticles |
| CN117305787A (en) * | 2023-09-28 | 2023-12-29 | 郑州大学 | Multilayer cooperative protection system of high-entropy coating and in-situ zirconium-silicon diffusion layer, preparation method and application |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TH93647A (en) * | 2007-08-17 | 2009-02-20 | นางสาวอรุณศรี ศรีธนะอิทธิพล | Method for growing oxenitride film by gas time control in reactive RF magnetron sputtering system. |
| CN101921982A (en) * | 2010-09-06 | 2010-12-22 | 厦门大学 | Method for preparing nano-structured nitrogen silicon zirconium coating on surface of hard alloy substrate |
| WO2017136971A1 (en) * | 2016-02-11 | 2017-08-17 | 广东工业大学 | (ti, al, zr)n multi-component composite coating, graded structure ultrafine hard alloy cutting tool with the composite coating, and method for manufacturing same |
| US20170287578A1 (en) * | 2014-09-17 | 2017-10-05 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Nuclear fuel claddings, production method thereof and uses of same against oxidation/hydriding |
| CN107513694A (en) * | 2017-08-22 | 2017-12-26 | 四川大学 | A kind of zirconium cladding surface resistance to high temperature oxidation ZrCrFe/AlCrFeTiZr complex gradient coating preparation technologies |
| CN111206217A (en) * | 2020-03-25 | 2020-05-29 | 郑州大学 | Preparation method of Zr-Si-O amorphous protective coating for nuclear power |
| CN112813399A (en) * | 2021-02-04 | 2021-05-18 | 郑州大学 | High-entropy metal glass protective coating and preparation method thereof |
| CN112831751A (en) * | 2021-02-04 | 2021-05-25 | 郑州大学 | High-temperature self-transition amorphous/nanocrystalline high-entropy oxide film, preparation method and application |
| CN113789503A (en) * | 2021-09-15 | 2021-12-14 | 郑州大学 | In-situ synthesis method of high-entropy silicide film with anti-oxidation characteristic |
-
2022
- 2022-08-16 CN CN202210980844.1A patent/CN115305443B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TH93647A (en) * | 2007-08-17 | 2009-02-20 | นางสาวอรุณศรี ศรีธนะอิทธิพล | Method for growing oxenitride film by gas time control in reactive RF magnetron sputtering system. |
| CN101921982A (en) * | 2010-09-06 | 2010-12-22 | 厦门大学 | Method for preparing nano-structured nitrogen silicon zirconium coating on surface of hard alloy substrate |
| US20170287578A1 (en) * | 2014-09-17 | 2017-10-05 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Nuclear fuel claddings, production method thereof and uses of same against oxidation/hydriding |
| WO2017136971A1 (en) * | 2016-02-11 | 2017-08-17 | 广东工业大学 | (ti, al, zr)n multi-component composite coating, graded structure ultrafine hard alloy cutting tool with the composite coating, and method for manufacturing same |
| CN107513694A (en) * | 2017-08-22 | 2017-12-26 | 四川大学 | A kind of zirconium cladding surface resistance to high temperature oxidation ZrCrFe/AlCrFeTiZr complex gradient coating preparation technologies |
| CN111206217A (en) * | 2020-03-25 | 2020-05-29 | 郑州大学 | Preparation method of Zr-Si-O amorphous protective coating for nuclear power |
| CN112813399A (en) * | 2021-02-04 | 2021-05-18 | 郑州大学 | High-entropy metal glass protective coating and preparation method thereof |
| CN112831751A (en) * | 2021-02-04 | 2021-05-25 | 郑州大学 | High-temperature self-transition amorphous/nanocrystalline high-entropy oxide film, preparation method and application |
| CN113789503A (en) * | 2021-09-15 | 2021-12-14 | 郑州大学 | In-situ synthesis method of high-entropy silicide film with anti-oxidation characteristic |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784308A (en) * | 2022-11-13 | 2023-03-14 | 重庆交通大学 | Method for preparing amorphous multicomponent refractory transition metal oxide nanoparticles |
| CN115784308B (en) * | 2022-11-13 | 2024-05-31 | 重庆交通大学 | Method for preparing amorphous multicomponent refractory transition metal oxide nano particles |
| CN117305787A (en) * | 2023-09-28 | 2023-12-29 | 郑州大学 | Multilayer cooperative protection system of high-entropy coating and in-situ zirconium-silicon diffusion layer, preparation method and application |
| CN117305787B (en) * | 2023-09-28 | 2024-06-18 | 郑州大学 | Multilayer cooperative protection system of high-entropy coating and in-situ zirconium-silicon diffusion layer, preparation method and application |
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|---|---|
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